Clean and Renewable Energy Production [1 ed.] 139417442X, 9781394174423

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Clean and Renewable Energy Production

Publishers at Scrivener Martin Scrivener ([email protected]) Phillip Carmical ([email protected])

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Scrivener Publishing 100 Cummings Center, Suite 541J Beverly, MA 01915-6106

Surajit Mondal Adesh Kumar Rupendra Kumar Pachauri Amit Kumar Mondal Vishal Kumar Singh

Amit Kumar Sharma

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Clean and Renewable Energy Production

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Preface xvii 1 Vegetable Seed Oils as Biofuel: Need, Motivation, and Research Identifications 1 Deepak Kumar, Vijay Kumar Chhibber, Ajay Singh and Adesh Kumar 1.1 Introduction to Vegetable Oils 2 1.2 Motivation 4 1.3 Need of Research 6 1.3.1 Biodiesel Considerations 8 8 1.3.2 Energy Balance and Security 1.3.3 Air Quality 8 1.3.4 Engine Function 9 1.3.5 Safety 9 1.4 Detailed Survey 10 16 1.5 Identification of the Research Gaps 1.5.1 Toxicity 18 19 1.5.2 Biodegradability 1.6 Conclusions 20 References 20 2 Methodology and Instrumentation for Biofuel with Study on Cashew Nut Shell Liquid Deepak Kumar, Vijay Kumar Chhibber, Ajay Singh and Adesh Kumar 2.1 Methodology 2.2 Procedure 2.2.1 Common Points 2.3 Fourier Transform Infrared Spectroscopy 2.4 Gas Chromatography–Mass Spectrometry 2.5 Nuclear Magnetic Resonance

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Contents

2.6 CNSL Study 2.7 Conclusions References 3 Emerging Technologies for Sustainable Energy Applications Swagata Sarma, Gaurav Pandey, Uttamasha B. Borah, Nadezhda Molokitina, Geetanjali Chauhan and Monika Yadav 3.1 Introduction 3.2 Carbon Dioxide Sequestration 3.2.1 Biological Carbon Sequestration 3.2.2 Geological Carbon Sequestration 3.2.3 Technological Carbon Sequestration 3.2.4 Hydrate-Based CO2 Sequestration Technology 3.2.5 Carbon Sinks and Types 3.2.5.1 Estuarine Ecology as Sediment Carbon 3.2.5.2 Mangroves and Mudflat Soils as Carbon Sink 3.2.5.3 Tidal Marsh Soils as Carbon Sink 3.2.5.4 Soils of Coastal Agroecosystem as Carbon Sink 3.2.5.5 Sediments of Marine Coastal Ecologies as Carbon Sink 3.2.6 CO2 Sequestration Utilization in Enhanced Oil Recovery 3.3 Carbon Capture, Utilization, and Storage 3.3.1 Global CCUS Development 3.3.2 Risk Analysis of CCUS 3.4 Renewable Energy 3.4.1 Solar Energy 3.4.2 Hydro Energy 3.4.3 Geothermal Energy 3.4.4 Biomass Energy 3.4.5 Wind Energy 3.5 Conclusion References 4 Affordable and Clean Energy: Natural Gas Hydrates and Hydrogen Storage Uttamasha B. Borah, Gaurav Pandey, Swagata Sarma, Nadezhda Molokitina and Geetanjali Chauhan 4.1 Introduction

35 51 51 53 54 56 57 60 60 61 63 63 63 65 66 67 69 70 71 74 74 75 77 77 79 80 81 81 87 88

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89 4.2 Gas Hydrates 4.2.1 Extraction Methodologies 90 4.2.1.1 Thermal Stimulation Method 91 4.2.1.2 Depressurization Method 91 4.2.1.3 Inhibitor Injection Method 92 4.2.1.4 Gas Exchange Method 92 4.2.2 Geological Hazards 93 4.2.2.1 Hydrate-Associated Risks for Oil and Gas Exploitation 100 4.2.3 Sustainable Applications 102 4.2.4 Solidified Natural Gas 103 4.2.5 Seawater Desalination 103 105 4.2.6 CO2 Sequestration and Methane Recovery 4.2.7 Gas Separation 107 4.3 Hydrogen Energy 108 4.3.1 Types of H2 108 4.3.2 Hydrogen Storage 110 4.3.2.1 Compressed Gas 111 111 4.3.2.2 Underground Hydrogen Storage 4.3.2.3 Liquid Hydrogen 111 4.3.2.4 Solid Storage 112 112 4.3.3 H2 as Fuel 112 4.3.4 Industrial Applications of H2 4.4 Recent Advancement Toward Clean Energy Applications 114 4.5 Conclusion 115 References 115 5 Wind and Solar PV System-Based Power Generation: Imperative Role of Hybrid Renewable Energy Technology Madhura K. Pardhe, Rupendra Kumar Pachauri and Priyanka Sharma 5.1 Introduction 5.2 Renewable Energy for Sustainable Development 5.3 Global Energy Scenario 5.4 Solar Energy Potential 5.5 Wind Potential for Power Generation 5.6 Hybrid Renewable Energy Systems 5.7 Pros and Cons of the Hybrid Renewable Energy System 5.7.1 Pros of the Hybrid Renewable Energy System 5.7.2 Cons of the Hybrid Renewable Energy System

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Contents  vii

5.8 Conclusion References

137 137

6 A Systematic Review of the Last Decade for Advances in Photosynthetic Microbial Fuel Cells with Bioelectricity Generation 143 Vijay Parthasarthy, Riya Bhattacharya, Roshan K. R., Shankar R., Siddhant Srivastava and Debajyoti Bose 144 6.1 Introduction 6.2 Background 145 6.3 Methodology 148 6.4 Study Selection Criteria 149 6.5 Configurations and Performance Evaluation of 150 Photosynthetic Microbial Fuel Cells 6.5.1 Algal-Based p-MFC 157 6.5.2 Plant-Microbial Fuel Cells or P-MFCs 161 6.6 Outlook 163 Data Availability Statement 165 Funding 165 Conflict of Interest 165 References 165 7 Hydrothermal Liquefaction as a Sustainable Strategy for Integral Valorization of Agricultural Waste 175 Manisha Jagadale, Mahesh Jadhav, Nagesh Kumar T., Prateek Shrivastava and Niranjan Kumar 7.1 Introduction 176 177 7.2 Generation of Biofuels 178 7.3 Biomass Conversion Routes 7.4 HTL Reaction Mechanism 179 7.5 HTL Process Yield Calculations 180 7.6 HTL Advantage Over Pyrolysis 180 7.6.1 Energy Content from the Biomass 181 7.6.2 Bio-Oil and Bio-Coal Yields 181 7.6.3 Oxygen Content in Bio-Oil 181 182 7.6.4 Carbon Content Utilization 7.6.5 No Pretreatment and Drying 182 182 7.6.6 Energy Saving 7.7 Types of Reactors for the Hydrothermal Liquefaction Process 182 7.7.1 Batch Reactor 183

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7.7.2 Continuous Reactor 7.7.2.1 Continuous Plug Flow Reactor 7.7.2.2 Continuous Stirred Tank Reactor 7.8 Influence of Operating Parameters 7.8.1 Biomass Type 7.8.2 Operating Temperature 7.8.3 Heating Rate 7.8.4 Residence Time 7.8.5 Pressure 7.8.6 Type of Catalyst 7.9 Product Distribution and Evaluation 7.9.1 Liquid (Bio-Oil) 7.9.2 Solid (Hydrochar) 7.9.3 Aqueous Water and Gases 7.10 Potential Applications of HTL Products 7.11 Challenges and Limitations of the HTL Process 7.12 Techno-Economic and Environmental Analysis 7.13 Conclusions References

183 183 184 184 184 186 186 189 189 190 190 190 191 192 192 193 194 194 195

8 Imperative Role of Proton Exchange Membrane Fuel Cell System and Hydrogen Energy Storage for Modern Electric Vehicle Transportation: Challenges and Future Perspectives 201 Rupendra Kumar Pachauri, Deepa Sharma, Surajit Mondal, Shashikant and Priyanka Sharma 8.1 Introduction 202 8.2 Modeling of the PEMFC System 206 207 8.3 Electrical Vehicle Categories 211 8.4 Hydrogen Energy Storage 8.4.1 Hydrogen Energy Production: Approaches with Challenges 212 8.4.2 Methods of Hydrogen Energy Storage: Approaches and Challenges 212 8.5 Future Scope, Challenges, and Benefits of FCEVs 214 8.6 Pros and Cons of Electric Vehicles in the Aspect of Modern 216 Transportation System 8.7 MATLAB/Simulink Study of FC-Powered Electric Drive System 216 8.8 Conclusion 221 References 221

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Contents  ix

9 Ocean Energy—A Myriad of Opportunities in the Renewable Energy Sector R. Raajiv, R. Vijaya Kumar and Jitendra Kumar Pandey 9.1 Introduction 9.2 International Agencies Promoting Ocean Energy Projects 9.3 Ocean Energy Potential 9.4 Types of Ocean Energy 9.5 Tidal Energy 9.5.1 Tidal Stream Generator 9.5.2 Tidal Stream Barrage 9.5.3 Tidal Lagoon 9.5.4 Dynamic Tidal Power 9.6 Tidal Currents 9.7 Wave Energy 9.8 Ocean Thermal Energy Conversion 9.9 Salinity Gradient 9.10 Marine Energy Projects in India 9.10.1 Case Study 1 9.10.2 Case Study 2 9.11 Conclusion Author Contributions References 10 Performance of 5 Years of ESE Lightning Protection System: A Review Sachin Kumar, Gagan Singh and Nafees Ahamad Introduction Theoretical Background External Lightning Protection Structure for the PV Power Plant Results and Analysis Conclusion References

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11 Solar Photovoltaic System-Based Power Generation: Imperative Role of Artificial Intelligence and Machine Learning 267 Rupendra Kumar Pachauri, Jitendra Yadav, Stephen Oko Gyan Torto, Ahmad Faiz Minai, Vikas Pandey, Shashikant and Priyanka Sharma 11.1 Introduction 268 11.2 Solar Energy Power Generation Scenario in the 271 Indian Context 11.3 Applications of AI and ML in Solar PV Systems 271 273 11.3.1 Maintenance Prediction 11.3.2 Optimization of Orientation of the Solar Panels 274 to Maximize Energy Generation 11.3.3 Weather Forecasting for PV System Power Assessment 274 11.3.4 Forecasting of PV System Performance During 275 Dust Accumulation 11.3.5 Solar Parameter Prediction 276 11.3.6 Fault Detection Using Artificial Intelligence 276 11.4 Pros and Cons of AI and ML Techniques in Solar PV System 277 11.5 Application of GA-Based Optimal Placement of PV Modules in an Array to Reduce PSCs 277 11.5.1 Modeling of PV System 277 11.5.2 Genetic Algorithm-Based PV Array Reconfiguration 279 280 11.5.3 Shading Scenarios and Electrical Performance 11.6 Conclusion 283 References 283 12 Waste to Energy Technologies for Energy Recovery Senthil Kumar Kandasamy and Ramyea R. 12.1 Introduction 12.2 Preparation Methods 12.3 Carbonization and Activation 12.3.1 Uses of Carbonization 12.3.2 Uses of Activation 12.3.2.1 Phosphoric Acid Activation 12.3.2.2 Zinc Chloride Activation 12.3.2.3 Potassium Hydroxide Activation 12.3.2.4 Potassium Carbonate Activation 12.3.2.5 Nitric Acid Activation 12.4 Electrode Materials Extracted from Biowastes

287 287 290 290 290 291 292 292 292 293 293 293

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Contents  xi

12.4.1 Carbon Nanotube 12.4.2 Graphene Oxide 12.4.3 Carbon Aerogel 12.4.4 Activated Carbon 12.5 Energy Storage Applications 12.6 Importance of Electrolyte 12.7 Conclusions References

294 294 294 294 297 304 304 305

13 A Review of Electrolysis Techniques to Produce Hydrogen 313 for a Futuristic Hydrogen Economy Vijay Parthasarthy, Siddhant Srivastava, Riya Bhattacharya, Sudeep Katakam, Akash Krishnadoss, Gaurav Mitra and Debajyoti Bose 13.1 Introduction 314 13.1.1 Chemistry Behind Electrolysis 315 13.1.2 Step 1 315 315 13.1.3 Step 2 13.1.4 Anion Exchange Membrane Water Electrolysis 315 13.2 Methodology 317 13.2.1 Search Strategy 317 13.2.2 Search Scope 317 318 13.2.3 Search Method 13.2.4 Search String 318 13.2.5 Study Selection Criteria 318 13.3 Configurations and Performance Evaluation of AEM Electrolyzer 319 329 13.4 Scope for Improvements 331 13.5 Conclusion References 331 14 Prospects of Sustainability for Carbon Footprint Reduction 335 Riya Bhattacharya, Debajyoti Bose, Gaurav Mitra and Abhijeeta Sarkar 336 14.1 Introduction 14.2 Context and Outcomes of the United Nations Climate 337 Change Framework 339 14.3 Monitoring Direct and Indirect Carbon Emissions 14.4 Sustainable Alternatives to Reduce Carbon Footprints 341 14.4.1 Policies for Reducing Carbon Footprints 342 14.4.2 Technologies and Strategies Designed for Specific Sectors 342

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14.4.3 Innovative Carbon Reduction Strategies and Technologies 14.4.3.1 Buildings and Cities  14.4.3.2 Transportation 14.4.4 Societal Contribution Toward Carbon Reduction 14.5 Carbon Elimination from the Atmosphere 14.6 Outlook Conflict of Interest References

345 345 346 346 347 348 350 350

15 Conventional and AI-Based MPPT Techniques for Solar Photovoltaic System-Based Power Generation: Constraints 355 and Future Perception Rupendra Kumar Pachauri, Vaibhav Sharma, Adesh Kumar, Shashikant, Akhlaque Ahmad Khan and Priyanka Sharma 15.1 Introduction 356 359 15.2 MPPT Systems 15.2.1 Conventional MPPT Techniques 359 15.2.2 AI-Based MPPT Techniques 364 15.2.3 Pros and Cons of Conventional and AI-Based MPPT 367 369 15.3 Challenges and Future Perspective 15.4 Radial Diagram-Based Relational Performance of MPPT Techniques 370 15.5 Conclusion 370 References 371 16 Bioethanol Production and Its Impact on a Future Bioeconomy 375 Apurva Jaiswal, Riya Bhattacharya, Siddhant Srivastava, Ayushi Singh and Debajyoti Bose 376 16.1 Introduction to Bioenergy 16.1.1 Bioethanol 377 16.1.1.1 Bioethanol as an Alternative Fuel 377 16.1.1.2 Simultaneous Saccharification and Fermentation379 380 16.2 Overview of Lignocellulosic Biomass 16.2.1 Composition and Structure 382 16.2.2 Pretreatment Techniques for Lignocellulosic Biomass 383 16.2.2.1 Physical Pretreatment 384

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Contents  xiii

385 16.2.2.2 Physiochemical Pretreatment 16.2.2.3 Chemical Pretreatment 387 16.2.2.4 Biological Pretreatment 389 16.3 Challenges and Opportunities 389 16.3.1 Pretreatment Constraints in LCB Production 390 16.3.2 Role of Microbes in LCB Production 390 16.3.3 Cost Constraints in LCB Production 392 392 16.3.4 Genetic Manipulation of Energy Crops 16.3.4.1 Increasing Cellulose Content 393 16.3.4.2 Reduction of Plant Cell Wall Recalcitrance and Cellulose Crystallinity 393 16.3.4.3 Production of Hydrolases in Plants 394 394 16.3.4.4 Lignin Modification 16.4 Bioethanol Economy 395 16.4.1 Synthetic Biology of CBP Microbes 397 16.4.1.1 Cellulose Expression and Secretion Systems398 399 16.4.1.2 Enhanced Tolerance 16.4.1.3 Metagenomics 400 16.4.1.4 Advanced Biofuel Production 400 16.4.2 Future Perspective for LCB Production 401 References 403 17 Waste-to-Energy Technologies for Energy Recovery Shivam Pandey, Anjana Sharma, Naveen Kumar, Nupur Aggarwal and Ajay Vasishth 17.1 Energy 17.1.1 Global Issues and Renewable Energy 17.2 Alternatives to Waste-to-Energy Routes that Might Be Used 17.2.1 Technology Limitations of WTER 17.2.2 Waste-to-Energy 17.2.3 Worldwide Sector for Waste-to-Energy 17.3 The Situation of the Waste-to-Energy Market Today 17.3.1 Environmental Advantages of Waste-to-Energy 17.3.2 Pollutants from Landfills 17.3.3 Release of Arsenic from Garbage 17.3.4 Vaporized Organic Substances 17.3.5 Municipal Solid Waste Management 17.4 Technical and Economic Considerations

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17.4.1 Fuel from Plastic 17.4.2 Biochemical Conversion 17.4.3 Thermochemical Conversion 17.4.4 Thermal Treatment 17.5 Conclusion References 18 Biodiesel Production, Storage Stability, and Industrial Applications: Opportunities and Challenges Girdhar Joshi 18.1 Biodiesel 18.2 Feedstocks for Biodiesel Production 18.3 Biodiesel Conversion Methods 18.3.1 Homogenous Catalysis 18.3.2 Heterogenous Catalysis 18.3.3 Enzymatic Catalysis 18.4 Physicochemical Properties of Biodiesel 18.5 Storage Stability of Biodiesel 18.5.1 Addition–Elimination Reaction 18.6 Combustion Characteristics of Biodiesel 18.7 Conclusions and Future Perspectives of Biodiesel References 19 Biomass Energy and Its Conversion Naval V. Koralkar, Mohit Kumar, Raj Kumar and Praveen Kumar Ghodke 19.1 Introduction 19.2 Sources of Biomass 19.3 Techniques for Converting Biomass Into Energy 19.3.1 Thermochemical Conversion 19.3.1.1 Pyrolysis 19.3.1.2 Biomass Gasification 19.3.1.3 Combustion 19.4 Biochemical/Biological Conversion 19.5 Physical Conversion 19.6 Power Plant Dynamic Modeling and Simulation Using Biomass as Fuel 19.6.1 Biomass Combustion Modeling 19.7 Summary References

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20 Co-Gasification of Coal and Waste Biomass for Power Generation 505 Naval V. Koralkar, Mohit Kumar, Raj Kumar and Praveen Kumar Ghodke 506 20.1 Introduction 20.1.1 Combined Usage of Biomass and Coal 507 20.2 Co-Gasification 509 20.2.1 Gasification Technologies 510 20.3 Biomass Gasification Co-Generation 516 516 20.4 Summary References 517 Index 523

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xvi  Contents

In an era marked by growing concerns over climate change, environmental degradation, and the sustainability of energy resources, the quest for cleaner and more sustainable energy production has never been more critical. As the world’s demand for energy continues to rise, so too does the urgency to transition from traditional fossil fuel-based sources to cleaner and renewable alternatives. The title Clean and Renewable Energy Production encapsulates a journey into the heart of this transformative endeavor. This book delves into the profound changes taking place in the realm of energy, exploring the innovative technologies, policy shifts, and scientific breakthroughs that are shaping the landscape of energy production and consumption. All the chapters in the book follow a comprehensive exploration of various clean and renewable energy sources, ranging from solar, biofuel, and hydrothermal, to ocean energy, carbon neutrality, hydrogen energy, and wind energy. Throughout this book, not only the technical aspects of clean energy production are examined but also the broader implications for our planet and society. Moreover, the economic, geopolitical, and social ramifications of transitioning to renewable energy sources, as well as the challenges that must be overcome to make this transition a reality on a global scale. Moreover, Clean and Renewable Energy Production will serve as a valuable reference for students, researchers, policymakers, and anyone seeking a deeper understanding of the multifaceted facets of sustainable energy. Each chapter is meticulously crafted to offer a balanced blend of scientific explanations, real-world case studies, and forward-thinking visions. Moreover, this book stands as a testament to the power of human ingenuity and determination in the face of one of the greatest challenges of our time. The journey towards a cleaner and more sustainable energy future is not without its obstacles, but it is a journey that promises a world of untapped potential, innovation, and hope. As you embark on this reading xvii

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Preface

adventure, may you find inspiration and knowledge that empower you to play a role in shaping the future of energy production and the well-being of our planet. Chapter-1: Presents the need, motivation, and research gapes with detailed survey for biofuel. Chapter-2: Delivers the methodology and Instrumentation for Biofuel with Study on Cashew Nut Shell Liquid. Chapter-3: This chapter significantly explored the various diverse topics pertaining to sustainable energy. Carbon dioxide sequestration and carbon capture, utilization, and storage have been discussed in conjunction with sustainable energy solutions and the global deployment of the de-­ carbonization mission. Chapter-4: Presents the methods of recovering gas hydrates from extreme conditions of pressure and temperature that aid their production requires the correct equipment and techniques. Chapter-5: Shows the importance of wind and solar photovoltaic ­system-based power generation and the imperative role of hybrid renewable energy technology as well. Chapter-6: Study is based on the a systematic review of the last decade for advances in photosynthetic microbial fuel cells with bioelectricity generation. Chapter-7: Explores the hydrothermal liquefaction as a sustainable strategy for integral valorization of agricultural waste. Chapter-8: Study is based on the PEM fuel cell for modern transportation systems along the current challenges and future perspectives. Chapter-9: Delivers the detailed reviewed study for ocean energy and a myriad of opportunities in the renewable energy Sector. Chapter-10: This article shows a five-year performance review of an early streamer emission air terminal lightning protection system for a large-scale photovoltaic power plant. Chapter-11: Study demonstrates the potential of AI and ML to play essential functions in boosting the reliability, effectiveness, and longevity of PV systems, making them more economically viable and environment-friendly. Chapter-12: Explores the waste to energy technologies for energy recovery and the ecological conditions of large populated cities may improve with the help of energy storage devices. Chapter-13: A comprehensive review on electrolysis techniques to produce hydrogen for a futuristic hydrogen economy. Chapter-14: Discusses the prospects of sustainability for carbon footprint reduction.

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xviii  Preface

Chapter-15: Study on the conventional and AI-based MPPT techniques for solar photovoltaic system-based power generation, constraints and future perception. Chapter-16: Explains the refinement in production techniques through synthetic biology and its effect on microbial metabolism are also reviewed. Chapter-17: This chapter suggests that that waste has the ability to be used as a power source for both advanced and developing economies. Chapter-18: Provides the methods of biodiesel production, storage stability, and industrial applications: opportunities and challenges. Chapter-19: In this chapter, a detailed description of the conversion technology has been discussed based on the previous studies. It was also suggested that thermochemical conversion techniques have been significantly used for converting biomass into useful fuels. Chapter-20: The chapter discusses biomass-waste co-conversion and the fuels’ complimentary features to minimize individual consumption impacts. Different co-generation processes produce heat and electricity alongside other things, making them more economically viable. Dr. Surajit Mondal Dr. Adesh Kumar Dr. Rupendra Kumar Pachauri Dr. Amit Kumar Mondal Dr. Amit Kumar Sharma Vishal Kumar Singh Editors

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Preface  xix

Vegetable Seed Oils as Biofuel: Need, Motivation, and Research Identifications Deepak Kumar1*, Vijay Kumar Chhibber2, Ajay Singh3 and Adesh Kumar4 Department of Chemistry, Uttarakhand Technical University, Dehradun, India 2 Indian School of Petroleum (IIP), Dehradun & Dean Baba Farid Institute of Technology, Dehradun, India 3 Department of Chemistry, Uttaranchal University, Dehradun, India 4 Department of Electrical and Electronics Engineering, University of Petroleum and Energy Studies, Dehradun, India 1

Abstract

The sources of fossil fuels are running out more quickly due to the rising population and fuel consumption. Over the previous 50 years, the world’s energy requirements have tripled; in the following 30 years, they are expected to do so again in nations like China and India. Research on converting non-edible vegetable oils into biofuels, lubricants, and alternative energy sources is being done in developing countries. Vegetable oils have potential benefits in comparison to mineral oils due to their properties such as biodegradability, nontoxicity, reasonable product cost resource renewability, great viscosity index, and disreputable content of the lubricants. The amount of blending changes according to the cost of crude oil throughout the world and the supply of biofuel feedstock. As a result, they are no longer negatively impacted by the global crude oil price. This chapter explains the introduction to lubricants, motivation, and the need for research. Some potential research aspects and gaps are also discussed. Keywords:  Additives, biodiesel, environment emissions, engine operation, lubricants

*Corresponding author: [email protected] Surajit Mondal, Adesh Kumar, Rupendra Kumar Pachauri, Amit Kumar Mondal, Vishal Kumar Singh and Amit Kumar Sharma (eds.) Clean and Renewable Energy Production, (1–26) © 2024 Scrivener Publishing LLC

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1.1 Introduction to Vegetable Oils Vegetable oils are generally derived from renewable agricultural sources. These sources are harmless and yield good environmental and safety aspects. Vegetable oils are interesting replacements for lubricants based on petroleum and former applications because of their qualities. Vegetable oils can be divided into two categories based on their chemical composition. The majority of vegetable oils are triglycerides (TGs), which are triesters of glycerol in different forms of fatty acids (FAs) (Biresaw et al. 2003). Fatty alcohols and monoesters of long-chain FAs with variable degrees of unsaturation make up a few vegetable oils. Most vegetable oils are classified as amphiphilic because they contain separate sections of polar and nonpolar clusters in an identical molecule. One ester functional group is at least present in the polar groups. Hydrocarbons with different chain lengths, stereochemistry, and degrees of unsaturation make up the nonpolar groups. The hydrocarbon portion may contain functional groups like epoxides and hydroxides of the molecule contingent on the kind of vegetable oil. Vegetable oil’s tribological and other qualities are greatly influenced by the chemical composition of their polar and nonpolar groups. A triglyceride with a lower degree of unsaturation is going to be more oxidative stable than one with a higher degree of unsaturation. Moreover, vegetable oils are categorized as functional fluids because they include at least one ester as a functional group and, at room temperature, are present in liquid form. These oils can be employed as base oils because of this feature in lubricant formulations (Ahmad et al. 2022). There are three different types of lubrication regimes: boundary, mixed, and hydrodynamic. These oils can be used in all three regimens because they are functional fluids. However, the effect of vegetable oils on both fluid and boundary properties should be known as it is required for the effective use of vegetable oils in lubricant compositions. Adsorption and reaction are two mechanisms that influence the boundary lubrication qualities of these oils. During a tribological process, the ability of oils to adsorb on the friction surfaces and to prevent contact is referred to as adsorption. Adsorption occurs primarily as a result of the interface of the functional groups of vegetable oils with the friction surfaces, and it may be measured using adsorption free energy phrases (Chidambaram et al. 2021). The reaction ability refers to the ability of vegetable oils in the interaction of friction zone to undertake chemical reactions on their own or with other materials, such as metals, moisture, and oxygen. The high pressure, temperature, and shear of the lubricating method cause reaction. Tribochemical reactions are the name for these processes, which are poorly understood

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and accountable for a variety of sensations, including the oxidation of oil and the formation of friction polymers. A full understanding of these tribal–chemical processes is required for the effective use of vegetable oils in lubrication. Vegetable oils (Issariyakul et al. 2014) are promoted as superior to their conventional counterparts. Vegetable oils are TGs that comprise long-chain unsaturated free fatty acids (FFAs) linked by an ester linkage to hydroxy groups. Variations in the physical and chemical properties, as well as behavior, are based on these elementary blocks. They are chosen over toxic complements owing to their competitive methodological qualities such as viscosities, greater oiliness and indices, greater flash points, reduced evaporative losses, and cheaper complete accounting costs, which include operating and nature replenishment costs. Although they have some disadvantages, such as weaker oxidation and thermal stabilities, poor cold flow qualities, and shorter shelf life, they can be enhanced through rigorous modification procedures and methodical study. Edible and non-edible oils are available. There are several variations throughout the world, but only a small percentage of them has been exploited to their full potential. Researchers have spent a lot of time studying edible oils all across the world. Using edible oils for non-food purposes (fuel/lubricant) disrupts their household use. India is the world’s largest importer of edible oils, and rising bills for an ever-increasing population harm its economy. Alternatives in the shape of non-edible types, on the other hand, represent no such hazard and contribute to the urban economy. Lubricants (Karmakar et al. 2017) are required in nearly every aspect of contemporary technology. Lubricants are chemicals that are used to lubricate surfaces in common interactions to simplify the component movement and reduce friction and wear. Saving energy and resources, as well as reducing emissions, has become critical environmental concerns as sustainability (Leung et al. 2010) has become a motivating force in the domain. As a result, business activity is increasingly focused on resource shortage and accountability for future requirements. Lubricants are gaining popularity among the general public because they help to achieve environmental, economic, and social sustainability goals. Lubricants help to conserve resources and so subsidize long-term sustainability. Choosing the right lubricant for the job prolongs the life of the machinery and its modules while also improving reliability and efficiency. A large amount of the lubricants used around the world causing harm to the environment. Spills and evaporation are minimized to the greatest extent possible. The creation of environment-friendly lubricants was motivated by the substantial lubricant effects on the environment (Hájek et al.

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Vegetable Seed Oils as Biofuel  3

2021). Additionally, as the use of non-edible plant oils has gradually expanded in recent years, businesses have been searching for a low-cost, sustainable supply of lubricants due to the risk of oils becoming scarce in the near future. Even though some markets on plant oil-based products have been explored, the field of plant oils still has a lot of room for growth. Many countries, including the United States, India, Canada, Malaysia, Brazil, and Indonesia, have significant untapped potential for generating edible and non-edible tree-derived oils, which might be exploited as the basis for plant oil-related biolubricants. The increased demand and markets for common seed oils like castor, cashew nut, rapeseed, mahua, karanja, sal, and Jatropha and plant oils like canola, sunflower, soy, and palm oil, among others, might boost farmer incomes and exploit agricultural product applications. Plant oils are applicable in different varieties of industrial applications like surfactants, solvents, biolubricants, plastics, plasticizers, resins, and emulsifiers due to their exceptional eco-friendly credentials, such as being integrally biodegradable (Hoekman et al. 2012), having low toxicity affecting humans, paying no volatile biological chemicals, and being derived from renewable resources. Plant oils have a lot of good qualities, but they are not generally employed as biolubricants base oils right now. This is mostly owing to the physical qualities of the most commonly used plant oils, such as the viscosity index, low-temperature properties, poor oxidation stability, and so on. Moreover, plant oil-based biolubricants have achieved exceptional lubricating characteristics on par with ordinary lubricants thanks to cutting-edge technology, expertise, and modification methods for the global eco-labeling system.

1.2 Motivation The key difficulties in conventional lubricants are the rising costs, environmental safety, and toxicity. These difficulties have sparked interest in using biolubricants and their additives to develop industrial lubricants that can be used in diesel engines to improve their performance, efficiency, and cost-effectiveness. Lubricants can help improve the performance of basic oil. It is possible that the base oil is weak even without additives and that it lacks desirable characteristics. Basic oil and its additives determine the oil’s performance. Sulfur, zinc, phosphorus, and zinc dialkyl dithiophosphate (ZDDP) (Spikes et al. 2004) are some of the most commonly used additives. Sulfur is a lubricant (Ajithkumar et al. 2009) that has been used since the beginning. The latest study has focused on the possibilities of oil as an extreme pressure (EP) additive and an anti-wear (AW). Sulfur,

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phosphorus, and chlorine are frequently used additives in oil, and they protect the oil from EP conditions. Alcohols, FAs, esters, and amines are the AW additives that form a molecular film after chemical and physical adsorption. Researchers are investigating the manufacture of biodiesel and the usage of vegetable oil as a diesel engine fuel. Vegetable oil has been used as engine fuel for many years. The low cost of petroleum diesel has piqued the world’s interest in using vegetable oil as a fuel and additive. Mahua, coconut, palm (Masjuki et al. 2000), olive, sal, castor, canola, neem, cashew nut, Pongamia, Jatropha, corn, cottonseed, flaxseed, avocado, peanut, safflower, soybean, sunflower, mustard, karanja, and rice bran oil are some of the vegetable oils available. Some vegetable oils are edible, while others are not. Mahua, karanja, Jatropha, castor, sal, neem, and rice bran are examples of non-edible vegetable oils. Vegetable oil lubricants offer a renewable energy source in an ecologically friendly setting with the potential to biodegrade items. It has recently been discovered that biodegradable vegetable oil can be utilized in lubricants while posing safety and health risks. From the standpoint of emission, biodegradable lubricants differ from low-­ emission conventional lubricants. Vegetable oils contain no polycyclic aromatic hydrocarbons and are therefore safe for human consumption. Vegetable oils contain fewer contaminants, such as sulfur, that can harm the environment. The biggest advantages of vegetable oils in lubricants as base oils are that the mineral oils are biodegradable, nontoxic, have greater viscosity index, are resource renewable, and under optimized and affordable cost (Sharma et al. 2015). Vegetable oils are much cheaper in comparison to ester oils and give more capability for the lubricants in the base oil. The most significant advantages of vegetable oils in lubricants as base oils are that they are biodegradable, nontoxic, have a higher viscosity index, have renewable resources, are cost-effective, and are biodegradable (Alam et al. 2014). Vegetable oils are substantially less expensive than ester oils and have a higher lubricating capacity than base oils. Lubricants protect any tribosystem and have a wide range of utilities and applications. Lubricants are multifunctional substances that help tribo-­ pair processes run more smoothly. They are wavered from nature-based to conservative mineral-based over and done with the ages depending on the qualities required, availability, technology, and compatibility. The excessive extraction of restricted crude reserves for a variety of uses has been necessitated by the global population expansion. Conventional lubricants generated from mineral oils and additive packages are possibly detrimental to water and soil due to their higher content and slower biodegradability. Increasing raw oil prices, improper disposal procedures, and a lack of

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Vegetable Seed Oils as Biofuel  5

lubricant consumption regulations have all contributed to a global environmental concern, forcing companies to work on natural alternatives. Lubricants are commonly utilized to lubricate equipment and materials in the industry and the automobile sector. Lubricant demand is growing at a 1.6% annual rate. Petroleum-related lubricants produce a lot of waste, which is both polluting and dangerous to the environment. Biolubricants are more environment-friendly than crude oil derivative lubricants since they are biodegradable and renewable. Furthermore, they have the characteristics that are required from excellent lubricants. Biolubricants made from high-oleic-content vegetable oils can be used instead of conventional mineral oil-based lubricants. Different vegetable oils have been explored in this context for the production of the variability of lubricating base stocks, which have uses in the vehicle and chemical industries. On the other hand, the lubricants prepared from vegetable oils provide low oxidative stability, which can be improved by removing polyunsaturation from these oils. The following are some of the benefits of using vegetable oils as diesel fuel: • • • • • • • • • • • • •

Nature’s liquidity–portability Accessibility on short notice Renewable energy Biodegradability high value of cetane Lower content of sulfur Lower content of aroma Efficient in terms of energy. Energy efficiency is one of the key advantages of utilizing biodiesel. Reduced reliance on foreign oil Health benefits Positive economic impact Sustainability High-quality engine performance Reduction of greenhouse gases

The lower volatility and unsaturated hydrocarbon chains with higher viscosity are some of the major drawbacks of the use of vegetable oils as diesel fuel.

1.3 Need of Research India is looking at some renewable alternative fuel sources to reduce its reliance on foreign oil imports. Given that India mainly imports 70% of its

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oil, increased costs and uncertainties have had a significant impact on the economy. Biomass resources have recently been used as alternative fuels, and their successful implementation is gaining traction as a feasible solution to the global warming and energy crisis problems. Various resources based on biomass, which can prove as an extender or completely replace diesel fuels, could play a vital role in the development of industry, transportation, and agriculture in the face of the current energy crisis. Because of its ever-increasing use, diesel fuel’s importance in these industries cannot be overstated. Indeed, the agricultural and industrial sectors are nearly entirely reliant on diesel. Products based on crude oil and petroleum are expected to become extremely rare and expensive in this century. Although engine fuel efficiency has substantially improved, the growing number of automobiles indicates that a high need for gasoline will be required. In the coming decades, the availability and the use of alternative fuel technology are going to become more prevalent. Another factor driving the development of alternate fuels for internal combustion (IC) engines concerns the gasoline engine emissions. The enormous number of automobiles, when combined with some air polluting technologies, is contributing to the global air quality issue. A major percentage of crude oil should be imported from countries controlling the larger oil reserves, and it is the third factor driving alternative fuel development. According to the latest estimate of the Grand View Research, the demand for global lubricants is predicted to reach US $68.54 billion by 2022. Increased exploration and drilling operations are expected to boost the demand for oilfield chemicals, which will benefit the market. Motorcycle sales are on the rise, as requests for heavy-duty trucks and other marketable vehicles. Lightweight passenger cars are also on the rise, which is good news for lubricant demands. On the other hand, the underlying local lube market dynamics of the previous 15 years were massive in terms of numbers and quantity. Due to the increased motorization and industrialization, as well as increasing consumption, the Asia-Pacific area, Middle East, and Africa are accounted for slightly more than one-third of the world volume in 2000 and, at present, interpreted for more than half of it. The mature markets of North America and Western Europe have seen a steady shift to higher-quality lubricants, resulting in longer oil change intervals and, as a result, decreasing demand each year. Asia-Pacific now consumes twice as much lubricant annually as North America. Given Asia’s development perspective, where per capita ingestion in certain regions remains extremely low, and the further capacity reductions

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Vegetable Seed Oils as Biofuel  7

or stagnation in Western industrialized countries, universal development is expected to be reasonable. Because of the rising globalization of technologies, high-value products will be promoted even in developing and emerging lubricant markets such as India, and the value increase will be more prominent. These countries’ machines and plants will be similar to or identical to those utilized in developed industrialized countries.

1.3.1 Biodiesel Considerations Biodiesel is an unpolluted burning and is a renewable substitute to petroleum diesel, which is synthetic in the USA and worldwide. Biodiesel in vehicle fuel improves the environment air quality (Connell et al. 2009) and energy security and also provides safety profits.

1.3.2 Energy Balance and Security Despite the fact that it imports 7.86 million barrels per day to meet the demands and supply of international and domestic markets, the United States is going to become a net exporter of petroleum products by 2020, with margins exceeding the imports. The transportation industry accounts for roughly 70% of the US petroleum lubricant consumption and 30% of the worldwide US energy consumption. Businesses and consumers are using other alternative fuels along with biodiesel, as well as cutting-edge technologies, to reduce the fuel usage, boost the national security, and lower the transportation costs (Mirchi et al. 2012; Honcharuk et al. 2020). Biodiesel is produced in the United States and utilized in traditional diesel engines, either directly or replacing the supplementary diesel supplies (Nik et al. 2005). Soybean biodiesel offers a supportive energy balance, which means it creates 4.56 units of energy for each component of fossil energy used in its entire life cycle.

1.3.3 Air Quality The engines that were manufactured after 2010 are expected to provide minimum emission, irrespective of whether they run on diesel, biodiesel, or some other alternate fuel (Zeng et al. 2007). It is impossible as the selective catalytic reduction (SCR) method plays an important role that helps to reduce the nitrogen oxide (NOx) emissions to count down to zero levels. Engines that run on diesel fuel yield emissions that are analogous to those that are produced by biodiesel blends. The carbon dioxide released by burning biodiesel is offset by the carbon dioxide that is absorbed from

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the various feedstocks used to create the fuel, resulting in a low life cycle carbon footprint. Investigation on the life cycle was done by Argonne National Laboratory, and it was discovered that utilizing B100 reduces the carbon dioxide emission by 74% in comparison to petroleum diesel. The California Air Resources Board (CARB) presented the same data, which were compiled from several sources to obtain the details of their biodiesel life cycle analysis. The benefits of biodiesel on air quality appear to be disproportionately related to the amount of biodiesel in the blend.

1.3.4 Engine Function The cetane number of fuel contributes to improved lubricity. A higher cetane number indicates a quicker ignition. As a result, biodiesel increases the cetane number of gasoline while also improving its lubricity. The current diesel engine relies heavily on the lubricity of the fuel in order to keep the moving parts of the engine from wearing out quickly. The lubricity of petroleum diesel has been reduced as a result of government regulations that cut the allowed fuel sulfur to 15 ppm and reduced the aromatics content. The ASTM D975 diesel fuel standards (Sahoo et al. 2007; Pradhan et al. 2011; Misra et al. 2010) were utilized to update the lubricity requirements in the engine, and a high-frequency reciprocating rig (HFRR) testing was used to determine the maximum wear scar diameter, which is approximately 520 µm. With minimal effects of 1%, biodiesel can improve the lubricity of blended fuel.

1.3.5 Safety It has been discovered that if biodiesel is dropped or liquidated into the environment in its pure, unbleached state, it does significantly less environmental damage than petroleum fuel. The rationale for this is that it is less flammable when compared to petroleum diesel, making it a safer choice. Petroleum diesel has a flashpoint value of 52°C, whereas biodiesel has a flashpoint value of over 130°C. Biodiesel is completely risk-free to store, transport, and handle. Here is where one can learn more about the handling, storing, and shipping of biodiesel. As large quantities of scientifically genetically advanced modified types of “high-oleic” vegetable oils arose in the environment, the US and European businesses became interested in the advancement of vegetable oils and their chemically changed derivative products as fuels and lubricants, like sunflower, soybean, and rapeseed oils (Taheri et al. 2017). A surge in environment protection and eco-preservation of endangered animals that were being slaughtered indiscriminately

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Vegetable Seed Oils as Biofuel  9

for their oils and fats drove the development even further. The major concerns can be addressed such as lubricant accumulation, low toxicity, emissions, and the release of fuels in the environment, land, water, and air. The use of traditional lubricants based on petroleum has been discouraged in a variety of applications, including industrial lubricants, total loss lubricants, two-stroke engine lubricants, lubricants for water machinery, and food processing. To minimize particle emissions, which considerably worsen the respiratory concerns in megacities, attempts are being made to replace the lubricants based on mineral oils in high-powered diesel cars with lubricants based on low-evaporation-loss ester.

1.4 Detailed Survey A detailed survey of biodiesel is presented by Pali et al. (2014, 2020), which discussed that “Shorea robusta” vegetable seed is a viable feedstock for the manufacture of biodiesel, which can significantly improve feedstock availability. The enormous 1.5 million tons of sal seed oil that might be produced annually and the plant’s subcontinental geoclimatic penetration, with special presence in Madhya Pradesh, Odisha, and Chhattisgarh. The pressure-filtered sal seed and the transesterified sal seed methyl ester (biodiesel) were combined having a 1:9 oil-to-methanol molar ratio, 450  rpm agitation speed, catalyst potassium hydroxide with 0.5% by weight, and 65°C reaction temperature, producing an ester yield of 96.8%. The physicochemical analyses results demonstrated that the density (0.884 gm/cc), heating value (40.28 MJ/kg), and the kinematic viscosity (5.8 cSt) of the sal oil methyl ester (SOME) were as per the ASTM standards. The biodiesel Rancimat had an oxidation stability that lasted longer than 6 h. It was observed that the FA profiles of SOME were rich enough in saturated FAs such as mysteric acid and pentadecanoic acid. Rai et al. (2020, 2021) made biodiesel from S. robusta seed oil by utilizing a ­single-stage transesterification process with KOH acting as a catalyst. The blending of the diesel-based S. robusta biodiesel was done and the performance traits, along with the heat loss and emission characteristics, examined. In the trials created using the Taguchi method, the compression ratio, percentage fuel mixtures with four levels, and the load were considered for each employed control parameter. The experiment performance was investigated based on brake-­specific fuel consumption (BSFC), brake mean effective pressure (BMEP), volumetric efficiency, exhaust gas heat loss (HJGAS), water heat loss (HJW), and environment emissions such as HC, NOx, and CO emissions. Chaurasia et al. (2020) introduced

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nanoparticles as additions to make sal oil a sustainable and bio-based lubricant. The wear and friction characteristics of the chemically altered sal oil were explored with the epoxidation method in their research study. Moreover, copper oxide nanoparticles (CuO) were added to the modified oil with varied ratios. Through tribological investigation, the thermophysical characteristics of the lubricants were evaluated, including the viscosity index increment, kinematic viscosity, pour point, flash point, and dispersion stability. Various factors were taken into consideration while the test was conducted by utilizing a pin-on-disc tribometer setup. Reduced anti-wear and friction properties were generated at concentrations of 0.5% and 0.25% copper oxide nanoparticles. Hasan et al. (2020) applied S. robusta to study the fuel properties of sal seeds for their proximate and ultimate analysis. The study was conducted in Bangladesh. Sal trees are found in the major part of the forest that makes up around 10% of the total forestland coverage in Bangladesh. The solvent extraction process was applied on sal seeds using n-hexane as a solvent. When the kernel and coat of the seeds were removed simultaneously, the seeds’ oil content was 15.39%. When only the kernels of the seeds were removed, the seeds’ oil content was 20.16%. The analysis revealed that the oil has oleic acid (34.69%), stearic acid (49.38%), palmitic acid (7.35 %), and arachidic acid (8.56%). The fundamental composition of the oil was brought into (H = 13.5%, C = 75.9%, N = 3.6%, and S = 0.06%). Different physicochemical characteristics such as the iodine value, acid value, refractive index, viscosity, peroxide value, and saponification value were also measured. Larger heating values and Specific kinetic energy for the sal seeds and sal oil were found to be 17.99 and 41.61 MJ/kg, respectively. Hajra et al. (2014) synthesized the SOME biodiesel by applying an ion exchange resin catalyst using sal oil. The production of SOME biodiesel was based on the esterification process, in which water is continuously removed while glycerides of FAs and FFAs are transesterified. To maximize the conversion of sal oil into SOME biodiesel, the effects of catalyst loading and methanol were investigated. The productivity of biodiesel using recycled catalysts was also recognized, and a constant yield of the fuel was attained during all catalyst recycling trials. Sal biodiesel was vacuum-purified and put through an ASTM-required product testing procedure. Pradhan et al. (2017) emphasized the thermal kinetics of sal seeds that were studied using the pyrolysis technique as a biofuel feedstock that can be applied in the manufacturing, chemical, and bioenergy sectors. Their work aimed to look into the physicochemical properties of the seeds. Based on their research work, it was discovered that sal seeds are a low-ash, high-calorific value, and high-­volatile biomass that is suitable for pyrolysis applications.

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Vegetable Seed Oils as Biofuel  11

Specific emphasis was carried out on the kinetic characterization of the thermal deterioration of this biomass. Two substantial deterioration zones were identified, and the activation energy was investigated using different methods with maximum values of temperature at 321°C and 405°C. The model-­free pyrolysis kinetic approach, which was proven to be effective, states that unprocessed sal seed biomass can immediately become a potential renewable feedstock for chemicals, energy, and charcoal. Marandi et al. (2016) detailed the major concern of the tribal people in Jharkhand, India, regarding S. robusta Gaertn., which is also known as the sal tree. It is found in the tribal and costal regions rather than main city. It combines the plant components with other constituents and creates a cure for a variety of illnesses. The entire plant was subjected to an introductory phytochemical screening, which exposed the existence of significant concentrations of bioactive components. Moreover, the plant extracts have shown strong antimicrobial properties. GC-MS and HPLC analyses revealed the presence of numerous phytochemicals with very high concentrations, including trimethylsilyl 3-methyl-4-[(trimethylsilyl)oxy]­ benzoate, phytol, sorbitol, hexamethylcyclotrisiloxane, β-caryophyllene, d-mannitol, 1,2,4-benzenetriol, etc., which are crucial for the industrial and pharmaceutical industries. Vimalanathan et al. (2016) assessed the biodegradability of the composite sample with wet soil on S. robusta filler-­ reinforced polyester composites. The weight of the sample was recorded before burying the sample in the ground, and its preliminary weight was recorded. Thereafter, the sample was obtained regularly, and its weight was measured to check for any changes. The calculated density value for S. robusta was 1.05 g/cm3. The results of the mechanical tests showed that adding 20  vol% filler to the polyester matrix improved the composite’s flexural, tensile, and impact strengths. Shrestha et al. (2021) concentrated on how activating chemicals affect the electrochemical and physical characteristics of the activated carbon (AC) electrodes, which were made from S. robusta wood dust. KOH, H3PO4, and Na2CO3 were utilized as three separate stimulating agents to make ACs, which were then specified the names Sr–KOH, Sr–H3PO4, and Sr–Na2CO3. S. robusta (sal) sawdust is a suitable pioneer material for the manufacture of nanoporous ACs. For the production of phosphoric acid–activated carbon (Sr–H3PO4), a carbonization temperature of 400°C was found to be suitable. This temperature was insufficient for producing Na2CO3 and KOH-activated carbon (Sr– Na2CO3 and Sr–KOH). Vedaraman et al. (2012) transformed sal oil into SOME and evaluated its performance by direct application into direct injection (DI) diesel engines. The ideal process parameters included a catalyst concentration of 0.25 wt.% (NaOH), with 150% excess of methanol

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(alcohol) having a reaction temperature of 65°C, which was carried out for a 1.5-h reaction period. This work investigated the different process variables including the reaction temperature, catalyst volume, reaction time, and alcohol molar ratio. The results enclosed that the NOx, HC, and CO exhaust emissions were reduced by 11%, 45 %, and 25% respectively, in the case of utilizing the SOME biodiesel as fuel in DI diesel engines compared to diesel, with no discernible reduction in thermal efficiency. Abraham et al. (2010) detailed the seed variability of Madhuca longifolia. The seeds of M. longifolia contain 20%–50% oil and the seed cake is utilized as manure. The tree has medicinal characteristics, and rural areas use the oil for protection against storage pests. The oil has lubricity and is used for bioenergy production in an eco-friendly environment. Baskar et al. (2016) used manganese-doped zinc oxide as a nanocatalyst for the production of biodiesel. A yield of 97% was produced when mahua oil was transesterified to biofuel. Fourier transform infrared spectroscopy (FTIR) and GC-MS analyses were carried out on the hydrogen function groups and chemical compounds. Dhanavath et al. (2017) used response surface methodology (RSM) with mahua press seed cake and processed it in a pyrolysis batch reactor. The process yielded 49 % bio-oil at 475°C with a retention time of 45 min. The GC-MS analysis of bio-oil provided major compounds such as octadecanoic acid, 6-octadecenoic acid, and FFAs. FTIR analysis also indicated the decrement in C–H (alkanes), O–H (hydroxyl), and C–O (primary alcohol) with increment of temperature to derive C=C (aromatics) functional groups. Joshi et al. (2017) studied the production of biodiesel from mahua oil using the transesterification method with KOH (0.5 wt.%) as a catalyst using a mechanical stirrer. The following physicochemical properties were observed: density (at 30°C), 0.883; kinematic viscosity at 40°C, 37.86; saponification value, 1.12; iodine value, 7.03; flash point, 169°C; pour point, −6°C; and cetane index, 24.6325. Kumar et al. (2018) presented the emission parameters of mahua oil such as exhaust gas temperature, hydrocarbon (HC), oxides of nitrogen (NOx), and carbon monoxide (CO) mixed with diesel fuel. These parameters were experimentally studied in the diesel engine. It was revealed that the residual oxygen, HC, and NOx were lower than those of the mahua biodiesel. Mahua oil has all the features that can be a sustainable source as biodiesel. Mishra et al. (2019) focused on the bioenergy potential of M. longifolia using the pyrolysis technique. The Madhuca seed was pyrolyzed in the presence of NaOH, CuO, and Al2O3 catalysts in a semibatch cylinder. The FTIR spectra of the obtained pyrolytic oil confirmed the presence of aromatics, water, phenols, and acids, which were maintained by the H-NMR investigation. Furthermore, GC-MS analysis was carried out to get the oxygenated compounds available in alcohol. Muthukumaran

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Vegetable Seed Oils as Biofuel  13

et al. (2018) synthesized the cracked mahua oil with the help of a coal ash catalyst for the production of hydrocarbon fuel in diesel engine applications. The performance of the engine was evaluated based on HC, NOx, CO, and smoke emissions. The alkane and ester carboxylic acid functional groups and the existence of the hydrocarbon groups CH were identified using FTIR. The GC-MS spectrum showed that the cracked oil comprises traces of paraffin and unsaturated acids such as lauric acid olefins, oleic, linoleic, palmitic, and stearic acids, and olefins identified by dominant peaks. Narayanasamy et al. (2018) worked on enhancing the oxidation stability of mahua biodiesel by adding antioxidants that are natural or may be synthetic. Natural antioxidants including Moringa oleifera, ginger, basil, clove, and oregano were extracted and utilized as natural antioxidants, which have shown better results in comparison to synthetic antioxidants. Pradhan et al. (2016) used the co-pyrolysis method to characterize bio-oil. Two independent feedstocks were used for the co-pyrolysis technique: one was polystyrene (PS) and the other was mahua seed. Blending of mahua seed and polystyrene was performed in a semi-batch reactor at 525°C and yielded 71% oil, which was larger than the 22% yield of mahua oil alone. FTIR and GC-MS were performed to determine the hydrogen functional groups and the chemical compounds available in the pyrolysis. Pradhan et al. (2020) performed co-pyrolysis for mahua seeds to obtain biodiesel in the temperature range of 450–600°C, which yielded 74.2% product at 525°C. The physiochemical behavior has been proven that co-pyrolysis oil has suitable properties as biofuel and can be used as an alternative fuel. It has specific gravity (0.91 ml g−1), kinematic viscosity (1.94 cSt), and calorific value (40.6 MJ kg−1). Saxena et al. (2019) performed a transesterification process on M. longifolia (mahua) oil, in which mahua oil and methanol were mixed and the mixture heated at 333 K temperature for 30 min. The resultant mixture was continuously stirred for 3–4 h, and progress was monitored using thin-layer chromatography. Moreover, FTIR and GC-MS were performed to obtain the functional groups and hydrocarbon compounds. Senthil et al. (2016) studied the impact of exhaust gas recirculation on the emission behavior of Madhuca indica-generated biodiesel. Red mud was used as a catalyst in the process, which was carried out at 65°C temperature inside a reactor. The physicochemical properties of biodiesel were studied, such as the flash point, calorific value, fire point, and specific gravity. The performance was compared with the neat diesel, and the emission behavior was evaluated in a water-cooled-based single-cylinder, DI diesel engine. Shadangi et al. (2014) carried out thermal and catalytic pyrolysis of mahua seed oil. The process was done at 525°C. It was observed that catalytic pyrolysis had better response than thermal pyrolysis as yield of pyrolytic oil. The CaO catalyst improved the calorific value and reduced the viscosity.

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14  Clean and Renewable Energy Production

The catalytic pyrolysis method provided properties closer to those of diesel fuel. Yadav et al. (2011) detailed that M. longifolia is mainly found in Tamil Nadu state, India. The oil contents vary in range from 44.4% to 61.5%. It also contains linoleic acid (9.4%–15.4%), stearic acid (19.1%–32.2%), palmitic acid (11.7%–25.9%), and oleic acid (32.9%–48.6%), which are the main FAs in mahua seeds. It has stretched range properties: iodine value, 52.0–68.6; saponification value, 198.3–202.8; and cetane number, 58.0–61.6. Gangil et al. (2014) discussed that, based on thermogravimetric profiling, the cashew shell cake and cashew shell both have two different biomaterials. Patel et al. (2011) used the vacuum pyrolysis method for the extraction of the cashew nut shell liquid (CNSL). The process of distillation was used to minimize the polymeric material. The experiments were performed at a mass flow rate of 0.7–1.2 kg/h, pressure of 120–300 bar, and temperature of 303– 333 K. The distilled technical CNSL had 2% polymeric material, 8% cardol, 12% of contents made of other residual substances, and 78% cardanol. The oil samples were examined using FTIR and GC-MS. Gomez-Caravaca et al. (2010) used the GC-MS method, a cold processing technique to determine the additional tropical compounds in raw and roasted cashew nut oils and alkyl phenols. The oil, which was obtained from roasted cashew nuts, produced a higher concentration of cardanols. The HPLC method was utilized to determine the tocopherols. Kasiraman et al. (2012) used direct injection and an additional camphor oil blending to evaluate the performance of a four-stroke diesel engine using cashew nut shell oil as a fuel. The mixture of camphor oil (30%) and cashew nut shell oil (70%) was called CMPRO 30. The diesel efficiency achieved was 30.14%, while the brake thermal efficiency (BTE) achieved was 29.1%. At the full load condition, the CMPRO 30 blend and the NO emissions of the diesel fuel were 1,040 and 1,068 ppm, respectively. The NO emission was a little bit higher compared to the diesel emission. Loganathan et al. (2020) used CNSL to generate biofuel and verified its performance in a single-cylinder diesel engine operating at 1,500 rpm. Cardanol was used to derive the thermal-cracked CNSL in the temperature range between 180°C and 380°C. The diesel and the oil performance were compared to estimate the kinematic viscosity density, cetane index, flash point, calorific value, and boiling point. Luz et al. (2008) discussed the separation of fructose and glucose sugars in cashew juice, widely used in the separation, concentration, and purification of bioproducts. Patel et al. (2006) used supercritical carbon dioxide (CO2) to examine the extraction of CNSL. The physical and chemical properties of the oil were improved after the extraction process. Radhakrishnan et al. (2018) reviewed the effect of alumina nanoparticles on the emission characteristics and the engine performance of the cashew nut shell biodiesel. It was discovered that, compared

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Vegetable Seed Oils as Biofuel  15

with diesel fuel, the BTE of CNSL fuel dropped by approximately 1.1%. The CNSL fuel parameters like NOx, smoke, CO, and HC were reduced by 10.23%, 16.1%, 5.3%, and 7.4%, respectively. Reis et al. (2016) discussed a method to improve the enzymatic digestibility of cashew apple bagasse (CAB) using sugar-fermented derived bioproducts. The behavior of CAB was examined using chemical processing, FTIR, and NMR. Senthil et al. (2020) used cashew nut shell for biodiesel production. The biodiesel performance was examined based on BTE and the carbon dioxide and carbon monoxide emissions. Sajin et al. (2020) analyzed the ignition characteristics of ethyne (acetylene) and cashew nut shell biodiesel. It was observed that the ethyne– biodiesel mixture, when compared to the neat biodiesel, yielded higher thermal efficiency. Smith et al. (2003) studied a technique to separate CNSL from the pericarp of cashew nuts where supercritical carbon dioxide (CO2) was utilized at a pressure of 14.7–29.4 MPa and a temperature of 40–60°C. The CNSL, which was extracted here, was light brownish pink in color, and it revealed no degradation or polymerization. Trevisan et al. (2006) studied the cardols, anacardic acids, and cardanols in roasted cashew nuts, raw cashew nuts, and cashew apples. The CNSL was investigated using NMR and GCMS. Torres Gadelha et al. (2018) emphasized the utilization of cashew nut husk as biofuel and analyzed its energetic characteristics. The agro residue properties of the cashew nut husk were observed to understand their contiguous requirements with advanced heating values. The results depicted the energy density to be 5,200 MJ/m3 and the bulk density to be 294 kg/m3. Vedharaj et al. (2014) used a double-stage transesterification method for the extraction of CNSL to synthesize CNSL biodiesel. The experimental results showed that the BTE of the engine was increased by 6% when compared to the coated engine. The emissions of smoke, CO, and HC were reduced by 14.3%, 27.7%, and 7.2%, respectively, under full conditions. It was also observed that the NOx emission was increased under full conditions.

1.5 Identification of the Research Gaps Temperature increases and climate changes brought on by global warming have adverse effects on the overall environment. According to the Intergovernmental Panel on Climate Change (IPCC), there is a large danger that roughly 1 million species could go extinct if the average temperature increases by 1.5°C. Global warming is largely caused by anthropogenic activities that cause greenhouse gas (GHG) emissions, which include the burning of fossil fuels for energy. GHG emissions must be reduced by at least 40%, according to reports, to keep global warming at an average of

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16  Clean and Renewable Energy Production

1°C by 2050. This problem compels the community to look for environment-friendly solutions in both platforms including chemical and energy. Among the most significant substitutes for traditional fuels, biodiesel has garnered a lot of attention. The American Society for Testing and Materials (ASTM) specifies biodiesel as “mono-alkyl esters of longchain fatty acid which are generated from vegetable oils or animal fats,” in addition to having GHG emissions that are at least 50% reduced than the baseline. Biodiesel production has greatly expanded recently. Its quick industrial development has been supported by lower GHG emissions, a molecular structure with compatibility with current engines, fuel delivery infrastructure, and low combustion toxicity. Most of the work has been done in the field of engine emission parameters and FTIR and GC-MS analyses to determine the FAs, functional groups, and hydrocarbons. In the research work, the tribological behavior of mahua oil methyl ester (MOME) biodiesel was also considered so that the magnitude of the friction of coefficient (COF) can be studied. Eco fuels should have a lower magnitude of COF in comparison to diesel due to their higher viscosity, density, and lubricating properties. The comparative performance will estimate the future research directions to determine the lubricity of MOME biodiesel. Therefore, the problem statements of the work were to perform transesterification to obtain mahua oil biodiesel and to study the physicochemical properties, emission parameters, and tribological nature of MOME. Based on the survey of different research articles related to this area, it was identified that a lot of research work has already been done in this domain concerning the utilization of CNSL as biodiesel. Furthermore, the CI engine performance based on environment emission and combustion parameters was evaluated. Few researchers have carried out research work in the field of blended fuels. It has been observed that a little percentage of diesel and the remaining portion of CNSL were used to analyze the performance of this engine in different load conditions. Recently, the effect of diethyl ether along with hydrogen to achieve an enriched performance of CNSL biodiesel engine was also investigated. The sample was processed in GC-MS (CLARUS SQ8S) Perkin Elmer (Perkin Elmer) and with the Frontier FTIR apparatus to calculate the functional groups. In the presented research work, thermal-cracked (TC) CNSL oil was utilized in the blended mode. The blend of TC-CNSL and diesel was used directly without any kind of modification in the engine structure. The blended biodiesel was given as B100 (100% TC-CNSL), B25 (25% TC-CNSL and 75% diesel), B75 (25% TC-CNSL and 25% diesel), and B50 (50% TC-CNSL and 50% diesel). The main objective of this research work was to study the behavior of TC-CNSL blended B100, B75, B50, and B25 biodiesel. The performance of the engine was evaluated based on the

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Vegetable Seed Oils as Biofuel  17

emission parameters. To perform the engine-based calculations, LabVIEW software-based GUI was used. Embedded ‘C’ programming language was used to program the controller in an OpenECU system. To minimize particle emissions, comprehensively hydroprocessed diesel fuels were commonly combined with esters derived from vegetable oils. Pure vegetable oils and fuels based on ester are now used to power outboard engines, generators, and pump sets, powered by two-stroke engines. Although the worldwide lubricant market has proven the future predictions and estimations about the utilization of a capacity of approximately 40 million tonnes, lubricants derived from seed oils and chemically altered esters are now considered for only 10%–15% of the market. India makes extremely limited use of vegetable oil esters and lubricants. These are only used in very big industrial units like power plants, conveyers, and hydraulic lifts, as well as in shaping, rolling, cutting, earth-moving equipment, and drawing processes in the automotive industry, conveyers, and hydraulic lifts. Most such lubricants are obtained from providers recommended by original equipment manufacturers (OEMs) or are supplied with the machinery from OEMs. Balmer Lawrie FUCHS and the FUCH’s Petrolubes attempted to sell these goods across the country. Despite the massive soil, air, and water pollution caused by generators, cutting fluids, tractor oils, pump sets, and two-stroke engine oils, the industry for such lubricants has not expanded as much as desired due to the lack of public pressure for environmental protection and the low efforts of the government agency. Other causes of hazardous environmental degradation include the management of food processing facilities and water resources. The criteria for meeting environmental regulations are as follows.

1.5.1 Toxicity Toxicity relates to the capability of fuels and lubricant additives to affect live beings biochemically or physically. The following aspects are commonly used to determine toxicity: Dermal and aquatic oral toxicity: LD50 less than 2 g/kg Irritation in eye—cornea opacity: 2 or more Redness due to conjunctivitis (24–72 h): 2.5 or more Redness due to skin irritation: 2.0 or more In numerous countries, the toxicity of the produced additives and lubricants has been assessed using a range of test methodologies.

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18  Clean and Renewable Energy Production

1.5.2 Biodegradability Biodegradability refers to a substance’s ability to disintegrate by microbial action. A variety of screening methods are used to evaluate the biodegradability of additives and lubricants. The valid inputs for the biodegradability of several lubricants are examined with the help of (CEC-L-33)-(A-94) protocols. Biodegradability tests also need to be utilized in various countries. Polyalkylene glycols, their esters, vegetable oils, and synthetic esters are the sole possibilities for nontoxic, rapidly biodegradable base fluids. This is true, even though different locations, each with its unique sociopolitical climate, have adopted differing biodegradability and toxicity regulations and constraints. Based on a momentary examination of the applications and properties of quickly biodegradable nontoxic vegetable oils and their esters, with a focus on chemically desired derivatives and vegetable oil FAs, some suggestions for the advancement of chemically processed esters and vegetable oils, which are based on FAs as fuels and lubricants, in India are presented below. It is considered that vegetable oil-based esters must be adopted as lubricants for two-stroke engines, water management equipment, generators, food processing equipment, and pumps, as soon as possible. • Biodegradable lubricants should be employed in place of machine tool lubricants like gear oils, metalworking fluids, and other lubricants that usually come into contact with people or the environment. • The stabilized FA esters must be utilized as lubricants in some other manufacturing applications in addition to hydraulic fluids. • Since rapidly biodegradable greases are simple to make from vegetable oil-focused thickeners and stabilized vegetable oils, followed by their esters, they should be used in place of the majority of mineral oil-based greases. • Monoester-based fuels must be utilized in pump sets, diesel transport vehicles, generator sets, and other applications as fuels in mixtures with highly processed diesel fuels. • It is possible to generate, gather, and convert inexpensive non-traditional vegetable oils derived from wastelands and woods into lubricants and fuels, such as castor oil, rapeseed oil, mahua oil, Jatropha curcas, neem oil, rice bran oil, and karanja oil.

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Vegetable Seed Oils as Biofuel  19

1.6 Conclusions Countries have to develop innovative technologies and use alternative feedstocks in order to produce transportation fuels from biomass resources sustainably. As of right now, there is no proof in research to support the establishment of non-food biomass feedstock. The International Energy Agency (IEA) estimates that, with the right investments and policies, biofuels might supply more than a quarter of the world’s transportation fuel needs by 2050. Governments currently support biofuels in a variety of ways, such as blending mandates or targets, subsidies, tax exemptions (exemptions from excise and pollution taxes and corporate tax breaks for biofuel producers), reduced import duties, support for research and development (R&D) and direct involvement in biofuel production, as well as other incentives to promote local biofuel production and use. An important consideration is striking a balance between the economic advantages and the social and environmental effects. Biofuels must also pass economic sustainability tests even if they satisfy the environmental sustainability requirements. This means that ensuring production efficiency and profitability necessitates having access to sustainable resources and stable output markets. Thus, the difficulty is achieving all of these while maintaining economic viability and reducing adverse environmental and socioeconomic repercussions.

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Baskar, G., Gurugulladevi, A., Nishanthini, T., Aiswarya, R., Tamilarasan, K., Optimization and kinetics of biodiesel production from Mahua oil using manganese doped zinc oxide nanocatalyst. Renew. Energ., 103, 641–646, 2017. Biresaw, G., Adhvaryu, A., Erhan, S.Z., Friction properties of vegetable oils. J. Am. Oil Chem. Soc, 80, 7, 697, 2003. Chidambaram, P.K., Lokhande, D.A., Ramachandran, D.M., Saravanan, V., Prasanth, V., A review on biodiesel properties and fatty acid composites. REST J. Emerg. Trends Model. Manuf., 7, 3, 87–93, 2021. Chaurasia, S.K., Singh, N.K., Singh, L.K., Friction and wear behavior of chemically modified sal (shorea robusta) oil for bio based lubricant application with effect of CuO nanoparticles. Fuel, 282, 118762, 2020. Connell, A., Kousoulidou, M., Lonza, L., Weindorf, W., Considerations on GHG emissions and energy balances of promising aviation biofuel pathways. Renew. Sust. Energ. Rev., 101, 504–515, 2019. Dhanavath, K.N., Shah, K., Bankupalli, S., Bhargava, S.K., Parthasarathy, R., Derivation of optimum operating conditions for the slow pyrolysis of mahua press seed cake in a fixed bed batch reactor for bio–oil production. J. Environ. Chem. Eng., 5, 4, 4051–4063, 2017. Gangil, S., Dominant thermogravimetric signatures of lignin in cashew shell as compared to cashew shell cake. Bioresour. Technol., 155, 15–20, 2014. Hájek, M., Vávra, A., de Paz Carmona, H., Kocík, J., The catalysed transformation of vegetable oils or animal fats to biofuels and bio-lubricants: A review. Catalysts, 11, 9, 1118, 2021. Hasan II, M., Mukta, N.A., Islam, M.M., Chowdhury, A.M.S., Ismail, M., Evaluation of fuel properties of Sal (shorea robusta) seed and its oil from their physico-chemical characteristics and thermal analysis. Energ. Source. Part A, 1–12, 2020. Hajra, B., Pathak, A.K., Guria, C., Optimal synthesis of methyl ester of Sal oil (shorea robusta) using ion-exchange resin catalyst. Int. J. Ind. Chem., 5, 3, 95–106, 2014. Honcharuk, I., Use of wastes of the livestock industry as a possibility for increasing the efficiency of AIC and replenishing the energy balance. Visegr. J. Bioecon. Sustain. Dev., 9, 1, 9–14, 2020. Hoekman, S.K., Broch, A., Robbins, C., Ceniceros, E., Natarajan, M., Review of biodiesel composition, properties, and specifications. Renew. Sust. Energ. Rev., 16, 1, 143–169, 2012. Issariyakul, T. and Dalai, A.K., Biodiesel from vegetable oils. Renew. Sust. Energ. Rev., 31, 446–471, 2014. Joshi, H.C. and Negi, M., Study the production and characterization of Neem and Mahua based biodiesel and its blends with diesel fuel: An optimum blended fuel for Asia. Energ. Source. Part A, 39, 17, 1894–1900, 2017.

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Vegetable Seed Oils as Biofuel  21

Kasiraman, G., Nagalingam, B., Balakrishnan, M., Performance, emission and combustion improvements in a direct injection diesel engine using cashew nut shell oil as fuel with camphor oil blending. Energy, 47, 1, 116–124, 2012. Kumar, S., Kumar, S., Kumar, A., Maurya, S., Deswal, V., Experimental investigation of the influence of blending on engine emissions of the diesel engine fueled by mahua biodiesel oil. Energ. Source. Part A, 40, 8, 994–998, 2018. Kumar, S., Pradhan, R.C., Mishra, S., Exploration of shorea robusta (sal) seeds, kernels and its oil. Cogent Food Agric., 2, 1, 1186140, 2016. Karmakar, G., Ghosh, P., Sharma, B.K., Chemically modifying vegetable oils to prepare green lubricants. Lubricants, 5, 4, 44, 2017. Loganathan, M., Thanigaivelan, V., Madhavan, V.M., Anbarasu, A., Velmurugan, A., The synergetic effect between hydrogen addition and EGR on cashew nut shell liquid biofuel-diesel operated engine. Fuel, 266, 117004, 2020. Loganathan, M., Madhavan, V.M., Balasubramanian, K.A., Thanigaivelan, V., Vikneswaran, M., Anbarasu, A., Investigation on the effect of diethyl ether with hydrogen-enriched cashew nut shell (CNS) biodiesel in direct injection (DI) diesel engine. Fuel, 277, 118165, 2020. Leung, D.Y., Wu, X., Leung, M.K.H., A review on biodiesel production using catalyzed transesterification. Appl. Energy, 87, 4, 1083–1095, 2010. Luz, D.A., Rodrigues, A.K.O., Silva, F.R.C., Torres, A.E.B., Cavalcante Jr., C.L., Brito, E.S., Azevedo, D.C.S., Adsorptive separation of fructose and glucose from an agroindustrial waste of cashew industry. Bioresour. Technol., 99, 7, 2455–2465, 2008. Marandi, R.R., Britto, S.J., Soreng, P.K., Phytochemical profiling, antibacterial screening and antioxidant properties of the sacred tree (shorea robusta gaertn.) of Jharkhand. Int. J. Pharm. Sci. Res., 7, 7, 2874, 2016. Mirchi, A., Hadian, S., Madani, K., Rouhani, O.M., Rouhani, A.M., World energy balance outlook and OPEC production capacity: Implications for global oil security. Energies, 5, 8, 2626–2651, 2012. Masjuki, H.H., Maleque, M.A., Kubo, A., Nonaka, T., Palm oil and mineral oil based lubricants—Their tribological and emission performance. Tribol. Int., 32, 6, 305–314, 1999. Mishra, R.K. and Mohanty, K., Pyrolysis characteristics, fuel properties, and compositional study of Madhuca longifolia seeds over metal oxide catalysts. Biomass Convers. Biorefin., 10, 621–6397, 2020. Mishra, R.K. and Mohanty, K., Mahua and neem seeds as sustainable renewable resources towards producing clean fuel and chemicals, in: Sustainable Energy Technology and Policies, pp. 271–296, Springer, Singapore, 2018. Muthukumaran, N., Prasanna Raj Yadav, S., Saravanan, C.G., Sekar, T., Synthesis of cracked Mahua oil using coal ash catalyst for diesel engine application. Int. J. Ambient Energy, 41, 3, 241–256, 2020.

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22  Clean and Renewable Energy Production

Narayanasamy, B., Jeyakumar, N., Saran, A., Kumar, V., Enhancing the oxidation stability of Mahua oil methyl ester with the addition of natural antioxidants. Energ. Source. Part A, 40, 21, 2572–2579, 2018. Nik, W.W., Ani, F.N., Masjuki, H.H., Giap, S.E., Rheology of bio-edible oils according to several rheological models and its potential as hydraulic fluid. Ind. Crops Prod., 22, 3, 249–255, 2005. Nik, W.W., Maleque, M.A., Ani, F.N., Masjuki, H.H., Experimental investigation on system performance using palm oil as hydraulic fluid. Ind. Lubr. Tribol., 59, 5, 200–208, 2007. Pradhan, D., Singh, R.K., Bendu, H., Mund, R., Pyrolysis of Mahua seed (Madhuca indica)–Production of biofuel and its characterization. Energy Convers. Manag., 108, 529–538, 2016. Pali, H.S. and Kumar, N., Biodiesel production from Sal (Shorea robusta) seed oil. NIET J. Eng. Technol., 5, 24–29, 2014. Pali, H.S., Kumar, N., Alhassan, Y., Performance and emission characteristics of an agricultural diesel engine fueled with blends of Sal methyl esters and diesel. Energy Convers. Manag., 90, 146–153, 2015. Pradhan, D., Volli, V., Singh, R.K., Murgun, S., Co-pyrolysis behavior, engine performance characteristics, and thermodynamics of liquid fuels from mahua seeds and waste thermocol: A comprehensive study. Chem. Eng. J., 393, 124749, 2020. Patel, R.N., Bandyopadhyay, S., Ganesh, A., Extraction of cardanol and phenol from bio-oils obtained through vacuum pyrolysis of biomass using supercritical fluid extraction. Energy, 36, 3, 1535–1542, 2011. Rai, R.K. and Sahoo, R.R., Taguchi-Grey method optimization of VCR engine performance and heat losses by using Shorea robusta biodiesel fuel. Fuel, 281, 118399, 2020. Rai, R.K. and Sahoo, R.R., Engine performance, emission, and sustainability analysis with diesel fuel-based Shorea robusta methyl ester biodiesel blends. Fuel, 292, 120234, 2021. Radhakrishnan, S., Munuswamy, D.B., Devarajan, Y., Mahalingam, A., Effect of nanoparticle on emission and performance characteristics of a diesel engine fueled with cashew nut shell biodiesel. Energ. Source. Part A, 40, 20, 2485– 2493, 2018. Reis, C.L.B., e Silva, L.M.A., Rodrigues, T.H.S., Félix, A.K.N., de Santiago-Aguiar, R.S., Canuto, K.M., Rocha, M.V.P., Pretreatment of cashew apple bagasse using protic ionic liquids: Enhanced enzymatic hydrolysis. Bioresour. Technol., 224, 694–701, 2017. Spikes, H., The history and mechanisms of ZDDP. Tribol. Lett., 17, 3, 469–489, 2004. Saxena, N., Saxena, A., Mandal, A., Synthesis, characterization and enhanced oil recovery potential analysis through simulation of a natural anionic surfactant. J. Mol. Liq., 282, 545–556, 2019.

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Vegetable Seed Oils as Biofuel  23

Sharma, R.V., Somidi, A.K., Dalai, A.K., Preparation and properties evaluation of biolubricants derived from canola oil and canola biodiesel. J. Agric. Food. Chem., 63, 12, 3235–3242, 2015. Sahoo, P.K., Das, L.M., Babu, M.K.G., Naik, S.N., Biodiesel development from high acid value polanga seed oil and performance evaluation in a CI engine. Fuel, 86, 3, 448–454, 2007. Shrestha, D. and Rajbhandari, A., The effects of different activating agents on the physical and electrochemical properties of activated carbon electrodes fabricated from wood-dust of Shorea robusta. Heliyon, 7, 9, e07917, 2021. Senthil, M., Visagavel, K., Avinash, A., Effects of exhaust gas recirculation on emission characteristics of Mahua (Madhuca Indica) biodiesel using red mud as catalyst. Energ. Source. Part A, 38, 6, 876–881, 2016. Senthil Kumar, D. and Thirumalini, S., Investigations on effect of split and retarded injection on the performance characteristics of engines with cashew nut shell biodiesel blends. Int. J. Ambient Energy, 1–9, 2020, doi: 10.1080/01430750.2020.1730961. Senthil kumar, G., Sajin, J.B., Yuvarajan, D., Arunkumar, T., Evaluation of emission, performance and combustion characteristics of dual fuelled research diesel engine. Environ. Technol., 41, 6, 711–718, 2020, doi: 10.1080/09593330.2018.1509888. Senthilkumar, G., Sajin, J.B., Yuvarajan, D., Arunkumar, T., Evaluation of emission, performance and combustion characteristics of dual fuelled research diesel engine. Environ. Technol., 41, 6, 711–718, 2020. Shadangi, K.P. and Mohanty, K., Comparison of yield and fuel properties of thermal and catalytic Mahua seed pyrolytic oil. Fuel, 117, 372–380, 2014. Smith, E.G., Janzen, H.H., Newlands, N.K., Energy balances of biodiesel production from soybean and canola in Canada. Can. J. Plant Sci., 87, 4, 793–801, 2007. Smith Jr., R.L., Malaluan, R.M., Setianto, W.B., Inomata, H., Arai, K., Separation of cashew (Anacardium occidentale L.) nut shell liquid with supercritical carbon dioxide. Bioresour. Technol., 88, 1, 1–7, 2003. Taheri, R., Kosasih, B., Zhu, H., Tieu, A.K., Surface film adsorption and lubricity of soybean oil in-water emulsion and triblock copolymer aqueous solution: A comparative study. Lubricants, 5, 1, 1, 2016. Vimalanathan, P., Venkateshwaran, N., Santhanam, V., Mechanical, dynamic mechanical, and thermal analysis of Shorea robusta-dispersed polyester composite. Int. J. Polym. Anal. Charact., 21, 4, 314–326, 2016. Vedaraman, N., Puhan, S., Nagarajan, G., Ramabrahmam, B.V., Velappan, K.C., Methyl ester of Sal oil (Shorea robusta) as a substitute to diesel fuel—A study on its preparation, performance and emissions in direct injection diesel engine. Ind. Crops Prod., 36, 1, 282–288, 2012.

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24  Clean and Renewable Energy Production

Vedharaj, S., Vallinayagam, R., Yang, W.M., Chou, S.K., Chua, K.J.E., Lee, P.S., Experimental and finite element analysis of a coated diesel engine fueled by cashew nut shell liquid biodiesel. Exp. Therm Fluid Sci., 53, 259–268, 2014. Yadav, S., Suneja, P., Hussain, Z., Abraham, Z., Mishra, S.K., Prospects and potential of Madhuca longifolia (Koenig) JF Macbride for nutritional and industrial purpose. Biomass Bioenergy, 35, 4, 1539–1544, 2011. Zeng, X., Li, J., Wu, X., Ren, T., Liu, W., The tribological behaviors of hydroxyl-­ containing dithiocarbamate-triazine derivatives as additives in rapeseed oil. Tribol. Int., 40, 3, 560–566, 2007.

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Vegetable Seed Oils as Biofuel  25

Methodology and Instrumentation for Biofuel with Study on Cashew Nut Shell Liquid Deepak Kumar1*, Vijay Kumar Chhibber2, Ajay Singh3 and Adesh Kumar4 Department of Chemistry, Uttarakhand Technical University, Dehradun, India 2 Indian School of Petroleum (IIP), Dehradun & Dean Baba Farid Institute of Technology, Dehradun, India 3 Department of Chemistry, Uttaranchal University, Dehradun, India 4 Department of Electrical and Electronics Engineering, University of Petroleum and Energy Studies, Dehradun, India 1

Abstract

A substitute for traditional fossil fuel that is biodegradable, renewable, and nontoxic is biodiesel. Typically, it is made from non-edible plant oil, waste cooking oil, animal fat, and vegetable oil. The quality of the biodiesel could be impacted by contamination during handling and storage, by-products and residue oil from the production process, or contamination during transportation. This chapter focuses on the methodology for biodiesel and the instrumentation used for the analysis of the behavior of the obtained biodiesel. The content of biodiesel in the reaction mixture can be determined analytically using Fourier transform infrared (FTIR) spectroscopy to track the transesterification reaction. Additionally, it is demonstrated that it could be used to estimate the biodiesel percentage in biodiesel–petrodiesel blends. A combination of NMR spectroscopy techniques was used to examine the molecular makeup of the biodiesel samples. To comprehensively characterize and assign the molecular structure of the biodiesel samples, as well as to identify and quantify the molecular moieties, especially the unsaturated long-chain alkyl esters, the NMR spectroscopy behavior technique was used for biodiesel characterization. This chapter presents the study

*Corresponding author: [email protected] Surajit Mondal, Adesh Kumar, Rupendra Kumar Pachauri, Amit Kumar Mondal, Vishal Kumar Singh and Amit Kumar Sharma (eds.) Clean and Renewable Energy Production, (27–52) © 2024 Scrivener Publishing LLC

27

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2

on general methodology and instrumentation for biofuel and study on cashew nut shell liquid. Keywords:  Additives, biodiesel, FTIR, GC-MS, NMR spectroscopy

2.1 Methodology The methodology of the research work is shown in Figure 2.1. The methodology diagram shows the flow of the work, in which the first step is about the extraction of oil (sal, mahua, and cashew nut) from the seeds [1], followed by its purification using n-hexane as a solvent and applying the structure elucidation with the analytical methods Fourier transform infrared (FTIR) spectroscopy and GC-MS. Moreover, further work was carried out in the direction of preparation of the derivatives of sal, mahua, and cashew nut and the study of these derivatives based on their physical and chemical properties and biodegradability. The experimental process is followed by adding the nanoparticle and using the blended fuel in different rations for the experimental

Extraction of Oil (Sal, Mahua and Cashew nut) from seeds Purification of oil using solvent n-hexane Structure elucidation by analytical methods FTIR, and GCMS Preperation of derivatives of (Sal, Mahua and Cashew nut) Derivatives Study based on Physical and Chemical Properties and Bio degradablity Adding the nanoparticle and use the blended fuel for experimental set-up Analyze the behaviour of the biodiesel in DI engine with different parameters under full and part load Analyze the eco-friendly behaviour of biodiesel based on the study on the emission parameters Estimate the performance of the system using machine learning and statistical techniques

Figure 2.1  Methodology of the biodiesel process.

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28  Clean and Renewable Energy Production

setup. Analysis followed to understand the behavior of the biodiesel in direct injection (DI) engines with different parameters under full and part loads. Further study was carried out to analyze the eco-friendly behavior of the biodiesel based on the study of the emission parameters such as CO, CO2, NOx, hydrocarbon (HC), and smoke. Machine learning [2] and statistical techniques were applied for estimation of the performance of the system and the eco-friendly behavior of biodiesel [3].

2.2 Procedure The two primary methods utilized to create modern biodiesel with alcohol were catalytic and non-catalytic esterification/transesterification of free fatty acids/triglycerides. The synthesis of biodiesel most usually employs chemical catalysts because of their short reaction times and large yields. Chemical catalysis does have drawbacks, such as challenging downstream product purification, an oversupply of alkaline effluent, and the need for catalyst recycling and recovery. To prevent saponification, the chemical catalytic process also needs high-quality raw materials. Figure 2.2 shows the different biodiesel processes in biodiesel production and analysis. These materials can influence the economics of the

1st generation (edible oils)

2nd generation (edible oils) 3rd generation (edible oils)

Waste oils (Animal fats, Used vegetable oils)

Alkali Catalysed Heterogeneous Acid catalysed

Fermentation

1-3 propanediol

Dehydration

Acrolein

Etherification

Fuel Oxygenates

Selective oxidation

1-3 digydroxyacetatone

Inter Esterification

Glycerol Crbonate

Biodiesel

Acid catalysed Supercritical (non alkalytic)

Glycerol

Enzyme catalyzed

Conversion Technologies

Feedstock Diversity

Figure 2.2  Biodiesel processes.

Products & Potential Services for Value added Co-products

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Methodology for Biofuel and CNSL  29

production process and increase product costs. The biocatalytic technique has been considered a promising option because of its favorable reaction conditions, low waste formation, ease of adaptability of source materials, and purification. Vegetable oils may be replaced with new, inexpensive raw materials like second- and third-generation feedstock to lower the price of biodiesel. The development of next-generation waste biofuels, like biodiesel, has been the focus of research. This has been accomplished by linking the esterification processes with the recovery of organic acid from diverse waste sources. Recent studies have also examined the efficiency of biodiesel blends in DI diesel engines, employing alternative fuels mixed with diesel and biodiesel made from water hyacinth, tamarind biodiesel, palm biodiesel, and Garcinia gummi-gutta biodiesel.

2.2.1 Common Points • To eliminate moisture, 150 g of vegetable oil was preheated to 105–110°C in a 250-ml glass vessel. It was then cooled to 45–50°C. • The catalyst potassium hydroxide (KOH) was paired with methanol-to-oil molar ratios of 6:1, 4:1, and 8:1 at 1.0, 0.5, and 1.5 wt.% of the oil, respectively. • KOH, a catalyst, and 150 g of methyl alcohol were uniformly combined with 150 g of safflower oil [4]. • At constant temperatures of 50–60°C, the conical flask holding the oil, alcohol, and catalyst mixture was agitated in a water bath for 75, 60, and 90 min. • The products were held in a separate funnel for an additional hour or two after the reaction interval to facilitate phase separation. The articles were split into two layers in the separating funnel. Glycerol sunk to the bottom due to its higher specific weight, whereas biodiesel holds the top layer. In the next step, glycerol was thrown away. • Hot distilled water was used to wash the biodiesel after separation to get rid of any catalyst or methyl alcohol that might have lingered. • The surplus water content was then removed from the biodiesel by roasting it at 100°C in a hot air oven. The seeds were collected from the tree or different regions in India. A hot air oven was used to dry the seed at 30–50°C for 24 h. Moisture, ash,

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30  Clean and Renewable Energy Production

volatile contents, and fixed carbons were determined using the ASTM D3172-07 standard method [5]. The cold processing method was used to extract the oil from the seeds. The extracted sal oil had odor properties and a greenish-brown color because of the existence of fatty saturated contents in higher amounts. FTIR and GC-MS testing was performed to determine the functional groups and hydrocarbon compositions and the fatty acids, respectively.

2.3 Fourier Transform Infrared Spectroscopy In the FTIR process [5], 50  g of sal oil was taken and dissolved in about 100 ml of toluene using a glass rod and then cooled up to 10°C. Moreover, 50  g of anhydrous aluminum chloride (AlCl3) was gradually supplemented approximately for 1  h. The process was marinated for 12  h with constant stirring. Thereafter, the contents were added into water with 10% amount of HCL, and the upper layer was washed with water regularly to reduce the effect of acid. This contact water in the upper layer was eliminated using the Dean–Stark trap. Toluene was cleaned off and missing traces were detached under a vacuum. The resulting vacuum-­dried product was infiltrated over Fuller’s earth to eliminate organic acidity to acquire a pale yellow product. Perkin Elmer FTIR was used for this process. Figure 2.3 presents the FTIR apparatus from Perkin Elmer’s Frontiers. Perkin Elmer company provided the new generation of robust infrared systems with an extensive selection of FTIR and diode array (DA)-based

Figure 2.3  Fourier transform infrared (FTIR) spectrometry apparatus from Perkin Elmer’s Frontiers.

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Methodology for Biofuel and CNSL  31

spectrometers, which are very strong and versatile and provide accurate and dependable analytical findings to meet all the necessities for present analysis demands and could be expanded according to goal changes. These help in the investigation of production issues, spotting product impurities, examining fuels, and learning more about the characteristics of unique and advanced materials. • Identification of the functional groups and description of the data on covalent bonds. • Stretching and binding the vibrations of the cellular bodies. • Aid in the identification of the mixture of constituents. • Detail the materials and the structure’s construction. • Understanding the contamination in industrial samples that are known to exist. The apparatus of the Spectrum 100 FTIR system works at a power frequency of 50 or 60 Hz with a voltage range of 100–230 V without needing to be adjusted. The instrument’s nominal power consumption is 120 VA. The line supply must have a nominal voltage that is within 10% of this to avoid connecting the device to circuits that have powerful machinery. FTIR avoids the use of photocopiers, radio transmitters, discharge lamps, and other devices, which are of high or frequent transient weights on the same supply circuit. The facility of the spare fuse is in the same drawer as the primary fuse (2AT, 250 V) and is located adjacent to the main intake back on the instrument side. The live line is connected to the primary fuse. The sample was positioned in a holder in the path of the infrared (IR) source. The analog signal was read by a detector, which then transformed it into a spectrum. The signals were analyzed by a computer, which also located the peaks. A partially silvered mirror split an IR beam into two equal-intensity beams.

2.4 Gas Chromatography–Mass Spectrometry GC-MS is one of the core analytical methods that have a wide scope of applicability. One foremost application of GC-MS is the detection of compounds by considering both important aspects such as the chemical formula, molecular weight, and the relative abundance of the properties of fragment ions. Therefore, the technique accumulates more reliable and

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32  Clean and Renewable Energy Production

accurate results. The method has been adopted to determine the analysis of toxic residues in vegetable oils and foods. Many researchers have reported GC-MS analysis in their work about the identification of antioxidants in water, volatile organic compounds, and fatty acid methyl esters in fuel oil [6-8]. The GC-MS [9] setup is one of the fast quadrupole mass spectrometers and works on large spectra (12,500 amu/s) against each GC peak. Figure 2.4 depicts the view of the apparatus. It supports the quantification of exceptionally narrow chromatographic peaks and provides a clear definition for precise and exceptional data. This instrument also provides the largest mass range accessible in gas chromatography (1–1,200 amu); however, finding limits is not possible in single quadrupole GC-MS. The mass spectrometer was set to work in the electron impact (EI) mode of ionization and scanned the results in the range of 50–550 m/z with peaks. The splitless operation was performed based on pressure (velocity or flow), and pulse injection was endorsed for a smooth operation. It was applied when the analysis is done for large volumes and a large range of boiling point mixtures. This method enhances the pressure (velocity and flow) in the injection system, and this time oil expansion is also minimized in the injector linearly and maximized the oil sample transmission into the column. Therefore, maximum pressure was chosen to obtain better recovery and better peak shapes, and no discrimination was considered for both high and low boiling compounds. In the beginning, the pressure (velocity and flow) was high (approximately 70 psi), and this pressure was kept for 0.25–2.0  min to send the samples into

Figure 2.4  Clarus SQ8S for GC-MS [9].

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Methodology for Biofuel and CNSL  33

the columns. This time was observed and determined experimentally for the sampled oil and injector temperature. It is required to obtain the time when the entire sample has been transferred into one column and maintained good solvent to analyze the peak shape. If this period is short, the sample may be lost. If the time is large, then the solvent will be tailed and probably obscure or affect the shape of the peaks. The split outlet was kept at zero or off at the time of injection. The pressure was kept below the normal column working pressure and programmed at a controlled rate. During the same duration, the split outlet was fed back at a normal flow for cleaning the rest of the sample in the liner and to give some pressure in the injector based on the requirement. It is also required that the pressure be programmed to not go down too rapidly, as it may cause a backflush in the column. In this situation, the sample can be returned to the injector and either may lose out the split vent or create peak broadening. The instrument works in the multi-program mode, in which the autosampler runs two programs consecutively. It was mounted on top and precisely sampled delivery, never twisting the needle. The program specified the technique, the size of the injector, and the number of injections per vial. The autosampler processes at least one injection against each vial in the desired range. The GC oven delivers the minimum injection-to-­ injection time and larger throughput for the samples. With the help of a touchscreen interface on the Clarus SQ8S GC-MS and TurboMass software, the spectrum was analyzed or saved for future reference against the sampled sal oil.

2.5 Nuclear Magnetic Resonance With the aid of a technique called spectroscopy, we could examine how matter and electromagnetic waves interact. There are numerous types of spectroscopy, including infrared, UV, and NMR, among others. NMR spectroscopy is a type of spectroscopy that allows identifying the quality and purity of a sample as well as its molecular makeup. It can ascertain the sample’s composition and purity in addition to the molecule’s structural information. One of the NMR techniques most frequently employed by organic chemists is proton (1H) NMR. It is possible to determine the structure of a molecule by studying how its protons respond to the chemical environment around them. The NMR principle states [10] that all nuclei are electrically charged and that many nuclei have spin. When an external

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34  Clean and Renewable Energy Production

magnetic field is given, an energy transfer from the base energy to a higher energy level is possible. • Electrical charge permeates every nucleus, and many have spin. • When an external magnetic field is provided, energy can be transferred from lower energy levels to higher energy levels. • Energy is transferred at a wavelength that matches the radio frequency. • Also, when the spin returns to its initial base level, energy is released at the same frequency. • Hence, the processing of the NMR spectrum for the concerned nucleus is produced by measuring the signal that fits this transfer.

2.6 CNSL Study Cashew nut shell liquid (CNSL), also well known as cashew shell oil, is a natural oil with a yellowish hue that is produced as a result of cashew nuts with a honeycomb arrangement. It serves as the starting point for a number of biomaterials, fungicides, folk remedies, anti-termite medications, antioxidants, and timer treatments. The quantity used for processing determines the oil’s makeup. CNSL [11] is composed of phenolic structures with alkyl substitutions, and as a result, the molecules exhibit antioxidant properties. The solvents in the oil

OH

OH

OH

OH

COOH R Anacardic Acid

H 3C HO

R Cardol

R

HO

Cardanol

R

2-methyl-cardol

R = C15 H31 C15 H29 C15 H27

n=0 8' 8'

11'

8'

11'

C15 H25

Figure 2.5  Composition of the cashew nut shell liquid (CNSL) [11].

n=1 14'

n=2 n=3

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Methodology for Biofuel and CNSL  35

were removed with the help of the hot oil treatment method. Cardol, cardanol, anacardic acid, and 2-methyl-cardol are all components of normal CNSL [12]. The present amounts of cardol (15%–20%), cardanol (5%– 10%), anacardic acid (65%–70%), and 2-methyl-cardol (3%–5%) make up the CNSL. Figure 2.5 shows the composition of the cashew nut oil components [13, 14]. The Perkin Elmer Frontier FTIR equipment was used to prepare the thermal-cracked cashew nut shell liquid (TC-CSNL) sample for FTIR. The X-axis displays the wavelength (per centimeter), while the Y-axis displays the transmittance percentage [15–21]. Figure 2.6 displays the FTIR spectrum of the TC-CNSL, with numerous wavelengths against various present functional groups. The detailed spectrum can be seen in the range 4,000–440 cm−1 absorption regions. The first broad O–H widening vibration absorbance peak, which shows phenolic compounds and is present between 3,600.00 and 3,009.59 cm−1, indicates the presence of water impurities and supplementary polymers (O–H) available in the oil. Alkanes are demonstrated by the long-lasting (C–H) vibration absorbance peak between 2,927.49 and 2,654.42 cm−1. Aldehydes and ketones exhibit (C–H) deformation vibrations at wavelengths 1,594.86 cm−1: 1,154.15 cm−1. Carboxylic acids and their potential esters derivatives are indicated by the presence of (O–H) and stretching vibrations. Alkenes are most likely present when the absorbance points lie between 1,594.86 and 1,154.15 cm−1. The peaks between 1,266.60 and 695.76 cm−1 are accounted for by the presence of ethers, primary, secondary, and tertiary alcohols, esters, and phenols that help to determine the stretching vibration (C–O) and deformation (O–H). Figure 2.7 presents the GC-MS study of TC-CNSL, sample 1, while Figure 2.8 displays the GC-MS study of TC-CNSL, sample 2. Table 2.1 lists the results and compounds from the GC-MS study of TC-CNSL of sample 1, while Table 2.2 lists the results and compounds from the GC-MS study of TC-CNSL of sample 2. Figure 2.9 presents the GC-MS study of TC-CNSL, sample 3, and Table 2.3 lists the results and compounds from the GC-MS study of thermal-cracked cashew nut shell liquid (TC-CNSL) of sample 3. Figure 2.10 presents the GC-MS study of TC-CNSL of sample 4, while Table 2.4 lists the results and compounds from the GC-MS study of TC-CNSL of sample 4. In the same way, Figure 2.11 presents the GC-MS study of TC-CNSL of sample 5, and Table 2.5 lists the results and compounds from the GC-MS study of TC-CNSL of sample 5.

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36  Clean and Renewable Energy Production

Wavenumbers (cm–1)

Figure 2.6  Fourier transform infrared (FTIR) spectrometry analysis of the thermal-cracked cashew nut shell liquid (TC-CNSL).

529.52 623.71 15

10

5

500 1000 1500 2000

695.76 20

458.87 938.68 912.67 868.03 844.48 778.51 1079.97 25

2500

994.60

30

1154.15 1348.43

45

1266.60 50

1824.69 1915.94 55

1457.12 2728.37 35

1594.86 3009.59 0

3000

2854.42 –10

3500 –15 4000

2927.49 –5

3461.27 40

% Transmittance

70

65

60

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Methodology for Biofuel and CNSL  37

CASHEW NUT 499 (14.461) 151

100 136 108 104

%

76 80 52 50 64 68 61 81 94

0

42

62

82

121 150

109

102

134 149

122

142

152 165 178 192 162

182

208214223 234 250

202

222

242

268 281 262

282

327 302

322

343 355 342

362

377

434

382

402

422

442

m/z

CASHEW NUT 716 (19.016) 56 54

100

68

104 7682 96

% 50 0

33

53

84

66

121 110

94 97

73

93

113

151 122136 150 154 178 191 206 160170 224 240

133

153

173

193

213

233

259269 283 297307

253

273

293

313

341 353 369379 328 346 394404

333

Figure 2.7  GC-MS study of thermal-cracked cashew nut shell liquid (TC-CNSL), sample 1.

353

373

393

413

430 444

433

453

475481 496

473

493

513

m/z

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38  Clean and Renewable Energy Production

CASHEW NUT 810 (20.989) 100

104 121

56 76 70

%

54 50

0

47

108

68 66

67

82

92 96

87

151 110 126136150

107

127

147

163169 193 208 182 223 239 250255267 279 293 305309 327 341 355 371378387397406 418 430 444456461 479484 167

187

207

227

247

267

287

307

327

Figure 2.8  GC-MS study of thermal-cracked cashew nut shell liquid (TC-CNSL), sample 2.

347

367

387

407

427

447

467

487

m/z

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Methodology for Biofuel and CNSL  39

Table 2.1  Results and compounds from the GC-MS study of thermal-cracked cashew nut shell liquid (TC-CNSL) of sample 1. Hit

Rev

For

Compound name

MW

Formula

CAS

1

599

356

1,10-Decanediol

174

C10H22O2

112-47-0

Library

NIST

2

591

367

8-Azabicyclo[5.1.0]octane

111

C7H13N

286-44-2

NIST

3

575

374

10-Dodecenol

184

C12H24O

35237-63-9

NIST

4

568

372

7-Dodecenol

184

C12H24O

16695-40-2

NIST

5

561

340

10-Dodecenol

184

C12H24O

35237-63-9

NIST

6

557

353

1,11-Undecanediol,di(4-nitrobenzoate)

486

C25H30O8N2

900197-47-9

NIST

7

555

343

9-Decen-1-ol, pentafluoropropionate

302

C13H19O2F5

900352-65-6

NIST

8

552

341

(Z)-4-decen-1-ol, trifluoroacetate

252

C12H19O2F3

900352-33-5

NIST

9

549

303

2-(Propen)-1-(amine), N-2-(propenyl)

97

C6H11N

124-02-7

NIST

10

543

341

2H-cyclopentacycloocten-2-one, decahydro

180

C12H20O

55103-65-6

NIST (Continued)

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40  Clean and Renewable Energy Production

Table 2.1  Results and compounds from the GC-MS study of thermal-cracked cashew nut shell liquid (TC-CNSL) of sample 1. (Continued) Hit

Rev

For

Compound name

MW

Formula

CAS

Library

11

541

316

3-Nonen-1-ol, (Z)-

142

C9H18O

10340-23-5

NIST

12

535

301

1,9-Nonanediol

160

C9H20O2

3937-56-2

NIST

13

507

308

9-Decen-2-ol

156

C10H20O

900164-44-8

NIST

14

504

319

9,11-Dodecadien-1-ol, acetate, (E)

224

C14H24O2

50767-78-7

NIST

15

503

347

3,9-Dodecadiene

166

C12H22

54764-65-7

NIST

16

503

322

4-Cyclohexyl-1-butanol

156

C10H20O

4441-57-0

NIST

17

501

321

5-Butyl-2-methyl-.delta.1-pyrroline

139

C9H17N

106119-01-1

NIST

18

497

312

Bicyclo[4.2.0.]octane, 6,7-dimethyl

138

C10H18

900063-19-2

NIST

19

488

323

Methanamine, N-cyclohexylidene-

111

C7H13N

6407-35-8

NIST

MW, molecular weight; NIST, National Institute of Standards and Technology.

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Methodology for Biofuel and CNSL  41

Table 2.2  Results and compounds from the GC-MS study of thermal-cracked cashew nut shell liquid (TC-CNSL) of sample 2. Hit

Rev

For

Compound name

MW

Formula

CAS

Library

1

573

315

3-[3-Phthalimidopropyl]-2oxazolidinone

274

C14H14O4N2

23545-33-7

NIST

2

532

337

4-Nitrobenzoic acid, 2-Ethylhexyl ester

279

C15H21O4N

16397-70-9

NIST

3

515

362

Benzoic acid, 4-nitro-, octyl ester

279

C15H21O4N

6500-50-1

NIST

4

503

358

4-Nitrobenzoic acid, cyclobutyl ester

221

C11H11O4N

70335-00-1

NIST

5

472

326

4-Nitrobenzoic acid, heptyl ester

265

C14H19O4N

14309-44-5

NIST

6

446

301

4-Nitrobenzoic acid, nonyl ester

293

C16H23O4N

6500-27-2

NIST

7

440

301

4-Nitrobenzoic acid, decyl ester

307

C17H25O4N

6500-30-7

NIST

MW, molecular weight; NIST, National Institute of Standards and Technology.

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42  Clean and Renewable Energy Production

Table 2.3  Results and compounds from the GC-MS study of thermal-cracked cashew nut shell liquid (TC-CNSL) of sample 3. Hit

Rev

For

Compound name

MW

Formula

CAS

Library

1

723

330

5-Acetyl-2-methylpyridine

135

C8H9ON

42972-46-3

NIST

2

723

336

5-Acetyl-2-methylpyridine

135

C8H9ON

42972-46-3

NIST

3

702

324

Pyridine, 4-(1,1-dimethylethyl)-

135

C9H13N

3978-81-2

NIST

4

665

327

Ethanone, 1-(2-aminophenyl)-

135

C8H9ON

551-93-9

NIST

5

662

334

Ethanone, 1-(6-methyl-3-pyridinyl)-

135

C8H9ON

36357-38-7

NIST

6

661

334

Benzoic acid, 4-amino-, 2,2,6,6-tetramet

290

C16H22O3N2

900261-13-4

NIST

7

642

347

Benzoic acid, 4-amino-, 2,2,6,6-tetramet

276

C16H24O2N2

900261-13-3

NIST

8

640

366

Pyridine, 4-(1,1-dimethylethyl)-

135

C9H13N

3978-81-2

NIST

9

629

337

Acetophenone, 4ʹ-amino-

135

C8H9ON

99-92-3

NIST

10

617

331

Acetophenone, 4ʹ-amino-

135

C8H9ON

99-92-3

NIST

11

611

315

N-(methylsulfinyl)diethylamine

135

C5H13ONS

900306-26-3

NIST

12

605

348

Ethanone, 1-(2-aminophenyl)-

135

C8H9ON

551-93-9

NIST (Continued)

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Methodology for Biofuel and CNSL  43

Table 2.3  Results and compounds from the GC-MS study of thermal-cracked cashew nut shell liquid (TC-CNSL) of sample 3. (Continued)

Hit

Rev

For

Compound name

MW

Formula

CAS

Library

13

599

321

3-Aminoacetophenone

135

C8H9ON

99-03-6

NIST

14

594

307

Benzenamine, N-(1-methylethyl)-

135

C9H13N

768-52-5

NIST

15

590

343

Pyridine, 4-(1,1-dimethylethyl)-

135

C9H13N

3978-81-2

NIST

16

578

310

Benzenamine, N-ethyl-3-methyl-

135

C9H13N

102-27-2

NIST

17

576

337

Acetophenone, 4ʹ-amino-

135

C8H9ON

99-92-3

NIST

18

568

302

N-ethyl-p-toluidine

135

C9H13N

622-57-1

NIST

19

565

326

Ethanone, 1-(2-aminophenyl)-

135

C8H9ON

551-93-9

NIST

20

561

323

3-Aminoacetophenone

135

C8H9ON

99-03-6

NIST

MW, molecular weight; NIST, National Institute of Standards and Technology.

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44  Clean and Renewable Energy Production

CASHEW NUT 885 (22.564)

100

64 70 82 56

Figure 2.9  GC-MS study of thermal-cracked cashew nut shell liquid (TC-CNSL), sample 3.

491

m/z 511

491 471 451 431 411 391 371 351 331 311 291 271 251 231 211 191 171 151 131 111 91 71 51 31

402 418 50

135 92 96104 121 97 110 124 136 151 164 180 194 206 222 239 255 267277282 298 313 328 341 354 217

0

120

%

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Methodology for Biofuel and CNSL  45

Table 2.4  Results and compounds from the GC-MS study of thermal-cracked cashew nut shell liquid (TC-CNSL) of sample 4. Hit

Rev

For

Compound name

MW

Formula

CAS

Library

1

903

513

2,3-Pyrazinedicarbonitrile,5-amino-6

307

C14H9O2N7

52197-20-3

NIST

2

813

494

1H-benzimidazole-2-carboxaldehyde

146

C8H6ON2

3314-30-5

NIST

3

771

523

2(1H)-quinoxalinone

146

C8H6ON2

1196-57-2

NIST

4

753

532

2(1H)-quinoxalinone

146

C8H6ON2

1196-57-2

NIST

5

735

520

Benzoimidazole-1-carbaldehyde

146

C8H6ON2

900294-58-3

NIST

6

718

506

2-Propenoic acid, 3-(2-hydroxyphenyl)

164

C9H8O3

614-60-8

NIST

7

712

499

2(1H)-quinoxalinone

146

C8H6ON2

1196-57-2

NIST

8

712

513

2(1H)-quinazolinone

146

C8H6ON2

7471-58-1

NIST

9

708

542

Benzimidazole-2-carboxaldehyde, 4-nitrop

281

C14H11O2N5

900263-74-9

NIST

10

705

490

1H-benzimidazole-2-carboxaldehyde

146

C8H6ON2

3314-30-5

NIST

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46  Clean and Renewable Energy Production

(Continued)

Table 2.4  Results and compounds from the GC-MS study of thermal-cracked cashew nut shell liquid (TC-CNSL) of sample 4. (Continued) Hit

Rev

For

Compound name

MW

Formula

CAS

Library

11

702

509

Trans-2-hydroxycinnamic acid, methyl ester

178

C10H10O3

900352-49-0

NIST

12

690

434

2-Hydroxy-1,8-naphthyridine

146

C8H6ON2

15936-09-1

NIST

13

689

511

2-Propenoic acid, 3-(2-hydroxyphenyl)

164

C9H8O3

583-17-5

NIST

14

686

506

2-Hydroxyzimtsaeureethylester

192

C11H12O3

17041-46-2

NIST

15

672

408

2-Hydroxy-1,7-naphthyridine

146

C8H6ON2

54920-82-0

NIST

16

668

509

4(4-Azidobenzoyl)aminobenzoylchloride

300

C14H9O2N4Cl

900286-89-2

NIST

17

667

483

2-Propenoic acid, 3-(2-hydroxyphenyl)

178

C10H10O3

20883-98-1

NIST

18

663

450

4-Aminobenzo-1,2,3-triazine

146

C7H6N4

89795-80-2

NIST

19

646

479

1(2H)-naphthalenone, 3,4-dihydro-

146

C10H10O

529-34-0

NIST

20

643

410

Oxazolidine, 2-phenyl

149

C9H11ON

3394-32-9

NIST

MW, molecular weight; NIST, National Institute of Standards and Technology.

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Methodology for Biofuel and CNSL  47

CASHEW NUT 1042 (25.860)

100

146 %

91

Figure 2.10  GC-MS study of thermal-cracked cashew nut shell liquid (TC-CNSL), sample 4.

476

m/z

461 401 415

456 436 416 396 376 356 336 316 296 276 256 236 216 196 176 156 136 116 96 76 56 36

333 341 355 63 90 104 120 72 76 92 206 5154 135 147 82 254 306 108 127 164 178 191 221 227 239 270 281 289 316

0

118

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48  Clean and Renewable Energy Production

CASHEW NUT 1066 (26.364) 118

100

91 54 66

%

53 50 0

31

51

82 63 76 83 95104 120 109 86 97 134 71

91

111

131

146 306 147 151

164 180 192 171

191

206

222228 239

211

231

256 265 281 289 251

271

291

307 316 333 341355361 375 311

331

351

371

403410423429 391

411

431

462 451

491

471

491

511

m/z

CASHEW NUT 1094 (26.952) 118

100

107 91 104 146 76 5663 120 90 70 96 108 50 127 134 152 164171

%

0

30

50

70

90

110

130

150

170

306 206 246 208 256 289 192202 228 238 264 281 214 190

210

230

250

270

290

307 316 333 341355368 377382 401410415429 442 454 310

330

350

Figure 2.11  GC-MS study of thermal-cracked cashew nut shell liquid (TC-CNSL), sample 5.

370

390

410

430

450

475 489 470

490

m/z 510

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Methodology for Biofuel and CNSL  49

Table 2.5  Results and compounds from the GC-MS study of thermal-cracked cashew nut shell liquid (TC-CNSL) of sample 5. Hit

Rev

For

Compound name

MW

Formula

CAS

Library

1

496

306

8-Chlorooctyl ethyl carbonate

236

C11H21O3Cl

900373-78-5

NIST

2

523

304

Ethene,-1-(4-ethoxyphenyl)-2-nitro

193

C10H11O3N

6946-30-1

NIST

MW, molecular weight; NIST, National Institute of Standards and Technology.

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50  Clean and Renewable Energy Production

2.7 Conclusions Many biodiesel producers are interested in using gas. GC-MS is a sensitive and specific technique for the separation and identification of fatty acids as a means of identifying the fatty acid profiles of seed oils, monitoring the reaction process, and figuring out how much biodiesel can be produced from them. FTIR analysis was carried out on CNSL to determine the functional groups and wavelengths. GC-MS analysis was done successfully on CNSL using autosampler of Perkin Elmer’s Clarus SQ8S GC-MS.

References 1. Anand, O.N. and Chhibber, V.K., Vegetable oil derivatives: Environmentfriendly lubricants and fuels. J. Synth. Lubr., 23, 2, 91–107, 2006. 2. Hooda, A., Kumar, A., Goyat, M.S., Gupta, R., Estimation of surface roughness for transparent superhydrophobic coating through image processing and machine learning. Mol. Cryst. Liq. Cryst., 726, 1, 90–104, 2022. 3. Kumar, D., Chhibber, V.K., Singh, A., Nano additives in cashew nut shell liquid biodiesel and environment emissions of diesel engine. J. New Mater. Electrochem. Syst., 25, 2, 87–97, 2022. 4. Hooda, A., Goyat, M.S., Kumar, A., Gupta, R., A facile approach to develop modified nano-silica embedded polystyrene based transparent superhydrophobic coating. Mater. Lett., 233, 340–343, 2018. 5. Singh, A., Kumar, D., Yadav, M., Modification of ” Shorea robusta oil” by esterification for getting improved property. Int. J. Pharm. Res., 9, 0976–2167, 2019. 6. Anyakudo, F., Adams, E., Van Schepdael, A., Analysis of volatile organic compounds in fuel oil by headspace GC-MS. J. Environ. Anal. Chem., 98, 4, 323–337, 2018. 7. Tariq, M., Ali, S., Ahmad, F., Ahmad, M., Zafar, M., Khalid, N., Khan, M.A., Identification, FT-IR, NMR (1H and 13C) and GC/MS studies of fatty acid methyl esters in biodiesel from rocket seed oil. Fuel Process. Technol., 92, 3, 336–341, 2011. 8. Guo, L., Xie, M.Y., Yan, A.P., Wan, Y.Q., Wu, Y.M., Simultaneous determination of five synthetic antioxidants in edible vegetable oil by GC–MS. Anal. Bioanal.Chem., 386, 6, 1881–1887, 2006. 9. Manual CLARUS SQ 8 GC/MS Gas Chromatograph/Mass Spectrometer, Perkin Elemer. https://resources.perkinelmer.com/lab-solutions/resources/ docs/bro_clarus_sq_8_gcms_009724c_01.pdf 10. Doudin, K., II, Quantitative and qualitative analysis of biodiesel by NMR spectroscopic methods. Fuel, 284, 119114, 2021.

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Methodology for Biofuel and CNSL  51

11. Rois, D.S., M.A., Nascimento, T.L., Santiago, S.N., Mazzetto, S.E., Cashew nut shell liquid: A versatile raw material utilized for syntheses of phosphorus compounds. Energy Fuels, 23, 11, 5432–5437, 2009. 12. Bangjang, T., Saisangtong, R., Kaewchada, A., Jaree, A., Modification of diesohol fuel properties by using cashew nut shell liquid and biodiesel as additives. Energy Technol., 2, 9–10, 825–831, 2014. 13. Balgude, D. and Sabnis, A.S., CNSL: An environment friendly alternative for the modern coating industry. J. Coat. Technol. Res., 11, 169–183, 2014. 14. Kumar, D., Chibber, V.K., Singh, A., Review of vegetable seeds oils as biolubricants. Energy Environ. Focus, 6, 2, 103–113, 2017. 15. Majer, S., Mueller-Langer, F., Zeller, V., Kaltschmitt, M., Implications of biodiesel production and utilisation on global climate–A literature review. Eur. J. Lipid Sci. Technol., 111, 8, 747–762, 2009. 16. Kumar, D., Chibber, V.K., Singh, A., Physical and chemical properties of mahua and sal seed oils, in: Intelligent Communication, Control and Devices: Proceedings of ICICCD 2017, pp. 1391–1400, Springer, Singapore, 2018. 17. Kumar, D., Chhibber, V.K., Singh, A., Emissions prediction of cashew nut shell liquid biodiesel using machine learning. Natl. Acad. Sci. Lett., 45, 5, 397–400, 2022. 18. Kumar, D., Chhibber, V.K., Singh, A., Adding ZnO Nanoparticle in Mahua Oil Methyl Ester (MoME) biodiesel for eco-friendly and better performance in DI engine. Natl. Acad. Sci. Lett., 45, 161–164, 2022. 19. Singh, B.K., Bala, M., Rai, P.K., Fatty acid composition and seed meal characteristics of Brassica and allied genera. Natl. Acad. Sci. Lett., 37, 3, 219–226, 2014. 20. Singh, V.K., Soni, A.B., Kumar, S., Singh, R.K., Pyrolysis of sal seed to liquid product. Bioresour. Technol., 151, 432–435, 2014. 21. Singh, R.K., Kukrety, A., Kumar, A., Chouhan, A., Saxena, R.C., Ray, S.S., Jain, S.L., Synthesis, characterization, and performance evaluation of N, N-Dimethylacrylamide–Alkyl acrylate copolymers as novel multifunctional additives for lube oil. Adv. Polym. Technol., 37, 6, 1695–1702, 2018.

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52  Clean and Renewable Energy Production

Emerging Technologies for Sustainable Energy Applications Swagata Sarma1, Gaurav Pandey1,2*, Uttamasha B. Borah1, Nadezhda Molokitina2 Geetanjali Chauhan3 and Monika Yadav4 Department of Petroleum Engineering and Earth Sciences (Energy Cluster), School of Engineering, University of Petroleum and Energy Studies, Dehradun, India 2 Earth Cryosphere Institute, Tyumen Scientific Center, SB, RAS, Tyumen, Russia 3 Department of Petroleum Engineering, Indian Institute of Petroleum and Energy, Visakhapatnam, India 4 Electrical Cluster, School of Advanced Engineering, University of Petroleum and Energy Studies, Dehradun, India 1

Abstract

Amidst rising concerns of increasing greenhouse gas emissions, achieving net negative emission of carbon marks the upsurge of research in the carbon capture aspect. The increased global warming, climate change impacts, and ocean acidification are the prime concerns. Researchers need to quantitatively comprehend the global carbon stores to predict and mitigate the impacts of anthropogenicinduced climate change. In light of the ever-increasing amounts of greenhouse gas emissions in the environment, renewable energy is an important part of the global effort to create a more sustainable and cleaner future. Aiding in recovering from the climate change impacts, the renewables are steadily finding popularity. The major technologies in this regard are solar, wind, geothermal, biomass, and hydro. Solar energy is the form of energy obtained from sunlight by conversion through photovoltaic devices. The energy from the wind is exploited to produce energy by turning the blades of wind turbines. Other non-conventional sources of energy, such as geothermal, biomass, and hydro, have also found major applications in the past decades. These are helping the globe pace toward sustainability since they are derived from the Earth’s thermal energy, organic waste materials, *Corresponding author: [email protected] Surajit Mondal, Adesh Kumar, Rupendra Kumar Pachauri, Amit Kumar Mondal, Vishal Kumar Singh and Amit Kumar Sharma (eds.) Clean and Renewable Energy Production, (53–86) © 2024 Scrivener Publishing LLC

53

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3

and flowing water, respectively. Leading-edge technology will enhance the storage of such energy, like the batteries for storing renewable energy that are less expensive. This review gives the reader a general introduction to carbon cycling, including the major sources and sinks of carbon. An overview of the carbon fluxes and their driving factors, transformations, and some consequences of alterations in these processes is provided. The carbon dioxide sequestration methodology is applied to stem the ecological changes. The major carbon dioxide sequestration techniques (biological, geological, and technological) are discussed in this review. This chapter also provides a perspective on the emerging research undertaken in various aspects of engineering, optimization, and the applications of this technology. Undertaking the global carbon capture, utilization, and storage development, the paper further fosters upon the risk analysis of its deployment, roles in carbon reduction, flexibility enhancement, and negative emission targets. Furthermore, the discussion directs toward the influences of other low-carbon technologies on the operation of carbon capture to provide more insight on the low-carbon transformation of the energy system. Lastly, this review examines the potential benefits of renewable energy sources, including energy security, and climate change mitigation to lessen its negative effects on the environment and human health. Keywords:  CO2 sequestration, CCUS, renewable energy, net zero emission, CO2 enhanced oil recovery

3.1 Introduction When it comes to climate change information, the industries dependent on fossil fuels have not had a really great reputation and have received criticism from the public. Fossil fuels contribute tremendously to global warming, and major business participants, most noteworthy of which is ExxonMobil, deliberately worked toward hiding and denying the fact of climate change. Aside from concealment and denial, the fossil fuel industry sought to disregard climate scientists in the public’s view. With the growing knowledge of the public regarding the anthropogenic climate change rising, and the increasing challenge of dismissing global warming considering the effects due to climate change and the related damages, stakeholders partaking in the fossil fuel business, other stakeholders, and even the general public have steadily started increasing their demands for change from fossil fuel companies. These expectations range from a complete phaseout of the fossil fuel-dependent industry to a transition to cleaner energy sources. The industry is responding to these demands in a variety of, at times contradictory, ways. Carbon dioxide sequestration and renewables are contrastingly different, yet go hand in hand in aiding to effectively reduce/omit CO2 from the atmosphere [1].

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54  Clean and Renewable Energy Production

An effective solution that can simultaneously minimize CO2-induced emissions and utilize the CO2 for improving sustainability in the coming decades is needed. A few objectives have been established to attain this goal. i.

Identify the major cause or point source of CO2 emissions and assess their impact on the biodiversity; ii. Identify pollution-reduction technologies, such as carbon capture and sequestration (CCS), and identify the major challenge of the CCS technology, such as storage and implementation; and iii. Innovate an idea for using CO2 in feedstock synthesis for the production of biofuel. Carbon capture and sequestration or storage refers to the extraction of CO2 directly from industrial or utility plants and its long-term storage in a stable medium. It is one of the most essential technologies for reducing CO2 emissions [2]. The argument for CCS is to enable biofuel production while lowering CO2 release into the environment, hence mitigating worldwide climate change [3]. CO2 collection and storage is one potentially scalable technology for reducing greenhouse gas (GHG) emissions (CCS). By 2050, CCS will have the potential to contribute approximately 19% of the needed reducing emissions. CCS includes capturing and separating the CO2 from industrial exhaust emissions and then moving it to safe geological reservoirs. Capture techniques include post-combustion capture, pre-combustion capture, oxy-fuel combustion, and chemical looping combustion. The prominent formations of interest, such as exhausted oil and gas reservoirs, inaccessible reserves of coal, and saline aquifers, are among the storage choices. In contrast to other low-carbon choices, CCS may be an alternative fit to the existing power stations run by fossil fuels, lowering the emissions of CO2 from flue gas by up to 90%. As a result, CCS can play a major role in CO2 management, assisting the rapid transformation to a worldwide minimal carbon energy system [2]. In spite of its potential to reduce the consequences of climate change, the CCS method is projected to add to the additional expenses of CO2 capture, transportation, and sequestration or injection. The use of CCS will raise the electricity costs owing to tremendous losses of power (due to CO2 capture and compression), as well as the necessary capital investments. Due to these economic challenges, 26 (9%) of the total 275 projects (the majority of which are concentrated in the electricity domain) have been scrapped or further delayed.

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Technologies for Sustainable Energy Applications  55

Because CCS is expensive, economic inducement and carbon taxation are required for encouraging its disposition, particularly in the power industry. Instead of viewing the captured CO2 as having a negative financial value, it can be utilized for a variety of positive-value purposes. CO2 capture and utilization (CCU) is the name given to this method. Such implementations may allow for cost savings in the installation of the CCS framework. CCU, thus, can be used in conjunction with the CCS method to minimize the cost of summed up CO2 capture, transport, sequestration, and storage (CCUS) systems. This unified CO2 management system allows for the generation of fossil fuel-based electricity, the curtailment of CO2 emissions, and the generation of revenue all at the same time [3]. Renewable energy is derived from a variety of resources in nature, all of which have the potential to self-renew themselves, such as sunlight, flowing water, wind, the internal heat of Earth, and biomass such as energy crops, industrial and agricultural waste, and municipal trash. These natural resources have the capacity to produce power for economic precincts, transport fuels, and heating for buildings and commercial activity [4]. Renewable energy resources produce negligible pollution, which ultimately minimizes or nullifies impacts such as urban smog, acid rain, and other health ailments. They therefore need not necessitate environmental cleanup or waste disposal expenditure. The recent environmental concern is global climate change due to excess CO2 and other pollutants in the atmosphere [2, 4].

3.2 Carbon Dioxide Sequestration Human anthropogenic activities have been on the rise in the recent decade, which has contributed to an overburdening effect on the planet. The emission of CO2 is on a rapid rate of increase. Owing to these changes, the GHG concentrations in the atmosphere are at alarmingly high levels, and the calamities have become severe, if not worse [5]. Civilization has tremendously underestimated the exhaustive use of fossil fuels in an unchecked manner; thus, we are now faced with the primary goal to tackle the CO2 emission rates and address the rising climate change concerns [2]. CCS is a concept developed and modeled to curb the CO2 addition in the atmosphere. The process begins by capturing the CO2 at a point source of emission, and further separation can be strategically achieved using numerous methods such as cryogenic distillation, adsorption, physical and chemical absorption, hydrate-based separation, and membrane-based separation [29].

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56  Clean and Renewable Energy Production

The CCS methodology is based on the consideration of CO2 being a waste and is merely sequestered with no intention of further exploitation. However, there has been technological advancement with regard to utilizing CO2 and not just merely storing it useless. The concept of CCU has been recently revolutionized to help curb CO2 emissions into the atmosphere. Undoubtedly, CCS and CCU are two competing and appealing alternatives for reducing CO2 emissions. Both of these concepts, however, have drawbacks and difficulties of their own. The captured CO2 is either used to produce value-added products such as methanol and dimethyl ether (DME) (the CCU option) or treated for sequestration purposes (CCS) [6, 28, 29].

3.2.1 Biological Carbon Sequestration With the furtherance of society and the increased demand for fossil fuelbased energy resources, the goal to reduce CO2 into practical chemical fuels is still a distant vision, but is not unattainable [7]. Figure 3.1 gives a flowchart representation of the biological and nonbiological technology pathways for the reduction of carbon dioxide. The degradation of organic contaminants and the conversion of CO2 into end products are accomplished using complex biological and nonbiological treatment methods, such as photochemical and electrochemical methods [7, 30]. For instance, microbial electrochemical technology (MET), such as microbial electrosynthesis (MES), microbial electrolytic capture (MECC), microbial carbon-capture cell (MCC), and plant microbial fuel cell (P-MFC), is a promising technology utilized in capturing CO2 with simultaneous treatment of contaminated water and the recovery of value-added products. In MES, CO2 is employed as a substrate, which is then further reduced in the presence of biocatalysts to create multi-carbon organic molecules [7, 31]. However, P-MFC provides efficient wastewater

CO2

Biological process Light

Photosynthetic

Electrical energy/ chemicals

Non-Biological process

Heat

Heat

Electrical Hydrogen energy/ heat

Low energy Electricity products

Non-Photosynthetic

Figure 3.1  Non-biological and biological CO2 reduction technologies [7].

Light

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Technologies for Sustainable Energy Applications  57

treatment by using atmospheric CO2 during photosynthesis and consuming phosphate, nitrates, and other pollutants miscible in wastewater as substrates for plant growth. The CO2 can be reduced by the microalgae– bacterial consortium, which can also be exploited as a source of carbon for algal and bacterial growth. Furthermore, according to various studies, microalgae fix CO2 at a rate that is roughly 10–50 times higher than that of terrestrial plants. Biological treatment based on algae could therefore be a solution for reducing the potential effects of global warming [7]. A novel technique called microbial carbon fuel cells (MCFC) treats wastewater while using photosynthetic bacteria to capture carbon and produce electrical energy. In MCC, photosynthetic microorganisms in the cathodic compartment can use the CO2 generated during the oxidative breakdown of an organic chemical by anaerobic electrogenic microbes in the anodic compartments to generate power, sequester CO2, and create biomass or other products [8]. – – + 2H2O CH3COO CH3COO + 2H2O

2CO2 + 7H + 8e+ + 8e 2CO + +7H 2

(3.1)

In the cathodic compartments of MCCs, two chemical reactions occur, categorized into light-dependent and light-independent, as shown by Equations 3.2–3.4, respectively. Light-dependent reaction + nH2O O nCOnCO +2nH 2 2 + + 8e nO2 +nO8H 2 + 8H++8e

(CH + nO+ O) (CH 2O)n 2 2

n

nO2

4H2OO 4H 2

(3.2) (3.3)

Light-independent reaction 2O2 C2HC42OH24O+2 +2O 2

2CO2 + 2H O O + 22H 2CO 2 2

(3.4)

Kumar and Jujjavarappu [69] reviewed the various CO2 sequestration methods using microbial carbon fuel cells (MCFC). The microbial sequestration of CO2 exploiting MCCs, CO2 sequestration utilizing P-MFCs, and MES cells are the prominent applications [8]. Future entry into the industrial sector may depend on bioelectrochemical systems (BES) such as the capacity of MCCs, P-MFCs, and MES in absorbing and converting CO2 gas and biomass in wastewater from a variety of sources into a variety of valuable products. Additionally, it is seen as another practical solution for tackling the growing problem of climate change and the rising carbon concentrations. Nevertheless, these BESbased systems currently need viable field applications and demonstrations.

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58  Clean and Renewable Energy Production

The operational aspects impacting the effectiveness of these frameworks must be improvised prior to their broad and effective implementation [8, 32]. The improvement of long-term energy generation, wastewater treatment, and CO2 sequestration, along with the creation of value-added products in BES such as MCCs, P-MFCs, and MES for a varied number of applications still depends on a number of variables: pH, CO2 concentration (carbon source), and the electrode material including temperature. Figure CO2

e–

e–

CO2

CO2

–

–

e CO2

e

e– +

H

e– CO2 H+ Wastewater

H+ +

H

Organic waste

H+

Electro-genic microbes

CO2

PROTON EXCHANGE MEMBRANE

Treated effluent

ANODE COMPARTMENT

+

H

O2

H+ H+

O2 Photosynthetic microbes

e–

H+

H2O

CATHODE COMPARTMENT

Figure 3.2  Configuration of microbial carbon fuel cells (MCFC) [8].

CO2

R

e–

O2

e–

Air inlet e–

Treated effluent

Rhizodeposits + Organic waste +

H

Electro-genic bacteria e– Wastewater

+

H

+

H e–

ANODE COMPARTMENT

H+

PROTON EXCHANGE MEMBRANE

e–

O2 +

H

H+

e– H+ H2O

H+

CATHODE COMPARTMENT

Figure 3.3  Configuration of plant-based microbial fuel cells (P-MFCs) [8].

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Technologies for Sustainable Energy Applications  59

3.2 depicts the configuration of a microbial carbon fuel cell (MCFC) and the direction of flow of ions across the circuit. Figure 3.3 depicts the configuration of a plant-based microbial fuel cells (PMFC) and the direction of flow of ions across the circuit. Another key issue with such systems is their low energy production, which could be solved through strategically piling several small-scale configurations [8, 33]. In addition to these, the photosynthesis rate of photosynthetic organisms and the formation of biofilm by electrogenic microorganisms play a significant part in the development of an efficient system for storing CO2, the production of electricity, and the treatment of wastewater in MCCs and P-MFCs [8].

3.2.2 Geological Carbon Sequestration The CCS technique is an emerging and prospective option to store CO2 in reservoirs of great depths, which may be under the Earth’s surface or located in deep oceanic regions [9]. Shukla et al. [9] reviewed the various options available and the process for sequestration. 1. The CO2 is captured from the point source of high-intensity emissions. These are mostly industries and power plants. After capture, the CO2 separation process takes place. 2. Next, the CO2 that has been captured is transported to the site of injection. Beforehand, proper treatment processes are ensured. These include pressurization, liquefaction, or the formation of hydrate. 3. The final stage involves injecting the CO2 into the underground reservoirs or geological formations for its storage [9]. The geo-sequestration systems that have recently piqued the interest of researchers are as follows: CO2 sequestration in saline aquifers, sequestration in dead or depleted oil and gas reservoirs, and sequestration in coal seams [53].

3.2.3 Technological Carbon Sequestration There are various technological methods for capturing atmospheric CO2 and sequestrating the same in one of the geological pools. The selection of one or a mix of methods is critical for enhancing the energy policies for future economic maturation and enhancement at the regional and global levels. a. Abiotic sequestration: Abiotic sequestration depends on the physical and chemical interactions and the engineering

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60  Clean and Renewable Energy Production

solutions, which do not include live creatures (e.g., plants and microbes). Because abiotic sequestration has a bigger sink capacity compared to biotic sequestration, the abiotic process of carbon sequestration into oceanic and geologic structures has garnered a lot of traction. Rapid progress has been witnessed in terms of developing and testing the CO2 capture, transport, sequestration, and injection technologies [10]. b. Biotic sequestration: Biotic sequestration is the controlled separation of CO2 from the atmosphere by higher taxa of flora and microorganisms. It is different from the options that reduce or offset emissions. Another strategy utilized in regulating the terrestrial carbon pool is to improvise the resource efficiency (e.g., water and energy) [10].

3.2.4 Hydrate-Based CO2 Sequestration Technology Gas hydrates or methane clathrates are found predominantly in permafrost regions and in marine sediments. They have tremendous gas storage capacity and methane reserve potential [11]. Gas hydrates or methane clathrates are crystalline compounds that are non-stoichiometric in nature and have a cage-like structure. In recent times, these have received tremendous interest [49]. Gas hydrates are characterized by higher-pressure and lower-temperature conditions, which are characteristic of the permafrost regions of the world. Herein, guest molecules such as act as CH4 molecules and CO2 molecules are resided in the rigid cage lattice surrounded by the water (host) molecules, within which the guest molecules are sequestered. The structure I (sI) hydrate is the most prevalent configuration for CO2 and CH4 molecules [11]. Based on the distinctive features of methane hydrates, hydrate-based technological applications have demonstrated considerable promise and are currently the center of interest [11, 34]. Hydrate-based CO2 sequestration techniques have received tremendous attention recently owing to their adaptability for a variety of geological and marine environments [52]. Under low-temperature and highpressure conditions that are below 10°C and above 3  MPa, respectively, CO2 hydrates typically develop. One cubic meter of CO2 hydrate is capable of releasing 175 m3 of CO2 gas at standard pressure and temperature, which helps with CO2 sequestration. CO2 hydrates can form quickly in the presence of plenty of water, the right pressure, and the right temperature [50]. Additionally, the kinetics dealing with the quick formation of hydrates

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Technologies for Sustainable Energy Applications  61

Arctic Ocean

Arctic Ocean

Atlantic Ocean

Pacific Ocean

Pacific Ocean

Indian Ocean

Antarctic Ocean Recovered Gas Hydrate Inferred Gas Hydrate

Figure 3.4  Locations of the world’s methane hydrates [12].

makes it unlikely that cracks will develop, accomplishing some degree of self-containment. Furthermore, numerous investigations have demonstrated that it is both kinetically and thermodynamically viable to replace CH4 hydrates with CO2. The stability of the CH4 hydrate reservoirs can be maintained, and the extraction procedure is made safer by the ability of the replacement reaction to proceed spontaneously. Although this innovative method of using CH4 hydrate resources is exceptional, its low efficiency prevents it from being widely used. A good alternative would be to directly inject CO2 into marine sediments to create CO2 hydrates for sequestration, taking into account the size of the oceans and the ideal environmental conditions [35]. Depleted oil and gas reserves or even depleted CH4 hydrate reserves following future commercial extraction, depending on existing infrastructure, would be viable areas for future CO2 sequestration. In summary, hydrate-based CO2 sequestration is a green technique that can store CO2 in sediments found in the earth and the ocean. However, several earlier assessments either did not go into great detail about sequestration processes and sites or they mostly examined just one sequestration technique [36]. However, because CO2 sequestration is a rapidly expanding subject, it is essential to analyze and debate the current advancements [51]. In light of this, this paper conducts a thorough literature analysis to comprehend the fundamental concepts of hydrate-based CO2 sequestration technology and discusses all possible options. Additionally, it depicts the current frontier issues and the development trends [11, 37]. Figure 3.4  denotes

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62  Clean and Renewable Energy Production

the locations of the world’s methane hydrate reserves, marking the major regions of concentration with red and yellow dot.

3.2.5 Carbon Sinks and Types 3.2.5.1 Estuarine Ecology as Sediment Carbon The incredibly distinctive semi-closed coastal areas where freshwater from rivers and saltwater from the sea mingle, forming an interface between terrestrial and marine species, are classified as estuaries. The finer soil particles (clay) are carried and deposited by the action of rivers. Depositional activity takes place at the mouth of rivers, which is further exaggerated through the intermixing of the fluvial water, which is predominantly rich in sediments, with the saline marine water [64]. The phyllosilicate sheetlike particles are negatively charged and repulse each other in freshwater. Neutral salts of Ca2+, Mg2+, and Na+ present in saltwater lead to the neutralization of charge, rapid coagulation, and the flocculation of clay particles [54]. Apart from clay deposition, estuaries also receive significant amounts of terrigenous organic carbon. The majority of the organic carbon (organic C) that is preserved in coastal sediments is terrigenous and is deposited at estuaries. According to estimates, the variation in flux is approximated to be between 460 and 800 Tg C year (Tg = teragram, 1 Tg = 1,012 g) in several different estuaries. Due to its extremely high primary production, the estuarine system is also regarded as among the most prolific natural ecosystems. According to estimates, the net annual production of estuarine ecosystems might reach 3,000 Tg. In estuary wetlands, buried carbon takes a long time to decompose due to regular submersion and to nitrogen-poor sediments [65]. However, owing to the varied sedimentation rates, uneven biogeography (temperature and botanical community organization), and human activities, the composition and balance of the C sediment vary greatly in estuaries (aquaculture, agriculture, human-induced erosion, urban settlement, and construction of dams and reservoirs). Seawater constantly deposits sulfate, and it is then reduced (by sulfate-reducing bacteria). Activities in the estuarine soils of wetlands and sediments also prevent the loss of carbon through the creation of methane, a GHG [13].

3.2.5.2 Mangroves and Mudflat Soils as Carbon Sink Mangroves cover a sizable portion of the world’s coastlines. Coastal mangroves can grow along the shorelines of the ocean and in intertidal estuaries (estuarine mangrove and oceanic mangrove). Seagrass beds are considered as another global potential carbon sink alongside salt marshes.

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Technologies for Sustainable Energy Applications  63

This is due to their enormous potential for biomass production and periodic accumulation of carbon in the sediments and soils. Another term for this is “blue C.” The main principle through which mangroves preserve water in their roots and bodies is by reducing the transpiration rates [66]. To compensate for this, the mangroves have adapted themselves to have stomata that are buried, and stomatal apertures only appear on the abaxial leaf surface. This does not alter the uptake of CO2, but it does limit water loss and maintain a plant’s body temperature, which is conducive to photosynthesis. Mangroves also have tiny leaves, which in sunlight maintain almost vertical orientations. Reduced mutual shadowing and improved light absorption result from this [55]. These elements lead to a low requirement for evaporative cooling, but a considerable rate of photosynthesis. These morphological adaptations are the main causes of the high uptake of CO2 and the healthy carbon balance of mangroves. Given that the mangrove ecosystem stores a majority of its carbon in soils, the significance of soil in carbon sequestration by mangroves is crucial. A significant amount of the 4.19  Pg  C (Pg  =  pentagram, 1  Pg  =  1,015  g) that the mangrove ecology has stored as of 2018 was found in the soils of these ecosystems. Over 70% of the carbon in the Micronesian mangrove ecosystem was discovered to be stored in the soil. The soil continues to accumulate carbon, whereas the carbon sequestered into mangrove biomass (above and below the ground) achieves a flat end over time. In general, the majority of mangrove C in the soil is autochthonous, and factors including soil moisture, the proportion of smaller soil particles, etc., largely determine the concentration of soil C. Additionally, the mangrove soil C stocks are influenced by the type of coastal ecology (such as riverine deltas, estuaries, and sea margins) [63]. The capacity of mangroves to store carbon varies according to species and geographical location. The equatorial region showed the highest C-storing capacity. The mangroves in the Indo-Pacific regions are among the world’s most carbon-rich forests, and their highest concentrations of carbon are found in deep soils (>30 cm). Because of its intricate root system, saturated anaerobic soil, and rapid sedimentation rate, mangrove soil C has a very long residence time. Microbial activities in coastal mangrove soils are impacted by salinity as well. The longer residence times of carbon in coastal mangrove soils are impacted by lower C mineralization associated with the low enzyme activity under conditions of high salinity. In saline anoxic mangrove environments, the deposited organic matter only partially decomposes, gradually increasing the soil C stock [56]. The

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64  Clean and Renewable Energy Production

gradient of coastal salinity affects mangrove soil’s ability to store carbon. Salinity was observed to negatively correlate with the biomass of mangrove stands. Interior mangroves have been shown to have more litter fall and more soil C buildup than peripheral mangrove ecology. As a result, under mangrove ecology, the proportion of the soil to the carbon pool of the biosystem grows from the seaward to the landward side [13].

3.2.5.3 Tidal Marsh Soils as Carbon Sink From polar to subtropical climate zones, salt marshes are notable intertidal estuarine habitats of protected coastlines. Herbaceous plants predominate in marshes, which have a high rate of production and belowground biomass. There are a variety of morphological and physiological adaptation mechanisms that contribute to the marsh vegetation’s high biomass. One such adaptation is the presence of aerenchyma, which is necessary for photosynthesis, in many of these wetland plants. Both Typha latifolia, a perennial herbaceous plant, and Phragmites australis were found to use aerenchyma CO2 (wetland grass) [66]. The marsh soil of tidal terrains sequesters more carbon than any other terrestrial forest systems by a wide margin. Due to the extreme variability of their climatic conditions, the carbon stock differs greatly among tidal marsh soils. Given the large amounts of carbon they absorb from sediments, the daily tidal cycles also have an impact on the carbon dynamics of tidal marshlands. Regular tidal sediment loading traps organic materials, leading to substantial carbon accumulation in intertidal marsh low-lying terrains [57]. Because the coastal geomorphology and plant community patterns affect the deposition of allochthonous carbon from tidal and fluvial inputs, they also affect the pace at which carbon accumulates in marsh soils. Fluvial marshes reportedly store more carbon than seaward marshes. In wetlands, where majority of the marsh soils are either Histosol or Entisol, regular inundation by saltwater restricts the microbial activity in the soil, resulting in the inefficient oxidation of carbon. As previously indicated, these bacteria have the potential to further limit the soil C mineralization and, more specifically, to reduce methane production. High biomass input and a slow carbon cycle result in huge organic C stocks in tidal marsh soils [58]. The fact that plant invasion has caused many coastal marshes’ carbon offset potential to become unstable is a cause for concern. Other issues that are causing a significant loss of marsh soil C include the ongoing anthropogenic encroachment, the conversion of tidal marshes into

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Technologies for Sustainable Energy Applications  65

croplands, for aquaculture, and communities. This topic could be covered by any international agreement that seeks to protect coastal wetlands from anthropogenic disturbances, given its effect on the coastal and global C budget [13].

3.2.5.4 Soils of Coastal Agroecosystem as Carbon Sink Over the past few decades, the world’s soil health has significantly declined due to the rapid development of croplands and poor management practices. Natural land covers have been transformed into croplands, drastically altering the equilibrium of soil C, which ultimately caused cultivated soils to become more of a source of carbon than a sink. Affected by ongoing management methods, agricultural soils in coastal ecological systems also exhibit different dynamics from coastal mangroves, marshes, or other soils. There are not many scientists studying how well these soils can sequester carbon. However, because other coastal ecosystems are known sinks of soil C, evaluation of the soil C stock in coastal farmed areas is also crucial. For an ecosystem to be sustainable, there needs to be a significant capacity for soil C sequestration [59]. In coastal agroecosystems, it is usual practice to cultivate salt-tolerant crops and varieties. Various nations practice shrimp–rice farming and shrimp culture in mangrove swamps. All of these cultivation techniques are, however, widely dispersed. They may be situated inland, sheltered by dikes, with much less salinized soil, or close to the shore, severely damaged by seasonal saltwater submergence. Regular waterlogging, saltwater seepage into the groundwater table and the subsequent capillary rise, restricted drainage, etc., have significant negative impacts on the soil C chemistry in croplands close to coastlines [67]. Similar to the soils of other coastal environments, the balance between soil C and microbial activity is impacted by salinity in coastal croplands. The variations in soil metric potential brought on by salinity limit the microbial activity and slow down the soil respiration. In the end, it guarantees that soil C has a longer residence period [60]. Additionally, soil C gains an aromatic and humic quality from salinity. Low crop biomass and high salinity in coastal agroecosystems reduce the amount of carbon (particularly labile carbon) that returns to the soil. For soil bacteria, this labile C serves as their primary source of energy due to its rapid turnover rate. Limited microbial activity and low carbon mineralization in saline coastal cultivation soils may also be caused by a cut in carbon (labile C). The existence of Ca2+ and Mg2+ causes a large amount of formulation of aggregates and a higher level of C occlusion in salty coastal farmland soils [61]. Now, carbon is protected from microbial oxidation by soil aggregates,

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66  Clean and Renewable Energy Production

especially microaggregates. For soil microorganisms, physical barriers are created by the narrow pore sizes of microaggregates and the microaggregates within macroaggregates. In saline water-intruded soils, the presence of a water layer in the pores further creates an anaerobic environment within the pore, rendering the environmental conditions unfavorable for the quick microbial oxidation of carbon. Thus, selecting a salt-tolerant crop or variety for a coastal zone is wise crop planning. More research needs to be done to improve agricultural production and prevent the salt damage to crops at vital periods, whether through soil moisture retention or any other means. To prevent the encroachment of croplands into coastal natural ecologies, rigorous observation is necessary [13].

3.2.5.5 Sediments of Marine Coastal Ecologies as Carbon Sink Seagrass, a marine coastal plant that is itself referred to as a carbon sink, beds down in coastal estuarine environments and the shallow continental shelves. Shallow water flowering plants are called seagrasses [68]. They produce a large amount of biomass by capturing the carbon that is soluble in saltwater (mostly dissolved CO2 and a minor amount of carbonate). They can utilize CO2 via the C3 or C4 pathway depending on the species. The above- and belowground portions of the vegetative structure of seagrasses may be separated, and each of them shares about an equal quantity of biomass. Seagrasses develop large amounts of carbon stock in their rapidly expanding leaves, massive root networks, and rhizomes [13]. Figure 3.5 depicts the global distribution of seagrasses, tidal marshes, and mangroves.

Seagrass Salt Marsh 0

1,250 2,500 Kilometers

5,000

Figure 3.5  Global distribution of seagrasses, tidal marshes, and mangroves [13].

Mangoves

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Technologies for Sustainable Energy Applications  67

Only the top 1  m of marine sediments contain 3,117  Pg (3,006– 3,209 Pg) of carbon, placing coastal sediment C dynamics in a key place in the global C budget. The continental shelves receive the greatest amount of this C-loaded material. The constant deposition of organic and inorganic inputs accounts for the majority of the C stock. Reportedly, there is a distinct boundary between terrestrial and marine C deposition in the top continental shelf sediments of the Amazon Delta. Coastal C biogeochemistry and the C budget of both marine and terrestrial coastal ecologies are controlled by continental shelf carbon dynamics, regardless of the sources [62]. Figure 3.6 denotes the distribution of carbon in coastal mangroves and mudflat soils. Figure 3.7 denotes the global distribution of carbon stock in marine sediments with concentrations given in Mg C km2. Mudflat

Fringe mangrove

Interior mangrove

High tide Mean tide

• Soil bulk density • Surface accretion • Allochthonous source

• C content • N content • C/N ratio • C density

• C burial • C stocks • Autochthonous source

Hydroperiod and geomorphology gradient

Figure 3.6  Distribution of carbon in coastal mangroves and mudflat soils [18].

Mg C km2 125,000 25,000 10,000 8,000 6,000 4,000 2,000

Figure 3.7  Global distribution of carbon stock in marine sediments [13].

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68  Clean and Renewable Energy Production

3.2.6 CO2 Sequestration Utilization in Enhanced Oil Recovery The following possibilities have been mentioned in several publications that discuss the various CO2 storage strategies and options: oil and gas reserves, coal beds, the ocean, and forests are all deep-saline formations. There are several underground natural CO2 reserves located all over the world, some of which date back hundreds to thousands of years [14, 39]. These reservoirs resemble natural gas reservoirs in many ways. The fact that CO2 occurs naturally is evidence that, in the right conditions, it may be held in particular types of structures over the course of the geological epoch. Furthermore, a lot of natural gas reservoirs combine large amounts of CO2 with other hydrocarbon gases, demonstrating the integrity of containment for both these and oil reservoirs. The main drawbacks of other storage methods include less permanent storage and unrealistic expenditures. Examples of these methods include reforestation and oceans [14]. One method of reducing GHG emissions into the environment is the disposal of CO2 in oil reservoirs through enhanced oil recovery (EOR) procedures. Figure 3.8 gives a flowchart representation of the pathway of energy consumption in the CO2 sequestration/enhanced oil recovery (EOR) process. Additionally, this choice permits a more sustainable

Energy Consumer in Sequestration/EOR process compressing requirement factor Electricity Consumed in EOR process

cooling requirement factor

Energy consumption during EOR

CO2 consumption per oil bbl reservoir switch

producing oil

transportation requirement factor

Heat Generated

drying requirement factor

reservoir requirement factor

Energy consumption for drying

CO2 consumption per oil bbl

Figure 3.8  Energy consumed in the CO2 sequestration/enhanced oil recovery (EOR) process [14].

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Technologies for Sustainable Energy Applications  69

method of using fossil fuels as energy sources. Given the high price of oil right now, this is a very attractive option. Due to the low cost of the technology or even the money generated by the extra oil produced, it appears that the oil reservoirs that have been subjected to EOR operations are the best choice in these conditions [14].

3.3 Carbon Capture, Utilization, and Storage The transforming pace toward clean energy and accelerated decarbonization targets must concentrate on the current industrial system in accordance to the Paris Agreement of 2015, which was ratified by 196 nations. Particularly, utilizing the currently available methods, the industrial domain is regarded as the most expensive and complex for decarbonization. In other words, the reliance on fossil fuels like oil, coal, and natural gas as feedstock makes it impossible for the current heavy industries, which create carbon-intensive end products like steel, cement, and chemicals, to reduce CO2 emissions. As a result, increasing focus has recently been placed on the use of CCUS technology. The two major technologies utilized for managing CO2 emissions are: 1) carbon capture and storage (CCS), which involves capturing the CO2 by physical, chemical, or membrane separation and storing it underground, and 2) carbon capture and utilization (CCU) technology, in which the CO2 that was captured is processed into other substances through chemical reactions with hydrogen and other substances with the aim of achieving net zero CO2 emissions [15]. The CCU method is regarded as a carbon-neutral method since, through chemical interactions with H2, the captured CO2 from the industrial segment can be transformed into carbon-neutral fuels and chemicals. This is primarily due to the industrial sector’s manufacturing operations, which include the production of chemical products and iron and steel, all of which are known to release significant volumes of CO2. Notably, it is difficult to electrify this sector. Only a handful known instances of CCU or CCU-EOR have been quantitatively assessed in an energy system model due to the fact that the CCU methodology is still in its infancy [41]. It is assumed that the CO2 emissions from the entire power systems, including the industrial segment, as well as the overall system cost, should be taken into account when contemplating the carbon neutrality of the industrial sector. For instance, not only the production of naphtha and gasoline at refineries in the industrial sector will have an impact on the future impact of zero-emission vehicles (ZEVs), including hydrogen vehicles and electric vehicles, but also the decarbonization operations of petrochemical

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70  Clean and Renewable Energy Production

compounds. Notably, it is necessary to take into account CO2 capture from the industrial, transportation, and power sectors, as well as emissions from the production of thermal power. To create a net zero carbon society in the coming years, cross-sectoral technology assessment, sometimes referred to as sector coupling, is required [15, 41].

3.3.1 Global CCUS Development The carbon capture, utilization, and storage (CCUS) technology is the quickest way to reduce GHG emissions and achieve large-scale carbon neutrality. CCUS is used to extract CO2 from either flue gas or atmosphere and then transfer it for end use or long-term storage. It is one of the most promising decarbonization technologies. For existing industrial and the power units that would otherwise release around 600 Gt of CO2 over the span of 50 years ahead, CCUS provides a CO2 reduction alternative. Typically, these difficult-to-abate businesses include chemical, steel, and cement production. CCUS is considered as one of the most economical methods for producing low-carbon hydrogen. Therefore, significantly, without CCUS, it will be extremely difficult to achieve carbon neutrality by the middle of the 21st century. Following recent policy announcements by governments, it has been revealed that, as of today, more than 130 nations have expressed a commitment to being carbon-neutral. Over 90% of these nations, which include the United States, the European Union, Japan, and the United Kingdom, chose 2050 as their goal to become carbon neutral. Prior to 2060, China, Ukraine, and Kazakhstan have set a goal of becoming carbon neutral. In addition to establishing specific goals, 24 countries have made climate goals part of the official policy, while six countries have passed laws enacting carbon-neutral goals. These nations or areas, which account for more than 70% of the global emissions, have set or are contemplating adopting carbon-neutral targets, as per the Climate Action Tracker. The pursuit of more affordable technology solutions and the widest range of technologies with the least amount of risk has been sparked by the global consensus on carbon neutrality. As shown in Figure 3.3, “CCUS” refers to a group of technologies that include CO2 capture from highemission sources and the atmosphere, CO2 transportation from the source to the sink, and CO2 reuse or long-term storage. Pre-combustion capture, post-combustion capture, and oxy-fuel combustion are three common CO2 capture processes. Pre-combustion capture, one of these three methods, is primarily used in integrated gasification combined cycle (IGCC) power plants to produce energy since it has greater efficiency and lower economic expenses than the other two. Post-combustion capture is the most

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Technologies for Sustainable Energy Applications  71

extensively utilized technology considering its high selectivity and capture rate. Oxy-fuel combustion is the combustion of fuel in pure oxygen, directly recovering CO2 from the condensed water vapor. Pipelines, ships, and tanks are frequently used to transport CO2 from the point of capture to sinks. Currently, the cost of moving CO2 within a 1-km radius by pipeline is between US $1 and $10 per tonne, which is less expensive than moving liquid CO2 by ship. Concerning the usage of CO2, it is frequently used as a raw material or as an input to produce goods or services, including EOR, chemicals, synthetic fuels, and building materials. Around 90% of the world’s oil reservoirs may be used for CO2-EOR, which has become a widely accepted and tested technique throughout time. However, compared to geological storage, ocean carbon storage has less developed technologies, and there are worries about its possible effects on the ecosystem [16]. Figure 3.9 is the statistical representation of the development trend of the carbon capture, utilization, and storage (CCUS) literature from 2001 to 2021. There has been substantial advancement in CO2 storage, and numerous ongoing industrial projects have demonstrated its technical plausibility. The majority of these initiatives focus on the field of improved oil recovery. Therefore, relatively little is known about CO2 storage in saline

200

Number of publications

180 160 140 120 100

30

Rest Spain Australia Italy South Korea Netherlands Canada Germany UK China USA

25

17 13

80

9

60

0

15 12

10

7

40 20

20

19

3 1

1

3

3

4

5

5

Number of publications relating to CCUS & carbon neutrality

220

1

0 2000 2002 2004 2006 2008 2010 2012 2014 2016 2018 2020 2022

Figure 3.9  Development trend of the carbon capture, utilization, and storage (CCUS) literature from 2001 to 2021.

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72  Clean and Renewable Energy Production

aquifers, and the majority of knowledge is restricted to the oil and gas sector. Screening for the quantities of CO2 that are being stored and the degree of plume migration, among others, are needed for development. Additionally, it is crucial to keep an eye out for leaks, which are crucial for CO2 storage. Important CO2 leakage indicators include monitoring the flux and pressure of CO2 at the surface above the site of storage. Pressure management technology advancements and chemical sealing are crucial for stopping CO2 leaks. There are tried-and-true techniques for site characterization. Extensive research on the hydrocarbons already present in the geological system, as well as the contaminants present in the CO2 stream, is necessary to stop the CO2 from leaking. A static capacity model or another dynamic storage capacity model can be used to calculate the amount of CO2 that can be stored. The development and integration of these models with energy systems can offer profound insights into the potential effects of CO2 storage. The enormous amounts of CO2 that must be pumped (millions to trillion tonnes annually), the protracted sequestration times required for some temperature benefit, and the potential for CO2 bubbles in the subsurface are the general hazards of geological sequestration (GS). Numerous studies have documented the potential risks associated with GS, which can be broadly categorized into local and global categories [17]. Figure 3.10 denotes the status of the worldwide carbon capture, utilization, and storage (CCUS).

Figure 3.10  Status of the worldwide carbon capture, utilization, and storage (CCUS) (pink) and CO2 storage (blue) projects. Red dots denote the proposed fields for CO2 utilization for enhanced oil recovery (EOR) [17].

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Technologies for Sustainable Energy Applications  73

3.3.2 Risk Analysis of CCUS The hazards of the CCUS methodology, CO2 emission sources, and GS, as well as external factors including policy and market dynamics, are expected to change the economics and competitiveness of CCUS as compared to alternative low-carbon alternatives, altering the CCUS deployment routes to carbon neutrality. A complete risk analysis of CCUS projects is offered to further understand the unpredictability of the deployment of CCUS and its layout in a carbon-neutral setting, with a focus on pinpointing the risk factors and investigating the evaluation approaches [18]. There is very little research available that adequately describes the sources, quantification, and coping mechanisms of CCUS; hence, the various significant gaps to fill. Low-carbon investments frequently face substantial risks, particularly in developing countries; thus, economical de-risking is critical for mobilizing private financing [40]. The technical risks are inevitable and have prohibited the progressive testing and also the commercialization of CCUS, and its application for carbon neutrality may be delayed. Hence, uncertainty prediction and reliable risk in CCUS is always a top concern for key stakeholders and for future CCUS deployment. A variety of research studies regarding the quantitativeness of multidimensional technical hazards have been conducted to this purpose [18, 40]. These research works could assist the public in understanding various technical hazards that CCUS projects may encounter, as well as analyzing cost differences. We discovered that the technical hazards of the CCUS technique differ considerably by project type; for example, capturing CO2 through post-combustion from biomass in a fluidized bed combustion resulted in larger losses in production efficiency compared to plants producing power by burning coal [69].

3.4 Renewable Energy Energy, being the currency of technology, has bound the whole fabric of society. The modern era is hungry for developments and, in the quest for a better life, is aggressively boosting its pace of energy usage. Fossil fuels are now being cited as the major source of pollution and are beginning to draw criticisms from several stakeholders and government alike. As is expected, we need to explore newer and cleaner forms of energy. One such solution to our cries of energy crisis is the use of renewables as an alternative form of energy supply and technology [19]. Figure 3.11 shows the numerical values of global electricity production from various technologies in 2013.

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74  Clean and Renewable Energy Production

Fossil fuels and nuclear 77.9%

Renewable energy 22.1%

Hydro power 16.4%

wind 2.9% Bio power 1.8% Solar PV 0.7% Geothermal, CSP and ocean 0.4%

Figure 3.11  Global electricity production, 2013 [20].

3.4.1 Solar Energy The most abundantly available energy source on Earth that is not expected to be exhausted in the lifetime of humans is the sun. The energy from the sun is emitted at the rate of 3.8  ×  1023  kW, out of which approximately 1.8  ×  1014  kW is intercepted by the Earth. This energy from the sun is received on the surface of the Earth in various forms, like heat and light. However, not all of the incident energy is available to us. A considerable portion of this energy is lost through various phenomena, such as reflection, refraction, absorption, and scattering. The agents responsible for this are the dust particles present in the atmosphere and the clouds [21]. “Solar energy is the conversion of sunlight into useable forms.” The sun moving at a distance of about 93,000,000  mi [42] forms the basis of all other secondary energy sources and is also the largest source of possible conversions on Earth. The balance between the incoming solar radiation and the outgoing radiation maintains the hospitable climate conditions on Earth for human habitation, making it possible for the diverse Plantae to thrive and sustain. It has been estimated that out of the 340 W/m2 of solar radiation that reaches the Earth, only 241  W/m2 reaches the Earth after penetrating the atmospheric layers [43]. The Earth’s surface, being a good conductor, absorbs almost 71% of the electromagnetic radiation from the sun, simply termed as “sunlight.” These atmospheric interferences play a role in reducing the amount of “total” sunlight that reaches the surface. “Atmospheric interferences” may broadly include the subsurface and atmophile elements like air molecules, water vapor, clouds, dust, pollutants, or emissions from natural cataclysms like forest fires, volcanoes that aid in absorbing, emitting, or scattering the sunlight [44].

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Technologies for Sustainable Energy Applications  75

Solar cells are designed to convert the incident sunlight into electricity. These cells are made up of semiconductor materials [46]. The basic principle behind the working of a solar cell is that the sunlight, which is incident on these cells, is absorbed by the material, and if the frequency of the sunlight is greater than the threshold frequency, it knocks out the lose electrons from their atoms. These lose electrons are now free to flow through the material, thus generating electricity. The power output from a solar cell can be calculated as:

P = I × V The performance of a solar cell can be determined by measuring its efficiency of turning sunlight into electricity. The photovoltaic (PV) industry aims to better the solar modules, arrays, and cell efficiency to extract more overall power from a single cell and also consequently bring down the cost input for the project at the same time. PV converts sunlight direct to electricity, without the need of any external agency to aid in the process. The entire system that helps in the conversion of light to electricity has several components, including cells, mechanical and electrical circuit components, inverters, the mountings, and the means of regulating and modifying the electrical output from the modules. Silicon is the dominant material that has been used in solar cells for effective PV conversions [45]. Figure 3.12 is the map of global horizontal irradiation (GHI).

Long-term average of: Annual sum < 700 Daily sum

< 2.0

900 1100 1300 1500 1700 1900 2100 2300 2500 2700 > 2.5

3.0

3.5

4.0

4.5

5.0

5.5

Figure 3.12  Maps of global horizontal irradiation (GHI) [22].

6.0

6.5

7.0

7.5 >

kWh/m2

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76  Clean and Renewable Energy Production

There has been remarkable technological development that has taken place in the current PV aspect, which can be broadly grouped under the categories of first-generation PV, second-generation PV, and third-generation PV [47].

3.4.2 Hydro Energy Solar energy is the primary source of energy from which several other forms of energy may be derived. One such indirect form is hydro energy. Due to various parameters and operational behavior, hydro energy is considered to be the cleanest and the most environment-friendly conventional energy resource. Water falling from an elevation that is at a high potential to a region of low elevation and low potential is harnessed to produce electricity. The basic components constituting every hydro energy generation plant include a dam, penstock, and turbines [23].

3.4.3 Geothermal Energy The Earth’s interior is a potential source of energy as well. The interior of the Earth is characterized by very high temperatures and temperature gradients. The Earth’s interior includes energy as heat, and this is what is exploited to generate electricity, which is termed as geothermal energy. Therefore, the source of this heat is tied to the interior composition of our planet and the physical processes that occur there. Despite the fact that this heat exists in massive quantities, basically endless quantities in the Earth’s crust and the deeper portions of our planet, it is unevenly distributed, rarely concentrated, and generally extremely deep to be exploited for commercial purposes [24]. Figure 3.13 gives a flowchart representation of the various types of hydropower turbine technologies. Hydropower Turbines

Impulse Turbines

Pelton

Turgo

Reaction Turbines

Crossflow

Figure 3.13  Types of hydropower turbines [23].

Francis

Propeller Pump as turbine

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Technologies for Sustainable Energy Applications  77

Although this point is typically overlooked, heat goes from the interior of the Earth to its surface, where it evaporates. The geothermal gradient, which averages 30°C/km of depth, is realized because of the temperature rise of the rocks with depth [24]. With the pressing need to minimize fossil fuel emissions, the global use of renewable energy has increased, and geothermal energy is increasingly being regarded as a key potential provider. In addition to being a renewable resource with minimal carbon GHG emissions, geothermal energy has a small land footprint. The most significant environmental influences on these plants are thought to be geological dangers. Because of the geothermal energy in protected regions, managerial and regulatory measures can mitigate the harmful effects of geothermal development [25]. In comparison to fossil fuel power plants, which may generate GHGs, geothermal energy has a minor impact on the environment. The advancement of technology and the understanding of the necessity for environmental protection have considerably decreased the effects of geothermal energy [38]. In this section, the environmental implications of geothermal energy are compared to those of alternatives. The first segment investigates the environmental benefits of geothermal energy, such as reduced gas emissions and a small land use footprint [25]. Figure 3.14 is the diagram of the geothermal steam field with its elements.

Recharge area Hot spring or steam vent Geothermal well Cold meteoric waters

Impermeable caprock

Hot fluids

Reservoir

Impermeable rocks

Flow of heat (conduction) Magmatic intrusion

Figure 3.14  Geothermal steam field with its elements: recharge area, impermeable cover, reservoir, and heat source [24].

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78  Clean and Renewable Energy Production

3.4.4 Biomass Energy Keeping pace with the energy transition and the decarbonization goal, and simultaneously advancing to meet the development goals, finding alternate carbon source reserves for bio-based fuels in gaseous, solid, and liquid forms is essential. Lignocellulosic biomass, which includes agricultural wastes, wood chippings and scraps, forestry wastes, and some energy crops, serves as an appropriate source of biofuels and bio-based products [26]. Biogas, a by-product of anaerobic digestion, is the most prevalent energy product of waste biomass. Methane, which may be purified to make it compatible with natural gas, makes up 50%–60% of biogas in most cases. Heat, light, chemicals, and power are produced by biogas. Liquid fuels utilized in the chemical and transportation industries, such as ethanol, acetone, and butanol, are produced by fermentation. To compete with gasoline on the market, lignocellulosic biomass must significantly reduce the cost of producing biofuels like ethanol and butanol. By now, the cost of manufacturing biofuels via biochemical processes is primarily driven by the manufacture of enzymes and biomass feedstock. Figure 3.15 gives a flowchart representation of the Primary and secondary energy resources via hydrothermal processing of biomass. Figure 3.16 is a schematic diagram of a hydraulic wind turbine. The conversion of biomass to energy involves heating, pressure, solvents, catalysts, and various enzymes; likewise, thermal, physical, and Biomass Processing

Liquefaction (300–400°C, 10–20 MPa)

Pyrolysis (400–600°C)

Hydrothermal Carbonization (180–250°C, 0.5–8 h)

Gasification (700–1100°C)

Combustion (1300–1400°C)

Heat and Power Bio-oil Bio-char Upgrading

Fuel and Chemicals

Syngas Catalytic Synthesis

Figure 3.15  Primary and secondary energy resources via hydrothermal processing of biomass [26].

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Technologies for Sustainable Energy Applications  79

chemical  techniques. They have both been used in biomass conversion, individually and in combination [26].

3.4.5 Wind Energy The year 2020 saw a significant increase in the amount of newly installed wind-generating capacity worldwide, with 93  GW setting a new record. This number has a total capacity of about 743  GW and is 53.9% larger than that of 2019. It is clear that the emerging energy signified by the wind energy belt would indubitably contribute to the advancement of humanity. The energy of the wind has various benefits. However, because wind energy is unpredictable and intermittent, it will unavoidably lead to issues like unstable and unreliable electric energy when used to generate power [48]. These issues not only represent a serious risk to the safe operation of wind power but will also have an impact on how quickly wind power is incorporated into the grid. Therefore, the industry experts’ top research concerns are how to address the unstable and unsustainable issues associated with wind power generation, achieve uninterrupted energy conversions and its transmission, meet the load matching requirements of the power system, handle peak and valley filling, improve power quality and reliability, thereby improving the penetration level of wind power in the power grid, and frequency and phase modulation. Traditional wind turbines, such as doubly fed wind turbines and permanent magnet synchronous generators, are also attempted to increase performance with the aid of increased controls and the upgrade of the existing structures in response to the aforementioned requirements. The space for improving the performance of the unit is constrained because of the stiff transmission style. The unit itself really exhibits the following flaws at the same time. The drawbacks of doubly fed wind turbines include their large gearboxes, high cost, Wind turbine

Variable displacement motor

Power grid

G

Fixed displacement pump

Synchronous generator

Figure 3.16  Schematic diagram of a hydraulic wind turbine [27].

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high failure rate, and challenging maintenance requirements. Permanent magnet-synchronized generators require full-power rectifier inverters due to the numerous generating stages they have [27].

3.5 Conclusion This paper significantly explored the various diverse topics pertaining to sustainable energy. Carbon dioxide sequestration and carbon capture, utilization, and storage have been discussed in conjunction with the sustainable energy solutions and the global deployment of the decarbonization mission. The renewables have been available for a few decades now. All these methods and technologies have been developed with the sole purpose of decarbonizing the planet and preventing the global greenhouse effect from worsening. Even though the goals may seem unattainable in the short term, in the longer perspective, effective planning and execution would ensure proper delivery of the aim to reduce climate change. Playing the blame game and just criticizing the fossil fuel industry would not help in any way to work toward a shared goal. Although renewables are viewed as prospective energy resources, not all of humankind’s everyday needs could be fulfilled with their help because fossil fuels are exploited not just as fuels but for several other purposes as well. Carbon capture storage and utilization has been proposed and is being worked upon to utilize the technology to its maximum potential.

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69. Kumar, T. and Jujjavarappu, S. E, A critical review on an advanced bio-­ electrochemical system for carbon dioxide sequestration and wastewater treatment, Total Environment Research Themes, Volume 5, 100023, ISSN 2772-8099, 2023, https://doi.org/10.1016/j.totert.2022.100023. (https:// www.sciencedirect.com/science/article/pii/S2772809922000235)

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Affordable and Clean Energy: Natural Gas Hydrates and Hydrogen Storage Uttamasha B. Borah1, Gaurav Pandey1,2*, Swagata Sarma1, Nadezhda Molokitina2 and Geetanjali Chauhan3 Department of Petroleum Engineering and Earth Sciences (Energy Cluster), School of Engineering, University of Petroleum and Energy Studies, Dehradun, India 2 Earth Cryosphere Institute, Tyumen Scientific Center, SB, RAS, Tyumen, Russia 3 Department of Petroleum Engineering, Indian Institute of Petroleum and Energy, Visakhapatnam, India 1

Abstract

Gas hydrates are a reliable source of energy that might be used in the future in many different ways, including those that are both safe and efficient. Crystalline solid gas hydrates are produced by a thermodynamically driven process, with gas molecules imprisoned in cages created by water molecules bound together by strong hydrogen bonds. Natural gas storage, CO2 sequestration, hydrogen storage, desalination, gas purifications, and gas separations are the major applications where industrial utilization is associated. Hydrogen energy has witnessed an exponential growth in developing and developed economies, owing to its ecological usage in hydrogen cells, batteries, and supercapacitor hybrid power systems. In order to focus on Sustainable Development Goals 7 (SDGs 7), decarbonization plays a vital role, and it is crucial to prioritize the development of hydrogen as a large-scale alternative to non-renewables. Gas hydrate technology reduces greenhouse gas concentrations by trapping gas in the hydrate lattice and eliminating it from the atmosphere, thus minimizing global warming. Strict monitoring and restrictions are needed to effectively and sustainably extract gas molecules from gas hydrates. Recovering gas hydrates from extreme conditions of pressure and temperature that aid their production requires the correct equipment and techniques. Thermal stimulation, pressure decrease, chemical injection, insulation *Corresponding author: [email protected] Surajit Mondal, Adesh Kumar, Rupendra Kumar Pachauri, Amit Kumar Mondal, Vishal Kumar Singh and Amit Kumar Sharma (eds.) Clean and Renewable Energy Production, (87–122) © 2024 Scrivener Publishing LLC

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4

depressurization, and cold production are some of the techniques applied for gas hydrate extraction. Gas hydrates are discussed in this chapter because of their significance in the energy business as a source of power generation and a huge storage capacity, as well as its numerous prospects and obstacles. The progress made in developing storage solutions for hydrogen and the various ways of hydrogen production have been highlighted in this paper using gas hydrate-based technology for clean energy applications. Further emphasis is placed on the economics of hydrogen energy and the advancement of using it as a fuel. Future directions for the widespread deployment of hydrogen energy to inspire further study will also be covered. Future applications of this technology will facilitate the switch to renewable energy sources, lowering global dependency on fossil fuels and the resulting carbon emissions. Keywords:  Gas hydrates, CO2 sequestration, carbon footprint, hydrogen hydrate, clean energy

4.1 Introduction The usage of fossil fuels has detrimental effects on the ecosystem, which hastens their depletion. There has been a recent resurgence of interest in the role that eliminating subsidies for fossil fuels can play in speeding up the transition to a decarbonized economy. Clean and affordable alternatives to traditional forms of energy generation are urgently needed to meet rising energy demands. As a matter of fact, the carbon emissions and economic growth of a country are intertwined: the former cannot expand without the latter. Breaking the paradigm that associates carbon emissions with population and economic growth is essential for this shift [1]. Clean energy sources, such as natural gas hydrates and hydrogen energy, can help us wean ourselves off fossil fuels rapidly. Energy from these sources does not harm the environment, and there are plenty of ways to put that power to use. Achieving decarbonization by 2050 will only be possible through the reduction of fossil fuel extraction and production [2]. Almost 90% of the world’s economy and around 90% of its emissions, according to COP26 (the 26th UN Climate Change Conference of the Parties), are currently covered by net zero commitments. A total of 153 countries have proposed new or revised emission targets, officially known as nationally determined contributions (NDCs), which account for around 80% of the global greenhouse gas (GHG) emissions. The United Nations predicts a reduction in GHG emissions of about 5 billion tonnes by 2030, which is equal to the United Kingdom’s emissions over the course of more than 10 years at the current rate. Countries have recognized that

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they need to speed up progress because not all are compatible with net zero by mid-century [3]. Emerging clean sources of energy, like natural gas hydrates, hold natural gas that is mostly composed of methane and ethane, two basic hydrocarbons that can be burned to provide energy. Nitrogen and sulfur compounds are far less common in natural gas hydrates than they are in coal. Therefore, unlike the combustion of crude oil and coal, which inevitably produces toxic by-products including nitrogen oxides (NOx), sulfur dioxide, volatile organic compounds, and heavy metal compounds, the combustion of natural gas produced from hydrates does not do so. Another important source of energy that is discussed in this chapter is hydrogen energy. Hydrogen energy is required in order to fully decarbonize the industry, transportation, and the larger energy sector. Hydrogen has the potential to develop into a globally traded, emission-free energy carrier. National hydrogen strategies and international studies are proliferating, and there has never been more of a global push to create a hydrogen economy [4].

4.2 Gas Hydrates Natural gas hydrate, a clathrate that resembles ice, is created when water and hydrocarbon molecules are combined. At low temperatures and high pressures, hydrate formation is notably more durable and favorable [5]. A volume of natural gas hydrate typically produces between 160 and 180 L of methane gas. As the challenges of efficiently collecting natural gas hydrate are resolved [6], it will be an immensely useful energy source. Due to its new uses in a variety of disciplines and businesses, such as the long-term storage of CO2 contained in exhaust emissions by generating gas hydrates under seas, gas hydrates are at the focus of sustainable chemistry research. The formation and the accumulation of these solid crystalline substances in crude oil and gas pipeline systems cause total flow blockage [7, 8]. The main goal of the initial study on gas hydrates was to increase flow assurance by lowering the possibility of hydrate formation in oil and gas subsea pipelines. Because of its growing significance to a wide range of industries, including energy recovery, CO2 capture and storage, gas separation, water desalination, gas storage and transportation, refrigeration, and many more, there has been an increase in the study on the subject in recent years. Due to methane’s tremendous greenhouse warming potential (GWP), it has recently drawn a lot of concern since it may escape from sediments containing hydrates and ultimately enter the atmosphere [9].

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Natural Gas Hydrates and Hydrogen Storage  89

4.2.1 Extraction Methodologies The techniques for extracting natural gas hydrates have garnered a lot of interest because they are essential to making the most of these resources. Since its discovery in the 1960s, when it was found buried beneath permafrost in an Arctic gas field, natural gas hydrates have captivated geologists. Three permafrost locations have already seen the experimental extraction of natural gas hydrates. Despite the use of depressurization methods in the Messoyakha gas field in the northwest of West Siberia in the former Soviet Union and depressurization and thermal excitation methods in the McKenzie Delta in the northwest of Canada, extraction investigations in the North Slope region of Alaska, United States, were unsuccessful because there was no layer that contained natural gas hydrates. Natural gas hydrate extraction is difficult on a global scale since there is no trustworthy technology available for this purpose. These methods are still in the infancy stages of development. There have been four main types of treatment used so far: thermal stimulation, depressurization, inhibitor injection, and gas exchange [10, 11]. Figure 4.1 is a schematic diagram of the dissociation methods for methane gas hydrates. 25

Pressure (MPa)

20

15

Methane gas hydrates + Water

Methane gas hydrates + Ice

Methane gas + Water

Inhibitor injection

10 Thermal stimulation 5

0

Depressurization

Methane gas + Ice -5

0

5

10 Temperature (˚C)

15

Figure 4.1  Dissociation methods for methane gas hydrates [12].

20

25

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4.2.1.1 Thermal Stimulation Method Any method that raises temperature to an appropriate level to encourage hydrate breakdown is referred to as a “thermal excitation approach.” The temperature of natural gas hydrate reservoirs is raised using a variety of techniques so that the gas hydrate could dissociate. To help with the recovery of heavy oil, hot fluids are injected into the hydrate layers from the Earth’s surface, such as steam, hot water, hot brine, or other hot fluids. Alternative techniques involve fire floods or drilling with string heaters. There are two methods for regulating heat conduction in the heat excitation model: 1. Heating wells by injecting hot water or steam. When heated, the hydrate dissociates into gas and water and can be accomplished with steam or hot water. According to research, a hydrate reservoir’s thickness and porosity must be at least 7.5 cm and 15%, respectively. Injecting steam or hot water at a temperature of 340–395 K is adequate for economic viability. The most researched method is hot water injection, although it loses a lot of heat and is therefore inefficient, especially in permafrost zones. The frozen layers may reduce the amount of heat that is effectively transferred to the reservoirs even when heated insulated tubes are employed. In thin hydrate reservoirs, for instance, fire flooding and steam injection suffer significant heat losses and are only thermally efficient in reservoirs above 15  m thick. Even though hot water injection loses less heat than the other two approaches, its use is limited by the pace with which water must be injected into hydrate reservoirs [13–15]. 2. Directly heating anything with electromagnetic radiation. Down-hole heating techniques have recently been used to increase the efficacy of the thermal excitation method even further. One of these is the use of electromagnetic heating down the hole. Through the use of alternating current (AC), hydrate zones throughout the length of a vertical (or horizontal) well are heated by strategically placing electrodes above and below (or within) the zones [10].

4.2.1.2 Depressurization Method Natural gas hydrate is more prone to disintegrate when the pressure is reduced, as it is during the depressurization process. Gas hydrates

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Natural Gas Hydrates and Hydrogen Storage  91

commonly break down and divide into natural gas and water when exposed to natural gas. This is due to the fact that fluid extraction from the deposit, decreased borehole pressure, or decreased pressure of the free gas below the hydrate layer have all reduced the pressure on the hydrate zone. The gas hydrate will start to dissolve and absorb heat from its surroundings if the pressure in the gas reservoir falls below the three-phase (liquid water– hydrate–methane vapor, LW–H–V) equilibrium value. The pressurereducing extraction method is an excellent choice when a natural gas hydrate deposit is near to another natural gas reservoir. Depressurization extraction often works with hydrate gas reservoirs that are highly permeable and have depths greater than 700 m. If there are heavy hydrocarbons in the gas, a bigger pressure drop is necessary. Additionally, by adjusting the pace of natural gas extraction, the reservoir pressure can be managed, which will also control the hydrate dissociation [10, 16].

4.2.1.3 Inhibitor Injection Method Chemical reagents including saltwater, methanol, ethanol, ethylene glycol, and glycerol may influence the phase equilibrium conditions of gas hydrates and, therefore, their stability temperature. By introducing inhibitors (such as methanol, ethylene glycol, and glycerol) that cause part of the natural gas hydrate to dissociate, the pressure and temperature (T–P) equilibrium point of a gas hydrate reservoir can be changed. The layer’s hydrate will then split and weaken. The dissociation rate of natural gas hydrates corresponds to the injection rate, contact area of the hydrate inhibitor, the inhibitor concentration, temperature, and pressure, as has been demonstrated experimentally. While the effect of the chemical reagent technique is slower than that of thermal excitation, less energy is needed initially. Methanol injection into the Messoyakha gas field increased the gas production by a factor of 6 at the outset of gas hydrate extraction [10, 17].

4.2.1.4 Gas Exchange Method By injecting CO2 gas into the natural gas hydrate reservoir, which has a low in-phase equilibrium pressure, hydrate may easily form. The heat produced during the hydrate production process causes natural gas hydrate to dissociate [18]. Type I hydrates encompass both CO2 and CH4 hydrates. The following describes the displacement process between CO2 and CH4 hydrates:

CO2 + CH4 · nH2O → CH4 + CO2 · nH2O

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92  Clean and Renewable Energy Production

Table 4.1  Advantages and disadvantages of gas hydrate extraction methods [19]. Method

Advantages

Disadvantages

Depressurization

Can be used in NGH reservoirs with low hydrate saturation, high porosity, and low free gas without extra energy input

Causes land subsidence and submarine landslides Hydrate reforming occurs readily during depressurization

Thermal stimulation

The rate of heat injection can be varied to control productivity

Low productivity High heat loss and high cost

Chemical injection

Productivity can be improved in a short time

Recycling is difficult, easy to cause environmental pollution High cost

Gas replacement

Good strategy for CO2 capture and sequestration

Not suitable for lowpermeability gas hydrate reservoirs Production efficiency is low

NGH, natural gas hydrate

In contrast to CH4, CO2 and H2O have a higher chemical affinity, favoring a forward reaction. Methane gas is sucked out of the air, while surplus CO2 gas is piped into the ocean and stored there as CO2 hydrate, reducing GHG concentrations and keeping the seafloor stable to avoid natural calamities like slides brought on by hydrate extraction. However, the existing approach can only extract natural gas hydrates by substituting CO2 for CH4 at very slow reaction rates [10]. Table 4.1 lists the advantages and disadvantages of gas hydrate extraction methods.

4.2.2 Geological Hazards Both tectonic processes and variations in sea level have affected the soft, unconsolidated sediments along the continental borders, resulting in many alterations to the seabed morphology. The regularity of the seafloor’s relief dictates the form, size, and length of these objects (Figure 4.2). These collapses typically occur on the continental shelf or slope zones when the force of gravity is insufficient to counteract the mechanical shear strength of the sediments. Slide slump and debris flow are two sedimentary processes that are primarily driven by gravity. A slide is the forward

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Natural Gas Hydrates and Hydrogen Storage  93

Gravity-Driven Downslope Processes in Deep Water Slope

Shelf Slide

Coherent Mass

Slump

Plastic Deformation

Incoherent Mass (Plastic)

Fluidal (Newtonian)

Slump

Planar Guide Plane

Debris Flow

Turbidity Current

Concave Up Glide Plane

Rockfall

Increase in Mass Disaggregation

(A)

Debris Flow

(B)

Mud Flow

Sediment concentration: 100% by volume

(C)

Mass-transport porocesses Mechanical behavior: Elastic and plastic

(D)

Sandy mass-transport deposits (SMTD): Sand concentration: > 20% by volume

25-100%

1-23% Viscous fluid Turbidite

Figure 4.2  (A) Simplified representation of the four most typical gravity-driven downslope processes that carry sediment into deep-marine settings [20]. (B) Percentage by volume of the sediments present in processes driven by gravity. To emphasize, turbidity currents are low-density flows characterized by a low concentration of sediment [21]. (C) It is considered that mass transport processes such as slides, depressions, and debris flows are dependent on the mechanical behavior of gravity-driven downslope processes, while turbidity currents are not [22]. (D) Sandy deposits are those that have a grain concentration value of at least 20% by volume (>0.06 mm: sand and gravel) and are classified as a type of mass transport deposit. The 20% is calculated based on the sedimentary rock type originally used in the field [23].

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94  Clean and Renewable Energy Production

motion of a huge sedimentary mass over an undisturbed natural seafloor. Slump is a distortion of the sediment body into a concave shape caused by unequal gravitational force application due to height differences between the different parts of the mass relative to the seafloor. Sediment slides on the continental slope are characterized by their wide, flat surfaces and the absence of internal deformation, both of which are unique to this type of movement driven by gravity. Due to gravity, sediment mass moves downhill along an inclined seafloor. The shear strength of sediments along the surface opposes this motion. Slope failure occurs when the gravity’s pull is greater than the sediment’s ability to resist [24]. When the forces pushing on the sediments are greater than the forces’ resistance to the sediments, subterranean and undersea landslides can occur. Increased shear stress or decreased shear strength in the sediments sustaining the slope may both cause slope collapse. These pressures originate from either the environment or from processes occurring inside the sediment matrix itself. Oversteepening of slopes, quicker sediment deposition, tectonics, and earthquakes are all possible causes of slope collapse in marine environments. Gas hydrate deposits may be discovered in the deep sea on continental slopes, which typically have gentle slopes of just a few degrees. Contrary to the concepts of fracture mechanics, which suggest that changes in earth stresses or mechanical characteristics cannot cause low-angle failures, low-angle failures do occur. Only one scenario can account for the observed low-angle failures in the geological record: 1. Strong transient tensions, such those produced by earthquakes; 2. Abrupt modifications in material characteristics, such as those brought on by the gas hydrate’s speedy breakdown; or 3. Rapid shifts in pore pressure, which may be caused by the breakdown of hydrates or the migration of gas from somewhere else. The following are other examples of the suggested mechanisms for shear failure. a. b. c. d.

Lateral supports are removed. Increased pressure from the sediment layers below Upward movement of fluid [25] Generated by friction in the subduction zone [26]

Gas hydrates can generate geological risks due to the sediment pile being unstable as a result of hydrate breakdown or potentially severe methane

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Natural Gas Hydrates and Hydrogen Storage  95

leaks into the water column and atmosphere. When hydrates break down, it has to come fast enough to set off dangerous phenomena. The formation of gas hydrates is influenced by a number of variables, including temperature, pore pressure, gas chemistry, and pore water salinity. When methane and water freeze together, gas hydrates are created, which have smaller pores and slower fluid flow [27]. Hydrates prevent consolidation by filling the pore space left by sedimentation and mineral cementation. In contrast, they have the potential to bind sediment grains together. As gases and liquids mix to produce hydrates, the process continuously reduces the sediment’s permeability. By continuing to accumulate silt, the gas hydrate is buried deeper and deeper. The gas hydrate starts to collapse when temperatures fall below its stability zone after being buried for a sufficient amount of time. The storage zone of the gas hydrate under-consolidates and may become overpressured as a result of the significant gas loss, creating a weak spot [27]. Gas volume expansion causes the sediment to separate and lose its compactness, which in turn leads to the pore fluids being strongly pressured. The production of huge pore spaces also causes the sediment to fracture, which has the potential to create undersea landslides. Gas hydrate dissociation and submarine landslides are related processes (Figure 4.3). Short-area phenomena on the continental slope, such as tectonics, sea-level variations, tremors, or changes in gravity, may trigger landslides under the gas hydrate-bearing layer. Sediments lose a significant amount of their mechanical strength during decomposition, making it impossible for them to maintain the weight of the layers above them. Large amounts of gas and liquid would be released if the gas hydrate destabilized, raising the pore pressure, lowering the shear stress, and reducing the shear strain in the sediment layer due to the larger pore size. The top layer slides down the hill under the force of gravity as the sediment deteriorates and the hydrated layer thins, releasing more gas and liquid [29]. When the pressure and temperature conditions close to the surface change, gas hydrates become an issue. The gas hydrate stability zone (GHSZ) thickens with increasing water column height and thins in low-pressure regions, both of which are correlated with the differences in pressure across continental boundaries. The methane emitted during gas hydrate dissociation may partially dissolve in the saltwater above it or persist in the gaseous phase within the seawater. Any of the aforementioned factors may result in this. Mass transfer, a drawn-out process, results in the decreased density of seawater brought on by dissolved methane. A regular pattern may be seen in the estimated methane emissions that result from the dissociation of a unit volume of

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96  Clean and Renewable Energy Production

atmospheric CH4

gas plume

large block of hydrated sediment breaking off and sliding down slope

hydrated zone

original slope surface

debris f low

dissociated (gas-fluidized) gas hydrate lower boundary of hydrate at high sea stand lower boundary of hydrate at low sea stand

Figure 4.3  Champagne cork effect: illustration of what happens when a slope failure occurs above a gas hydrate and large quantities of gas can be released [28].

gas hydrate in a marine environment [30]. Higher water temperatures and the tendency of free gas to flow to the flanks cause hydrated sediments to lose strength and slide more easily. By filling pore spaces and cementing sediments, gas hydrates increase slope stability and shear strength. Depending on how they affect fluid flow, hydrates can either strengthen the sediments by binding the grains together or weaken the underlying sediment by trapping fluids and free gas. While gas hydrates thrive in coarsegrained sediments, doing so lowers the host sediments’ total permeability. The sediment is weakened from the inside by the increased porosity, pore pressure, and gas bubbles within the pores. Any action that disturbs the stability balance of the gas hydrate can cause it to dissociate (transform into free gas or a water–gas mixture) or dissolve (change into a mixture of water and dissolved gas). By turning the water and gas trapped in the pores of the sediment into a solid, gas hydrate production strengthens the sediment. However, the sediment may become weaker due to the gas and water released by the liquefaction of the gas hydrate. The main source of the instability of sediments containing hydrates is assumed to be excessive

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Natural Gas Hydrates and Hydrogen Storage  97

pore pressure brought on by hydrate dissociation [31, 32]. The effective stress and shear strength of sediments are decreased as pore pressure rises, leading to shear failure. The decomposition of gas hydrates causes a rise in pore pressure, the magnitude of which is proportional to the saturation of the pore with hydrate, the solubility of the gas, and the compressibility of the medium [33]. Both the concentration of methane and the hydrostatic pressure at the outset affect how much pressure is exerted outside the pores. A wide pore space makes the sediment more malleable, and gas hydrate breakdown along the higher shelf edge could result in a massive pore pressure that significantly reduces compactness. Gas hydrate breakdown is more likely to encourage slips on slopes steeper than 4°, which is consistent with the general observation of the likelihood of a slide increasing with increasing sediment slope. Slope stability investigations, smallscale physical modeling, and theoretical tests all showed that even a little amount of hydrate dissociation could result in a substantial loss of sediment strength. It is possible that hydrate dissociation plays a crucial role in initiating slope collapses for low-permeability sediments at deeper water depths [34]. It is important to note that the pore pressure response varies greatly depending on the properties of the medium. Clayey rocks, due to their low dissipation pore pressure, are more prone to deformation and slope collapse. Although pore pressure builds slowly, it dissipates quickly in sandstone. Pore pressure in coarse-grained rocks, together with other external pressures like earthquakes and faster rates of sedimentation, may contribute to the collapse or failure of the seabed [35]. Hydraulic permeability is a key factor in controlling the production of pore pressure. The total quantity of gas hydrate present, the pace at which it dissociates, the permeability of the sediment, background fluid flow, capillary pressure, and the depth to which the base of the GHSZ sinks are some variables that influence the formation of excess pore pressure [36]. Since greater gas pressure is needed to overcome capillary entry pressure, fine-grained sediments are more conducive to hydraulic fracturing. This action increases the bulk permeability of the sediments locally while also repairing the fluid channel. Examples of fine-grained, low-permeability sediments that sustain marine gas hydrate deposits may be found in the Indian Krishna–Godavari Basin, Gulf of Mexico hydrate deposits, and the Ulleung Basin sediments. Because of the lack of distinguishable differences in physical properties, the upper GHSZ is frequently a diffuse (hydrate or seawater) boundary that is challenging to detect in geophysical field recordings. Gas hydrate dissociation near the foot of the GHSZ is frequently cited as the cause of sediment deformation and underwater slope collapses. It is expected that increased pore pressure and the shear discontinuities brought

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98  Clean and Renewable Energy Production

on by hydrate dissociation do not provide any significant dangers. The gas hydrate stability law predicts that the hydrate dissociation process in the natural environment would result in an increase in temperature, a drop in surplus pore pressure, and a finite shear discontinuity at the base of the GHSZ. Nonetheless, hydrate breakdown toward the top of the GHSZ is a potentially dangerous process that may trigger regional-scale landslides of catastrophic proportions. When gas hydrates undergo hydrate dissociation, they become liquids and the sediments relax. If the gas hydrates were to completely disappear, the free gases that would be trapped behind them would make up a thin layer of overpressed sediments. Together, these processes have the potential to cause slope failure [37]. Extensive slumping along the borders is a result of changes in sea level, especially the fall’s dramatic drop in sea level. These subterranean slides, as well as perhaps related slides on other continental borders where gas hydrates are plentiful, were undoubtedly caused by changes in the global climate. Approximately 70% of the slope failure that happened during the previous 45,000 years was relocated over two time periods, the first between 15 and 13 ka and the second between 11 and 8 ka. The Blling-Aollerd and Preboreal epochs are characterized by rising sea levels and methane record peaks, respectively. During the glacial and interglacial eras, there was also a shift in the temperature pattern along the continental boundaries. When sea levels are lower, hydrates may enjoy higher surface temperatures. Additionally, the ocean’s sub-bottom temperature is periodically changed by the patterns of global-scale currents. This is significant since the material with the highest probability of containing gas hydrates is submerged in waters between 200 and 1,500 m deep. In other words, the expected warming of the intermediate depth of the ocean poses a threat to the stability of marine gas hydrates. The hydrate’s stability might be greatly increased by the anticipated slight sea-level rise of up to 1 m, but it is completely insufficient to stop the warming. Greater temperatures must reach the phase transition zone at the hydrate–gas boundary, which is situated under the gas hydrate layer, in order to destabilize the gas hydrates. When considering factors like the hydrate depth, temperature gradient, and sediment type, thermal diffusivity may be a “sluggish process.” Thus, an increase in temperature might encourage hydrate dissociation and cause sediments to become mechanically fragile. Using the bottom simulator reflectance (BSR) method near a deformed structural configuration, researchers have concluded that a significant portion of underwater slope collapses are caused by a decrease in shear strength. Slope collapses in hydrate-bearing sedimentary formations on the seafloor may be caused by, or at least set off in motion by, the decomposition of gas

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Natural Gas Hydrates and Hydrogen Storage  99

hydrates. Slope collapse and its potential connection to gas hydrates has been extensively discussed and researched for over three decades. Nearly all of the research has focused on establishing an association between gas hydrate breakdown and slope collapses. Using BSRs or other geophysical, geochemical, and geological markers, slope failure near gas hydrate-bearing strata may be located, and inferences regarding the connection between the gas hydrate and the slope collapse can be made [29, 38, 39]. Some of the extensively studied gas hydrate provinces are as follows [27]: • • • •

Storrega Slide—Norwegian Sea Cape Fear Slide—Atlantic Margin Beaufort Sea Cascadian Margin

4.2.2.1 Hydrate-Associated Risks for Oil and Gas Exploitation Methane extraction from gas hydrate deposits carries with it both promising benefits and potentially devastating results. Over the continental margins, the oil and gas are primarily restricted to shallow seas that are mostly confined to continental shelves. About a quarter of a mile beneath the surface is where conventional oil and gas are found. Gas hydrates can be found at depths of more than 500 m on the continental slope or rise and around the margins of the continent. Hydrates occur in the shallow subsurface layers around the platform’s wellheads, pipelines, installations, anchoring support, and blowout preventers at these depths [40]. Gas hydrate breakdown may result in mass wasting, including slope collapses and the deformation of sediment layers, since it weakens the sediment, releases more gas and water, and elevates the pore pressure at shallow depths. BSRs have been regarded as reliable indicators of the existence of free gas and gas hydrate in seismic data below the hydrated layer. There are several indicators that gas hydrates are developing and dissociating nearby, including gas venting, see-through sediments, seabed pockmarks, gas hydrate molds, and mud volcanoes. In particular, at deeper levels, the fluidization of sediment brought on by the dissolution of gas hydrates and the discharge of excessive gas and water may result in overburden, fault instability, sand formation, mass waste as debris flow, and other problems [41]. Methane hydrates are mostly found in relatively shallow subsurface sediments. Oil and gas production near the continental margins needs drilling rigs that can descend through more than 500 m of water because the hydrate layer can be hundreds of meters below the seabed. Care must be taken while drilling through the layer since the gas hydrate may dissociate if drilling

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100  Clean and Renewable Energy Production

mud causes changes in temperature or pressure. This can weaken the sediment and perhaps damage the drilling equipment. To avoid this, a pricey casing must be placed over the whole sediment column of the hydrate layer. On the slopes of continents, where the inclination may vary greatly, gas hydrate deposits are often seen in the ocean. Slopes near the convergent edges may have a very different topology from those near the divergent ones. If the seafloor is disturbed by drilling operations, massive silt flows could travel for miles down the continental slope. Large tsunamis, like the one that hit the Indian Ocean in December 2004, would be caused by the displacement of a large amount of sediment. In addition, the grades on the slope and the abyssal plane vary, which makes it difficult to install pipelines. Pipelines installed on the seafloor are especially vulnerable to damage from mass movement caused by slope collapse and debris flow. Offshore drilling places the pipelines and production equipment in the bottom sediments at risk from gas hydrates that abruptly break apart and release expanded gas. Since methane hydrate is unstable once it is exposed to conditions other than the extreme pressure and cold temperatures of the deep sea, a safe rig placement is of limited utility. Even when methane is being brought to the surface, some of it leaks out. Effective natural gas extraction is impossible until this seepage can be stopped. Wellbore pressure might rise as hydrate decomposes, leading to gasification and perhaps a blowout. Due to the existence of gas hydrates, it has proven difficult to stop the Deepwater Horizon oil disaster in the Gulf of Mexico. Offshore drilling that fractures or disrupts the gas hydrate-bearing marine sediments may cause damage to the wellbore, pipelines, rig support, and other machinery used in oil and gas extraction from the seabed. During and after penetrating the hydrate zone, the breakdown of hydrates may be managed by regulating the temperature of the flowing mud [42]. However, because greater mud temperatures are inevitable in deeper drilling, it is still crucial to identify the existence of a hydrate zone in order to install sufficient casing. Several cases of gas kicks during hydrate decomposition were described by Davidson et al. [43]. It is currently standard practice to chill the drilling mud before use, to carefully regulate the density of the mud, and to constantly monitor the mud gases in northern Canada, where hydrate formation is common. Briaud and Chaouch [44] offer a scenario in which gas hydrates are dissociated using a model that makes use of the heat produced by the passage of hot oil via the pipes between the well and the platform. They claim that a lot of gas is produced during the melting process, which may be dangerous to the structure’s integrity. On rare occasions, the integrity of the seabed or borehole has been compromised due to the destabilization of natural hydrates, well control issues have arisen,

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Natural Gas Hydrates and Hydrogen Storage  101

and shallow water flows have occurred [45]. Subsea sediments around the mud line may contain gas hydrates, which may have a negative effect on wellbore integrity and equipment placement when extracting hydrocarbons from deeper layers. The fluids from a subsurface reservoir warm the near-well sediments as they move to the mud line, dissociating hydrates and releasing gas that may move and fracture the nearby soil [46]. Due to the rising demand for deepwater operations, production efforts that look for deeper conventional hydrocarbons are becoming less practical, rendering the long-standing industry practice of simply avoiding areas with confirmed gas hydrates increasingly obsolete [27].

4.2.3 Sustainable Applications A lot of progress has been achieved in the last year in describing the characteristics of gas hydrates, comprehending their surroundings, and creating gas hydrate-based applications for renewable technology. Several techniques for recovering gas hydrates have been made possible by the discovery of numerous natural gas hydrate reserves. However, there is growing concern about how these reservoirs can interact with the atmosphere, particularly in light of their potential to contribute to marine stability and to greenhouse warming. Numerous sustainable development applications for gas hydrate-based technologies are developing, such as CO2 sequestration and methane recovery, desalination, energy storage in the form of solidified natural gas, and gas separation. Experiments using a CO2/CH4 exchange/replacement mechanism to recover methane gas have yielded widespread positive results for researchers [47]. Since the 1940s, hydrates have been used in the process of desalinating saltwater. Since then, scientists around the world have conducted extensive studies to identify hydrate formers that meet desirable criteria, such as those for sustainability, nontoxicity, stability, availability, and economic feasibility [48]. To meet the needs of the expanding energy market, it is essential that natural gas (NG) be efficiently stored and transported at a reasonable cost [49]. Efforts to improve the capacity of hydrates or to speed up their formation or dissociation by developing new equipment, procedures, or promotional chemicals have resulted in a plethora of efficient approaches for employing gas hydrates in sustainable development. Although gas hydrate applications in environment-friendly sectors are only getting started, diligent research into characterizing gas hydrates has already led to substantial advances that have pushed technology forward conceptually. This suggests that, when these new gas hydrate-based applications in sustainable

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102  Clean and Renewable Energy Production

industries come to fruition, the gas hydrate community will be able to continue playing a significant part in the shift to a lower-carbon economy [9].

4.2.4 Solidified Natural Gas Natural gas may take over petroleum as the principal fuel in the world since it has a higher hydrogen-to-carbon ratio than any other fossil fuel and contains less sulfur and nitrogen. Reduced carbon, sulfur oxide, and nitrogen oxide emissions are the consequence. Natural gas may be stored in a variety of methods, including compressed natural gas (CNG), liquefied natural gas (LNG), and adsorbed natural gas (ANG) [50]. The technology for increased natural gas storage that has received the most interest and research is gas hydrate-based storage, sometimes referred to as “solidified natural gas” (SNG). This system offers many advantages over its predecessor, including reduced energy requirements (under normal circumstances), reduced environmental concerns, almost complete recovery, and improved safety. Hydrate-based technologies could be more affordable and offer capacities that are on par with or greater than those of conventional physical storage systems [51, 52]. As the most common hydrocarbon in the Earth’s crust, methane has been the subject of several studies that have focused on detecting and describing its hydrates. Some researchers then set out to improve upon the storage capacity of clathrates by altering the T–P conditions under which they form. Some of the methods they tried included using ice powder, tetrahydrofuran (THF), semi-clathrates, and so on [53]. Methane hydrate has a far lower formation pressure than hydrogen does at the same temperatures, and this drops even more when combined with other heavy natural gas components. This is the main driving force behind clathrate-based natural gas storage technology. As the commercialization of gas hydratebased natural gas storage approaches, the dynamics of hydrate formation, dissociation, and energy recovery—driven principally by constrained heat transport and the self-preservation effect—remain major technological hurdles [9].

4.2.5 Seawater Desalination To make seawater or brackish water suitable for drinking or irrigation, salt must be removed. This process is known as desalination. The world’s freshwater supplies are being placed under a pressure never previously witnessed due to the rising population, demands of industry, and agricultural needs. The current rates of population growth, industrialization, urbanization,

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Natural Gas Hydrates and Hydrogen Storage  103

and overexploitation of freshwater resources are primarily responsible for the world’s water scarcity [54, 55]. Numerous saltwater desalination technologies have been developed over the past several decades to meet the rapidly rising global water demand due to the restricted overall supply of potable freshwater. Common desalination methods include reverse osmosis (RO), multi-effect desalination (MED), and thermal/membrane/ chemical desalination. These energy-heavy processes frequently use fossil fuels, which add to global warming [56, 57]. With its classification as a freezing or crystallization method, desalination using clathrate hydrates (Figure 4.4) has been proposed as a practical technique for the treatment of saltwater for almost seven decades. A hydrate-forming agent comes into contact with an electrolyte solution, such as saltwater or brackish water, at the proper pressure and temperature (P–T; which could be above the freezing point of water). The former hydrate molecules are enclosed by water to create a clathrate hydrate, which shields the crystal structure from salts and other toxins. By acting as a thermodynamic inhibitor and shifting the hydrate phase equilibrium to a higher pressure at a specific temperature, salt lowers the energy barrier for hydrate synthesis. The shape of a hydrate crystal is unaffected by the addition of salt. It is possible to recycle the hydrate former and the water used to dissolve the hydrate crystal once it has been mechanically extracted from the brine [58]. The quantity of freshwater recovered from the feed solution (a component of hydrate formation kinetics), the amount of water converted to hydrates, and the amount of hydrate crystals recovered during the brine separation phase are all factors that influence the

Guest gas Gas hydrates

Saline water

Brine Portable water

Figure 4.4  Schematic diagram of the clathrate hydrate-based desalination process [9].

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104  Clean and Renewable Energy Production

volumetric efficiency of the process. The eutectic composition of the feed solution restricts the quantity of water that may be recovered [9]. The hydrate-based desalination method makes use of a variety of chemicals. These substances include carbon dioxide (CO2), refrigerant gases [hydrofluorocarbon (HFC), hydrochlorofluorocarbon (HCFC), and chlorofluorocarbon (CFC)], propane (C3H8), cyclopentane (C5H10), and sulfur hexafluoride (SF6). Since then, a lot of research has been done by scientists all over the globe to identify the hydrate formers that are stable, nontoxic, safe for the environment, accessible to most people, and profitable [48]. It has been challenging to develop a commercial hydrate-based desalination plant due to the necessity for an ideal hydrate formation and other technological challenges. For instance, flammable liquids like alkanes and cycloalkanes pose safety concerns for commercial usage, while dioxide compounds like SF6, CFC, HFC, and HCFC have been deemed undesirable as atmospheric hydrate formers. However, it has been hypothesized that ethane and propane are effective hydrate formers using a mixed thermodynamic approach [5]. The hydrate-based desalination process has not yet been successfully implemented on a wide scale, despite much research and advancements aimed at overcoming technical obstacles as well as energy efficiency and environmental concerns. Since the cost of running the operation is affected by variables such the required thermodynamic conditions, yield, concentration of salt, brine temperature, and salt mobility, economic viability is an important consideration. Therefore, there is still a need to create hydratebased desalination techniques that are practical to use on an industrial scale and that are both energy and environmentally benign [59].

4.2.6 CO2 Sequestration and Methane Recovery At highly specific temperature and pressure circumstances, CH4 hydrates, a type of sub-stable state mineral, develop and expand in response to the availability of hydrocarbon gas sources. During the vast bulk of the formation process, pressures greater than 10  MPa and temperatures below 10°C are the norm [60]. Nowadays, CH4 hydrates have been found on the muddy ocean floor, in the permafrost zone, and in a small fraction of the Arctic land. These hydrates are generated in low-temperature environments at depths of 100–250 m. As the stable-phase equilibrium state would be broken owing to pressure and temperature changes, several ways for extracting CH4 hydrates have been suggested. Depressurization, heat stimulation, chemical injection, and the CO2 replacement strategy are some of these techniques.

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Natural Gas Hydrates and Hydrogen Storage  105

The CO2 replacement approach may be used to collect and store CO2 hydrates in reservoirs. According to various mechanical studies, the replacement procedure assists in the stability of the CH4 hydrate layer [61]. Even the simplest CO2 sequestration operation requires the purchase of supplementary equipment to reduce the sequestration risk in addition to the high financial cost of CO2 capture, collection, and purification. However, throughout the replacement process, the income from the recovered CH4 is adequate to cover the expenses of the CO2 treatment and the investment in the project [62, 63]. In addition, studies have shown that the temperature, pressure, and CH4 hydrate position are all optimal for CO2 sequestration. CO2 hydrates are more thermodynamically stable than CH4 hydrates because their equilibrium pressure, at around 283 K, is lower and lower temperatures are required. This was discovered by studying the CH4–CO2–H2O system’s hydrate–liquid vapor equilibria [64]. About 20 trillion m3 of CH4 hydrate deposits is thought to exist worldwide. More than 90% of them are marine CH4 hydrate resources, which are primarily found in undersea sediments at depths of 300–4,000  m [65]. According to studies of the geological characteristics of sediments that have become hydrate-saturated after CO2–CH4 replacement, recent CO2 hydrates may help preserve the mechanical stability of the marine sediment repositories. CO2 replacement of CH4 hydrates is seen as a helpful addition given that the carbon capture, utilization, and storage (CCUS) technology can recover CH4 hydrates while lowering CO2 emissions and sequestering CO2 [66]. The CO2 sequestration process is shown in Figure 4.5.

CO2 capture stage

Mixing stage

Other gas components Gas mixture containing CO2

H2O

CO2 sequestration stage

Ocean

CO2

CO2

H2O

Stored CO2 CO2 hydrate

Proper condition Gas-liquid mass transfer

Mechanical methods; Chemical additives; Materials

CH4-CO2 replacement CO2 storage

Figure 4.5  Schematic diagram of the hydrate-based CO2 capture and sequestration technique [67].

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106  Clean and Renewable Energy Production

4.2.7 Gas Separation The term “‘gas separation”’ refers to any technique used to remove impurities or isolate desired substances from a raw gas supply. Many different sectors rely on technologies revolving around gas separation, such as natural gas purification [68], CO2 separation [69], hydrogen separation [70], and biogas separations [71]. In multiphase systems, this technique is often used. The most often used techniques for separating gases are membranes, cryogenic distillation, and solvent/sorbent-based separation. Gas separation using hydrates is a new, promising technique. This method is feasible because some gas molecules have a strong affinity for the hydrate phase [9]. Hydrates may be initially produced and then dissociated after they have separated from the gas phase, making advantage of the wide variety of gas occupancies to collect and filter out the less desired species from the input gas. Using gas hydrate as a means of gas separation is economically feasible as well since the synthesis of hydrates is endothermic, reducing the amount of energy required to cool the system during the process. Figure 4.6 shows the gas separation process. Temperature and pressure have an impact on the selectivity of gases in the hydrate phase, which in turn has an impact on the occupancy of the gas cage. Because it relies on the differences in cage occupancies, this method

B

B

B

Gas

A

B

A

Liquid B

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B B

B A

Hea t

A A

A A

B B

A

Solid

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B

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A A

B B

A

A B

A

B A

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Dissolution

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A

A

B A

B

at io

B

A

B

Co Cl ol at hr at eF or m

A

B

A

A

B A

A Phase Separation B

Figure 4.6  Schematic diagram of hydrate-based gas separation [9].

B

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Natural Gas Hydrates and Hydrogen Storage  107

has one major limitation: it cannot be used to distinguish gases with the same cage occupancy. As a result, CO2 collection and separation, which has a substantially lower HSZ and, hence, larger cage occupancies, is typically linked with hydrate-based separation. The extraction of refrigerant gases such as N2, H2, H2S, CH4, SF6, N2O, CHF3, and many more is also done using this method. Recent research has proposed enhancing the gas separation efficiency by combining this method with membranes [72, 73] or chemical absorption [74]. While hydrate-based gas separation has been studied extensively since its inception and offers many benefits over traditional procedures, including being the greenest option, there are still a number of issues that need to be fixed before industry and society can embrace the technologies that have been created for hydrate-based gas separation [9].

4.3 Hydrogen Energy Around the world, hydrogen is a promising option for future power system advancements since it does not contribute to pollution. The energy shift has become a major challenge for the next 30 years as a result of the inherent demand to minimize GHG emissions [75]. This global energy transition is being sped up by the rapid growth in the usage of renewable energy sources, which aim to halt the worsening effects of fossil fuel consumption on the environment and on human beings. The potential of hydrogen as an alternative energy carrier is being investigated in an effort to build on this momentum and reduce emissions [76]. The most readily available renewable energy is hydrogen because it is extremely plentiful. Furthermore, when hydrogen is burned, only water vapor is created. Consequently, it is regarded as the cleanest form of energy. It is believed that if hydrogen is created using renewable resources, it will be an appropriate answer to environmental challenges. With an energy density of 120–142 MJ/kg, [lower heating value (LHV) − higher heating value (HHV)] hydrogen is a fairly low-fuel source. Hydrogen’s potential and usefulness are extensive, but depend on a variety of criteria including storage capacity, energy density, adaptability, transport, and environmental effects [77]. The applications of hydrogen have been discussed in this chapter.

4.3.1 Types of H2 Different color codes are allotted to differentiate the types of hydrogen. Color codes and other nomenclature are usually based on the

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108  Clean and Renewable Energy Production

manufacturing process. Below is a rundown of the several forms of hydrogen, of which the low-carbon-producing ones are the green, blue, and aqua hydrogen [78]. Green hydrogen: The hydrogen that is produced in a way that does not lead to the release of GHGs is called “green hydrogen.” Green hydrogen is produced by electrolyzing water using clean energy derived from renewable resources (such as solar or wind). Electric current is used in water systems to divide water molecules into hydrogen and oxygen, releasing just the oxygen and water while retaining all of the carbon dioxide [79]. Blue hydrogen: The method of steam reformation, which combines natural gas with steam created by heating water, produces the overwhelming majority of blue hydrogen. Carbon dioxide is released into the atmosphere as a consequence of hydrogen synthesis. Blue hydrogen, a transition energy carrier, may use existing infrastructure and assets, making it cheaper compared to other alternative sources. Due to the fact that steam reforming is used to create blue hydrogen, some GHGs are still released throughout the process. The term “low-carbon hydrogen” is also used to describe this energy [80, 81]. Aqua hydrogen: The aqua hydrogen technology enables the generation of hydrogen from economically unrecoverable oil reservoirs without bringing anything else to the surface [82]. The ground itself serves as the reaction vessel, while unswept petroleum is used as a fuel in this innovative step forward in aqua hydrogen technology [79]. Gray hydrogen: This is the most common technique for producing hydrogen at the moment. Steam methane reformation converts natural gas (methane) into gray hydrogen without recovering the GHGs [78]. Black and brown hydrogen: Black and brown hydrogen, on the other hand, are the most harmful to the environment since they are made by heating black coal or lignite (brown coal) to make hydrogen. There is some similarity between the terms “black hydrogen” and “brown hydrogen” when referring to the hydrogen created from fossil fuels via the “gasification” process [83]. Turquoise hydrogen: There has been no evidence of a large-scale synthesis of this new addition to the hydrogen color wheel. Here, the pyrolysis of methane produces solid carbon and hydrogen. The only feedstock used is natural gas; electricity is used to heat and split the methane. To put it another way, if the electricity is generated via renewable sources, the procedure has negligible environmental impact. If the heating process is driven by renewable energy and the carbon is either permanently stored

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Natural Gas Hydrates and Hydrogen Storage  109

or burned, turquoise hydrogen could one day be recognized as a low-emission hydrogen [78, 84]. Pink hydrogen: The production of pink hydrogen is accomplished by nuclear-powered electrolysis. Purple hydrogen, also called crimson hydrogen, is another name for the hydrogen created during nuclear fission. The extremely high temperatures generated by nuclear reactors could also be employed in alternative hydrogen processes, such as steam methane reforming based on fossil gas or for more efficient electrolysis [78, 85]. Yellow hydrogen: The hydrogen created using solar-powered electrolysis is known as “yellow hydrogen,” a term that has only recently gained popularity. The cleanest gas produced by humans using electrolyzers is yellow hydrogen, second only to wind power. In the pursuit of a circular economy that is sustainable in the long term, this type is one of the most favorable [78, 86]. White hydrogen: Fracking produces white hydrogen, a kind of geological hydrogen that is found naturally in underground deposits. This type of hydrogen is not produced by people, but is instead found in its unaltered state, as a free gas, in the deep oceanic crust, volcanic gases, geysers, and hydrothermal systems [78, 87].

4.3.2 Hydrogen Storage Due to its high energy density per mass, hydrogen has promise as an energy source in the future. Compared to gasoline and diesel, which both contain Hydrogen storage

Compressed gas

Underground storage

Liquid hydrogen

Metal hydrides

Solid hydrogen

Complex hydrides

Figure 4.7  Different technologies for hydrogen storage [98].

Chemical hydrides

Adsorbents

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110  Clean and Renewable Energy Production

12 kWh of energy per kilogram, hydrogen has 33.33 kWh/kg [88]. However, to hold the same quantity of hydrogen, a larger volume is needed. Thus, improvements in hydrogen storage technology are essential for the development of hydrogen energy systems. Although it may be kept as a cryogenic liquid or compressed gas, subterranean storage is preferable for industrial usage. Since its inception, solid-state hydrogen storage has advanced rapidly and is currently widely regarded as the most secure technique of hydrogen storage. Figure 4.5 provides a summary of the various hydrogen storage systems. Figure 4.7 is a flowchart depicting the different technologies for hydrogen storage.

4.3.2.1 Compressed Gas High-pressure compression can hold more hydrogen in a smaller space. Longterm storage usually involves compressing hydrogen into steel gas cylinders at 700 bar [89]. Modern lightweight composite steel high-pressure gas cylinders are suitable for this [90]. Hydrogen pipelines and hydrogen tube trailers use compressed hydrogen storage to carry hydrogen, but the gas cylinder weight limits the transport capacity. Another technological issue is compression heat transfer. If the temperature within the tank gets too high, composite degradation could occur. Application of research into high-thermal-conductivity materials and structural design has improved heat transfer performance [91].

4.3.2.2 Underground Hydrogen Storage There have been several designs for large-scale hydrogen storage published. Large amounts of hydrogen might be kept for a long time in salt caverns, depleted natural gas and oil deposits, and aquifers. As a result of their stability and impervious walls, salt caverns have recently attracted significant interest for storing hydrogen gas. At a pressure of 200 bar, the volume of salt inside the cavern changes from 100,000 to 1,0000,000m3 [92]. About 75% of the world’s subsurface hydrogen storage is located in exhausted deposits [93]. Although the potential for storing hydrogen in salt caverns is interesting, technical obstacles such as the tightness of the boreholes and the transfer capacity of the surface installation have slowed development in this field [93].

4.3.2.3 Liquid Hydrogen Liquid hydrogen, which can be made at low temperatures and atmospheric pressure (20–21 K), is another compact storage option. Only slightly denser than hydrogen in solid form (70.6 kg/m3), hydrogen’s greatest volumetric density in liquid form is 70.8  kg/m3. However, liquefying hydrogen is a

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Natural Gas Hydrates and Hydrogen Storage  111

time-consuming and power-intensive process that wastes around 40% of the energy used in the process. Since it has not been widely commercialized, liquid hydrogen is currently only used in specific high-tech applications like space travel [76].

4.3.2.4 Solid Storage In order to create chemical compounds, hydrogen is absorbed into the bulk of the material and stored there. Metal hydrides, which can store a lot of hydrogen, are becoming an increasingly popular option. Normal room temperature and pressure allow palladium to take in 900 times its own volume in hydrogen. In order to facilitate the broad-scale use of metal hydrides, researchers have worked to cut costs, improve operating temperatures, and enhance thermal management [94]. However, the primary issues with these techniques are that they are not reversible and that the steps required to extract hydrogen from chemical hydrides (LiH, NaH, CaH2, etc.) and complex hydrides are difficult (Mg2NiH4, LiAlH4, NaBH4, etc.) [76].

4.3.3 H2 as Fuel Although there are many vital applications for hydrogen, fuel is one of the most significant. While battery-powered vehicles have range issues, hydrogen-fueled electric powertrains are the clean energy-based alternative for long-distance travel. In 2030, 3% of the new cars sold globally are anticipated to be hydrogen-fueled; by 2050, that number may rise to 36% [95]. The aerospace industry uses hydrogen most often as fuel because it can be combined with oxygen to create a rocket propellant. In automobiles, hydrogen may be used in two different ways: directly in the internal combustion engine or indirectly by using fuel cells to produce energy to power cars and other appliances. The actual cost of producing and storing H2 as fuel is higher than that of other gases [96]. Combustion and fuel cells represent the two most common methods of converting hydrogen into usable energy. Hydrogen serves as a safe coolant in several industrial applications, including power plant generators, the pharmaceutical industry, the food sector (unsaturated fatty acid hydrogenation in vegetable oil), and many others [97].

4.3.4 Industrial Applications of H2 Hydrogen is used widely in the manufacturing sector as a reactant (in the creation of fertilizers) and as a refining material (in the treatment of metals) and in the food industry. Hydrogen is used as a fuel in automobiles,

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112  Clean and Renewable Energy Production

Table 4.2  Uses of hydrogen in different industries [98]. Type of industry

Uses

Oil

• Removal of sulfur and other impurities • Hydrocracking of large hydrocarbons to fuel distillates

Chemical

• Synthesis of ammonia, methanol, etc.

Food

• Conversion of sugars to polyols • Conversion of tallow and grease to animal feed

Plastics

• Synthesis of nylons, polyurethanes, polyesters, and polyolefin • Cracking used plastics to produce lighter molecules that can be recycled

Metals

• O2 scavenger • Reductive atmosphere for the production of iron, magnesium, molybdenum, etc. • Welding torches • Heat treatment to improve the ductility and machining quality, to relieve stress, to harden, and to increase the tensile strength, changing magnetic or electrical characteristics

Electronics

• “Epitaxial” growth of polysilicon • Manufacture of vacuum tubes • Heat bonding materials

Glass

• • • •

Electric power

• Coolant for large generators of motors • Nuclear fuel processing

High-temperature cutting torches Glass polishing Heat treatment of optical fibers Reductive atmosphere for float glass process

and H2O mixtures are used as a propellant in the aerospace industry, as well as in the purification of glass, the production of semiconductors, the creation of fertilizers, the annealing of metals, the manufacture of pharmaceuticals, and the cooling of power plant generators. Recently, electrochemical reactions have used hydrogen to generate electricity in fuel cells. In the petroleum sector, hydrogen is mostly used as a reactant in the manufacturing of petrochemicals or petroleum processing. Hydrocracking

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Natural Gas Hydrates and Hydrogen Storage  113

and hydro-processing are the terms used for the reactions that occur when hydrogen and hydrocarbons are combined to treat petroleum. In hydro-processing, hydrogen is used to convert the product’s toxic sulfur and nitrogen components into safe ammonia and hydrogen sulfide, respectively. In order to refine fuels with a smaller hydrocarbon size and a high hydrogen-to-carbon (H/C) ratio, hydrocracking entails the cracking and hydrogenation of heavy hydrocarbons. In the process of making petrochemicals, hydrogen and carbon monoxide are combined with high pressure, high temperature, and a catalyst to create methanol. Ammonia, which is utilized as a fertilizer, is produced using a process that also uses hydrogen as a reactant. Around half of the hydrogen created is used to create ammonia, the most fundamental component of fertilizers. A mixture of nitrogen and hydrogen (N2H4) may be used to heat equipment in the metallurgical process, and hydrogen has also been employed as an O2 scavenger. In the context of nuclear research and industry, hydrogen is also used to reduce the oxygen level in a boiling water reactor to below 100 ppb [77, 98, 99]. Hydrogen has a wide variety of uses, which are described in Table 4.2.

4.4 Recent Advancement Toward Clean Energy Applications An increased amount of attention has recently been paid to the advancement of renewable energy technology. The transition to clean energy is being actively pursued by many governments and businesses agencies worldwide. Some of the most important recent developments in green energy technology are listed below [100]. Solar energy: Solar energy is a renewable energy source that is widely accessible and used. Solar energy is simply the sun’s beams transformed into heat and light that may be used. This is a sustainable energy option, and the market is flooded with products that harness the sun’s rays. Floating solar farms: Most photovoltaic solar power plants tend to be installed on or near a body of water due to the increased efficiency this provides. Without sacrificing any usable land, these farms may generate vast quantities of electricity. They save money by lowering the need for costly water treatment and cutting down on energy waste. Building-integrated photovoltaics (BIPV) solar technology: A recent development in renewable energy technology is the incorporation of photovoltaic panels into the fabric of structures. This design trade-off is no longer

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required. BIPV also has the added benefit of reducing our monthly power bill. It helps in the reduction of the additional cost of solar panel mounting systems as well. Photovoltaic solar noise barriers (PVNB): In recent years, the volume of the noise caused by highway traffic has reached an unsafe level. Traffic noise barriers are an effective solution to this issue. Energy blockchain: The invention of blockchain technology was first motivated by the need to secure cryptocurrency transactions. It is a great option for cutting out the middlemen in the power distribution chain. Clean transportation: Clean transportation has emerged as a new trend in recent years. People immediately adapted to this new technology when Tesla introduced its electric vehicles because they are beneficial for the environment and ensure the improvement of our planet. The desire of governments to work with such renewable energy technology is increasing.

4.5 Conclusion One of the primary topics in focus in the COP26 The Glasgow Climate Pact was “mitigation-reducing emissions.” GHG emissions can extensively be reduced by cutting down on fossil fuel extraction and production. While it would be ideal, achieving net zero is a long way off. As commodity prices rose dramatically over the world, so did the cost of producing energy. In this chapter, therefore we mainly discussed the two emerging clean and affordable sources of energy, i.e., natural gas hydrates and hydrogen energy, and their applications. While in the here and now these objectives may appear unreachable, with a longer view, sound planning and execution would guarantee adequate achievement of the purpose to achieve the required transition of energy and decrease climate change.

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38. Summerhayes, C.P., Bornhold, B.D., Embley, R.W., Surficial slides and slumps on the continental slope and rise of South West Africa: A reconnaissance study. Mar. Geol., 31, 3–4, 265–277, 1979. 39. Nisbet, E.G. and Piper, D.J.W., Giant submarine landslides. Nature, 392, 6674, 329–330, 1998. 40. Hovland, M. and Gudmestad, O.T., Potential influence of gas hydrates on seabed installations, Geophysical Monograph-American Geophysical Union, 124, Wiley-Blackwell Publishing Ltd., Statoil, pp. 307–315, 2013. 41. Birchwood, R.A., Dai, J., Shelander, D., Collett, T.S., Developments in gas hydrates, Oilfield Review, 22, 1, 18–33, 2010. 42. Bily, C.A. and Dick, J.W., Naturally occurring gas hydrates in the Mackenzie Delta, N.W.T. Bull. Can. Petrol. Geol., 22, 340–352, 1974. 43. Davidson, D.W., El-Defrawy, M.D., Fulgem, M.O., Judge, A.S., Proceedings of the 3rd International Conference on Permafrost, vol. 1, National Research Council of Canada, pp. 938–943, 1978. 44. Briaud, J.-L. and Chaouch, A., Hydrate melting in soil around hot conductor. J. Geotech. Geoenviron. Eng., 123, 7, 645–653, 1997. 45. Dutta, N.C., Utech, R.W., Shelander, D., Role of 3D seismic for quantitative shallow hazard assessment in deepwater sediments. Leading Edge, 29, 8, 930–942, 2010. 46. Peters, D.B., Hatton, G.J., Mehta, A.P., Hadley, C., Gas hydrate geohazards in shallow sediments and their impact on the design of subsea systems, 2008. 47. Poothia, T., Mehra, D., Singh, J., Rawat, P.B.S., Pandey, G., Role of CO2 capture and sequestration (CCS) using gas hydrate based technology for sustainable energy, 2021. 48. Sahu, P., Krishnaswamy, S., Ponnani, K., Pande, N.K., A thermodynamic approach to selection of suitable hydrate formers for seawater desalination. Desalination, 436, 144–151, 2018. 49. Pandey, G., Kumar, A., Veluswamy, H.P., Sangwai, J., Linga, P., Morphological studies of mixed methane tetrahydrofuran hydrates in saline water for energy storage application. Energy Proc., 143, 786–791, 2017. 50. Celzard, A. and Fierro, V., Preparing a suitable material designed for methane storage: A comprehensive report. Energy Fuels, 19, 2, 573–583, 2005. 51. Veluswamy, H.P., Kumar, A., Seo, Y., Lee, J.D., Linga, P., A review of solidified natural gas (SNG) technology for gas storage via clathrate hydrates. Appl. Energy, 216, 262–285, 2018. 52. Tsimpanogiannis, I.N., Costandy, J., Kastanidis, P., el Meragawi, S., Michalis, V.K., Papadimitriou, N.I., Karozis, S.N., Diamantonis, N.I., Moultos, O.A., Romanos, G.E., Stubos, A.K., Economou, I.G., Using clathrate hydrates for gas storage and gas-mixture separations: Experimental and computational studies at multiple length scales. Mol. Phys., 116, 15–16, 2041–2060, 2018. 53. Yang, L., Lan, X., Liu, D., Cui, G., Dou, B., Wang, J., Multi-cycle methane hydrate formation in micro droplets of gelatinous dry solution. Chem. Eng. J., 374, 802–810, 2019.

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54. Vörösmarty, C.J., Hoekstra, A.Y., Bunn, S.E., Conway, D., Gupta, J., Fresh water goes global. Science, 349, 6247, 478–479, 2015. 55. Vörösmarty, C.J., McIntyre, P.B., Gessner, M.O., Dudgeon, D., Prusevich, A., Green, P., Glidden, S., Bunn, S.E., Sullivan, C.A., Liermann, C.R., Davies, P.M., Global threats to human water security and river biodiversity. Nature, 467, 7315, 555–561, 2010. 56. Shannon, M.A., Bohn, P.W., Elimelech, M., Georgiadis, J.G., Mariñas, B.J., Mayes, A.M., Science and technology for water purification in the coming decades. Nature, 452, 7185, 301–310, 2008, https://doi.org/10.1038/ nature06599. 57. Ghaffour, N., Missimer, T.M., Amy, G.L., Technical review and evaluation of the economics of water desalination: Current and future challenges for better water supply sustainability. Desalination, 309, 197–207, 2013. 58. Babu, P., Nambiar, A., He, T., Karimi, I.A., Lee, J.D., Englezos, P., Linga, P., A review of clathrate hydrate based desalination to strengthen energy–water nexus. ACS Sustainable Chem. Eng., 6, 7, 8093–8107, 2018. 59. Javanmardi, J. and Moshfeghian, M., Energy consumption and economic evaluation of water desalination by hydrate phenomenon. Appl. Therm. Eng., 23, 7, 845–857, 2003. 60. Sun, S., Gu, L., Yang, Z., Lin, H., Li, Y., Thermophysical properties of natural gas hydrates: A review. Nat. Gas Ind. B, 9, 3, 246–263, 2022. 61. Liu, W., Luo, T., Li, Y., Song, Y., Zhu, Y., Liu, Y., Zhao, J., Wu, Z., Xu, X., Experimental study on the mechanical properties of sediments containing CH4 and CO2 hydrate mixtures. J. Nat. Gas Sci. Eng., 32, 20–27, 2016. 62. Zhao, J., Chen, X., Song, Y., Zhu, Z., Yang, L., Tian, Y., Wang, J., Yang, M., Zhang, Y., Experimental study on a novel way of methane hydrates recovery: Combining CO2 replacement and depressurization. Energy Proc., 61, 75–79, 2014. 63. Lee, Y., Kim, Y., Seo, Y., Enhanced CH4 recovery induced via structural transformation in the CH4/CO2 replacement that occurs in sH hydrates. Environ. Sci. Technol., 49, 14, 8899–8906, 2015. 64. Anderson, R., Llamedo, M., Tohidi, B., Burgass, R.W., Characteristics of clathrate hydrate equilibria in mesopores and interpretation of experimental data. J. Phys. Chem. B, 107, 15, 3500–3506, 2003. 65. Lu, S.-M., RETRACTED: A global survey of gas hydrate development and reserves: Specifically in the marine field. Renewable Sustainable Energy Rev., 41, 884–900, 2015. 66. Gebauer, J., Lausmann, M., Redmann, F., Krause-Rehberg, R., Leipner, H.S., Weber, E.R., Ebert, Ph., Determination of the Gibbs free energy of formation of Ga vacancies in GaAs by positron annihilation. Phys. Rev. B, 67, 23, 235207, 2003. 67. Xia, Z., Zhao, Q., Chen, Z., Li, X., Zhang, Y., Xu, C., Yan, K., Review of methods and applications for promoting gas hydrate formation process. J. Nat. Gas Sci. Eng., 101, 104528, 2022.

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68. Saha, D., Grappe, H.A., Chakraborty, A., Orkoulas, G., Postextraction separation, on-board storage, and catalytic conversion of methane in natural gas: A review. Chem. Rev., 116, 19, 11436–11499, 2016. 69. Tomé, L.C. and Marrucho, I.M., Ionic liquid-based materials: A platform to design engineered CO 2 separation membranes. Chem. Soc. Rev., 45, 10, 2785–2824, 2016. 70. Ockwig, N.W. and Nenoff, T.M., Membranes for hydrogen separation. Chem. Rev., 107, 10, 4078–4110, 2007. 71. Basu, S., Khan, A.L., Cano-Odena, A., Liu, C., Vankelecom, I.F.J., Membranebased technologies for biogas separations. Chem. Soc. Rev., 39, 2, 750–768, 2010. 72. Warrier, P., Naveed Khan, M., Carreon, M.A., Peters, C.J., Koh, C.A., Integrated gas hydrate-membrane system for natural gas purification. J. Renewable Sustainable Energy, 10, 3, 034701, 2018. 73. Kumar, R., Linga, P., Ripmeester, J.A., Englezos, P., Two-stage clathrate hydrate/membrane process for precombustion capture of carbon dioxide and hydrogen. J. Environ. Eng., 135, 6, 411–417, 2009. 74. Xu, C.-G., Yu, Y.-S., Xie, W.-J., Xia, Z.-M., Chen, Z.-Y., Li, X.-S., Study on developing a novel continuous separation device and carbon dioxide separation by process of hydrate combined with chemical absorption. Appl. Energy, 255, 113791, 2019. 75. Coleman, D., Kopp, M., Wagner, T., Scheppat, B., The value chain of green hydrogen for fuel cell buses – A case study for the Rhine-Main area in Germany. Int. J. Hydrogen Energy, 45, 8, 5122–5133, 2020. 76. Yue, M., Lambert, H., Pahon, E., Roche, R., Jemei, S., Hissel, D., Hydrogen energy systems: A critical review of technologies, applications, trends and challenges. Renewable Sustainable Energy Rev., 146, 111180, 2021. 71. Abdalla, A.M., Hossain, S., Nisfindy, O.B., Azad, A.T., Dawood, M., Azad, A.K., Hydrogen production, storage, transportation and key challenges with applications: A review. Energy Convers. Manage., 165, 602–627, 2018. 78. The hydrogen colour spectrum | Hydrogen colours, National Grid Group. 79. Yu, M., Wang, K., Vredenburg, H., Insights into low-carbon hydrogen production methods: Green, blue and aqua hydrogen. Int. J. Hydrogen Energy, 46, 41, 21261–21273, 2021. 80. https://www.cedelft.eu/en/publications/2149/. 81. https://www.irena.org/publications. 82. https://www.linkedin.com/in/grant-strem-017aa112. 83. Colors of hydrogen: Green, blue, grey, black, brown, pink, turquoise, yellow, red, and white hydrogen (PDF) – what is piping. 84. Achieving net zero: What is turquoise hydrogen?, Spectra (mhi.com). 85. Pink purple red hydrogen uses radioactive nuclear powered to electrolyze water leaving harmful toxic waste to be dumped in the ocean (hydrogenbatteries.org). 86. Yellow hydrogen solar powered electrolysis (hydrogenbatteries.org).

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Wind and Solar PV System-Based Power Generation: Imperative Role of Hybrid Renewable Energy Technology Madhura K. Pardhe1, Rupendra Kumar Pachauri1* and Priyanka Sharma2 1

Electrical and Electronics Engineering Department, School of Engineering, University of Petroleum and Energy Studies, Dehradun, India 2 School of Basic Science and Technology, IIMT University, Meerut, Uttar Pradesh, India

Abstract

Global warming, rising oil costs, and a drop in fossil fuel use have all drawn attention despite decreasing fossil fuel use. It is hoped that the new renewable energy technologies decrease the issue of energy shortages or imbalances in the distribution of energy between nations and within a country. Without energy, life is an illusion. It has only been in the last few decades that hybrid renewable energy systems have emerged as a viable option for providing electricity in isolated rural regions where grid expansion is both impossible and prohibitively expensive. Renewable energy sources, such as solar photovoltaic, wind energy, micro-hydro, biomass energy, and geothermal energy, are all part of these systems, including conventional backup generators. In addition to providing clean electricity, large-scale wind and solar power facilities contribute to trash buildup and other environmental problems. Due to the extended life cycle of these items, environmental concerns connected to decommissioning and disposals have not been thoroughly addressed. Keywords:  Renewable energy, wind energy, solar energy, hybrid renewable energy system

*Corresponding author: [email protected] Surajit Mondal, Adesh Kumar, Rupendra Kumar Pachauri, Amit Kumar Mondal, Vishal Kumar Singh and Amit Kumar Sharma (eds.) Clean and Renewable Energy Production, (123–142) © 2024 Scrivener Publishing LLC

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5

5.1 Introduction Renewable energy sources, such as wind and solar power, are widely available and can be found in many regions around the world. However, the availability and potential for renewable energy sources can vary depending on location. For example, areas with high wind speeds and ample sunlight are well suited for wind and solar energy production, while other regions may not be as conducive to these forms of energy. Fossil fuels, such as coal and natural gas, are also widely available, but their extraction and use can have significant environmental impacts. Additionally, fossil fuel reserves are finite and will eventually be depleted. Renewable energy sources, on the other hand, are considered to be sustainable, meaning they can be used without depleting the Earth’s resources [1]. In recent years, the cost of renewable energy technology has decreased significantly, making it more competitive with fossil fuels, and many countries have set ambitious targets for increasing their renewable energy capacity. However, the infrastructure for renewable energy is still under development, and there is still a long way to go for them to fully replace fossil fuels as the primary source of energy. Electricity production from wind and solar photovoltaic (PV) systems involves the use of renewable energy sources to generate electricity. Wind turbines convert the kinetic energy of wind into mechanical energy, which is then converted into electricity through a generator. Solar PV systems convert sunlight into electricity through the use of solar cells. Both wind and solar energy are considered to be clean, renewable sources of energy that do not produce greenhouse gases or other pollutants. However, they are also dependent on weather conditions and therefore not as consistent as traditional sources of energy such as coal or natural gas. Multiple elements determine the pace at which climate change will continue to increase in the 21st century, making it a serious reason for alarm. According to the Paris Agreement, the objective is to keep global temperatures “well below” 2°C and, preferably, below 1.5°C in this century [2]. As a response to the mounting risk of global climate change, numerous countries have looked to renewable energy sources for a solution. Wind and solar energy are two of the most promising and fastest growing renewable energy sources. In 1997, the worldwide installed wind-generation capacity, onshore and offshore, was 7.5  GW, and by 2018, it had increased to 564 GW [3]. A total of 78 GW of the solar PV capacity has been installed globally as of 2016, more than twice as much that in 2014 and 32 times as much that in 2000 [4]. The capacity is anticipated to grow; however, the speed of development will vary from nation to nation. More than 6% of the

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world’s electricity demands will be met by wind turbines built by the end of 2019. According to predictions, the most significant future development will be the creation of new solar energy sources [5]. Although wind and solar power have various advantages, a better product comes at a price in terms of garbage accumulation and other environmental impacts. Waste from turbine blades alone is estimated to total around 43 million metric tons in 2050 [6]. Approximately 8,000 blades are removed annually in the US alone. By 2050, the quantity of solar panel waste is expected to reach 9.57 million metric tons [7]. As a general rule, wind turbines and solar panels are projected to last 20–30  years. In the early days of wind turbines and solar panels, recycling was not a concern since they had a long life expectancy. As many wind turbines and solar panels reach the end of their useful lives, sound recycling is becoming more important to keep the environment safe. In spite of these technical advancements, the wind and solar industries have failed to achieve actual sustainability, from the building phase through to the decommissioning and removal of their equipment. Longterm solutions to wind and solar energy will need further study into their environmental impacts after their useful lives have passed. Wind and solar farms are reaching the end of their design lives and must be disposed of, which has been neglected recently. To put it another way, this problem will only become more serious as more farms approach the end of their lives. There must be a feasible reuse or recycling plan in place as soon as possible for landfills that are already running short on space. The next step is to assess and expose the environmental effects of this energy throughout its life cycle in order to reduce and improve the current technology. It is critical to know how long wind turbines and solar panels last in order to measure their environmental impact. Some product life cycles are simpler to comprehend than others, and this is due to the degree of complexity involved. As can be seen in Figure 5.1, the life cycle begins with raw

DC/AC

AC/DC Load

Figure 5.1  Hybrid wind turbine/photovoltaic (WT/PV) power generation system.

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materials and ends with decommissioning. At each step of the life cycle, resources and energy are brought in, while products such as wastes and emissions are produced (i.e., air, water, soil, etc.). There are two alternatives once the end of a system’s life cycle is reached and it is ready for decommissioning. Instead of throwing something away, recycling or repurposing it in some other manner is an option. There are several options for this ecologically responsible method of disposal.

5.2 Renewable Energy for Sustainable Development Renewable energy refers to energy sources that are replenished naturally and can be used indefinitely, such as solar, wind, hydro, geothermal, and biomass. These sources of energy can contribute to sustainable development by reducing the dependence on fossil fuels, which are a major contributor to climate change and air pollution. In addition, renewable energy can also provide reliable, affordable power to communities and businesses, especially in rural or remote areas where access to electricity is limited. Investing in renewable energy can also create jobs and stimulate economic growth. Diesel generators and the extension of main grids have typically been used for electricity in rural areas. Grid construction in these regions is either financially impossible or just not feasible to satisfy society’s demands as a whole because of their isolation, sparse population, and low energy usage. Because they are more costly to run, maintain, and fuel, diesel generators also affect the environment. For this reason, rural areas must depend on their own ingenuity in the search for answers to power outages. Kerosene for lighting, diesel for milling, and traditional biomass for cooking have all been used for decades in these locations. Dry cells for radios and tape recorders have been used for decades to provide electricity. Because of rising oil costs and the negative effect fossil fuels have on the environment, people are becoming more interested in finding sustainable alternatives. As long as the source is available, renewable energy sources like the sun and wind are only as reliable as the amount of power they can provide. To put it another way, if there is a solar or wind power system, its output power will never be the same because of climate change. Consequently, if a power grid has a significant proportion of renewable energy sources, the whole grid’s reliability might be jeopardized. On the other hand, a power system’s quality is a significant consideration since contemporary electrical devices are more sensitive to voltage change than in the past. Voltage fluctuation, frequency variation, and harmonics all contribute to the quality of

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a power system. To keep quality and dependability in check and overcome the difficulties associated with the renewable energy’s design, implementation, and eventual societal application, it is necessary to have a thorough knowledge of the various renewable energy sources [8].

5.3 Global Energy Scenario There are a variety of global energy scenarios that have been proposed, each with different assumptions about factors such as population growth, economic development, and technological progress. Some scenarios envision a rapid transition to renewable energy sources and a significant reduction in greenhouse gas emissions, while others anticipate a slower transition and a continued reliance on fossil fuels. The International Energy Agency (IEA) has developed several scenarios, including the “Sustainable Development Scenario,” which envisions a rapid transition to renewable energy sources and a 70% reduction in greenhouse gas emissions by 2040. The IEA’s “Stated Policies Scenario” is based on current policies and targets and projects a more gradual transition to renewables and a slower decline in emissions. The Intergovernmental Panel on Climate Change (IPCC) has also developed several scenarios, including the “Representative Concentration Pathways” (RCPs), which describe different levels of greenhouse gas emissions and their projected impacts on the climate. The most stringent RCP, RCP2.6, projects that the world will reach net zero emissions by around 2070. It is worth noting that all these scenarios are based on a set of assumptions and projections and that the actual outcomes may vary. Every country’s ability to thrive in the face of climate change depends on its ability to generate electricity from renewable sources of energy. Global population increase, industrial expansion, and urbanization have resulted in an ever-increasing need for energy. A country’s economic development is more closely tied to expanding its manufacturing sector, which is the largest user of energy. There are severe environmental issues with the use of fossil fuels to create 80% of the nation’s total energy supply. Within the next six decades, fossil fuels may be exhausted [7]. The project predicts that oil will run out in 2040, coal in 2030, and natural gas in 2060. The greenhouse effect is a consequence of CO2 emissions, and this has an impact on global warming. As the Earth’s temperature rises due to human-caused global warming, an increase in carbon dioxide emissions could be expected. About 38% of India’s total CO2 emissions come from electricity production, which accounts for 4% of the world’s CO2 emissions. Figure 5.2 depicts the BP

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Wind and Solar PV-Based Power Generation  127

6

Thousand TWh

5 4 3 2 1 0 –1 –2

Renewables Nuclear Gas

Hydro Coal Oil

–3 China OECD Countries (36 member countries)

India & Other Other Asia

Figure 5.2  Growth of power generation (year: 2016–2040). Source: BP Energy Outlook, 2018 edition.

(British Petroleum Company) energy forecast of the 2018 edition’s global power generation growth estimate. It is expected that the fuel mix utilized in power production will change significantly, with renewable energy gaining significance over the next several decades. In 2040, nearly a third of all electricity will still be generated by burning coal. After a steady rise over the previous 25 years, the share of natural gas is expected to stabilize at about 20%. A reduction in coal-fired power production will begin around 2030 in the Organization for Economic Cooperation and Development (OECD) countries, while a rise in renewable energy will begin around 2030 in China. Non-fossil fuels are expected to account for around the same percentage of the total electricity generation in the OECD countries and in China by 2040. However, China’s coal-to-gas ratio will remain much higher. For the remainder of Asia, coal continues to be the dominant energy source for power production, and this growth in power output in the area is primarily due to coal. Because of this, the speed of change in the structure of power production in other Asian countries is less noticeable. According to the energy technology (ET) scenario, India’s power sector fuel mix in 2040 is expected to be comparable to that of China today. However, there is good news: India and China have committed to decrease their greenhouse gas emissions by 20%–25% by 2020.

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This is excellent news. Government agencies, academics, and policymakers are motivated to find a solution to create clean energy at a reasonable cost since greenhouse gas emissions are a serious threat to ecological sustainability [9].

5.4 Solar Energy Potential The potential for solar energy varies depending on location, with regions closer to the equator having higher potential due to more consistent sunlight. Desert regions also have high potential for solar energy generation due to the abundance of clear and sunny days [9]. Solar energy can be harnessed through a variety of technologies, including PV cells, which convert sunlight directly into electricity, and concentrated solar power, which uses mirrors to concentrate sunlight to generate heat and power turbines [10]. As the cost of solar energy technology continues to decrease, and the efficiency of solar panels continues to increase, it has become increasingly competitive with traditional fossil fuels and has the potential to play a major role in meeting the global energy demand sustainably [11, 12]. It is worth noting that harnessing the potential of solar energy is limited not only by technology but also by factors such as land availability, regulatory environment, and investments [13].

5.5 Wind Potential for Power Generation Wind power is the fastest growing renewable energy industry in the United States. The length of India’s coastline is 7,517 km, and its territorial waters stretch out to a distance of 12 nautical miles. For both local and international investors, India is the third largest yearly wind power market globally. At the time, India’s Ministry of Nonconventional Energy Resources was responsible for implementing the country’s wind energy program. During the 1990s, India’s wind power industry started to proliferate, and it has continued to do so in the previous several years. At 2% land availability, wind energy has a potential of 102,778 MW at 80 m and 49,130 MW at 50 m. The selection of possible wind farm regions is a constant process of wind resource evaluation. Among the 220 locations with a wind energy density of 200 W/m2 or more at a height of 50 m, there are 220 sites. As of March 2012, India’s total installed wind power capacity was 17,350 MW. [14] shows a state-by-state comparison of wind power development. The prospective locations have a total estimated gross potential of 75,000 MW.

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Wind and Solar PV-Based Power Generation  129

Across the nation, wind energy generators with outputs ranging from 225 kW to 1.65 MW have been put into service [14]. The Indian wind sector represents yearly growth in new installations of 2.1  GW in India, a dominant market for the wind industry. During the previous decade, the total installed capacity of wind farms worldwide increased by an average of 28% every year. By 2020, India will need 327 GW of electricity-generating capacity, according to the IEA’s projections. Approximately 81 TWh per year by 2020 and 174 TWh by 2030, as well as 48 million tonnes of CO2 in 2020 and 105 million tonnes in 2030, would be saved by wind power. By 2030, India’s investment in wind power would fall to about 910 million dollars. India’s wind power investment is expected to fall from its present level of €3.7 billion per year to just €2.4 billion by 2020 [15]. As many as 20 different companies manufacture wind turbine equipment. Wind energy conversion systems (WECS) are manufactured in India via joint ventures and licensing agreements with multinational wind turbine manufacturers. In order to increase the quality of wind power production, research institutes, national laboratories, universities, and industry are working together to conduct research and development operations. The Center for Wind Energy Technology (C-WET) is in charge of coordinating research and development (R&D) efforts [16]. There is no question that wind power will play a significant part in India’s renewable energy industry, bringing clean and non-polluting electricity to the national grid to a significant level [17].

5.6 Hybrid Renewable Energy Systems Power electronic converters, which are used to convert the unregulated power generated by renewable sources into usable power at the load end, have made advances in renewable energy technologies, allowing hybrid renewable energy systems (HRES) to be either connected to the grid or better used in a stand-alone mode [18]. As an added bonus, HRES may take advantage of the operational characteristics of renewable power generation technologies and achieve efficiencies that are greater than those that would be possible if just one power source were used in a particular area. Many aspects must be taken into account when it comes to generating energy. Research shows that hybrid power systems are more reliable and cost-­ effective than systems relying on only one source of energy [19]. Off-grid hybrid renewable power systems have been shown to be economically viable in several research studies [20]. A hybrid system’s profitability may also

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130  Clean and Renewable Energy Production

be influenced by factors such as the local climate and geography. It is best to use PV hybrid systems (photovoltaic–diesel–battery) in warm climates. In general, energy deployment systems, as mentioned earlier, are crucial for supply security, decreased carbon emissions, increased power quality, dependability, and job opportunities for the local population. Hybrid power production methods and storage combinations may enhance the system’s performance since renewable energy (RE) resources are climate-­ dependent. As a result, it is possible to overcome the problems posed by climate change and meet the needs of a given place. Advances in renewable energy technology and an increase in the price of petroleum products have led to a surge in popularity for power production applications in remote regions. It is good to integrate these technologies into developing nations’ power production capacity because of their potential economic elements. Even if the environmental impact of non-renewable energy sources is limited, they cannot supply the world’s expanding need for electricity. People may benefit from renewable energy sources like solar and wind once they are installed. Renewable energy sources such as wind and solar cannot be relied upon to supply the country’s energy demands because of their unpredictable nature. It is possible to combine wind turbines and solar systems into a HRES that can overcome the limitations of either source alone. These systems are easy to build because of the use of numerous mathematical models, elements, and simulation models. It is the type of application (simulation, design, etc.) and the amount of interest of the designer in the project that largely define the difficulty of building these models while accounting for all of the hybrid system components [21]. The ideal economic designs for hybrid systems, such as solar PV, wind turbines, and diesel engines, have been written by a great number of scholars [21]. A hybrid system’s levelized cost of energy (LCE) is calculated by dividing its total cost (including the initial investment and all future operating expenses) by its energy output (measured in kilowatt-hours) to arrive at the best design. However, both methods have their own merits. In certain countries, hybrid energy systems are not linked to the country’s primary power grid [21]. Because of a wide range of circumstances that make it impractical to provide energy from a central grid in rural and isolated places, these systems are often employed in such areas [22]. The power supply’s dependability, availability, and cost are critical concerns for distant regions of the globe today. The standard method utilizes diesel or gasoline generators to supply power needs in remote places away from established electrical systems. Running a diesel or petrol generator on its own has a variety of drawbacks, including noise, pollution, and high operating expenses. Generators may also be troublesome to utilize on a

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Wind and Solar PV-Based Power Generation  131

large scale. Operating a generator 24 h a day, 7 days a week, may not be financially feasible. Some disadvantages associated with generator-only systems may be avoided or minimized by using hybrid energy systems, including PV and wind resources. Less fuel usage, improved system performance [23, 24], and reduced noise and pollution are all possible benefits of using these renewable energy-based systems. Diesel generators are often used to satisfy the peak load demand during brief times when there is a lack of available energy [25] in PV–wind hybrid systems. A battery bank may be utilized to reduce the need for a diesel generator. When batteries are maintained near their total capacity or promptly restored to that level after a partial or deep drain, their life span is extended. Batteries are not usually protected against severe discharges when used alone in solar panels. Solar panels cannot provide enough power during times of little or no sunlight. Wind turbines are a more dynamic source of energy. Protecting batteries from deep discharges by including a wind turbine in the system might improve their life span [26]. A hybrid energy system is a combination of different renewable energy sources, such as solar, wind, and hydro, which are integrated together to provide a reliable and consistent source of power [27]. This type of system can be particularly useful in remote or isolated areas, where access to grid-connected electricity is limited. In summary, hybrid energy systems can provide a more reliable, efficient, and cost-effective source of renewable energy and can play an important role in meeting the energy needs of remote and isolated communities, as well as supporting sustainable development [28]. Furthermore, the taxonomy for various hybrid power generation systems are discussed regarding the findings and the sources of RE are considered, as shown in Table 5.1.

5.7 Pros and Cons of the Hybrid Renewable Energy System Hybrid wind/PV power generation refers to the use of a combination of wind turbines and PV panels to generate electricity. Here are some of the pros and cons of this type of hybrid power generation [51, 52].

5.7.1 Pros of the Hybrid Renewable Energy System • Improved reliability: By combining different energy sources, a hybrid wind/PV system can provide a more consistent and reliable source of power, as the output from one source can compensate for the variability of another.

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132  Clean and Renewable Energy Production

Table 5.1  Work preview of the existing studies. Reference

Authors

Energy source

Findings

[29]

Kumar et al.

PV/wind energy

• Cost-effective and reliable

[30]

Abd El-Shafy

PV/wind energy

• Hybrid PV/WT systems are less expensive. • Remote load powering became most cost-effective and reliable.

[31]

MyeongJin et al.

PV/wind energy

• Life cycle cost, RE adoption, and emissions of greenhouse gases were examined. • HES design was accomplished by utilizing a non-dominated sorting GA.

[32]

Koutroulis et al.

PV/wind energy

• The size of a hybrid PV/WT/battery-based system was optimized using GA. • GA optimized the target function net present cost in simulations.

[33]

Mohamed et al.

PV/wind energy

• Simulation results showed that PSO is a promising novel optimization strategy. • Simulations demonstrated that this is quicker than the serial PSO implementation.

[34]

Amer et al.

PV/wind energy

• PSO’s high intensity and sensitivity were effective in optimization. • It works for independent and grid storage solutions.

[35]

Jemaa et al.

PV/wind energy

• Hybrid PV/WT/battery systems offer energy reliability at the lowest cost. • Cost reduction was their goal due to technological scalability. (Continued)

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Wind and Solar PV-Based Power Generation  133

Table 5.1  Work preview of the existing studies. (Continued) Reference

Authors

Energy source

Findings

[36]

Kamaruzzaman et al.

PV/wind energy

• The hybrid PV/WT system’s load profile performance was assessed

[37]

Benatiallah et al.

Wind energy

• Assessed the WT system performance using power quality

[38]

Koutroulis et al.

PV/wind energy

• Hybrid PV/WG systems cost less than PV or WG systems.

[39]

Al-Shamma’a et al.

PV/wind energy

• Compared it to other hybrid energy systems to determine the cost • The proposed hybrid energy system is always cheaper than diesel.

[40]

Mellit

PV system

• GA-based optimal coefficients for each site to anticipate PV and battery capacity • Demonstrated by analysis and comparison with traditional models

[41]

Benatiallah et al.

Wind energy

• GA-based ideal size of a wind power system • Cost-effective system component sizing for local needs

[42]

Heyrman and Dupré

PV/wind energy

• At the lowest total cost, more robust and efficient systems were built. • Defined optimal size and cost

[43]

Sopian et al.

PV/wind energy

• GA was used to identify the size of hybrid energy system. • Hybrid energy systems are the most cost-effective and dependable approach.

[44]

Ramoji

PV/wind energy

• The optimization method created the right component sizes for the RE source. (Continued)

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134  Clean and Renewable Energy Production

Table 5.1  Work preview of the existing studies. (Continued) Reference

Authors

Energy source

Findings

[45]

Borhanazad et al.

PV/wind energy

• Provided the most dependable load profile solution • The proposed algorithm was employed to get accurate results.

[46]

Lotfi et al.

PV/wind energy

• Analyzed the system using yearly cost function, substitution, operation, repair, and annual revenue

[47]

Tafreshi et al.

PV/wind energy

• Determined the optimal size and design of a grid-connected hybrid PV/WT • Reduced system costs while maintaining excellent system dependability

[48]

Menniti et al.

PV/wind energy

• Improved global optimum searching ability • Comparative cost of a hybrid WT/PV system

[49]

Bansal et al.

PV/wind energy

• PSO surpassed GA in convergence to the optimum global solution, speed, accuracy, and computing complexity. • PSO can handle hybrid systems of optimum size with good outcomes.

[50]

Kaviani et al.

PV/wind energy

• Solved power costs and compared system planning numerical findings • Optimum dispatch problem revealed that the proposed modifications were better than the old system.

PV, photovoltaic; WT, wind turbine; RE, renewable energy; HES, hybrid energy system; GA, genetic algorithm; PSO, particle swarm optimization; WG, wind power generation

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Wind and Solar PV-Based Power Generation  135

• Increased energy efficiency: The hybrid system can make use of the most efficient energy source for a given weather or time of day, thus increasing energy efficiency and reducing energy losses. • Enhanced energy storage: A hybrid system can incorporate energy storage technologies such as batteries or thermal storage, which can help to smooth out fluctuations in energy production and provide power during periods of low renewable energy generation. • Cost-effectiveness: Hybrid systems can be more cost-­ effective than stand-alone renewable energy systems, as they can make use of smaller and less expensive equipment while providing a more reliable and efficient source of power [53]. • Flexibility: Hybrid systems can be customized to suit specific energy needs and site conditions, making them more adaptable to different locations and contexts.

5.7.2 Cons of the Hybrid Renewable Energy System • Complexity: Hybrid systems can be more complex to design, install, and maintain than stand-alone systems, which can add to costs. • Intermittency: Both wind and solar power are intermittent energy sources, meaning that their production can be affected by weather conditions. • Dependence on technology: The performance of a hybrid wind/PV system may be affected by the type and quality of the technology used. • Cost: The initial cost of installing and maintaining a hybrid wind/PV system may be higher than that of a single-source system. • Land use: Hybrid systems can be relatively large and require a significant amount of land, which may not be available or may be in high demand for other uses. Overall, a hybrid wind/PV system can provide a more reliable and efficient source of renewable energy, but it also comes with some challenges such as complexity, cost, and land use. Careful consideration of these factors is important when assessing the potential of a hybrid wind/ PV system.

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136  Clean and Renewable Energy Production

5.8 Conclusion Since the increasing depletion of conventional sources of energy, scholars have been asked to do substantial research on new, more efficient, and green power plants using advanced technology. There is growing interest in alternative energy and clean fuel technologies throughout the world because of environmental concerns. Biomass and solar power are only a few of the sources of renewable energy that may be converted into electricity and sent into the utility grid directly or to isolated loads. There is a wide disparity in how electricity is distributed between nations and within countries. This disparity is more pronounced in underdeveloped nations than in developed ones. • For example, just 27% of Ethiopia’s 105.57 million people have the opportunity to use electricity. Most of these people reside in rural areas, where power availability is less than 5%. • Low coverage and an unbalanced distribution are present here, necessitating further scrutiny to narrow the apparent gap. • This survey article summarized the benefits and drawbacks of wind and solar energy in balancing the electricity demand, and several studies were cited and examined. • Sizing and optimizing all of the system’s components is critical for obtaining enough energy at a reasonable cost throughout the system’s life span. • This section discusses the various components of a wind and solar hybrid renewable energy system in depth. With those parameters affecting energy consumption in mind, the net current cost (original or capital expenditures, replacement costs of system components, annual operation and maintenance expenses, and cost for diesel generators) was examined. Finally, simulation tools based on user-supplied raw input data are built for simulation, optimization, and sensitivity analysis.

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Wind and Solar PV-Based Power Generation  137

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Wind and Solar PV-Based Power Generation  141

A Systematic Review of the Last Decade for Advances in Photosynthetic Microbial Fuel Cells with Bioelectricity Generation Vijay Parthasarthy1*, Riya Bhattacharya2, Roshan K. R.3, Shankar R.3, Siddhant Srivastava4 and Debajyoti Bose2† Department of Examinations, Dr. Vishwanath Karad MIT World Peace University, Pune, Maharastra, India 2 School of Technology, Woxsen University, Hyderabad, Telangana, India 3 Department of Chemical Engineering, School of Engineering, University of Petroleum and Energy Studies, Energy Acres, Bidholi, Dehradun, India 4 Faculty of Applied Sciences & Biotechnology, School of Biotechnology, Shoolini University of Biotechnology & Management Sciences, Solan, Himachal Pradesh, India

1

Abstract

Microbial fuel cells are an emerging field in which microorganisms are used to generate energy from trash. Plants’ photosynthetic ability is used in a subset of microbial fuel cells to cultivate microorganisms. Various types of microbial fuel cells have been tested over the last two decades to cleanse wastewater while also producing bioelectricity. This paper presents a comprehensive overview of the topic of bioelectricity from bacteria, highlighting the most recent developments and advancements in photosynthetic microbial fuel cells. The review begins with keywords that have been chosen, which were narrowed down to the topic of interest. An examination of the contributions of various countries, universities, and publications that are engaged in this topic of research is also offered. This study conducted a critical analysis of the systematically selected literature. After early studies, lateral literature inclusion was accomplished by snowballing using forward and backward search. An attempt has been made to identify the gaps and areas for improvement in this new field of waste energy recovery. Keywords:  Microbial fuel cells, microbes, photosynthetic, bioelectricity, energy *Corresponding author: [email protected] † Corresponding author: [email protected] Surajit Mondal, Adesh Kumar, Rupendra Kumar Pachauri, Amit Kumar Mondal, Vishal Kumar Singh and Amit Kumar Sharma (eds.) Clean and Renewable Energy Production, (143–174) © 2024 Scrivener Publishing LLC

143

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6

6.1 Introduction Various forms of microbial fuel cells have been researched for treating real wastewater and producing power at the same time over the last two decades [1]. Organic waste recycling is important not only in underdeveloped countries but also in developed countries. A global energy crisis is currently occurring as a result of huge energy needs and limited financial resources. Non-renewable energy sources are running out, and renewable energy sources are underutilized [2]. An instant backup strategy is required for energy generation. The use of energy extends back to the dawn of civilization [3]. The Industrial Revolution ushered in a move away from fossil fuels as a source of energy. The need for non-renewable energy sources increased dramatically as the world’s population doubled [4]. This set off a cascade of events that impacted every aspect of the ecology. The United Nations General Assembly created Sustainable Development Goal 7 (SDG 7) or Global Goal 7 in 2015, with five aims to be met by 2030 [5]. Universal access to modern energy; raising the worldwide percentage of renewable energy; doubling energy efficiency; boosting access to clean energy research, technology, and investments; and expanding and upgrading energy services for developing nations are among the objectives. SDG 7 aims to increase the proportion of renewable energy in the global energy mix while also making it easier for all nations to obtain affordable and clean energy [6]. Microbial fuel cells (MFCs) have seen great growth in research and development in recent years, which fits the goals set by SDG 7. One of the cleanest ways of creating energy is to use microbes to transform the synthesis energy of organic molecules into electricity, which also helps with wastewater treatment [7]. Chemical energy in the biomass that surrounds us can be utilized in the presence of biological catalysts such as enzymes and bacteria. Many scientists have begun to study the ability of microbes to generate electrical energy in biological systems [8]. The conversion of chemical energy to electrical energy has been known since the 18th century, when Volta, the creator of the voltaic pile, was a contemporary of Luigi Galvani, who first detected animal electrical energy [9]. The chemical energy available in the biomass that surrounds us can be utilized in the presence of biological catalysts such as enzymes and bacteria. Many scientists have begun to study the ability of microbes to generate energy in biological systems. Potter [10, 11] discovered in 1911 that, using glucose as a substrate and Pt as an electrode, Saccharomyces cerevisiae could create a maximum voltage of 0.3–0.5 V. In comparison to classical fuel cells, which produce 103–105 times greater current, MFCs lag behind. In recent years, MFC with wastewater treatment using various

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144  Clean and Renewable Energy Production

types of organic waste materials has attracted greater attention [12]. There are a lot of industrial wastes that are hard to get rid of [13]. Insecticides, dyes, polyalcohols, and heterocyclic compounds are examples of these substances. These toxins pose a threat to the ecosystem and natural habitats when released into the environment [14]. MFCs, which use microbes to recover energy, have only recently acquired popularity. Biochemical procedures have gotten a lot of attention in recent years because of their environment-­friendly approach and utilization of wastewater resources [15, 16]. MFCs are bioelectrochemical systems that can be used to obtain energy from wastewater while also reducing pollution levels in the process [17]. These systems can also be modified to produce hydrogen [18]. Rather than being an energy waste, these systems can take advantage of the organic load in the wastewater to assist bioremediation processes and generate electricity. MFC research based on the oxidation of organic matter has been conducted for than a century, with the goal of producing electricity with enough room for alternative energy [18]. The energy utilization study is largely concerned with obtaining energy from existing resources, such as creating electricity through the combustion of fossil fuels and renewable energy sources, as well as recovering and reusing energy that would otherwise be squandered. Energy use is often the greatest energy expense for wastewater treatment operations, and savings can have a substantial impact on ecological, financial, and social issues. These effluents have been found to have detrimental consequences on biological communities and humans at the national and global scale [19]. Energy production has the most numerous techniques for creating energy from conventional and unconventional sources today; nevertheless, considering the growing load of carbon emissions from burning fossil fuels, it is worth looking into non-combustion energy production sources. MFCs can help with this by generating bioelectric energy from contaminated water streams through degrading the complex chemicals present [20]. The goal of this paper was to provide readers with a comprehensive assessment of the literature on photosynthetic MFCs for bioelectricity generation. The approach utilized in searching the literature, comparison of primary and secondary literature sources, identification of the research, and, ultimately, the scope of improvement in this field of study will be discussed in the following sections.

6.2 Background Sewage produces a large volume of wastewater, and treating this wastewater requires a huge amount of energy. As a result, costly chemicals are

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Photosynthetic MFC with Bioelectricity Generation  145

required to clean wastewater before it can be discharged at a tolerable level for the environment [21]. MFCs are a form of fuel cell that generates power from wastewater from homes and businesses. They can assist with standards for both fuel efficiency and power generation. These technologies are critical to a sustainable future that can generate electricity from non-fossil fuels while simultaneously cleaning wastewater [22, 23]. MFCs use bacterial metabolism to generate power. The bacteria in wastewater use chemical pollution as a source of electrons, which are subsequently delivered to one electrode (anode) within the MFC, where the process is completed at another electrode (cathode) [24]. When contemplating chemical treatment, the environment and the ease with which wastewater can be treated must be considered. Furthermore, chemical processes are the opposite of what is now being invested in, given the overwhelming focus on lowering carbon emissions and investing in combustion-free technologies [25]. Figure 6.1 depicts the main elements of a MFC: wastewater is charged into the anode, where bacteria grow and colonize; the organic content in the wastewater is oxidized; and the electrons are released into the anode [26]. To enhance the dissolved oxygen for the triphasic reactions of electrons, protons, and oxygen at the terminal, the cathode could be air-sparged. Since the last century, people have been looking for clean, renewable energy. Photosynthetic organisms produce a variety of energy-producing compounds, including biofuel and

e-

e-

RESISTOR

ee-

e-

Clear water with conductive solution

eOraganics-rich wastewater

e-

Membrane

O2 e-

Microbes and biofilm formation

H+

H+ H2O

Anode

Cathode

Figure 6.1  Schematic representation of a double-chambered microbial fuel cell [25].

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146  Clean and Renewable Energy Production

bioelectricity, which can be extracted via a variety of methods. MFCs are energy converters that use the anaerobic respiration of microorganisms to transform organic matter directly into electricity. In addition to treatment, waste/wastewater represents a possible renewable feedstock for generating various forms of bioenergy by managing the biological process. Bioenergy has attracted a lot of attention as a viable and long-term alternative to fossil fuels. Waste treatment as bioenergy has sparked tremendous interest and opened a new channel for the utilization of renewable and non-renewable energy sources [27]. Venkata Mohan [28] evaluated possible value-adding paths from waste treatment while also embracing current research. In the context of waste/wastewater treatment, biohydrogen, bioelectricity, algaebased biodiesel, and bioplastics were highlighted. Previously, the uses of MFCs were limited to bioelectricity production, but they are now finding use in a variety of fields. Wastewater is filled at the anode chamber, and a conductive solution, usually phosphatebuffered saline (PBS), is filled at the cathode chamber to use the cathode surface as a meeting point for the oxygen, proton, and electron. Bioelectrochemically assisted microbial reactors (BEAMRs) or MFCs that have been altered can be utilized to create biohydrogen production from any organic material that is biodegradable [29]. With sediment MFCs breaking away organic matter from the silt/organic matter inside the microbial reactors, the possibilities of providing power in an inaccessible place, which is generally limited by battery life, can be stretched out [30]. Bioremediation is an intriguing option with MFC advancements because it is commonly utilized for both synthetic compound oxidation at the anode (natural toxin oxidation) and synthetic compound reduction at the cathode (inorganics like nitrates and phosphates) [31]. MFCs are bioelectrochemical devices that use bioelectronic microorganisms to produce bioelectricity from a variety of substrates, with a particular emphasis on supplying energy to small devices while also serving as a renewable energy source [32]. Based on bioelectrochemistry, Fourier transform infrared (FT-IR) spectroscopy, and SEM illumination, Qi et al. [33] demonstrated that the MFC framework with IR and poly(lactic) acid (PLA) could provide supported bioelectricity and achieve anaerobic biodegradation of PLA materials [34]. An anoxygenic phototrophic bacteria (APB) consortium can be improved using the MFC with IR illumination, according to a microbial local area structure examination [35]. Furthermore, the presence of IR light could not only predict green growth development in the MFC framework but also make the functional designing application more feasible. Water demand has risen dramatically as a result of rapid urbanization and

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Photosynthetic MFC with Bioelectricity Generation  147

industrialization [36]. Membrane filtration, ion exchange, photochemical oxidation, nanotechnologies, and a variety of other physicochemical processes can all be used to treat dyes. According to Bhardwaj and Bharadvaja [37], algal cells are important raw materials for a variety of industries, including biofuels, microalgal biochars, nutrients, MFCs for bioelectricity, and phyconanoparticles for environmental and medical uses.

6.3 Methodology Most researchers, as can be seen from our review, search databases using specific keywords to find existing materials. Electricity generated by microorganisms is finding a new home as the field of alternative energy sources expands tremendously [38, 39]. The number of articles expanded quickly as academics began to investigate the viability and feasibility of bioelectricity generation. Those who want to begin their research career in this discipline should conduct a literature review to learn about the current trends and methods. The methodology used in this paper narrows down the issue of “photosynthetic microbial fuel cells for bioelectricity generation” from wastewater-derived generic MFCs. The procedure used for the study will be explained in the following sections [39].

Search Strategy The goal of this study was to compile all primary research on bioelectricity generation utilizing photosynthetic MFCs [40]. It is critical to have a well-developed approach for conducting literature searches in order to achieve high precision. This section discusses the search strategy for the reviews, including the search scope (publication time, zone, etc.), search method (manual and automatic), and search string [40].

Search Scope There are four dimensions of search scope in this systematic literature review: publication period, publication databases, zones, and institutes. Because this field of research is still in its infancy, this study only looked at the last 26  years of publications. Although fuel cell research has been expanding since 1999, the starting date chosen was January 1995. The articles published after March 2022 were not included in this study because it lasted until March 2022. Scopus, Web of Science, ScienceDirect, and Taylor & Francis (T&F) were used to conduct the search. We were able to identify

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148  Clean and Renewable Energy Production

the countries and institutes focusing on this study topic based on our preliminary observations.

Search Method In this study, we employed an automated literature search to conduct a systematic review. The scanning of selected keywords in electronic databases is referred to as automatic search. This automatic scan procedure was applied for each publisher. After the previous narrowing process, it was discovered that the number of types of literature is far too small. As a result, the study was enriched by adding a few types of literature utilizing manual search and snowballing (both forward and backward).

Search String The Boolean operation (“AND”) was used to discover literature linked to photosynthetic MFCs for bioelectricity generation. Keywords were utilized. We started with a broad concept and narrowed it down to a more particular one. Figure 6.2 depicts the final search string for all databases: “Bioelectricity” AND “Fuel” AND “Cell” AND “microbial” AND “photosynthetic”. The figure depicts a simplified diagram of the search and selection strategy process. The process began with a keyword search that was carried out automatically. Then, if there were any duplicate studies, they were deleted. Following that, research was chosen based on the inclusion and exclusion criteria. Snowballing of literature was done as the quantity of studies decreased. Finally, a list of all relevant publications was compiled for our investigation.

6.4 Study Selection Criteria The data for all the studies were gathered for the systematic literature review from major databases such as Web of Science, Scopus, T&F, and ScienceDirect. The selection criteria were applied to all fields first, followed by the title, abstract, and keywords. The overall number of studies was cut in half, from 1,231 to merely 8. The process for including and excluding papers in this study is depicted in Figure 6.3. We deduced from pool 2 that the number of articles has been steadily increasing since 2013, as shown in Figure 6.3a. In addition, we discovered that China, the United States, and India are the top three countries researching on photosynthetic MFCs for bioelectricity

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Photosynthetic MFC with Bioelectricity Generation  149

Start

Performing Automated Search

Using selected keywords

Removing duplicate Studies

Snowballing

Selecting Primary Studies

Primary Studies

Using inclusion and exclusion criteria

End

Figure 6.2  Schematic diagram of the search and selection strategy.

generation (based on publications). The number of publications based on different document formats is shown in Figure 6.3b.

6.5 Configurations and Performance Evaluation of Photosynthetic Microbial Fuel Cells To allow plant microbial fuel cells (p-MFCs) to reach the industrial conclave, evaluations are required to further optimize the performance of such reactors. This is done with different configurations, as shown in Figure 6.4. The primary aim is to address the limiting factors owing to thermodynamic and mass transfer limitations. Studies have shown that this system suffers from poor kinetics from electroactive bacteria with low electron transfer mechanism from the cells. This performance is attributed to the

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150  Clean and Renewable Energy Production

(a) Scopus

WoS

Science Direct

T&F

All studies 1832

Removing duplicates

Filter 1: Checking all searchable fields (titles, abstract, keywords, and any other searchable terms)

100 50

400 200 0

2 0 2 0 0 8 1 2 0 0 1 2 2 0 1 2 4 0 1 2 6 0 2 1 0 8 2 2 0 0 2 2

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Pool 2: 155 studies

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R ew evi

Filter 2: Checking titles, abstract, and keywords

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A cle rti

Pool 1: 1231 studies

# of Publications

(b) # of Publications

113 duplicate studies were removed

488 duplicate studies were removed

Filter 3: Checking only in titles

Pool 3: 23 studies

Excluded14 duplicate studies

Included 09 studies

11 studies were added

Snowballing

Total Primary studies 20 papers

Figure 6.3  (a) Criteria for selecting relevant documents with plant microbial fuel cell (p-MFC) studies. (b) Publications in the domain of bioelectricity from p-MFC and its increasing trend, including the current year of 2022.

complex underwater conditions for biofilm growth along with substrate flux to the electrode. For most p-MFCs, sustainable performance and stable operations remain a challenge as the bioelectricity production is low. However, if the output is stabilized, supercapacitors for low-power electronics can be used, such as sensors or remote power systems. By testing different reactor configurations, studies have shown that bioelectricity production can be improved by changing the electrode material and the distance between the electrodes and allowing heterotrophic microbial growth on the cathode; through various arrangement mechanisms, stability is possible. Additionally, as a component of such reactor is light-dependent

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Photosynthetic MFC with Bioelectricity Generation  151

(a)

(b)

R

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+

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Electro-catalyst Molecular hydrogen

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Figure 6.4  Different configurations of photosynthetic microbial fuel cell mechanism. (a) Photosynthetic bacteria at the anode with artificial mediators. (b) Hydrogengenerating photosynthetic bacteria with an electrocatalytic anode. (c) Synergism between phototrophic microorganisms and mixed heterotrophic bacteria in sediments. (d) Synergism between plants and mixed heterotrophic bacteria in sediments. (e) Ex situ photosynthesis coupled with mixed heterotrophic bacteria at a dark anode. (f) Direct electron transfer between photosynthetic bacteria and electrodes. (g) Photosynthesis at the cathode to provide oxygen. However, the combinations are not limited to the abovementioned configurations.

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152  Clean and Renewable Energy Production

photosynthetic process, microbial reactors of such nature are significantly affected by the external environment. Figure 6.4a shows the dark phase setup of MFC with the microbe’s cyanobacterial species of Anabaena and Synechocystis in the presence of 2-hydroxy-1,4-naphthoquinone (HNQ), an artificial redox mediator, and glucose as the carbon source for the microorganism, which will produce more power in the dark phase because the oxygen produced in the light phase due to the intracellular carbon source was refueled in the cells [42– 44]. Figure 6.4b shows the setup where the platinum catalyst was used on the cathode to receive hydrogen ions that are generated by the microorganisms present in the MFC in this setup, and it was also determined that this setup generates 3 W/m3 power. This setup is currently under investigation for manufacturing at the industrial level [45–47]. In a symbiotic relationship, the bacteria obtain refuge in plant roots, divide there, and fix nitrogen in the environment, which can be used in a configuration shown in Figure 6.4c to generate renewable electricity [48–50]. Plants are widely known for producing organic matter and releasing it into the soil, where microorganisms such as Rhizobium use it and thrive. This heterotrophic–plant in situ relationship is shown in Figure 6.4d. The study found that using the Glyceria maxima plant in photosynthetic MFC will generate 67 mW/m2 power [51]. Figure 6.4e further illustrates this point, i.e., ex situ p-MFC systems require separate photobioreactors for optimal algal growth (no shadowing by electrode material) and less complicated dark MFC systems for optimal energy generation. Feeding complex organic matter (i.e., algal cells) to a mixed heterotrophic bacterial community in an MFC has limitations due to the low coulombic efficiency (2.8%). Carboxylic acids obtain substantially better efficiency in the MFC than complicated compounds [52–54]. It has been debated for a long time whether direct electron transfer (DET) from bacteria to the anode is possible or not; however, it has been recently discovered that DET is possible in MFCs, with microbes using nanowires for DET, as shown in Figure 6.4f. Microbial species such as Synechocystis sp. PCC 6803, Cyanobacteria, were found to use nanowires for DET. Bicarbonate reduction was demonstrated in the MFC in the presence of light in the DET process, with the organic material present, and this was achieved by autotrophic microorganisms [55–57]. P-MFCs can generate oxygen by providing aeration to the MFC system with the use of microorganisms. Evaluations have used algae in the MFC to achieve this, and algae are much more capable of generating electricity in the MFC than bacteria because the metabolism of bacterial species is much lower than that of algal species. Chlorella vulgaris was used to generate electricity in the setup shown in Figure 6.4g, which helped improve system

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Photosynthetic MFC with Bioelectricity Generation  153

Table 6.1  Review of the preliminary studies for this work.

S. no.

Year

Novelty

Inferences

Country

Reference

1

2010

The less frequent direct electron transfer mechanism was highlighted, with emphasis on areas that need to be further explored.

Various biological methods used to harvest light energy were discussed.

USA

[41]

2

2014

Usage of algal biomass for bioelectricity production and other value-added products such as astaxanthin and β-carotene.

The electrodes used were plain graphite: anode, enriched bacteria consortium; cathode, C. vulgaris under two different light intensities (LI) and nitrogen starvation in culture medium.

Portugal

[61]

3

2017

13+ days continuous supply of higher current density.

Co-culture at anode (Shewanella oneidensis and Synechocystis). Cathode was supplied with cyanate solution. The electrodes used were 10 nm gold on polymethylacrylate and Nafion 117.

USA

[62]

4

2017

A few applications such as biohydrogen production, BOD sensing, and powering underwater monitoring devices were also discussed.

Various methods of harvesting light energy and the ways in which they can be attached to the catalyst were discussed.

India

[63]

(Continued)

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154  Clean and Renewable Energy Production

Table 6.1  Review of the preliminary studies for this work. (Continued) S. no.

Year

Novelty

Inferences

Country

Reference

5

2018

An innovative method to biodegrade PLA textiles and produce bioelectricity.

Anaerobic degradation of PLA textiles for biodegradation in a dual- chamber MFC using hybrid anoxygenic photosynthetic bacteria. The electrodes used were carbon felt with stainless steel wire.

China

[64]

9

2021

The ability of different plant species and soil conditioners to influence the bioelectricity generation in a plant-based p-MFC was tested, with the underlying microbial interaction studied.

A plant-based p-MFC was constructed to study the effect of different waterlogged agricultural plant species (paddy and water bamboo) and different kinds of soil conditioners (compost and biochar) on bioelectricity generation. The electrodes were made from carbon felt, while the electrolyte was a mixture of soil and tap water.

Taiwan

[65]

10

2021

The study includes observations relating to the prospective advantages of p-MFCs in various fields, such as biosensing, bioremediation, and water quality monitoring.

The authors conducted a comprehensive study on the literature pertaining to plant-based MFCs using the keywords “plant microbial fuel cell,” “treated wetland microbial fuel cell,” “CW-MFC,” “constructed wetland microbial fuel cell,” “wetland microbial fuel cell,” and “floating treatment wetlands plant microbial fuel cell.”

India

[66]

(Continued)

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Photosynthetic MFC with Bioelectricity Generation  155

Table 6.1  Review of the preliminary studies for this work. (Continued) S. no.

Year

Novelty

Inferences

Country

Reference

11

2021

The author discussed the effectiveness of stress- and disease-resistant variety of plants and plants with a well-developed rhizodermal system.

A study on the performance of p-MFCs in various types of wetlands based on the changes in the microbiome due to environmental factors was included. The feasibility of integrating p-MFCs into agricultural fields on a continuous basis was analyzed.

Ukraine

[67]

p-MFC, plant microbial fuel cell; BOD, biological oxygen demand; PLA, poly(lactic) acid

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156  Clean and Renewable Energy Production

performance. The presence of light during the day will run the light cycle of photosynthesis in the algae, which creates oxygen in the MFC; however, in the dark, the photosynthetic dark cycle will run, and no oxygen will be produced in this cycle [58–60]. Table 6.1 provides an overview of the preliminary investigations, which applied major articles in the field in the last decade and the advances included.

6.5.1 Algal-Based p-MFC MFCs based on microalgae have shown good performance for the removal of nitrogen, phosphorous, and carbon dioxide from wastewater streams, along with bioelectricity production and waste valorization. Microalgae can be integrated with MFCs as part of the cathode system or in configurations that allow carbon capture. These reactors have low carbon emissions from the dissolved gases and have sufficient nitrogen and phosphorus removal for power generation. The presence of microalgae further reduces the need for oxygen for cathodic reactions in double-chambered systems, which, in general, require aeration. Gouveia et al. [61] employed plain graphite as electrodes for bioelectricity production using photosynthetic algal MFC. With two distinct light intensities, they used an enriched consortium of bacteria at the anode and C. vulgaris at the cathode. They also investigated the effect of nitrogen shortage in the culture media on pigment formation in the culture [61]. They proposed a synergistic relationship between the phototrophic microbes at the cathode and the heterotrophic bacteria at the anode. However, only a few researchers have carried out these photosynthetic processes at the cathode [64, 68]. In addition to the authors in [64] and [68] were able to show, the authors discussed the impact of pigment growth in the cathode chamber. They were able to show that the overall cell performance could be maintained under food deprivation for a longer period, as opposed to Arachchige Don and Babel [70], who found that the performance decreased after 8 days. In an evaluation with kitchen wastewater (KWW), for electrodes, Mohamed et al. [68] employed graphite plates, and the proton exchange membrane (PEM) used Nafion 117. The cathodic chamber was filled with BG-11 medium containing Synechococcus and Chlorococcum, while the anodic chamber was filled with KWW and swirled at 200 rpm with a magnetic stirrer. While the anodic chamber was kept anaerobic, the cathodic chamber was left open to the atmosphere. The CO2 created in the anode was used in the cathode to boost voltage, and the cathodic chamber was lit at various light intensity (LI) levels (800 and 1,600 lx). For plotting the polarization curve with regard to the previously specified parameters, the MFC’s performance in terms of cell voltage, current density, and power density

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Photosynthetic MFC with Bioelectricity Generation  157

External Resistance

External Resistance

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Bacteria PLA TEXTILE

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Wastewater Fe(Cn)6]3-

Fe(Cn)6]4-

Bacteria PLA TEXTILE

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External Resistance

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Anloyte

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e-

H+

H+

H+

Wastewater Fe(Cn)6]3-

Fe(Cn)6]4-

Bacteria PLA TEXTILE Outlet

Cathode

H+ H+ H+ H+

Outlet

Fe(Cn)6]3-

Fe(Cn)6]4-

H+ Anode

PEM

Outlet Cathode

C4

Figure 6.5  Experimental schematic diagram for a photosynthetic microbial fuel cell (MFC) device as conducted by Qi et al. [64].

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was measured. The concentrations of Chlorococcum and Synechococcus cells were also measured using a UV spectrophotometer on a regular basis. The development patterns of both algae under consideration were studied, and the scope of bioelectricity generation was tested using cyclic voltammetry and electrochemical impedance spectroscopy. The authors also varied the chemical oxygen demand (COD) of KWW (2,500 and 5,000 mg COD/L) to investigate the effect of organic load on bioelectricity production. They discovered that, as the said parameter was increased, bioelectricity production and the degradation efficiency of the organic content present in the anolyte both decreased, possibly due to substrate inhibition. In a study by Qi et al. [64], the MFC reactor has a dual chamber with a 125-ml working volume connected by a PEM and made electrodes from carbon felt with stainless steel wiring. The same is shown in Figure 6.5. The cathode chamber contained a mixture of potassium ferricyanide, K3[Fe(CN)6], and potassium dihydrogen phosphate, KH2PO4, while the anode chamber contained hybrid APB mixed with gelatin wastewater, PLA textiles, and certain critical micronutrients. The experiment was carried out for four distinct configurations. The lighting agent, gelatin wastewater, and PLA textiles were used in the C1 configuration, but the illumination agent was removed in the C2 configuration and gelatin wastewater was not used in the C3 configuration. Finally, there were no APB in the C4 arrangement. PLA textiles were photodegraded using anoxygenic photosynthesis and a depolymerization enzyme released by the APB in response to the presence of gelatin effluent. The enzyme broke down the intramolecular ester bonds in the PLA textiles, forming oligomers, dimers, and monomers, which can be used as carbon sources for APB. One evaluation by Liu and Choi [62] used a co-culture of photosynthetic and heterotrophic bacteria at the anode to create a self-sustaining micro-sized MFC. The electrodes were made by depositing 10  nm gold on polymethyl methacrylate substrates, with chromium as an adhesive layer and Nafion 117 as a PEM. The anodic chamber was initially loaded with Shewanella oneidensis in BG-11 medium, and when the heterotrophic bacteria developed a stable biofilm, the phototrophic bacterium Synechocystis was added. The cathodic chamber was exposed to air to act as an electron acceptor, and potassium ferricyanide solution was added to the chamber. The supply of anolyte (BG-11 medium) was ceased once the creation of a cooperative stable biofilm between the heterotrophic bacteria and phototrophic microbes was demonstrated, allowing the MFC to attain self-sustainability. On the other hand, two more MFCs were set up as control experiments: one with S. oneidensis that was fed an organic load and another with Synechocystis that had its anolyte supply reduced at the same

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Photosynthetic MFC with Bioelectricity Generation  159

time. It was discovered that the control MFC with Synechocystis formed a photosynthetic biofilm on the anode surface at a slow rate, with few layers and low current generation when compared to the heterotrophic bacteria S. oneidensis, but the device was able to achieve self-sustainability for a short time. To overcome the possible limits of photosynthetic MFC, the authors employed the idea of synergism between the heterotrophs and autotrophs at the anode and were able to improve the MFC performance [69]. An interesting evaluation by Arachchige Don and Babel [70] built electrodes out of carbon fiber cloth with titanium wires as a core and the MFC out of acrylic plates with a 1-L working capacity in both chambers separated by a cation exchange membrane (CMI-7000). The anodic chamber was populated by a variety of microorganisms derived from anaerobic sludge, while the anolyte was synthetic wastewater with acetate as the principal carbon source. The anodic effluent from the previous batch of experiments with different hydraulic retention times (HRTs) was fed to the cathodic chamber, and the catholyte fed to the chamber was the anodic effluent from the previous batch of experiments with varying HRTs. HRT is a critical parameter that determines the efficacy of the waste treatment process; for example, a sample with a greater organic load (COD) requires a longer HRT to ensure that the treatment process is as efficient as possible. Arachchige Don and Babel [70] employed a COD value of 1,500 mg/L and HRTs of 10, 20, and 40 days, evenly split between the two chambers. The electrical performance of the photosynthetic MFC was investigated using a polarization test, as well as measurements of the cell voltage, current density, and power density over time. They also examined the treatment efficiency of the MFC by looking at the COD values and NH+ ion concentrations [71, 72]. The total dissolved oxygen content and the microalgal biomass concentration were used to evaluate the performance of C. vulgaris in the cathode chamber [73]. Enamala et al. [74] reviewed recent experiments and organized the findings into categories, such as the role of algae in MFCs, the role of heterotrophic bacteria and phototrophic algae during the current generation process, the various types of MFC reactor and cell designs, and the various types of algal MFC substrates. From 2007 to the present, the authors have provided a quick overview of the number of articles filed by countries that have actively participated in the themes of renewable energy, sustainability, environment, energy engineering, and power technology [74]. They also provided a detailed overview of the various challenges and factors to be considered during the construction of an MFC, as well as the parameters that influence the performance of algae in the MFC, the metabolic role it plays during the current generation process, and the interaction with bacteria and its effect

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on current generation if it is present [75, 76]. They mentioned microbial solar cells, microbial remediation cells, nontoxic substance testing, wastewater treatment, and biohydrogen production as examples of photosynthetic algal MFCs [77]. Chandra et al. [63] discussed different techniques of harvesting light energy, including chemical-based (PV cell), anoxygenic photosynthesis at the anode, photosynthesis at the anode using artificial mediators, and plant root-based MFC, among others [78, 79]. They also discussed ecologically engineered systems (EES), which are essentially MFCs for wetlands, with benefits such as the ability to create bioelectricity from active microbial metabolism in sediment beds when paired with sediment microbial fuel cell (SMFC) [80, 81]. Various light-harvesting proteins were also discussed, as well as the ways in which they can be connected to the catalyst [82, 83]. Also reviewed were numerous applications of MFCs in wastewater treatment, power supply to underwater devices, biological oxygen demand (BOD) detection, and biohydrogen production, as well as the role of light-harvesting proteins in the ability to transfer electrons and the potential gradient in MFCs [84].

6.5.2 Plant-Microbial Fuel Cells or P-MFCs P-MFCs have received a lot of attention in recent years as a technique to transform organic waste, such as low-strength wastewaters and lignocellulosic biomass, into electricity and bioremediate inorganic minerals [91]. Because MFCs can extract electric current from a wide range of soluble or dissolved complex organic wastes and renewable biomass, microbial electricity production could become an important source of bioenergy in the future. A wide range of substrates has been examined as a feed. As significant substrates, many types of artificial and actual wastewaters, as well as lignocellulosic biomass, have been employed [92]. Although the current and power yields are currently low, as the technology and knowledge about these unique systems improves, the amount of electric current (and electric power) that can be extracted from these systems is expected to skyrocket, providing a long-term solution for directly converting lignocellulosic biomass or wastewaters to useful energy [93]. Plants produce rhizodeposits, which are primarily sugars, which bacteria subsequently convert into electrical energy via fuel cells. Tongphanpharn et al. [65] detailed the building of a plant-based p-MFC in polyvinyl chloride (PVC) buckets with carbon felt as electrodes and an electrolyte made up of a mixture of soil and tap water that was refilled every day [85]. Agricultural plants, particularly waterlogged plants, have been proven to be capable of being employed in p-MFC with the anode

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Photosynthetic MFC with Bioelectricity Generation  161

buried in the soil and the cathode placed on the soil’s surface [65]. The soil in the flood plains for such plants will be in distinct redox zones, resulting in microscale chemical and electrochemical gradients that can be used to generate bioelectricity [66, 86]. The researchers looked at the influence of different waterlogged agricultural plants such as rice (Oryza sativa) and water bamboo (Zizania latifolia) on bioelectricity generation, as well as two distinct forms of soil conditioners, compost and biochar [91, 92]. A control experiment using a soil MFC was also set up. The experiment lasted 200 days in a controlled environment of 25°C and 75% humidity inside a lighting incubator that produced an average of 2,095 lx of light intensity, with cell voltage monitored at regular intervals. A bibliometric analysis of plant- and soil-based MFCs was undertaken by Prasad and Kalla [66]. From January 2008 to June 2021, the authors searched for “plant microbial fuel cell” or “treated wetland microbial fuel cell” or “CW-MFC” or “built wetland microbial fuel cell” or “wetland microbial fuel cell” or “floating treatment wetlands plant microbial fuel cell.” With the minimum number of occurrences was set to 10, and VO Viewer software was used to conduct an analysis of the keywords used in the received papers, yielding 39 relevant keywords and a concurrence analysis. They also performed a source-by-source analysis. The role of bacteria in several parts of a p-MFC, such as the anode, cathode, and electrolyte, was suggested by Rusyn [67]. A survey of all the literature on plant-based MFCs was used to conduct the research. A thorough investigation into the involvement of bacteria in soil and rhizodermal secretions was also conducted [86, 87]. There was also comparative research on the different types of plant traits and how they affect the photosynthetic process and the environment’s microbiome [88]. The observations were then tabulated by segregation, which included the type of plant, alterations to the plant, performance of the different species in various habitats, the microbiome associated with various environments, and how all these factors affected the electrogenesis efficiency [89, 90]. The maximum output of the p-MFC with reed mannagrass species was 67 mW/m2, and it can be implemented in wetlands and low soils without competing with food or conventional bioenergy production, making it a new bioenergy source. A potential power production of 21 GJ ha−1 year−1 (5,800  kWh  ha−1  year−1) was expected [94]. The electricity generation dynamics were detected before, during, and after the wet seasons, which were explained by paddy field management. Tubular p-MFCs, on the other hand, are viewed as more viable for large-scale applications since they do not require topsoil excavation. A maximum daily average density of 9.6 mW/m2 plant growth area was achieved with triple p-MFCs. Over

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the course of a crop season, 9.5–15 Wh/m2 power can be generated at an average of 0.4 0.1 mW/m tube [95]. Because of its ability to resist a saline climate, the plant specie Canana India was chosen. For various organic loadings, the mass balance of COD and total dissolved solids (TDS) was examined, and the results were compared to the removal efficiency and energy generation in laboratory-scale microcosms. The maximum cell voltages for constructed wetland microbial fuel cell (CW-MFC) with plant (CW-MFC-1) and CW-MFC without plant (CW-MFC-2) were 0.86 and 0.75 V, respectively, according to the data [96]. In this study, we showed that a chemical ferricyanide cathode may be replaced with a biological oxygen-reducing cathode in a p-MFC. Plants cultivated in chemical ferricyanide produced 679 mW/m2 [97]. In p-MFC systems, the soil pH was altered from slightly acidic to neutral during the operation, lowering the electrical conductivity. The efficacy of Cr(VI) removal in soils might reach 99%, and the total Cr in soils could be reduced as well [98].

6.6 Outlook After reviewing a variety of literature on the advances in the field of photosynthetic MFCs for bioelectricity, we agree with other authors that there is still a lot of room for development. The next section discusses the wide-ranging changes that must be made to improve the performance of p-MFCs. Different configurations have been tried to improve the efficiency of p-MFCs, as highlighted by Hindatu et al. [41], in contrast to Chandra et al. [63] who did not discuss the possibility of ex situ photosynthesis coupled with mixed heterogeneous bacteria at the anode and proposed that development with scale-up of photosynthetic algal MFCs under sunlight needs to be studied further as both the power output and pigment production are dependent on the light intensity [99, 100]. The production cost of p-MFC should be reduced, and its efficiency should be enhanced, to make scaling up feasible [101]. Because the theoretical potential of a fuel cell is only 1.2 V, the stacking of fuel cells in series or parallel must be increased to give actual power. To improve economic feasibility, more research on the critical end products like hydrogen or proteins is required [102]. Enamala et al. [74] emphasized the short duration of the trials (3  months) and proposed that they be conducted for a longer period of time (>12 months). They also advised decreasing the problem’s complexity by utilizing a single microbial culture rather than a mixed microbial culture. The MFC’s deactivation at low temperatures and low light intensities was also discussed. Arachchige Don and Babel [70] observed a reduction

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Photosynthetic MFC with Bioelectricity Generation  163

in power generation when scaling up a laboratory-sized model. As a result, they recommended that more pilot plant studies be conducted to investigate the viability of p-MFCs, so that the problems encountered when scaling up may be discovered and rectified, and the overall p-MFC efficiency can be improved [103]. Liu and Choi [62] reported a progressive drop in the overall performance of the cell containing both species after 6 days, perhaps lowering the voltage produced by the MFC due to nitrogen depletion in the electrolyte solution. Therefore, more research on the nitrogen cycle is needed to investigate the impacts of synergism in driving nitrogen between the autotrophic and heterotrophic phases, as well as the rate of nitrogen depletion as a result of long-term mobilization [104, 105]. The rate of the production of electricity and pigments is dependent on the intensity of sunlight received, as shown by Gouveia et al. [61] and Mohamed et al. [68], which in turn controls the rate of photosynthesis in the p-MFC under study. As a result, Gouveia et al. [61] suggested that it is critical to increase the research done in real sunlight conditions, which leads to the overall development of the p-MFC, as well as scale-up studies, which are required to produce a p-MFC that can be used in any practical application in the field of wastewater treatment and the rapid production of valuable value-added compounds from elements such as carbon, nitrogen, and phosphate [61]. Qi et al. [64] investigated a novel approach to dealing with white pollution before it could cause major environmental harm, namely, degrading the pollutants in an MFC using appropriate bacteria that can break down the pollutants. To maximize the degrading efficiency and bioelectricity generation, more research is needed to determine the optimal PLA textile concentration, electrode material, and external resistance. Tongphanpharn et al. [65] found that bioelectricity is dependent on the type of waterlogged agricultural plant and the soil conditioner employed. They also found that rice plants (O. sativa) with compost as a soil conditioner produced the most cell voltage. As a result, this study emphasized the necessity for more research into the many relationships between anodic microorganisms, the electrochemical gradient’s formation process, and the rhizodeposition of various plant roots. The output of bioelectricity created by the MFC was relatively low when compared to the input given to the cell, according to Prasad and Kalla [66]. They also stressed the need to improve the design efficiency by optimizing the operating conditions, electrode material, and reactor design [66]. The amount of research done in the topic of p-MFC has recently gained traction, with an exponential increase in the number of articles published each year. The ability of photosynthetic algae to generate products that are

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of high interest in fields such as biofuels, food, pharmaceuticals, and cosmetics, as well as the ability of heterogeneous microbes to degrade a variety of complex substrates into simpler chemicals, highlighted the importance of the rapidly developing p-MFC technology. For the technology to have any practical application in any industry, the loss in the overall performance of the cell must also be overcome when it is scaled up. P-MFCs provide a significant advantage in attaining the goals of the UN General Assembly. The technology is simple to adjust to local conditions and can be used in conjunction with other community activities. The proper development of MFC technology will aid in achieving the objectives in a shorter time frame.

Data Availability Statement Data will be available from the corresponding author on request.

Funding No funding was received for this work.

Conflict of Interest The authors declare that the research was conducted in the absence of any commercial or financial relationships that could be construed as a potential conflict of interest.

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59. Powell, E.E., Mapiour, M.L., Evitts, R.W., Hill, G.A., Growth kinetics of Chlorella vulgaris and its use as a cathodic half cell. Bioresour. Technol., 100, 269–274, 2009. 60. Strik, D.P., Hamelers, H.V., Buisman, C.J., Solar energy powered microbial fuel cell with a reversible bioelectrode. Environ. Sci. Technol., 44, 532–537, 2010. 61. Gouveia, L., Neves, C., Sebastião, D., Nobre, B.P., Matos, C.T., Effect of light on the production of bioelectricity and added-value microalgae biomass in a photosynthetic alga microbial fuel cell. Bioresour. Technol., 154, 171–177, February 2014. 62. Liu, L. and Choi, S., Self-sustaining, solar-driven bioelectricity generation in micro-sized microbial fuel cell using co-culture of heterotrophic and photosynthetic bacteria. J. Power Sources, 348, 138–144, April 2017. 63. Chandra, R., Venkata Mohan, S., Roberto, P.-S., Ritmann, B.E., Cornejo, R.A.S., Biophotovoltaics: Conversion of light energy to bioelectricity through photosynthetic microbial fuel cell technology, in: Microbial Fuel Cell, pp. 373–387, Springer International Publishing, India, December 2017. 64. Qi, X., Bo, Y., Ren, Y., Wang, X., The anaerobic biodegradation of poly(lactic) acid textiles in photosynthetic microbial fuel cells: Self-sustained bioelectricity generation. Polym. Degrad. Stab., 148, 42–49, February 2018. 65. Natagarn, T., Chung-Yu, G., Wei-Shan, C., Chao-Chin, C., Chang-Ping, Y., Evaluation of long-term performance of plant microbial fuel cells using agricultural plants under the controlled environment. Clean Technol. Environ. Policy, 25, 633–644, 2021. 66. Prasad, P.N. and Kalla, S., Plant-microbial fuel cells - a bibliometric analysis. Process Biochem., 111, 250–260, 2021. 67. Rusyn, I., Role of microbial community and plant species in performance of plant microbial fuel cells. Renewable Sustainable Energy Rev., 152, 111697, 2021. 68. Mohamed, S.N., Hiraman, P.A., Muthukumar, K., Jayabalan, T., Bioelectricity production from kitchen wastewater using microbial fuel cell with photosynthetic algal cathode. Bioresour. Technol., 295, 122226, January 2019. 69. Cheng, S., Liu, H., Logan, B.E., Increased performance of single-chamber microbial fuel cells using an improved cathode structure.  Electrochem. Commun., 8, 3, 489–494, 2006. 70. Yahampath Arachchige Don, C.D.Y. and Babel, S., Circulation of anodic effluent to the cathode chamber for subsequent treatment of wastewater in photosynthetic microbial fuel cell with generation of bioelectricity and algal biomass. Chemosphere, 278, 130455, 2021. 71. Aghababaie, M., Farhadian, M., Jeihanipour, A., Biria, D., Effective factors on the performance of microbial fuel cells in wastewater treatment–a review.  Environ. Technol. Rev., 4, 1, 71–89, 2015. 72. Chandrasekhar, K., Amulya, K., Mohan, S.V., Solid phase bio-electrofermentation of food waste to harvest value-added products associated with waste remediation. Waste Manage., 45, 57–65, 2015.

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73. Don, C.D.Y.A. and Babel, S., Effects of organic loading on bioelectricity and micro-algal biomass production in microbial fuel cells using synthetic wastewater. J. Water Process Eng., 39, 101699, 2021. 74. Enamala, M.K., Dixit, R., Tangellapally, A., Singh, M., Dinakarrao, S.M.P., Chavali, M., Pamanji, S.R., Ashokkumar, V., Kadier, A., Chandrasekhar, K., Photosynthetic microorganisms (algae) mediated bioelectricity generation in microbial fuel cell: Concise review. Environ. Technol. Innovation, 19, 100959, 2020. 75. Gupta, S., Srivastava, P., Patil, S.A., Yadav, A.K., A comprehensive review on emerging constructed wetland coupled microbial fuel cell technology: Potential applications and challenges. Bioresour. Technol., 320, 124376, 2021. 76. Do, M.H., Ngo, H.H., Guo, W.S., Liu, Y., Chang, S.W., Nguyen, D.D., Nghiem, L.D., Ni, B.J., Challenges in the application of microbial fuel cells to wastewater treatment and energy production: A mini review. Sci. Total Environ., 639, 910–920, 2018. 77. Arun, S., Sinharoy, A., Pakshirajan, K., Lens, P.N., Algae based microbial fuel cells for wastewater treatment and recovery of value-added products. Renewable Sustainable Energy Rev., 132, 110041, 2020. 78. Chandra, R., Venkata Mohan, S., Roberto, P.S., Ritmann, B.E., Cornejo, R.A.S., Biophotovoltaics: Conversion of light energy to bioelectricity through photosynthetic microbial fuel cell technology, in: Microbial Fuel Cell, pp. 373–387, Springer, Cham, 2018. 79. Kumar, K., Gunaseelan, K., Gajalakshmi, S., Insights into the role of bioinspiration, photosynthetic organisms, and biomass-derived electrodes/membranes in the development of bioelectrochemical systems. Sustain. Energy Technol. Assess., 48, 101570, 2021. 80. Shaikh, R., Rizvi, A., Quraishi, M., Pandit, S., Mathuriya, A.S., Gupta, P.K., Singh, J., Prasad, R., Bioelectricity production using plant-microbial fuel cell: Present state of art. S. Afr. J. Bot., 140, 393–408, 2021. 81. Vinh, M.N.T., Determination of forage grass capability for electricity production in plant microbial fuel cell, Doctoral dissertation, Thammasat University, Bangkok, Thailand, 2018. 82. Pullerits, T. and Sundström, V., Photosynthetic light-harvesting pigment– protein complexes: Toward understanding how and why. Acc. Chem. Res., 29, 8, 381–389, 1996. 83. Proppe, A.H., Li, Y.C., Aspuru-Guzik, A., Berlinguette, C.P., Chang, C.J., Cogdell, R., Doyle, A.G., Flick, J., Gabor, N.M., van Grondelle, R., HammesSchiffer, S., Bioinspiration in light harvesting and catalysis.  Nat. Rev. Mater., 5, 11, 828–846, 2020. 84. Pandit, S., Chandrasekhar, K., Kakarla, R., Kadier, A., Jeevitha, V., Basic principles of microbial fuel cell: Technical challenges and economic feasibility, in: Microbial Applications, vol. 1, pp. 165–188, Springer, Cham, 2017.

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85. Guan, C.-Y., Tseng, Y.-H., Tsang, D.C.W., Hu, A., Yu, C.-P., Wetland plant microbial fuel cells for remediation of hexavalent chromium contaminated soils and electricity production. J. Hazard. Mater., 365, 137–145, 2019. 86. Foster, R.C., The ultrastructure of the rhizoplane and rhizosphere.  Annu. Rev. Phytopathol., 24, 1, 211–234, 1986. 87. Compant, S., Cambon, M.C., Vacher, C., Mitter, B., Samad, A., Sessitsch, A., The plant endosphere world–bacterial life within plants.  Environ. Microbiol., 23, 4, 1812–1829, 2021. 88. Turner, T.R., James, E.K., Poole, P.S., The plant microbiome. Genome Biol., 14, 6, 1–10, 2013. 89. Manriquez, B., Muller, D., Prigent-Combaret, C., Experimental evolution in plant-microbe systems: A tool for deciphering the functioning and evolution of plant-associated microbial communities. Front. Microbiol., 12, 896, 2021. 90. Botta, C., Ferrocino, I., Pessione, A., Cocolin, L., Rantsiou, K., Spatiotemporal distribution of the environmental microbiota in food processing plants as impacted by cleaning and sanitizing procedures: The case of slaughterhouses and gaseous ozone. Appl. Environ. Microbiol., 86, 23, e01861–20, 2020. 91. Nawaz, A., Hafeez, A., Abbas, S.Z., Haq, I.U., Mukhtar, H., Rafatullah, M., A state of the art review on electron transfer mechanisms, characteristics, applications and recent advancements in microbial fuel cells technology. Green Chem. Lett. Rev., 13, 4, 365–381, 2020. 92. Kadier, A., Simayi, Y., Kalil, M.S., Abdeshahian, P., Hamid, A.A., A review of the substrates used in microbial electrolysis cells (MECs) for producing sustainable and clean hydrogen gas. . Renewable Energy, 71, 466–472, 2014. 93. Pant, D., Van Bogaert, G., Diels, L., Vanbroekhoven, K., A review of the substrates used in microbial fuel cells (MFCs) for sustainable energy production.  Bioresour. Technol., 101, 6, 1533–1543, 2010. 94. Strik, D.P., Hamelers, H.V.M., Snel, J.F., Buisman, C.J., Green electricity production with living plants and bacteria in a fuel cell.  Int. J. Energy Res., 32, 9, 870–876, 2008. 95. Sudirjo, E., De Jager, P., Buisman, C.J., Strik, D.P., Performance and long distance data acquisition via LoRa technology of a tubular plant microbial fuel cell located in a paddy field in West Kalimantan, Indonesia. Sensors, 19, 21, 4647, 2019. 96. Das, B., Thakur, S., Chaithanya, M.S., Biswas, P., Batch investigation of constructed wetland microbial fuel cell with reverse osmosis (RO) concentrate and wastewater mix as substrate.  Biomass Bioenergy, 122, 231–237, 2019. 97. Wetser, K., Sudirjo, E., Buisman, C.J., Strik, D.P., Electricity generation by a plant microbial fuel cell with an integrated oxygen reducing biocathode.  Appl. Energy, 137, 151–157, 2015. 98. Guan, C.Y., Tseng, Y.H., Tsang, D.C., Hu, A., Yu, C.P., Wetland plant microbial fuel cells for remediation of hexavalent chromium contaminated soils and electricity production. J. Hazard. Mater., 365, 137–145, 2019.

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Photosynthetic MFC with Bioelectricity Generation  173

Hydrothermal Liquefaction as a Sustainable Strategy for Integral Valorization of Agricultural Waste Manisha Jagadale1*, Mahesh Jadhav2, Nagesh Kumar T.1, Prateek Shrivastava1 and Niranjan Kumar1 ICAR-National Institute of Natural Fibre and Engineering Technology, Kolkata, (WB), India 2 Dr. Balasaheb Sawant Konkan Krishi Vidhyapeeth, Dapoli, (MH), India 1

Abstract

A possible thermochemical approach for turning biomass into useful goods or biofuel is the hydrothermal liquefaction (HTL) process. Depending on the specific temperature range, hydrothermal processes can be classified into carbonization, liquefaction, or gasification. The major products of HTL, which occurs at temperatures between 250 and 450 C and pressure between 5 and 35  MPa, are solvent organics known as bio-crude or bio-crude oil, an aqueous phase (with a high amount of organic carbon), and light gases. The yield and the quality of products depend on the process variables, which include the type of catalyst, temperature, pressure, pH, solid-to-liquid ratio, residence time, and type of biomass. The optimization of these parameters is crucial since they significantly affect the characteristics of the hydrothermal products and open up a range of opportunities for their use in diverse industries. This chapter covers the reaction mechanisms of the HTL process, the impact of the process variables, the properties of the liquid and solid products, and the different applications of the products. Furthermore, the challenges and limitation of the HTL process, along with the economic and environmental impacts of these techniques, are also presented. Keywords:  Hydrothermal liquefaction, sustainable conversion of biomass, agricultural waste, bio-oil, hydrochar

*Corresponding author: [email protected] Surajit Mondal, Adesh Kumar, Rupendra Kumar Pachauri, Amit Kumar Mondal, Vishal Kumar Singh and Amit Kumar Sharma (eds.) Clean and Renewable Energy Production, (175–200) © 2024 Scrivener Publishing LLC

175

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7

7.1 Introduction The increasing energy demand and diminishing fossil fuels called for the exploration of new alternative, clean, and renewable energy sources. It is estimated that the energy demand will increase by 35% in the next two decades [1]. On the other hand, increasing fuel costs and emissions of hazardous materials to the environment have initiated research on renewable biofuel production from lignocellulosic biomass [2]. The valorization of lignocellulosic biomass through the biorefinery approach is emerging as a potential area to capitalize the biomass into various industrial bio-­ products, including renewable resources. The major lignocellulosic biomass are generated from forest residue, agro residue, energy crops, and agroprocessed industrial waste [3]. Studies have shown that India alone produces 500 million tons of lignocellulose biomass every year from the agricultural sector [4]. The major sources of waste are cereal crops, oil crops, fiber crops, and pulses. Instead of using this biomass for resource recovery, farmers generally burn this residue in open fields to clear the land for the next season’s crops, which leads to the deterioration of soil and air quality [5]. This biomass has huge potential in biofuel production because of its abundance, low cost, and environmental friendliness. Therefore, it is essential to convert this biomass into biofuels as a suitable alternative to fossil fuel through thermochemical or biochemical routes. Presently, pyrolysis and hydrothermal liquefaction (HTL) are considered the main leading processes to convert lignocellulosic biomass into biofuels [6–8]. In comparison, the HTL process can efficiently convert lignocellulosic biomass into four different products and by-products, i.e., bio-oil, aqueous water, solid biochar, and gaseous phase, at the temperature range 250–450 C and high autothermal water pressure of 5–35  MPa with or without the addition of a catalyst [6, 9, 10]. The HT process provides two major advantages over other conversion processes: there is no requirement of drying the feedstock, which saves energy, and the beneficial properties of water at subcritical conditions, such as the high ionic product and lower dielectric constant [11]. This chapter highlights the basics of the different biomass conversion routes, generation of biofuels, reaction mechanisms of the HTL process, parameter effects on the product yield and distribution, technical and economic analysis of the HTL process, and the challenges and limitations of the HTL process.

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176  Clean and Renewable Energy Production

7.2 Generation of Biofuels

Figure 7.1  Different generations of biofuels.

• Algal biomass (macroalgae, microalgae) • Non-arable land can be used • Easy conversion • Waste, saline and nonportable water can be used

Fourth Generation

• Non-edible biomass (wood, straw, grass, waste) • Require arable land or forest • Need sophiticated downstream processing • Portable water required

Third Generation

• Edible biomass (Sugarcane, beet, wheat, corn) • Require arable land • Easy conversion • Portable water required

Second Generation

First Generation

Based on the type of feedstock, biofuels are classified into four generations; first, second, third, and fourth generation biofuels (Figure 7.1). In the first generation, edible biomass with starch (from potato, barley, wheat, or maize) or sugars (from sugarcane or beetroot) or edible oil (rapeseed, soybean, and palm) showed promising results for commercial production [12] and from the environmental aspect. Countries like the USA and Brazil are the world’s largest producers of first-generation fuels [13]. However, concerns on the production of these fuels arose due to the increase cost of production, the energy spent in cultivation, and food conflicts [12]. Commercial production of first-generation biofuels has negative impacts on greenhouse gas emissions, biodiversity, and land and water use [13]. All these issues have prompted researchers to explore new avenues for biofuel production. Second-generation biofuels generated from non-edible lignocellulosic biomass wastes are from agriculture, forest, and municipal wastes. The advantage of this biomass is that the net carbon emission is zero, there is abundant availability due to the high yield per area of land, inexpensive, can be produced with less land use, and there is no competition with food stuff [14]. However, the production cost is high due to the complex structure of biomass composed of lignin, hemicellulose, and cellulose, which are recalcitrant in nature so that

• Breakthrough (pyrolysis, solar to fuel, microalgae, gasification) • Non-arable land can be used • Easy conversion • Waste, saline and nonportable water can be used

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HTL as Strategy for Agricultural Waste Valorization  177

pretreatment is required. Third-generation biofuels are from algae and the fourth generation produced from genetically modified algae [12]. Thirdand fourth-generation biofuels have some limitations, i.e., high cost of production, less stability, and more volatility in nature at high temperature. Therefore, second-generation non-edible lignocellulosic biomass has become a fascinating solution to solve the issues of fossil fuel and environmental complications.

7.3 Biomass Conversion Routes The conversion of biomass into fuels and chemicals is generally done by four routes: biochemical, thermochemical conversion, mechanical process, and chemical reaction process. The details are shown in Figure 7.2. The output of the process varies based on the operating conditions, the technology used, and the type of feedstock. The biochemical conversion route involves pretreatment, hydrolysis, and fermentation to convert biomass into biofuel. In fermentation, the soluble sugars produced in earlier processes are converted into biofuels such as ethanol, butanol, biogas, and hydrogen. Thermochemical conversion of biomass can be accomplished using direct or indirect techniques. Direct combustion converts biomass into heat and electricity. Indirect processes including pyrolysis, HTL, and gasification produce bio-oil and synthesis gas (syngas, CO+H2). The syngas produced by this method can be converted into biofuel, such as ethanol.

Palletization: Solid fuels

Mechanical process

Gasification: Fuel gas, hydrogen Pyrolysis: Bio-oil, fuel gas, bio solids

Fermentation: Alcohols Thermochemical

Biomass

Liquefaction: Bio-oil, hydrochar, gas Direct combustion: Heat, electricity

Chemical reaction

Transesterification: Biodiesel

Figure 7.2  Main biomass conversion routes.

Biochemical

Anaerobic digestion: Methane, hydrogen

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The third conversion process involves chemical reactions that produce biodiesel through transesterification processes. The solid fuel for thermal power plants can be obtained by mechanical process routes [15, 16].

7.4 HTL Reaction Mechanism

Biomass

De

gra d

ati

on

HTL is a biomass to bioliquid conversion process carried out in compressed hot water at a temperature range of 250–450 C and high pressure in the range of 5–35 MPa [2, 17]. Along with bio-crude, some amounts of solid, aqueous, and gaseous by-products are generated in the HTL process. HTL keeps water in the condensed phase, which can prevent gaseous conversion of the medium. The increased density of water at high pressure makes it easier to penetrate in lignocellulosic biomass and the chemical interaction between the medium and targeted reactants. The reaction mechanism of the HTL process for lignocellulosic biomass is not clear in the literature because lignocellulose is a complex structure of cellulose, hemicellulose a lignin, and each component has complex chemical reactions, making it difficult to establish a proper reaction mechanism and a kinetic model. Several researchers [18–20] have attempted to illustrate the mechanisms involved in the HTL process, and it is widely assumed that there are three basic HTL reaction routes: 1) depolymerization of various biomolecules; 2) decomposition of various biomass monomers; and 3) recombination and repolymerization of reactive compounds. Figure 7.3 shows an overview of the reaction mechanisms of lignocellulosic biomass.

Gas

Wate-dissolved material

Polymerization Oil

Polymerization Degradation

Figure 7.3  Overview of the reaction mechanisms of lignocellulose biomass.

Char

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HTL as Strategy for Agricultural Waste Valorization  179

7.5 HTL Process Yield Calculations The yields of the HTL process are dependent on different parameters such as the structure of biomass (percentages of cellulose, hemicellulose, lignin, and ash), the operating parameters (temperature, pressure, residence time, type of catalyst, solid-to-liquid ratio, and heating rate), the type of reactor, and biomass pretreatment. The most commonly used equations [21, 22] are given below.





Liquid yield (LY)

Solid yield (SY)

Gas yield (GY) = 1 Yield of aqueous water



Bio oil weight 100% Mass of biomass

(7.1)

Weight of residue 100% Mass of biomass

(7.2)

Bio oil weight Weight of residue Mass of biomass

100%

(7.3)

Bio oil weight Weight of residue Gas yield 1 Mass of biomass 100%



(7.4)



7.6 HTL Advantage Over Pyrolysis HTL, a thermochemical conversion method, has made a lot of progress in the last decade because it is capable of handling wet biomass that must be dried before being processed in conventional pyrolysis. Conventional pyrolysis involves processing the biomass at moderate to high temperatures (400–600 C) and atmospheric pressure and requires the drying of the feedstock. HTL, in contrast, occurs at low temperature (250–450 C) and high pressure (5–35 MPa). The details are shown in Table 7.1. While HTL is also a pyrolysis process in which water acts as a solvent and a reactant, it offers advantages over conventional pyrolysis.

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Table 7.1  Difference between hydrothermal liquefaction (HTL) and pyrolysis. Parameters

Pyrolysis

Liquefaction

Drying

Necessary

Unnecessary

Pressure (MPa)

0.1–0.5

5–35

Temperature (°C)

370–526

200–450

Catalyst

No

Sometimes

Energy yield and value

Low (~17 MJ/kg)

High (~30 MJ/kg)

Oxygen content

High

Low

Viscosity

Low

High

Upgrade

Hard

Easy

7.6.1 Energy Content from the Biomass Since the thermochemical conversion process is done at different temperature conditions, both the HTL and pyrolysis processes require appreciable energy. HTL and pyrolysis can recover between 85%–91% and 75%–80% of the energy from biomass, respectively [23]. Demirbas [24] found that the biomass produced by pyrolysis had a low energy content of 16–19 MJ/ kg, while the biomass produced by HTL had a higher energy content of 30–35 MJ/kg.

7.6.2 Bio-Oil and Bio-Coal Yields The major advantage of HTL and pyrolysis is that both increase the bio-oil and bio-coal yields. The reason for the increase is that, besides lipid, proteins and carbohydrates greatly contribute to the increase in bio-oil yield due to heating. In comparison to pyrolysis (up to 21.9%), HTL generates 38.8%– 45.7% more bio-oil [25]. They are, however, similar in terms of bio-coal yield.

7.6.3 Oxygen Content in Bio-Oil The oxygen content of bio-oil determines its heating value. The excess oxygen content in most bio-crudes limits their use. In contrast to pyrolysis oil, which produces a high oxygen content of 40–50 wt.%, HTL produces low oxygen content (30–35%) in bio-oil [26] owing to the lower temperatures and heating rates.

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HTL as Strategy for Agricultural Waste Valorization  181

7.6.4 Carbon Content Utilization The amount of carbon in the fuel contributes to its overall heating value. HTL is termed a complete carbon utilization process, while pyrolysis can be described as a partial carbon utilization process. A study indicated that the value of 11.37 g CO2 equivalent MJ−1 for the HTL process was significantly lower than that of the pyrolysis process (210–290 g CO2 equivalent MJ−1 [27].

7.6.5 No Pretreatment and Drying To get better bio-oil and bio-coal yields in conventional pyrolysis, agricultural waste must be dried and pretreated. It is recommended that the moisture content should be less than 5% for pyrolysis. The HTL process can be used to process biomass feedstock with moisture content between 55% and 85%.

7.6.6 Energy Saving Since the thermochemical conversion process is done at different temperature conditions, both the HTL and pyrolysis processes require appreciable energy. The process of pyrolysis requires a considerable amount of energy since biomass must be dried before it can be processed. Since HTL does not require pretreatment and drying, it saves a significant amount of energy [28]. Yang et al. [29] compared the energy consumption of HTL, fast pyrolysis (FP), and microwave pyrolysis (MWP) and found that HTL consumed less energy than the other methods. Furthermore, HTL recovered higher energy (90%) compared to FP (79%) and MWP (57%).

7.7 Types of Reactors for the Hydrothermal Liquefaction Process HTL is usually conducted in batch and continuous reactors. Both systems require high stability in terms of tolerance to the processing conditions and the handling of different types of feedstocks [30]. Continuous systems are of particular interest to maximize bio-crude production efficiently, economically, and sustainably. Energy requirements, isolation, and feedstock availability may also affect the implementation of these technologies.

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182  Clean and Renewable Energy Production

7.7.1 Batch Reactor Reactors in batch form are commonly used for small-scale implementations and in laboratories for modeling and research as they do not require a high level of capital investment; they are cost-effective. Typically, the reaction mixture [with the feedstock and solvent(s) proportionally] is loaded into an autoclave. The autoclave is then sealed to prevent gases from leaking out. Depending on the end product and feedstock composition, catalysts, pressure, and the type of reaction environment are selected. The apparatus is quenched either by a cooling coil or a water bath after it is maintained at the desired reaction temperature for a set amount of time. The extraction of products occurs with the use of appropriate solvents, after which they are analyzed [31]. Batch reactor systems provide flexibility in operating conditions and feedstocks, making them ideal for preliminary studies of catalysts, solvents, and the reaction parameters on yields and compositions. This batch mode of operation avoids products getting plugged, pumped, and pressurized in the process line.

7.7.2 Continuous Reactor The continuous flow reactor (CFR) has a continuous flow of reactants into it and a continuous flow of products out of it. It has several advantages over batch systems, including greater productivity in terms of bio-crude yields, safety, and process operability. Studies comparing both processes showed that semi-flow treatment dissolves 30%–50% more organic matter compared to batch treatment [32]. Furthermore, continuous tubular reactors offer control over pressure and temperature independently, do not require a pressure reactor or mixing, and do not require impellers. Continuous HTL can be cost-effective, with a lower residence time and fast heating rates. Studies have indicated that continuous reactors increase the biocrude yields beyond 60% and the energy recovery beyond 90% [33]. Plug flow reactor (PFR) and the continuous stirred tank reactor (CSTR) are the CFRs available in the market.

7.7.2.1 Continuous Plug Flow Reactor The CFR system comprised a feed tank, high-pressure metering pump, coil preheater, vertical plug flow reactor, dual inline filters, cooling coil heat exchanger, back-pressure regulator, and product tank. Substrates enter a stirred tank, are filtered in a cylinder, and are pumped under pressure through a metering pump. A preheater then heats the substrate before it

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HTL as Strategy for Agricultural Waste Valorization  183

enters the vertical plug flow reactor. Solid residues are collected periodically in the blow-down pots underneath the filter vessels after the HTL products exit the reactor’s top and enter the high-pressure filters. A water-cooled condenser cools the solid-free bio-crude oil/aqueous phase/gas phase, and a back-pressure regulator reduces the pressure to ambient. Finally, gaseous products are vented from the liquid products in a flat-bottom product drum.

7.7.2.2 Continuous Stirred Tank Reactor CSTRs are reactor tanks with impellers that ensure that the slurry is constantly mixed. Furthermore, a CSTR is equipped with an electric heater, which ensures that the reaction temperature is maintained. Consequently, the mixture is more easily heated in the CSTR than in the PFR due to the mix of the slurry, which increases turbulence and, thus, the heat transfer throughout the reactor. As a result of the short residence time in the reactor, the theoretical conversion of biomass to bio-crude in the CSTR is lower compared to purely using the PFR, and scaling-up is limited by the high pressure [34].

7.8 Influence of Operating Parameters The main product of the HTL process of agricultural and forest waste is bio-oil. The yield and quality of bio-oil is significantly affected by several operating parameters, including biomass type, operating temperature, heating rate, residence time, pressure, liquid-to-solid ratio, and the type of catalyst. Therefore, the effects of the operating parameters on bio-oil yield and quality from HTL of agricultural and forestry wastes are discussed below.

7.8.1 Biomass Type Biomass feedstock significantly affects the yield and quality of the HTL products [6, 10]. The bio-oil yields of different agricultural waste biomasses under different HTL conditions are shown in Table 7.2. The results showed that the composition of biomass (i.e., cellulose, hemicellulose, and lignin) plays a major role in conversion. For example, Tian et al. [35] studied the liquefaction of four types of biomass, namely, rice straw, corn straw, soybean stalk, and peanut straw, under the same operating conditions.

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184  Clean and Renewable Energy Production

Table 7.2  Bio-oil yields from different biomass feedstocks through hydrothermal liquefaction (HTL). Biomass

Cellulose (%)

Hemicellulose (%)

Lignin (%)

Bio-oil yield (%)

Reference

Rice straw

46.33

31.09

10.17

15.1

[35]

Wheat straw

42.7

24.9

22.3

24.25

[22]

Sugarcane bagasse

37.69

17.02

13.84

61.75

[37]

Coconut shell

40

32

28

13.9

[38]

Barley straw

46

23

15

34.9

[7]

Corns straw

39.54

24.86

19.30

32.52

[39]

Soybean stalk

42.39

22.05

18.93

15.8

[35]

Peanut straw

36.56

20.27

18.36

14.6

[35]

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HTL as Strategy for Agricultural Waste Valorization  185

They found that the higher bio-oil yield for soybean stalk (15.8%) can be attributed to the high content of cellulose (42.39%), and the lowest yield for corn straw (7.9%) is likely due to the lower cellulose percentage (30.81%). The literature shows that biomass with higher percentages of cellulose and hemicellulose yield more bio-oil [17]. However, some researchers found the opposite trend in the biomass of palm kernel shell, palm husk, pomace, and pulp fiber due to the high lignin content [36]. The obtained bio-oil had a high phenolic compound (>72.86%). These findings suggest that the effect of cellulose, hemicellulose, and lignin contents on HTL bio-oil and bio-char yields is uncertain [17].

7.8.2 Operating Temperature Temperature is one of the most important parameters in the HTL process and greatly affects the bio-oil yield and properties. As per the literature, the temperature range varied between 200 C (T1) and 450 C (T2) [9]. Several researchers worked on the liquefaction of agricultural waste biomass including barley straw, corn straw, coconut coir, sorghum bagasse, and wheat stalk. Table 7.3 shows that the bio-oil yield increases with increasing temperature; however, in all cases, there was a temperature limit beyond which an increase in the temperature reduces the bio-oil yield [4, 22, 35, 37, 38]. From the results, it can be seen that the endothermic reaction happened in the range of two temperatures (T1 and T2). When the operating temperature is below T1, bio-oil is exceptionally low due to insufficient activation energy for bio-oil exploitation, and when the temperature is greater than T2, the bio-oil yield either decreases or there is a small increase in percentage yield, which is not economical. In the temperature range of T1–T2, reactions like depolymerization, hydrolysis, and dehydration are favored [40]. Therefore, researchers have drawn the conclusion that the stable temperature range for bio-oil production depends upon the type of feedstock, catalyst, and other processing parameters. However, within a given temperature range, the bio-oil yield first increases and then decreases with increasing liquefaction temperature [6].

7.8.3 Heating Rate The effect of the heating rate on HTL of biomass is still contentious. Some experts believe that the effect of the heating rate on the bio-oil yield and its reaction is non-significant and depends on the temperature. Brand et al. [11] studied the effect of the heating and cooling rates on the liquefaction of biomass at temperatures of 250–350 C and heating rates of 2 C and

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186  Clean and Renewable Energy Production

Table 7.3  Effect of operating parameters on hydrothermal liquefaction of biomass. Biomass

Operating condition

Bio-oil yield (wt.%)

HHV(MJ/kg)

Impact

Reference

Barley straw

Temperature: 280–400°C Time: 15 min Pressure: 350 bar Solid-to-liquid ratio: 3:20 (g/ml) Catalyst: K2CO3

34.9

24.87

Low temperature was favorable for bio-oil yield; high temperature was favorable to reduce the O content and increase the calorific value of bio-oil

[7]

Corn straw

Temp: 260–320°C Time: 5–60 min Pressure: 0–6MPa Solid-to-liquid ratio: 1:4 (g/ml) Catalyst: Na2CO3,K2CO3, HZSM-5, and NKC-11

26.60

–

The bio-oil yield obtained by heterogeneous catalysts was higher than that from the homogeneous catalyst.

[41]

Coconut Coir

Temperature: 250–350°C Time: 10–60 min Solid-to-liquid ratio: 1:10 (g/ml) Catalyst: K2CO3

34.6

31

By simultaneously optimizing the temperature and time of hydrothermal liquefaction, the bio-oil yield and calorific value can be effectively increased.

[42]

(Continued)

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HTL as Strategy for Agricultural Waste Valorization  187

Table 7.3  Effect of operating parameters on hydrothermal liquefaction of biomass. (Continued) Biomass

Operating condition

Bio-oil yield (wt.%)

HHV(MJ/kg)

Impact

Reference

Sorghum bagasse

Temperature: 300–350°C Heating rate: 25°C/min Residence time: 1 h Catalyst: K2CO3, KOH, formic acid Ni/Si–Al, Ni2P, and zeolite

61.8

33.1

K2CO3 was considered an excellent catalyst, and adding K2CO3 resulted in high C content and low N and S contents.

[37]

Wheat stalk

Temperature: 300°C Pressure: 12 MPa Catalyst: Na2CO3+Fe

24.25

–

The biocatalytic system can significantly promote the low-temperature degradation of biomass and had better catalytic effect on some specific monophenyl compounds.

[22]

HHV, higher heating value

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188  Clean and Renewable Energy Production

20 C/min, which showed little effect of the heating rate. A high heating rate increases the bio-oil yield due to a faster decomposition reaction and the breakdown of the macromolecular structure, while a lower heating rate increases the polymerization reaction and the coke yield [36]. HTL in a continuous reactor reduces the coke formation and reactor plugging problems. In order to maintain the rate of coke formation and reduce gaseous products, an in-depth study of the heating rates is necessary to understand the HTL reaction mechanism [43].

7.8.4 Residence Time The effect of the residence time on liquefaction is less significant than that of temperature in the liquefaction process. Residence time is the time of HTL reaction during which the operating conditions are maintained, excluding the heating and cooling times. Residence time affects the reaction mechanism of lignocellulosic biomass. A high residence time intensifies the polymerization and condensation reactions, which increases the cracking of bio-oil, forms gaseous compounds, and reduces the bio-oil yield, while a too short duration leads to an incomplete decomposition reaction [6]. Residence time depends on the reaction temperature [36]. For a higher operating temperature, the residence time should be short to avoid the formation of coke. From the literature, it can be seen that, to optimize the residence time for lignocellulosic biomass along with temperature, other parameters like pressure and the catalyst also play important roles. Therefore, all factors should be considered for the different reactions and obtain the optimal residence time and optimal temperature.

7.8.5 Pressure The operating pressure is another important operating parameter in the HTL process that, along with temperature, maintains the single phase in the subcritical and supercritical states to ensure energy loss. During the subcritical state, the medium is in liquid form; during the supercritical state, the medium is in gaseous form, while the critical state is the coexistence of the gas–liquid phase [42]. The increased water density under high-pressure conditions penetrates more easily into lignocellulosic biomass, promotes lignocellulose decomposition, and improves bioconversion [40]. Researchers concluded that, if pressure increased the above critical value, i.e., 221 bar, there is no significant increase in the bio-oil yield. This may be because, at high pressures, the free radical reaction becomes reluctant, which reduces the decomposition reaction. It is concluded that

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HTL as Strategy for Agricultural Waste Valorization  189

temperature and pressure are highly correlated up to a certain range. An increase of the pressure beyond a certain range has no significant effect on bio-oil production, and maintaining the critical state during the liquefaction process is the best choice to ensure maximum energy balance.

7.8.6 Type of Catalyst The roles of catalysts are to overcome char formation and to reduce the condensation and polymerization reactions formed during the decomposition of lignin while enhancing the liquid yield and its quality. Researchers have shown promising results due to the use of catalysts. Table 7.3 shows the catalysts used and their impacts on bio-oil yield and calorific value. Presently, the catalysts used in the HTL process for lignocellulosic biomasses include Na2CO3, K2CO3, sulfuric acid, alkali salts, and metal catalyst. Chen et al. [22] studied the synergetic effects of homogeneous and heterogeneous catalysts on wheat straw during the HTL process and found that Na2CO3+Fe evidently increased the conversion. Although the use of catalysts has been extensively studied, their specific effects on the HTL process are unclear. Therefore, more research on the catalytic effects of catalysts is needed to achieve further comprehensive development of HTL.

7.9 Product Distribution and Evaluation Biomass HTL treatment generates four main products, namely, liquid (biooil), aqueous water, solid products (hydrochar), and gaseous products at high temperature (250–450 C) and pressure (5–35 MPa) in pure water or alcohol/water co-solvents with or without the addition of homogenous/heterogeneous catalysts [6, 9, 10]. HTL treatment of lignocellulosic biomass will generate bio-oil as the main product and solid residue, gaseous product, and aqueous water as by-products at the temperature range 200–450 C and pressure range 5–25 MPa. Based on the operating parameters and the type of feedstock, the percentages of product distribution will change.

7.9.1 Liquid (Bio-Oil) The prime motive of the HTL process is to maximize the yield and quality of bio-crude (blackish and viscous oil). Bio-oil consists of different chemical constituents, viz. aromatics (CnHn), aldehydes, ketones, alcohols (CnH2n), carboxylic acids, and straight and cyclic hydrocarbons [44]. The presence of all these compounds suggests the use of the obtained bio-oil as replacement

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190  Clean and Renewable Energy Production

of fossil fuel and as a renewable and environment-friendly cleaner fuel for sustainable development in the green energy sector [45]. The high refining cost, lower energy value, high viscous nature, corrosive nature, and the high solid content of bio-oil limit its application [46, 47]. The nature of bio-oil varies strongly with residence time and operating temperature [48]. The ranges for both parameters are not fixed for any lignocellulosic biomass because the type of feedstock and the chemical composition behave differently during the reaction mechanism of the HTL process. As per studies, the decided ranges of the residence time and operating temperature are 0–60 min and 200–450 C, respectively [7]. Not only the residence time and operating temperature but also the type of catalyst affect the bio-oil yield and quality [49]. About a fourfold upsurge can be observed in the yield of bio-oil with the application of the K2CO3 catalyst, with a maximum conversion rate of 70% according to Karagöz et al. [50]. The chemical composition of bio-crude oil can be determined by gas chromatography–mass spectrometry (GC-MS), Fourier transform infrared (FTIR), and NMR.

7.9.2 Solid (Hydrochar) The solid material obtained from the HTL process known as hydrochar (char) has gained attention in recent years due to its high carbon content, less ash content, stable oxygen content, and high nutrient content [51, 52]. The high carbon content in hydrochar enables its use as a substitute of coal in traditional thermal power plants. Hydrochar can be used for carbon sequestration, to prepare low-cost adsorbents by the activation of carbonaceous materials, carbon catalyst, carbon material in fuel cells, and as magnetic carbon composite [53–57]. The International Biochar Initiative (IBI) recommended that solid materials should be characterized before utilizing mainstream and downstream. The presence of different elements, i.e., carbon, hydrogen, oxygen, nitrogen, and sulfur, is determined by the CHNS/O analyzer. The heating value can be determined based on the equations generated by different reviewers and with the help of a bomb calorimeter. The surface area and reaction mechanism during the HTL process can be determined with Brunauer–Emmett–Teller (BET) and scanning electron microscope (SEM) analyses [58]. In order to characterize the surface of hydrochar, X-ray photoelectron spectroscopy (XPS) and Boehm titration techniques can be helpful. The thermal behavior, stability of the material with temperature, activation energy, and the reaction kinetics can be determined by thermogravimetric analysis (TGA) [59]. The presence of different functional groups in hydrochar can be determined using FTIR, X-ray photo-electron (XRPE), X-ray fluorescence, and RAMAN spectroscopy.

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HTL as Strategy for Agricultural Waste Valorization  191

7.9.3 Aqueous Water and Gases Aqueous water is one of the by-products formed during the HTC process in higher amounts (20%–50%), which depends on the type of feedstock and the operating conditions, i.e., temperature, pressure, residence time, type of catalyst, and liquid-to-solid ratio [53]. The aqueous water should be tested for chemical oxygen demand (COD), total nitrogen (TN), total phosphorous (TP), ammonia nitrogen, and metal presence. As per reviews, aqueous water contains 10%–50% carbon and 50%–70% nitrogen [53, 60, 61]. The composition of the aqueous solution can be analyzed by high-performance liquid chromatography (HPLC). The lignocellulosic biomass showed majority of the organic acid compounds (lactic acid, acetic acid, and formic acid), alcohols (methanol and ethanol), and inorganic metals (sodium, silicon, and sulfur) [62]. The last product of the HTL process is in the form of gas, with yields varying from 5% to 10% of biomass feedstock [63]. The gas product is CO2, with negligible concentrations of CH4, CO, and H2 due to decarboxylation reaction [64].

7.10 Potential Applications of HTL Products The bio-oil produced by the HTL process contains a variety of organic compounds (alkanes, aromatic hydrocarbon, organic acid, furan, alcohols, aldehydes, esters, and phenols), so can be used as a fuel to replace fossil

ion at Hydro char

Bio oil

ific

Frac dist tional illat ion

od

Bio chemicals

Carbon Material

Cat a crac lytic king

M

Liquid fuels

HTL Products

bic Aqueous ero ion; a water An est tic n dig taly atio a C sific o ga ctr al Ele mic s s e ch roce Biogas p

Gaseous products Wat er reac shift tion

Algal growth Greenhouse gas fertilizer Fuel gas

Figure 7.4  Applications of hydrothermal liquefaction (HTL) products.

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192  Clean and Renewable Energy Production

fuel [18]. Bio-oil can be converted into various bioproducts such as polyols, epoxy resin, and polyurethane foam materials [65]. The solid material (hydrochar) has less specific area compared to pyrolytic biochar, but has high capacity for the adsorption of metals, dyes, and other pollutants [66]. Hydrochar can be used as a carbon sequester to increase soil fertility and to reduce soil water contamination [67]. Shanmugam et al. [68] used biochar in anaerobic digestion to increase the rate of redox reaction for methane gas production. Aqueous water can be used as a growth medium for microalgae as a source of nutrients. Aqueous water can be used as a substrate for microbial electrolysis cells. Presently, there are some studies on the application of gas-phase products: as gas fertilizer in the greenhouse, algal growth, and fuel gas. Figure 7.4 details the applications of the products and by-products of the HTL process.

7.11 Challenges and Limitations of the HTL Process Lignocellulosic agricultural waste can be converted into energy by the HTL process. The HTL process shows important advantages over other liquefaction processes [69, 70], but there are some challenges that need to be solved in order to convert laboratory-scale research to pilot plant. (1) The cost of production is high because high temperature and pressure involve highly advance equipment for the HTL process. (2) Each feedstock behaves differently under different operating parameters, so maintaining optimum operating conditions is difficult. (3) During the depolymerization and decomposition reactions, the conversion of the solubility of coke, char, and tar in solvent is much less, leading to the deposition of substances in the reactor, which obstructs the functionality of equipment. (4) Studies on the relationships between bio-crude oil yield and value-added chemical species and the effects of catalysts on the production of individual specific chemical compounds are very limited. (5) Very few literature works are available on theoretical, especially the computational fluid dynamics-based models to analyze the complex inherent properties like the thermodynamic properties of bio-crudes, viscosity effects, etc., so that the optimization of the process parameters will be easier.

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HTL as Strategy for Agricultural Waste Valorization  193

(6) Bio-oil extraction has several hurdles, such as composition complexity and low quality (i.e., high nitrogen content). In addition, the upgrading and refining of bio-oil, as well as the denitrification technology, need further investigation.

7.12 Techno-Economic and Environmental Analysis To implement the HTL process in larger scales techno-economic and environmental analysis should be evaluated. The HTL products’ quantity and quality mainly depend on the operating parameters, availability of feedstock, market requirements, and technical features. Therefore, detailed information on the economic outputs based on the input variables is an important step. The HTL process carried out at high temperature and pressure and the energy consumption in the process can be reduced with the design of advanced reactors having good insulation properties and fouling and corrosion resistance [10]. Catalysts have very positive impacts on the yield and quality of bio-oil. The use of multifunctional catalysts with long service life and the reduction of the residence time and temperature reduce the energy consumption, which automatically reduces the economic burden. In order to make the HTL process more economic, the focus should not only be on bio-oil but also on the better utilization of the by-­products. The bio-oil obtained by HTL requires more cost for its upgrade to make it commercial. In order to reduce this cost, a novel method for bio-oil refining and upgrade should be developed. Since the main component of HTL gas is CO2, it can be released into the atmosphere. Greenhouse gases, including CO2, produced by HTL can also be captured, considering the environmental aspects. However, there will be additional operating costs.

7.13 Conclusions The conversion of petroleum products to fuel and other biochemicals is a well-processed and developed technology. However, the conversion of biomass into fuels to compete with fossil fuels is still in the research stage. The promising results of HTL for the engenderment of bio-oil equipollent to conventional crude oil have garnered increased attention from researchers in the last decades. This book chapter focuses on the generation of biofuel, the different conversion routes for processing biomass, the HTL reaction mechanisms, advantages of the HTL process over pyrolysis, different types of reactors for the HTL process, the effect of

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194  Clean and Renewable Energy Production

operating parameters on the yield and quality of bio-oil, product distribution and their evaluation, potential applications of HTL products, and the different challenges and limitations of HTL. However, further studies are needed to address cost-­effective liquefaction process to compete with petroleum-based products.

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37. Bi, Z. et al., Biocrude from pretreated sorghum bagasse through catalytic hydrothermal liquefaction. Fuel, 188, 112–120, 2017, doi: 10.1016/j. fuel.2016.10.039. 38. Lee, J.H., Hwang, H., Moon, J., Choi, J.W., Characterization of hydrothermal liquefaction products from coconut shell in the presence of selected transition metal chlorides. J. Anal. Appl. Pyrolysis, 122, 415–421, 2016, doi: 10.1016/j.jaap.2016.11.005. 39. Chen, Y. et al., Hydrothermal liquefaction of corn straw with mixed catalysts for the production of bio-oil and aromatic compounds. Bioresour. Technol., 294, September, 122148, 2019, doi: 10.1016/j.biortech.2019.122148. 40. Fan, Q., Fu, P., Song, C., Fan, Y., Industrial crops & products valorization of waste biomass through hydrothermal liquefaction: A review with focus on linking hydrothermal factors to products characteristics. Ind. Crops Prod., 191, PB, 116017, 2023, doi: 10.1016/j.indcrop.2022.116017. 41. Zhang, S. et al., Effect of operating parameters on hydrothermal liquefaction of corn straw and its life cycle assessment. Environ. Sci. Pollut. Res., 27, 6, 6362–6374, 2020, doi: 10.1007/s11356-019-07267-4. 42. Gundupalli, M.P. and Bhattacharyya, D., Hydrothermal liquefaction of residues of Cocos nucifera (coir and pith) using subcritical water: Process optimization and product characterization. Energy, 236, 121466, 2021, doi: 10.1016/j.energy.2021.121466. 43. Zhang, B., Von Keitz, M., Valentas, K., Thermal effects on hydrothermal biomass liquefaction. Appl. Biochem. Biotechnol., 147, 1–3, 143–150, 2008, doi: 10.1007/s12010-008-8131-5. 44. Jiang, W., Kumar, A., Adamopoulos, S., Liquefaction of lignocellulosic materials and its applications in wood adhesives—A review. Ind. Crops Prod., 124, July, 325–342, 2018, doi: 10.1016/j.indcrop.2018.07.053. 45. Isikgor, F.H. and Becer, C.R., Lignocellulosic biomass: A sustainable platform for the production of bio-based chemicals and polymers. Polym. Chem., 6, 25, 4497–4559, 2015, doi: 10.1039/c5py00263j. 46. Ramirez, J.A., Brown, R.J., Rainey, T.J., A review of hydrothermal liquefaction bio-crude properties and prospects for upgrading to transportation fuels. Energies, 8, 7, 6765–6794, 2015, doi: 10.3390/en8076765. 47. Baloch, H.A. et al., Recent advances in production and upgrading of bio-oil from biomass: A critical overview. J. Environ. Chem. Eng., 6, 4, 5101–5118, 2018, doi: 10.1016/j.jece.2018.07.050. 48. Jindal, M.K. and Jha, M.K., Effect of process parameters on hydrothermal liquefaction of waste furniture sawdust for bio-oil production. RSC Adv., 6, 48, 41772–41780, 2016, doi: 10.1039/c6ra02868c. 49. Tekin, K., Karagöz, S., Bektaş, S., Hydrothermal conversion of woody biomass with disodium octaborate tetrahydrate and boric acid. Ind. Crops Prod., 49, 334–340, 2013, doi: 10.1016/j.indcrop.2013.05.014. 50. Karagöz, S., Bhaskar, T., Muto, A., Sakata, Y., Oshiki, T., Kishimoto, T., Lowtemperature catalytic hydrothermal treatment of wood biomass: Analysis

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63. Magdeldin, M., Kohl, T., Järvinen, M., Techno-economic assessment of the by-products contribution from non-catalytic hydrothermal liquefaction of lignocellulose residues. Energy, 137, 679–695, 2017, doi: 10.1016/j. energy.2017.06.166. 64. Garcia Alba, L. et al., Hydrothermal treatment (HTT) of microalgae: Evaluation of the process as conversion method in an algae biorefinery concept. Energy Fuels, 26, 1, 642–657, 2012, doi: 10.1021/ef201415s. 65. Jindal, M.K. and Jha, M.K., Hydrothermal liquefaction of wood: A critical review. Rev. Chem. Eng., 32, 4, 459–488, 2016, doi: 10.1515/revce-2015-0055. 66. Leng, L.J. et al., Characterization and application of bio-chars from liquefaction of microalgae, lignocellulosic biomass and sewage sludge. Fuel Process. Technol., 129, 8–14, 2015, doi: 10.1016/j.fuproc.2014.08.016. 67. Beims, R.F., Hu, Y., Shui, H., Xu, C., Hydrothermal liquefaction of biomass to fuels and value-added chemicals: Products applications and challenges to develop large-scale operations. Biomass Bioenergy, 135, February, 105510, 2020, doi: 10.1016/j.biombioe.2020.105510. 68. Shanmugam, S.R., Adhikari, S., Nam, H., Kar Sajib, S., Effect of bio-char on methane generation from glucose and aqueous phase of algae liquefaction using mixed anaerobic cultures. Biomass Bioenergy, 108, March, 479–486, 2018, doi: 10.1016/j.biombioe.2017.10.034. 69. Gerber Van Doren, L., Posmanik, R., Bicalho, F.A., Tester, J.W., Sills, D.L., Prospects for energy recovery during hydrothermal and biological processing of waste biomass. Bioresour. Technol., 225, 67–74, 2017. 70. Tekin, K., Karagöz, S., Bektaş, S., A review of hydrothermal biomass processing. Renew. Sustain. Energy Rev., 40, February, 673–687, 2014, doi: 10.1016/j. rser.2014.07.216.

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Imperative Role of Proton Exchange Membrane Fuel Cell System and Hydrogen Energy Storage for Modern Electric Vehicle Transportation: Challenges and Future Perspectives Rupendra Kumar Pachauri1*, Deepa Sharma2, Surajit Mondal1, Shashikant3 and Priyanka Sharma4 Electrical Cluster, School of Engineering, University of Petroleum and Energy Studies, Dehradun, India 2 School of Basic Science, IIMT University, Meerut, Uttar Pradesh, India 3 Electrical Engineering Department, Babu Banarasi Das University, Lucknow, India 4 School of Basic Science and Technology, IIMT University, Meerut, Uttar Pradesh, India 1

Abstract

Proton exchange membrane fuel cell (PEMFC) systems and hydrogen energy storage play a crucial role in modern electric vehicles (EVs). PEMFCs convert the chemical energy of hydrogen fuel into electricity, emitting only water vapor as a by-product. This makes them a clean and efficient alternative to traditional internal combustion engines. However, there are several challenges associated with the widespread adoption of PEMFC-powered EVs. One major challenge is the lack of infrastructure for producing, distributing, and storing hydrogen fuel. This makes it difficult for consumers to find a nearby fueling station and for manufacturers to produce hydrogen-­powered vehicles at a large scale. Another challenge is the cost of PEMFCs and hydrogen storage systems, which is currently higher than that of traditional gasoline-powered vehicles. However, as technology improves and economies of scale are achieved, it is expected that the cost of these systems will decrease. Despite these challenges, the future perceptive of PEMFC-powered EVs is promising. As concerns about *Corresponding author: [email protected] Surajit Mondal, Adesh Kumar, Rupendra Kumar Pachauri, Amit Kumar Mondal, Vishal Kumar Singh and Amit Kumar Sharma (eds.) Clean and Renewable Energy Production, (201–224) © 2024 Scrivener Publishing LLC

201

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8

climate change and air pollution continue to grow, there is an increasing demand for clean and sustainable transportation options. PEMFCs and hydrogen energy storage are well suited to meet this demand, and as the technology and infrastructure continue to improve, it is likely that we will see a significant increase in the number of PEMFC-powered EVs on the road in the future. In this chapter, MATLAB/Simulink modeling explores the PEMFC-based power assistance motor drive system to investigate the performance behavior in terms of rotor speed and torque. Keywords:  Fuel cell, renewable energy, hydrogen energy, electrical vehicle, energy storage

8.1 Introduction Electric vehicles (EVs) can play a significant role in improving air quality and reducing greenhouse gas emissions, which can have a positive impact on human health and the environment. Additionally, EVs can reduce the dependence on fossil fuels and help to lower fuel costs for individuals and businesses [1]. However, the widespread adoption of EVs also requires a significant investment in infrastructure, including charging stations, and the development of more efficient and cost-effective battery technology. Overall, EVs have the potential to greatly improve the sustainability of transportation and reduce the negative impacts on human life and the planet [2]. EVs are powered by batteries that store electrical energy and convert it into mechanical energy to drive the vehicle’s motor [3, 4]. These batteries can be charged using a variety of power sources, including: • Grid electricity: As of now, this is the most popular way to charge an EV. To recharge the battery, just connect the car to a charging station or outlet that is connected into the electrical grid. • Solar power: A common way for owners of EVs to charge their batteries is using power generated by solar panels installed on their land. • Wind power: Similar to solar power, some EV owners use wind turbines to generate electricity and charge their vehicle’s battery. • Hydroelectric power: Owners of EVs often use energy from hydropower facilities to charge their vehicles’ batteries. • Biomass: An increasing number of EV drivers are opting to use renewable energy sources, such as plant and animal wastes, to charge their vehicles’ batteries.

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• Fuel cells: Some EVs get their juice from fuel cells, which utilize hydrogen and oxygen to generate electricity. It is worth mentioning that some EV charging stations are especially designed to be powered by renewable energy sources like solar or wind power [5]. Fuel cells have several advantages over traditional batteries as a power source for EVs. Some of these advantages include: • High energy density and longer range: Fuel cells (FCs) are preferable than batteries because they can store more energy in a smaller package. This has the potential to increase the EV range by creating a lighter and smaller car. Also, FCs have a larger range than batteries, which might come in handy on long road trips. • Quick refueling and durability: The FC system is more convenient than batteries since they can be recharged with hydrogen in the same amount of time it takes to fill a gas tank. Also, the duration between FC replacements is longer than battery changes. • Zero emission: FCs are a clean power source for EVs since they convert hydrogen and oxygen into electricity with just water vapor as a waste. However, it is worth noting that the FC technology is still relatively new and more expensive than the traditional battery technology, and the hydrogen fuel infrastructure is not as well developed as the charging infrastructure for battery–EVs [6]. Fuel cell-assisted electric vehicles (FCEVs) are currently being developed and tested by several major automakers and technology companies. a) Toyota has been a leading developer of FC technology and has been selling its Mirai FCEVs since 2014. The car uses a fuel cell to convert hydrogen into electricity, which powers the electric motor. b) In addition, Honda has been working on FC technology and has been marketing the Clarity FCEV since 2016. c) Hyundai has been selling its Tucson FCEV since 2013. d) Mercedes-Benz has been working on the GLC F-Cell, a sports utility vehicle (SUV) powered by FC technology that integrates an electric driving system.

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PEMFC Systems and Hydrogen Energy Storage in EVs  203

e) BMW’s 7 Series luxury vehicle has been undergoing testing of FC-assisted electric powertrain. This drivetrain employs a fuel cell to create energy that supplements the battery. f) Audi has been working on an electric powertrain for its e-tron SUV that features a fuel cell to create energy to augment the batteries. g) General Motors has been developing FC technology and testing FCEVs in its Chevrolet Equinox and GMC Sierra models. h) Ford has been testing FC-assisted electric drivetrain in its Transit Connect commercial van, which uses a fuel cell to generate electricity that supplements the battery. When it comes to FCEVs, the market is still in its infancy. The high production costs and the limited hydrogen refueling infrastructure might delay the widespread adoption of FCEVs [7, 8]. Future prospects for FCEVs, however, might change in light of technological developments and heightened investment. Researchers may always benefit from a more thorough grasp of the current status of their area thanks to a thorough literature study [9]. All the diverse fuel cell designs, their advantages and disadvantages, and the problems that still require fixing are covered here. A literature review may also point out where further study is needed by highlighting the gaps in the existing body of work. Overall, doing a literature review is an important part of the research process since it guarantees that future studies will be well informed and will expand upon the foundation already laid [10, 11]. A generalized diagram of a FC-assisted electrical vehicle is shown in Figure 8.1. The types of important FCs and the required fuel to operate for various applications are explored in Table 8.1, as follows:

H2 Storage

Power Distributor unit

Inverter

Battery

FC converter (Boost converter)

FC stack

Traction Motor

Figure 8.1  Generalized diagram of a fuel cell-assisted electrical vehicle.

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204  Clean and Renewable Energy Production

Table 8.1  Fuel cell (FC) types, fuel required, and applications [12, 13]. FC types

PEMFC

AFC

PAFC

MCFC

SOFC

Fuel required

Hydrogen

Hydrogen

Hydrogen

H2, CO, CH4

CH4

Efficiency (%)

53–58

60

>40

45–47

35–43

Operating temp (°C)

50–100

90–100

150–200

600–700

800–1,000

Switching time

Seconds

Seconds

Hours

>Hours

>Hours

Applications

• Hospital, EVs • Banking power

• Military • Space

• Distribution generation

• Marine • Railway

• Residential power backup

PEMFC, proton exchange membrane fuel cell; AFC, alkaline fuel cell; PAFC, phosphoric acid fuel cell; MCFC, molten carbonate fuel cell; SOFC, solid oxide fuel cell; EVs, electric vehicles.

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PEMFC Systems and Hydrogen Energy Storage in EVs  205

The present chapter comprised the following sections to describe the study of the FC-powered EV: Section 8.1 explores the introduction, and the subsequent section is followed by the literature review. Furthermore, modeling and EV categories based on the power sources are explored in Sections 8.2 and 8.3. Moreover, the methodologies and limitations for hydrogen fuel generation are elaborated in Section 8.4. In addition, Sections 8.5 and 8.6 are more about the future scope, challenges, and pros–cons as well. Section 8.7 explains the transient study of FC-driven EVs. Lastly, Section 8.8 concludes the chapter.

8.2 Modeling of the PEMFC System To model a PEMFC means to simulate its internal physical, chemical, and electrochemical processes. These models may be used to make predictions about performance of PEMFC under various situations and to tweak the fuel cell’s architecture to better suit a certain use case [14]. Additionally, the models are essential to the study and improvement of the PEMFC technology. A schematic diagram of FC is shown in Figure 8.2. The FC voltage (Vfc) can be stated using Eq. (8.1), and the Nernst voltage (E) is reduced by three types of voltage drops during the operation and load conditions [16]. In addition, the chemical reactions at the anode and cathode sides are shown in Eq. (8.2), as follows:

Vfc = E − Vact – Vconc − Vohm



Anode

(+)

(–)

H2 Inlet

(8.1)

Cathode

O2 Inlet A

M

C

H2 Outlet

O2 Outlet H 2O

Figure 8.2  Fuel cell (FC): schematic diagram [15].

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206  Clean and Renewable Energy Production



Anode : H 2 = 2H + + 2e − 1 Cathode : O 2 + 2H + + 2e − = H 2 O 2 1 Cell : H 2 + O2 = H 2 O 2

(8.2)

8.3 Electrical Vehicle Categories There are several categories of EVs based on their power source and propulsion system [17–19]. Table 8.2 explores the major components and the roles are defined. a) B  attery–electric vehicles (BEVs): Building a model of a PEMFC involves simulating its internal physical, chemical, and electrochemical processes. These models may be used to forecast how a PEMFC will function in different scenarios and to optimize the fuel cell’s design for a given application. Research and development on the PEMFC technology also rely heavily on these models [20]. b) Plug-in hybrid electric vehicles (PHEVs): These automobiles are equipped with both electric and conventional powertrains. They have the option of running on gasoline or being charged by an external power source, two examples of such are the Toyota Prius Prime and the Chevrolet Volt [21]. c) Fuel cell electric vehicles (FCEVs): These vehicles use a fuel cell to convert hydrogen into electricity, which powers an electric motor. They produce zero emissions while driving and only emit water vapor as a by-product. d) Extended-range electric vehicles (EREVs): These vehicles have an electric motor and a small internal combustion engine that acts as a generator to charge the battery. They can run on both electricity and gasoline, e.g., Chevrolet Volt. e) Hybrid electric vehicles (HEVs): A hybrid vehicle uses two or more distinct types of power, such as an internal combustion engine to drive an electric generator that powers an electric motor, e. g., Toyota Prius [22, 23].

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PEMFC Systems and Hydrogen Energy Storage in EVs  207

Table 8.2  Electric vehicle categories. Type

Major components

Role of components

BEVs [24]

• • • • • • •

Battery pack Electric motor Power electronics Power electronics Charging system Vehicle control unit Other components such as inverter and DC–DC converter. A battery management system (BMS) is also integrated with the EV for optimal performance.

1. Battery pack: Main source of power for the EV. It stores and supplies electrical energy to the electric motor. 2. Electric motor: Converts electrical energy into mechanical energy to power the vehicle. 3. Power electronics: Regulates the flow of electrical energy between the battery pack and the electric motor. 4. Charging system: Used to charge the battery pack, typically through a plug-in connection to an external power source. 5. Vehicle control unit: Controls and coordinates the various systems in the EV, including the electric motor, power electronics, and charging system.

PHEVs [25]

• • • • • • • •

Battery pack Electric motor Power electronics Internal combustion engine (ICE) Transmission Charging system Vehicle control unit Energy management system

1. Battery pack: This is the main source of power for the electric drive system. It stores and supplies electrical energy to the electric motor. 2. Electric motor: This is the component that converts electrical energy into mechanical energy to power the vehicle. 3. Power electronics: This component regulates the flow of electrical energy between the battery pack and the electric motor. 4. Internal combustion engine (ICE): This is the traditional gasoline or diesel engine that acts as a generator to charge the battery pack or provide power to the electric motor. 5. Transmission: This component connects the electric motor and the internal combustion engine to the drive wheels of the vehicle. (Continued)

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208  Clean and Renewable Energy Production

Table 8.2  Electric vehicle categories. (Continued) Type

Major components

Role of components 6. Charging system: This component is used to charge the battery pack, typically through a plug-in connection to an external power source. 7. Vehicle control unit: This is the computer that controls and coordinates the various systems in the PHEV, including the electric motor, internal combustion engine, power electronics, and charging system. 8. Energy management system: This component controls the flow of energy between the different power sources and the drive system to optimize the performance of the vehicle.

FCEVs [26]

• • • • • • • •

Fuel cell stack Hydrogen storage Electric motor Battery Power electronics On-board diagnostics Refueling system Cooling system

1. Fuel cell stack: Core component of the FCEV, where hydrogen is converted into electricity through a chemical reaction. 2. Hydrogen storage: High-pressure tanks to store hydrogen fuel. 3. Electric motor: Converts the electricity generated by the fuel cell into mechanical energy to power the vehicle. 4. Battery: Stores energy from regenerative braking and can provide power to the electric motor when needed. 5. Power electronics: Control the flow of electricity between the fuel cell, battery, and electric motor. 6. On-board diagnostics: Monitors the performance of the fuel cell and other components. 7. Refueling system: A system that allows the vehicle to be refilled with hydrogen fuel. 8. Cooling system: Generates a lot of heat during operation, so a cooling system is necessary to keep the temperature within safe limits. (Continued)

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PEMFC Systems and Hydrogen Energy Storage in EVs  209

Table 8.2  Electric vehicle categories. (Continued) Type

Major components

Role of components

HEVs [27]

• • • • • • • •

1. Internal combustion engine (ICE): Primary source of power in a hybrid vehicle, which runs on gasoline or diesel fuel. 2. Electric motor: Uses electricity generated by the battery to power the vehicle or to assist the ICE when more power is needed. 3. Battery: Stores energy generated by the vehicle’s brakes during regenerative braking and provides power to the electric motor when needed. 4. Power electronics: Control the flow of electricity between the battery, electric motor, and ICE. 5. Transmission: Connects the ICE, electric motor, and wheels of the vehicle and allows them to work together to power the vehicle. 6. On-board diagnostics: Monitors the performance of the battery, electric motor, and other components. 7. Charging system: Allows the battery to be recharged using an external power source. 8. Hybrid control unit: Coordinates the operation of the various components of the hybrid powertrain and determines when and how to use the ICE and electric motor to power the vehicle.

Internal combustion engine Electric motor Battery Power electronics Transmission On-board diagnostics Charging system Hybrid control unit

EV, electric vehicle; BEVs, battery–electric vehicles; PHEVs, plug-in hybrid electric vehicles; FCEVs, fuel cell-assisted electric vehicles; HEVs, hybrid electric vehicles.

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210  Clean and Renewable Energy Production

8.4 Hydrogen Energy Storage The term “hydrogen energy storage” refers to the practice of storing hydrogen gas or molecules rich in hydrogen for use as a power source at a later time. Hydrogen storage may be done in a number of different ways, some of which are included in Table 8.3 below. In spite of the fact that every one of these strategies has some redeeming qualities—high energy density, high safety, high efficiency, low cost, etc.—they also each have certain negatives [31]. The capacity needs and other considerations will define the storage type that is eventually selected, whether it is for transit or stationary power. Hydrogen storage, which enables hydrogen to be stored for later use, increases the supply and demand flexibility and is widely seen as a game changer for the widespread acceptance of hydrogen as an energy carrier [32]. Table 8.3  Methods for hydrogen energy storage [28–30]. Storage methods

Details

Hydrogen in carbonbased materials

• Graphite, a carbon-based substance, can adsorb hydrogen onto its surface, making it a suitable hydrogen storage medium.

Hydrogen in chemical hydrides

• Chemical compounds like borohydrides may be used to store hydrogen; when heated, they release their stored hydrogen.

Hydrogen in metal hydrides

• Stored in metal hydrides, which are materials that can absorb and release hydrogen in a reversible manner. • This method can have a higher energy density than compressed hydrogen storage.

Liquefied hydrogen storage

• Compressed to a liquid state, which allows for a much higher energy density than compressed hydrogen storage. • This method is commonly used for large-scale energy storage, such as for power generation or industrial applications.

Compressed hydrogen storage

• Stored at high pressures, typically between 300 and 700 bar. • This method is commonly used for transportation applications, such as fuel cell vehicles.

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PEMFC Systems and Hydrogen Energy Storage in EVs  211

8.4.1 Hydrogen Energy Production: Approaches with Challenges There are a variety of ways for producing hydrogen, and each one has its own set of challenges [33]. Some of the most common methods for creating hydrogen are included in Table 8.4. Large quantities of energy are required, the process is expensive, and there is a current shortage of infrastructure that might support hydrogen generation. Several existing techniques for producing hydrogen also entail burning fossil fuels, which releases harmful emissions such as carbon dioxide and other pollutants. This highlights the need for further study into how hydrogen may be produced more cheaply, efficiently, and sustainably [34].

8.4.2 Methods of Hydrogen Energy Storage: Approaches and Challenges Many strategies exist for accumulating and releasing hydrogen energy, each with its own advantages and disadvantages. Some means of storing hydrogen include: a) C  ompressed hydrogen storage: Hydrogen gas is stored at high pressures, typically between 300 and 700 bar (4,351– 10,152  psi). Transport applications, such as fuel cell cars, frequently use this technique. The method is easy to implement and yields substantial results. High-pressure storage tanks are required for this procedure, which may be costly and cumbersome and can cause leaks and explosions if not managed correctly [35]. b) Liquefied hydrogen storage: Liquid hydrogen has a greater energy density than compressed hydrogen because the gas is cooled and compressed to a liquid condition. This strategy is widely utilized for utility-scale and industrial-scale energy storage. Cryogenic storage tanks are essential for this procedure, but they may be costly and time-consuming to maintain, and they pose a risk of leaks and explosions if not managed correctly. c) Hydrogen in metal hydrides: Metal hydrides are reversibly absorbing and releasing hydrogen storage compounds. The energy density of this approach may be greater than that of compressed hydrogen storage. High-temperature storage

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212  Clean and Renewable Energy Production

Table 8.4  Hydrogen energy production: approaches with challenges. No.

Production method

Details

Challenges

(a)

Steam methane reformation

• Hydrogen is produced by reacting methane (natural gas) with steam to produce carbon dioxide and hydrogen. • Most widely used method of hydrogen production

• Challenge of producing carbon dioxide as a by-product

(b)

Electrolysis

• Produced by using electricity to split water into hydrogen and oxygen • It is considered a clean and renewable method of hydrogen production

• It uses a lot of expensive and high electric power.

(c)

Biological methods

• Produced by microorganisms through the fermentation of organic matter or by algae through photosynthesis • It has the potential to be a sustainable and lowcarbon method of hydrogen production.

• Scalability and costeffectiveness are issues in its early development.

(d)

Gasification

• Produced by gasifying solid or liquid hydrocarbons • Method has the potential to use a wide range of feedstocks.

• High energy, carbon dioxide, and capital expenses

(e)

Nuclear methods

• Produced by nuclear methods, such as hightemperature electrolysis or thermochemical methods

• Under study and face substantial capital costs, energy consumption, and nuclear waste disposal

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PEMFC Systems and Hydrogen Energy Storage in EVs  213

tanks are required for this procedure, which may be costly and cumbersome to maintain, and there is always the risk of leaks and explosions if not done correctly. d) Hydrogen in chemical hydrides: Hydrogen may be stored in chemical compounds like borohydrides, which can be heated to release the stored hydrogen. High-temperature storage tanks are necessary for this procedure, but they may be costly and time-consuming to maintain, and there is always the risk of leakage and explosions if they are not managed correctly. e) Hydrogen in carbon-based materials: Graphite and other carbon-based materials have the ability to adsorb hydrogen, making them suitable for hydrogen storage. Hightemperature storage tanks are required for this procedure, which may be costly and cumbersome to maintain, and there is always the risk of leaks and explosions if not done correctly. Overall, the challenges for hydrogen energy storage include the need for high-pressure or cryogenic storage tanks, which can be expensive and difficult to maintain and has the potential for leaks and explosions if not handled properly [36]. In addition, the existing state of hydrogen storage and transportation infrastructure might make it challenging to store and transfer hydrogen. As a result, further study is required to enhance the efficacy, affordability, and security of hydrogen storage technologies.

8.5 Future Scope, Challenges, and Benefits of FCEVs FCEVs have the potential to play a significant role in the future of transportation as they offer several advantages over traditional battery–EVs, such as longer range and faster refueling [37]. However, there are also several challenges that must be overcome for FCEVs to become widely adopted, such as the high cost of FC technology and the lack of hydrogen refueling infrastructure. a) C  ost reduction: Hydrogen storage systems must be improved to increase efficiency, cost-effectiveness, and safety. b) Hydrogen infrastructure: As more FCEVs are sold and governments and private enterprises invest in hydrogen fuelling stations, hydrogen refueling infrastructure will expand.

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214  Clean and Renewable Energy Production

c) G  overnment support: Government support, such as research and development funding and incentives for the adoption of FCEVs, can play a significant role in their development and deployment. d) Increased demand: As FCEVs become more widely available and the cost of FC technology continues to decrease, the demand for FCEVs is expected to increase. e) Improved performance: With advances in technology, FCEVs are expected to have longer ranges, faster refueling times, and improved fuel efficiency. FCEVs have a potential future, but they will need sustained research, investment in hydrogen infrastructure, and government assistance to become broadly accepted. FCEVs are more feasible than gasoline-powered automobiles and battery-­ powered EVs. Notwithstanding their benefits, FCEVs are hindered by many limitations. The negatives include high cost, insufficient infrastructure, inefficient hydrogen production, durability issues, and safety concerns. FCEVs are less convenient and accessible due to the high production costs and a lack of hydrogen fueling infrastructure. Fuel cell stacks wear out and must be replaced. Most hydrogen is still generated from fossil fuels, reducing the environmental benefits of FCEVs. The FC system’s inefficiency reduces the range. Moreover, hydrogen is highly flammable, making it a safety risk in FC system crashes. FCEVs must overcome several challenges to become mainstream. a) H  ydrogen availability: When compared to gasoline, hydrogen fuel is more expensive since it is less readily accessible and must be transported and stored. b) Durability: Long-term durability and reliability testing of FCs and associated components is ongoing. c) Safety concerns: Hydrogen fuel is flammable and requires careful handling, storage, and transport. d) Weather-dependent performance: Cold temperatures may lower the FC range and increase refilling requirements. e) Limited model availability: Limited number of FC-powered EV models available in the market. f) Public perception: FC-powered EVs still face public misconceptions and lack of awareness. FC-powered EVs offer numerous potential advantages, but they are still a novel technology and must overcome several obstacles before being

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PEMFC Systems and Hydrogen Energy Storage in EVs  215

generally used. FC-powered EVs also have benefits. They have a longer range than battery–electric automobiles and can be refueled as rapidly. FCs generate only hydrogen gas, making them more efficient and less polluting. FC vehicles emit only water vapor as a waste, making them more environment-­friendly than gasoline or diesel automobiles.

8.6 Pros and Cons of Electric Vehicles in the Aspect of Modern Transportation System Modern transportation networks may benefit from EVs over gasoline-­ powered automobiles. When considering their usage in current transportation networks, EVs have certain drawbacks. Table 8.5 lists several pros and cons of EVs. EVs have the potential to provide considerable advantages over gasoline-powered cars, but they must overcome various obstacles to be widely adopted in the current transportation system.

8.7 MATLAB/Simulink Study of FC-Powered Electric Drive System A MATLAB/Simulink study was carried out to develop the FC-powered electric drive system shown in Figure 8.3. Using MATLAB tools, users are able to simulate and study the system’s dynamics, including the interplay between the FC, power electronics, and electric motor. New beginners can be motivated to carry out the development of FC-powered EVs based on the fundamental mathematical modeling, as given in Table 8.6, using

Table 8.5  Pros and cons of EVs in the aspect of modern transportation system. Pros

Cons

• Lower emissions

• Limited range

• Better performance

• High upfront cost

• Increased energy security

• Limited charging infrastructure

• Reduced noise pollution

• Limited availability of models

• Lower fuel costs

• Battery degradation and replacement cost

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216  Clean and Renewable Energy Production

+ v –

Discrete 2e-06 s.

+ v – Speed (RPM)

Torque

Scope 1 Tm

w

-K-

fcn Pulses PEMFC +

g

+

Conn3

+

–

Po2

Ph2

PEMFC Conn4

A

PO2

H2

Figure 8.3  MATLAB/Simulink modeling of fuel cell (FC).

Tm

B

C

C

–

A

B

IGBT Inverter H2 Oxygen Pressure1 Pressure

Torque (N.m)

DC-DC Chopper

m

Induction Motor 5 HP / 460 V1

-K-



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PEMFC Systems and Hydrogen Energy Storage in EVs  217

Table 8.6  Mathematic modeling of proton exchange membrane fuel cell (PEMFC) [15, 16, 37, 38].

Vfc = E − Vact – Vconc − Vohm

Fuel cell voltage (Vfc)

E is the open circuit potential; Vact the activation voltage; VConc the concentration voltage; and Vohm is the Ohmic voltage Nernst voltage

E

E0

RT ln 2F

PH2 PH2 O

PO2

1 2

E0 is the reference voltage; R the gas constant; T the cell temperature; F the Faraday constant; PH2 , PO2 , PH2O are the hydrogen, oxygen, and water flow pressure, respectively Activation voltage (Vact) and oxygen concentration

Ohmic voltage and membrane resistance

Conc .O2

PO 2 6

498

Vact

k1 k2T

5.08 10 e K1, K2, and K3 are constants and Ifc is the fuel cell current T

Vohm = Ifc Rmem,… Rmem =

ln

(I fc )k3 (Conc.O2 )k4T

tm σ

tm is the membrane thickness; σ is fuel conductivity; and Rmem is the membrane resistance (Continued)

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218  Clean and Renewable Energy Production

Table 8.6  Mathematic modeling of proton exchange membrane fuel cell (PEMFC) [15, 16, 37, 38]. (Continued)

Concentration voltage

Vconc = η1 − η2 (T − 273)e (η3l ) F1, F2, and F3 are coefficients

Hydrogen fuel pressure

PH2

mH2 RH2 Vanode

T

Vanode is the anode voltage; mH2 is the hydrogen molar flow rate; and RH2 is the hydrogen gas constant Oxygen fuel pressure

PO2

mO2 RO2 Vcathode

T

Vcathode is the cathode voltage, mO2 is the oxygen molar flow rate; and RO2 is the oxygen gas constant

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PEMFC Systems and Hydrogen Energy Storage in EVs  219

1000

VFC (V)

800 600 400 200 0

0

0.5

1 Time (Sec)

1.5

2

Figure 8.4  Transient response of proton exchange membrane fuel cell (PEMFC) voltage.

Stator current: Iabc (A)

600 400 200 0 –200 –400 0

0.5

1 Time (Sec) (a)

1.5

2

0

0.5

1 Time (Sec) (b)

1.5

2

0

0.5

1 Time (Sec) (c)

1.5

2

ω (rad/sec)

2000 1500 1000 500 0

EM Torque (N.m)

400 200 0 –200 –400

Figure 8.5  Transient response. (a) Stator current. (b) Rotor speed. (c) Electromagnetic (EM) torque.

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220  Clean and Renewable Energy Production

some control schemes related to EVs’ related methodologies, which may be beneficial in the study of FC-powered EVs by enhancing the system’s performance and efficiency and spotting possible flaws before physical prototypes are produced. The transient response of the PEMFC-powered electric drive system is explored through the investigation on the generated FC voltage and behavior of the assisted electric drive system in terms of the stator current, settling response of the rotor speed, and electromagnetic (EM) torque, as displayed in Figures 8.4 and 8.5.

8.8 Conclusion Ultimately, future EVs for transportation may depend on PEMFC systems and hydrogen energy storage. PEMFC systems have various advantages over batteries, including higher energy density and range. The expensive cost of FC technology and the lack of a hydrogen refueling infrastructure prevent the widespread adoption of PEMFC systems. Hydrogen energy storage is essential for hydrogen’s widespread usage as an energy carrier. Hydrogen storage improves the supply and usage flexibility. Hydrogen energy storage requires high-pressure or cryogenic storage tanks, which are expensive and difficult to maintain and may leak or explode if not handled properly. Hydrogen storage and transport are lacking. PEMFC systems and hydrogen energy storage in EVs are promising, but they will need sustained research and development, investment in hydrogen infrastructure, and government assistance to become widely utilized. The mathematical modeling of PEMFC and a MATLAB/Simulink model to aid the electric drive system illustrate newcomers in the same study field the essential orientation toward EVs.

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PEMFC Systems and Hydrogen Energy Storage in EVs  221

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PEMFC Systems and Hydrogen Energy Storage in EVs  223

storage and power generation with wind energy. Renew. Sustain. Energy Rev., 168, 1–14, 2022. 35. Usman, M.R., Hydrogen storage methods: Review and current status. Renew. Sustain. Energy Rev., 167, 1–11, 2022. 36. Sun, Y., Xia, C., Yin, B., Gao, H., Han, J., Liu, J., Energy management strategy for FCEV considering degradation of fuel cell. Int. J. Green Energy, 20, 1, 28–39, 2023. 37. Pachauri, R. and Chauhan, Y.K., A study, analysis and power management schemes for fuel cells. Renew. Sustain. Energy Rev. (Elsevier), 43, 1301–1319, 2015. 38. Pachauri, R.K., Chauhan, Y.K., Gupta, A., Proton exchange membrane fuel cell: Investigation of control schemes for reactants flow pressure. Energy Sources Part A: Recovery Util. Environ. Eff., 39, 1, 75–82, 2016.

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224  Clean and Renewable Energy Production

Ocean Energy—A Myriad of Opportunities in the Renewable Energy Sector R. Raajiv1*, R. Vijaya Kumar2 and Jitendra Kumar Pandey3 Indian Navy, Mumbai, India Indian Institute of Technology IIT(M), Chennai, India 3 University of Petroleum and Energy Studies, Dehradun, India 1

2

Abstract

Oceans constitute 70.8% of the Earth’s surface and accounts for approximately 97% of the water on Earth. Massive depletion of fossil fuels has been a cause of concern in the world scenario primarily due to its depletion and because of its effects on the environment. According to the National Oceanic and Atmospheric Administration (NOAA) reports, the carbon dioxide level from its Mauna Loa Atmospheric Baseline Observatory is 421 ppm, which is in stark comparison to the level of 220 ppm measured during the start of the Industrial Revolution. The widespread oceanic region on earth is an enormous source of renewable energy and has diverse forms of low-carbon technologies, which will enable nations a faster and reliable transition to greener energy. These transitions will enable coastal countries and island nations to achieve lesser greenhouse gas (GHG) emissions. A comprehensive study involving life cycle assessment of the technology, environmental impacts, and sustenance of the project toward future proofing will enable better promotion of ocean energy resources. Europe leads the world’s nations in design and in research and development of ocean energy projects. The European Commission has allocated 47% and 25% of funds toward the development of wave and tidal energy projects and 17% toward environmental research. It is imperative that nations should come together toward the promotion of ocean energy and its importance in future. Keywords:  Wave energy, tidal energy, OTEC, salinity gradient, IRENA

*Corresponding author: [email protected] Surajit Mondal, Adesh Kumar, Rupendra Kumar Pachauri, Amit Kumar Mondal, Vishal Kumar Singh and Amit Kumar Sharma (eds.) Clean and Renewable Energy Production, (225–246) © 2024 Scrivener Publishing LLC

225

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9

9.1 Introduction The rapidly depleting fossil fuel reserves and the increasing volatility in the oil-rich nations of the Middle East have forced world nations to recourse their energy strategy toward dependency on coal and other fossil fuels [1]. The Middle East oil crisis in the 1970s is a classic example as to how volatile oil prices can surge [2]. The search for better renewable resources to reduce the dependency on fossil fuels began, with many nations coming forward to promote funding and research. The concept has been fairly successful in a few sectors, such as solar and wind; however, project implementation is yet to start in other sectors, especially in the ocean energy sector. The main causes of reluctance toward implementation are the high initial capital costs, timelines toward the implementation of enormous projects, sustainability of the firm execution of the project, and the non-availability of continuous research and development in the area. Migration from fossil fuels to complete renewable energy source requires very large-scale implementation of projects for a sustainable future. However, the complexity of project implementation is more often social and political rather than being technological and economic causes. In order to prevent the catastrophic depletion of the ozone layer, it is imperative that the implementation of renewable energy projects around the world be advanced at a faster pace. The implementation of green banks by many nations is one of the many approaches to promote cleaner energy sources. These green banks, in partnership with private sectors, aid in promoting cleaner energy technologies. The Green Bank Network (GBN) was formed at the Conference of Parties (COP 21) held in Paris in 2015 [3]. COP 21 is also known as the Paris Agreement. The GBN comprised the Japan Green Fund, the Australian Clean Energy Finance Corporation, Malaysian Green Technology and Climate Change Center, Connecticut Green Bank, NY Green Bank, and the Green Investment Group, UK. These agencies work in close proximity with two nonprofit organizations, viz., the National Resources Defense Council (NRDC) and the Coalition for Green Capital (CGC), with funding from Climate Works, California. The International Renewable Energy Agency (IRENA) reported that, by mid-2022, around 176 countries would have invested toward setting up one or more forms of renewable energy projects within their country. Toward its mission 2050 goal, IRENA has identified six vital technological avenues [4], which would cut down 37  Gt of CO2 emissions. These reductions can be achieved through: (a) electrification through renewable

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226  Clean and Renewable Energy Production

energy means (25%); (b) usage of clean hydrogen and its derivatives as fuel (10%); (c) improvements in energy efficiency (25%); (d) electrification of vehicles and heat pumps (end-use sectors, 20%); (e) usage of bioenergy coupled with carbon capture and storage (6%); and (f) last mile usage of carbon capture and storage. Phasing out coal energy is an important step toward the transition to cleaner energy. However, this task is largely complex for many nations, where the dependency on coal is still at its peak, as over 30% of coal consumption is utilized in iron, steel, cement, and other industries [5]. Hence, there is an urgent need for international cooperation to tackle these trivial issues and to move toward achieving a common goal toward utilizing renewable sources as primary sources of energy. Several types of renewable energy resources, viz., wind, solar, and hybrid sea–wind energy have been deployed all over the world. However, there is a tremendous source of energy available in oceans in the forms of tide and waves. Wave energy is an endless source of sustainable renewable energy, which can sustain coastal nations and islands for a very long time in the future [6]. The change in climatic conditions has caused variations in the generation of electricity from renewable sources such as solar and wind. However, climatic conditions do not affect the energy generated by waves [7]. Europe is leading in the implementation of wave and tidal energy projects around the world. The La Rance Tidal power plant in France has been operational since 1966 [8] and has shouldered approximately 0.12% of the total energy demand of the country. Unlike wind and solar energy, the complexity of energy conversion and the necessity of high-capacity energy storage devices will be prerequisites to realizing the true potential of ocean energy. A focused approach, heightened interest, and public awareness of the true potential of energy extraction from the ocean will pave the way for achieving a sustainable renewable energy source for the future.

9.2 International Agencies Promoting Ocean Energy Projects Many international agencies comprising several nations have come together toward promoting the potential of energy generation from oceans. (a) The International Renewable Energy Agency (IRENA) [9], which comprises 167 countries, is a lead intergovernmental agency that promotes research and international

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Ocean Energy in the Renewable Energy Sector  227

cooperation in the area of renewable energy, enables the sharing of resources, and aids in acceleration toward the transition to renewable energy sources worldwide. (b) Ocean Energy Europe (OEE) is the largest network of various institutes, energy professionals, and academics from over 120 organizations working toward enhancement of growth of Europe’s ocean energy [10]. (c) Ocean Energy Systems (OES) is derived from the Technology Collaboration Programme on OES [11], an agency formed under the aegis of the International Energy Agency (IEA) in 2001 to promote and develop methodologies to extract energy from the ocean. The agency has collaborations with 29 countries with the singular aim of advancing ocean energy research. (d) The European Marine Energy Centre (EMEC) was established in 2003 and is one of the leading wave and tidal energy test facilitators around the world. The broad purpose of EMEC is to reduce the cost and maximize the results for wave and tidal projects. The center has 13 grid-connected test berths for undertaking the trials [12] and has a large network of collaborations with academic institutions and developer companies all around the world. (e) WECANet is a consortium of 31 partner countries to promote training, awareness, and funding opportunities for researchers irrespective of any country [13]. It also propagates the main challenges toward the development of wave energy projects.

9.3 Ocean Energy Potential Ocean energy has tremendous potential to shoulder a greater chunk of the entire Earth’s energy requirements. Promoting the advantages of a clean energy resource and improving the global knowledge about the resourcefulness of ocean energy potential will pave ways toward more countries investing in this form of renewable energy. The world ocean energy statistics report states that there has been a rising trend in the installations of wave and tidal energy projects (1.39 and 3.12 MW, respectively) from 2021 [14]. There has been significant development in the ocean energy sector after the coronavirus disease 2019 (COVID-19) pandemic, and

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228  Clean and Renewable Energy Production

World consumption

Shares of global primary energy

Exajoules

Percentage

600

Renawables Hydroelectricity Nuclear energy Coal Natural gas Oil

Oil Coal Natural gas

Hydroelectricity 50 Nuclear energy Renewables

500 40

400 30 300 20 200

10

100

00

03

06

19

12

15

18

21

0

00

03

05

09

12

15

18

21

0

30,000

8,000 7,000

25,000

6,000

20,000

5,000

15,000

4,000 3,000

10,000

2,000

5,000

1,000 0

2010 2011 2012 2013 2014 2015 2016 2017 2018 2019 2020 2021 Annual - Europe Cumulative - Europe

(b)

Annual - Rest of the world Cumulative - Rest of the world

0

3,000

14,000

2,500

12,000

2,000

10,000 8,000

1,500

6,000

1,000

4,000

500

2,000

0

0

Cumulative capacity additions (kW)

Annual capacity additions (kW)

9,000

Cumulative capacity additions (kW)

35,000

10,000

Annual capacity additions (kW)

(a)

2010 2011 2012 2013 2014 2015 2016 2017 2018 2019 2020 2021 Annual - Europe Cumulative - Europe

Annual - Rest of the world Cumulative - Rest of the world

(c)

Figure 9.1  Clockwise from bottom: (a) Wave energy projects around the world [15]; (b) tidal energy projects around the world; and (c) world energy consumption, data sector wise [16].

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Ocean Energy in the Renewable Energy Sector  229

many multinational companies, viz., Schneider Electric, GE Renewable Energy, Kawasaki Kisen Kaisha, and Chubu Electric Power, have signed deals in 2021. Despite the steady rise in the ocean energy projects, these developments only form a part of the miniscule percentage in the renewable energy sector. Statistical review of the world’s energy by the British Petroleum (BP) company reports that oil remains the primary source of energy across all continents [15]. A graphical representation of the world energy consumption as per energy resource, as well as a comparative growth of the world’s wave and tidal energy projects over the years, is shown in Figure 9.1. The solar renewable era has progressed ahead in multidimensions with the introduction of newer concepts, such as floating solar energy farms. These farms have widespread acceptance and have been adapted over various countries because of their distict advantages.

9.4 Types of Ocean Energy Ocean energy is broadly classified under two major heads: mechanical energy, the energy generated from tides and waves, and thermal energy, the energy derived from the temperature difference between the layers [17]. The subcategories under these major heads are illustrated in Figure 9.2 below.

9.5 Tidal Energy The surging of the ocean waves causes the rise and fall of seawater known as tides. These tides, based on the position of the crest and trough of waves at a particular position, are categorized into high tide and low tide. These tides vary based on the gravitational effect of the moon. Tidal energy can be defined as the energy extracted from the movement of tides through a series of mechanical installations, which in turn is converted into electrical energy [18]. Water has far greater power than the wind because of its dense nature and, thus, generates a greater force output. Depending upon the weather in a particular region, the height of tides is usually mapped. This enables predicting the tidal energy generation in a particular region. The usage of tidal power dates back to the Middle Ages, when mills were constructed on river estuaries close enough to the sea to cause tidal variations. Many of these tide mills are still functioning on a very small scale

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230  Clean and Renewable Energy Production

TIDAL

TYPES OF OCEAN ENERGY

CURRENTS

WAVE

HOLE

SEA LEVEL SEA WATERLINE PIPE

PIPE Machine wheel water

OTEC

PIPE WATER BASE

TRANSFER PIPE

THYLINE

ELECTRIC PIPELINE HOLE LINE WATER LINE WATER LINE [500mm]

HOLE LINE PIPE

ELECTRICITY QUALIFICATIONS Top motor

SALINITY GRADIENT

Air pollution

Pressure management

Ball magnet

Air pollution

Electric magnet Parameter

Figure 9.2  Types of ocean energy sources.

Ball magnet

BUTTON PIPE

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Ocean Energy in the Renewable Energy Sector  231

around the world. Tidal power can be classified into four major types [19], as follows: (a) Tidal stream generator (b) Tidal barrage (c) Tidal lagoon (d) Dynamic tidal power

9.5.1 Tidal Stream Generator Tidal stream generator operates in a similar concept to a wind turbine. The water current provides the requisite energy to these turbines. Tidal stream generators are also known as tidal energy converters (TECs), which extract energy from tides. There are six main types of tidal stream generators recognized by the EMEC [20]. For energy generation, these generators are required to be placed in areas where there is presence of faster currents. The various types of tidal energy converters are shown in Figure 9.3. (a) Horizontal axial turbines (b) Vertical axial turbines (c) Oscillating hydrofoils (d) Archimedes’ screws (e) Venturi devices (f) Tidal kites

9.5.2 Tidal Stream Barrage In a tidal stream barrage, the energy is captured from the flow of water masses through a dam-like structure fitted with turbines. Tidal power stations across the world are depicted in Table 9.1. Tidal stream barrages have very high capital costs, but extremely low running costs. In addition to the above, tidal barrages are plagued with environmental impacts, viz., sediment flow, salinity, fish mortality, and change in biological diversity.

9.5.3 Tidal Lagoon Tidal lagoons capture large volumes of water behind a man-made structure, which is then released to drive turbines and generate electricity. The structure spans an entire river estuary in a straight line, while a tidal lagoon encloses an area of coastline with a high tidal range behind a breakwater catering for the local environment. By optimizing the levels between the

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232  Clean and Renewable Energy Production

Figure 9.3  Clockwise from bottom: (a) Archimedes’ screw [20]; (b) Flumill technology tidal turbine [21]; (c) Venturi-based tidal turbine technology [22]; (d) standard Venturienhanced turbine technology (VETT) turbine installation at Eaton Socon, Cambridgeshire, UK [22]; (e) Minesto tidal kites [23]; (f) Minesto 100-kW Dragon-4 tidal energy device [24]; (g) oscillating wave surge converter [25]; (h) oscillating hydrofoil [26]; (i) 30-kW ocean mill prototype [27]; (j) CMN HydroQuest tidal turbine [28]; (k) Sea Monster tidal turbine [29]; and (l) O2 680-tonne tidal turbine [30].

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Ocean Energy in the Renewable Energy Sector  233

Table 9.1  Important tidal power stations around the world.

Sl. no.

Name

Location

Capacity

Status

(a)

Rance Tidal Power Station [31]

Rance River, Brittany, France

240 MW

Active

(b)

Kislaya Guba Tidal Power Station [32]

Kislaya Guba, Russia

1.7 MW

Active

(c)

Jiangxia Tidal Power Station [33]

Wuyantou, Wenling City, Zhejiang Province, China

3.2 MW

Active

(d)

Sihwa Lake Tidal Power Station [34]

Sihwa Lake, Gyeonggi Province, South Korea

254 MW

Active

(e)

Annapolis Royal Generating Station [35]

Annapolis Royal, Nova Scotia, Canada

20 MW

Decomissioned

(f)

Uldolmok Tidal Power Station [36]

Uldolmok, Jindo, South Korea

1 MW

Active

(g)

MeyGen Tidal Energy Project [37]

Scotland

6 MW

Active

(h)

Eastern Scheldt Barrier Tidal Power Plant [38]

Netherlands

1.25 MW

Active

(i)

Bluemull Sound Shetland Tidal Array [39]

Bluemull Sound, Shetland, UK

0.4 MW

Active

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234  Clean and Renewable Energy Production

lagoon and the sea, the energy generated can be easily predicted. On an average, there are about two low tides and two high tides in a day; hence, tidal lagoons will generate electricity almost four times a day [33]. Turbines are “bidirectional” aids in the generation of power during flooding and during ebbing. Due to continuous delays, the Swansea Tidal Lagoon Project, touted to be the first large-scale tidal energy project in the world, has not yet completed construction as of date [40].

9.5.4 Dynamic Tidal Power Dynamic tidal power (DTP) is a futuristic power generation concept patented by two Dutch engineers, Kees Hulsbergen and Rob Steijn, in 1997 [41]. This tidal project involves the construction of a long dam-like structure perpendicular to the coastline. This T-shaped structure, when interfering with tides, causes a difference in levels, which in turn enables the turbines to rotate, producing electricity. Powerful hydraulic currents are present in oscillating tidal waves that are found near the continental shelf regions of Korea, China, and the UK [42]. The technology looks promising; however, there has not been real inclination toward further research or award of project under this particular renewable energy head.

9.6 Tidal Currents The kinetic energy stored in tidal streams or tidal currents is converted into usable energy. Tidal current energy converters are classified into three major types [43]. (a) Horizontal axis tidal current turbines (HATCTs) (b) Vertical axis tidal current turbines (VATCTs) (c) Other non-turbine devices As per statistics, HATCTs account for over 76% of the tidal current turbines, VATCTs for 12%, and the remaining 12% comprises reciprocating and other tidal current systems [44].

9.7 Wave Energy The wind that passes over the sea surface causes waves. The extraction of stored energy from these waves is undertaken using a device known as

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Ocean Energy in the Renewable Energy Sector  235

PCM Nose tu

be

Yoke

e

b Mid tu

Mid

tube

be

End tu

Latching assembly Dynamic down feeder cable

Yaw restraint line

Forward moorings

PELTON WHEEL & GENERATOR

OSCILLATOR

SUB STATION

SEA RETURN SEA WATER PISTON FLOW LINE

air flow

rising water column

wave trough

falling water

Displacer

Reactor

Figure 9.4  Clockwise from bottom: (a) Schematic of the pressure differential [45]; (b) pressure differential submerged/semi-submerged device [46]; (c) schematic of waveactivated device [47]; (d) 3D DEXA wave device [48]; (e) Oyster 800 [49]; (f) Oyster oscillating wave surge converter [50]; (g) Pelamis Wave Energy Converter at Orkney [6]; (h) AquaBuOy point absorber [51]; (i) Ocean Power Technologies point absorber [52]; (j) PowerBuoy point absorber [53]; and (k) land-installed marine power energy transmitter (LIMPET) oscillating water column (OWC) on the Isle of Islay [54].

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236  Clean and Renewable Energy Production

wave energy converter (WEC). On the basis of its working principles, these WECs are classified into the following types (as shown in Figure 9.4). (a) Oscillating water columns (OWCs) (b) Point absorber buoy (c) Surface attenuator (d) Oscillating wave surge converter (e) Wave-activated bodies (f) Submerged pressure differential converters (g) Floating-in air converters The world’s first commercial wave power device was installed at Islay and was connected to the national grid of the UK. The land-installed marine power energy transmitter (LIMPET) device in Islay was based on the OWC concept, where, in the column, variations push the air in and out of the chamber driving a Wells turbine [55]. The project had an initial capacity of 75 kW in 1991 [56] and was scaled up to 500 kW in 2000. The LIMPET Project was decommissioned in 2018.

9.8 Ocean Thermal Energy Conversion The temperature difference between subsurface (lower) and surface (higher) water is utilized to drive a heat engine, which in turn produces usable energy. Ocean thermal energy conversion (OTEC) systems are classified into three major types: (a) open-cycle OTEC plants; (b) closed-cycle OTEC plants; and (c) hybrid OTEC plants. Currently, the only functional land-based OTEC plant is situated in Kume Island, Japan. Although touted Table 9.2  Ocean thermal energy conversion (OTEC) plants around the world. Sl. no.

Name

Location

Capacity

Status

(a)

Okinawa OTEC Plant [57]

Kume Island, Japan

100 kW

Active

(b)

OTEC powered test bed facility [58]

Hawaii

105 kW

Ongoing

(c)

NER 300 Project Nemo [59]

St. Martinique

10 MW

Failed due to technical issues

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Ocean Energy in the Renewable Energy Sector  237

to be a renewable energy with immense energy generation potential, OTEC technology is plagued with several constraints, such as very high capital investments, failure of pipelines, biofouling in heat exchangers’ reduced efficiency, high maintenance costs, and higher system downtime. A few of the notable OTEC projects around the world are listed in Table 9.2.

9.9 Salinity Gradient The difference in the salinity levels between two water bodies creates a chemical pressure differential from which electricity can be generated. The high salinity content in seawater causes a higher osmotic pressure when compared with freshwater. Salinity gradient projects are classified into two major types. (a) Pressure retarded osmosis [60]: Osmotic pressure arising from saline solutions is converted into hydraulic pressure, which in turn drives a turbine generating electricity.

IJssel Lake closure dam pilot plant Blue energy Brakish water

Wadden sea

fresh water

salt water

Figure 9.5  Pictorial representation of reverse electrodialysis (RED) installed in the Netherlands [62].

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238  Clean and Renewable Energy Production

(b) Reverse electrodialysis (RED) [61]: The creation of reaction similar to positive and negative terminals of a battery is achieved using a mixture of two varying compositions of saline solutions. The world’s first RED was inaugurated in the Netherlands in 2014. The pilot plant uses freshwater from Ijssel Lake and seawater from the Wadden Sea [62], as shown in Figure 9.5. It is estimated that approximately 50 kW/h will be generated on an average.

9.10 Marine Energy Projects in India 9.10.1 Case Study 1 Many of the ocean energy projects do not sustain due to discontinuation of funding, loss of interest/confidence in the project, downtime of equipment, high maintenance costs, limited knowledge, and lack of public support. The world’s first wave energy project based on OWC was installed in Vizhinjam, Thiruvananthapuram, Kerala (Figure 9.6). The 150-kW plant utilized the change in the level of waves inside a caisson to generate power. When the water level increases inside the caisson, the

Figure 9.6  Clockwise from bottom: (a) Present status of the Vizhinjam oscillating water column (OWC) project. Photo credit: Cdr (Dr) R. Raajiv; (b) OWC project during its operational period at Vizhinjam, Kerala [63]; and (c) OWC plant view from the beach [64].

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Ocean Energy in the Renewable Energy Sector  239

(a)

100 MW OF POWER ~120,000 Hawaiian Homes Powered by Seawater

ONSHORE OTEC (OPERATIONAL) MAKAI OTEC

OFFSHORE OTEC (FUTURE) WARM WATER INTAKE

OTEC

Temperature: 25˚C (77˚F) Ocean Depth: 60ft (18m)

100 MW OF POWER ~120,000 Hawaiian Homes Powered by Seawater

MIXED WATER RETURN Temperature: 16˚C (61˚F) Ocean Depth: 330 ft (100m)

COLD WATER INTAKE Temperature: 5˚C (41˚F) Ocean Depth: 3,000 ft (1,000m)

(b)

Figure 9.7  (a) Floating test platform OTEC plant [69] and (b) schematic of the ocean thermal energy conversion (OTEC) technology [70].

air becomes compressed, which in turn drives an air turbine. The plant generated maximum electricity during the monsoon months. The plant was non-operational for a considerable duration and was finally decommissioned in 2011.

9.10.2 Case Study 2 India has tested its first floating OTEC power plant near Tuticorin (Figure 9.7(a)), Tamil Nādu, in 2000 [65]. The project is currently non-functional due to a technical issue. It is estimated that the generation capacity of

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the OTEC technology in India is around 180,000  MW, including 40% as parasitic losses [66]. Despite the efforts, OTEC technology (Figure 9.7(b)) could not be established as of date. Several projects have been conceived with the inclusion of OTEC technology for island areas, viz., Lakshadweep [67] and Andaman and Nicobar Islands [68]. A pilot study was undertaken by the then French conglomerate M/s DCNS (now M/s Naval Group) to set up a 20-MW OTEC plant in Andaman and Nicobar Islands to power up the naval bases (which were utilizing fossil fuel) [69].

9.11 Conclusion Ocean energy, when truly realized, will be an enormous resource for sustaining the energy requirements of the human civilization for a considerable time in the future. The key takeaway prior to considering project implementation is to undertake a comprehensive life cycle assessment (LCA) study. It has been observed, especially in the ocean energy sector, that pilot projects and theoretical study reports often do not see the light of day. This is primarily due to incorrect assessment of the technology, inability to deploy it on a larger scale, extreme capital costs, long lead time for the realization of investment, high maintenance costs, higher system downtime, inadequate knowledge among masses, and less social and political support. Government incentives and promotion of private investments in the ocean energy sector will provide the necessary impetus toward the ocean energy sector. Impact analysis criteria must also include the impacts of energy generation, energy transportation, energy storage, efficiency, and continuous supply to the national grid. A considerable amount of investments has taken place in the last 5 years in the renewable energy sector to an extent; in hybrid ocean energy involving ocean–wind energy, there is considerable scope for investment in the mainstream sectors of ocean energy. Taking into account the theoretical energy generation capability, ocean energy is to be carefully configured for integration into the energy grid at the earliest opportunity.

Author Contributions RR contributed to the review, writing, and editing data analysis, as well as collation of data and discussion. RVK and JKP worked in writing review and visualization.

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Ocean Energy in the Renewable Energy Sector  241

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242  Clean and Renewable Energy Production

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Ocean Energy in the Renewable Energy Sector  243

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Performance of 5 Years of ESE Lightning Protection System: A Review Sachin Kumar*, Gagan Singh† and Nafees Ahamad Department of Electrical and Electronics & Communication Engineering, DIT University, Dehradun, Uttarakhand, India

Abstract

This article shows a 5-year performance review of an early streamer emission (ESE) air terminal lightning protection system for a large-scale photovoltaic (PV) power plant. The differentiation of a Franklin lightning protection system and the ESE lightning protection system was evaluated for the PV power plant. The ESE lightning protection system was preferred to be executed in the PV power plant. In an area of 150,000  m2, the calculated total capacity of the PV power plant was 8 MWp in Phetchaburi Province of Western Thailand. A Franklin-type lightning rod was also planned to be executed in this PV power plant. The Franklin-type lightning rod involved 122 pieces; however, the ESE-type lightning rod involved only 11 pieces. The technical design of the Franklin-type rod followed the standard of the Council of Engineers, Thailand, while the ESE-type lightning rod followed the NFC17102 standard of France. The approximate cost of installation was a basic differentiation to choose the lightning protection system. The total installation cost of the Franklin-type lightning rod was USD 197,363.60, while that of the ESE-type lightning rod was USD 44,338.16. The lightning structure was applied to the lightning arrester in the power plant to give fine protection, through which the equity of the pole to the mounting position is needed to improve the system performance. The outcome of the simulation also displayed that the shading effects of the Franklin-type rod were larger than those of the ESE-type rod. The installation cost of the Franklin-type lightning rod was 4.45 times more costly than that of the ESE-type lightning rod. Thus, the ESE lightning protection system was preferred to be applied in the PV power plant. From the list of recorded data of the 5-year (2016–2020) performance of the ESE lightning protection system, there were three *Corresponding author: [email protected] † Corresponding author: [email protected] Surajit Mondal, Adesh Kumar, Rupendra Kumar Pachauri, Amit Kumar Mondal, Vishal Kumar Singh and Amit Kumar Sharma (eds.) Clean and Renewable Energy Production, (247–266) © 2024 Scrivener Publishing LLC

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10

incidents of a lightning strike on the PV power plant. The ESE lightning protection system more effectively protected and prevented the lightning strike to the PV power plant. Thus, this analysis can help with and support the choice of a lightning system for the protection of broad-scale PV power plants in the future. Keywords:  Power plant, Franklin lightning protection, ESE lightning protection

Introduction A solar power system is a system that converts energy from sunlight, which is widely used nowadays because the price per unit has decreased. Furthermore, the technology builds the performance of the equipment higher. Anyhow, the blocking of light to the solar panel decreases the efficiency held into account. Thus, an installation draw must escape the incident light to the solar panel installed. Nowadays, photovoltaic (PV) applications contain ground- and roof-mounted installations. The building range for solar panel installation has also been installed inside the sea or large water sources for the highest benefit. One thing to study when installing a PV system is the precaution of lightning strikes on the solar panels, which cause damage to the installed solar power system. Lightning protection is needed for the installed solar system in open areas or high-rise range, such as outdoor installations. A lightning protection system will issue lightning to come down to the protection system in place of cutting to the installed power system. It is essential to design a lightning protection system that is suitable for all applications. Nowadays, lightning protection systems include the Franklin air terminal lightning protection system with the streamer emission air terminal protection system. The variation between these two systems is the protection radius at the same height, in which the early streamer emission (ESE) system uses a lower number in the same range. By using this lower number, the grounding system of the two systems varies suitably, resulting in the Lower installation cost of the lightning arrester. The protection range of the Franklin air terminal lightning protection system at a pole with a height of 10 m has a protection radius of 21.6 m, while an ESE system with a height of 10 m has a protection radius of 109 m. This variance, if installed in the same area, will result in a separate grounding system. Lightning is a natural incident that affects humans, properties, and the environment, also it can be the reason of huge damage such as blast, fire, or death. Hence, there have been many investigations to protect against lightning effects. Normally, the damage forms of the lightning strike can be split into three parts: electrical, thermal, and mechanical damage. Several researchers have measured the effects of lightning, from which the draw for

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248  Clean and Renewable Energy Production

PV power plants and property protection has been suggested [1–6]. Research has been conducted to analyze the installation costs of PV power plants [7, 8], in which the investigation included the two types of lightning protection systems [9]. There have been investigations on the variations between two points of the lightning effects on the PV rooftop [10]. One of the studies used a vector modulation method of equivalence circuits to inspect the transient generated from the lightning strikes in a PV power plant [11]. There was a research on the systemic effects of lightning [12], where a grid ground protection system for helping lightning strikes was implemented, although at a high cost of installation [13]. The effects of lightning have been examined on the change in soil resistivity, in which lightning affected the contraction of the ground resistance value [14]. The repeating effect of impulse voltage on the panel caused the panel power to reduce accordingly [15]. A research on the risks of installing a PV rooftop system was done to confirm that the installation of this system was successful by estimating the risks of many structural systems connected to the type of installation on the roof [16]. In Ahmad et al. [17], the effect of lightning-induced high voltage on a hybrid solar system applying Electromagnetic Transients Program— Restructured Version (EMTP-RV) software was introduced. This software was established by investigating the results of lightning-induced overvoltage by applying indirect lightning strikes close to the system. It was established that the induced results on the system and on the impulse opposing the voltage of the DC and AC systems should be removed. Due to the above details, this paper studies the effects of light cover and the initial installation costs of both data systems to determine the installation costs of the lightning protection structure of the studied power plants.

Theoretical Background Lightning is due to the transferring of electric charges between clouds and the ground. They are: 1) negative charge from the cloud to earth, 2) positive charge from the cloud to earth, 3) negative charge from the earth to the cloud, and 4) positive charge from the earth to the cloud. The striking space or lightning return stroke is described by the current magnitude of the lightning strike along the rolling sphere, as of Equation (10.1) [4] as follows:

i(o, t)

t t1

i0 1

n

t t1

n

exp

t t2

(10.1)

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Performance of ESE Lightning Protection System  249

where i0 is the current magnitude of the lightning strike; t1 is the front time of the lightning strike; t2 is the decay time of the lightning strike; and n is the exponent value (2–10), which can be expressed by Equation (10.2) [18].

exp

t1 t2

1 n

t2 n t1

(10.2)



LIGHTNING CONDUCTOR INSTALLATION DIAGRAM

ESE Lightning rod Copper strip/wire connected through lug to lightning conductor Staywire Hook 2m 6m

Nylon/SS tie

6m 5m GI pipe shaft

GI coupler

Test Joint Pit Cover

Hook

50 sq.mm conductor

50mm2 Copper conductor

m

Starywire ≥50mm

≥

10 0m

Lightning Counter

≥ 12 mm

Protection pipe (1”–1 ”) ¼

Hook fastener Clamp 600 × 600mm concrete

Earth pit tripod type consisting of copper bonded rod 17.2mm dia 3m long 250µ, backfill compound & pit cover

≥ 110 mm

≥ 350 mm (5mm thick)

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250  Clean and Renewable Energy Production

The design idea of external lightning is explained by utilizing two systems for a design procedure related to the conventional and ESE systems. Hence, the lightning protection design included an air termination system and a separator space. The down conductors, earth termination, and lightning equipotential bonding were not concentrated on in this pattern. (A) The conventional system is explained by utilizing IEC/EN 32305 for a pattern reference connected to three methods for protecting the PV power plant. 1. The protective angle technique is explained by utilizing the height level of the lightning rod and the angle under shade theory. Hence, the height level may affect the PV power plant and required to be explained as the separation space clearance. 2. The rolling sphere method is commonly named the electro-­geometric model, which is utilized to illuminate by a radian, from Equation (10.3) [19], to discover the air terminator rod position for installation and is enforced by utilizing the protective angle technique for the PV power plant protection. It includes four lightning protection categories connected by the calculation of value r. The value r was also utilized to determine the position of the lightning rod, specified in Table 10.1.

r = 10 × I 0.65

(10.3)

where r is the rolling sphere radian and I is the current amplitude of the current strike. 3. The mesh technique is utilized to draw the lightning protection on the flat and complicated shape of the building Table 10.1  Estimation of the lightning radius protection. Class of lighting protection zone (LPS)

Radius of the rolling sphere (r)

I

20 m

II

30 m

III

45 m

IV

60 m

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Performance of ESE Lightning Protection System  251

or infrastructure. The mesh technique is explained by the dimension of the mesh that is connected to the lightning protection level. (B) The ESE system is explained by utilizing the French NFC17102 level on the ESE rods. This technique is designed by utilizing the rolling sphere technique, but is separate from the rolling sphere radius dimension, which still utilizes a rolling sphere plus the upward streamer. Hence, the protection radius of the ESE is introduced to the height relative to the surface or region. It is displayed in Table 10.2, with the protective zone calculated as follows:



Rp(h) = {√2rh − h2 + ∆ (2r + ∆)

; h ≥ 5 m



H × Rp(5)/5

; ∈ 2 m ≤ h ≤ 5 m

(10.4)

where Rp(h) is the rolling sphere radian at a given height (h); h is the height of the ESE arrester over the protection zone; r is the radius of the rolling sphere (Table 10.2); and ∆ is the earlier upward streamer with a common rod by the addition of ∆T, which is equal to ∆ = ∆T × 106. Table 10.2  IEC/EN 32305 class of protection level. Lightning radius protection Lightning protection level, h (m)

1 (D = 20)

2 (D = 45)

3 (D = 60)

2

31

38

42

3

47

58

64

4

63

77

85

5

78

97

106

10

78

98

108

15

80

101

111

20

80

102

112

45

80

104

118

60

80

104

120

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252  Clean and Renewable Energy Production

(C) The separation space of lightning protection was calculated by utilizing Equation (10.5) [19] and was connected to the space between the lightning protection pole or rod and the PV as display in Figure 10.1 along with the PV design. It can be indicated as follows:



S = Ki

Kc

l/Km

(10.5)



Here, S is the separation space; ki builds on the selected level of the lightning protection space (LPS); kc is the lightning current passing through the down conductor; km is the type of material of the electrical insulation; and l is the length together with the air terminal structure or the down conductor from the point of the separation space. (D) The lightning strike frequency (LSF) was utilized to detect the LPS. The LSF was computed using the lightning flash density and the equivalent range for protection. It can be indicates as follows [9]:

Nd = Ng × Ae × C1 × 10−6

(10.6)

Here, Ng is the per year average flash density in the area where the design is located or positioned to protect, as indicated in Figure 10.2, and Ae is the equivalent region of the

High

R

S

PV Pa n

el θ Tilt angle

Soil resistance ≤ 10 Ω

Figure 10.1  Separation space of the lightning protection method.

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Performance of ESE Lightning Protection System  253

–120

–90

–60

–30

0

30

60

90

120

150 60

60

–150

30

30

0

0

–30

–30

50 40 30 20 10 8 6 4 2 1 .8 .6 .4 .2 .1

–60

–60

–150

–120

–90

–60

–30

0

30

60

90

120

150

Figure 10.2  Global yearly average flash density [21].

structure. It can be calculated by the sizing of the design in a width (W), length (L), and height level (H) using Equation (10.7) [9].

[LW + 6H (L + W) + π9H2]

(10.7)

C1 is the environmental coefficient. The global incident of lightning was reported as a statistic, as shown in Figure 10.2. Thailand has almost 30 lightning strikes per square kilometer yearly. Hence, to stop the damage to the PV power plant, it is essential to correctly design the effective lightning protection structure.

External Lightning Protection Structure for the PV Power Plant This study requires to be delivered by utilizing the field installation that is connected to the profitable and performance ratio (PR) of the PV power plant. The effect of the LPS is connected to the shading in the sunlight. It is directly impacted by the power creation of the PV power plant. The quantity of the lightning rods in the normal type and the ESE required measuring to estimate the optimal situations and capital costs. The position of the PV power plant in this research is in the Nong Ya Plong district, Phetchaburi Province, Thailand. The total space of the PV power plant is 150,000 m2 on

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254  Clean and Renewable Energy Production

a latitude of 13.108121°N and a longitude of 99.700025°, as displayed in Figure 10.3. The PV power plant lightning structure utilizes the ESE lightning NFC17102 standard of France. The PV power plant lightning protection was planned using a polling sphere method inside the PV power plant range. The properties about are 5 m high, so the maximum pole of the lightning protection of the PV power plant is 9 m for normal protection of the building and the surrounding properties. Figure 10.4 shows the ESE-type lightning rod. The radius of the lightning protection is 107 m, as displayed in Figure 10.5. Hence, the PR and the shading results utilized by the PV system program simulation were applied for the survey of the results on power

Figure 10.3  Position of the implementation of the photovoltaic (PV) power plant [22].

ESE lightning rod type Galvanized ф 1½” Down to conductor 95 mm2

Figure 10.4  Early streamer emission (ESE)-type lightning protection rod.

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Performance of ESE Lightning Protection System  255

creation of the PV power plant. Figure 10.5 also displays the situation of the ESE-type lightning rod in the PV power plant. There is a total quantity of 11 ESE lightning rods for the PV power plant. Figure 10.6 shows the Franklin lightning-type rod, while Figure 10.7 displays the situation of the Franklin lightning-type rod as fixed in the PV power plant.

7

6

Water

8

PV 5

4

10

9

PV 3

11

PV 2

PV

1

Water

Figure 10.5  Arrangement of the early streamer emission (ESE) rod system in the photovoltaic (PV) power plant.

Franklin lightning rod

Insulator Nut Down conductor

Figure 10.6  Franklin-type lightning rod.

Brass holder

Top tube

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256  Clean and Renewable Energy Production

Water

PV

PV PV

PV

Water

Figure 10.7  Structure of the Franklin rod system in the photovoltaic (PV) power plant.

The ESE-type lightning protection rod was utilized in the preferred PV power plant, which was planned based on the source of the standard. The arrangement structure of the ESE-type lightning protection rod was utilized in the PV power plant. The range pole of the ESE lightning protection rod had a radius of lightning protection of 107 m. The arrangement structure of the ESE-type lightning protection rod was utilized, as shown in Figure 10.4. In Figure 10.6, it is the Franklin-type lightning protection rod, which was utilized for the simulation in the PV power plant. The Franklin lightning protection rod was planned based on the source of the standard. The location space of the Franklin-type lightning protection rod simulation was planned for differentiation from the ESE lightning protection rod. Figure 10.8 shows the lightning counter for calculating the lightning incidents at the PV power plant. L

Lightning counter Down to ground

Figure 10.8  The lightning counter.

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Performance of ESE Lightning Protection System  257

Results and Analysis A computer design simulation was applied to simulate the results of shading on the PV power plants. In this analysis, the simulation was established on two types of lightning protection in an 8-MWp PV power plant. The simulation involved the ESE-type and the Franklin-type lightning protection. The ESE lightning protection simulation applied 11 rods along a height of 9 m. The arrangement was placed on level 3 for protection and with the NFC17102 standard, the range length of the ESE-type lightning protection was around 107 m, as displayed in Figure 10.9. The Franklin-type lightning protection simulation applied 122 rods along a height of 10-meter, with the structure placed on level 4 for protection of the quality of the Council of Engineers, Thailand. The space length of the ESE-type lightning protection was about 21.4 m, as displayed in Figure 10.10. The simulation outcomes of the PV system program displayed that the shading of the PV power plant along the ESE-type lightning protection could create energy of 13,107,000 kWh/year. Hence, the PR of the PV power plant was 78.8% and the result of shading on the PV power plant was 0.73%. The PV power plant together with the Franklin-type lightning protection could create energy of 13,096,000 kWh/ year. The PR of the PV power plant was 78.7%, while the result of shading on the PV power plant was 0.81%. The installation cost was the basic concern for the investment costs to be approved for the best payback duration. This section displays the investment cost differentiation between the ESE-type Near shadings parameter Perspective of the PV field and surrounding shading scene Zenith

North

West

East

South

Figure 10.9  Early streamer emission (ESE) lightning protection shading simulation [23].

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258  Clean and Renewable Energy Production

Near shadings parameter Perspective of the PV field and surrounding shading scene Zenith

North

West

East South

Figure 10.10  Franklin-type lightning protection shading simulation.

lightning protection and the Franklin lightning system, as displayed in Tables 10.3 and 10.4. Table 10.3 displays the installation cost, which showed that the total cost of the ESE-type lightning protection was USD 44,833.28, while that of the Franklin type was USD 97,363.02. The cost of the ESE-type lightning system was less than that of the Franklin-type system by about 2.17 times. Table 10.4 displays the installation costs, which established that the total cost of the ESE-type lightning grounding system was USD 2837.08 and that of the Franklin type was USD 100,000.68. It was established that the ESE lightning Table 10.3  Differentiation of the investment costs of the two lightning systems. Details

ESE lightning system (in USD)

Franklin lightning system (in USD)

Lightning rods

36,666.65

7,393.63

Copper cable #95 mm2

3,333.32

36,363.37

Lightning counters

833.32

9,242.41

Galvanized mast height, 9 m

2,333.31

25,878.77

Installation cost

1,666.68

18,484.84

Total costs

44,833.28

97,363.02

ESE, early streamer emission.

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Performance of ESE Lightning Protection System  259

Table 10.4  Differentiation of the investment costs of the grounding systems. Details

Units

ESE lightning system (USD)

Franklin lightning system (USD)

Cu cable #95 mm2

1 m

1,000

44,363.62

Cu rod, 5/8ʺ × 10 ft.

1 set

1,350

44,918.19

Installation accessories

1 set

234

897.87

Installation cost

1work

253.08

9,821

Total costs

 

2,837.08

100,000.68

ESE, early streamer emission.

system was less costly than the Franklin lighting system by 35.24 times. Table 10.5 displays the installation costs, which established that the total cost of the ESE lightning system was USD 47,671.40 and that of the Franklin lightning was USD 178,878.90. It was established that the total costs of the ESE lightning system were less compared the Franklin lighting system by 3.752 times. The ESE-type lightning protection was applied due to having the best outcomes of the simulation and the lesser installation costs. The data evidence displayed that there were only three incidents of a lightning strike on the PV power plant in the last 5 years, as displayed in Table 10.6. As it can be seen in the table, in 2017, there were two incidents of lightning strikes at poles 4 and 5, with another one in 2018 along with lightning strikes at pole 5. From the obtained outcomes, the lightning strikes inside the PV power plant and the ESE lightning protection could secure from lightning strikes successfully. Figure 10.9 displays the lightning simulation design by the PV system program following the position distance of the ESE lightning poles in the PV power plant. Table 10.5  Differentiation of the total investment costs of the lightning protection systems. Details

ESE lightning system (USD)

Franklin lightning system (USD)

Lightning rods

44,833.33

78,878.20

Ground systems

2,838.07

100,000.70

Total costs

47,671.40

178,878.90

ESE, early streamer emission.

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260  Clean and Renewable Energy Production

Table 10.6  Lightning events at the photovoltaic (PV) power plant. Lightning protection poles Year

1

2

3

4

5

6

7

8

9

10

11

2017

0

0

0

0

0

0

0

0

0

0

0

2018

0

0

0

1

1

0

0

0

0

0

0

2019

0

0

0

0

1

0

0

0

0

0

0

2020

0

0

0

0

0

0

0

0

0

0

0

2021

0

0

0

0

0

0

0

0

0

0

0

Figure 10.10 shows the lightning simulation pattern by the PV system program next to the position space of the Franklin lightning poles in the PV power plant. Figure 10.11 shows the ESE-type lightning rod installation at the PV power plant. The ESE lightning pole was arranged as the structure in the PV power plant.

Figure 10.11  Early streamer emission (ESE) lightning installed at the photovoltaic (PV) power plant.

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Performance of ESE Lightning Protection System  261

Table 10.6 shows the 5-year data report of the lightning incidents at the monitored PV power plant. In the last 5 years, there have been three lightning events as track: in 2017 at poles 4 and 5 and in 2018 at pole 5. The ESE-type lightning protection system can secure the PV power plant successfully.

Conclusion The report investigates the comparison of the simulation and the analysis results of the lightning effects at a PV power plant. The simulation procedure displays that the shade results of the PV power generation as the simulation of the ESE-type lightning protection system was around 0.73% [23], while that of the Franklin-type lightning protection system was around 0.81% [23]. We planned and checked the lightning protection system to perform secure protection of the coverage of the solar plant region. It is a small space that did not utilize multiple protective heads. The rod arrangement needed an identical installation to secure efficient lightning protection at the solar power plant. The identical lightning rod arrangement permitted lightning protection throughout the whole solar power plant. The installation position of either the ESE or the Franklin lightning rods needed an estimate position of the lightning rod to improve its performance. However, the range of the shielding radius must be perfectly overlapped to successfully protect the solar power plant. It was based on the largest protection radius of the selected lightning arrester. As an example, the protected range must overlap in stability, as displayed in Figures 10.7 and 10.9. It can be noticed that the radius of the two protection stable systems overlapped each other to produce the largest protection performance of the arrangement. The installation cost of the ESE-type lightning protection system was less compared to that of the Franklin-type lightning protection system by 3.752 times, in which the cost was lower than the shadow one. The installation costs of the PV power plant were utilized in the application of the ESE-type lightning protection system. The lightning data in the research were calculated over 5 years. It was observed that lightning occurred at poles 4 and 5 in 2017 and at pole 5 in 2018. The ISI lightning design could avoid harming the power plants and other electrical instruments. It can be decided that selecting an ESE can protect the lightning structure, and the installation costs were also reduced. The research can provide support to the selection of a lightning arrester structure for the protection of a property. The lightning protection of the 8-MWp PV power plant space was 150,000 m2 in Phetchaburi Province,

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262  Clean and Renewable Energy Production

Thailand. The lightning protection involved 122 lengths with the Franklintype rod and 11 lengths with the ESE-type rod. These were simulated with the Franklin-type rod by the Council of Engineers, Thailand, standard, while the ESE-type lightning rod through the NFC17102 standard of France. The approximated costs of installation were utilized for observation and introduced that the total costs of the installed Franklin-type rod amounted to USD 178,878.90 and the ESE-type rod to USD 47,671.40. The data collected from this review can be used by investors to make conclusions regarding the selection of a lower-priced lightning protection system for PV power plants in the future.

References 1. KernF, A., Krichel, F., Mueller, K., Lightning protection design of a renewable energy hybrid-system without power mains connection. Soc. Automot. Eng., 1, 2932, 2001. 2. Kokkinos, N., Christofides, N., Charalambous, C., Lightning protection practice for large-extended photovoltaic installations, in: Proceedings of the 2012 International Conference on Lightning Protection (ICLP), Vienna, Austria, 2–7 Sep. 2012. 3. Yamamoto, K., Takami, J., Okabe, N., Over voltages on DC side of power conditioning system caused by lightning stroke to structure anchoring photovoltaic panels. Electr. Eng. Jpn., 187, 29–41, 2014. 4. Zaini, N.H., Ab-Kadir, M.Z.A., Izadi, M., Ahmad, N.I., Radzi, M.A.M., Azis, N., Hasan, W.Z.W., On the effect of lightning on a solar photovoltaic system, in: Proceedings of the 2016 33rd International Conference on Lightning Protection (ICLP), pp. 1–4, Estoril, Portugal, 25–30 September 2016. 5. Zaini, N.H., Ab-Kadir, M.Z.A., Radzi, M.A.M., Izadi, M., Azis, N., Ahmad, N.I., Nasir, M.S.M., Lightning surge analysis on a large scale grid-connected solar photovoltaic system. Energies, 10, 2149, 2017. 6. Karim, M.R. and Ahmed, M.R., Lightning effect on a large-scale solar power plant with protection system, in: Proceedings of the 2019 1st International Conference on Advances in Science, Engineering and Robotics Technology (ICASERT), Dhaka, Bangladesh, 3–5 May 2019. 7. Tan, P.H. and Gan, C.K., Methods of lightning protection for the PV power plant, in: Proceedings of the 2013 IEEE Student Conference on Research and Development, pp. 221–226, Putrajaya, Malaysia, 16–17 December 2013. 8. Hunt, H., Nixon, K., Naudé, J., Using lightning location system stroke reports to evaluate the probability that an area of interest was struck by lightning. Electr. Power Syst. Res., 153, 32–37, 2017.

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Performance of ESE Lightning Protection System  263

9. Lee, S.W. and Roh, M.S., Application of Early Streamer Emission (ESE) air terminal in lightning systems of NPP, in: Proceedings of the Transactions of the Korean Nuclear Society Autumn Meeting, Gyeongju, Korea, 24–25 October 2013. 10. Nasir, M.S.M., Ab-Kadir, M.Z.A., Radzi, M.A.M., Izadi, M., Ahmad, N.I., Zaini, N.H., Lightning performance analysis of a rooftop grid-connected solar photovoltaic without external lightning protection system. PLoS One, 14, 2–6, 2019. 11. Zhang, Y., Chen, H., Du, Y., Lightning protection design of solar photovoltaic system methodology and guidelines. Electr. Power Syst. Res., 174, 1–3, 2019. 12. Damianaki, K., Christodoulou, C.A., Kokalis, C.C.A., Kyritsis, A., Ellinas, E.D., Vita, V., Gonos, I.F., Lightning protection of photovoltaic systems, computation of the developed potentials. Appl. Sci., 11, 337, 2021. 13. Zhang, Y., Li, B., Du, Y., Ding, Y., Cao, J., Lv, J., Effective grounding of the photovoltaic power plant protected by lightning rods. IEEE Trans. Electromagn. Compat., 63, 1128–1136, 2021. 14. Hu, W., Yu, S., Cheng, R., He, J., A testing research on the effect of conductive backfill on reducing grounding resistance under lightning, in: Proceedings of the 2012 International Conference on Lightning Protection (ICLP), pp. 1–4, Vienna, Austria, 2–7 September 2012. 15. Jiang, T. and Grzybowski, S., Impact of lightning impulse voltage on polycrystalline silicon photo voltaic modules, in: Proceedings of the 2013 International Symposium on Lightning Protection (XII SIPDA), pp. 287–290, Belo Horizonte, Brazil, 7–11 October 2013. 16. Holland, I., Doorsamy, W., Nixon, K., Computational methodology for lightning risk assessment of small-scale rooftop photovoltaic systems, in: Proceedings of the 2018 IEEE International Conference on Environment and Electrical Engineering and 2018 IEEE Industrial and Commercial Power Systems Europe (EEEIC/I&CPS Europe), pp. 1–6, Palermo, Italy, 12–15 June 2018. 17. Ahmad, N., Ali, Z., Kadir, M.A., Osman, M., Zaini, N., Roslan, M., Impacts of lightning-induced overvoltage on a hybrid solar PV–battery energy storage system. Appl. Sci., 11, 3633, 2021. 18. Izadi, M., Ab Kadir, M.Z.A., Hajikhani, M., Rameli, N., Effects of lightning current and ground conductivity on the values of vertical electric fields. J. Teknol., 64, 33–36, 2013. 19. DEHN, Lightning protection guide, DEHN, Holmfirth, UK, 2021. 20. Charalambous, C.A., Kokkinos, N.D., Christofides, N., External lightning protection and grounding in large-scale photovoltaic applications. IEEE Trans. Electromagn. Compat., 56, 427–434, 2013. 21. The lightning map, Available online: https://earthobservatory.nasa.gov/ images/2002/where-lightning-strikes (accessed on 10 March 2021).

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264  Clean and Renewable Energy Production

22. The implementation PV power plant, Available online: https://www. google.com/maps/place/13$^\circ$06$’$28.8\T1\textquotedblrightN+99o42$’$00.0\T1\textquotedblrightE (accessed on 5 March 2021). 23. PVsyst 7 professional licensesV7-626d26b3859a13b58fa910bab3f1dd7f, 5/05/2021 to 15/05/22.

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Performance of ESE Lightning Protection System  265

Solar Photovoltaic System-Based Power Generation: Imperative Role of Artificial Intelligence and Machine Learning Rupendra Kumar Pachauri1*, Jitendra Yadav2, Stephen Oko Gyan Torto1, Ahmad Faiz Minai3, Vikas Pandey4, Shashikant4 and Priyanka Sharma5 Electrical Cluster, School of Engineering, University of Petroleum and Energy Studies, Dehradun, India 2 Mechanical Cluster, School of Engineering, University of Petroleum and Energy Studies, Dehradun, India 3 Electrical Department, Integral University, Lucknow, Uttar Pradesh, India 4 Electrical Engineering Department, School of Engineering, Babu Banarasi Das University, Lucknow, India 5 School of Basic Science and Technology, IIMT University, Meerut, Uttar Pradesh, India 1

Abstract

One significant advancement in the production of renewable energy is the use of solar photovoltaic (PV) systems, which collect sunlight and convert it into electricity. Due to its low environmental impact and cost-competitiveness with conventional fossil fuel-based power production, PV systems have been seeing rising demand worldwide. Storage options for extra energy, connectivity with the current grid, and laws are only a few of the remaining obstacles to the mainstream use of solar PV. Overcoming these obstacles and increasing the quantity of solar energy utilizing PV to generate electricity will need future technological advancements and additional government backing. Increased adoption of PV systems is anticipated due to their promise as a long-term, eco-friendly energy solution. The use of PV systems as a fuel source for renewable power plants has increased dramatically in recent years. During the past decade, the price of solar PV systems has dropped dramatically, making them *Corresponding author: [email protected] Surajit Mondal, Adesh Kumar, Rupendra Kumar Pachauri, Amit Kumar Mondal, Vishal Kumar Singh and Amit Kumar Sharma (eds.) Clean and Renewable Energy Production, (267–286) © 2024 Scrivener Publishing LLC

267

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11

increasingly competitive with conventional power generation using fossil fuels. Artificial intelligence (AI) and machine learning (ML) approaches are helpful for performance optimization and the prediction of the optimal degree of energy extraction, two areas where PV systems face technological challenges. Forecasting weather and sunlight changes helps PV systems operate at peak efficiency. Advanced automation and supervision enabled by AI and ML may improve the efficiency and output of PV systems. AI and ML allow for early detection and diagnosis of issues in PV systems, reducing the need for expensive repairs. To understand the concept of AI-based power enhancement of PV systems under partial shading conditions, a genetic algorithm-based PV array configuration explores the higher electrical performance in terms of higher fill factor and lower power loss (PL) compared to conventional series-parallel (SP) configuration. Keywords:  Solar photovoltaic system, machine learning, artificial intelligence, forecasting

11.1 Introduction Solar, wind, and hydropower are all examples of renewable energy that may be utilized forever without depleting the resources from which they were originally derived. There are no harmful emissions produced by these alternatives, in contrast to fossil fuels, which contribute to increased air and water pollution in addition to increased global warming. In addition, renewable energy sources may save money in the long term compared to their fossil fuel counterparts. There has been a rise in the adoption of photovoltaic (PV) systems because of their low environmental impact when compared to other forms of power generation [1]. They are completely emission-free and can run on only sunshine. Because of this, they contribute to reducing the use of fossil fuels and the release of their associated emissions. Solar PV systems have become more affordable in recent years, making them a viable option for a larger variety of households and businesses. The adoption of PV systems has also been aided by government incentives and legislation. The development of technology has also improved the efficiency and dependability of PV systems [2]. In comparison to other forms of renewable energy, solar PV systems have a number of advantages. One reason is that they need less maintenance than other forms of renewable energy, such as wind turbines.

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Furthermore, solar PV systems may be installed in homes, businesses, and on government structures. In addition, solar PV systems have become more economically feasible in recent years [3, 4]. In addition to being fully clean, solar PV systems also produce no greenhouse gases. PV systems, however, do have a few drawbacks, and they include: • Environmental dependence: PV systems depend on the sun irradiance majorly along with other environmental factors. It is well known that efficiency of the PV system can be affected by temperature, and partial shading (passing clouds, high-rise buildings, telecom towers, etc.) is one of the major causes of a PV system’s performance degradation. • High initial cost: PV systems have become more affordable in recent years, but they still have a high initial cost that can be a barrier due to technological development and market models regarding the hybrid power system to enhance the system’s reliability. • Limited energy storage impacts on reliability: In adverse weather, PV systems may not be able to satisfy peak energy needs because of their limited capacity for energy storage. Due to concerns about power outages, consumers are shifting toward hybrid power production and the next generation of energy extraction. • Maintenance and land utilization: To keep operating at peak performance, PV systems need to be cleaned and serviced on a regular basis. In addition, PV systems require a lot of space and need to be installed on specific locations based on the availability of sun irradiance. • Intermittent energy production and durability: Solar PV systems can only generate power when the sun is shining, which is not always the case. Due to their short lifetime, PV systems will need to be replaced after a number of years. A solar PV system’s overall performance may be greatly impacted by even a little amount of shadowing. As the output of shaded cells drops dramatically, the total system output might suffer as well [5]. In addition, shading causes a phenomenon called “power loss,” where the output of the PV system is reduced compared to ideal conditions. This can lead to decreased efficiency and a reduced overall power output of the PV system.

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AI and ML in Solar PV System-Based Power Generation  269

In this context, to minimize the shading impacts on a PV system, various advancements in terms of technological methodologies are adopted for PV performance enhancement. Partial shading conditions can occur when part of a solar panel is blocked from receiving sunlight by an obstacle such as a tree, building, or dust, or by self-shading due to PV module placements in the PV plants. This can happen due to a variety of reasons [6]. Figures 11.1 and 11.2 show the PV power generation issue and the nonlinear behavior of the power–voltage (P–V) and current–voltage (I–V) curves during adverse irradiation conditions.

Shading losses 7%

Array Mismatch 0.7%

Thermal losses 4.6%

AC Cable losses 0.5%

Dust & Dirt 2%

Losses due to passing clouds

Reflection 2.5%

Inverter losses 3%

Irradiation losses 1.5%

Spectral losses 1%

DC Cable losses 1%

Figure 11.1  Solar photovoltaic (PV) system-based power generation with limitations.

6 400

5 Im

Power (W)

Current (A)

Current Loss 4 3 2

GMPP

Misleading Power LMPP

200 100

1 0

300

MPP Power Loss

Uniform Irradiation Non-uniform Irradiation

0

20

40

60

Voltage (V) (a)

Uniform Irradiation Non-uniform Irradiation

Vm 80

100

0 0

20

40

60

80

100

Voltage (V) (b)

Figure 11.2  Power–voltage (P–V) and current–voltage (I–V) curves during adverse sun irradiance conditions.

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270  Clean and Renewable Energy Production

11.2 Solar Energy Power Generation Scenario in the Indian Context Solar power is expected to quickly overtake other renewable energy sources, according to the International Energy Agency (IEA). In their World Energy Outlook 2020 report, they forecast that solar energy will account for 60% of the growth in renewable power generation through 2022. However, it is worth noting that solar energy currently only accounts for a small percentage of the total renewable energy generation, with hydroelectric power and wind energy being forms of renewable energy that now account for the majority of all energy production [7]. In accordance with the Ministry of New and Renewable Energy (MNRE), as of December 2020, India had an installed solar PV capacity of 38.8 GW. This includes both hybrid grid-connected and autonomous systems. In terms of grid-connected systems, the state of Tamil Nadu has the highest installed capacity at 6.4  GW, followed by Maharashtra at 5.4  GW and Gujarat at 5.2 GW. In terms of growth, the amount of solar PV capacity in India has risen sharply in recent years. From April 2019 to March 2020, bringing the total to 34.2 GW [8, 9], the country added 9.6 GW of additional capacity. In the 2020–2021 fiscal year, India added 4.8 GW of new solar PV capacity. In terms of projects under development, as of December 2020, the MNRE reported that there were 33.6 GW of solar PV projects under implementation and another 32 GW under tendering. The Indian government plans to construct 175  GW of renewable energy capacity by 2022, with 100 GW coming from solar. As of now, India is on track to achieve this target.

11.3 Applications of AI and ML in Solar PV Systems Solar PV systems may benefit greatly from the use of artificial intelligence (AI) and machine learning (ML) in order to maximize their potential. Figure 11.3 delves into the potential uses of AI and ML in solar PV systems. • Maintenance prediction: Apart from the cyclic maintenance of PV plants, algorithms based on AI and or ML (genetic algorithm, support vector, etc.) are introduced, which may predict solar PV plant performance and, hence, real

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AI and ML in Solar PV System-Based Power Generation  271

Maintenance

Gr Conn idecte d

rity

r we Po

g

Pa en ram tif ete sig ica r tio ni ng n

De

Secu

PV Siz in

ive Pass

Application Artificial Intelligence for PV System

er Cyb

Stan d Alon e

Condition Monitoring

e Activ

Con trol

Remaining Useful Life

id

e id t d S en ng an em sti m g ca e De ana r Fo M

Figure 11.3  Application of photovoltaic (PV) system performance using artificial intelligence (AI) and machine learning (ML).

maintenance needs. This is helpful to panel and inverter failures, enabling proactive maintenance. • Maximum power point tracking: To extract maximum power from a PV system using maximum power point tracking (MPPT) techniques based on AI-based algorithms. This MPPT device helps deliver the true maximum power point to the load. • Cloud-based monitoring, automated fault detection, and control: AI-based algorithms allow for cloud-based monitoring and management of solar PV installations. Moreover, algorithms based on metaheuristics are used for fault identification and control of PV systems to avoid hot spots, etc. • Yield prediction and energy management: By examining historical data and forecasted weather conditions, AI-based algorithms can estimate the amount of energy produced by a solar PV system. Furthermore, energy management, including load shedding and forecasting, may be enhanced in solar PV systems using AI-based algorithms, leading to more reliable and consistent power output.

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272  Clean and Renewable Energy Production

11.3.1 Maintenance Prediction Data from solar PV systems are monitored and analyzed with the use of AI and ML to help spot problems ahead of time and schedule preventative maintenance [10]. Maintaining a solar PV system may be planned ahead of time by monitoring its operation and looking for trends that might point to a failing part. This can be done through regular inspections and monitoring of the PV panels, inverters, and other components of the system. Some key indicators that may signal a need for maintenance include a decrease in power output, an increase in the number of power outages or system failures, or an increase in the temperature of the PV panels [11]. There is also the option of using a predictive maintenance model, which use machine learning algorithms to examine data from the PV system and explore the trends that signal a need for repair. Information about the PV system performance, climate, and upkeep may be used to teach this model [12]. With this information, the model may foresee when servicing is required and send out a notification to the servicing crew. Furthermore, regular cleaning and dusting of the panels, securing any slack connections, and inspecting the system’s wiring and grounding should be remembered. Figure 11.4 is a graphic explaining the AI- and ML-based approaches used to  predict solar PV system maintenance for efficient operation and maximum power extraction in both ideal and suboptimal weather circumstances. Solar Power Station

Solar panels

Data Mining

IoT Hardware Band

Cloud IoT core

Maintenance Action

Error Estimation

Figure 11.4  Applications of artificial intelligence (AI)/machine learning (ML) for maintenance prediction.

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AI and ML in Solar PV System-Based Power Generation  273

11.3.2 Optimization of Orientation of the Solar Panels to Maximize Energy Generation By altering the panels’ angle and orientation to maximize energy production and by modifying the output of the system to fit the demand of the grid, AI and ML may improve the efficiency of solar PV systems. Solar PV module orientation is critical for maximum energy output [13, 14]. Generally speaking, PV panels should be oriented such that the maximum amount of sunlight hits them. PV panels should be oriented with their southern faces toward the sun in the Northern Hemisphere. As the sun spends most of its time in the south, positioning the panels in this way maximizes their exposure to sunshine. When it comes to increasing energy production, the tilt angle of the panels is just as important as the panels themselves. During solar noon, the panels should be perpendicular to the sun’s beams; therefore, the tilt angle should be set accordingly. When the sun is directly above, that moment is called the zenith of the day [15, 16]. The quantity of energy generated by a PV system may be estimated with the use of a solar radiation model. This model considers environmental factors including cloud cover and air conditions, in addition to PV panel position, orientation, and tilt angle. By feeding these data into the model, we can estimate the PV system’s power output over a specified time frame. This may help with performance planning and optimization [17].

11.3.3 Weather Forecasting for PV System Power Assessment Predictions like this may be used to evaluate the efficacy of a solar system. Energy production from a PV system may be predicted with reasonable precision using historical data and weather prediction algorithms [18]. Several applications may benefit from this, including: • Schedule energy production and use to improve efficiency and cut down on expenses • Finance-related considerations include things like projecting a PV system’s return on investment and determining how much it will cost to generate electricity from the sun. • Assessing the viability of the proposed PV systems and establishing the best system dimensions and setup for a given site It is possible to estimate the power of a PV system using a variety of models, including physical, statistical, and ML methods [19]. Whatever method is ideal will depend on both the specific use case and the available data.

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274  Clean and Renewable Energy Production

Forecasting

Figure 11.5  Weather forecasting of a photovoltaic (PV) system performance using artificial intelligence (AI) and machine learning (ML).

Using inputs such as weather data, location, and system design, artificial neural networks (ANNs) and ML can predict how well a solar PV system would perform. This may help with energy yield prediction and performance optimization of the current systems [20]. Furthermore, ML algorithms may be used to quickly and accurately identify the source of problems in solar PV systems, allowing for more effective troubleshooting and repairs. Furthermore, integrating weather predicting models with solar PV performance models is another interesting study field for enhancing the accuracy of solar PV forecasts. Weather forecasting for effective power production is shown in a schematic form in Figure 11.5.

11.3.4 Forecasting of PV System Performance During Dust Accumulation Predicting the performance of a PV system while dust is accumulating involves taking into account a number of variables, such as the quantity and kind of dust, the weather, and the cleaning and maintenance plan for the PV panels [21]. The collection of dust on the panels may be predicted using a dust accumulation model, which can be used for performance forecasts. In addition, weather forecasting may be utilized to anticipate the circumstances in which dust collection is expected to occur, taking into account variables such as wind speed and direction, both of which can impact the efficiency of a PV system [22, 23]. The need for cleaning and maintenance may be determined by keeping track of the PV system’s performance over time and comparing it to the predicted performance. Figure 11.6 depicts the use of AI and ML to forecast power output during the dust buildup effect.

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AI and ML in Solar PV System-Based Power Generation  275

Historical Performance Data

Performance prediction and life cycle assessment

Figure 11.6  Photovoltaic (PV) performance prediction based on the effect of dust accumulation on a PV system.

11.3.5 Solar Parameter Prediction Predicting the output of a solar power system, such as the amount of energy it will generate, requires the use of models or algorithms known as solar parameters. Methods for doing so include forecasting both the quantity of sunshine that will hit the system (known as solar irradiance) and the output of the solar panels themselves [24]. Solar parameters may be predicted with the use of past data, weather predictions, and other factors. Predicting solar parameters accurately is critical for the effective management and operation of solar energy systems [25].

11.3.6 Fault Detection Using Artificial Intelligence The purpose of using AI and ML for fault detection is to find and fix issues before they cause major damage or disruption to the system. Solar PV systems may benefit from the application of AI and ML for problem detection and diagnosis [26–28]. A number of approaches based on AI may be used to find problems in a system. • Supervised learning method: Labeled data to train a model to recognize patterns associated with different types of faults • Unsupervised learning method: Uses unlabeled data to identify patterns that may indicate a fault

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276  Clean and Renewable Energy Production

• Hybrid methods: Approaches combining supervised and unsupervised learning methods for the sake of making the defect detection system more effective Different methods may be needed to get to the bottom of the problem, depending on the kind of system being probed, the available data, and the desired outcome. Artificial intelligence (AI)-based flaw identification might have applications in many fields. As a whole, AI-based fault detection may lessen the likelihood of system failures and enhance uptime, which in turn reduces costs and boosts productivity [29, 30]. As a whole, AI and ML approaches help solar PV systems produce higher energy outputs.

11.4 Pros and Cons of AI and ML Techniques in Solar PV System AI and ML both have the potential to enhance solar PV system forecasting [31–33]. Nevertheless, the individual application and the kind of data being examined will decide which technique is more successful. See Table 11.1 for some of the benefits and drawbacks of adopting AI and ML for solar PV system prediction. Both ML and AI may be used to increase the efficiency of solar PV systems, but which one is best depends on the task at hand and the data being studied. With ML algorithms trained on past data, one can maximize the output of a solar PV system, while AI can make modifications in real time in response to changing environmental circumstances.

11.5 Application of GA-Based Optimal Placement of PV Modules in an Array to Reduce PSCs 11.5.1 Modeling of PV System The PV cell voltage is expressed in Eq. (11.1), and the combination series arranged cells are formed in the module.



VC

I ph I d AkTC ln e Id

IC

Rse Rsh IC Rsh Rse

(11.1)

where VC and IC are the cell voltage and current, respectively; k, T, and A are the Boltzmann’s constant, temperature, and diode ideality factor,

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AI and ML in Solar PV System-Based Power Generation  277

Table 11.1  Pros and cons of artificial intelligence (AI) and machine learning (ML) for solar photovoltaic (PV) system applications [34–36]. Techniques

Pros

Cons

AI

• Increased accuracy: Ability to find hidden patterns in massive datasets. Increasing prediction accuracy • Automation: Automates the forecasting process, reducing the need for human intervention and increasing efficiency • Handling complex data: Able to handle large and complex datasets • Allow for more efficient and accurate forecasting • Ability to sift through mountains of data and spot trends that people would miss • Improve the system’s efficiency

• High cost: Developing and implementing AI algorithms can be costly • Lack of transparency: Hard to figure out how AI models arrived at their conclusions • Data quality: If data are incomplete or inaccurate, the forecasts generated by the model may also be flawed • Historical data dependency: Usually trained on historical data, which may not be able to account for future changes or unexpected events • Complex, difficult, and expensive to implement, especially for small-scale solar PV systems

ML

• To predict and optimize the output of a solar PV system based on historical data • Less complex and less expensive to implement than AI • To identify patterns in the data that are not immediately obvious to humans

• Rely on historical data, which may not reflect current conditions • Unable to modify in real time a solar PV system to current circumstances • Good training data may not be enough or correct

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278  Clean and Renewable Energy Production

Ic Iph

i1

i2

i3

Id

i9

11

12

13

VR1

19

21

22

23 VR2

29

+

Rse

Ish Rsh

– VArray

Ic Iph

Id

Rse

Ish

+

Rsh

91

92

92 VR9

–

99

Electrical Equivalent circuit of PV cell

Figure 11.7  Development of a 9 × 9 size photovoltaic (PV) array.

respectively; Iph and Id are the photocurrent and diode saturation current, respectively; and Rse and Rsh are the series and parallel resistance, respectively. The 5-W power capacity (VOC = 11.25 V, ISC = 0.55 A, Im = 0.52 A, and Vm = 9.62 V) is considered for MATLAB/Simulink modeling of a 9  ×  9 size PV array system and investigated under shading cases. The schematic diagram is shown in Figure 11.7.

11.5.2 Genetic Algorithm-Based PV Array Reconfiguration By iteratively optimizing a solution to a problem, genetic algorithm (GA) may either maximize or minimize the value of a given variable. There are two primary aspects that determine how well GA performs in solving any optimization problem. There are two main steps in population genetics: (i)  population generation and (ii) fitness assessment function [37]. Assuming that array reconfiguration is an optimization issue, for each population, GA calculates its fitness using the formula in Eq. (11.2). In addition, the calculation of Sum(P) is explained in Eq. (11.3), as follows:



Max(Fitness(i)) Sum(P )

We Ee

(Wp Pa )

(11.2)

9

Sum(P) =

∑I V n n

(11.3)

i =1

where Fitness (i) is the population of the ith iteration and Vn and In are the voltage and current across nth row of the PV array, respectively [37]. Error

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AI and ML in Solar PV System-Based Power Generation  279

estimation is obtained in Eq. (11.4), which estimates the maximum current and the current produced in nth row of the PV array as, 9

Ee =

∑| I

m

− Ik |

(11.4)

i =1

11.5.3 Shading Scenarios and Electrical Performance The shading effect on PV array systems shows a higher power loss (PL), a reduced fill factor (FF), etc. This performance degradation can be avoided by using AI-based PV module placement in an array, i.e., the PV array reconfiguration method. In this context, genetic algorithm (GA) is used to disperse the shading effect on the PV array surface to achieve higher performance compared to the preexisting PV arrangements in an array, such as a 9 × 9 size series-parallel (SP) array. For extensive performance investigation, two shading instances are considered, as shown in Figures 11.8 and 11.9, which explored non-uniform irradiance conditions. Both the PV array configurations were investigated during the considered partial shading conditions. The above shading cases were investigated for the SP- and GA-based modified SP configuration such as GA-SP and the electrical performance behavior compared, such as the P–V and I–V curves in Figures 11.10 and 11.11. The quantitative analysis is given in Table 11.2 to explore the comparative study about the SP and SP-GA configurations under Partial shading conditions (PSCs). Figure 11.12 displays the bar chart representation of the 1000W/m2

800W/m2

600W/m2

300W/m2 Shade dispersion

Shading pattern 11

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54

25

86

67

38

99

51

52

53

54

55

56

57

58

59

51

22

83

64

35

96

77

48

19

61

62

63

64

65

66

67

68

69

61

32

93

74

45

16

87

58

29

71

72

73

74

75

76

77

78

79

71

42

13

84

55

26

97

68

39

81

82

83

84

85

86

87

88

89

81

52

23

94

65

36

17

78

49

91

92

93

94

95

96

97

98

99

91

62

33

14

75

46

27

88

59

(a) SP

(b) SP-GA

Figure 11.8  Shading case 1 with non-uniform irradiance levels. (a) Series parallel (SP). (b) Series parallel and genetic algorithm (SP-GA).

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280  Clean and Renewable Energy Production

1000W/m2

800W/m2

600W/m2

400W/m2

200W/m2

Shade dispersion

Shading pattern

69

11

12

13

14

15

16

17

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11

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24

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37

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1 8 79

31

32

33

34

35

36

37

38

39

31

92

63

44

15

76

57

28

89

49

41

12

73

54

25

86

67

38

99

59

51

22

83

64

35

96

77

48

19

58

29

41

42

51

52

43

44

53

54

45 55

46

47

56

57

48 58

61

62

63

64

65

66

67

68

69

61

32

93

74

45

16

87

71

72

73

74

75

76

77

78

79

71

42

13

84

55

26

97

68

39

81

82

83

84

85

86

87

88

89

81

52

23

94

65

36

17

78

49

91

92

93

94

95

96

97

98

99

91

62

33

14

75

46

27

88

59

(a) SP

(b) SP-GA

Figure 11.9  Shading case 2 with non-uniform irradiance levels. (a) Series parallel (SP). (b) Series parallel and genetic algorithm (SP-GA).

500

500 SP SP-GA

GMPPs

300 200

GMPP

300 200 100

100 0

SP SP-GA

400

Power (W)

Power (W)

400

0

20

40

60

80

0

100

0

20

Voltage (V) (a)

40

60

80

100

Voltage (V) (b)

Figure 11.10  Power–voltage (P–V) curves under shading cases 1 and 2.

6

6 5

Im

4

Current (A)

Current (A)

5

3 2 SP SP-GA

1 0

0

20

4 3 2 1

40

60

Voltage (V) (a)

80

100

0

SP SP-GA

20

Vm 40

60

Voltage (V) (b)

Figure 11.11  Current–voltage (I–V) curves under shading cases 1 and 2.

80

100

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AI and ML in Solar PV System-Based Power Generation  281

Table 11.2  Numerical results of series-parallel (SP) and SP and genetic algorithm (SP-GA) configurations under partial shading conditionss (PSCs). Performance parameters

Case 1

Case 2

SP

SP-GA

SP

SP-GA

PGMPP (W)

272.6

329.2

278.2

346.2

VGMPP (V)

88.22

88.14

88.10

86.40

Im (A)

3.02

3.70

3.10

4.02

VOC (V)

99.1

99.05

100.2

100.1

ISC (A)

4.85

4.42

4.90

4.58

PL (W)

132.4

75.8

126.8

58.8

FF

0.56

0.751

0.566

0.755

360 80

300

180

SP SP-GA

VGMPP (V)

PLGMPP (W)

240

120

40 20

60 0

60

SP SP-GA

Case-1

PSCs (a)

0

Case-2

Case-1

Case-2

PSCs (b)

0.8 SP SP-GA

120 0.6

80

FF

PL (W)

SP SP-GA

40

0

0.4 0.2

Case-1

PSCs (c)

Case-2

0.0

Case-1

PSCs (d)

Case-2

Figure 11.12  Bar chart representation. (a) Power. (b) Voltage at global maximum power point (GMPP). (c) Power loss (PL). (d) Fill factor (FF) under Partial shading conditions (PSCs).

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282  Clean and Renewable Energy Production

power and voltage at global maximum power point (GMPP), reduced PL, and improved FF for SP-GA compared to conventional SP configuration.

11.6 Conclusion In conclusion, the study on the efficient role of AI and ML for PV systems has highlighted the following key points: • AI and ML aid in the optimization of PV systems via features such as fault prediction and detection, system setting adjustments in response to forecasted weather, and the constant monitoring and analysis of data that can improve system performance. • The use of AI and ML leads to significant cost savings for PV system operators by reducing the need for manual monitoring and maintenance. AI-based control and optimization strategies can help to increase the energy output of PV systems, increasing the return on investment for the system owners. • AI and ML technologies also have a role to play in the integration of PV systems into the power grid by predicting and balancing how much energy is needed on the grid and how much is produced by PV systems. Integrating AI and ML into PV systems is a topic of active study with new advancements and possibilities being discovered regularly. • GA-based PV array reconfiguration strategy proved to disperse the shading impacts and observed higher performance in terms of GMPP and FF under PSCs compared to SP configuration. Overall, the study demonstrates the potential of AI and ML to play essential functions in boosting the reliability, effectiveness, and longevity of PV systems, making them more economically viable and environment-friendly.

References 1. Mellit, A. and Kalogirou, S., Artificial intelligence and internet of things to improve efficacy of diagnosis and remote sensing of solar photovoltaic systems: Challenges, recommendations and future directions. Renew. Sustain. Energy Rev., 143, 110889, 2021.

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AI and ML in Solar PV System-Based Power Generation  283

2. Dumitru, C.D., Gligor, A., Enachescu, C., Solar photovoltaic energy production forecast using neural networks. Proc. Technol., 22, 808–815, 2016. 3. Kaffash, M. and Deconinck, G., Ensemble machine learning forecaster for day ahead PV system generation, in: Proc. IEEE International Conference on Smart Energy Grid Engineering, pp. 92–96, 2019. 4. Mellit, A., Kalogirou, S.A., Hontoria, L., Shaari, S., Artificial intelligence techniques for sizing photovoltaic systems: A review. Renew. Sustain. Energy Rev., 13, 2, 406–419, 2009. 5. Dumitru, C.D., Gligor, A., Enachescu, C., Solar photovoltaic energy production forecast using neural networks. Proc. Technol., 22, 808–815, 2016. 6. Youssef, A., El-Telbany, M., Zekry, A., The role of artificial intelligence in photo-voltaic systems design and control: A review. Renew. Sustain. Energy Rev., 78, 72–79, 2017. 7. Yadav, A.K. and Chandel, S.S., Solar radiation prediction using artificial neural network techniques: A review. Renew. Sustain. Energy Rev., 33, 772–781, 2014. 8. Mellit, A., Menghanem, M., Bendekhis, M., Artificial neural network model for prediction solar radiation data: Application for sizing stand-alone photovoltaic power system, in: Proc. IEEE Power Engineering Society General Meeting, pp. 40–44, 2005. 9. De Giorgi, M.G., Congedo, P.M., Malvoni, M., Photovoltaic power forecasting using statistical methods: Impact of weather data. IET Sci. Meas. Technol., 8, 3, 90–97, 2014. 10. Mellit, A., Benghanem, M., Kalogirou, S.A., Modeling and simulation of a stand-alone photovoltaic system using an adaptive artificial neural network: Proposition for a new sizing procedure. Renew. Energy, 32, 2, 285–313, 2007. 11. Khatib, T., Mohamed, A., Sopian, K., A review of photovoltaic systems size optimization techniques. Renew. Sustain. Energy Rev., 22, 454–465, 2013. 12. Sohani, A., Sayyaadi, H., Cornaro, C., Shahverdian, M.H., Pierro, M., Moser, D., Li, L.K., Using machine learning in photovoltaics to create smarter and cleaner energy generation systems: A comprehensive review. J. Cleaner Prod., 362, 132701, 2022. 13. Elsheikh, A.H., Sharshir, S.W., Abd Elaziz, M., Kabeel, A.E., Guilan, W., Haiou, Z., Modeling of solar energy systems using artificial neural network: A comprehensive review. Sol. Energy, 180, 622–639, 2019. 14. Zahraee, S.M., Assadi, M.K., Saidur, R., Application of artificial intelligence methods for hybrid energy system optimization. Renew. Sustain. Energy Rev., 66, 617–630, 2016. 15. Mekki, H., Mellit, A., Salhi, H., Artificial neural network-based modelling and fault detection of partial shaded photovoltaic modules. Simul. Modell. Pract. Theory, 67, 1–13, 2016.

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16. Karatepe, E. and Hiyama, T., Artificial neural network-polar coordinated fuzzy controller based maximum power point tracking control under partially shaded conditions. IET Renew. Power Gener., 3, 2, 239–253, 2009. 17. Liu, L., Liu, D., Sun, Q., Li, H., Wennersten, R., Forecasting power output of photovoltaic system using a BP network method. Energy Proc., 142, 780–786, 2017. 18. Chakraborty, D., Mondal, J., Barua, H. B., Bhattacharjee, A., Computational solar energy – Ensemble learning methods for prediction of solar power generation based on meteorological parameters in Eastern India. Renew. Energy Focus, 44, 277–294, 2023. 19. Chen, S.X., Gooi, H.B., Wang, M.Q., Solar radiation forecast based on fuzzy logic and neural networks. Renew. Energy, 60, 195–201, 2013. 20. Mellit, A. and Pavan, A.M., Performance prediction of 20 kWp grid-­ connected photovoltaic plant at Trieste (Italy) using artificial neural network. Energy Convers. Manage., 51, 12, 2431–2441, 2010. 21. Ibrahim, M., Alsheikh, A., Awaysheh, F.M., Alshehri, M.D., Machine learning schemes for anomaly detection in solar power plants. Energies, 15, 3, 1082, 2022. 22. Zhou, Y., Zheng, S., Zhang, G., Artificial neural network based multivariable optimization of a hybrid system integrated with phase change materials, active cooling and hybrid ventilations. Energy Convers. Manage., 197, 111859, 2019. 23. Li, J., Ward, J.K., Tong, J., Collins, L., Platt, G., Machine learning for solar irradiance forecasting of photovoltaic system. Renew. Energy, 90, 542–553, 2016. 24. Mellit, A., Kalogirou, S.A., Shaari, S., Salhi, H., Arab, A.H., Methodology for predicting sequences of mean monthly clearness index and daily solar radiation data in remote areas: Application for sizing a stand-alone PV system. Renew. Energy, 33, 7, 1570–1590, 2008. 25. Kow, K.W., Wong, Y.W., Rajkumar, R.K., A review on performance of artificial intelligence and conventional method in mitigating PV grid-tied related power quality events. Renew. Sustain. Energy Rev., 56, 334–346, 2016. 26. Alphousseyni, N., Lamine, T., Gustave, S., Application of new modeling and control for grid connected photovoltaic systems based on artificial intelligence. J. Electr. Electron. Eng. Res., 7, 1, 1–10, 2015. 27. Ishaque, K. and Salam, Z., A review of maximum power point tracking techniques of PV system for uniform insolation and partial shading condition. Renew. Sustain. Energy Rev., 19, 475–488, 2013. 28. Ekici, B.B., A least squares support vector machine model for prediction of the next day solar insolation for effective use of PV systems. Measurement, 50, 255–262, 2014. 29. Mittal, M., Bora, B., Saxena, S., Gaur, A.M., Performance prediction of PV module using electrical equivalent model and artificial neural network. Sol. Energy, 176, 104–117, 2018.

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30. Amrouche, B. and Le Pivert, X., Artificial neural network based daily local forecasting for global solar radiation. Appl. Energy, 130, 333–341, 2014. 31. Gao, Y., Miyata, S., Akashi, Y., Multi-step solar irradiation prediction based on weather forecast and generative deep learning model. Renew. Energy, 188, 637–650, 2022. 32. Feng, C., Liu, Y., Zhang, J., A taxonomical review on recent artificial intelligence applications to PV integration into power grids. Int. J. Electr. Power Energy Syst., 132, 107176, 2021. 33. Sohani, A., Sayyaadi, H., Cornaro, C., Shahverdian, M.H., Pierro, M., Moser, D., Li, L.K., Using machine learning in photovoltaics to create smarter and cleaner energy generation systems: A comprehensive review. J. Cleaner Prod., 132701, 1–18, 2022. 34. Wang, H., Liu, Y., Zhou, B., Li, C., Cao, G., Voropai, N., Barakhtenko, E., Taxonomy research of artificial intelligence for deterministic solar power forecasting. Energy Convers. Manage., 214, 112909, 2020. 35. Kuo, P.H. and Huang, C.J., A green energy application in energy management systems by an artificial intelligence-based solar radiation forecasting model. Energies, 11, 4, 819, 2018. 36. Martinez, D.R., Nigam, K.D.P., Sandoval, L.A.R., Machine learning on sustainable energy: A review and outlook on renewable energy systems, catalysis, smart grid and energy storage. Chem. Eng. Res. Des., 174, 414–441, 2021. 37. Meerimatha, G. and Rao, B.L., Genetic algorithm based PV array reconfiguration for improving power output under partial shadings. Int. J. Renew. Energy Res., 10, 2, 803–812, 2020.

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286  Clean and Renewable Energy Production

Waste to Energy Technologies for Energy Recovery Senthil Kumar Kandasamy* and Ramyea R. Department of Electronics and Communication Engineering, Kongu Engineering College, Perundurai, Erode, India

Abstract

Currently, many research works have been done with respect to renewable energy sources across the globe. Similarly, energy storage devices such as batteries, capacitors, and supercapacitors have been developed to store the energy obtained through renewable sources. Several materials, including carbonaceous materials, metal oxides, and conducting polymers, have been investigated for the development of energy storage devices. To meet the demand of people’s need as well as being cost-efficient, devices were developed using carbon-based materials such as graphite and activated carbon. The features of graphite and activated carbon are higher surface area, higher conductivity, and higher capacity retention ratio. These materials may be obtained through biomass, even from waste materials. In this chapter, the waste materials used for energy technologies were discussed along with the precursors, synthesis methods, energy parameters, and applications. Keywords:  Waste material, energy storage, supercapacitor

12.1 Introduction In recent days, biowaste is considered as the resource or precursor for the development of energy generation or energy storage technologies. The materials obtained from highly available and naturally feasible biowastes can be used to make electrodes for energy storage devices such

*Corresponding author: [email protected] Surajit Mondal, Adesh Kumar, Rupendra Kumar Pachauri, Amit Kumar Mondal, Vishal Kumar Singh and Amit Kumar Sharma (eds.) Clean and Renewable Energy Production, (287–312) © 2024 Scrivener Publishing LLC

287

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12

as battery or supercapacitor. Highly efficient porous activated carbons can be produced using less expensive methods. Porous carbon structures possess good conductivity and electrochemical kinetics, making them attractive for use in supercapacitors. Carbonization and chemical activation create micropores and mesopores. For the effective transportation of ions, more porosity is required. To achieve this, KOH is employed in the process. With KOH, oxygen also comes into play in the carbon framework. It leads to more rapid redox reactions and results in the formation of pseudocapacitance. Renewable energy resources have become the need of the hour to meet the increasing energy requirements in various sectors. Supercapacitors are one of the attractive ways of storing a large amount of energy within a short duration. The electrodes used in supercapacitors are vital for the charging and discharging mechanisms. Carbon and carbon-based materials are one of the best for use as electrodes because of their high-capacity retention ratio, specific surface area (SSA), and electrical conductivity. The increasing need of energy other than fossil fuel has grown drastically to meet the demand and minimize emissions. Energy storage devices, mainly battery and supercapacitor, are the need of the hour. In this aspect, the usage of carbonaceous materials as electrodes is evolving to fulfill the current requirements. To meet the electrode requirements used in a battery, the material should have a higher surface area, good porous structure, high conductivity, higher capacity retention ratio, and, obviously, low cost [65]. These conditions are met by carbonaceous materials, especially activated carbon and graphene. Conversion of waste biomass into a useful energy reservoir makes a better world in the future. Pseudocapacitors, electrochemical double-layer supercapacitors (EDLCs), and hybrid supercapacitors are the major categories of supercapacitors [66]. Pseudocapacitors comprises of certain conductive polymers such as polyaniline [66], polypyrrole, and polythiophene etc., and metal oxides such as MnO2. They can be employed for the improvement of specific capacitance, but suffers from poor stability. Due to the presence of carbonaceous materials such as activated carbon, carbon nanotube, carbon aerogel, and graphene, EDLCs are more stable than others. Composites or hybrid capacitors overcome certain limitations of the other two methods. Biomass-based activated carbons are the new discoveries that focus on converting waste disposal into useful by-products for supercapacitors. These renewable biomass-based methods are highly accepted due to their wider availability and lower costs. The structure and composition of the biomass or biowaste resemble the characteristics of carbon

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288  Clean and Renewable Energy Production

nanomaterials. Developing sustainable and renewable carbon-based electrodes with high energy density and durability is a challenging task. Nanomaterial preparation from a biowaste precursor is decisive. For the bulk production of supercapacitors in large cities, a green and pollution-free mechanism is required to achieve ecological balance. Agricultural wastes are one such source for an extensive synthesis of carbonaceous materials. Nanobiomaterials possess a high surface area and a highly porous structure, which provide a larger space for energy storage. Developing high-performing supercapacitors using biomaterials is still under research because of their unpredictable chemical activity and conductivity. However, if this approach becomes successful, then it would be a low-cost production method for carbon materials. However, it is not an easy task to achieve a controlled porous structure and high yields of carbon at the same time. Piezoelectric biomaterials can also be used as an energy storage device. Graphene and its compounds have higher specific capacitance, and they are used for making electrodes for flexible supercapacitors. A three-­ dimensional (3D) structure of carbon materials with high surface area is mostly preferred. These 3D materials are the choice of interest because of their faster electron transport rates and high SSA. Activated carbon (AC) is one of the commercially used materials for electrodes in a wide variety of energy storage devices. AC has good porous structure and high SSA. Several research works have focused on improving the specific capacitance without compromising the durability. Owing to the abundant availability of natural sources and their waste portions, carbon-rich porous materials can be formed with lower costs. From the morphological perspective of biowastes, it can be estimated that higher porous carbons can be obtained. The conversion of biomass to low-cost carbon can lead to several challenges, such as the durability of carbon electrodes, limitation in the operating potential window, its conductive nature, and chemical reactions. Although hierarchical porous carbon obtained through waste materials possesses higher SSA, higher conductivity, and good electrochemical kinetics, there is still a problem with respect to the durability and specific capacitance. Similarly, nonbiodegradable wastes such as poly(ethylene terephthalate) (PET) and polystyrene (PS) cause problems to the environment. This can be avoided by converting PET and PS wastes into useful products such as porous carbon. The ecological conditions of large populated cities may improve with the help of energy storage devices. This can be done by green technology using agricultural wastes [1, 2].

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Waste to Energy Technologies for Energy Recovery  289

12.2 Preparation Methods In general, to prepare porous carbon, two methods are involved, as follows: 1. Carbonization a. Furnace-based b. Microwave-treated 2. Activation a. Chemical activation b. Physical activation In certain processes, nitrogen doping is also involved.

12.3 Carbonization and Activation 12.3.1 Uses of Carbonization This process is used to improve the electrochemical kinetics and conductivity of the carbon material. By adjusting the carbonization temperature, the following parameters are greatly influenced. 1. Conductivity 2. Morphology 3. Chemical composition When the carbonization temperature is increased, the material promotes the surface area, specific capacitance, and pore volume. However, in certain cases, due to the nature of the biowaste, pores become agglomerated at a higher temperature. Because of this, the carbonization temperature has to be optimized for different types of biomass; otherwise, the waste material will exhibit a lower SSA. Due to this, instead of carbonization, a steambased approach is preferred. Also, pretreatment improves the micropores, surface area, and the heteroatom content. However, after pretreatment, the sample may attain an amorphous nature. A melamine catalyst is used to improve the surface area and the level of nitrogen doping. Nitrogen doping enhances the wettability and creates a lot of active sites. Conventional and hydrothermal carbonization of Jatropha oilcake is shown in Figure 12.1. Conventional carbonization produces biochar, while hydrothermal carbonization produces hydrochar. Both can be used in supercapacitors.

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290  Clean and Renewable Energy Production

Carbonization

Jatropha oilcake

Biochar

Pristine Carbon

Conventional Carbonization

Hydrothermal Carbonization

Symmetric Supercapacitor

KOH Based Chemical Activation

Activated Carbon

Hydrochar

Figure 12.1  Conventional and hydrothermal carbonization of Jatropha oilcake [3].

The advantages are as follows: ™™ Attain maximum amount of carbon ™™ Biowaste is converted into carbon ™™ Operates up to higher temperature The limitations are: ™™ More time is needed. ™™ Low yield, energy density, and hydrocarbon content. However, torrefaction provides higher yield and energy density.

12.3.2 Uses of Activation The activation process is used to construct and control the pores properly from the base of a carbon channel by means of utilizing the contact between the activator and carbonized samples. Furthermore, the porous structure can be improved by a higher concentration of an activating agent. For preparing interconnected, hollow-structured samples, the pyrolysis process may be involved after activation. Pyrolysis

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Waste to Energy Technologies for Energy Recovery  291

is further used to eliminate toxic components. At the same time, the ash contains some unwanted metals. This activation process leads to creating meso- and micropores. By selecting the proper ratio of carbon materials and activating agent, not only a higher SSA but also a higher specific capacitance can be observed at a higher degree of graphitized level. Finally, to deal with the wet waste material, hydrothermal carbonization is preferred. Pros of chemical activation: ™™ Operates even at lower temperatures ™™ Uniform porous structure ™™ Very low environmental pollution ™™ Higher yield Cons of chemical activation: ™™ Lesser active area Pros and cons of physical activation: Pros include the sample containing a lot of micropores with a larger area, while the cons are non-uniformity and lesser yield. Several chemicals are used to activate the carbon prepared from biowastes. A few of them are given below.

12.3.2.1 Phosphoric Acid Activation This activation creates more space on the surface of the waste carbonized material for further activation using different activating agents such as KOH and ZnCl2. If the biowaste contains a huge amount of lignocellulose, this activation agent is highly preferred.

12.3.2.2 Zinc Chloride Activation Zinc chloride is used to create structured pores on the surface of a carbonized sample. Here, a higher surface area is observed than the surface area of phosphoric acid activation. This is due to the cleansing of the presence of zinc and chlorine.

12.3.2.3 Potassium Hydroxide Activation This activation suggests an excellent capacitive performance and improved efficiency. Also, this activation is used to improve the ion transportation

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292  Clean and Renewable Energy Production

and introduce oxygen functionalities into the framework of carbon, which further improves the pseudocapacitance.

12.3.2.4 Potassium Carbonate Activation With the help of this activation, a higher yield is observed.

12.3.2.5 Nitric Acid Activation This activation leads to a smaller surface area. But the presence of surface oxygen and carbonyl-type oxygen groups enhances the specific capacitance. Figure 12.2 depicts the collection of biomass materials that can be used for the mechanism of energy storage.

12.4 Electrode Materials Extracted from Biowastes The following materials are extracted from biomaterials. These are: Activated carbon Graphene oxide Carbon nanotube Carbon aerogel

Figure 12.2  Biomaterials for energy storage mechanism [4].

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Waste to Energy Technologies for Energy Recovery  293

12.4.1 Carbon Nanotube Although carbon nanotube (CNT) has the lowest specific capacitance, it is still considered as an electrode for supercapacitors. However, it is more costly. Cost-effective preparation of CNTs may be done through biowastes. Using a palm oil mill effluent, a CNT was prepared through hydrothermal carbonization and pyrolysis.

12.4.2 Graphene Oxide Several methods and waste materials have been used for the preparation of graphene oxide economically. Coconut shells, coir, papers, and palm oil are the commonly used precursors. For extracting graphene, carbonization, activation, and pyrolysis were performed.

12.4.3 Carbon Aerogel In general, uniform N-doping on aerogel improves the SSA, specific capacitance, presence of uniform mesopores, and power density. Carbon aerogel prepared from durian fruit waste showed higher N-doping, good number of mesopores, higher specific capacitance, and power density than the carbon aerogel obtained from wastes of jackfruit.

12.4.4 Activated Carbon Activated carbon is prepared from any waste materials or precursors. The precursors, activation methods, and agents used to prepare activated carbon are given in Table 12.1. For example, activated carbon obtained from paper mill sludge exhibited higher specific area of around 2,980  m2  g−1 through hydrothermal carbonization and chemical activation. Similarly, using lees, a specific surface area of 1,357 m2 g−1 was obtained. For smaller surface area materials, there is a need for oxygen-based functional groups, which may contribute to the specific gravity. Wastes such as orange peel can used to make interconnected, hollow activated carbon through chemical activation and pyrolysis, with a surface area of 2,521 m2 g−1 and higher porosity for higher concentrated potassium hydroxide. However, for a lower concentration, the material exhibited higher specific capacitance owing to micro- and mesopores. N2-free carbonization on rice husks exhibited higher SSA, pore size, and specific capacitance because of the availability of H2O and CO2. Alkali etching further supports the process and improves the surface area and capacitance.

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294  Clean and Renewable Energy Production

Table 12.1  Precursors, activation methods, and agents used to prepare activated carbon. Biomass precursor

Activation method

Activating agent

Palm oil biomass, coconut shell, orange peel, coal slime, walnut shell, pineapple crown, jute, banana peel, naturalwithered rose flower, shiitake mushroom, poly(ethylene terephthalate) beverage bottles,chestnut shell, wheat straw, corncob residue, soybean curd residue, waste coffee grounds, wild jujube pits, chestnutshell, mangosteen peel

Chemical activation, physicalactivation, microwaveactivation

Sulfuric acid, phosphoric acid, zinc chloride, sodium carbonate, calcium carbonate, sodiumsulfate, potassiumhydroxide, sodium hydroxide, potassiumcarbonate, calcium oxide,potassium nitrate,anhydrous iron chloride, potassium sulfate, calcium chloride, ammonium sulfate,hydrogen chloride

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Waste to Energy Technologies for Energy Recovery  295

Using catalysts, hydrothermal carbonization is done, following which activated carbon is used. Similarly, it can be directly obtained through chemical activation. This is shown in Figure 12.3. Microwave activation is also beneficial in terms of improving the porous structure [6–10]. Thermal carbonization on seaweed fiber provided higher conductivity, effective morphology, and good porous structure up to a certain temperature (~1,000°C). Similarly, palm oil can be used for the development of activated carbon through a hydrothermal process. Also, by using KOH, the carbon obtained from pollen cone waste was activated and used in electrodes for energy storage. For better environmental protection and resource conservation, effective usage of coal slime is helpful. In certain cases, the solar pyrolysis method is used with the help of high-intensity solar energy. Pretreatment reduces the crystallinity, but is used to improve the SSA and controlled micropores. Glycerated cherry wastes activated through the hydrothermal method provided a good number of mesopores, more reactive sites, and higher SSA. Blueberry wastes may affect the wettability of an electrolyte and electrochemical double layer thickness because of more chemisorbed oxygen. Battery containing activated carbon obtained from jute has improved battery capacity even for different temperature levels. For treating biowastes, the temperature should be optimized because, in higher temperatures, the porosity may decrease. This further reduces the surface area. Although this material exhibited a lower surface area, treating the sample with nitric acid improves the specific capacitance and some oxygen groups contributing to pesudocapacitance.

Hydrochar

Corn Grain

Production Wastes

Corn Wet Distillers’ Fiber

lyst l ata l 3 C erma n C e h F rot zatio Hydrboni Ca

Chem

ical Ac

Activated Carbon

Porous High Surface Area Nitrogen Rich

tivatio n

Figure 12.3  Nitrogen-rich activated carbon with a porous structure obtained from corn grain [5].

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296  Clean and Renewable Energy Production

Electrode materials for energy storage devices such as battery and supercapacitor can be developed using waste materials. Porous carbon from rose petals exhibited SSA of 1,980 m2 g−1 [11]. Some activated carbon-based electrodes obtained from waste materials have wind wave-like morphology, maintaining the capacity retention ratio of 95.6% even after 15000 cycles. Similarly, high-conductivity 3D porous carbon showed an SSA of 3,089 m2 g−1 [12]. Wheat flour is used for the production of bimodal porous carbon with an SSA of 1,620 m2 g−1 [13]. Hierarchical porous carbon is also obtained from mushrooms through KOH and H3PO4 activation [14]. A comparison of the SSAs of carbonaceous materials is given in Table 12.2.

12.5 Energy Storage Applications Figure 12.4 shows the methods involved in the preparation of energy storage materials from waste materials. Even paper flower-based activated carbon ultrathin sheets exhibited an SSA of 1,801 m2 g−1. Lignosulfonate waste obtained from the paper industry was used to prepare hierarchical carbon through mold casting [41]. Because the cross-linking molecules support graphitization, waste PET bottles can be converted into porous carbon, with an SSA of 2,236 m2 g−1 [27]. Environment-friendly carbonization of garlic peels exhibited SSA of 436.2 m2 g−1. Coin cell made from waste materials was observed to have an energy density of 32.6 Wh kg−1. In certain cases, increasing the current density leads to a drop in specific capacitance. Microporous carbon derived from waste PET maintains a capacitance of around 98.68% even after 10,000 cycles. The processes involved in the preparation of electrodes obtained from biowaste are shown in Figure 12.5. The specific capacitance values of the activated carbon obtained from waste materials are given in Table 12.3. Crumbling biomass carbons can be obtained from lotus leaves and seedpods. Activated carbon obtained from Areca palm leaf wastes through carbonization and in situ chemical activation exhibited specific capacitance of 343.1 F g−1 and retention of 96.2% [42]. From wood fiber, microporous carbon obtained via heteroatom doping exhibited specific capacitance of 262 F g−1 at 5 mV s−1 using PVA–Li2SO4 gel polymer. A melamine catalyst may be used for nitrogen doping. Waste of pea protein, which is rich in N2, was used to obtain carbon through pyrolysis and activation [43]. Oxygen functionality by KOH may establish pseudocapacitance. Fewer numbers of oxygen-based functional groups cause lower capacitance, although a higher surface area is obtained. Wheat

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Waste to Energy Technologies for Energy Recovery  297

Table 12.2  Comparisons of the specific surface area (SSA) of carbonaceous materials.

Bio-source Palm oil biomass

Materials obtained

Methods

SSA (m2g−1)

Reference

[15]

Activated carbon

Hydrothermal carbonization andpyrolysis

383.748

Graphene

Carbonization

401.17

Palm oil mill effluent

CNT

Polymerization and carbonization

526.24

Bombax malabaricum

Carbon

Carbonization

2,402

[16]

Paper pulp mill sludge biowaste

Carbon

Hydrothermal carbonization and chemical activation

2,980

[17]

Orange peel

Carbon

Pyrolysis and chemical activation

2,521

[18]

Eucalyptus globulus seed

Activated carbon

Hydrothermal carbonization and chemical activation

2,388.38

[19]

Coal slime

Activated carbon

Carbonization and chemical activation

3,037

[20]

Walnut shell

Activated carbon

Chemical activation

1,016.4

[21]

Pineapple crown

Activated carbon

Carbonization and physical activation

700

[22]

Jute

Carbon

Hydrothermal and chemical activation

1,769

[23]

Banana peel

Activated carbon

Carbonization and activation

581

[24]

Shiitake mushroom

Carbon

Activation

2,988

[13] (Continued)

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298  Clean and Renewable Energy Production

Table 12.2  Comparisons of the specific surface area (SSA) of carbonaceous materials. (Continued) Bio-source

Materials obtained

Methods

SSA (m2g−1)

Reference

Poly(ethylene terephthalate) beverage bottles

Carbon

Carbonization and catalytic activation

2,236

[25]

Chestnut shell

Carbon

Activation

2,298

[26]

Waste polyethylene terephthalate

Carbon

Carbonization and activation

2,238

[27]

Ground cherry calyces

Carbon

Carbonization

1,612

[28]

Wheat straw

Carbon

Pyrolysis

892

[29]

Corncob residue

Carbon

Carbonization and activation

1,210

[30]

Soybean curd residue

Carbon

Carbonization

1,088.11

[31]

Agaric

Carbon

Carbonization, chemical activation,and nitrogen-doped treatment

1,565.6

[32] (Continued)

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Waste to Energy Technologies for Energy Recovery  299

Table 12.2  Comparisons of the specific surface area (SSA) of carbonaceous materials. (Continued) Bio-source

Materials obtained

Methods

SSA (m2g−1)

Reference

Dumpling flour

Carbon

Carbonization, chemical activation,and nitrogen-dopedtreatment

2,853.6

[33]

Waste coffee grounds

Carbon

Catalytic carbonization and alkali activation

3,549

[34]

Waste printing paper

Carbon

Carbonation and KOH activation

2,616.1

[35]

Wild rice stem

Carbon

Carbonization and alkaline activation

1,228

[36]

Wild jujube pits

Carbon

Carbonization

2,438

[37]

Bean dregs

Carbon

Carbonization and activation

3,700

[38]

Chestnut shell

Carbon

Carbonization and activation

2,621

[39]

Mangosteen peel

Carbon

Carbonization and NaOH treatment

2,623

[40]

CNT, carbon nanotube.

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300  Clean and Renewable Energy Production

Energy Storage Applications: Carbonization Activation Pyrolysis

Waste Materials

Electrode Materials for Energy Storage

Figure 12.4  Electrodes from waste materials.

Drying

Carbonizing

Crushing

800°C KOH

Working electrodes

Drying Crushing

Activating

Carbonizing 800°C

Pressing

PVDF and NMP Carbon black

Coating on nickel foam respectively

Activating

PVDF and NMP

800°C KOH

Carbon black

Figure 12.5  Electrode preparation from biowaste [67].

straw-derived activated carbon exhibited specific capacitance of around 270 F g−1 at 6 M KOH, with Capacitance Retention Ratio (CRR) of 97% [29]. Some materials displayed poor rate capacity after several cycles. For a safer environment, plastic wastes should be recycled and used as an electrode material for supercapacitors [44]. Corncob residue obtained from the furfural industry exhibited higher surface area, higher specific capacitance, and zero degradation (1,210 m2 g−1, 314 F g−1, and 100% CRR) even after 1 lakh cycles [30]. Ground cherry calyx-based activated carbon [28] and dead Ficus religiosa leaf-based activated carbon [61] obtained through carbonization showed higher surface area and CRR. Similarly, without the usage of a catalyst, the carbon attained had low series resistance and charge transfer resistance. By comparing a commercial supercapacitor with soybean curd residue-­ based N-doped activated carbon, symmetric supercapacitor has a higher energy density [56] of 9.95  Wh  kg−1 at 0.236  kW  kg−1. From agaric [12] and dumpling flour, porous, highly interconnected carbon sheets can be prepared through carbonization, activation, and nitrogen doping. These look like graphene aerogels.

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Waste to Energy Technologies for Energy Recovery  301

Table 12.3  Specific capacitance of bioresource-derived activated carbon. Bio-source

Specific capacitance

Reference

Solanum tuberosum

94 F g−1 at 10 mV s−1

[45]

Musa paradisiaca

306 F g−1 at 10 mV s−1

[46]

Citrus sinensis flavedos

92 F g at 10 mV s

[47]

Coconut shell and coir

114 F g−1 at 10 mV s−1

[48]

Paper

1,122 F g−1 at 5 mV s−1

[49]

Jackfruit biowaste

292 F g−1 at 1 A g−1

[50]

Durian biowaste

591 F g−1 at 1 A g−1

Seaweed fiber

226.3 F g−1

[51]

Paper pulp mill sludge biowaste

190 F g−1

[17]

Orange peel

407 F g−1 at 0.5 A g−1

[18]

Black liquor

133.92 F g−1

[52]

Chinese rice wine lees

433.5 F g−1 at 1 A g−1

[53]

Polyalthia longifolia seeds

365 F g−1 at 1 A g−1

[54]

Eucalyptus globulus seed

150 F g at 1 A g

[19]

Coal slime

220 F g−1 at 0.1 A g−1

[20]

Walnut shell

169.2 F g−1 at 0.5 A g−1

[21]

Pineapple crown

150 F g−1

[22]

Citrus lamella

421.67 F g−1 at 1 A g−1

[55]

Newspaper

132 F g−1 at 1 A g−1

[56]

Moringa oleifera

130 F g−1

[57]

Acacia mangium wild

113 F g−1

[58]

Pecan nutshell

150 F g−1 at 5 mV s−1

[59]

Shiitake mushroom

306 F g−1 at 1 A g−1

[13]

Chestnut shell

387 F g−1 at 2 A g−1

[26]

Areca palm leaves

262 F g−1 at 5 mV s−1

[42]

−1

−1

−1

−1

(Continued)

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302  Clean and Renewable Energy Production

Table 12.3  Specific capacitance of bioresource-derived activated carbon. (Continued) Bio-source

Specific capacitance

Reference

Wheat straw

275 F g−1 at 0.2 A g−1

[29]

Corncob residue

314 F g−1

[30]

Soybean curd residue

215 F g−1 at 0.5 A g−1

[31]

Dumpling flour

311 F g−1 at 1 A g−1

[33]

Waste coffee grounds

440 F g−1 at 0.5 A g−1

[34]

Waste printing paper

385 F g−1 at 0.2 A g−1

[35]

Wild rice stem

301 F g−1 at 1 A g−1

[36]

Wild jujube pits

398 F g−1 at 0.5 A g−1

[37]

Mangosteen peel

357 F g−1 at 1 A g−1

[40]

Cotton yarn

10.06 F g−1 at 150 mV s−1

[60]

Although higher resistance was observed due to the presence of a catalyst, catalytic carbonization and alkali activation led to hierarchical porous carbon from waste coffee grounds [53], with good specific capacitance, higher surface area (~3,549 m2 g−1), and higher yield of carbon. Peels of lemon were used as electrode material, with a potential window of 1.65 V. Similarly, waste printing paper-derived activated carbon exhibited higher surface area, conductivity, and energy density [49]. By properly controlling the steam water and temperature, remarkable improvements in the surface area, pore size, pore volume, and specific capacitance were observed even from soybean waste [62]. Similarly, controlled inert gas flow improves the impedance and rate capability. Activated carbon electrode formation is shown in Figure 12.6. Activated carbon-based supercapacitor may be classified into two types: 1. Higher capacitance even with larger impedance 2. Moderate capacitance with lesser impedance Also, water steam-based activation leads to higher specific capacitance. At the same time, no water steam led to faster cyclic voltammetry (CV) response. Alkali activation of wild rice stem [36] and CO2 activation [63] showed good meso- and microporous structures. CO2 activation results in

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Waste to Energy Technologies for Energy Recovery  303

Energy storage Supercap

Activation

Precursor

Activated carbon

Figure 12.6  Formation of activated carbon from biowaste for energy storage applications [68].

different porous structures and further improves the surface area. Similarly, oxygen-rich jujube pit showed better specific capacitance and cyclability [37]. Cost-effective activated carbon prepared from bean dregs showed surface area of around 3,700 m2 g−1 [38], while and litchi pericarp exhibited a surface area of 3,438 m2 g−1 [64] with 407 F g−1. Activated carbon from chestnut shell and mangosteen peel gave surface areas of 2,621 and 2,623 m2 g−1, respectively [40]. The porosity of all the materials can be tuned by modifying the temperature and activator-to-precursor ratio. In general, sp2 forms micropores, while sp3 forms meso- and macropores.

12.6 Importance of Electrolyte Higher number of ions available in an aqueous electrolyte contributes to the specific capacitance and stability. Higher specific capacitance, energy, and power density can be obtained from organic electrolytes. Similarly, 1-ethyl-3-methylimidazolium tetrafluoroborate showed the highest energy density. Higher capacity retention ratio and specific capacitance were achieved for 6 M KOH. But the highest energy and power density were for 1 M Na2SO4 than 6 M KOH. For EDLCs, ionic liquid gel polymer electrolytes (ILGPEs) are highly preferred due to their wide potential window (~4.6 V), high ionic conductivity, and flexibility.

12.7 Conclusions Biowaste is considered as the resource or precursor for the development of energy generation or energy storage technologies. The ecological conditions of large populated cities may improve with the help of energy storage devices. Carbon and carbon-based materials are some of the best for use as

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304  Clean and Renewable Energy Production

an electrode because of their high-capacity retention ratio, SSA, and electrical conductivity. To meet the requirements of electrodes used in batteries, the material should hold a higher surface area, have good porous structure, high conductivity, higher capacity retention ratio, and, obviously, low cost. Highly efficient porous activated carbons can be produced using less expensive methods. Activated carbon is considered as an excellent material for energy storage purposes. Porous carbon structures possess good conductivity and electrochemical kinetics, making them attractive for use in supercapacitors. Specifically, hierarchical activated carbon and 3D porous carbon are considered as potential candidates as electrodes for energy storage devices due to their surface area, conductivity, and optimized pores. The conversion of waste biomass into a useful energy reservoir makes for a better world in the future.

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306  Clean and Renewable Energy Production

18. Ranaweera, C.K., Pawan, K., Kahol, M., Ghimire, S.R., Mishra, Ram, K.G., Orange-peel-derived carbon: Designing sustainable and high-performance supercapacitor electrodes. C-J. Carbon Res., 3, 3, 25, 2017. 19. Rajasekaran, S.J. and Raghavan, V., Facile synthesis of activated carbon derived from Eucalyptus globulus seed as efficient electrode material for supercapacitors. Diam. Relat. Mater., 109, 108038, 2020. 20. Li, J., Jiajun, H., Kai, W., Hongyan, X., Coal slime waste: A promising precursor to develop highly porous activated carbon for supercapacitors. Carbon Lett., 30, 6, 657–665, 2020. 21. Lan, D., Mingyan, C., Yucheng, L., Qingling, L., Wenwen, T., Yuanyuan, C., Jingjing, L., Feng, Q., Preparation and characterization of high value-added activated carbon derived from biowaste walnut shell by KOH activation for supercapacitor electrode. J. Mater. Sci.: Mater. Electron., 31, 21, 18541–18553, 2020. 22. Taer, E., Apriwandi, A., Ningsih, Y.S., Taslim, R., Agustino, A., Preparation of activated carbon electrode from pineapple crown waste for supercapacitor application. Int. J. Electrochem. Sci., 14, 2462–2475, 2019, 10.20964/2019.03.17. 23. Ciftyurek, E., Bragg, D., Oginni, O., Levelle, R., Singh, K., Sivanandan, L., Sabolsky, E.M., Performance of activated carbons synthesized from fruit dehydration biowastes for supercapacitor applications. Environ. Prog. Sustain. Energy, 38, 3, e13030, 2019. 24. Taer, E., Taslim, R., Aini, Z., Hartati, S.D., Mustika, W.S., Activated carbon electrode from banana-peel waste for supercapacitor applications. AIP Conf. Proc., 1801, 1, 040004, 2017. 25. Vinay, S.B., Pandiyaraj, K., Ganesan, S., Ramya, P.B., Neena, S.J., Murugan, V., Mahaveer, K., Gurumurthy, H., Low cost, catalyst free, high performance supercapacitors based on porous nano carbon derived from agriculture waste. J. Energy Storage, 32, 101829, 2020. 26. Hong, P., Xu, L., Xu, Z., Sijia, P., Zidong, W., Yue, Y., Rongjun, Z., Yude, W., Hierarchically porous carbon derived from the activation of waste chestnut shells by potassium bicarbonate (KHCO3) for high-performance supercapacitor electrode. Int. J. Energy Res., 44, 2, 988–999, 2020. 27. Liu, X., Wen, Y., Chen, X., Tang, T., Mijowska, E., Co-etching effect to convert waste polyethylene terephthalate into hierarchical porous carbon toward excellent capacitive energy storage. Sci. Environ., 723, 138055, 2020. 28. Yu, D., Chong, C., Gongyuan, Z., Lei, S., Baosheng, D., Hong, Z., Zhuo, L., Ye, S., Flemming, B., Miao, Y., Biowaste-derived hierarchical porous carbon nanosheets for ultrahigh power density supercapacitors. ChemSusChem, 11, 10, 1678–1685, 2018. 29. Liu, W., Jie, M., Guolong, L., Qian, K., Tingfeng, Y., Saijun, X., Nitrogendoped hierarchical porous carbon from wheat straw for supercapacitors. ACS Sustain. Chem. Eng., 6, 9, 11595–11605, 2018.

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Waste to Energy Technologies for Energy Recovery  307

30. Qu, W.H., Xu, Y.Y., Lu, A.H., Zhang, X.Q., Li, W.C., Converting biowaste corncob residue into high value added porous carbon for supercapacitor electrodes. Bioresour. Technol., 189, 285–291, 2015. 31. Ma, G., Ran, F., Peng, H., Sun, K., Zhang, Z., Yang, Q., Lei, Z., Nitrogendoped porous carbon obtained via one-step carbonizing biowaste soybean curd residue for supercapacitor applications. RSC Adv., 5, 101, 83129–83138, 2015. 32. An, Y., Zhimin, L., Yuying, Y., Bingshu, G., Ziyu, Z., Hongying, W., Zhongai, H., Synthesis of hierarchically porous nitrogen-doped carbon nanosheets from agaric for high-performance symmetric supercapacitors. Adv. Mater. Interfaces, 4, 12, 1700033, 2017. 33. Zhou, J., Min, W., Xin, L., Promising biomass-derived nitrogen-doped porous carbon for high performance supercapacitor. J. Porous Mater., 26, 1, 99–108, 2019. 34. Liu, X., Zhang, S., Wen, X., Chen, X., Wen, Y., Shi, X., Mijowska, E., High yield conversion of biowaste coffee grounds into hierarchical porous carbon for superior capacitive energy storage. Sci. Rep., 10, 1, 1–12, 2020. 35. Liu, D., Yesheng, W., Zhipeng, Q., Yanyan, L., Li, W., Yi, Z., Jin, Z., Porous carbons derived from waste printing paper for high rate performance supercapacitors in alkaline, acidic and neutral electrolytes. RSC Adv., 8, 8, 3974– 3981, 2018. 36. Tian, Q., Xiaoxue, W., Xiaoyang, X., Man, Z., Luyao, W., Xiaoxiang, Z., Zhaolin, A., Hongduo, Y., Jianping, G., A novel porous carbon material made from wild rice stem and its application in supercapacitors. Mater. Chem. Phys., 213, 267–276, 2018. 37. Sun, K., Shishun, Y., Zhongliang, H., Zhaohui, L., Gangtie, L., Qizhen, X., Yanhuai, D., Oxygen-containing hierarchically porous carbon materials derived from wild jujube pit for high-performance supercapacitor. Electrochim. Acta, 231, 417–428, 2017. 38. Jung, H.J., Kyung, H.P., Chan, K., Tae, Y.K., Jae, W.L., Highly porous carbon sorbents prepared from bean dregs for electric double-layer supercapacitor. Trans. Electr. Electron. Mater., 19, 3, 173–178, 2018. 39. Li, Y., Binshan, M., Yeru, L., Hanwu, D., Mingtao, Z., Yong, X., Yingliang, L., Component degradation-enabled preparation of biomass-based highly porous carbon materials for energy storage. ACS Sustain. Chem. Eng., 7, 18, 15259–15266, 2019. 40. Yang, V., Raja, A.S., Junqing, P., Abrar, K., Sedahmed, O., Liren, W., Wenchao, J., Yanzhi, S., Highly ordered hierarchical porous carbon derived from biomass waste mangosteen peel as superior cathode material for high performance supercapacitor. J. Electroanal. Chem., 855, 113616, 2019. 41. Wen, Y., Krzysztof, K., Jiakang, M., Xuecheng, C., Jiang, G., Ran, N., Xin, W., Jalal, A., Ewa, M., Tao, T., Porous carbon nanosheet with high surface area derived from waste poly (ethylene terephthalate) for supercapacitor applications. J. Appl. Polym. Sci., 137, 5, 48338, 2020.

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42. Le, P.A., Nguyen, V.T., Sahoo, S.K., Tseng, T.Y., Wei, K.H., Porous carbon materials derived from areca palm leaves for high performance symmetrical solid-state supercapacitors. J. Mater. Sci., 55, 24, 10751–10764, 2020. 43. Demir, M., Babak, A., Mugumya, J.H., Sushil, K.S., Hani, M.E., Ram, B.G., Nitrogen and oxygen dual-doped porous carbons prepared from pea protein as electrode materials for high performance supercapacitors. Int. J. Hydrogen Energy, 43, 40, 18549–18558, 2018. 44. Min, J., Shuai, Z., Jiaxin, L., Rüdiger, K., Xin, W., Xuecheng, C., Xi, Z., Tao, T., Ewa, M., From polystyrene waste to porous carbon flake and potential application in supercapacitor. Waste Manage., 85, 333–340, 2019. 45. Kandasamy, S.K., Balambigai, S., Hemalatha, K., Chandrasekaran, A., Suganthi, V., Yuvasri, M., Shreelogesh, D., Chemically treated activated carbon for supercapacitor electrode derived from starch of solanum tuberosum. J. New. Mater. Electrochem. Syst., 24, 2, 78–83, 2021. 46. Kandasamy, S.K., Arumugam, C., Vadivel, L., Ganapathi, M., Nattudurai, N., Kandasamy, K., Synthesis of chemically modified activated carbon for supercapacitor electrode derived from fibers of Musa paradisiaca. Int. J. Emerg. Technol., 11, 3, 565–569, 2020. 47. Devendran, M., Senthil, K.K., Shanmugam, P., Sangavi, S., Ragav, V., Roobak, S., Murugesan, G., Kannan, K., Preparation of chemically modified porous carbon networks derived from citrus sinensis flavedos as electrode material for supercapacitor. Int. J. Electrochem. Sci., 15, 4, 4379–4387, 2020, 10.20964/2020.05.08. 48. Tamilselvi, R., Ramesh, M., Lekshmi, G.S., Bazaka, O., Levchenko, I., Bazaka, K., Mandhakini, M., Graphene oxide – based supercapacitors from agricultural wastes: A step to mass production of highly efficient electrodes for electrical transportation systems. Renewable Energy, 151, 731–739, 2020. 49. Sing, D.C., Joseph, B., Velmurugan, V., Ravuri, S., Nirmala, G.A., Combustion synthesis of graphene from waste paper for high performance supercapacitor electrodes. Int. J. Nanosci., 17, 01&02, 1760023, 2018. 50. Lee, K., Shabnam, L., Faisal, S.N., Gomes, V.G., Aerogel from fruit biowaste produces ultracapacitors with high energy density and stability. J. Energy Storage, 27, 101152, 2020. 51. Jiang, L., Han, S.O., Pirie, M., Kim, H.H., Seong, Y.H., Kim, H., Foord, J.S., Seaweed biomass waste-derived carbon as an electrode material for supercapacitor. Energy Environ., 32, 1–13, 2019, 0958305X19882398. 52. Shanmugam, P., Kandasamy, S.K., Sathesh, T., Dhinesh, K., Marimuthu, P., Prasanna, V.R., Borje, S.G., Synthesis of activated carbon from black liquor for the application of supercapacitor. J. Mater. Sci.: Mater. Electron., 32, 20, 25175–25187, 2021. 53. Wu, D., Jinyan, C., Tao, W., Penggao, L., Liu, Y., Dianzeng, J., A novel porous N- and S-self-doped carbon derived from chinese rice wine lees as high-­ performance electrode materials in a supercapacitor. ACS Sustain. Chem. Eng., 7, 14, 12138–12147, 2019.

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Waste to Energy Technologies for Energy Recovery  309

54. Srinivasan, R., Elaiyappillai, E., Pandian, H.P., Vengudusamy, R., Johnson, P.M., Chen, S.M., Karvembu, R., Sustainable porous activated carbon from Polyalthia longifolia seeds as electrode material for supercapacitor application. J. Electroanal. Chem., 849, 113382, 2019. 55. Ahirrao, D.J., Tambat, S., Pandit, A.B., Jha, N., Sweetlime peels derived activated carbon based electrode for highly efficient supercapacitor and flow through water desalination. ChemistrySelect, 4, 9, 2610–2625, 2019. 56. Chen, Y., Rui, H., Jiqiu, Q., Yanwei, S., Yezeng, H., Qingkun, M., Fuxiang, W., Yaojian, R., Sustainable synthesis of N/S-doped porous carbon sheets derived from waste newspaper for high-performance asymmetric supercapacitor. Mater. Res. Express, 6, 9, 095605, 2019. 57. Palisoc, S., Dungo, J.M., Natividad, M., Low-cost supercapacitor based on multi-walled carbon nanotubes and activated carbon derived from Moringa Oleifera fruit shells. Heliyon, 6, 1, e03202, 2020. 58. Taer, E., Natalia, K., Apriwandi, A., Taslim, R., Agustino, A., Farma, R., The synthesis of activated carbon nanofiber electrode made from acacia leaves (Acacia mangium wild) as supercapacitors. Adv. Nat. Sci.: Nanosci. Nanotechnol., 11, 2, 025007, 2020. 59. Martínez-Casillas, D.C., Mascorro-Gutiérrez, I., Arreola-Ramos, C.E., Villafán-Vidales, H.I., Arancibia-Bulnes, C.A., Ramos-Sánchez, V.H., Cuentas-Gallegos, A.K., A sustainable approach to produce activated carbons from pecan nutshell waste for environmentally friendly supercapacitors. Carbon, 148, 403–412, 2019. 60. Kandasamy, S.K., Chandrasekaran, A., Logupriya, V., Saravanakumar, K., Deepa, K., Fabrication of ZnO–carbonized cotton yarn derived hierarchical porous active carbon flexible electrodes. AIP Conf. Proc., 2387, 1, 090005, 2021. 61. Senthilkumar, S.T. and Selvan, R.K., Flexible fibersupercapacitor using ­biowaste-derived porous carbon. ChemElectroChem, 2, 8, 1111–1116, 2015. 62. Sun, W., Yan, X., Qingyuan, R., Fuqian, Y., Soybean-waste-derived activated porous carbons for electrochemical-double-layer supercapacitors: Effects of processing parameters. J. Energy Storage, 27, 101070, 2020. 63. Xia, K., Qiuming, G., Jinhua, J., Juan, H., Hierarchical porous carbons with controlled micropores and mesopores for supercapacitor electrode materials. Carbon, 46, 13, 1718–1726, 2008. 64. Wang, P., Guoheng, Z., Wanjun, C., Haiyan, J., Liwei, L., Xiangli, W., Xiaoyan, D., Qiong, C., Highly porous carbon derived from litchi pericarp for supercapacitors application. J. Mater. Sci.: Mater. Electron., 29, 17, 14981–14988, 2018. 65. Arumugam, C., Senthil, K.K., Sabitha, R., Sangavi, M., Ruthra, P.T., Hierarchical structure of graphene oxide/MnO2 electrodes for supercapacitor. AIP Conf. Proc., 2387, 1, 090004, 2021.

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Waste to Energy Technologies for Energy Recovery  311

A Review of Electrolysis Techniques to Produce Hydrogen for a Futuristic Hydrogen Economy Vijay Parthasarthy1*, Siddhant Srivastava2, Riya Bhattacharya3, Sudeep Katakam4, Akash Krishnadoss4, Gaurav Mitra5 and Debajyoti Bose3† Department of Examinations, Dr. Vishwanath Karad MIT World Peace University, Pune, Maharastra, India 2 Faculty of Applied Sciences & Biotechnology, School of Biotechnology, Shoolini University of Biotechnology & Management Sciences, Solan, Himachal Pradesh, India 3 School of Technology, Woxsen University, Hyderabad, Telangana, India 4 Department of Chemical Engineering, School of Engineering, University of Petroleum and Energy Studies, Energy Acres, Bidholi, Dehradun, India 5 Department of Chemistry, University of Massachusetts, Amherst, United States

1

Abstract

Hydrogen is one of the most efficient sources of energy that is seen as an alternative fuel. Hydrogen can be produced by various methods. One of them is anion electrode membrane electrolysis. Electrolysis of water in an anionic exchange membrane with a basic electrolyte to yield hydrogen and oxygen through oxygen evolution reaction (OER) and hydrogen evolution reaction (HER) is called anion exchange membrane (AEM) electrolysis. AEM electrolysis is one of the technologies under research that can provide the solution for the energy crisis existing today and a future where all the hydrocarbon sources will be depleted. The source for this process is abundant in nature, and the pollution level is very minimal. If devised properly, this can be the perfect solution for the future. In this review, we will take a look at the various steps and methods devised to improve the performance of AEM electrolysis. The work done, its novelty, the inference we get from this paper, and its limitations are also discussed. Keywords:  Electrolysis, hydrogen, AEM, membranes, water *Corresponding author: [email protected] † Corresponding author: [email protected] Surajit Mondal, Adesh Kumar, Rupendra Kumar Pachauri, Amit Kumar Mondal, Vishal Kumar Singh and Amit Kumar Sharma (eds.) Clean and Renewable Energy Production, (313–334) © 2024 Scrivener Publishing LLC

313

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13

13.1 Introduction Ever since humans needed help to make their work easier, they started the quest for a source that can substitute their energy or perform over the energy capability [1]. Some of the energy sources that humans rely on now are heat and electricity [2]. To meet demands, coal (290 ZJ), oil (57 ZJ), and gas (57 ZJ) make up the majority of the total energy reserves (30  ZJ). Approximately 6.8% of scholars believe that oil production peaked before 2007, while 37.9% believe it will peak between 2008 and 2012, 34.5% believe it will peak between 2012 and 2013, 0.1% believe it will peak between 2013 and 2022, and 20.7% believe it will peak in 2023 or later [3, 4]. The use of these sources is also harmful to the environment due to pollution and global warming. Energy from hydrocarbon is mostly obtained through combustion, which involves the release of CO2. The CO2 in the atmosphere has risen from 380 to 410 ppm in the atmosphere due to the usage of hydrocarbons as fuel from 2000 to 2020. The annual average anomaly has also increased from 0.4 to 0.85°C from 2000 to 2021 [5]. These rising values demonstrate that, if the same situation continues, we would face a lot of problems. Hence, it is important to look for an alternate source of energy other than hydrocarbons. The fuel has to be clean, it should have high calorific value, and it should also be easily replaceable with conventional fuel. One such important alternative source of energy that has the potential to replace the conventional source of energy is hydrogen. Hydrogen is emission-free at the point of final use, avoiding both CO2 and air pollution emissions caused by transportation. The world governments have targeted net zero emissions by the end of 2050. Hydrogen can contribute efficiently to this cause. Hydrogen can contribute to the diversification of automotive fuel sources and supplies by being a secondary energy carrier that can be produced from any primary energy source. It also offers the long-term possibility of being solely produced from renewable energies. Hydrogen could also be employed as a storage medium for electricity generated by intermittent renewable energies, such as the wind. Any gains from using hydrogen as a fuel, similar to electricity, depend on how it is produced [6]. One of the ways to produce hydrogen is through electrolysis. Electrolysis is the process that involves oxidation and reduction reactions using current and potential. The electrolysis of water was first demonstrated by J.W. Ritter from Germany around 1800 AD. William Nicholson and Anthony Carlise used this same method to decompose water into hydrogen and oxygen. There are various methods of electrolysis available for the production of hydrogen. There are three types of electrolysis: ion transfer acidic or proton exchange membrane (PEM) electrolysis, anion exchange membrane (AEM) electrolysis, and solid oxide electrolyzer cells (SOECs) [7].

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314  Clean and Renewable Energy Production

13.1.1 Chemistry Behind Electrolysis The hydrogen evolution reaction (HER) at the cathode and the oxygen evolution reaction (OER) at the anode are the two half-reactions of water electrolysis [8]. Given that water dissociation (i.e., the Volmer step) is not rate-limiting in these instances, HER normally occurs in an acidic electrolyte with a low overpotential, while OER occurs swiftly in an alkaline electrolyte [9]. The primary reaction in HER is by the Volmer reaction. It is then continued either by the Heyrovsky or the Tafel reaction [10].

13.1.2 Step 1 H2O molecules are reduced inside an electrolyte solution to produce adsorbed hydrogen atoms (Hads) on active metal sites (M) and hydroxide ions.

H2O + e− + M → M − Hads + OH− 13.1.3 Step 2 Depending on the low/high coverage of adsorbed hydrogen (θH), the reaction will proceed through either the Heyrovsky or Tafel reaction, respectively. At low θH, the hydrogen atom which is observed to react with a proton or a molecule of water and an electron to create molecular hydrogen and free up one active site (M). This is the Heyrovsky reaction.

H2O + e− + M − Hads → H2 + OH− + M High values of θH increase the probability that two hydrogen atoms are adsorbed onto neighboring sites, resulting in recombination to form molecular hydrogen and freeing up two metal sites. This is the Tafel reaction [10, 11].



M − Hads → H2 + 2 M

13.1.4 Anion Exchange Membrane Water Electrolysis The structure of anion exchange membrane water electrolyzers (AEMWEs) is essentially the same as that of proton exchange membrane fuel cells (proton exchange membrane water electrolyzers, PEMWEs), with the exception that the solid membrane is an anion exchange rather than a proton exchange membrane. In AEMWEs, the charge carrier is OH, which transports from the cathode to the anode through the AEM, whereas in

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Electrolysis Techniques for Hydrogen Production  315

Electrolysers: AEC, AEM, PEM and SOE for hydrogen (and syngas) production

H2

Airplus O2

H2O as water

+ –

H2 (plus CO)

2–ˉ O2 O

H2O as water

Anode

Cathode

H2O as water

Anode

HH++ 1% KOH(aq)

Anode

Cathode

SOE

+ –

O2

Air

Cathode

H2

OHOH– 30% KOH(aq)

Anode

OH-– OH Diaphragm

PEM

+ –

O2

Cathode

H2

Electrolyte

AEM

+ –

Membrane

AEC O2

30% KOH(aq)

Notes: - In the AEC, AEM and PEM, lye or water flow from the electrolyser cell with the oxygen and/or hydrogen gases. These liquids are mixed and recirculated to the electrolyser. - Air is used to purge the SOE anode to avoid oxygen accumulation which may present a hazard at the high operating temperature. - Bipolar plates made of stainless steel (titanium for PEM) are used to stack adjacent cells in each electrolyser type.

Membrane

sbh4 consulting

©2021 sbh4 GmbH

H2O as steam (plus CO2)

Alkaline Electrolysis Cell AEC

Anion Exchange Membrane/ Alkaline Electrolyte Membrane AEM

Polymer Electrolyte Membrane/ Solid Oxide Electrolysis Cell Proton Exchange Membrane SOE/SOEC PEM/PEMEC

Electrode material

– Cathode: Ni, Co or Fe – Anode: Ni

– Cathode: Ni / Ni alloys – Anode: Fe, Ni, Co oxides

– Cathode: Pt/Pd – Anode: IrO2/RuO2

Electrolyte

Lye: 25– 30% Potassium Hydroxide solution in water 100% electrical power

Anion Exchange ionomer (e.g. AS-4) 100% electrical power

Fluoropolymer ionomer (e.g Nafion, a DuPont brand) 100% electrical power

Up to 0.5 A/cm2 Hydrogen

0.2–1 A/cm2 Hydrogen

Up to 3 A/cm2 Hydrogen

Up to 40 bar ~80 °C

Up to 35 bar H2, 1 bar 02 ~60 °C

Up to 40 bar ~60 °C

Energy source Current density Hydrogen or syngas product Gas outlet pressure Cell temperature

– Cathode: Ni – Anode: La/Sr/MnO (LSM) or La/Sr/Co/FeO (LSCF) Zirconium Oxide with ~8% Yttrium Oxide ~25% heat from steam, ~75% electrical power Up to 0.5 A/cm2 Hydrogen (or syngas if fed with steam and CO2) Close to atmospheric ~750 to 850 °C

Figure 13.1  Schematic representation of the types of electrolyzers [12], including details about proton exchange membrane (PEM) electrolyzers, alkaline electrolyzer cells, anion exchange membrane (AEM) electrolysis, and solid oxide electrolyzer (SOECs) cells.

PEMWEs, the charge carrier is H+, which transports from the anode to the cathode through the PEM [13]. An overview of such systems is shown in Figure 13.1. AEMWE is done in an alkaline medium using non-noble group metal catalysts, such as copper, nickel, and cobalt-based metal catalysts for OER. AEMWE also generates high-purity hydrogen. However, the drawback of AEMWE is that it shows low performance and durability compared to other methods of water electrolysis. To overcome these drawbacks, studies are ongoing to analyze various parameters affecting the performance of the electrolysis. Some of these are catalyst resistance, electrolyte degradation, and atmospheric resistance. The membrane electrode assembly (MEA) for AEMWE was performed using the catalyst-coated substrate (CCS) and catalyst-coated membrane (CCM) methods [14]. A catalyst layer is generated on the gas diffusion layer (GDL) substrate by the CCS process. The membrane is sandwiched between the catalyst-coated GDLs using hot pressing after the catalyst slurry is sprayed on the GDL. Hot pressing is essential for producing high-performance MEAs because it improves the adherence of the catalyst layer to the membrane, resulting in enhanced ionic connection [15]. In the CCM method, a catalyst layer

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316  Clean and Renewable Energy Production

is directly fabricated on a membrane without using hot pressing. By using the CCM method, we can avoid structural damage of the MEA and GDL, simplify the fabrication, and reduce ohmic resistance [16].

13.2 Methodology Most researchers search databases using select keywords to identify the existing literature. There are numerous topics in the field of alternate energy, the most popular among them being AEM electrolysis. There has been a wide range of work on the topic of AEM electrolysis as it has the potential to be an alternative fuel. To start work on this topic, a literature review is considered to be very important. The methodology we adopted in this manuscript narrows down from the production of hydrogen using electrolysis to the specific topic of “hydrogen production using AEM electrolysis.” In the following sections, the procedure employed for the study will be discussed.

13.2.1 Search Strategy This review was performed to collect all primary studies related to the production of hydrogen using AEM electrolysis. For this purpose, we needed a well-developed strategy for literature search to have good precision. This section explains the reviews’ search strategy, which includes the search scope (period of publication, zone, etc.), search method (manual and automatic), and search string used for this study.

13.2.2 Search Scope This literature review focuses on four dimensions of the search scope: publication period, publication databases, zones, and institutes. As this field of research is in the infancy stage, this study considered only the latest 20 years of publications. The starting point was taken as January 2000. Since the study lasted until January 2021, therefore, the articles published thereafter were not included in this study. The search was conducted in the following databases: Scopus, Web of Science, ScienceDirect, Wiley, and Taylor & Francis. From our initial observations, we were able to determine which countries and institutes were involved in this field of study.

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Electrolysis Techniques for Hydrogen Production  317

13.2.3 Search Method The literature survey for this work used the automated search method, which checks the digital database for all published works corresponding to this field, i.e., hydrogen production using AEM electrolysis.

13.2.4 Search String The search was carried out using general keywords that cover a wide area and then combined keywords to be specific to this study, which is “Hydrogen production using AEM electrolysis” using the Boolean operation “AND.” The final set of keywords for this search included “hydrogen production” and “electrolysis” and “anion exchange membrane,” “hydrogen production” and “electrolysis” and “anion exchange membrane” and “storage.”

13.2.5 Study Selection Criteria Initially, a general search was done and moved on to fields like the abstract, keywords, followed by the title for the above-mentioned set of SCIENCE DIRECT

TAYLOR AND FRANCIS

WEB OF SCIENCE

WILEY

Filter Stage 1: Check all fields (title, abstract, keywords and other searchable terms)

Collection 1: 33,136 studies

Filter Stage 2: Check title, abstract and keywords

Collection 2: 437 studies

Filter Stage 3: Check title

Collection 3: 23 studies

Considering 6 studies Considering 6 studies Final Collection: 12 studies

Figure 13.2  Search and selection process.

SCOPUS

Removing 14 repeated results

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318  Clean and Renewable Energy Production

keywords. The survey for this study was conducted from websites such as ScienceDirect, Web of Science, Scopus, Wiley, and Taylor & Francis. Satisfactory results were shown when searching in the title, abstract, and keyword sections, as shown in Figure 13.2.

13.3 Configurations and Performance Evaluation of AEM Electrolyzer Detailed reviews of AEM electrolysis are given in [20, 21, 25]. This paper summarizes the various works done to improve the performance of AEM electrolyzer, as shown in Table 13.1. It was found that the factors affecting the performance of the electrolyzer include the electrode material, MEA, and the electrolyte. Detailed works done are reviewed in this paper. The different materials and components used for research and development work on AEM electrolysis are shown in Table 13.2 [20], which discussed MEA, the operating conditions, and the electrolyte. The factors affecting the performance of AEM electrolyzers are stated below. Javier et al. [17] used platinum black and lead ruthenate pyrochlore as HER and OER catalysts, respectively. An AEM of area 25 cm2 was sandwiched between two porous media electrodes. Different cationic groups functionalized to the benzene position of polysulfone (PSF; four groups) were studied. The experiment evaluated whether or not CO2 intrusion was the cause of loss of system performance and was performed by systematically eliminating routes through which CO2 could enter the system. It was also concluded that the OER catalyst cost was lowered by the presence of a significant amount of lead. Mohammadreza et al. [18] employed multiple monopolar ion exchange membranes, which operated with dissimilar pH electrolytes. It was stated that the pH gradient chemically biases the cell by reducing the whole cell thermodynamic voltage and the energy required for hydrogen production. Unlike Javier et al. [17] and Mohammadreza et al. [18], Immanuel et al. [19] studied parameters such as the OER catalyst loading, amount of ionomer, temperature, electrolyte, and the use of various membranes. The A-201 membrane and a non-noble catalyst were employed. MEA was prepared using the CCS method, and the catalysts for OER and HER were Acta 3030 and Acta 4030, respectively. An ultra-thin AEM was proposed for low-cost AEM electrolysis by Immanuel et al. [22]. An ultra-thin A-901 membrane and a non-noble

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Electrolysis Techniques for Hydrogen Production  319

Table 13.1  Review on the materials and components used in anion exchange membrane (AEM) water electrolysis research and development in recent years. Membrane electrode assembly Anode

Cathode

Reference

GDL

Catalyst

Loading (mg cm−2)

Catalyst

Loading (mg cm−2)

Leng et al. [2012] [30]

Ti foam

IrO2

2.9

Pavel et al. [2014] [31]

Ni foam

Ni/CeO2−La2O3/C

36

Ti foam

Pt black

3.2

Carbon cloth

CuCoO3

7.4

Parrondo et al. [17]

Carbon paper

Pb2Ru2O6.5

2.5

Carbon paper

Pt black

2.5

Xiao et al. [2022] [32]

Ni foam

Ni–Fe

40

Stainless steel fiber felt

Ni–Mo

40

Carbon paper

Ni

0.085

Carbon paper

Ni

0.085

GDL

Ayers et al. [2021] [33] Ahn et al. [2014] [34] Faraj et al. [2012] [35]

Ni foam

Ni/CeO2−La2O3/C

Ni/C

CuCoO3

 

Scott et al. [2011] [36]

Stainless steel mesh

Cu0.7CO2.3O4

3

Stainless steel mesh

Pt

1

Stainless steel mesh

Cu0.7CO2.3O4

3

Stainless steel mesh

Nano-Ni

2

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320  Clean and Renewable Energy Production

(Continued)

Table 13.1  Review on the materials and components used in anion exchange membrane (AEM) water electrolysis research and development in recent years. (Continued) Membrane electrode assembly Anode

Cathode

Reference

GDL

Catalyst

Loading (mg cm−2)

GDL

Catalyst

Loading (mg cm−2)

Zeng et al. [2010] [37]

Ni foam

Ni/CeO2−La2O3/C

40

Carbon cloth

CuCoO3

40

Zeng et al. [2010] [37]

Ni foam

Ni–Fe

Carbon cloth

Ni–Mo

Velan et al. [2013] [38]

NiO

Graphene

NiO

Graphene

Sivakumar et al. [2014] [39]

Ni oxide

Graphene

Ni

Graphene

Pandiaranjan et al. [2015] [40]

Pt-coated Ti

Ce0.2MnFe1.8O4

Pt-coated Ni

Ni

GDL, gas diffusion layer.

3.5

3.5

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Electrolysis Techniques for Hydrogen Production  321

Table 13.2  Review of the literature survey presented in a tabular manner. Study no.

Year

Type

What have they done?

Novelty

Reference

1

2014

Research article

Performance of polysulfonate. The PSF produced by Frediel crafts reaction. Platinum black and lead ruthenate were used as catalysts. More lead was used for cost saving.

PSF membrane, usage of more lead

[17]

2

2017

Research article

Using multiple membranes with different pH for electrolysis

Basic anolyte, acidic catholyte, multiple membranes

[18]

3

2017

Research article

Anion exchange membrane was used along with non-noble catalysts to produce hydrogen. The best electrolysis performance recorded was 500 mA cm−2 for 1.95 V at 60°C with 1% K2CO3 electrolyte.

Non-noble catalysts were used (Acta 3030 and Acta 4030). Potassium chromate (1%) was used as the electrolyte. Commercial ionomer I2 was used.

[19]

4

2017

Review

Review of proton exchange membrane and anion exchange membrane.

–

[20]

5

2018

Review

Review of proton exchange membrane and anion exhange membrane.

–

[21]

(Continued)

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322  Clean and Renewable Energy Production

Table 13.2  Review of the literature survey presented in a tabular manner. (Continued) Study no.

Year

Type

What have they done?

Novelty

Reference

6

2018

Research article

Used an ultra thin anion exchange membrane for hydrogen production. Studied its performance and stability

A-901 membrane has so far not been considered as a candidate for AEM.

[22]

7

2019

Research article

Studied the influence of cell fabrication and operation parameters with the standard catalysts (iridium oxide and platinum at the anode and cathode). Four factors, i.e., fabrication pressing conditions for (i) electrode, (ii) cell assembly, (iii) electrolyte pre-feed methods and operating temperatures

–

[23]

8

2020

Research article

Combination of Ni–Fe–Ox for OER and Ni–Fe–Co HER electrodes with a PBI anion exchange membrane. Fabrication and characterization of the electrochemical reaction and performance of AME electrolysis resistance at different temperature using 1 M KOH at 60°C efficiency

Combination of Ni–Fe–Ox for OER and Ni–Fe–Co HER electrodes with a PBI anion exchange

[24]

(Continued)

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Electrolysis Techniques for Hydrogen Production  323

Table 13.2  Review of the literature survey presented in a tabular manner. (Continued) Study no.

Year

Type

What have they done?

Novelty

Reference

9

2021

Review

Review of different alkaline polymeric membranes

–

[25]

10

2021

Research article

Developed a novel nickel-based backing layer on PTL (NiMPLPTL) for AEMWE, which radically improved the cell performance under operation with pure water.

This study highlighted the effect of MPLs for AEMWE operated with pure water, which has not been explored to date. Multifunctional PTLs were developed by introducing highly porous NiMPL using the APS technique on the top of a PTL. This NiMPLPTL was applied to a pure water-operated AEMWE for the first time. The AEMWE cell with NiMPL-PTL showed a current density of 0.5 A cm−2 at a very low operating voltage of 1.90 V, which was 290 mV lower than that of AEMWE cell with the uncoated bare PTL.

[26]

(Continued)

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324  Clean and Renewable Energy Production

Table 13.2  Review of the literature survey presented in a tabular manner. (Continued)

Study no.

Year

Type

What have they done?

Novelty

Reference

11

2021

Research article

To optimize the commercial Fumatech anionic ionomer content in AEMWE anodes using nickel nanoparticles (NPs) synthesized by chemical reduction. Ni/Fe-based NPs with and without ceria (CeO2). In this work, the optimal amount of commercial Fumatech anionic ionomer content was determined to be 15 wt.%. Ni90Fe10 was the bestperforming Ni-based electrode, showing 1.72 V at 0.8 A cm2 in 1 M KOH after IR correction and a degradation rate of 3.3 mV/h.

Usage of ceria. PSD of the catalyst inks and the in situ testing of the monometallic Ni NPs. IR correction

[27]

(Continued)

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Electrolysis Techniques for Hydrogen Production  325

Table 13.2  Review of the literature survey presented in a tabular manner. (Continued) Study no.

Year

Type

What have they done?

Novelty

Reference

12

2021

Research article

To examine the contributions of ohmic and charge transfer resistance. To find the rate determining steps involved using EIS. To evaluate factors such as voltage, temperature, flow rate, and concentration of the electrolyte. Optimum working conditions: 1 M KOH liquid electrolyte, 60°C, 40 mL/min. Under these conditions, the following was achieved: best performance of 500 mA/cm2, with cell potential of 1.85V and cell resistance as low as 20 mΩ cm−2.

Liquid electrolyte flow rate affected the performance of AEM electrolysis.

[28]

AEM, anion exchange membrane; OER, oxygen evolution reaction; HER, hydrogen evolution reaction; PBI, polybenzimidazole; PTL, porous transport layer; AEMWE, anion exchange membrane water electrolyzer; MPLs, microporous layers; APS, air plasma spray; PSD, particle size distribution; EIS, electrochemical impedance spectroscopy.

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326  Clean and Renewable Energy Production

catalyst were used in the MEA. Immanuel et al. [22] used the same OER and HER catalysts used by Mohammadreza et al. [18]. The active area of AEM was 5 cm2. Preheated 1% K2CO3 was used as electrolyte, which was circulated through the anode side only with a peristaltic pump to allow a higher discharge pressure of hydrogen at the cathode side. Ahyoun et al. [23] studied the cell construction and operation factors (similarly to Immanuel et al. [19]). Ahyoun et al. [23] studied the influence of cell fabrication and operation parameters with the standard catalysts iridium oxide and platinum on carbon as the OER and HER catalysts, respectively. Four factors were considered for fabrication pressing conditions for the electrode, cell assembly, electrolyte preferred conditions, and operating temperature. The CCS method, similar to Immanuel et al. [19], was used. A 6.25-cm2 AEM (FAA-3-PK-27) was sandwiched between two sintered electrodes. The catalyst ink suspension containing the catalyst powder, polytetrafluoroethylene (PTFE) (60 wt.% PTFE dispersion in H2O; Aldrich, St. Louis, MO, USA), distilled water, and isopropyl alcohol were sprayed onto the GDL and Ti paper to form the catalyst layer. Before spraying, the catalyst suspension was homogenized in an ultrasonic bath for 1  h. The contents of the PTFE binder were 20 and 9.1  wt.% for the anode and cathode catalyst layers, respectively. Then, the electrodes were sintered at 350°C in Ar gas. Immanuel et al. [24] coated Ni–Fe–Ox and Ni–Fe–Co on the Ni foam and used it as the anode and cathode. The homogeneous catalyst ink solution was prepared by adding deionized water, ionomer (Sustainion® XB-7; Dioxide Material, Boca Raton, FL, USA), and catalyst powder (the particle diameters of Ni–Fe–Ox and Ni–Fe–Co were 0.5–1.7 mm), which was sonicated with ice for 15 min. Then, isopropyl alcohol was added and sonicated for 10 min with ice. The slurry was then ultrasonicated for 10 min using the ultrasonic probe with ice. It was ensured that there were no agglomerations found on the homogeneous ink. The uniformity of the ink’s composition is very important to ensure concordant results. The well-dispersed anode and cathode catalyst ink was brushed onto the surface of the Ni foam (80–110  ppi). MEA was prepared using the CCS method, and the OER and HER catalysts were coated on the Ni foam by spray coating. AEM was soaked in 1 M KOH before the reaction to convert its functional group into OH– groups and to increase the ionic conductivity of the AEM. In order to improve performance, Fatemeh et al. [26] developed a liquid gas diffusion layer by introducing a microporous layer on top of a porous transport layer. Porous nickel-based microporous layers (MPLs) were produced by spraying globular gas-atomized Ni-based powder by air plasma spraying on top of 4 cm2 metallic PTLs. The feedstocks were Ni–carbon

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Electrolysis Techniques for Hydrogen Production  327

powders with an average grain size of 10–15 mm. The presence of Ni and C in the feedstock powder was confirmed by X-ray diffraction (XRD) analysis. The schematic illustration of the multifunctional NiMPL-PTL fabrication using the direct current plasma spray method is provided. A Triplex-Pro210 plasma gun was used for air plasma spray (APS), where Ar was the primary plasma-forming gas and H2 and/or He were used as secondary gases. The Ni-based alloy was deposited on the top of the PTL using the APS process. The NiMPL coated on top of the PTL was designated as NiMPL-PTL and the bare substrate as PTL. The bare PTL and NiMPLPTL were implemented in the AEMWE cell assembly. NiMPL-PTLs were implemented as the multifunctional PTLs in the AEMWE cell in order to decrease the interfacial contact resistance and mitigate the mass transfer issues and subsequently improve the overall cell performance. Once the PTL was coated with Ni-based layers, the resulting structure was characterized by XRD to determine the induced changes in the crystallographic structure of the material. Emily et al. [27] optimized the commercial Fumatech fumion ionomer content in AEMWE anodes using nickel nanoparticles (NPs) synthesized by chemical reduction. All electrolysis experiments were carried out using the catalyst-coated substrate method. When optimizing the ionomer content using the monometallic Ni NPs, the anode layer ink was hand-sprayed onto a carbon fiber paper to a final loading of 5 mg cm−2 using an airbrush. Since using a carbon paper on the anode side significantly increased the initial cell resistance, a cell activation procedure was performed to hydrate the carbon paper before polarization curve measurements. For the electrolysis experiments using the optimized ionomer in the catalytic layers, Ni90Fe10 and Ni80Fe20 with and without CeO2 catalysts were sprayed onto a 1-mm-thick gold-coated titanium porous transport layer instead of the carbon paper. Immanuel et al. [28] investigated the contribution of ohmic and charge transfer resistance and the rate determining steps involved in AEM electrolyzers, which were determined using electrochemical impedance spectroscopy (EIS). The electrolysis reaction was carried out using a specially designed 5-cm2 AEM electrolyzer. In the MEA architecture, a polybenzimidazole (PBI) membrane was used as the AEM. The MEA was also prepared using the CCS method. The OER and HER catalysts were coated on the Ni foam GDL by spray coating. The AEM was soaked overnight in 1 M KOH, prior to electrolysis, to convert the functional group from Br into OH–. Ni–Fe–Ox and Ni–Fe–Co were used for the anode and cathode, respectively, coated on the Ni foam diffusion layer for the electrode (similarly to that in Immanuel et al. [24]). The catalyst loading was 5 mg cm−2.

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328  Clean and Renewable Energy Production

The MEA was housed between Ti and graphite flow fields. A pair of Teflon gaskets was utilized as a seal to prevent gas and liquid leakage. Stainless steel bars were used as end plates. The anode and cathode electrical supply probes were connected outside the end plate. A 500-mL glass tank with circulating water was used as a reservoir. A double-headed peristaltic pump circulated the electrolyte from the reservoir. Preheated 1 M KOH solution was continuously circulated through the anode side at a flow rate of 60 mL min−1. The electricity for the electrolysis experiments was supplied through a Potentiostat VSP Biologic instrument. The temperature was maintained at 60°C throughout with a water heating circulating system. The electrolyzer was operated under atmospheric pressure.

13.4 Scope for Improvements This section points out the improvements required to further enhance the performance of AEM electrolyzers. In the experimental work of Javier et al. [17] for hydrogen production by ultrapure water electrolysis using AEM, it was suspected that the decrease in performance was due to the presence of carbon dioxide. Further investigation was carried out by restricting CO2 intrusion, which showed that it was responsible for short-term loss in system performance and could be easily rectified. The investigation also revealed that the PSF backbone instability in the AEM would affect the performance in the long run. Mohammadreza et al. [18] found leakage across the monopolar membrane, indicating the use of higher selective membranes. Also, the Donnan potential became negative as the salt concentration decreased. Immanuel et al. [19] stated that an increased catalyst loading and low ionomer content cause cracks to develop on the catalyst layer. Another reason for the deformation was given by the interaction between the OH radical and H2O due to the incomplete reduction of oxygen at the cathode. In the review work of Immanuel et al. [20], it was stated that the lower conductibility of hydroxyl ions, lower catalyst performance of transition metals compared to noble metals, blocking of the active sites at high pressure by the hydrogen and oxygen trapped inside the membrane electrode assembly, slow OER when the number of hydroxy ions in the electrolyte was reduced, and the degradation of ionomer led to the lower performance of AEM electrolysis. Jun et al. [21] stated that AEM electrolysis requires a steady power input and a longer start-up duration. Water electrolysis at higher temperatures can

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Electrolysis Techniques for Hydrogen Production  329

lead to material degradation and hinder stability of the operation. Hydrogen mixed with water vapor (SOEC) requires additional cost for treatment. In another review work of Immanuel et al. [22], EIS analysis revealed that the contribution of OER to the overall cell resistance was high due to the higher catalyst thickness of the anode catalyst layer. Reduction of the anode catalyst layer is necessary to improve the AEM electrolyzer performance. Ahyoum et al. [23], in their study on electrode fabrication and the effect of various operating variables on the performance of AEM water electrolysis, faced the difficulty of reducing the gap between the developed material properties and device performance. Thus, performance was improved by controlling the electrode fabrication and operating factors when using standard materials. In another work of Immanuel et  al. [24], aging was said to affect the performance of the AEM electrolyzer. Stability and performance are two important aspects in electrolysis. In the experimental work of Emily et al. [25], the NiFe particles were too small in size (4–6 nm) to be viewed in TEM (flake-like phase detected). Ceria did not blend well, resulting in non-uniform samples; therefore, analysis of the particle was difficult. Another study carried out by Immanuel et al. [26] observed that, at higher flow rates, the removal of OH ions was very rapid. The available reaction time for oxidation and reduction was reduced, leading to the lower availability of OH ions for the catalysts, resulting in a significant increase in the overpotentials (especially for the OER). At a higher temperature, activation of the catalyst layer expedited the OER reaction, which reduced both the ohmic and charge transfer resistances. Furthermore, an increase in electrolyte concentration increased the availability of OH ions and the mobility of ions, directly reducing the charge transfer resistance. On the other hand, at a lower flow rate, the catalyst active sites may be blocked by oxygen bubbles. Hydrogen is an option that should be considered for use as a potential new energy carrier as a result of the pressing need for environment-friendly alternative energy sources to mitigate the effects of climate change. Hydrogen is currently seen as a potential alternative to the existing energy industries that are based on fossil fuels by both governments and energy firms. One can assume that societies can entirely limit the use of fossil fuels and instead rely solely on hydrogen, with encouraging catchphrases such as “hydrogen economy” and “hydrogen civilization.” The combustion of hydrogen with oxygen to produce energy results in the formation of water. This, in turn, creates a unique opportunity for nations that are short on water to not only import energy but also find a solution to water shortages by utilizing hydrogen in their energy production [29].

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330  Clean and Renewable Energy Production

13.5 Conclusion The need for an alternative source of energy has become imminent in the world we live in. Research works in the field of AEM electrolysis have shown promise that the time for it is as soon as possible. The production of hydrogen using this method can efficiently attract chloro-alkali industries to adapt this process for their production. Petrochemical industries, which need hydrogen for production, can also easily rely on the process if it is completed efficiently. If a proper combustion system is devised for hydrogen as a fuel, it can even replace the existing petroleum products that are used as fuel. Since the emission in this process is zero, it can also contribute in the zero emission target, which will be initiated by the UN by the year 2050. Promising research works in this field will surely help in increasing the efficiency of this process and will one day bring the AEM electrolyzer as an alternative fuel generator.

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Electrolysis Techniques for Hydrogen Production  331

8. Cheng, Y. and Jiang, S.P., Advances in electrocatalysts for oxygen evolution reaction of water electrolysis-from metal oxides to carbon nanotubes. Prog. Nat. Sci.: Mater. Int., 25, 6, 545–553, 2015. 9. Anantharaj, S., Ede, S.R., Karthick, K., Selvasundarasekar, S.S., Sangeetha, K., Karthik, P., Kundu, S., Precision and correctness in the evaluation of electrocatalytic water splitting: Revisiting activity parameters with a critical assessment. Energy Environ. Sci., 11, 744–771, 2018. 10. Ferriday, T.B., Middleton, P.H., Kolhe, M.L., Review of the hydrogen evolution reactionmdash;a basic approach. Energies, 14, 24, 8535, 2021. 11. Gennero de Chialvo, M.R. and Chialvo, A.C., Hydrogen evolution reaction: Analysis of the volmer-heyrovsky-tafel mechanism with a generalized adsorption model. J. Electroanal. Chem., 372, 1, 209–223, 1994. 12. Borm, O. and Harrison, S.B., Reliable off-grid power supply utilizing green hydrogen. Clean Energy, 5, 3, 441–446, 08 2021. 13. Maqsood, Q., Ameen, E., Mahnoor, M., Sumrin, A., Akhtar, M.W., Bhattacharya, R., Bose, D., Applications of microbial fuel cell technology and strategies to boost bioreactor performance. Nat. Environ. Pollut. Technol., 21, 3, 1191–1199, 2022 Sep 1. 14. Thanasilp, S. and Hunsom, M., Effect of MEA fabrication techniques on the cell performance of Pt–Pd/C electrocatalyst for oxygen reduction in PEM fuel cell. Fuel, 89, 12, 3847–3852, 2010. 15. Vielstich, Wolf, Hubert A. Gasteiger, and Harumi Yokokawa, eds. Handbook of fuel cells: Advances in electrocatalysis, materials, diagnostics and durability, 5, 6. John Wiley & Sons, UK, 2009. 16. Frey, T. and Linardi, M., Effects of membrane electrode assembly preparation on the polymer electrolyte membrane fuel cell performance. Electrochim. Acta, 50, 99–105, 2004. 17. Parrondo, J., Arges, C.G., Niedzwiecki, M., Anderson, E.B., Ayers, K.E., Ramani, V., Degradation of anion exchange membranes used for hydrogen production by ultrapure water electrolysis. RSC Adv., 4, 9875–9879, 2014. 18. Nazemi, M., Padgett, J., Hatzell, M.C., Acid/base multi-ion exchange membrane-­based electrolysis system for water splitting. Energy Technol., 5, 8, 1191–1194, 2017. 19. Vincent, I., Kruger, A., Bessarabov, D., Development of efficient membrane electrode assembly for low cost hydrogen production by anion exchange membrane electrolysis. Int. J. Hydrogen Energy, 42, 16, 10752–10761, 2017. 20. Vincent, I. and Bessarabov, D., Low cost hydrogen production by anion exchange membrane electrolysis: A review. Renew. Sustain. Energy Rev., 81, 1690–1704, 2018. 21. Chi, J. and Yu, H., Water electrolysis based on renewable energy for hydrogen production. Chin. J. Catal., 39, 3, 390–394, 2018. 22. Vincent, I., Hydrogen production by water electrolysis with an ultrathin anion-exchange membrane (AEM). Int. J. Electrochem. Sci., 13, 11347–11358, 12, 2018.

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23. Lim, A., Kim, H.J., Henkensmeier, D., Yoo, S.J., Kim, J.Y., Lee, S.Y., Sung, Y.-E., Jang, J.H., Park, H.S., A study on electrode fabrication and operation variables affecting the performance of anion exchange membrane water electrolysis. J. Ind. Eng. Chem., 76, 410–418, 2019. 24. Vincent, I., Lee, E.-C., Kim, H.-M., Highly cost-effective platinum-free anion exchange membrane electrolysis for large scale energy storage and hydrogen production. RSC Adv., 10, 37429–37438, 2020. 25. Zakaria, Z. and Kamarudin, S.K., A review of alkaline solid polymer membrane in the application of AEM electrolyzer: Materials and characterization. Int. J. Energy Res., 45, 13, 18337–18354, 2021. 26. Razmjooei, F., Morawietz, T., Taghizadeh, E., Hadjixenophontos, E., Mues, L., Gerle, M., Wood, B.D., Harms, C., Gago, A.S., Ansar, S.A., Friedrich, K.A., Increasing the performance of an anion-exchange membrane electrolyzer operating in pure water with a nickel-based microporous layer. Joule, 5, 7, 1776–1799, 2021. 27. Cossar, E., Barnett, A.O., Seland, F., Safari, R., Botton, G.A., Baranova, E.A., Ionomer content optimization in nickel-iron-based anodes with and without ceria for anion exchange membrane water electrolysis. J. Power Sources, 514, 230563, 2021. 28. Vincent, I., Lee, E.-C., Kim, H.-M., Comprehensive impedance investigation of low-cost anion exchange membrane electrolysis for large-scale hydrogen production. Sci. Rep., 11, 1, 1–12, 2021. 29. Bhattacharya, R., Kumari, A., Bose, D., Impact of COVID-19 on SDG 6 and integrated approaches for clean water access and sanitation. Sustainability Clim. Change, 15, 5, 298–306, 2022. 30. Leng, Y., Chen, G., Mendoza, A.J., Tighe, T.B., Hickner, M.A., Wang, C.Y., Solid-state water electrolysis with an alkaline membrane. J. Am. Chem. Soc., 134, 22, 9054–9057, 2012. 31. Pavel, C.C., Cecconi, F., Emiliani, C., Santiccioli, S., Scaffidi, A., Catanorchi, S., Comotti, M., Highly efficient platinum group metal free based membrane-electrode assembly for anion exchange membrane water electrolysis. Angew. Chem., Int. Ed., 53, 5, 1378–1381, 2014. 32. Lei, C., Yang, K., Wang, G., Wang, G., Lu, J., Xiao, L., Zhuang, L., Impact of catalyst reconstruction on the durability of anion exchange membrane water electrolysis. ACS Sustain. Chem. Eng., 10, 50, 16725–16733, 2022. 33. Dongguo, L., Motz, A.R., Bae, C., Fujimoto, C., Yang, G., Zhang, F.Y., Ayers, K.E., Kim, Y.S., Durability of anion exchange membrane water electrolyzers. Energy Environ. Sci., 14, 6, 3393–3419, 2021. 34. Park, J.E., Kang, S.Y., Oh, S.H., Kim, J.K., Lim, M.S., Ahn, C.Y., Sung, Y.E., High-performance anion exchange membrane water electrolysis. Electrochimica Acta, 295, 99–106, 2019.

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35. Faraj, M., Boccia, M., Miller, H., Martini, F., Borsacchi, S., Geppi, M., Pucci,  A., New LDPE based anion-exchange membranes for alkaline solid polymeric electrolyte water electrolysis. Int. J. Hydrog. Energy, 37, 20, 14992– 15002, 2012. 36. Wang, X., Li, M., Golding, B.T., Sadeghi, M., Cao, Y., Yu, E.H., Scott, K., A polytetrafluoroethylenequaternary 1, 4-diazabicyclo-[2.2.2]-octane polysulfone composite membrane for alkaline anion exchange membrane fuel cells. Int. J. Hydrog. Energ., 36, 16, 10022–10026, 2011. 37. Zeng, Q.H., Liu, Q.L., Broadwell, I., Zhu, A.M., Xiong, Y., Tu, X.P., Anion exchange membranes based on quaternized polystyrene-block-poly ­(ethylene-ran-butylene)-block-polystyrene for direct methanol alkaline fuel cells. J. Membr. Sci., 349, 1–2, 237–243, 2010. 38. Seetharaman, S., Balaji, R., Ramya, K., Dhathathreyan, K.S., Velan, M., Graphene oxide modified non-noble metal electrode for alkaline anion exchange membrane water electrolyzers. Int. J. Hydrog. Energ., 38, 35, 14934– 14942, 2013. 39. Joe, J.D., Kumar, D.S., Sivakumar, P., Production of hydrogen by anion exchange membrane using AWE. Int. J. Sci. Technol. Res., 3, 38–42, 2014. 40. Pandiarajan, T., Berchmans, L.J., Ravichandran, S., Fabrication of ­spinel ­ferrite based alkaline anion exchange membrane water electrolysers for hydrogen production. RSC Adv., 5, 43, 34100–34108, 2015.

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Prospects of Sustainability for Carbon Footprint Reduction Riya Bhattacharya1, Debajyoti Bose1*, Gaurav Mitra2 and Abhijeeta Sarkar3 School of Technology, Woxsen University, Hyderabad, Telangana, India Department of Chemistry, University of Massachusetts, Amherst, United States 3 Faculty of Applied Sciences & Biotechnology, School of Biotechnology, Shoolini University of Biotechnology & Management Sciences, Solan, Himachal Pradesh, India 1

2

Abstract

Industrial expansion and overexploitation of fossil fuels induced the emission of greenhouse gases (GHGs), which resulted in the rise of the global temperature and created environmental concerns. Therefore, it is an immediate necessity to reach the goal of having zero carbon emissions or to progress in that direction. Many international cooperations have expanded the synergies and co-benefits between mitigation and adaptation programs. Communities can create a more sustainable future through different routes. There is a growing body of research on the options for lowering carbon footprints in areas including food, housing, and transportation; however, a comprehensive framework is still lacking. In this work, a systematic and comprehensive framework to uncover improvement alternatives that assist climate change alleviation and to organize them according to their principal mode of impact on GHG emissions is provided. The framework is aimed at people and focuses on idealistic, yet socially and economically viable measures for reducing carbon footprints. By meticulously identifying potential areas for development, one can make strides toward a more complete comprehension of the many behavioral methods aimed at options to make that are in action at various points in the supply chain for various processes. As such, it serves as a platform for discussing important issues concerning the ability of local and national governments and private sectors to aid the efforts of mitigating climate change. Keywords:  Carbon emissions, fossil fuels, energy, footprint, framework *Corresponding author: [email protected] Surajit Mondal, Adesh Kumar, Rupendra Kumar Pachauri, Amit Kumar Mondal, Vishal Kumar Singh and Amit Kumar Sharma (eds.) Clean and Renewable Energy Production, (335–354) © 2024 Scrivener Publishing LLC

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14

14.1 Introduction The rapid rise in temperature and a range of environmental degradation issues have been linked to the widespread release of greenhouse gases (GHGs) because of the expanding global industrial sector and the excessive use of non-renewable energy sources [1]. The average level of carbon dioxide (CO2) in the atmosphere rose sharply from 285  ppm before the Industrial Revolution in the 1850s to 419  ppm in 2022 [2]. The United Kingdom Meteorological Office forecasts that the average worldwide surface temperature will increase by between 0.97°C and 1.21°C between 1850 and 2022, with a core estimate of 1.09°C, and that 2022 would be one of the warmest years on record [3]. As a result, the primary cause of the predicted 50% increase in GHG emissions by 2050 is CO2 emissions from coal, oil, and gas [4]. Unless effective policies or techniques are implemented to limit or manage CO2 emissions, the average global atmospheric CO2 concentration, ocean temperatures, and global surface are likely to increase. Substantial damage to our environment has already been caused by the increasing global temperature exacerbated by GHGs. This includes certain species extinction, ecological destructions, water shortages, floods, wildfires, acidification of the oceans, the melting of South and North Pole glaciers, and the rise in the level of the sea [5, 6]. Scientists are concerned that climate change poses a significant risk to the Earth’s ecosystems and, by extension, to the survival of mankind in the long run. Modifications in the consumption levels are considered an essential pillar to solve the world’s climate problems and alleviate challenges, which have been emphasized in recent policy discussions to achieve the requisite significant reductions in GHG emissions. According to the United Nations’ Intergovernmental Panel on Climate Change (IPCC) mitigation report, stabilizing or reducing consumption, migrating toward a collaborative economy, and implementing other lifestyle patterns have a high mitigation capacity since they have a large impact on the use of energy and associated emissions [7]. The Paris Agreement, which outlines the goals for global action to combat climate change after 2020 in response to the rising global GHG emissions and temperatures, was accepted by all 197 parties to the United Nations Framework Convention on Climate Change (UNFCCC) at the Paris Climate Change Conference on December 12, 2015 [8]. A total of 124 countries have committed to becoming carbon-free by 2050 or 2060 [9]. The European Union’s “Transport White Paper” and “Blueprint for changing to a competitive low-carbon economy in 2050” both recognize that modifying the behavior of the individual may be

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necessary to meet the emission objectives and that doing so may reduce the overall costs [10]. Therefore, shifting consumption and lifestyle habits is crucial to meeting the global mitigation problem. The goal of carbon neutrality is to create a situation in which no net emissions of carbon dioxide or other GHGs are emitted over a specific time period by any entity, be it a nation, business, item, industry, or individual. Furthermore, it was highlighted in a special report by the IPCC that global warming of 1.5°C stressed the necessity of reducing and phasing out fossil fuels and increasing renewable energy, improving energy efficiency, and stressing the importance of implementing these measures in urban centers to achieve carbon neutrality [7]. Additionally, carbon reduction or deduction in terrestrial and aquatic ecosystems must be encouraged to attain net-zero carbon emissions and sustainability. It is difficult to attain net-zero emissions of carbon, even though many regions, nations, and cities have established plans to increase carbon sequestration to attain carbon neutrality. This work gives a comprehensive examination of the consequences of the COP-26 for attaining net-zero carbon emissions, focusing on the ramifications of accomplishing this goal by 2050 or 2060 for most member nations. The examination dives into worldwide activities, with a focus on national policies and programs designed to attain zero carbon output. Additionally, the assessment maps both indirect and direct carbon dioxide emissions and suggests two key techniques for reaching decarbonization: lowering emissions and removing carbon from the atmosphere. Furthermore, the assessment gives future carbon-free plans in food waste, agriculture, transportation, industry, and other areas and analyzes the different carbon-neutral system mechanisms for the techniques or actions to fulfill these objectives. Finally, the study helps governments and people in diverse regions and nations comprehend the favorable ecological, social, and economic repercussions of carbon reduction by providing updated and relevant information, sustainable strategies, and technology for achieving cleaner production.

14.2 Context and Outcomes of the United Nations Climate Change Framework The COP-26 took place in Glasgow, Scotland, from October 31 to November 12, 2021, during a pivotal period for green recovery on a worldwide scale [11]. Countries that are responsible for 32% and 55% of global GHG emissions have submitted the increased reduction in emission goals (organized as nationally determined contributions) that they are

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Sustainability for Carbon Footprint Reduction  337

required to present to the COP-26 by the year 2030. Ergo, the COP-26 is now universally recognized as a pressing global concern. Here, the world’s policymakers, government leaders, companies, and individuals provided significant commitments from their respective governments to reduce carbon emissions. A review of the previous United Nations Conference of the Parties on Climate Change is necessary for the meanwhile. In 2015, something historic happened for the very first time. Global warming should be limited to well below 2°C, with a goal value of 1.5°C, as agreed upon by all countries at COP-21 [12]. There was also an agreement that money would be provided by all participating nations to make these things happen. This was the Paris Agreement conceived for a sustainable future. COP-26 had significant achievements in four areas: coal, vehicles, money, and forests. For the first two targets, there is a need for an international agreement to eliminate coal, which is one the major polluting fossil fuels. The second is to accelerate the creation of electric vehicles and replace those that run on fossil fuels [13]. Solutions to climate change, which are an integral component of the global change biology, must also be put in place and made available. Figure 14.1 depicts the four primary outputs of the COP-26. Rising global temperatures will continue to cause catastrophic flooding, bushfires, weather extremes, and the extinction of many species unless specific actions are taken. Progress has been made in the fight against global warming, with experts

Net zero carbon emissions targets

Community cooperations

Outcome of COP 26

Protecting habitats and communities

Accelerating finance

Figure 14.1  Illustration of the four primary outcome targets that were discussed at the 26th United Nations Climate Change Conference of the Parties.

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managing to shift the temperature curve by 2°C [12]. Scientific statistics, however, reveal that a lot of work needs to be done to maintain the temperature rise below 1.5°C. Goals must be promptly turned into action, with the developed world and countries with high carbon emissions taking the lead. Countries everywhere (especially the industrialized ones) need to quickly stop using fossil fuels to generate power and start helping others transition to clean energy [14]. Concurrently, switching to zero-emission automobiles, vans, and trucks is a crucial step in improving air quality and lowering carbon emissions [15].

14.3 Monitoring Direct and Indirect Carbon Emissions To reach carbon neutrality, it is essential to record emissions using statistical methods for identifying their amount and creating plans to reduce them. For instance, CO2 emissions from several Chinese industries were mapped through research [16]. These outputs can be quantified into emissions from industrialized nations such as the United States, or growing economies like India, both having prospects of being powerhouses. This is shown in Figure 14.2. Most CO2 exporters work in one of three industries: (1) thermal and electric power generation and distribution; (2) metal mining and processing; Carbon dioxide emissions per capita 25 20 15 10 5 0

2000 2002 2004 2006 2008 2010 2012 2014 2016 2018 2001 2003 2005 2007 2009 2011 2013 2015 2017 2019 USA

China

Japan

India

Figure 14.2  Carbon dioxide emissions released due to the combustion of fossil fuels for energy. Coal, oil, and natural gas are all significant contributors to this category of emissions, with high levels reached by the United States and growing economies such as India, China, and Japan aspiring for development, which follows a similar pattern.

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Sustainability for Carbon Footprint Reduction  339

or (3) petroleum refinery and coking. These three industries accounted for about 80% of all CO2 emissions [17]. China’s rapid urbanization has led to massive growth in the country’s construction sector, which has benefited greatly from the embodied carbon created by this growth. This suggested reducing carbon emissions by decreasing the demand for energy-intensive items in downstream industries and contributing to sustainable development in manufacturing processes. Similarly, a carbon footprint assessment in Romania found a density of 2,949 ha and a predicted crown area of 7,616 ha. The forest also contained 13,066 t of carbon and 27,800 m3 of green biomass. In South America, deforestation in the Amazon region of Venezuela prompted another investigation on the topic. The research showed that 24,480 ha of the Imataca Forest Reserve had been negatively affected by forest degradation. Selective logging liberated about 6,121.9 Mg C ha−1, with a harvest intensity of 2.81.2 trees hRa−1 [18]. Research findings like this are important for putting into action initiatives aimed at lowering emissions caused by deforestation and forest degradation. Many scientists have made city carbon maps to measure emissions. One work produced a carbon footprint map for Melbourne, which revealed an average annual emission rate of 25.1 t CO2-eq/capita [19]. Local and exported goods from industries account for 4.3 and 5.3 tonnes of carbon dioxide equivalent per resident, respectively. In addition, import-related emissions amounted to 10.8 t CO2 equivalents per person, while those from electricity generation and demand accounted for 10 t CO2 equivalents per person. Households, the government, and enterprises in Melbourne are the three largest emitters in the city, responsible for 64%, 15%, and 21% of all greenhouse gases, respectively. Here, policymakers should prioritize the social part of carbon emission reduction, educating citizens through awareness campaigns on how to cut back at home. There were more direct emissions from fossil fuels on the road connections than indirect emissions, suggesting that switching from gas to electric vehicles will significantly cut down carbon emissions. More investigation is needed into the indirect emissions caused using electricity to power electric vehicles. One study conducted in eastern Japan found that, because of Kinshi-Cho district’s dense population and lack of planning, its carbon emissions were higher than those of the neighboring SkyTree business district, which boasts well-designed, energy-efficient structures [20]. The writers of this piece recommend a change in commuter habits that would cut down carbon emissions at peak times in the morning and evening. Carbon emissions from heating, ventilation, and air conditioning (HVAC) systems in buildings can be reduced using renewable energy sources and by increasing their efficiency. Both direct and indirect carbon emissions are summarized in Figure 14.3.

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Monitoring direct and indirect carbon emissions

Mobile emissions

Electricity generation

Processed products

Industries

Heat production

Waste management

Direct emissions

Indirect emissions

Indirect value-chain emissions

Figure 14.3  Illustration of the direct emissions, indirect emissions, and indirect emissions via value chains as the three primary categories that are used to classify carbon emissions.

One study in China evaluated the direct and indirect carbon emissions caused by the tourism sector. In 2002, 2005, 2007, and 2010, yields of 2.489%, 2.425%, 2.439%, and 2.447% of China’s total carbon emissions, respectively, were the consequences of the tourism business [21]. This was based on the overall carbon pollutants released by the tourism industry each year. Indirect carbon emissions from tourism were three to four times as high as those from transportation. Due to the complexities involved, more work must be done to map the tourism industry’s indirect and direct emissions of carbon. Policymakers in such cases can use the results of this mapping research to target their efforts, resulting in more effective measures to combat climate change than general methods.

14.4 Sustainable Alternatives to Reduce Carbon Footprints Here, two main methods are discussed for reducing carbon footprints. The first strategy involves using existing programs, policies, and technologies to cut down on carbon emissions. To reach a net-zero carbon system, more

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Sustainability for Carbon Footprint Reduction  341

steps are needed beyond just reducing emissions. As a second strategy, many new energy-efficient technologies and natural solutions can be used to remove carbon from the atmosphere (also known as negative emissions).

14.4.1 Policies for Reducing Carbon Footprints Implementing low-carbon strategies helps cut down on carbon emissions. One work analyzed China’s carbon trading policy from 2008 to 2018 using simulated control methods. The results showed that, after some provinces adopted a carbon trading program, carbon emissions dropped significantly. In addition, the study proved that a carbon trading policy’s continuing implementation would eventually lead to carbon neutrality [22]. Algorithms and airline data were used in another study that looked at the potential of carbon tax incentive programs to cut down carbon emissions in the aircraft industry [23]. The results showed that incentive programs could encourage airline companies to improve fuel efficiency and, hence, reduce carbon emissions under favorable conditions, such as a small fuel price gap. Emissions of carbon dioxide can be decreased with the help of carbon trading and taxes, and this can eventually result in a state of carbon neutrality. Another study used Global Positioning System (GPS) tracing to look at how automobile emission policies affect the amount of carbon dioxide released into the atmosphere in European cities including Rome, London, and Florence [24]. Based on the findings, rather than imposing a blanket of carbon emission laws, interventions like electrification or modifying travel habits should focus on the large polluters. While low-carbon policies are essential for accomplishing this goal, officials must first assess the economic conditions in their own areas to avoid hindering economic growth through unintended consequences. Carbon tax, carbon trading, and policies, among others, play a crucial role in minimizing carbon emissions and should be thoroughly examined by policymakers.

14.4.2 Technologies and Strategies Designed for Specific Sectors Emissions from the energy sector account for most of the increase in the atmospheric concentrations of GHGs; hence, conventional policies and attempts to cut down emissions should focus on both the generation and consumption of energy [4, 25]. There are four main areas of focus in the literature on the topic of emission reduction: the power source and the industries, construction, and transportation sectors. Clean energy, carbon storage and sequestration, supply-side fuel, and nuclear power being

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replaced by low-carbon fuels can all contribute to lowering emissions in the power sector. Energy-efficient practices and specific technologies that lower energy usage are also included in demand-side carbon reduction efforts [26]. End-use fuel swapping from fossil-based to renewables and the deployment of renewable technologies are also examples of demandside carbon reduction [8]. The most effective ways to lower carbon emissions are through increased speculation of clean energy and to work on increasing its efficiency. The effect of globalization and renewable energy on the carbon balance goals in India, Brazil, South Africa, and China was studied by one work, which demonstrated the use of statistical models, including random-effect and fixed-effect models, to analyze the economic and energy variables from 1980 to 2018 [27]. According to the results, a 1% rise in globalization is associated with a 0.0342% rise in carbon emissions, whereas a 1% rise in the consumption of renewable energies like wind and hydropower is associated with a 0.0143% decline in emissions. These results show that switching to renewable energy is a sensible strategy for cutting down on the carbon output. However, this varies from country to country. For instance, researchers in Bangladesh used carbon footprint measurements to calculate the environmental costs of energy use from 1975 to 2016. The results showed that a 1% increase in per capita usage of hydroelectricity resulted in a 0.02%–0.03% reduction in the carbon footprint [28]. Even though carbon emissions can be reduced by using renewable energy sources to power homes and businesses, just 1% of electricity in Bangladesh is generated using renewable energy. This contrast of solar energy-based power generation is shown in Figure 14.4. This shows that becoming carbon neutral is not something that can be done overnight. Carbon emissions must be reduced and carbon neutrality achieved through the implementation of long-term initiatives that encourage sustainable energy and energy efficiency. To reach carbon neutrality in the future, it will be necessary to shift away from energy sources that rely on fossil fuels and toward those that rely on renewable resources. Shifting from fossil fuels to renewable energy sources is widely recognized as the most effective strategy for reaching net-zero carbon emissions in the energy sector. It is worth stressing that a transformation of this magnitude cannot occur by itself. Propagating renewable energy sources should be a priority for governments, investors, lawmakers, and the academia. Griffin and Hammond studied the process of reducing carbon emissions from the steel and iron industry in the UK, which is responsible for the nation’s total emission of GHGs from industrial sites (26%) [29]. The blast furnace served as the most effective and energy-intensive step in the steel­making process; thus, it had to be prioritized if zero emissions were to be achieved.

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Solar electricity generation, billion kilowatt hours 300 250 200 150 100 50 0

2000 2002 2004 2006 2008 2010 2012 2014 2016 2018 2020 2001 2003 2005 2007 2009 2011 2013 2015 2017 2019 USA

China

India

Bangladesh

Figure 14.4  Contrasting profiles of electricity generated from solar in billion kilowatthours from four countries. The USA is an industrialized nation, along with the economic powerhouses such as India and China, as well as Bangladesh, a country seeing a significant economic crisis in recent years.

Technologies like heat recovery in electric arc furnaces and coke ovens were identified as promising energy-saving options. By implementing such technology, one can cut down on energy use by 18% and on GHG emissions by 12%. In addition, the study found that cutting down carbon emissions until 2050 is doable if they switch to bioenergy and employ more efficient production methods [30]. Additionally, there is a necessity to address the issue of carbon dioxide emissions from the forestry sector, non-road machinery, transportation, and dryers. Dryers, purchasing power, and onsite energy production were identified as the sectors responsible for the most emissions in a study of the Finnish and Swedish forestry industries [31]. Several approaches have been suggested for decarbonization, including the use of biofuels and the electrification of vehicles in the forestry industry. However, meaningful decarbonization while minimizing negative repercussions requires efficient laws and incentives. Instances where this is seen include when there is an excessive demand for biofuels and, consequently, an excess demand for biomass, which drives up both price and scarcity. Generally, the industrial sector can take advantage of a wide range of methods to minimize carbon emissions. The transformation from fossil fuels to renewable energy sources and the use of energy-saving devices are examples. In addition,

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including renewable energy systems into the energy mix of such industrial operations and reusing waste energy sources are both potential avenues to explore [32]. Any number of sectors may put these practices into effect.

14.4.3 Innovative Carbon Reduction Strategies and Technologies In addition, carbon capture, utilization, and storage (CCUS) is emerging as an intriguing technology that has been discussed in the literature as a potential step to decreasing the emission levels in both the energy and industrial sectors [33]. Separating and capturing the CO2 gases that are created as a by-product of processes that make use of fossil fuels are what the approach includes. After the CO2 has been captured, it is transferred to geological reserves, where it is kept for extremely extended periods of time. Alternatively, the captured CO2 might be used in the production of chemicals, algae, and construction materials made of concrete [34]. It could also be used in the process of enhanced oil recovery. The reduction of emissions while maintaining the usage of fossil fuels is the fundamental goal of this endeavor. In the research that has been done, pre-combustion, post-combustion, and oxyfuel combustion have all been discussed as potential capture methods [35]. Each method has its own procedure for the extraction and capture of carbon dioxide. Post-combustion capture systems for instance are particularly well suited for retrofit projects and can be utilized in a wide variety of contexts. In hindsight, CCUS represents a developing technology that has the potential to play a pivotal role in achieving reductions in carbon emissions. CCUS is a method by which the collected carbon is either retained or used in other processes, such as the manufacturing of algae, chemicals, and concrete. Nevertheless, it must not be a solution that promotes the ongoing utilization of energy sources that are dependent on fossil fuels.

14.4.3.1 Buildings and Cities Cities and buildings are accountable for considerable levels of carbon emissions that lead to climate change. This is mostly attributable to the growing population of cities and the period of time people spend inside buildings. According to one study, approaches that cities may take to adapt to the effects of climate change include building resilient structures that are capable of withstanding natural calamities while simultaneously minimizing their influence on the natural environment [36]. The implementation of decentralized energy systems in urban areas is another approach to mitigating the problem; however, the upfront investment required for this strategy is substantial [37]. Enhanced building envelopes, the use of

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renewable materials, and additive manufacturing are some of the ways in which buildings can work toward a carbon-free future. In addition, this can be accomplished via the development of cooling and heating systems that are run by renewable energy and the implementation of technologies that are efficient with energy use. In addition, the utilization of sensors to monitor and control intelligent building technology such as lighting and the development of systems for the storage of electric and thermal energy are both potential avenues of investigation. In addition to this, every electromechanical equipment used in buildings should have an environmental label attached to it, and there should be minimum requirements for HVAC systems [4]. In general, both urban planning and the construction of structures are extremely important factors in the fight against climate change and the pursuit of carbon neutrality. The use of robust designs, decentralized energy systems, enhanced building envelopes, renewable energies, eco-labelling, and the utilization of wood in construction are some of the potential solutions proposed.

14.4.3.2 Transportation According to one evaluation, the transition from fossil fuels to renewable energy in the transportation industry is difficult, especially for large, longrange aircraft and vehicles. Biofuels, electro-fuels, and hydrogen are just some of the potential replacements for fossil fuels that have been suggested [38]. The use of electricity has a multitude of advantages, the most notable of which is an increase in productivity, a decrease in carbon dioxide emissions, and an enhancement of the quality of air in the transportation sector. For instance, with the technologies that are currently available, electricity has the potential to supply the total energy (72.3%) that is required for transportation in the European Union [39]. It has been concluded that the transportation sector’s electrification is the most effective strategy to reduce the sector’s overall carbon emissions. Other performance indicators, such as travel control and the promotion of collaborative economies, are also viable options.

14.4.4 Societal Contribution Toward Carbon Reduction Individuals and households, in addition to businesses and governments, play a crucial role in cutting down carbon emissions. To quantify residential GHG emissions in European cities, one study analyzed the average carbon footprint of a single family, which was calculated to be 6.93  metric tonnes of carbon dioxide equivalent per year [40]. This is the same amount

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Sustainable Approaches for Carbon Footprint Reduction

Plant Trees

Reuse water

Switch to sustainable energy

Figure 14.5  Different sustainable strategies toward net-zero carbon emission. Starting from reducing, reusing, and recycling, to electric vehicles with sustainable power from solar photovoltaic (PV) to biopolymer-based plastic alternatives, along with water reuse and encouraging tree planting.

of carbon that can be sequestered annually by 0.51 ha of forest. An essential part in lowering carbon emissions can be played by society, as has been pointed out. Facade shading, effective lighting, commuting by foot or bicycle, using energy-saving appliances, making the switch to electric vehicles, increasing tree coverage, and spreading awareness about climate change are some of the methods proposed. Figure 14.5 depicts the different societal contributions toward carbon footprint reduction.

14.5 Carbon Elimination from the Atmosphere Negative emissions techniques (otherwise known as carbon capture technologies) are necessary to reach carbon emission reductions because reducing emissions alone will not be enough [41]. The main negative emissions approaches studied in the reports encompass bioenergy carbon sequestration and storage, direct air carbon capture, biochar, and soil carbon sequestration [33]. This is in addition to other techniques, such as carbonization and the employment of biomass in construction; afforestation; managed

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to improve wetland construction, terrestrial weathering, and rehabilitation; increased ocean alkalinity and its fertilization; and alternative storage methods like these [9]. These methods are not devoid of their drawbacks and difficulties, but they each have their own unique beneficial features. The effects of negative emissions technology on food, energy, and water supply were studied in one evaluation [42]. The research found that, by 2035, with today’s prices and efficiencies, direct air carbon capture technology will have reduced emissions by 3 Gt CO2 year−1. In addition, unlike afforestation and the carbon capture and storage used in the bioenergy sector, direct air capture does not increase the need for agricultural land or exacerbate the global food supply crisis. Researchers determined that governments thinking about implementing negative emissions technology need to consider the environmental consequences beyond those related to climate change. Approaching carbon neutrality can be achieved by negative emissions technologies [43]. It is important for implementers to consider the varying costs, operating parameters, and power requirements of various technologies as they scale them up. To guarantee that these technologies are effectively implemented and at the lowest operational cost, researchers should do a full life cycle assessment of them. This should come as no surprise that achieving net-zero emissions has a favorable effect not only on the economy but also on society and the environment. The achievement of carbon reduction is a big step toward improving the environmental deterioration that has taken place over the course of the past few decades and toward fostering the growth of a more sustainable environment for the benefit of future generations. Reaching carbon neutrality is beneficial for society because it encourages the growth of existing communities, the production of innovative technologies and policies, and the maintenance of social order. Lastly, reaching carbon neutrality will induce a reposition in economic growth models, energy generation and utilization, and the ultimate formation of an advanced system of economics based on energy usage. This can be accomplished by reducing energy use through utilizing energy-efficient equipment.

14.6 Outlook One of the most crucial substances that support life on earth is carbon. The exploitation of carbon-based resources to generate electricity, food, and other consumables since the Industrial Revolution had a significant impact on the world’s ecosystems. Global climate change, which results from the greenhouse effect driven on by elevated CO2 in the atmosphere

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348  Clean and Renewable Energy Production

and other GHGs, is linked to the excessive utilization fossil fuels, deforestation, and anthropogenic factors. Researchers suggest that it is expected that the global carbon footprint market size might grow from USD 9 billion to USD 12.2 billion by 2025, at a compound annual growth rate (CGAR) of 6.2% during the forecast period [9]. There is a wide field of opportunities for emerging economies like India, China, and the Middle East to explore and make improvements in this market. Another reason for the increased demand for carbon footprint management software in the industries might be due to many companies increasingly adopting this software to follow the carbon emission norms [44]. Cloud-based solutions are being employed by various enterprises as it provides better control of data with better security, increased scalability, and convenient speed all around the clock. As per the International Energy Agency (IEA), there is a huge potential in the market, and with the increasing average growth rate, there is an exponential increase in energy consumption service [45]. The fossil fuel energy sources are slowly being transitioned to clean energy sources. The fossil energy sources seem to provide harm due to their increased price in the economy, pollution, and eventually getting exhausted. The first stage is to switch from using fossil fuels to using renewable energy sources and to creating low-carbon technologies. Improved energy services, boosting energy efficiency, and promoting renewable energy sources should be the three pillars of the energy transition strategy. Examples of climate change mitigation strategies include regenerating pastures, integrated agricultural system, farming, forest conservation, nitrogen fixation, and repurposing organic waste [46]. To achieve net-zero emissions of carbon, low-carbon agriculture must be adopted, consumption patterns must change, and the management of agricultural and food wastes must improve. Buildings should be made to be resilient to calamities while causing the least amount of harm to the environment, wherever possible, in cities. Places with decentralized energy systems and cutting-edge gear such as electric cars, the Internet of Things, and data can make a tremendous difference in slowing down global warming. Green buildings must be constructed and modified to achieve carbon-neutral goals and aspirations. On the industrial level, encouraging businesses to use biofuels as a source of energy through appropriate regulations and incentives is a wise move. The adoption of innovative technologies like CCUS along with climate and energy laws, the expansion of renewable energy sources other than hydro- and biofuels, and the circular economy can all help the industry achieve carbon neutrality in the future. Developing a hydrogen distribution

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network for fuel cell vehicles, maintaining secure hydrogen supply management, and expanding financial assistance are certain strategies to encourage sustainable change. Switching to green fuels in the transportation sector is a challenging feat. Financial assistance, research, and laws encouraging negative emissions alternatives are needed if the global communities want to achieve the sustainable goal of a carbon emission-free planet. Technology today has the potential for creating a carbon-neutral world. However, to close the gap between the propaganda of a carbon-neutral world and the truth of it, scientists, legislators, shareholders, and consumers from all over the world must act promptly and cooperatively with the goal of reducing carbon footprints and helping to promote carbon sequestration in technological and biological environments, and to expedite the trajectory toward reducing CO2 emissions, it is necessary to systematically and economically encourage scientific advancements that support sustainable cities and communities.

Conflict of Interest The authors declare that the research was conducted in the absence of any commercial or financial relationships that could be construed as a potential conflict of interest.

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Conventional and AI-Based MPPT Techniques for Solar Photovoltaic System-Based Power Generation: Constraints and Future Perception Rupendra Kumar Pachauri1*, Vaibhav Sharma2, Adesh Kumar1, Shashikant3, Akhlaque Ahmad Khan4 and Priyanka Sharma5 1

Electrical Cluster, School of Engineering, University of Petroleum Energy Studies, Dehradun, India 2 Incubation Centre, IIMT University, Meerut, Uttar Pradesh, India 3 Electrical Engineering Department, School of Engineering, Babu Banarasi Das University, Lucknow, India 4 Electrical Department, Integral University, Lucknow, Uttar Pradesh, India 5 School of Basic Science and Technology, IIMT University, Meerut, Uttar Pradesh, India

Abstract

Solar photovoltaic (PV) systems use perturb and observe (P&O) and incremental conductance (IC) maximum power point tracking (MPPT) methods. To maximize PV panel power, these methods adapt the PV system’s operating point to the MPP. Artificial intelligence (AI)-based MPPT solutions optimize the PV system operating points using sophisticated algorithms and machine learning. These techniques can be more efficient and accurate than conventional methods and can adapt to changing weather conditions and PV panel degradation. Some examples of AI-based MPPT techniques include neural network-based MPPT, fuzzy logic-based MPPT, and evolutionary algorithm-based MPPT. Overall, both conventional and AI-based MPPT techniques have their own advantages and disadvantages. Conventional methods are simple and easy to implement, but they may not be able to adapt to changing conditions as well as AI-based *Corresponding author: [email protected] Surajit Mondal, Adesh Kumar, Rupendra Kumar Pachauri, Amit Kumar Mondal, Vishal Kumar Singh and Amit Kumar Sharma (eds.) Clean and Renewable Energy Production, (355–374) © 2024 Scrivener Publishing LLC

355

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15

methods. AI-based methods can be more efficient and accurate, but they may be more complex and require more computational resources. In conclusion, the selection of the appropriate MPPT technique for a specific solar PV system depends on the specific requirements of the system, such as the complexity, cost, and efficiency. Keywords:  Solar photovoltaic system, artificial intelligence, maximum power generation, power enhancement, environmental conditions

15.1 Introduction To generate power, solar photovoltaic (PV) systems are a significant renewable resource. They use no moving components and produce no pollutants when they transform solar energy into electricity [1]. This makes them a clean and sustainable alternative to fossil fuels. Additionally, solar PV systems can be installed on a small scale for residential or commercial use or on a large scale for utility-grade power generation. The usage of solar PV systems to produce electricity is predicted to continue to rise in the future due to the combination of falling PV system costs and the rising public awareness of the need for renewable energy sources. In addition to lowering our reliance on non-renewable fossil fuels and our carbon footprint, solar PV installations also assist to cut down on emissions and boost energy independence [2]. The performance of a PV system may be improved by designing and installing it with consideration for local weather patterns and circumstances and by maintaining it periodically to keep it in peak condition [3]. Solar PV systems, like all outdoor systems, are subject to environmental factors that can affect their performance and life span. Some of the main challenges that solar PV systems face due to the environment include: • Temperature: Solar cells lose efficiency and degrade faster at higher temperatures, which may also reduce their lifetime. • Dust and debris: The efficiency of solar panels might be reduced if dust and particles accumulate on their surface. • Humidity: High humidity can lead to the corrosion of metal parts and degrade the performance of solar cells. • Wind and storms: High winds and storms can damage solar panels and supporting structures.

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• Snow and ice: Accumulation of snow and ice on solar panels can decrease their efficiency and increase the risk of damage. • Lightning: Lightning can cause damage to the solar panels, inverters, and grid-tie systems. • UV radiation: UV radiation can degrade the plastic and rubber components of solar PV systems and can also cause discoloration of the modules. To address these challenges, engineers and scientists are working on developing new materials, technologies, and designs that can improve the durability and performance of solar PV systems under different environmental conditions. When it comes to producing clean power, solar PV systems are crucial. Environmental circumstances and the properties of the PV cells themselves are two elements that may impact on the PV system efficiency [4, 5]. Maximum power point tracking (MPPT) methods are great methodologies to boost the efficiency of a PV system. By continuously modifying the operating point of the system to meet the maximum power point of the PV cells, the power output of a PV system may be maximized using MPPT methods. The total efficiency of the PV system may be greatly improved by altering the voltage and current provided to the PV cells. Traditional MPPT methods include perturb and observe (P&O) and incremental conductance (IC), while newer methods using AI such as artificial neural networks (ANNs) and fuzzy logic (FL) have been suggested to improve performance even further [6]. These strategies may boost the PV system’s overall performance in different climates and address the drawbacks of traditional MPPT techniques, such as sluggish tracking speed and steadystate inaccuracies. In conclusion, MPPT methods are a vital means of improving the functionality of solar PV systems and are required for maximizing both power production and efficiency. The development and use of MPPT techniques will continue to be an important area of research and development in the field of solar energy, especially in light of the rising popularity of solar PV systems for electricity generation and the rising public consciousness of the importance of using renewable energy sources [7]. The novelty of this work lies in the fact that it mainly focused on the chief attributes creating a technical datasheet of conventional and AI-based MPPT metaheuristic approaches [8]. This paper gives a tabular comparison of the

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MPPT Techniques for Solar PV-Based Power Generation  357

typical MPPT metaheuristic methods, rating them according to many parameters such as the array size, irradiance levels, a comparison of popular MPPT metaheuristics approaches is provided in this study. These methods are evaluated based on a number of criteria, including array size, irradiance levels, the percentage increase in the global maximum power point (GMPP) [9] by the best methodology tested, and the tracking time required to achieve this increase. • Using simpler flowcharts, the paper explains the fundamental principles behind both classic and AI-based metaheuristics procedures in separate sections. • A technical datasheet was created by reviewing 69 recently reported AI-based metaheuristic approaches and conventional MPPT techniques by considering the important attributes required to design any PV system. New learners can also easily understand the performance of these metaheuristic approaches in particular PV system configurations in Partial shading conditions (PSCs). • The pros and cons of all reviewed works in the end of each category enable identifying the aforementioned knowledge gaps and provide guidance on how to adapt an individual algorithm to the needs of a high-quality PV system. • Again, the most appropriate MPPT method may be chosen for a given application by first comparing all available methods based on the essential qualities needed when incorporating them into any PV system. A schematic diagram for the stand-alone application of a PV system integrated with MPPT is shown in Figure 15.1.

PV System

DC-DC Converter

Sun

Load

I V MPPT

Figure 15.1  Integration of maximum power point tracking (MPPT) with solar photovoltaic (PV) system in a stand-alone mode.

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358  Clean and Renewable Energy Production

15.2 MPPT Systems When exposed to various environmental factors, the maximum power point (MPP) of each individual PV module varies. MPPT algorithms are utilized to get the most juice out of them. Electronic converters are used to enforce these algorithms. Although these methods improve the PV system’s efficiency, designers are often concerned with the actual GMPP tracking when working with PSCs. Microcontrollers are used to implement these algorithms in realworld systems. These algorithms take regular samples of certain PV module characteristics and then change the duty ratio of the DC converter being used. By doing so, the impedance observed by the PV module is altered, allowing for maximum power to be generated. Different types of MPPT methods are displayed in Figure 15.2. Below, each technique is described in depth, and Table 15.1 that follows includes the most recent advancements in each field.

15.2.1 Conventional MPPT Techniques A literature study on MPPT methods is crucial since it provides a synopsis of current research in the field. This allows researchers to understand MPPT Techniques

Artificial Intelligence Based

Conventional

Perturb & Observation

Fuzzy Logic Controller

Firefly Algorithm

Incremental Conductance (IC)

Artificial Neural Network

Cuckoo Search

Constant Voltage Control (CVC)

ANFIS Particle Swarm Optimization Artificial Bee Colony Ant Colony Optimization

Flying Squirrel Search Salp Swarm Algorithm Gray Wolf Optimization

Figure 15.2  Classifications: conventional and artificial intelligence (AI)-based maximum power point tracking (MPPT) techniques.

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MPPT Techniques for Solar PV-Based Power Generation  359

Table 15.1  Taxonomy on recent reported work on conventional techniques to track the global maximum power point (GMPP).

Best MPPT techniques

Power of PV module (kW)

Size of PV system

MPP (W)

[14]

Variable step P&O

0.0718

2 modules (series)

29.22, 116.1, 106.2

Gil-Velasco et al.

[15]

Proposed

0.250

5 modules (series)

44.97, 30.49

Authors

Reference

Numan et al.

Efendi et al.

[16]

Modified P&O

0.050

3 modules (series)

6,037; 5,387; 7,051; 7,385; 6,322

Zand et al.

[17]

SP-INC

0.100

1 module

98.981, 94.097, 81.292

Baimel et al.

[18]

SPC

NA

NA

27.11, 15.76, 04.83

Hua et al.

[19]

Proposed

0.060

4 modules (series)

470.95

Nadeem et al.

[20]

Proposed

0.245

3 modules (series)

438.15

Fapi et al.

[21]

Proposed

0.145

1 module

85

Sarika et al.

[22]

Proposed

0.100

1 module

76.50, 65.27

Verma et al.

[23]

AFLC

0.360

3 modules (series)

521.5, 250.6, 198.1

Rahman et al.

[24]

PSO-ANN

0.0603

4 modules (series)

135.9, 202.1

Farzaneh et al.

[25]

Proposed

0.060

Series: 3 modules

87.12, 116.74

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360  Clean and Renewable Energy Production

(Continued)

Table 15.1  Taxonomy on recent reported work on conventional techniques to track the global maximum power point (GMPP). (Continued) Authors

Reference

Best MPPT techniques

Power of PV module (kW)

Size of PV system

MPP (W)

Manikandan et al.

[26]

Proposed

0.320

1 module

36.88, 37.2, 37.66

Al-Majidi et al.

[27]

ANFIS

0.185

Series: 5 modules

924

Aymen et al.

[28]

Neuro-Fuzzy

0.060

1 module

50.262, 45.736, 40.856, 35.633, 30.156

Farajdadian et al.

[29]

AF-FA

0.220

–

220.5, 175.1, 124.3

Eltamalya et al.

[30]

GWO-FLC

0.1852

–

54.6, 92.8

Chen et al.

[31]

Proposed

0.060

–

157.3, 46.83

Raj et al.

[32]

ANN-INC

NA

–

450

Abdellatif et al.

[33]

FB

0.3052

–

100.38, 80.17, 59.87

Mohammed et al.

[34]

GA, Fuzzy

0.060

1 module

44.17, 36.11, 41.68, 41.70, 24.07

Tandel et al.

[35]

GA

0.0200

Series: 16 modules

1,319.12

Karthika et al.

[36]

GA-tuned PI

0.200

7 × 7

7,020

Dehghani et al.

[37]

PSO-GA

0.100

–

98.85, 78.69, 58.64 (Continued)

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MPPT Techniques for Solar PV-Based Power Generation  361

Table 15.1  Taxonomy on recent reported work on conventional techniques to track the global maximum power point (GMPP). (Continued) Authors

Reference

Best MPPT techniques

Power of PV module (kW)

Size of PV system

MPP (W)

Bendary et al.

[38]

ANFIS-GA

0.0409

–

40.90, 27.78, 19.28

Firmanza et al.

[39]

Proposed DE

0.100

Series: 2 modules

170.5, 87.9, 152, 130.9

Neethu et al.

[40]

DE

0.215

Series: 4 modules

663.8

MPPT, maximum power point tracking; PV, photovoltaic; P&O, perturb and observe; SP-INC, self-predictive incremental conductance; SPC, solar charge controller; AFLC, adaptive fuzzy logic control; PSO-ANN, particle swarm optimization artificial neural network; ANFIS, adaptive neuro-fuzzy inference system; OFC, Optimal fuzzy controller; GWO-FLC, grey wolf optimization fuzzy logic controller; ANN-INC, artificial neural network and incremental conductance; GA, genetic algorithm; PI, proportional integral; DE, differential evolution; NA, not applicable.

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362  Clean and Renewable Energy Production

the various approaches and methods that have been proposed and used for MPPT, as well as the advantages and limitations of each method. This information can then be used to inform the design and implementation of new MPPT techniques and to improve the performance of the existing ones. Additionally, a literature review can also help identify gaps in the current research and areas where further study is needed. Overall, a literature review on the MPPT techniques is important for advancing the field and improving the efficiency of solar power systems. MPPT using a P&O-based controller is a method used in PV systems to get the most out of their PV modules and arrays. Modulating the PV module’s input voltage or current and measuring the resulting shift in power output are how the P&O algorithm gets the job done. The algorithm then adjusts the input voltage or current in order to maintain the MPP. P&O-based MPPT is becoming more popular because of its low actualized costs, ease of installation, minimal sensor requirements, and simplicity. MPP monitoring is now recursive. This method relies on making tiny adjustments to the voltage of the PV array and then observing how that affects the output. Changing the DC–DC converter’s duty cycle does this. These tremors can be used to calculate the power shift. The PV module operates at its optimum point on the left side of the power–voltage (P–V) curve, where voltage increases result in greater Start Start Start

PV Module V & I Measurement

PV Module V & I Measurement Δ i(n) = i(n) -i(n-1) Δ v(n) = v(n) -v(n-1)

P=V*I Yes

Yes

Δ P>0

No Yes

No

Δ V>0

Yes

No

Δ V>0

Yes

Δi=0

Δi>0

No

Δ i/Δv = -i/v

No Yes

Duty Cycle (Increment)

Δv>0

Yes

No No

Yes

Δ i/Δv > -i/v

No

Duty Cycle (Decrement)

Parameters (updation)

Operating Voltage (Increment)

Operating Voltage (decrement)

Return

Return

(a)

(b)

Figure 15.3  Perturb and observe (P&O) (a) and INC-based (b) maximum power point tracking (MPPT) techniques [11–13].

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MPPT Techniques for Solar PV-Based Power Generation  363

power output. The operational point of a PV module is on the right side of the PV curve if power decreases as the voltage rises. Therefore, monitoring the MPP requires a perturbation direction that tends to head in a certain direction. The iterative procedure is then repeated until the maximum possible performance is achieved. Standard P&O methods are effective when operating in relatively constant environments; it suffers from the drawback of tracking MPP in PSCs [10]. P&O are adjusted in the manner described in order to get around this shortcoming [11]. This method, which is a refinement of P&O, allows the monitoring of MPP in environments with high rates of change. Standard P&O methods are effective while operating in relatively constant environments [12, 13]. The P&O and INC incremental conductance (IC) MPPT methodologies are shown in Figures 15.3a, b.

15.2.2 AI-Based MPPT Techniques P&O are adjusted in the manner described in [11] in order to get around this shortcoming. This method, which is a refinement of P&O, allows the monitoring of MPP in environments with high rates of change. Standard P&O methods are effective while operating in relatively constant environments, and the fuzzy logic controller (FLC) input error “e” and its change “∂e” with samples in time “ki” can be expressed in Eq. 15.1 and 15.2. Moreover, block diagram of fuzzy logic controller (FLC)-based maximum power point tracking (MPPT) is shown in Figure 15.4 as,

e



Ppv (k) Ppv (k 1) Vpv (k) Vpv (k 1)

∂e = e(k) − e(k − 1)

(15.1) (15.2)

Due to its summary nature, a literature review on the MPPT approaches is essential. Lastly, they were reduced to their numeric forms [41]. In

Input

Fuzzification

Fuzzy Input

Inference

Fuzzy Output

Defuzzification

Output Control variable

Rule Base

Figure 15.4  Block representation of fuzzy logic controller (FLC)-based maximum power point tracking (MPPT).

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364  Clean and Renewable Energy Production

comparison to more traditional MPPT methods, this method exhibits less oscillations and faster reaction [42] and has a higher tracking efficiency. However, it has a high level of computing complexity, which limits its usefulness. An ANN is a collection of unchanging models of learning. This method mimics a biological neural system in its attempt to predict an exact output for each input. For example, as shown in Figure 15.5, ANNs typically consist of three layers, with different numbers of neurons distributed among them for each layer. As an MPP system, these networks estimate the optimal power or voltage levels that may be generated at any given instant. The converter’s duty cycle is set in large part by these variables. A set of input variables, including the PV module parameters and weather parameters, are processed by the network’s unseen layers. Unfortunately, the formula used to calculate offspring ages is backward and prone to mistakes. After that, it loops back over the input neurons using the center layer neurons. The ability to collect data from a fully equipped experiment is greatly enhanced. The dataset is obtained by training the ANN with inputs including the atmospheric conditions and array parameters to determine the

y1

Irradiance

Temperature

Bias

x1

y2

x2

y3

x3

Wxy

Bias Layer-1 (Input)

y4

z

Duty Cycle

Wyz

yn Layer-2 (Hidden)

Layer-3 (Output)

Figure 15.5  Three-layer structure of an artificial neural network (ANN) [43].

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MPPT Techniques for Solar PV-Based Power Generation  365

values of the variables of interest (Vm and Pm). These sets are then converted into an instructional one and fed into the planned ANN, which is then taught the necessary skills. Furthermore, the generated ANN model uses the functions of the input data as instruction data. The model then acquires the ability to act autonomously. After the instruction phase, the performance of the created ANN is evaluated using assessment datasets, and the ANN is fed back its errors until the weights of all of its neurons are properly adjusted. More stable performance around the MPP is observed while utilizing ANN for MPPT [43]. The high computational complexity is an issue with these algorithms. The high computational complexity of algorithms is a downside. The particle swarm optimization (PSO) method is a form of random search. A nonlinear continuous function is maximized as the guiding principle. Fish schooling and flocking in this way is a natural phenomenon; thus, it adheres to the laws. For this method, we utilized a flock of birds to symbolize individual atoms or molecules. Each particle in the search space is assigned a fitness value, which is represented as a vector of location and velocity. Each particle’s fitness value determines its movement in space and its ultimate direction. Then, each particle proposed a solution by integrating the data it had gathered throughout its own quest for a workable course of action. First, the technique generates solution groups at random, taking into account the position and speed of particles in the search region. After each iteration, the fitness value of particles is revised using cognitive and interpersonal trade-offs. As a result of compromise, both individuals and communities can improve their optimal situation. Each particle remembers its own best position relative to others as it contributes to a global best position [44]. The swarm iteratively seeks the optimal solution by increasing the location and velocity after each cycle. Each particle then rapidly converges to a global maximum after that. Refreshing condition for the nth molecule during the kth cycle, given its position (in Y) and velocity (in v), is expressed in Eqs. (15.3) and (15.4) as:



vn(k + 1) = ωvn(k) + α1μ1(pp,best−k − Yn(k)) + α2μ2(pg,best − Yn(k)) (15.3)



Yn(k + 1) = Yn(k) + vn(k + 1)   n = 1,2,3, … … … …, N (15.4)

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366  Clean and Renewable Energy Production

Start

Iteration Process

Randomly initialize particle position ‘Y’ and velocity ‘v’

Set Gbest = minimum of (local best fitness)

Is current fitness > global best fitness?

Each particle ‘Y’ & ‘v’ updation

Particle fitness value Computation Personal best fitness & position = current fitness & position (for each particle set)

N

Y Set global best fitness ft (pg,best) = current fitness ft (Yk)

function ‘ft(Y)’ (Each particle Computation) N

N Is ft (Yi) > ft (pp,best-(k-1))? Y

Swarm Reached the GMPP?

K=k+1

Y Output : global best position (pg,best)

Set pp,best-(k-1) at pp,best = current fitness at Yk

Stop

Figure 15.6  Artificial intelligence (AI)-based particle swarm optimization (PSO) maximum power point tracking (MPPT) technique [44].

If the initialization condition in Eq. (15.5) was met in an ad hoc manner, then the modified method conforms to Eq. (15.6) as:



ft(Yn−k) > ft(pp,best−k)

(15.5)



pp,best–k = Yn−k

(15.6)

‘ft’ must be maximized. Figure 15.6 shows the flowchart of AI-based PSO algorithm to track GMPP.

15.2.3 Pros and Cons of Conventional and AI-Based MPPT Pros and cons are important in research for several reasons: • To provide a balanced view of the topic being studied. By looking at both the positive and negative aspects of a given technology, method, or approach, researchers can gain a more complete understanding of its strengths and limitations.

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MPPT Techniques for Solar PV-Based Power Generation  367

• By evaluating the pros and cons of different options, researchers can choose the most appropriate approach for their study and avoid potential pitfalls. • By highlighting the pros and cons of a given approach, researchers can communicate the potential benefits and drawbacks of their work to other researchers, practitioners, and policymakers. • Identifying the limitations of current methods, researchers can identify areas where further research is needed to improve the state of the art. Overall, considering the pros and cons of a given approach is an important part of the research process as it helps ensure that the research is rigorous, balanced, and valuable to the wider community. Pros and Cons are explored in Table 15.2. Overall, AI-based MPPT techniques have the potential to offer improved performance and robustness compared to conventional techniques, but their implementation can be more complex and costly.

Table 15.2  Pros and cons of maximum power point tracking (MPPT) techniques. MPPT techniques

Pros

Cons

Conventional MPPT

• High tracking efficiency • Robustness during non-uniform weather conditions • Low cost and simple implementation

• Limited tracking accuracy • Slow response to changes in solar panel conditions • Limited compatibility

AI-based MPPT

• High tracking accuracy and efficiency • Faster response time to changes in solar panel conditions • Improved compatibility • Adaptable nature

• AI algorithms increase the implementation cost and complexity • Dependent on data • Increases computational power • Continuous monitoring requirement

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368  Clean and Renewable Energy Production

15.3 Challenges and Future Perspective There are several challenges associated with MPPT techniques, including: • Dynamic nature of the solar panel: Several variables, including temperature, insolation, and shading, may swiftly and unexpectedly alter the power output of a solar panel. MPPT algorithms must be able to adapt to these changes in order to maintain maximum power output. • Nonlinearity of the current–voltage curve: The relationship between the current and voltage of a solar panel is nonlinear, which makes it difficult to accurately determine the maximum power point. • Partial shading: It is possible for the maximum power point of a solar panel to change when it is partly shaded, causing a conventional MPPT algorithm to lose track of the maximum power point and, thus, degrade system efficiency. • Noise and measurement errors: Noise and measurement errors can also affect the accuracy of MPPT algorithms, which can reduce the overall system efficiency. • Cost and complexity: Implementing MPPT algorithms can be costly and complex, which can be a barrier for some system designers and operators. The future perspective of MPPT technology is expected to continue to advance and improve. MPPT technology is used to optimize the power output of a solar PV system, and as the use of renewable energy sources continues to grow, the demand for efficient MPPT technology is also expected to increase. • Researchers are working on developing new algorithms and control methods to further improve the efficiency of MPPT systems. • Additionally, the integration of MPPT technology with other technologies such as energy storage systems and smart grid systems is expected to become more widespread in the future. In summary, MPPT technology is an essential part of the renewable energy ecosystem, and as the renewable energy industry continues to grow, MPPT technology will continue to be a vital component of the industry.

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MPPT Techniques for Solar PV-Based Power Generation  369

Conventional MPPT Techniques

Oscillations

Cost 3 2.5 2 1.5 1 0.5 0

Tracking time

Accuracy

Computation time

(a)

AI based MPPT Techniques

Oscillations

Cost 3 2.5 2 1.5 1 0.5 0

Accuracy

Computation time

Tracking time

(b)

Figure 15.7  Radial diagrams for the relational performance of conventional (a) and artificial intelligence (AI)-based (b) MPPT techniques.

15.4 Radial Diagram-Based Relational Performance of MPPT Techniques With the use of a radial graph, relationships may be used to zero in on the most productive method of comparative research. All of the performance parameters were rated as either “poor” (1), “mid” (2), or “high” (3) in this analysis. The strengths of the AI-based MPPT approaches were compared to those of traditional methods, as demonstrated in Figure 15.7 through a contour radial relationship.

15.5 Conclusion A report comparing traditional MPPT methods with those based on AI could conclude that the latter provide the most hope for enhancing the operational effectiveness and efficiency of solar power systems. Although conventional MPPT techniques like P&O and IC have seen extensive applications in the industry, they suffer from drawbacks including sluggish tracking speed and steady-state inaccuracies. Alternatively, the MPPT performance may be enhanced by the use of AI-based approaches such as ANNs and FL. By improving the tracking speed and accuracy, these technologies have the potential to outperform more traditional approaches. Additional studies are required to completely understand the possibilities and limits of AI-based MPPT approaches and how to effectively utilize them in real applications.

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370  Clean and Renewable Energy Production

References 1. Kermadi, M., Salam, Z., Eltamaly, A.M., Ahmed, J., Mekhilef, S., Larbes, C., Berkouk, E.M., Recent developments of MPPT techniques for PV systems under partial shading conditions: A critical review and performance evaluation. IET Renew. Power Gener., 17, 34, 3401–3417, 2020. 2. Singh, N. and Goswami, A., Study of P-V and I-V characteristics of solar cell in MATLAB/simulink. Int. J. Pure Appl. Math., 118, 24, 1–8, 2018. 3. Selvan, S., Nair, P., Umayal, A review on photo voltaic MPPT algorithms. Int. J. Electr. Comput. Eng., 6, 2, 567–582, 2018. 4. Xu, L., Cheng, R., Yang, J., A new MPPT technique for fast and efficient tracking under fast varying solar irradiation and load resistance. Int. J. Photoenergy, 2020, 1–18, 2020. 5. Gupta, A.K., Chauhan, Y.K., Pachauri, R.K., A comparative investigation of maximum power point tracking methods for solar PV system. Sol. Energy, 136, 236–253, 2016. 6. Baba, A.O., Liu, G., Chen, X., Classification and evaluation review of maximum power point tracking methods. Sustain. Futures, 2, 68, 1–28, 2020. 7. Belhachat, F. and Larbes, C., A review of global maximum power point tracking techniques of photovoltaic system under partial shading conditions. Renew. Sustain. Energy Rev., 92, 513–553, 2020. 8. Nkambule, M., Hasan, A., Ali, A., Proportional study of Perturb & Observe and Fuzzy Logic Control MPPT Algorithm for a PV system under different weather conditions, in: Proceedings of the IEEE 10th GCC Conference and Exhibition, pp. 19–23, Kuwait, 2019. 9. Reddy, D.C.K., Satyanarayana, S., Ganesh, V., Design of hybrid solar wind energy system in a microgrid with MPPT techniques. Int. J. Electr. Comput. Eng., 8, 2, 730–40, 2018. 10. Szemes, T.P. and Melhem, M., Analyzing and modeling PV with ‘P&O’ MPPT algorithm by MATLAB/Simulink, in: Proceedings of the IEEE Conference on International Symposium on Small-Scale Intelligent Manufacturing Systems (SIMS), Gjovik, Norway, 10–12 June 2020. 11. Ahmed, J. and Salam, Z., A modified P&O maximum power point tracking method with reduced steady-state oscillation and improved tracking efficiency. IEEE Trans. Sustain. Energy, 7, 4, 1506–15, 2018. 12. Sera, D., Kerekes, T., Teodorescu, R., Blaabjerg, F., Improved MPPT algorithms for rapidly changing environmental conditions. 2006 12th International Power Electronics and Motion Control Conference, pp. 1614–19. 13. Bouksaim, M., Mekhfioui, M., Srifi, M.N., Design and implementation of modified INC, conventional INC, and fuzzy logic controllers applied to a PV system under variable weather conditions. Designs, 5, 4, 71, 2021. 14. Numan, B.A., Shakir, A.M., Ahmed, B.M., Enhancement of P&O algorithm for MPPT for partially shading PV systems, in: Proceedings of Academics Era International Conference, Antalya, Turkey, 21–22 Jan 2021.

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MPPT Techniques for Solar PV-Based Power Generation  371

15. Gil-Velasco, A. and Aguilar-Castillo, C., A modification of the perturb and observe method to improve the energy harvesting of PV systems under partial shading conditions. Energies, 14, 9, 1–12, 2021. 16. Efendi, M.Z., Suhariningsih, Murdianto, F.D., Inawati, E., Implementation of modified P&O method as power optimizer of solar panel under partial shading condition for battery charging system, in: AIP Conference Proceedings 1977, pp. 1–10, 2018. 17. Zand, S.J., Hsia, K.H., Eskandarian, N., Mobayen, S., Improvement of self-predictive incremental conductance algorithm with the ability to detect dynamic conditions. Energies, 14, 12–34, 2021. 18. Baimel, D., Tapuchi, S., Levron, Y., Belikov, J., Improved fractional open circuit voltage MPPT methods for PV systems. Electronics, 8, 321–340, 2019. 19. Hua, C., Chen, W., Fang, Y., A hybrid MPPT with adaptive step-size based on single sensor for photovoltaic systems, in: Proc. International Conference on Information Science, Electronics and Electrical Engineering, pp. 441–445, 2014. 20. Nadeem, A., Sher, H.A., Murtaza, A.F., Online fractional open-circuit voltage maximum output power algorithm for photovoltaic modules. IET Renewable Power Gener., 14, 2, 188–198, 2020. 21. Fapi, C.B.N., Wira, P., Kamta, M., Real-time experimental assessment of a new MPPT algorithm based on the direct detection of the short-circuit current for a PV system, in: Proc. International Conference on Renewable Energies and Power Quality (ICREPQ’21), Almeria (Spain), 28-30 July 2021, pp. 1–6. 22. Sarika, E.P., Jacob, J., Mohammed, S., Paul, S., A novel hybrid maximum power point tracking technique with zero oscillation based on P&O algorithm. Int. J. Renew. Energy Res., 10, 4, 1–12, 2020. 23. Verma, P., Garg, R., Mahajan, P., Asymmetrical fuzzy logic control-based MPPT algorithm for stand-alone photovoltaic systems under partially shaded conditions. Sci. Iran., 27, 6, 3162–3174, 2020. 24. Rahman, M.M. and Islam, M.S., PSO and ANN based hybrid MPPT algorithm for photovoltaic array under partial shading condition. Eng. Int., 8, 1, 9–24, 2020. 25. Farzaneh, J., A hybrid modified FA-ANFIS-P&O approach for MPPT in photovoltaic systems under PSCs. Int. J. Electron., 107, 5, 1–20, 2019. 26. Manikandan, P.V. and Selvaperuma, S., EANFIS-based maximum power point tracking for standalone PV system. IETE J. Res., 68, 1–14, 2020, DOI: 10.1080/03772063.2020.1788425. 27. Al-Majidi, S.D., Abbod, M.F., Al-Raweshidy, H.S., Design of an efficient maximum power point tracker based on ANFIS using an experimental photovoltaic system data. Electronics, 8, 8, 1–20, 2019. 28. Aymen, J., Ons, Z., Crăciunescu, A., Popescu, M., Comparison of fuzzy and neuro-fuzzy controllers for maximum power point tracking of photovoltaic modules. Renew. Energy Power Qual. J., 1, 14, 796–800, 2016.

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29. Farajdadian, S. and Hosseini, S.M.H., Design of an optimal fuzzy controller to obtain maximum power in solar power generation system. Sol. Energy, 182, 161–78, 2019. 30. Eltamalya, A.M. and Farh, H.M.H., Dynamic global maximum power point tracking of the PV systems under variant partial shading using hybrid GWOFLC. Sol. Energy, 177, 306–316, 2019. 31. Chen, Y.-T., Jhang, Y.-C., Liang, R.-H., A fuzzy-logic based auto-scaling variable step-size MPPT method for PV systems. Solar Energy, 126, 53–63, 2016. 32. Raj, A. and Gupta, M., Numerical simulation and performance assessment of ANN-INC improved maximum power point tracking system for solar photovoltaic system under changing irradiation operation. Ann. Rom. Soc. Cell Biol., 25, 2, 790–97, 2021. 33. Abdellatif, W.S.E., Mohamed, M.S., Barakat, S., Brisha, A., A fuzzy logic controller based MPPT technique for photovoltaic generation system. Int. J. Electr. Eng. Inform., 13, 2, 394–417, 2021. 34. Mohammed, S.S., Devaraj, D., Ahamed, T.P.I., GA-optimized fuzzy-based MPPT technique for abruptly varying environmental conditions. J. Inst. Eng. (India): Ser. B, 102, 3, 497–508, 2021. 35. Tandel, B.G. and Vora, D.R., MPP detection based on genetic algorithm for PV system in partial shading condition. Int. J. Res. Dev. Technol., 5, 6, 107–15, 2016. 36. Karthika, S., Rathika, P., Devaraj, D., Evaluation of GA tuned PI controller for maximum power point tracking for solar PV system under partially shaded conditions based on two diode model. World Appl. Sci. J., 35, 12, 2580–2590, 2017. 37. Dehghani, M., Taghipour, M., Gharehpetian, G.B., Abedi, M., Optimized fuzzy controller for MPPT of grid-connected PV systems in rapidly changing atmospheric conditions. J. Mod. Power Syst. Clean Energy, 9, 2, 376–83, 2021. 38. Bendary, F.M., Saied, E.M., Mohamed, W.A., Afifi, Z.E., Optimal maximum power point tracking of PV systems based genetic-ANFIS hybrid algorithm. Int. J. Sci. Eng. Res., 7, 4, 830–36, 2016. 39. Firmanza, A.P., Habibi, M.N., Windarko, N.A., Yanaratri, D.S., Differential evolution-based MPPT with dual mutation for PV array under partial shading condition. 2020 10th Electrical Power, Electronics, Communications, Controls and Informatics Seminar (EECCIS), pp. 198–203, 2020. 40. Neethu, M. and Senthilkumar, R., Comparison method of PSO and DE optimization for MPPT in PV systems under partial shading conditions. Int. Energy J., 20, 2A, 291–298, 2020. 41. Farajdadian, S. and Hosseini, S.M.H., Design of an optimal fuzzy controller to obtain maximum power in solar power generation system. Sol. Energy, 182, 161–178, 2019. 42. Almajid, S., Al-Raweshidy, H., Abbod, M., A novel maximum power point tracking technique based on fuzzy logic for photovoltaic systems. Int. J. Hydrogen Energy, 43, 31, 14158–14171, 2018.

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MPPT Techniques for Solar PV-Based Power Generation  373

43. Jyothy, L.P.N. and Sindhu, M.R., An artificial neural network based MPPT algorithm for solar PV system. 4th International Conference on Electrical Energy Systems (ICEES), pp. 375–80, 2018. 44. Oliveira, F.M., da Silva, S.A.O., Durand, F.R., Sampaio, L.P., Application of PSO method for maximum power point extraction in photovoltaic systems under partial shading conditions. 2015 IEEE 13th Brazilian Power Electronics Conference and 1st Southern Power Electronics Conference (COBEP/SPEC), pp. 1–6, 2015.

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374  Clean and Renewable Energy Production

Bioethanol Production and Its Impact on a Future Bioeconomy Apurva Jaiswal1, Riya Bhattacharya2, Siddhant Srivastava3, Ayushi Singh3 and Debajyoti Bose2* Plasma Bioscience Research Centre and Applied Plasma Medicine Centre, Department of Electrical and Biological Physics, Kwangwoon University, Seoul, South Korea 2 School of Technology, Woxsen University, Hyderabad, Telangana, India 3 Faculty of Applied Sciences & Biotechnology, Shoolini University of Biotechnology & Management Sciences, Solan, Himachal Pradesh, India 1

Abstract

With advances in bioprocessing in a world where carbon is limited, biofuels are gaining popularity as a cleaner alternative for transportation fuels such as gasoline, diesel, and jet fuel. Bioethanol, formed by the fermentation of biomass, is used as a replacement for or an additive to gasoline. For bioethanol production, agricultural residues can be used as feed materials, making it ideal to meet the energy demands in third-world countries. This review focuses on creating a delicate balance between the production of biofuels without creating a food and fodder conflict. Different types of feedstocks are available to produce bioethanol, such as lignocellulosic biomass derived from agricultural and forestry residues, making it an ideal alternative for second-generation bioethanol production. Additionally, the literature focuses on the major challenges faced by the energy sector; a pathway for circular bioeconomy is also proposed. Emphasis is also put on the different pretreatment techniques, methods for cost-effective production, and the scope of genetic manipulation of energy crops for boosting productivity. The refinement in production techniques through synthetic biology and its effect on microbial metabolism are also reviewed. The extraction of bioethanol from agricultural residues is a sustainable method for complete energy recovery, as opposed to burning it and causing air pollution.

*Corresponding author: [email protected] Surajit Mondal, Adesh Kumar, Rupendra Kumar Pachauri, Amit Kumar Mondal, Vishal Kumar Singh and Amit Kumar Sharma (eds.) Clean and Renewable Energy Production, (375–412) © 2024 Scrivener Publishing LLC

375

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16

Keywords:  Bioethanol, bioprocessing, lignocellulosic biomass, pretreatment, fermentation

16.1 Introduction to Bioenergy The world’s energy consumption is increasing every day, and the threat of fossil fuel depletion has become serious. To eliminate these challenges, alternative approaches emphasizing on energy consumption management and alternative fuel sources have been explored [1]. Bioenergy refers to the renewable energy obtained from biomass. The energy obtained from this biomass is primarily solar energy captured by plants via photosynthesis. Considering that the amount of biomass utilized is equivalent to or less than the amount that can be re-grown, this makes bioenergy limitless, hence a form of renewable energy [2]. Bioenergy includes power and fuel known as biopower, such as electricity, and biofuel such as bioethanol. Various factors such as the increasing concerns over environmental and climate impact, rising petroleum fuel prices, energy independence, and decreasing resources have stimulated the global interest in bioenergy. Various government-sponsored programs, research, and policies are the additional influences toward bioenergy development. Bioenergy is crucial not only for sustaining our future but also as a driving factor for major economic developments in rural areas. The current bioenergy projects focus on the production of advanced biofuels and bioenergy projects, as well as next-generation biomass crops [3]. Biofuels are a range of fuels that can be synthesized by a variety of methods from agro-industrial waste, algae, or various lignocellulosic biomass (LCB) sources [4]. Bioethanol is perhaps the most sustainable, bio-based, and environmentally benign fuel due to its superior combustion efficiency, high flame speed, low stoichiometric air/fuel ratio, and low heating value [4]. Bioethanol synthesis from biomass is a process of reducing crude oil consumption and the CO2, NOx, and SOx emissions discharged into the atmosphere because of fossil fuel combustion. Many studies have been conducted on bioethanol production, starting from basic fermentation of biomass sources such as sugarcane, corn, cassava, banana peels, rice straw, and other agricultural wastes to the multistage conversion system [1]. The current review focuses on the production of bioethanol that does not compete with the food supply chain and is both cost- and energy-efficient. This review aims to provide an overview of recent research on fermentation, ethanol yield, properties, and useful characteristics of bioethanol produced from lignocellulosic biomass as a fossil fuel replacement, as well as the genetic manipulation of energy crops for cost-effective ethanol production.

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376  Clean and Renewable Energy Production

16.1.1 Bioethanol One of the most widely used biofuels is bioethanol, also known as ethyl alcohol or grain alcohol. It is produced by the microbial fermentation of plants that are rich in sugar or starch, such as sugarcane, corn, maize, sweet sorghum, or lignocellulosic biomass. It is a colorless, flammable compound chemically represented as C2H5OH or EtOH. The properties are similar to those of gasoline in terms of the high-octane number, high fire speed, low stoichiometric air–fuel proportion, and low warming worth, making it a highly desirable product in the industry mostly in the transport sector [4–6]. However, its low energy density, corrosive nature, low flame luminosity, lower vapor pressure, miscibility, toxicity, and increased evaporative emission on blending with gasoline are some of the major disadvantages of using bioethanol [8, 9]. The physical and chemical properties of bioethanol were compared to those of methanol and gasoline. Table 16.1 shows the comparison of ethanol with other fuel sources.

16.1.1.1 Bioethanol as an Alternative Fuel Interestingly, bioethanol is already being used as alternative fuel in some countries, for instance, in Brazil, the US, and some European countries like Sweden. It has been used as early as 1894 in France and Germany, and since 1925 in Brazil as an alternative transportation fuel [9, 10]. Rudolph Diesel, in 1898, utilized biodiesel created from peanut oil in his diesel motor at the World Display in Paris, while Henry Ford designed his vehicle 1908T to utilize ethanol [11]. In the automobile sector, ethanol was used until 1940; however, due to the ease of accessibility of cheap petroleum, its use was stopped. The increasing global energy demand and depleting fossil fuels, dramatically increasing fuel prices, increasing environmental awareness, and greenhouse gas (GHG) emissions have led to the search for an alternative, clean, and sustainable energy source. Among the different biofuels, bioethanol represents the most reasonable, inexhaustible, bio-based, and eco-friendly alternative source of energy for SI motors [1]. Ethanol-mixed fuel or unadulterated ethanol has shown a radical reduction in exhaust emissions under various working conditions. Due to the extremely oxygenated fraction of ethanol, when utilizing the bioethanol-mixed and pure ethanol fuels, decreases in the exhaust emissions like hydrocarbons, carbon monoxide, and nitrogen oxides were observed. An additional advantage of ethanol is its higher octane rating,

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Bioethanol and its Impact on Future Bieconomy  377

Table 16.1  Physical and chemical properties of ethanol, methanol, and gasoline [7]. Property

Methanol

Gasoline

Ethanol

Molecular weight (g/mol)

32

~114

46

Boiling point (K)

338

300–518

351

Melting point (K)

175

–

129

Liquid density (g/cm3 at 298 K)

0.79

0.74

0.79

Vapor density relative to air

1.10

3.0–4.0

1.59

Specific gravity

0.789 (298 K)

0.739 (288.5 K)

0.788 (298 K)

Viscosity (cp)

0.54

0.56

1.20

Solubility in H2O (%)

Miscible (100%)

Negligible (~0.01)

Miscible (100%)

Heat of evaporation (BTU/lb)

472

135

410

Azeotrope with H2O

None

Immiscible

95% EtOH

Heating value (kilo BTUs per gallon of fuel)  Lower

58

111

74

 Upper

65

122

85

  (%) Lower (LFL)

6.7

1.3

3.3

  (%) Upper (UFL)

36

7.6

19

Peak flame temperature (K)

2,143

2,303

2,193

Auto-ignition temperature (K)

733

523–733

636

Tank design pressure (psig)

15

15

15

Minimum ignition energy in the air (mJ)

0.14

–

0.23

Flashpoint (K)

284

228

287

Flammability limits

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378  Clean and Renewable Energy Production

permitting motor plans with higher compression ratios, which means that ethanol-driven engines can be designed to have higher thermal efficiency. Improved ignition dependability and a superior ignition stage were also estimated as results of the high octane rating of the ethanol. The combustion performance in vehicular motors has been observed to be very similar or slightly increased over those utilizing ordinary gas fuel under different spark ignition timings and choke valve openings [12]. Nonetheless, ethanol has a lower energy volume than gas, approximately 34% lower in terms of energy per unit volume, which means that more ethanol—concerning volume and mass—should be combusted to create a similar measure of energy. Subsequently, 1.5 gal of ethanol contains around a similar measure of energy as 1 gal of gasoline does. Albeit, the energy contained per gallon of ethanol is not equivalent to that of gasoline; as the energy in ethanol is transformed to the industrial movements of a vehicle, the ethanol-based engine will squander less energy in contrast to that of gasoline. Hypothetically, an ethanol-powered car will have better performance and waste less energy if the engine is designed for a larger power output and higher thermal efficiency. Likewise, on utilizing bioethanol, the carbon dioxide emitted on the combustion of ethanol is balanced by the carbon dioxide captured by plants, which is later used in the process of ethanol production. The utilization of bioethanol could diminish GHGs by as much as 86% [13].

16.1.1.2 Simultaneous Saccharification and Fermentation Simultaneous saccharification and fermentation (SSF) is one of the processes for the production of ethanol from lignocelluloses [14]. In SSF, enzymatic hydrolysis is performed together with fermentation. The principal benefits of this method are the reduced end-product inhibition of the enzymatic hydrolysis and the reduced investment costs. The temperature is normally kept below 37°C, whereas the difficulty to recycle the yeast makes it beneficial to operate with a low yeast concentration and at high solid loading. Most processes for bioethanol production from lignocellulose starts with the thermochemical hydrolysis of the hemicellulose (pretreatment), followed by enzymatic hydrolysis of the cellulose and a yeast-based fermentation of the resulting sugars. This results in increased costs. Lignin, the main by-product in the process, can be directly used as solid fuel or as a source for higher value-added biorefinery products. Research projects have been

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Bioethanol and its Impact on Future Bieconomy  379

External Production

Hemicellulose hydrolyzate

Raw Materials

Pretreatment

Hemicellulose hydrolyzate

Enzyme Production

Cellulose Lignin (Hemicellulose)

Yeast Production

ENZYMES

SSF

YEAST

Separation (Distillation)

ETHANOL

Lignin

External Production

Figure 16.1  Schematic representation of the simultaneous saccharification and fermentation (SSF) procedure [15].

made toward decreasing the cost of enzymes, optimizing the methods of pretreatment, and developing novel yeast strains, primarily Saccharomyces cerevisiae strains capable of fermenting pentoses, to perform the enzymatic hydrolysis together with the fermentation instead of subsequent to the enzymatic hydrolysis, which is called SSF or simultaneous saccharification and fermentation. Figure 16.1 shows the schematic process of SSF. Today, SSF plays a crucial role in the dry-milling process in the corn-based ethanol industry, especially in the US [15].

16.2 Overview of Lignocellulosic Biomass Lignocellulose mainly consists of plant dry matter, i.e., biomass [16]. This includes forest residues, municipal solid wastes, waste paper, crop residues, and others. Lignocellulose is mainly composed of cellulose (40%–50%), hemicelluloses (25%–30%), and lignin (15%–20%). Apart from these major constituents, there are some other trace materials like pectin and

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380  Clean and Renewable Energy Production

nitrogen compounds [17, 18]. Cellulose, the major constituent, is the most abundant compound found on the earth that is responsible for the strength of the cell wall. It has some novel components like biocompatibility, hydrophobicity, and stereoregularity. Lignin is a hydrophobic 3D heterogeneous polycrystalline polymer that inhibits the hydrolysis process. Phenyl propane is the structural unit of this polymer, which is linked by ether linkages and carbon–carbon bonds. Hemicellulose is a cross-linked polymer with a low level of polymerization and without a crystalline area, which causes them to effectively degrade/break into various monosaccharides such as fructose, galactose, xylose, arabinose, dextrose, and mannose [19, 20]. To make maximum use of cellulose and lignocellulose, it is very important to degrade the cell wall stability. For this, several factors such as high crystallinity, the binding forces present between cell walls, and the level of polymerization are taken into consideration. Pretreatment is one such process that deals with matters such as biomass susceptibility to microorganism, enzymes, and pathogens. Henceforth, an appropriate pretreatment strategy should satisfy the accompanying conditions, rescue the hemicellulose division, be energy proficient and cost effective, limit the formation of degradation products, and produce less inhibitors, and high-value co-products should be produced from lignin [3]. Figure 16.2 gives an overview of the composition of the biomass material used extensively for biofuel production.

Lignin (%)

Cellulose (%)

Hemicellulose (%)

Ash (%)

Willow

Miscanthus Hazelnut shell Switchgrass Bamboo Corn leaves Corn cobs Corn stover Sweet sorghum bagasse Sugarcane bagasse Rice husk Oat straw Rye straw Barley straw Rice straw Wheat straw

Cherry wood Aspen Poplar Beech 0

20

40

60

80

100 120

0

20

40

60

80

100 120

Hardwood biomass

Fir Japanese cedar Spruce P. armandii Franch

0

20

40

60

80

100

120

Agricultural and herbaceous biomass

Pine

Softwood biomass

Figure 16.2  Various lignocellulosic biomass compositions.

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Bioethanol and its Impact on Future Bieconomy  381

16.2.1 Composition and Structure Celluloses and hemicelluloses, like starch, are made up of sugars, although lignocellulose makes up the majority of the cellulose found in nature. Lignocellulose itself is a complex structure of natural materials (natural polymers like lignin, cellulose, and tannins) found in plants [21]. Agricultural, forestry, and agro-industrial wastes are all good sources of low-cost lignocellulosic biomass. The compositions of various types of lignocellulosic biomass such as poplar trees, sugarcane, grasses and straws, leaves and stems, shells and peels from corn, grains, and barley. Lignocellulose wastes are still accumulated every year in large quantities and are managed poorly, which leads to environmental pollution. Conversely, utilizing these materials to produce reliable products will decrease pollution and environmental stress. Lignocellulose consists of celluloses, hemicelluloses, and lignin and always exists besides other extracts and mineral traces. The general composition of lignocellulose includes cellulose fiber strands formed by cellulose linked to each other by hydrogen bonding. The cellulose structure within the polymer is not homogeneous. This structure naturally protects the polysaccharides from enzymatic and chemical hydrolysis, making the chemical and bioconversion of lignocellulose into other products more challenging (like ethanol). Figure 16.3 gives an overview of the three primary components that make up the biomass material. Hemicellulose is a linear and branched heterogeneous polymer typically made up of five different sugars: l-arabinose, d-galactose, d-glucose, d-mannose, and d-xylose. The backbone of the chains of hemicelluloses can be either a homopolymer or a heteropolymer (a mixture of different sugars) [21]. Hemicelluloses differ from cellulose not just in terms of sugar units but also in terms of their amorphous molecular shape, in which

Lignocellulose

Lignin

Hemicellulose

Cellulose

Figure 16.3  Typical chemical composition of lignocellulosic biomass.

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382  Clean and Renewable Energy Production

shorter chains branch off from the main chain molecules. This chemistry of hemicelluloses makes them easier to hydrolyze than cellulose.

16.2.2 Pretreatment Techniques for Lignocellulosic Biomass Pretreatment is a process for cellulose transformation measures and is vital for changing the composition of cellulosic biomass to make cellulose more accessible to the catalysts that convert the starch polymers into fermentable sugars [22]. It additionally increases the microbial activity, which then improves enzyme saccharification. It also improves the enzyme hydrolysis rate, surface area, and the porosity. A blend of the commonly utilized pretreatment techniques for such interaction is addressed in Figure 16.4. An ideal and powerful pretreatment should be practical, produce less inhibitors, and give a critical level of cellulose support [23]. A few cycles like physical, chemical, and biological or their combinations are engaged in the

Lignocellulosic biomass

Cellulose

Hemicellulose

Lignin

Pretreatment

Chemical

Physical

• • • • • •

Mechanical extrusion Milling Microwave Ultrasounf Pyrolysis Pulsed eletric field

• • • • • • •

Dilute acid Mild alkali Ozonolysis Organosolv Ionic liquids Deep eutectic solvents Natural deep eutectic solvents

Physicochemical

• • • • • • •

Steam explosion Liquid hot water SPORL Ammonia based Carbon-dioxide explosion Oxidative pretreatment Wet oxidation

Biological

• Fungi

Brown fungi White fungi Soft rot fungi • Bacterial • Archaeal

Enzymatic hydrolysis Fermentation Bioethanol

Figure 16.4  Different approaches highlighting the pretreatment of lignocellulosic biomass (LCB) for bioethanol production.

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Bioethanol and its Impact on Future Bieconomy  383

pretreatment interaction. Each interaction has explicit purposes; for example, in physical treatment, the size is decreased to build the accessibility of the surface and lessen polymer formation, i.e., the crystalline structure of cellulose [24]. Different chemicals, including ionic fluids, organic solvents, alkali, etc., are associated with chemical pretreatments. A mixture of both physical and chemical measures can be described by the term “physiochemical” process. Assortments of strategies are engaged in the physiochemical process, such as steam explosion, ammonia fiber explosion (AFEX), and CO2 explosion. The application of microorganisms such as soft-rot fungi, brown-rot fungi, and bacteria is included as a component of biological pretreatment. These organisms have specific enzymes that help them to degrade the cell wall of lignocellulosic biomass. Among all the processes mentioned, the physical and chemical methods yield better results, but cause severe pollution, whereas no such pollution is observed in biological methods. Additionally, this method is environment-friendly, with low energy consumption, although some disadvantages such as extra costs, very slow enzyme activity, and long duration decomposition are associated with it [25].

16.2.2.1 Physical Pretreatment 16.2.2.1.1 Biomass Size Decrease

Different industrial techniques are utilized in size reduction methods, including milling, grinding, chipping, freezing, shredding, and coarse size reduction to build the edibility/digestibility of lignocellulosic biomass, which decreases the degree of polymerization and cellulose crystallinity and the increment of the surface region [24, 26]. Studies have demonstrated that the size must be 0.4  nm for a significant yield on hydrolysis, and milling before pretreatment has a few advantages, such as low energy utilization and no maturation inhibitors, furthermore diminishing the expense of the division of solids from fluids [27]. One important benefit of the milling method is that it does not create any harmful mixtures like levulinic acid and hydroxymethyl furfuraldehyde (HMF).

16.2.2.1.2 Extrusion

Extrusion incorporates quick blending, decreased habitation phase, moderate barrel temperature, high shear, no washing, no furfural, and molding. To have an effective expulsion pretreatment, various components should be

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384  Clean and Renewable Energy Production

taken care of, such as the pressure proportion, temperature, and the speed of screw [28]. The highest percentage of glucose transformation was achieved in a trial by Yoo et al., at 94.8% (glucose production of 0.37 g/g biomass) [29]. A further consequence of zero effluent waste with a 62.4% change rate was demonstrated by Lee et al. [30].

16.2.2.1.3 Microwave

Due to lower energy interest, less production of inhibitors, simple activity, corrupted primary association of cellulose division, and high warming limit in a short length, microwave is broadly utilized in the pretreatment cycle. When a material is exposed to microwave radiation, electromagnetic radiation generates vibrations in the polar bond and warms the material inside, bringing about the breakage of complex structures and extends the surface region for subsequent enzymatic attack. Switchgrass salts and alkali heated in a microwave produced between 70% and 90% sugar, respectively [31].

16.2.2.2 Physiochemical Pretreatment 16.2.2.2.1 Steam Explosion

In this method, biomass is applied at high-pressure steam for a fixed interval going from 160°C to 260°C. This interaction is dubbed as “auto-hydrolysis,” as the acidic corrosion framed from the hemicellular acetyl clusters is carried out during this pretreatment by the hydrolysis of hemicellulose into glucose and xylose monomers. Some factors, e.g., the size of biomass, opposition time, temperature, and moisture content, influence the pretreatment [32]. The proficiency of this cycle is improved by the utilization of H2SO4, CO2, or SO2 as an impetus. This pretreatment enjoys a few advantages over different cycles due to the low energy requirement, restricted compound use, no reusing cost, and is harmless to the ecosystem. This pretreatment is very effective for agriculture and hardwood residues. Steam pretreatment, followed by fermentation and enzymatic hydrolysis, can be used to produce ethanol from lignocellulosic biomass.

16.2.2.2.2 Liquid Hot Water

The corresponding variant of the stream pretreatment approach is liquid hot water, also known as hot compressed water. In this strategy, water is utilized rather than steam at high temperatures of 170–230°Celsius and high pressing factors up to 5 MPa. It disrupts lignin and hydrolyzes hemicellulose into its oligosaccharide or monosaccharide depending on the reaction

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Bioethanol and its Impact on Future Bieconomy  385

conditions [33–35]. Controlled pH (between 4 and 7) is needed for sugar debasement and the development of inhibitors. This strategy is appropriate for biomass containing softwood. With benefits like no inhibitory mixture development at high temperature, low-evaluated dissolvable, and conservative fluid, heated water is exceptionally preferred. A few investigations tracked down a 90% transformation pace of cellulose to glucose through enzymatic hydrolysis at 190°C for 15 min.

16.2.2.2.3 Ammonia Fiber Explosion

Liquid ammonia is used for the pretreatment of lignocellulosic biomass using processes such as ammonia fiber blasting, ammonia recycling percolation, and aqueous ammonia soaking [33]. In AFEX, the pretreatment of biomass starts by utilizing liquid ammonia and depends on the idea for a steam explosion process, which involves treating lignocellulosic biomass with ammonia at an optimum temperature ranging from 60°C to 100°C and high pressure of around 250–300 psi for a short amount of time. Conversely, with steam explosion that produces slurry, AFEX, because of the low boiling point of ammonia, creates just solid material. It does not free any sugar straightforwardly on account of the low hemicellulose solubilization, yet opens up the construction of lignocellulosic biomass and expands the surface region and, therefore, the enzymatic digestibility. AFEX been shown to bring about higher conversion of various types of cellulosic biomass.

16.2.2.2.4 Carbon Dioxide

To produce bioethanol, the utilization of carbon dioxide (CO2) as supercritical fluid innovation is a doable procedure. Lignocellulosic biomass is pretreated with supercritical CO2, indicating the fact that the gas behaves as a dissolvable material. Because of elevated pressure, the biomass structure becomes disarranged and, accordingly, builds the open surface region. Biomass that is not sufficiently humid is unsuitable to undergo this pretreatment phase [36]. It is ideal for bioethanol production because of the low inhibitory product development and the expulsion of lignin in a more efficient manner.

16.2.2.2.5 Wet Oxidation

This strategy includes high temperatures of about 170–200°C and high pressures of 500–2,000 kPa for 10–15 min. This is an exceptionally straightforward technique that debases the lignocellulosic biomass and produces less inhibitors, and it is appropriate for lignin-improved biomass. In this interaction, when the temperature rises above 170°C, water acts as a corrosive agent

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386  Clean and Renewable Energy Production

and catalyzes the hydrolytic reactions. The productivity of this methodology relies on three variables: temperature, response time, and oxygen pressure. An investigation proposed that rice husk has been the significant hotspot for ethanol production by boosting the wet oxidation condition.

16.2.2.3 Chemical Pretreatment 16.2.2.3.1 Dilute Acid Pretreatment

Two approaches are employed in the acid pretreatment method: 1. High acid concentration and temperature lower than 120°C for 30–90 min 2. Low acid concentration and temperature more than 180°C for 1–5 min [3] The reactors used in this pretreatment are plug stream, contracting bed, permeation, and course through, and to make it more doable and economical, this cycle is performed utilizing concentrated corrosive under low temperature [3]. The acids used in this process are: • • • •

Hydrochloric acid Dilute sulfuric acid Nitric acid Phosphoric acid

Different natural acids like acetic acid and peracetic acid are utilized, which are fit for changing over lignin into solvent parts. Pretreatment with sulfuric acid is a standard technique where polysaccharides are hydrolyzed to monosaccharides, prompting the higher availability of cellulose to chemical hydrolysis; however, it also prompts certain impediments such as the consumption of response and the composition of inhibitory mixtures.

16.2.2.3.2 Mild Alkali Pretreatment

This technique, at a defined pressure and temperature, allows the separation of the lignin content and makes it accessible for hydrolysis afterwards. Alkali pretreatment can solubilize a higher percentage of hemicellulose depending on the reaction temperature, alkali concentration, and lignin content. The alkali reagents used in this process are hydroxyl subordinates of sodium, potassium, calcium, and ammonium salts. Among these, sodium hydroxide

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Bioethanol and its Impact on Future Bieconomy  387

is the best. Eliminating lignin, the acetyl group, and the distinctive uronic corrosive replacement, which restrain the openness of cellulose for enzymatic saccharification, is the most pivotal benefit of this strategy. A certain disadvantage of this method is that the degree of polymerization is decreased. To neutralize the alkali, a neutralizing step is employed. The lime pretreatment approach involves the neutralization of lime with CO2 before hydrolysis, which leads to an 89% retrieval of glucose from leaf star rice straw.

16.2.2.3.3 Organic Solvent Pretreatment

Organic solvents like acetone, ethylene glycol, methanol, ethanol, and tetrahydrofurfuryl alcohol are utilized in this technique, which break up the lignin from lignocellulosic biomass [37]. The cycle is addressed in Figure 16.5. An investigation recommended that a phosphoric corrosive and (CH3)2CO detailed 93% of value bioethanol production. The low boiling point of solvents, the significant risk of pressure operation, and the volatility of strong solvents are all disadvantages of this approach.

16.2.2.3.4 Ionic Liquid Pretreatment

This method can hydrolyze carbohydrates and lignin simultaneously and is considered as a sustainable and green method (Figure 16.6). 1-Butyl3-methylimidazolium chloride and 1-allyl-3-methylimidazolium chloride are the best ionic fluids for such an approach [39]. Minimal expense recuperation, poisonous to microorganisms, and chemicals are a few of the disadvantages related to the cycle.

PRIMARY BIOREFINERY

Pulp/Paper

SECONDARY BIOREFINERY Fermentation

Cellulose

Lignocellulosic Biomass

Organosolv pretreatment

Enzymatic Hydrolysis or Acid

Conversion and Synthesis

Hemicellulose Lignin

Butanol, Lactic Acid, Propanediol Ethanol Chemical derivatives, e.g. Furfural, xylitol Fuel Additives

Lignin process Power or Heat

Heat

Figure 16.5  Organic solvent pretreatment processes [38].

Power

Chemicals e.g. Phenolic, styrene

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388  Clean and Renewable Energy Production

Biomass

Deconstruct of ionic liquid

Ionic liquid Water

Ionic liquid clean up

Filtration

Hemicellulose/Cellulose

Biofuel

Lignin Volatiles Extractives

Aromatic Chemicals

Lignin recovery

Ionic liquid Water

Volatiles Extraction

Filtration

Aliphatic Chemicals

Extraction Solvent

Figure 16.6  Methods for ionic pretreatment [40].

16.2.2.4 Biological Pretreatment Microorganisms like brown-white and delicate decay parasites are involved in organic pretreatment for the corruption of lignocellulosic biomass. Their catalysts are equipped for cell wall annihilation. This technique enjoys a few advantages over pretreatment strategies as it does not include cruel synthetic substances, does not create undesirable items, and low energy is required. White and delicate decay organisms are the most generally utilized microorganisms for lignin debasement because of the presence of lignin peroxidases, polyphenol oxidases, manganese subordinate peroxidases, and laccase. Certain detriments such as a long cycle time, an enormous space prerequisite, and the need for constant inspection of microorganisms are associated with this strategy as well. The industrial application of these microscopic organisms for the biological pretreatment of lignocellulosic biomass necessitates a comprehensive study.

16.3 Challenges and Opportunities Pretreatment is the expensive step in bioethanol production; genetic and metabolic engineering can help reduce the cost of this step. Numerous genetic methods are utilized to upgrade the pretreatment and hydrolysis

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Bioethanol and its Impact on Future Bieconomy  389

of lignocellulosic biomass. The plant cell wall structure is a significant hindrance that makes pretreatment and enzymatic processing costly. Along these lines, changing the plant cell wall structure toward suitable characteristics, such as high cellulose content, low lignin content, recalcitrance, and high hydrolase activity, is the key step for further developing the biomass quality.

16.3.1 Pretreatment Constraints in LCB Production Combinations of chemical, mechanical, hydrothermal, and biological pretreatment methods have been studied. The fundamental target of these procedures is to disrupt the lignocellulose framework to improve the recovery of cellulosic sugars [26, 41]. Feasible pretreatment reduces the lignin and hemicellulosic contents, while it further creates suitable hydrolysis rate, surface area, porosity, and microbial development, which, accordingly, will be ideal for enzymatic saccharification. Successes in these pretreatment approaches have facilitated the development of processes that utilize lignocellulose as a starting raw material; however, there remain certain drawbacks such as the inhibitory and toxic compounds produced during chemical pretreatment. The liquid hydrolysates produced during chemical pretreatment is a mixture of soluble sugars, by-products, lignin, and various inhibitory compounds such as phenolics, weak acids, heavy metals, furfurals, HMF, and tannins. Hence, pretreated hydrolysates are detoxified, increasing the cost of consolidated bioprocessing (CBP). Pretreatment methods utilizing sulfuric acid and water solubilize hemicelluloses together with lignin and result in solids with cellulosic components only [42, 43]. Although this pretreatment method makes the biofuel generation from the cellulose-rich substrate easier, the drawback is the decreased yield since the hemicellulosic components are rendered useless. The alkaline pretreatment methods are the most efficient for CBP since most of the hemicellulosic components are retained with the solids, which can then be used for bioconversion simultaneously along with the cellulose-rich portion.

16.3.2 Role of Microbes in LCB Production Saccharification and fermentation are the two principal measures in the production of LCB that employ fungi for the conversion of biomass and

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390  Clean and Renewable Energy Production

Table 16.2  Application of consolidated bioprocessing (CBP) microorganisms in proficient lignocellulosic biomass (LCB) production [50]. Pretreatment condition

No. of cellulose expressed

Final product

Cellulose with yeast extract

Phosphoric acid

Endoglucanas, β-glucosidase

Ethanol

Birch wood xylan in TB

Acid hydrolysis

Xylanase, acetylxylan esterase, xyloside permease, β-xylosidase

Ethanol

CBP strain

Substrate

Yeast Escherichia coli Bacillus subtilis

Avicel

Phosphoric acid

Native endoglucanase

Lactate

Thermobifida fusca

Switchgrass

N/A

–

n-Propanol

Trichoderma reesei and E. coli

Corn stover

AFEX pretreated

–

Isobutanol

Yeast

Rice straw

Hydrothermal (cell recycle)

3 copies of endoglucans, 3 copies of exoglucanase and β-glucosidase

Ethanol

TB, terrific broth; AFEX, ammonia fiber explosion; N/A, not applicable.

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Bioethanol and its Impact on Future Bieconomy  391

sugars into bioethanol. Hence, fungi play a crucial role in efficient LCB production. One can employ either naturally available cellulolytic microbes or industrial microbes, each with its limitations [44]. Cellulolytic fungi can produce only simple secondary metabolites. Despite the fact that they can be modified to synthesize advanced biofuel, they are generally not receptive to genetic manipulation. However, Clostridium and Thermobifida spp., in recent studies, have shown the capability of genetic manipulation [45, 46]. Industrial organisms ordinarily do not have the cellulolytic capacity, nor would they be able to penetrate different sugars in the presence of glucose because of a phenomenon known as carbon catabolite repression (CCR), rendering them useless heterogeneous substances, for example, lignocellulosic biomass. This restriction has since been overwhelmed by hereditarily designing Escherichia coli and yeast to co-utilize several combinations of sugars such as xylose, galactose, glucose, mannose, or cellobiose [47, 48]. Hence, a great CBP microbe or consortium, as represented in Table 16.2, of microbes for LCB production must be able to express cellulose, secrete protein, show tolerance to toxic substances such as lignin and microbial metabolites, and eliminate CCR, thereby metabolizing multiple sugar components [49].

16.3.3 Cost Constraints in LCB Production The crucial assessment for the employment of LCB production is the improvement of proficient, conservative cycles to isolate lignin, hemicellulose, and cellulose and convert fractionated mixtures to monomeric substrates, which would then be used for biofuel production. The expense of feedstock, chemical, and pretreatment would represent around 66% of the overall production cost, of which the protein cost is the biggest [41]. By changing and consolidating different pretreatment strategies and designing a CBP microorganism or a consortium of CBP organisms, the necessary costs can be met without much of a stretch.

16.3.4 Genetic Manipulation of Energy Crops The plant cell wall structure is a significant hindrance that makes pretreatment and enzymatic processing costly. Along these lines, modifying the plant cell wall structure toward suitable attributes such as low lignin

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392  Clean and Renewable Energy Production

content, high cellulose content, and obstinate as well as high hydrolase action is the vital advancement for further enhancing biomass quality. According to some research, genetic and metabolic engineering plays a vital role in expediting the pretreatment and hydrolysis processes, as well as in the cost-effective generation of ethanol [51].

16.3.4.1 Increasing Cellulose Content Increasing the cellulose content of plant biomass is possibly one of the most effective ways to reduce pretreatment costs. There are more than a thousand genes that can control cellulose biosynthesis in the plant cell wall, and research is ongoing to discover new genes [52]. cesA and csl are the two significant gene superfamilies that have been distinguished in cellulose biosynthesis. KORRIGAN, COBRA, and KOBITO are the proteins that are associated with cell wall amalgamation and could likewise be utilized for energy crop adjustment [53]. Coleman et al. demonstrated that overexpression of the SuSy gene in poplar increased the cellulose content by 2%–6% with no deleterious effects on plant development propensities [54]. The overexpression of this gene in other plants was similarly suggested to substantially increase the cellulose content of plant biomass [53].

16.3.4.2 Reduction of Plant Cell Wall Recalcitrance and Cellulose Crystallinity Plant cell wall is a heterogeneous multiscale structure that causes recalcitrance to enzyme hydrolysis, and the factors (structural and chemical) that are associated with LCB recalcitrance are strongly interconnected and difficult to disassociate. New studies have found that wet chemistry and spectroscopy give higher throughputs; however, these techniques require costly mechanics and manual input. Biomass recalcitrance is a multi-­ variant and multiscale phenomenon that it simply cannot be assayed by one chemical or structural factor due to its complex nature. Recent studies have concluded that spectral analysis based on the infrared and fluorescence properties of LCB, together with the water-related characteristics, seems to represent the chemical and structural properties of LCB, combining nano- and macroscale properties (water acts as a swelling agent, allowing enzyme diffusion toward the plant cell wall). It has been

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Bioethanol and its Impact on Future Bieconomy  393

reported that the water retention value (WRV) can serve as a predictor of the hydrolysis rate [55–58].

16.3.4.3 Production of Hydrolases in Plants Lignocellulosic biomass bioconversion involves a hydrolytic treatment of the lignocellulose cell wall that is mediated by cellulose [59]. These hydrolyzing catalysts produced in microbial bioreactors are costly. Nonetheless, plants are increasingly being used for enzymes and other industrial polymer synthesis due to their ability to produce cell wall hydrolyzing enzymes more efficiently than microbial production, as they require less energy. Furthermore, the widespread accessibility of information on plant genetic modification and biomass processing lends credence to their potential as a promising hotspot for such enzyme production [60]. A few endeavors have been made to introduce microbial cellulose genes and it was shown that there was no impact on biomass yield and plant development. It is preferable for these hydrolyzing enzymes to aggregate in the subcellular compartments rather than in the cytoplasm, as these enzymes show correct folding and movement, just as they are steadier and show less degradation when amassed in the subcellular compartments, including vacuoles, the Golgi apparatus, endoplasmic reticulum, apoplast, and microbodies [60, 61]. Subcellular targeting has been used to develop a number of microbial hydrolyzing enzymes in plants. The vast majority of the exploration has been led on tobacco and horse feed; however, these are not biofuel crops, so ongoing examination has started on biofuel crops like maize, potato, sugarcane, rice, and grain. The apoplast is utilized most of the time for the aggregation of catalysts since the cytosol is certainly not an optimal area for collection, while the apoplast is extensive and can gather an enormous amount [62, 63].

16.3.4.4 Lignin Modification To decrease the lignin level, it is very important to select the genes that are involved in lignin synthesis. Figure 16.7 shows the genes regulated in various plants for the modification of lignin. RNA interference is the technology that could be used to silence the genes involved in lignin synthesis. Diverse lignin digestion enzymes are found in dicot plants; therefore, the downregulation of these compounds is a promising method to decrease the pretreatment cost [53].

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394  Clean and Renewable Energy Production

Plant Genetic Engineering

Lignin Reduction

• • • • • •

Downregulation of cinnamoyl-CoA reductase and low phytic acid Downregulation of the caffeic acid O-methyltransferase Downregulation of Leucaena leucocephala cinnamoyl CoA reductase (LlCCR) gene Caffeoyl CoA 3-Omethyltransferase (CCoAOMT) Silencing (RNAi) of 4coumarate:coenzyme A ligase (4CL) 4-coumarate CoA ligase (4CL)

Wheat, Barley, Alfalfa, Tobacco, Pinus radiata, Sweet sorghum, Switchgrass, Aspen

Lignin Modification

• •

Overexpression of the ferulate 5hydroxylase (F5H) gene Mutation in the gene encoding caffeic acid O-methyltransferase (comt) with overexpression of ferulate 5-hydroxylase (F5H1)

Arabidopsis, Poplar

Figure 16.7  Overview of lignin production and modification techniques.

16.4 Bioethanol Economy The cost of bioethanol is a lot higher than that of a petroleum derivative fuel, which makes bioethanol certifiably not a reasonable elective answer for gas. Given this, national governments have been forced to establish special regulations to boost the production and utilization of bioethanol in the transportation sector. As a rule, the accompanying three principal approaches recognized in the execution of biofuels supporting arrangements and guidelines that promotes biofuel production and “fuel commands” refers to the laws or mandates related to sales of biofuel-blended fuel: (1) tax collection-based strategies, (2) farming-based arrangements/sponsorships, and (3) fuel commands [64]. As of now, biofuel production and advancement are chiefly determined by the farming area and green halls as opposed to the energy area. Notwithstanding, most biofuel programs actually rely upon endowments and government programs, additionally prompting market

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Bioethanol and its Impact on Future Bieconomy  395

bending and are exorbitant for governments. By and by, at supported high oil costs and furthermore with a consistent movement of more proficient and less expensive innovation, biofuels could be a practical option soon in numerous nations, particularly in developed nations [65]. The expense for bioethanol production changes generously, relying upon a few elements, namely, feedstock costs and income generated from by-­products and products, costs of cycle energy, speculation costs (identified with the sort of feedstock), transportation costs and the planting area, and financing costs [66]. Brazilian bioethanol is more aggressive than the corn-based bioethanol produced in the US or the sugar beet-based bioethanol generated in Europe due to its shorter handling times, reduced labor costs, and lower transportation and information costs [67]. Bioethanol production from sugarcane is exceptionally prudent in Brazil in view of two essential reasons. To begin with, the sugar prices are cut down to boost the bioethanol economy, which is bolstered by government laws that require bioethanol to be mixed with gasoline. This has significantly reduced the feedstock and sugarcane costs and created a market that supports bioethanol pricing. Furthermore, they have huge cultivable lands, which means that the land used for bioethanol sugarcane production is not in conflict with that used for food production, which has been of tremendous help [68]. Sugarcane-derived bioethanol costs US $0.23–0.29/L in Brazil [69], while the bioethanol produced from sugar beet and corn costs US $0.29/L [70] and US $0.53/L [71] in the EU and US, respectively. Other proficient sugar-delivering nations, e.g., Pakistan, Swaziland, and Zimbabwe, have production costs similar to those of Brazil [65]. The expense of crude material, which shifts impressively between various examinations (US $22–$61 per metric ton dry matter), and the capital expenses, which makes the absolute expense subject to the plant limit, contribute most to the overall production cost [72]. The expense and accessibility of feedstock are critical on the grounds that, in many biofuels, feedstock addresses 60%–75% of the total bioethanol production cost [73]. The expense figures can measure up to the expense of delivering fuel of around US $0.70/L at oil cost of US $100 per barrel [74]. Bioethanol is typically made from corn grain and sugarcane derivatives; however, due to the finite supply of these commodities, there may be conflicts between their utilization in bioethanol production and the food supply [75]. Utilizing food harvests to deliver bioethanol raises major health and moral concerns. Almost 60% of people on the planet are presently malnourished, so the requirement for grains and other essential food sources is basic.

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396  Clean and Renewable Energy Production

Developing yields from fuel wastes, land, water, and energy assets is essential for the production of nourishment for individuals [76]. In 2007, when the US retail food costs transcended the 2006 levels twice as quick as that of overall center inflation (2.3%), buyers paid heed [77]. Corn prices have risen sharply as a result of the bioethanol-fueled boom in corn demand. The March 2007 maize futures contract on the Chicago Board of Trade, for instance, surged from US $2.50 per bushel in September 2006 to nearly US $4.16 per bushel in January 2007 (an increase of 66%). Corn prices have risen sharply as a result of its increased demand, which has been fueled by the massive growth of corn-based bioethanol productivity in the United States since mid2006 [78]. Higher corn costs were, to some extent, driven by requests to produce bioethanol, and these more exorbitant costs successfully bid sections of land away from different harvests that gave lower returns, like soybeans, wheat, and feed [77]. Corn-based bioethanol raises the price of beef, poultry, eggs, pork, cereals, milk, and bread in the United States from 10% to 30% [76]. Today, the cost of producing bioethanol from lignocellulosic biomass is still prohibitively high, which is one of the primary reasons why bioethanol has yet to achieve commercial success. Pretreatment is considered to be one of the most costly components in the bioconversion of fermentable sugars from cellulosic biomass, reaching costs up to US $0.08/L of bioethanol [22]. Catalyst evaluation is accepted to such an extent that the overall commitment of chemicals to production costs is about US $0.04/L of bioethanol, with some varieties relying on genuine bioethanol yields coming about because of the specific pretreatment approach [79]. The discovery of innovative technologies to convert cellulosic biomass from industrial crops and waste materials into bioethanol will be critical for future growth of the bioethanol sector [80].

16.4.1 Synthetic Biology of CBP Microbes It has been observed that the growth of recombinant organisms on LCB is due to the numerous celluloses utilized in its production. Hence, the associated enzymes must be well organized in such a way that they should show enhanced activity without interfering, disrupting, or overriding the different steps in the process. Advances in synthetic biology have made further strides in designing proficient CBP microorganisms and further developing proteins for LCB production [81].

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Bioethanol and its Impact on Future Bieconomy  397

16.4.1.1 Cellulose Expression and Secretion Systems For the efficient hydrolysis of lignocellulosic biomass, cellulosomes, which are bound to the surface, or free cellulose, which is secreted extracellularly, are the two different ways that cellulose can be produced. In excess of 400 cellulose-related compounds are accessible in eminent cellulolytic organisms in various combinations, and to foster an optimal CBP microorganism, a larger part of these chemicals should be presented for an effective breakdown of lignocellulosic biomass and their subsequent conversion to primary sugar molecules. Consequently, the outflow of the different qualities and discharge of its individual cellulose is a fundamental and perhaps the most difficult step in planning modern cellulolytic microorganisms. Celluloses with better efficacy, broad substrate specificity, chemical tolerance, and thermo-tolerance are obtained from either metagenomic libraries or by normal protein evolution to reduce the number of cellulose necessary for optimum CBP strains [82, 83]. Optimal CBP organisms should have the option to capably emit different celluloses into the medium, roughly as high as 20  mg cellulose per gram of cellulosic material [84], and express unequivocal cellulose subject to distinction in the different constituents and focuses in the biomass. Protein secretion sufficient for appropriate cellulose release could not be achieved, most likely due to the substantial energy consumption noted in the protein’s transit through either the TAT/SecB axis, which exhausts approximately 105 protons or 104 ATP molecules per protein [85]. Several efforts were undertaken to either produce free cellulose or to express cellulosomes in the surface of recombinant microorganisms. In E. coli, for example, using fusion proteins or enhancing the membrane porosity by deleting lipoproteins boosted the extracellular concentration of heterologous proteins to 70 mg/L (Qian et al., 2008) [86]. The utilization of surface display technology has allowed the visualization of the cellulosomal structures present in anaerobic cellulolytic microbes [87]. There are two chief benefits of cellulosomes over free cellulose: (1) there is no diffusion in the surrounding medium and (2) the proximity of diverse cellulose boosts their ability to digest the biomass [88]. During cellulose hydrolysis, Trichoderma spp., a cellulolytic fungus, possesses an intracellular β-glucosidase that prevents cellobiose from inhibiting other celluloses. Accomplishing productive cellobiose digestion in industrial microorganisms is an initial step toward CBP development.

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Accordingly, recombinant microorganisms were created for useful take-up and the intracellular hydrolysis/assimilation of cellobiose and cello-oligosaccharides [47, 49]. To avoid the external buildup of cellobiose during CBP, the metabolism rate of cellobiose in genetically engineered cultures should be higher than the glucose metabolism. Over the years, various attempts have been undertaken to generate various celluloses in yeast and other recombinant hosts. E. coli and Trichoderma reesei have recently been successfully co-cultured to break down cellulosic materials [89]. Using corn stover that has undergone AFEX pretreatment as the substrate, a 62% potential production of isobutanol was attained by modifying the co-culture of cellulolytic components. This is the largest yield documented from a CBP approach to date [89]. Harvests containing heterologous thermally tolerant cellulose will help in the relaxation of the cell wall by means of implosion during pretreatment and work with microbial hydrolysis. Cellulose articulation in plants may be the best answer for diminishing the protein overexpression’s metabolic burden in industrial settings [48]. A mix of changed microorganisms, plants, and catalysts can be a viable method to achieve CBP.

16.4.1.2 Enhanced Tolerance Optimal CBP microorganisms having higher resilience toward biofuels and toxic by-products delivered during pretreatment of lignocellulosic biomass are critical to the production of sustainable LCB. The improved resilience will prompt better usefulness and higher biofuel yield. The resistance of industrial organisms to solvents like ethanol, butanol, and other biofuels can be improved by utilizing judicious and transformative methodologies. One such method is known as global transcription factor engineering. It is an arbitrary developmental methodology where a mutant organism with better development and higher resilience is chosen. For instance, yeast tolerant to ethanol and E. coli tolerant to n-butanol have been designed [90]. A portion of the reasonable methodologies incorporate the use of proteins to check the pressure impact made because of harmful mixtures and solvents. Countless microorganisms additionally use export pumps through which poisons can be exported by means of proton motive pumps. E. coli utilizes solvent-specific efflux pumps in the presence of longer branched-chained and cyclic alkenes [91].

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16.4.1.3 Metagenomics It is a scientific method that can be utilized to screen the newer and better qualities of genes from a pool of uncultivable microorganisms, which would then be utilized for designing hosts with high resistance. One can search for the gene responsible for increasing the tolerance of natural cellulolytic microbes toward lignin in order to produce more efficient cellulose with further created qualities and hydrolysis rate [81, 92]. For instance, the metagenomic library from the archaeal climate helped in the recognizable proof and improvement of the warm resistance of cellulose, which is steady as long as 5 h at 100°C [40]. This can be utilized during the pretreatment interaction and further aids in speeding up the saccharification step. One of the serious issues in the advancement of an optimal CBP strain is the low resilience of cellulolytic microorganisms, for example, Clostridium thermocellum that cannot endure in excess of 10 g/L of ethanol [46]. Some thermophiles like Thermobifida fusca show resistance even at a grouping of 50 g/L of n-propanol, although this focus is harmful for E. coli development [45].

16.4.1.4 Advanced Biofuel Production An ideal CBP microbe must produce biofuel such as ethanol, isopropanol, and n-butanol at a higher titer. For example, Zymomonas mobilis produces ethanol naturally at 160 g/L. The energy content of isopropanol and ethanol, be that as it may, is low, and these cannot be developed as independent fuel sources. This results in the requirement of advanced biofuels that resemble current petrochemicals, and these are also being produced by microbes. As a result of the difficulty in addressing the metabolic pathway of microbes, heterologous synthesis of these complex biofuels is a major roadblock in advanced biofuel production. A poor yield of roughly 0.5 g/L was achieved during the underlying preliminary test for n-butanol biosynthesis in E. coli. A yield of 30 g/L was obtained by substituting the reversible reaction with a irreversible one in E. coli for heterologous n-butanol synthesis [93]. In another endeavor, a large portion of the host metabolite was exploited and an amino acid biosynthesis pathway delivered isobutanol as an end product. This included a mutant strain that overexpressed the amino acid biosynthesis pathway and resulted in 20 g/L of n-butanol production [94]. One of the most important groups of advanced biofuels is the fatty acid-based chemicals since they closely mirror the currently used

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petrochemicals in their energy and composition. These, after several modifications, can now be produced in E. coli up to 4.5 g/L [95]. Therefore, an ideal CBP microbial strain must be able to produce a combination of these advanced fuels at titer equivalent to >2 g L−1 h−1 per ethanol-delivering strain. The methods to recycle wastes, enzymes, yeast, and stillage need the attention of the scientific community as they negatively impact the overall economy of the bioethanol generation unit.

16.4.2 Future Perspective for LCB Production CBP productivity in past examinations depended on the degradable components of celluloses, including phosphoric corrosive swollen cellulose (phosphoric acid swollen cellulose, PASC), ionic liquid (IL)-pretreated miscanthus, or Avicel; thus, the mixture of one or two compounds empowered developing on a basic model substrate. Lignocellulosic biomass is complex and heterogeneous in nature, which requires a superior and productive CBP microbe that can adequately arrange and communicate an enormous number of celluloses. For instance, even though birch wood xylan fills in as a model substrate for hemicelluloses, which is essential for cellulosic buildup, it may be complex and can be composed of various mixtures making up its spine, e.g., xyloglucan, glucomannan, etc., contingent upon shifting plant deposits. In this way, the best CBP strain should have all the composition of cellulose and have the option to proficiently organize their expression at the same time based on the various parts of biomass. These strains should have an enhanced protein framework with the end goal that a lot of the cellulose can be emitted into the medium. To reduce the need for incalculable cellulose without compromising the productivity of the CBP strain, a superior and more proficient catalyst can be assessed by high-throughput screening techniques and metagenomics [96]. Native cellulolytic organisms can depolymerize lignocelluloses with no pretreatment measures, while only thermophiles bar the requirement for pretreatment on account of industrial bioprocessing, albeit the yield of the fermentable product is, for the most part, low (15–500 mg/L). On typical substrates such as glucose, biofuel generation is extremely simplified. The productivity from the model medium must be enhanced at least 10-fold in the instance of biofuel generation from lignocellulosic materials.

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Bioethanol and its Impact on Future Bieconomy  401

A better yield or titer could be accomplished by enhancing the lignocellulosic content with supplements, e.g., yeast concentrate or glucose, or by taking a high inoculum size. Advances in engineered biology do not just provide a wide extent of communicating different heterologous metabolic pathways inside a solitary cell but also the reasons for the low production from biosynthetic processes. For example, the output of fatty acid ethyl esters (FAEE) was ~1.5  g/L when the production pathway was set under a powerful guideline system reliant upon FadR and free unsaturated fat fixation inside the cell [97]. A system like this could help transmit the energy status of the downstream synthesis pathway from the upstream hydrolysis pathway. To make lignocellulosic bioethanol generation production a cost-­ effective and an efficient technology, the scientific community needs to conduct further investigations to improve the pretreatment techniques, fermentation, and enzymatic hydrolysis processes. The efficacy and cost-­ effectiveness of bioethanol generation from LCB depends significantly on the pretreatment techniques. According to the statistical report presented by Andrade et al. (2017), the overall yield of ethanol from LCB is positively correlated with the maximum glucose/xylose recovery. Furthermore, the availability of precursors, the structural variability, and the chemical compositions are the key parameters influencing glucose/xylose recovery [98]. Consequently, a high carbohydrate content in LCB is highly desirable as it would lead to high sugar recovery. Recently, to simpilfy the pretreatment technique and accelerate the enzymatic release for high sugars (glucose/xylose), various systematic genetic engineering techniques, such as incorporating genes in the precursors, are employed. The incorporation would facilitate reducing the natural recalcitrance and modifying the lignin structure, reducing the crystallinity and enhancing the overall carbohydrate content in the precursors. Low-cost and environment-friendly pretreatment techniques that would require less energy and could be performed with ease are highly desirable. Selection of the proper pretreatment technique could reduce the overall biomass crystallinity, degrade the complex lignin carbohydrate matrix, and would eventually generate low-toxicity inhibitors and improve the efficacy toward the overall bioethanol yield from LCB. To reduce the overall cost of ethanol production from LCB, integrating the unit to generate value-added by-products is essential. For instance, lignin, which is obtained as the major by-product from the bioethanol generation unit, can be valorized in bulk by a chemical or a biochemical approach to generate value-added products like carbon fibers, adhesives, and vanillin. Moreover, lignin could also be utilized to generate electricity

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by burning it in boilers. To conclude, policymakers and financial leaders can bring cooperative biofuel investment and policies to support the sustainable strategy of converting LCB to bioethanol and implementing units to convert major by-products to other value-added products in order to reduce the overall cost of production.

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61. Horn, M.E., Woodard, S.L., Howard, J.A., Plant molecular farming: Systems and products. Plant Cell Rep., 22, 711–720, 2004, https://doi.org/10.1007/ S00299-004-0767-1/TABLES/2. 62. Ziegler, M.T., Thomas, S.R., Danna, K.J., Accumulation of a thermostable endo-1,4-β-D-glucanase in the apoplast of Arabidopsis thaliana leaves. Mol. Breed., 6, 37–46, 2000, https://doi.org/10.1023/A:1009667524690/METRICS. 63. Hyunjong, B., Lee, D.S., Hwang, I., Dual targeting of xylanase to chloroplasts and peroxisomes as a means to increase protein accumulation in plant cells. J. Exp. Bot., 57, 161–169, 2006, https://doi.org/10.1093/JXB/ERJ019. 64. Gnansounou, E., Bedniaguine, D., Dauriat, A., Promoting bioethanol production through clean development mechanism: Findings and lessons learnt from ASIATIC project. 7th IAEE Eur. Energy Conf., 2005, https://infoscience. epfl.ch/record/104096 (accessed August 8, 2023). 65. De Fraiture, C., Giordano, M., Liao, Y., Biofuels and implications for agricultural water use: Blue impacts of green energy. Water Policy, 10, 67–81, 2008, https://doi.org/10.2166/WP.2008.054. 66. Elam, N., Alternativefile:///C:/Users/user/Downloads/139_ieaarweb.pdf fuels (ethanol) in Sweden, Investig. Eval. IEA Bioenergy, Task. 27, 2000. 67. Mathews, J., A biofuels manifesto: Why biofuels industry creation should be ‘priority number one’for the World Bank and for developing countries, Macquarie Grad. Sch. Manag. Macquarie Univ. Sydney, Aust., 2006. 68. Shapouri, H. and Salassi, M., The economic feasibility of ethanol production from sugar in the United States, 2006, https://doi.org/10.22004/ AG.ECON.322769. 69. Kojima, M. and Johnson, T., Potential for biofuels for transport in developing countries, 2006, https://www.academia.edu/download/91438955/­ 374860KE40Biof1also0ESM31201PUBLIC1.pdf (accessed August 7, 2023). 70. Baffes, J., A note on rising food prices. Appl. Econ. Lett., 4, 69–75, 2008, https://doi.org/10.1080/758521836. 71. Christensen, K. and Smith, A., The case for hemp as a biofuel, Vote Hemp Inc. Report, Brattleboro, VT, 2008. 72. Hahn-Hägerdal, B., Galbe, M., Gorwa-Grauslund, M.F., Lidén, G., Zacchi, G., Bio-ethanol - The fuel of tomorrow from the residues of today. Trends Biotechnol., 24, 549–556, 2006, https://doi.org/10.1016/j.tibtech.2006.10.004. 73. Balat, M. and Balat, H., Recent trends in global production and utilization of bio-ethanol fuel. Appl. Energy, 86, 2273–2282, 2009, https://doi. org/10.1016/J.APENERGY.2009.03.015. 74. The complete guide to climate change, Ref. Rev. 23, pp. 30–32, Emerald Group Publishing Limited, United Kingdom, 2009, https://doi.org/10. 1108/09504120910958476. 75. Endo, A., Nakamura, T., Ando, A., Tokuyasu, K., Shima, J., Genome-wide screening of the genes required for tolerance to vanillin, which is a potential inhibitor of bioethanol fermentation, in Saccharomyces cerevisiae.

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408  Clean and Renewable Energy Production

Biotechnol. Biofuels, 1, 1–6, 2008, https://doi.org/10.1186/1754-6834-1-3/ FIGURES/3. 76. Pimentel, D., Marklein, A., Toth, M.A., Karpoff, M.N., Paul, G.S., McCormack, R., Kyriazis, J., Krueger, T., Food versus biofuels: Environmental and economic costs. Hum. Ecol., 37, 1–12, 2009, https://doi.org/10.1007/ S10745-009-9215-8/METRICS. 77. D.T.-R.E. Development, undefined, Economic and environmental impacts of US corn ethanol production and use, 2009, Res. Tiffany Regional Econ. Dev. 2009•researchgate.Net. (2009), https://www.researchgate.net/ profile/Douglas-Tiffany-2/publication/46566673_Economic_and_environmental_impacts_of_US_corn_ethanol_production_and_use/ links/5697c4b208ae1c4279051b8c/Economic-and-environmental-impactsof-US-corn-ethanol-production-and-use.pdf (accessed August 7, 2023). 78. Yacobucci, B. and Schnepf, R., Ethanol and biofuels: Agriculture, infrastructure, and market constraints related to expanded production, Congressional Research Service, USA, 2007, http://nationalaglawcenter.org/wp-content/ uploads/assets/crs/RL33928.pdf (accessed August 7, 2023). 79. Eggeman, T. and Elander, R.T., Process and economic analysis of pretreatment technologies. Bioresour. Technol., 96, 2019–2025, 2005, https://doi. org/10.1016/J.BIORTECH.2005.01.017. 80. Woodson, M. and Jablonowski, C.J., An economic assessment of traditional and cellulosic ethanol technologies. Energy Sources, Part B, 3, 372–383, 2008, https://doi.org/10.1080/15567240701232527. 81. Sommer, M.O., Church, G.M., Dantas, G., A functional metagenomic approach for expanding the synthetic biology toolbox for biomass conversion. Mol. Syst. Biol., 6, 360, 2010, https://doi.org/10.1038/MSB.2010.16. 82. Pottkämper, J., Barthen, P., Ilmberger, N., Schwaneberg, U., Schenk, A., Schulte, M., Ignatiev, N., Streit, W.R., Applying metagenomics for the identification of bacterial cellulases that are stable in ionic liquids. Green Chem., 11, 957–965, 2009, https://doi.org/10.1039/B820157A. 83. Graham, J.E., Clark, M.E., Nadler, D.C., Huffer, S., Chokhawala, H.A., Rowland, S.E., Blanch, H.W., Clark, D.S., Robb, F.T., Identification and characterization of a multidomain hyperthermophilic cellulase from an archaeal enrichment. Nat. Commun., 21, 2, 1–9, 2011, https://doi.org/10.1038/ ncomms1373. 84. Bokinsky, G., Peralta-Yahya, P.P., George, A., Holmes, B.M., Steen, E.J., Dietrich, J., Lee, T.S., Tullman-Ercek, D., Voigt, C.A., Simmons, B.A., Keasling, pretreated J.D., Synthesis of three advanced biofuels from ionic liquid-­ switchgrass using engineered Escherichia coli. Proc. Natl. Acad. Sci. U. S. A., 108, 19949–19954, 2011, https://doi.org/10.1073/PNAS.1106958108/ SUPPL_FILE/PNAS.1106958108_SI.PDF. 85. Palmer, T. and Berks, B.C., The twin-arginine translocation (Tat) protein export pathway. Nat. Rev. Microbiol., 107, 10, 483–496, 2012, https://doi. org/10.1038/nrmicro2814.

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86. Ni, Y., Reye, J., Chen, R.R., lpp deletion as a permeabilization method. Biotechnol. Bioeng., 97, 1347–1356, 2007, https://doi.org/10.1002/BIT.21375. 87. Ueda, M. and Tanaka, A., Cell surface engineering of yeast: Construction of arming yeast with biocatalyst. J. Biosci. Bioeng., 90, 125–136, 2000, https:// doi.org/10.1016/S1389-1723(00)80099-7. 88. Matano, Y., Hasunuma, T., Kondo, A., Cell recycle batch fermentation of high-solid lignocellulose using a recombinant cellulase-displaying yeast strain for high yield ethanol production in consolidated bioprocessing. Bioresour. Technol., 135, 403–409, 2013, https://doi.org/10.1016/J. BIORTECH.2012.07.025. 89. Minty, J.J., Singer, M.E., Scholz, S.A., Bae, C.H., Ahn, J.H., Foster, C.E., Liao, J.C., Lin, X.N., Design and characterization of synthetic fungal-bacterial consortia for direct production of isobutanol from cellulosic biomass. Proc. Natl. Acad. Sci. U. S. A., 110, 14592–14597, 2013, https://doi.org/10.1073/ PNAS.1218447110/SUPPL_FILE/SAPP.PDF. 90. Alper, H., Moxley, J., Nevoigt, E., Fink, G.R., Stephanopoulos, G., Engineering yeast transcription machinery for improved ethanol tolerance and production. Sci. (80-.), 314, 1565–1568, 2006, https://doi.org/10.1126/ SCIENCE.1131969/SUPPL_FILE/ALPER.SOM.PDF. 91. Dunlop, M.J., Dossani, Z.Y., Szmidt, H.L., Chu, H.C., Lee, T.S., Keasling, J.D., Hadi, M.Z., Mukhopadhyay, A., Engineering microbial biofuel tolerance and export using efflux pumps. Mol. Syst. Biol., 7, 487, 2011, https://doi. org/10.1038/MSB.2011.21. 92. Hess, M., Sczyrba, A., Egan, R., Kim, T.W., Chokhawala, H., Schroth, G., Luo, S., Clark, D.S., Chen, F., Zhang, T., Mackie, R.I., Pennacchio, L.A., Tringe, S.G., Visel, A., Woyke, T., Wang, Z., Rubin, E.M., Metagenomic discovery of biomass-degrading genes and genomes from cow rumen. Sci. (80-.), 331, 463–467, 2011, https://doi.org/10.1126/SCIENCE.1200387/SUPPL_FILE/ HESS.SOM.PDF. 93. Shen, C.R., Lan, E.I., Dekishima, Y., Baez, A., Cho, K.M., Liao, J.C., Driving forces enable high-titer anaerobic 1-butanol synthesis in Escherichia coli. Appl. Environ. Microbiol., 77, 2905–2915, 2011, https://doi.org/10.1128/ AEM.03034-10/ASSET/A054BFD1-A7FE-4131-B399-368A74C11E25/ ASSETS/GRAPHIC/ZAM9991020370005.JPEG. 94. Atsumi, S., Hanai, T., Liao, J.C., Non-fermentative pathways for synthesis of branched-chain higher alcohols as biofuels. Nat. 2007, 451, 7174, 86–89, 2008, https://doi.org/10.1038/nature06450. 95. Liu, T., Vora, H., Khosla, C., Quantitative analysis and engineering of fatty acid biosynthesis in E. coli. Metab. Eng., 12, 378–386, 2010, https://doi. org/10.1016/J.YMBEN.2010.02.003. 96. Peralta-Yahya, P., Carter, B.T., Lin, H., Tao, H., Cornish, V.W., Highthroughput selection for cellulase catalysts using chemical complementation.

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J. Am. Chem. Soc., 130, 17445–17452, 2008, https://doi.org/10.1021/ JA8055744/SUPPL_FILE/JA8055744_SI_001.PDF. 97. Zhang, F., Carothers, J.M., Keasling, J.D., Design of a dynamic sensor-­ regulator system for production of chemicals and fuels derived from fatty acids. Nat. Biotechnol., 304, 30, 354–359, 2012, https://doi.org/10.1038/ nbt.2149. 98. Andrade, L.P., Crespim, E., de Oliveira, N., de Campos, R.C., Teodoro, J.C., Galvão, C.M.A., Maciel Filho, R., Influence of sugarcane bagasse variability on sugar recovery for cellulosic ethanol production. Bioresour. Technol., 241, 75–81, 2017, https://doi.org/10.1016/J.BIORTECH.2017.05.081.

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Bioethanol and its Impact on Future Bieconomy  411

Waste-to-Energy Technologies for Energy Recovery Shivam Pandey, Anjana Sharma*, Naveen Kumar, Nupur Aggarwal and Ajay Vasishth Chandigarh University, Gharuan, Punjab, India

Abstract

Energy is a fundamental driver of modern society, playing a crucial role in various sectors such as manufacturing, transportation, telecommunications, agriculture, and social services. The widespread reliance on non-renewable energy sources like coal, nuclear, oil, and natural gas has led to concerns over resource scarcity and environmental issues, including global climate change. With the escalating global electricity consumption keeping pace with economic growth, particularly in developed and affluent regions, the need for sustainable and renewable energy solutions becomes paramount. To address the pressing challenges of resource depletion and environmental degradation, there is a growing global emphasis on transitioning towards renewable energy sources like solar, wind, hydro, biomass, and geothermal energy. Concurrently, researchers are exploring the potential of renewable waste-to-energy routes, converting various waste materials into sustainable energy sources. However, the implementation of waste-to-energy technology faces technical and economic limitations that require innovative solutions to ensure efficient energy recovery from waste. One promising alternative is the generation of fuel from plastic using pyrolysis, which can repurpose waste plastics into renewable fuels with economic benefits and environmental advantages. As the world's energy needs continue to surge, especially in developing nations like India and China, investments in renewable energy technologies and waste-to-energy strategies become crucial for achieving sustainability and combating resource depletion and climate change. A comprehensive and integrated approach that prioritizes sustainable energy production and responsible waste management is essential to secure a flourishing and sustainable future for our planet. *Corresponding author: [email protected] Surajit Mondal, Adesh Kumar, Rupendra Kumar Pachauri, Amit Kumar Mondal, Vishal Kumar Singh and Amit Kumar Sharma (eds.) Clean and Renewable Energy Production, (413–436) © 2024 Scrivener Publishing LLC

413

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17

Keywords:  Resource scarcity, global climate change, electricity consumption, sustainable development, geothermal energy, fuel from plastic, pyrolysis, economic considerations

17.1 Energy As energy is a key component of practically every activity, it is indeed essential in increasing life satisfaction. Its widespread use in a variety of industries and areas, including manufacturing, business, transportation, telecommunication, and a broad variety of agricultural and other social assistance, has enforced concentrating efforts on ensuring its reliable source in order to meet the ever-growing need. There have always been issues with power. Resource issues dated back as far as 2,000 years. Because firewood was the dominant source of energy for the ancient Romans and Greeks, there existed a power scarcity. Timber would have to be transported from incredibly remote locations. Power is still primarily obtained from energy resources. The use of petroleum and natural gas has now reached its pinnacle. Energy reserves are not limitless. In fact, non-renewable energy sources, such as petroleum, natural gas, and coal, are finite resources and require thousands of years to develop. Within just a few centuries, these supplies might be depleted. According to statistics, the global electricity consumption has also increased at the same rate as that of the global output. Although individuals make up a tiny portion of the global total, those in urbanized or wealthy nations utilize a significantly substantial amount of energy generated globally. Energy can be divided into two main categories: renewable and non-renewable. Non-Renewable Resources

Coal

Oil

Gas

Water

Nuclear

Other

Figure 17.1  Some of the important non-renewable sources of energy.

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414  Clean and Renewable Energy Production

Non-renewable forms of energy are in short supply, typically since these take a while to regenerate. Such non-renewable sources have the benefit of allowing the generators that employ them to generate additional electricity as needed. The following are some non-renewable sources of energy: coal, nuclear energy, oil, and natural gas. Petroleum products, including coal, gasoline, or lubricants, could be considered as non-renewable resources. Due to the finite amount of zirconium in the Earth’s mantle, nuclear energy is also viewed as a non-renewable fuel source. Since energy sources are derived from the remnants of decomposed organic cells, it takes many generations to produce fuel. Energy sources should not be squandered as the creation of these resources inside the Earth’s mantle is a complex process. Non-Renewable Energy

Liquid

Gas

1. Crude Oil 2. Petroleum Products

1. Hydrogen Gas 2. Natural Gas

Solid

1. Coal 2. UraniumNuclear Fuel

Figure 17.2  Distribution of non-renewable energy. Storage and transport

Hydrogen

Primary renewable energy source

Hydrogen production

Hydrogen

Hydrogen utilisation

Oxygen

Oxygen

Water

Water Environment

Figure 17.3  How renewable sources of energy work.

Useful energy

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Waste-to-Energy Technologies for Energy Recovery  415

On the other hand, renewable resources regenerate. The five major emission sources are as follows: (1) (2) (3) (4) (5)

Solar; Wind; Water, also called hydro; Biomass, or organic material from plants and animals; and Geothermal, which is naturally occurring heat from the earth.

17.1.1 Global Issues and Renewable Energy Global stability has been put at risk by the use of fossil fuels, which has led to global climate change, energy wars, and resource shortages. Their detrimental repercussions are seen at all societal levels, i.e., locally, regionally, and internationally. The following paragraphs provide a summary of these world issues. There is a decrease in fossil fuel reserves as a result of rising energy demands and global population expansion. Global climate change was brought on by the increase in atmospheric CO2 concentration. Solid and liquid waste levels have increased as a result of the global population growth. To achieve sustainability and transition to waste-to-energy methods, varieties of wastes from the agricultural (plant and animal wastes), industrial (sugar refinery, dairy wastes, confectionary wastes, pulp and paper, tanneries and slaughterhouses), and residential (kitchen and garden wastes) sectors are potential renewable energy sources (waste-to-energy routes, WTERs). Numerous research and development (R&D) projects are being undertaken globally to address the local, regional, and global issues covered in the aforementioned areas. The majority of researchers have demonstrated their reliance on renewable energy technologies (RETs) for sustainable development and long-term existence by using WTER routes that have no adverse effects on society. The tides, winds, and solar radiation are generally renewable and, consequently, maintainable over long-term use. Sustainable energy sources that are available in different ways, viz., energy reserves, decrease air, water, and land pollution. Energy associated with deaths and illnesses is also reduced. In light of this, developing nations in particular should expand their investments in renewable WTERs to promote the transition to sustainable renewable resources.

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416  Clean and Renewable Energy Production

17.2 Alternatives to Waste-to-Energy Routes that Might Be Used By 2100, the world’s energy needs will have multiplied by a factor of almost six. If this demand is divided between industrialized and emerging nations, there would be no power deficit in the former. Conversely, in growing nations such as India and China, the amount of energy available and the amount of energy needed are fundamentally incompatible. Technology must be created to serve as a backup supply of energy and to lessen the effects of the global energy crisis caused by the unequal distribution of energy worldwide. It would be wise to create alternative fuels that emit less carbon dioxide and can be readily made using trash from the environment. WTER technology could be a viable substitute as it has the potential for recycling the organic, biodegradable fraction of solid wastes produced by a variety of processes in addition to providing a renewable source of energy. In this chapter, only two alternatives to WTER technology are taken into consideration.

17.2.1 Technology Limitations of WTER The use of waste substrates as quick sources of energy is, however, constrained by a number of factors. The primary issue is the inability of the present anaerobic digestion systems to recover useful energy at a cost that is currently competitive with fossil fuel technologies. If renewable wastes are to be used as bioenergy resources, the energy recovery efficiency will need to be significantly improved, or more value-added benefits will need to be created for trash reduction or greenhouse gas (GHG) mitigation in order to make these processes more profitable. Their spread or dispersed nature is another important aspect in the development of renewable waste substrates as energy resources. Large waste substrate sources are frequently spread from prospective energy production sites. For instance, up to 25%–35% of the total residues, or considerable amounts of livestock manure (cow dung), may not be recovered. Renewable waste processing, transportation, and collection provide considerable barriers to their usage as energy sources.

17.2.2 Waste-to-Energy The method of converting wastes into useful products, often known as “waste-to-energy” or ”energy-from-waste,” entails either turning trash into biofuel feedstock or producing biofuel in the form of electric power or

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Waste-to-Energy Technologies for Energy Recovery  417

Municipal Solid Waste Organic Fraction

OREX Extrusion Process

Biogas

Inorganic Fraction Liquid Fertilizer RDF (Refused Driven Fuel)

Electricity

Electricity

Metal/Glass Recyclable

Figure 17.4  Full systematic diagram of the waste-to-energy method [17].

heat. Resource restoration is a form of waste-to-energy conversion. The majority of disposal operations either create flammable fuels such as gas, formaldehyde, alcohol, or fuel sources, which can be burned to produce the required power and/or heat [16].

17.2.3 Worldwide Sector for Waste-to-Energy Approximately 650 waste-to-energy facilities burn roughly 1 billion ton of municipal solid wastes yearly to provide power, heat for solar thermal, or reclaimed materials for recycling. The total waste produced by the world’s waste-to-energy industry has grown by almost over 17,000 ton. Waste-to-energy installations are actually stationed across 40 countries, spanning big ones such as that in Russia and short ones as that in Madeira. Asia is home to a number of the latest and greatest flora. In accordance with the European Union directive [1], inside a generation, flammable items should be disposed of appropriately. Nevertheless, it is indeed unclear whether each of the member states will contribute the necessary funds. A few countries, including Albania, have really no wasteto-energy capability whatsoever, while others have almost nothing. The overall quantity or waste-to-energy per person in Japan is 312 kg, in Singapore is 251 kg, and in the United States is 106 kg. The Chinese are among the most recent entrants to waste-to-energy, with eight units currently operating and a projected output of over 1.9 metric ton.

17.3 The Situation of the Waste-to-Energy Market Today In accordance with the Worldwide Waste Management Institution’s evaluation of a European waste processing business in 2002, the company’s total

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418  Clean and Renewable Energy Production

output was over 40 billion tons annually, and the thermoelectric energy production totalled 42,000,000 and 110 GJ, correspondingly (Table 17.1). It should be emphasized that the United States uses the extracted energy from energy rotors as municipal or commercial heating much less frequently than Europe does. The Verona waste-to-energy plant in France, which delivers about 600 kWh energy per ton of waste burned, is indeed a prime illustration of the energy conversion of both thermal and electric resources. This actually provides the same or more gas as geothermal during the winter. Approximately 23% of the world’s waste-to-energy from the United States and seven cities along the Eastern Seaboard account for 66% of that total (Table 17.2).

Table 17.1  Present capacity factor within the EU and the individual use wasteto-energy for the disposal of garbage.

Country

Tonnes/year (in 1999)

Kilograms/ capita

Thermal energy (GJ)

Electric energy (GJ)

Austria

450,000

56

3,053,000

131,000

Denmark

2,562,000

477

10,543,000

3,472,000

France

10,984,000

180

32,303,000

2,164,000

Germany

12,853,000

157

27,190,000

12,042,000

Hungary

352,000

6

2,000

399,000

Italy

2,169,000

137

3,354,000

2,338,000

Netherlands

4,818,000

482

Norway

220,000

49

1,409,000

27,000

Portugal

322,000

32

1,000

558,000

Spain

1,039,000

26

Sweden

2,005,000

225

22,996,000

4,360,000

Switzerland

1,636,000

164

8,698,000

2,311,000

UK

1,074,000

18

1,000

1,895,000

Total reported

40,484,000

154.5 (average)

109,550,000

40,761,000

9,130,000

1,934,000

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Waste-to-Energy Technologies for Energy Recovery  419

Table 17.2  Functional waste-to-energy plants in the United States. State

No. of plants

Capacity (short US ton/day)

Connecticut

6

6,500

New York

10

11,100

New Jersey

5

6,200

Pennsylvania

6

8,400

Virginia

6

8,300

Florida

13

19,300

Total

53

69,600

17.3.1 Environmental Advantages of Waste-to-Energy Several other environmentalists in the United States still oppose the new waste-to-energy infrastructure on concept due to significant emission reductions, which waste-to-energy amenities had also achieved in the past 15 years. These organizations seem oblivious that dumpsites, the only other option for waste disposal, have far worse air pollution. A minimum of 1.3 tonne more carbon dioxide is released into the atmosphere for every tonne of garbage that is usually discarded. Alluvial discharges are collected and processed biologically during the lifetime of a contemporary dump and for a period specified following closing; nevertheless, chemical changes and water loss of landfill wastes might last for millennia.

17.3.2 Pollutants from Landfills Today’s dumpsites make an attempt to capture the methane generated in anaerobic processes. Unfortunately, there are only a few drilling operations offered (about one well per 4,000 m2 of landfill) [5]. In order to simply capture a portion of methane, bioenergy from landfills normally includes 46% CO2 from the atmosphere and 54% methanol. The highest volume of organic energy created by bioremediation has indeed been calculated at 140 cubic meters per hour of organic energy produced from bioremediation, based on 25% of the landfill garbage being reversible (food, plants, wastes, papers, leatherette, or timber) [6]. Franklin Associates reported that the greatest amount of gas that can be produced ends up as landfill waste [7].

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420  Clean and Renewable Energy Production

17.3.3 Release of Arsenic from Garbage Mercury pollution from landfills has now been predicted to be approximately one component in billions of US waste [8]. Accordingly, over 118 ton of Hg is thrown off yearly in US dumpsites (or almost 25% of a country’s current mercurial usage). Although majority of the mercury within wastes is now in elemental state (compact fluorescent, thermostats, etc.), and even at dump conditions (40°C), the evaporation rate is equal to 0.78  mm as opposed to 4.76 mm in freshwater. Mercurial particles with the same dimensions would dissipate in 4 weeks if such unprotected droplets dissipate inside a minute [8].

17.3.4 Vaporized Organic Substances When combining the anticipated quasi-waste gas supply (about 46 performed as expected of gas and carbon dioxide leaving every kilogram of waste), even by the stated quantities of volatiles in pollutants, the yearly noxious gases produced from dumpsites in the United States can be calculated. Table 17.3 [9] displays the projected output of US dumpsites in kilograms every thousand ton of waste landfilled. High starting industrial effluents for such residential generation of biodiesel, in order to increase the quality antecedents, heat, and energy, include greywater, sewage sludge, and explosives, which end up as wastes. Waste materials provide a sizable but underutilized collection of biomass resources for the production of sustainable products and fuels. The amount of garbage produced annually—more than 2 billion metric tons, is anticipated to increase by 70 percentage points by the year 2050. We have long searched for ways to convert these wastes into useful energy, but this typically includes an incinerator, or destroying the garbage—a practice that many conservationists believe to be excessively damaging disposal (waste-to-energy) methods, including any trash methodology that converts trash into power, heat, or liquid fuel (such as gasoline). Such methods may be used to treat a diverse range of generated wastes, including fluid (e.g., home sewerage) and thermal (e.g., refining fumes) trash. Moderate refuse, such as thicker slurry after industrial effluents, are also treated using these methods. Waste-to-energy projects must be developed by combining activities in various distinct angles. It is currently essential to consider the societal, economical, and climatic challenges that may arise in the project life cycle of such methods, as well as further technical advances, including the emergence of market-based alternatives to an incinerator.

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Waste-to-Energy Technologies for Energy Recovery  421

Table 17.3  Project outputs of the United States.

Volatile compound

Molecular weight

Mean concentration in landfill gas (ppbv)

Acetone

58.08

6,838

826

Benzene

78.01

2,057

339

Chlorobenzene

112.56

82

17

Chloroform

119.39

245

61

1,1-Dichloroethane

98.97

2,801

574

Dichloromethane

84.80

25,694

4,539

Diethylene chloride

58.00

2,835

339

Ethyl benzene

106.16

7,334

1,626

Methyl ethyl ketone

72.10

3,092

461

1,1,1-Trichloroethane

133.42

615

174

Trichloroethylene

131.40

2,079

565

Toluene

92.13

34,907

6,704

Tetrachloroethylene

165.85

5,244

1,809

Vinyl chloride

62.50

3,508

461

Styrenes

104.15

1,517

330

Vinyl acetate

62.50

5,663

1,017

Xylenes

106.16

2,651

583

Total VOC emissions

Landfill emissions (kg/million ton of MSW)

20,435

Ammonia

17.03

550,000

–

Sulfides/mercaptans

60.00

500,000

–

VOC, volatile organic compound; MSW, municipal solid waste.

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422  Clean and Renewable Energy Production

17.3.5 Municipal Solid Waste Management The municipal solid waste management rates are associated with sediment load, and possible treatments have been drastically altered as a result of rising urbanization levels and productivity expansion. According to recent research by the World Economic Forum (2012), the industry generates over 1.3 billion metric tons of solid waste annually, or 1.2 kg per person per day [18]. Moreover, it should be mentioned that, according to the degree of urbanization, as well as the level of financial prosperity, the per person trash creation rates might vary between nations and localities. Within the following decades, it really is anticipated that the quantity of municipal solid trash produced may increase more quickly with the level of urbanization, exceeding 2.2 billion metric tons annually by 2025 and 4.2 billion by 2050 (World Bank, 2012; Markopoulos, 2012) [19]. On the other hand, growing nations in Asia, Latin America, and South Africa are predicted to experience the biggest increase in waste management systems during the next 10 years. Regarding trash breakdown, there is indeed a trend toward a higher proportion of paper products within the waste production formation, especially in high-income countries. With both rise in the urbanization rates and the industrial progress in such nations, it is indeed anticipated that these and low-income economies will adhere to similar tendencies.

17.4 Technical and Economic Considerations Technology that turns garbage to power can transform the energy that is stored in recyclable materials into a variety of solar fuels. Using regional and international power grids, energy can be extracted and transmitted. Either extreme or low degrees can create heat, which can be used for specialized thermodynamic parameters or dispersed for space heating. These green waste sections can be utilized to produce a variety of bioenergy, which can be processed and sold in the marketplace. At this time, integrated power and heat stations are the most widely used advanced techniques. These facilities use incineration to handle solid wastes in addition to potentially a mixture of two commercial, medical, and toxic materials, depending on the processing parameters. Such type of facility will consequently solely be the subject of funding concerns [20]. As necessary, the material is burned during the burning of garbage. Such degradation products exhaust gas that enters the atmosphere, leaves behind waste generation, and energy is released (Hulgaard and Velho 2011) [21].

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Waste-to-Energy Technologies for Energy Recovery  423

For this type of operation, a thermal range is required due to emissions and safety concerns. A heating rate of 1,050°C is necessary for combined garbage. In waste incineration, the process typically involves feeding the garbage into a bunker, from where it is then transferred to a revolving grating within the incinerator. Depending on the composition and characteristics of the waste, as well as the specific technology used in the incineration facility, certain techniques or methods may be employed to optimize the burning process and ensure efficient waste-to-energy conversion. The by-products of burning (flue gases) subsequently interchange the temperature inside a boiler to power a Rankine cycle. Eventually, the process will produce energy and water by turning on a turbine and using a heating element, accordingly. The preferred ultimate usage of the available power directly determines the type of mechanism, such as a furnace. Additionally, by concentrating on that exhaust stream, it is indeed feasible to accomplish a turbo charging well within the treatment system. The burning process also yields solid leftovers, mainly in the form of bottom wastes, clinker, and fly ash, some of which may be easily recycled as fillers for the construction and development sectors, in addition to the combustion products that are utilized to generate energy in the treatment facility. This incinerator procedure usually has wind and solar efficiency of 20%–25% when running in combined heat and power (CHP) function and power generation without heat consumption [24]. The intended meaning is related to the efficiency of the incinerator process when it is used in different modes: combined heat and power (CHP) function and power generation without heat consumption. Both within the terms of the ability to accept trash and the quantity of energy produced, CHP units may be found in a variety of sizes. A standard performance consists of only one (or more) subsystem that can individually handle 35 tonnes of waste per hour (Energinet, 2012) [22]. The Afval Energie Bedrijf CHP facility in Amsterdam, which has been in operating since 2007, is indeed the clearest illustration of waste-to-energy incinerator method presently offered, in accordance with the Energy Styrelsen study regarding Technology Information on Electricity Production (2012) [23]. This method is typically employed as a future power component inside the mixture of energy production because it operates continuously at maximum capacity. It is feasible to gain major operational versatility by

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424  Clean and Renewable Energy Production

downregulation, particularly when a new selection is made, while going over the predetermined limits on steaming quality and ecological effectiveness. This type of emerging fuel has direct bearing on the single most substantial economic distinction among waste management systems and other emission energy-producing devices. Waste does have a positive cost, which would be controlled through a marked entry, and therefore is commonly seen as the primary source of revenue by most waste treatment facility operators. In this view, waste treatment is indeed the main objective of incinerators. The production of power and heat can be seen as a beneficial result with certain added revenue. In addition, energy from the waste-to-energy unit is preferred when dispatching above energy from many other distributed generations, resulting inside a secure additional income across all services. Due to the magnitude of such facilities and the major integrated elements, the initial costs incurred again for the building of a plant comprise an important factor in the expenses associated with the technology. Furthermore, depending on the chosen strategies for the treatment of combustion products and other generated leftovers, the capital spending can differ widely. A facility’s actual costs are much less affected by the installation and maintenance expenditures, which are primarily determined by the volume of processed trash.

17.4.1 Fuel from Plastic Despite increasing within the past five centuries, it is predicted that plastic use would again double in the coming two decades. The polymers sector needs priority recovery valuation of commodities above separate polymers in order to alleviate ecological problems. This vision of a supply chain has received attention and involves a goal-oriented plan to improve thread reprocessing concepts. Reduction of use, lengthening of life, composting, and thread waste-to-energy all seem to be the recommended methods toward reducing environmental problems [25]. This entire cyclical economy is based on reprocessing; however, it is hampered by factors including inappropriate mixtures, diminished characteristics, and reinforced additions. The concept of using thermal recycling or burning to dispose of materials is becoming more popular. The treatment of waste plastics offers considerable potential for regenerative braking. Plastics contain molecules that are an ideal energy because of quiet their flame. Pyrolysis is a technique that extracts energy from exhaust plastics that has the potential to repurpose waste materials as a form of energy in liquid fuels, as well as being economically advantageous and eco-friendly. Several areas, along with the automobile, farming, and electricity production sectors, utilize

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Waste-to-Energy Technologies for Energy Recovery  425

Waste plastics Catalyst

Fuel gas Gasoline Condenser

Gas

Pyrolysis reactor

Mixed oil

Fractionating tower

Plastics Knapper

Diesel oil

Figure 17.5  Step-by-step pyrolysis procedure.

fuel oil extensively because it offers better thermal performance and specific fuel consumption. Materials are pyrolyzed to create renewable fuels that can be used as gasoline engine fuel. Dependent only on the quality, the resins used, and the decomposition method employed, waste plastic fuels can have a variety of chemical properties [26]. The two major disadvantages of using waste gasoline in a gasoline engine are insolubility and poor caloric density. High-density polythene is known to have a straight lengthy architecture without limited branches and a great amount of crystallinity, which results in exceptional durability properties. High-density polythene is among the largest contributors of plastic wastes, with predictions that, by 2025, there would be a world market for almost 105 billion metric tons of the material [27]. Very dense alkaline solutions, weak bases, and lubricates are well withstood by polyethylene. It is often used to make dairy jars, lubrication oil canisters, shampoos and bottle caps, recyclables, and supermarket sacks, among many other items, owing to its favorable durability. Waste products made of high-density polythene have promising basis to be used as pyro-fuel and may be reused repeatedly. Any catalysts are used to influence the conversion during catalyzed reactions. Scrap is pyrolyzed using a variety of chemical processing parameters, including temperature, extraction temperature, catalyst used, particle density, storage time, humidity level, and material mixture. This approach has demonstrated a high possibility of converting artificial trash into petroleum and an enhanced quality with less reaction exposure times than had been originally understood, as compared to fast decomposition.

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426  Clean and Renewable Energy Production

The impacts of only using exotic alloys as catalysts—materials that can accelerate the transition process with changing the key processing parameters such as temperature and humidity—have been examined by certain researchers in an attempt to enhance the process. It was observed that 90% of the total plastic garbage may be converted into fuel in only 1 h [28] at a relatively low temperature of 220°C utilizing organometallic metals and carbon as catalysts. Comparing this situation to the existing recycling and recovery standards has revealed how far more convenient and cost-effective this process is.

17.4.2 Biochemical Conversion Bioconversion and digesters are two examples of bioconversion mechanisms. Relative to exothermic reactions, these reactions take place at reduced temperatures and slow response levels. Wastage and other higher humidity bioproducts are typically excellent choices for biological mechanisms. Biomass conversion entails converting biomass to produce liquid or gas biofuels, such as methane or bioenergy, using microbes and catalysts [29]. Despite the absence of oxygen, this anaerobic treatment procedure generates gas primarily composed of both methane and carbon dioxide, and the occasional addition of humidity, sulfur dioxide, ammonium, methadone, and particulates. Anaerobic digestion can occur in regulated units, in-vessel biogas plants, graves, or dung dumps (closed or otherwise). One major energy output in anaerobic digestion processes is biogas. With rotary or combustion engine, turbomachinery, or hydrogen fuel, bioenergy can be turned into power or directly used to heat water or steam [30]. In addition, gas can be converted into biomass fuels and Gas utilization: Electricity generation and/or heat

Gas Handling

Manure Source And collection

Manure handling

Manure handling

Digester

Manure storage

Figure 17.6  Full structural diagram of biochemical conversion.

Land application

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Waste-to-Energy Technologies for Energy Recovery  427

Feedback logistics

Biochemical Conversion

Biofuels Distribution

Heat and Power Lignin Residue Combustion

Processing and Handling

Gasification

Gas Cleanup

Gas Conditioning

Fuel Synthesis

Figure 17.7  Systematic diagram illustrating fuel synthesis.

utilized as transportation fuels, added to the fossil fuel network, or transformed into liquid hydrogen. The liquid–vapor leachate from anaerobic digestion may be used as a liquid or dried fertilizer, a composting material, or a soil conditioner.

17.4.3 Thermochemical Conversion Progress is necessary to bring new economically viable methods toward lowering the social and ecological issues related to the existing treatments of sewer sludge due to the increased inequality for activated sludge. Effluents can be transformed into valuable goods or used as a fuel source. The discussion of sludge valorization methods involves hard rock extraction from sludge, charcoal creation, the processing and application of adsorbents, and the use of burning ash of wastewater in structural concrete. Hydrothermal methods, including decomposition, founder, or enzymatic thermal decomposition, as well as roasting and burning for processing optimization, power generation through activated sludge, or resource conservation, are therefore analytically examined. Regarding powerplants, proper disposal devices, and pollutants, the burning of sludge is examined. For the very first time, reactor methods are also examined in thermal decomposition affected by technological prowess

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428  Clean and Renewable Energy Production

and commercial viability with both the particular device and the sewerage waste. Several drying methods, programmable logic controller (PLC), enzymatic methods, reaction mechanisms, engine systems, operational parameters that can be adjusted, impurity elimination, fuel attributes, their limitations, and necessary changes are all compared critically [31]. The research focuses on promoting sustainable development enabling processing optimization and infrastructure extraction from decomposition, roasting, and burning using acquits from sludge dewatering and wastes, which seem to have the ability to be utilized for power generation. Sludge regenerative braking alternatives, including combustion, have been proposed as alternatives to the currently highest rated technique. Both technical and sociological benefits and drawbacks within each fast pyrolysis method are covered. Compared to conventional procedures, heat transfer transformation may well have superior business application success, greater productivity, and much more reduction of waste. This is despite the fact that it requires sophisticated instruments or methods. The advantages and disadvantages of physiological sources, the company expenses, and the working circumstances for hydrothermal and bacterial approaches have been recently thoroughly compared [32]. In comparison to exothermic reactions, it was found that the digestate requires a particulate duration of several months, a significant area for the biogas plant, a small range of choices, and increased cash expenditure. Rapid degradation of organic contaminants, effective neutralization of Thermochemical Conversion

ADVANTAGES: • Shortened Duration • Low Cost • Reduced tar

Biomass

AAEMs zeolites Acid and Base Ni-based Transition metal

Air Gas

Figure 17.8  Systematic diagram of thermochemical conversion.

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Waste-to-Energy Technologies for Energy Recovery  429

organisms, and reduced amount of waste are all benefits of gasification. The end results of sludge decomposition are synopsis; charcoal; bright vapors comprising hydrogen, carbon, and methane; and gases including carbon dioxide. Fragments of parts 1. Concentration of humidity: There are various types of sludge, including basic, trash processed, or processed gunk, all of which could be used to generate electricity. The clarified liquid is separated and considered biodegradable, resulting in activated sludge, which appears like a slush and contains a significant amount of water. Prior to using the activated sludge to dumping or thermodynamic efficiency, the humidity must be decreased to a minimum utilizing one of the current treatments. 2. Using thermochemistry to extract the maximum power from sludges: Although effluents are recognized to have considerable humidity and ash, heavy metal, and contaminant concentrations, they also have a large amount of usable power. The methods for regenerative braking include physiochemical approaches. Anaerobic treatment, a type of bioremediation for energy recovery using sludge, brings benefits from a cost perspective, but will have negative environmental effects due to the release of contaminants [33]. 3. Thermal decomposition without a catalyst: Since this converts sludge to generate oil, spore, and fuel (hydrogen and other gentle hydrocarbons) while emitting the same few toxins as possible, thermal decomposition is regarded as a beneficial activated sludge screening tool. Thermal decomposition is carried out in an inert environment at maximum operating temperatures [32]. In order to create the required development, vaporization entails the exothermic reaction of the solid components of sludge at a range between 400°C and 600°C inside an environment devoid of air (using atmospheric nitrogen and carbon dioxide). 4. Slurry from sewerage is burned: The thermal combustion of sludge in abundant air is indeed the topic of this chapter. Sludge burns in a manner that is generally comparable to those of other fuels. Both graphite and flammable liquids are burned at heating rates usually higher than that supplied by

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430  Clean and Renewable Energy Production

oxygenated blood. There are also three main goals of sludge burning: to produce hydropower and to reduce the impact of harmful substances already existing in the sludge.

17.4.4 Thermal Treatment Some negative consequences of humankind and industrialization include rising pollution levels, depletion of natural resources (due to the utilization of fossil resources for energy generation), and significant soil degradation and material contamination of both soil and water. This generation of garbage is a substantial consequence that is also rising steadily. For instance, the amount of urban pollution caused per person in nations went from 415 kg in 1980 to 580 kg in 2007 [10]. Among the biggest markets in the European Union is the garbage sector. The laws governing the garbage sector in the EU have always been at the level of supplementary regulation or legal principles (especially as rulings and directives). The delegated legislation of a European must be consistent with the level of the nation’s laws. Some of the fundamental practices for treating trash are laid out in Regulation 2008/98/EC. It prioritizes the prevention of creating trash. These laws, however, fluctuate depending on where in the world you are.

Common MSW

Waste gases

Hazardous and industrial waste

Sewage sludge

WASTE-TO-ENERGY CENTERS

Energy

Alternative fuel

Figure 17.9  Diagram of energy and fuel generation.

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Waste-to-Energy Technologies for Energy Recovery  431

In addition, the equipment for thermal sewage disposal with a throughput beyond a certain limit must comply with the Combined Preventive and Environment Protection criteria (Integrated Pollution Prevention and Control, IPPC) [12]. The fundamental tenet of the IPPC (Integrated Pollution Prevention and Control) is to control any significant long-term consequences that could have negative impacts on public health. Its primary goal is to prevent the protection of one essential aspect at the expense of another. Specific limitations on emissions or other quantifiable technical characteristics serve as the thresholds for all advanced technologies. The objective is to reduce overall emissions while optimizing feedstock density and energy use simultaneously, adhering to the principle of Best Available Techniques (BAT) - the most advanced and up-to-date technologies that prevent pollution at its source. Whether establishing technological advances or modifying old technologies, the concept mandates the use of the most up-to-date technology while adhering to the principle’s consideration. This Base Just on Bats for Incinerators outlines the most efficient techniques presently offered for the heat treatment of various wastes [13]. The endeavor that minimizes proper disposal supports the gradual advancement of technology focused on burning or any other methods of power generation using trash, even using garbage as a renewable fuel in some industries. The fundamental presumption for using trash for biodiesel production, as stated by Dvořák et al. [14], is that it has a suitable calorific value. Among such techniques, several heating procedures that result in combustibles or oils or the use of anaerobic techniques for the generation of methane were listed. Proper processing of such wastes is indeed the primary purpose of incineration facilities. Over history, tools that met extremely strict requirements for the integrity of the outgoing streams of a process needed to be added to the initial technology. Recently, requests to use the power inside the cremated trash were added to a law that governs this subject [15].

17.5 Conclusion Throughout this research, garbage was evaluated as a significant bioenergy and a global potential for power generation utilizing waste-to-energy. In addition, the various waste-to-energy amenities created so far, including their connection to the method statement, were discussed. Several instances from around the globe were given for this purpose. This suggests

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432  Clean and Renewable Energy Production

that waste has the ability to be used as a power source for both advanced and developing economies. However, it is obvious that there is not much knowledge exchange between such nations. There are different types of sensors available to create electricity using waste. Following refining and condensing, methane, via microbial phytoprocesses, can generate heat inside a furnace, electricity and heating in CHP, and diesel fuel. Using a different approach, immediate combustion of trash could lead to the generation of heat, which could then be used to generate power for machines. In addition, methane gas can be used as a source of environment-friendly energy, but this possibility has not been realized yet. Regenerative braking using trash is one technique to effectively and efficiently handle wastes. The quantity of wastes produced annually, which is now at 1.3 million tons, would rise to almost 200 million tons annually by 2025. The quantity of solid wastes could be viewed as a chance to acquire goods such as composting, recycled products, heat, or electricity.

References 1. European Union, Council Directive 1999/31/EC of 26 April 1999 on the landfill of waste. Off. J. Eur. Communities, L182, 1–19, July 1999. 2. International Solid Wastes Association, Energy from waste, state-of-the art report, www.wte.org. 3. Bonomo, A., WTE advances: The experience of Brescia, in: Keynote Presentation at the 11th North American Waste-to-Energy Conference, Tampa FL, April 2003. 4. Kiser, J. V. L. and Zannes, M., The 2002 IWSA directory of waste- to-energy plants. Integrated Waste Service Association, Washington DC, 2002. 5. Berenyi, E., Methane recovery from landfill yearbook methane recovery from landfill yearbook, 5th Edition, Governmental Advisory Associates, Westport, CT, 1999. 6. Themelis, N.J. and Kim, H.Y., Material and energy valances in a large-scale aerobic bioconversion cell. Waste Manage. Res., 20, 234–242, 2002. 7. Franklin Associates, The role of recycling in integrated waste management in the US, Rep. management in the US, Rep. EPA/530-R-96-001 EPA/530-R-96-001, USEPA, Munic. Industrial Waste Division, Washington, DC, 1995. 8. Themelis, N.J. and Gregory, A., Mercury emissions from high temperature sources in Hudson Basin. Proceedings NAWTEC 10 Proceedings NAWTEC 10, Solid Wastes Processing Division, ASME International, pp. 205–215, May 2002.

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Waste-to-Energy Technologies for Energy Recovery  433

9. Tchobanoglous, G., Theisen, H., Vigil, S., Integrated solid waste integrated solid waste management management, Chapter 4, McGraw-Hill, New York, 1993. 10. Zitney, S.E., Process/equipment co-simulation for design and analysis of advanced energy systems. Comput. Chem. Eng., 34, 9, 1532–1542, 2010. 11. Donatelli, A., Iovane, P., Molino, A., High energy syngas production by waste tyres steam gasification in a rotary kiln pilot plant. Experimental and numerical investigations. Fuel, 89, 10, 2721–2728, 2010. 12. Klemeš, J., Dhole, V.R., Raissi, K., Perry, S.J., Puigjaner, L., Targeting and design methodology for reduction of fuel, power and CO2 on total sites. Appl. Therm. Eng., 17, 8–10, 993–1003, 1997. 13. Pavlas, M., Touš, M., Bébar, L., Stehlík, P., Waste to energy – an evaluation of the environmental impact. Appl. Therm. Eng., 30, 16, 2326–2332, 2010. 14. Dvořák, R., Chlápek, P., Jecha, D., Puchýř, R., Stehlík, P., New approach to common removal of dioxins and NOx as a contribution to environmental protection. J. Cleaner Prod., 18, 9, 881–888, 2010. 15. Donatelli, A., Iovane, P., Molino, A., High energy syngas production by waste tyres steam gasification in a rotary kiln pilot plant. Experimental and numerical investigations. Fuel, 89, 10, 2721–2728, 2010. 16. Fackler, N., Heijstra, B. D., Rasor, B. J., Brown, H., Martin, J., Ni, Z., Shebek, K. M., Rosin, R. R., Simpson, S. D., Tyo, K. E., Giannone, R. J., Hettich, R. L., Tschaplinski, T. J., Leang, C., Brown, S. D., Jewett, M. C., Köpke, M., 2021, June 7. 17. Periathamby, A. (2011). Chapter 8 - Municipal waste management. In T. M. Letcher & D. A. Vallero (Eds.), Waste (pp. 109–125). Academic Press. 18. Periathamby, A., Chapter 8 - Municipal waste management, in: Waste, T.M. Letcher and D.A. Vallero (Eds.), pp. 109–125, Academic Press, 2011. 19. Björklund, A., Dalemo, M., Sonesson, U., Evaluating a municipal waste management plan using orware. J. Cleaner Prod., 7, 4, 271–280, 1999. 20. Psomopoulos, C.S., Bourka, A., Themelis, N.J., Waste-to-energy: A review of the status and benefits in USA. Waste Manage., 29, 5, 1718–1724, 2009. 21. Kothari, R., Tyagi, V.V., Pathak, A., Waste-to-energy: A way from renewable energy sources to sustainable development. Renewable Sustainable Energy Rev., 14, 9, 3164–3170, 2010. 22. Sabbas, T., Polettini, A., Pomi, R., Astrup, T., Hjelmar, O., Mostbauer, P., Cappai, G., Magel, G., Salhofer, S., Speiser, C., Heuss-Assbichler, S., Klein, R., Lechner, P., Management of municipal solid waste incineration residues. Waste Manage., 23, 1, 61–88, 2003. 23. Eboh, F.C., Andersson, B.-Å., Richards, T., Economic evaluation of improvements in a waste-to-energy combined heat and power plant. Waste Manage., 100, 75–83, 2019. 24. Habibollahzade, A., Houshfar, E., Ahmadi, P., Behzadi, A., Gholamian, E., Exergoeconomic assessment and multi-objective optimization of a solar chimney integrated with waste-toenergy. Sol. Energy, 176, 30–41, 2018.

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434  Clean and Renewable Energy Production

25. Kunwar, B., Cheng, H.N., Chandrashekaran, S.R., Sharma, B.K., Plastics to fuel: A review. Renewable Sustainable Energy Rev., 54, 421–428, 2016. 26. Thahir, R., Altway, A., Juliastuti, S.R., Susianto, Production of liquid fuel from plastic waste using integrated pyrolysis method with refinery distillation bubble cap plate column. Energy Rep., 5, 70–77, 2019. 27. Faussone, G.C., Transportation fuel from plastic: Two cases of study. Waste Manage., 73, 416–423, 2018. 28. Wijesekara, T.A., Sargent, P., Ennis, C.J., Hughes, D., Prospects of using chars derived from mixed post waste plastic pyrolysis in civil engineering applications. J. Cleaner Prod., 317, 128212, 2021, ISSN 0959-6526. 29. Singh, A. and Olsen, S.I., A critical review of biochemical conversion, sustainability and life cycle assessment of algal biofuels. Appl. Energy, 88, 10, 3548–3555, 2011. 30. Gumisiriza, R., Hawumba, J.F., Okure, M. et al., Biomass waste-to-energy valorisation technologies: A review case for banana processing in Uganda. Biotechnol. Biofuels, 10, 11, 2017, https://doi.org/10.1186/s13068-016-0689-5. 31. Gao, N., Kamran, K., Quan, C., Williams, P.T., Thermochemical conversion of sewage sludge: A critical review. Prog. Energy Combust. Sci., 79, 100843, 2020. 32. Arvanitidis, I., Siche, D., Seetharaman, S., A study of the thermal decomposition of BaCO3. Metall. Mater. Trans. B, 27, 409–416, 1996. 33. Gao, N., Kamran, K., Quan, C., Williams, P.T., Thermochemical conversion of sewage sludge: A critical review. Prog. Energy Combust. Sci., 79, 100843, 2020. 34. Perera, S. M. H. D., Wickramasinghe, C., Samarasiri, B. K. T., Narayana, M., Modeling of thermochemical conversion of waste biomass – A comprehensive review. Biofuel Res. J., 8, 4, 1481–1528, 2021.

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Waste-to-Energy Technologies for Energy Recovery  435

Biodiesel Production, Storage Stability, and Industrial Applications: Opportunities and Challenges Girdhar Joshi Department of Chemistry, Sri Dev Suman Uttarakhand University Campus (Govt. P G College) Gopeshwar, Uttarakhand, India

Abstract

Energy has become the primary parameter for the social and economic growth indexing of any country. This has resulted in the explosive growth in the global energy demand in recent years. Conventional energy sources are not able to serve the current global energy demands. Thus, to combat the excess energy demand and the strict environmental regulations, researchers and investors have been forced to shift the energy paradigm toward the environment-friendly and renewable sources of energy. Biodiesel is one of the candidates of such environment-friendly and renewable sources of energy that has gained significant attention in recent years as a potential alternative for fossil diesel. This chapter focused primarily on the feasibility and challenges associated with sustainable biodiesel production technologies, as well as the various barriers and possible solutions in the effective commercialization of biodiesel in order to make it a sustainable alternative to conventional diesel. Keywords:  Biodiesel, storage stability, biodiesel production technologies, auto-oxidation

Email: [email protected] Surajit Mondal, Adesh Kumar, Rupendra Kumar Pachauri, Amit Kumar Mondal, Vishal Kumar Singh and Amit Kumar Sharma (eds.) Clean and Renewable Energy Production, (437–488) © 2024 Scrivener Publishing LLC

437

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18

18.1 Biodiesel More than 80% of the current primary energy demand of the entire world is met by petroleum-based fuel, out of which ~60% of the share is consumed by the transportation sector [1]. However, growing environmental concerns have imposed serious restrictions on fuel combustion emissions, which stimulated the development in the area of alternative sources of fossil fuel. Among the several alternatives, biodiesel has gained significant attention as one of the most promising sources derived from renewable sources with high quality, which allows the replacement of fossil diesel oil without engine modifications [2, 3]. Biodiesel not only is an alternative to diesel fuel, it is also well recognized due to various factors like renewability, sulfur-free and oxygenated nature, sustainability and biodegradability, nontoxicity, high flash point, and its eco-friendly nature when compared to conventional diesel fuel [2, 3]. Biodiesel can be easily blended with conventional diesel because the blended diesel demonstrates similar fuel characteristics to conventional diesel, but with significant reduction in harmful emissions [4–6]. Vegetable oils (edible and non-edible), algal oils, animal fats, waste cooking oils, and microbial oils are the potential sources of feedstock used for biodiesel production. These oils, upon treatment with alcohol (methanol/ethanol) in the presence of an acid or base catalyst, can be transformed into biodiesel and the high-value co-­ product glycerol (Scheme 18.1) [7]. The catalysts used for biodiesel production could be either acid or base and homogenous or heterogeneous. Homogeneous transesterification is a reversible chemical process in which reactants (oil + alcohol) are being mixed together with the catalyst, which is also a liquid acid or liquid base.

O O O O

R3

R1 R2 O

R1

+

R'OH

O

O

recation conditions

Alcohol

Scheme 18.1  Transesterification of vegetable oils.

OR'

R2

+

OH HO

OH

O R3

Triglyceride

OR' O

catalyst

OR'

Biodiesel

Glycerol

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438  Clean and Renewable Energy Production

18.2 Feedstocks for Biodiesel Production As stated, various types of feedstocks are available for biodiesel production, such as edible and non-edible oils, algal oils, animal fats, waste cooking oils, and microbial oils. These feedstocks are categorized into different generation feedstocks for biodiesel production. Although more than 350 feedstock sources have been reported in different scientific reports for the production of biodiesel, listing all of them in a single manuscript is quite difficult. Table 18.1 summarizes the potential feedstocks used for biodiesel production under different generations. Therefore, one has to be very ingenious in the selection of particular feedstocks for biodiesel production since it affects various factors, such as the cost of production, composition, purity, and the yield of biodiesel [3, 16]. The proper selection of feedstock can be done by analyzing various feedstock parameters such as oil content, suitability, chemical composition, and physical properties. The biomass sources/feedstocks for biofuel production are summarized in Figure 18.1. Feedstock selection for biodiesel production is also contingent on the region, availability, and the type of source (e.g., edible, non-edible, waste, etc.). For example, countries like the US and Brazil produce biodiesel from edible feedstocks, such as soya oil, sunflower oil, rapeseed oil, starch, and maize, and use this as diesel alternative in transportation. These countries could continue with this trend for the coming years mainly because of the sufficient availability of these edible feedstocks. Whereas in Europe and tropical countries, the major sources for the production of biodiesel are palm oil and rapeseed oil [3, 4]. However, in developing countries, like India, China, etc., biodiesel production from edible sources has not received much attention. In these countries, the edible oil production is much less than its actual demand; therefore, the use of edible oils as a source of biodiesel feedstock competes with the food supply and results in a higher production cost. Therefore, other non-edible oils sources [e.g., Jatropha, Pongamia (karanja), mahua, algae, and sal, etc.] would be the proper choice of feedstock for biodiesel production. These feedstocks would eradicate the competition with food usage and also allow for compliance with the regional and ecological needs for biofuel [5, 10, 18]. Other important feedstocks such as waste cooking oil, animal fats, and microbial oils have also been used for biodiesel production [19–21]. Thus, depending on the feedstock development at various stages, the biodiesel is usually classified as first-, second-, third-, and fourth-generation biodiesel (Figure 18.2).

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Biodiesel Production, Storage, and Applications  439

Table 18.1  Potential feedstocks used for first-, second-, third-, and fourth-generation biodiesel production [3, 8–15]. S. no.

First generation

Second generation

Third generation

Fourth generation

1.

Soybean

2.

Sunflower

Jatropha (Jatropha curcas)

Microalgae

Genetically modified algae

Karanja (Pongamia pinnata)

Beef tallow

Yeast

3.

Rapeseed

4.

Palm

Neem (Azadirachta indica)

Poultry fat

Fungi

Sal

Pork lard

Cyanobacteria

5.

Palm seed

Castor (Ricinus communis)

Waste cooking oil

Photobiological processes

6. 7.

Olive

Rubber Seed (Hevea brasiliensis)

Lather tanning waste

Mustard

Mahua (Madhuka longifolia)

8.

Cottonseed

Jojoba

9.

Coconut

Tall

10.

Rice bran

Nagchampa

11.

Walnut

Chinese tallow seed

12.

Corn

Silybum marianum (Milk thistle)

13.

Canola

Nicotiana tabacum (Tobacco)

14.

Linseed

Sapindus mukorossi (Soapnut) (Continued)

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440  Clean and Renewable Energy Production

Table 18.1  Potential feedstocks used for first-, second-, third-, and fourth-generation biodiesel production [3, 8–15]. (Continued) S. no.

First generation

Second generation

15.

Peanut

Candlenut (Aleurites moluccanus)

16.

Radish

Polanga (Calophylluminophyllum L.)

17.

Sorghum

Bottle tree

18.

Agricultural waste

Yellow oleander

19.

Kusum (Carthamus tinctorius)

20.

Eucalyptus oil

21.

Linseed

22.

Mexican prickly poppy (Argemone mexicana)

23.

Coffee ground

24.

Moringa (Moringaoleifera)

25.

Cumaru

26.

Sea mango (Cerberaodollam)

27.

Tung (Vernicia fordii)

28.

Soapnut (Sapindus mukorossi)

Third generation

Fourth generation

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Biodiesel Production, Storage, and Applications  441

Biomass

Agro based Biomass

Waste biomass

Starch/sugar crops

1. 2. 3. 4.

Oil seed plants

Edible/non-edible oils Palm, soya, sunflower Jatropha, Pongamia, Polanga

Aquatic plants Wood Grass

Grains Sugarcane Potatoes Corn

1. Sea weed 2. Algae, Water hyacinth 1. Switch Grass 2. Alfalfa

Agro waste

1. 2. 3. 4.

Straw Bagasse Corn Stover Sugarcane Tops

Forest waste

1. Saw Dust 2. Pine leaves 3. Pulp waste

Municipal/ Industrial waste

Figure 18.1  Sources of biomass feedstocks for biofuel production [17].

1st generation biofuels (Edible biomass)

2nd generation biofuels (Nonedible biomass)

4th generation biofuels (Futuristic, breakthrough technologies)

3rd generation biofuels (Nonedible, highly productive biomass)

Figure 18.2  Classification of biodiesel based on feedstock development.

The biodiesel produced from edible oils is known as first-generation biodiesel and the respective feedstocks as first-generation feedstocks. These edible feedstocks include soybean oil, rapeseed oil, palm oil, sunflower oil, peanut oil, corn, rice bran oil, coconut oil, olive oil, castor oil, etc. [2, 3]. The use of such edible feedstocks for biodiesel production was

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442  Clean and Renewable Energy Production

highly popular at the beginning of biodiesel development. However, serious concerns arose with these feedstocks, such as adequate availability of land for cultivation, biodiversity, and food supply, which restricted the use of such feedstocks for biodiesel production particularly in developing countries [15, 22]. In addition, the higher cost of feedstock and their intense growth specifications are some other disadvantages associated with their use [15, 18]. Furthermore, the extensive use of these feedstocks led to serious environmental issues such as soil and water contamination and increase in greenhouse gas (GHG) emissions due to violation of traditional agriculture patterns. These constraints have forced users to shift to non-­ edible feedstocks for biodiesel production as alternative sources [10]. The biodiesel produced from non-edible sources is categorized as secondgeneration biodiesel. Second-generation feedstocks include Jatropha oil, karanja oil, polanga oil, neem oil, sal oil, mahua oil, Nag Champa oil, rubber seed oil, Aleurites moluccanus, salmon oil, Madhuca longifolia, tobacco seed, sea mango, etc. [8, 23, 24]. In comparison to the first-­generation feedstocks, biodiesel production from second-generation feedstocks offered several benefits like less production cost, more eco-friendly in nature, eradicates food inequality, and less requirement of agriculture land for cultivation. However, some disadvantages are also associated with these feedstocks, as farmers have started cultivation of high-demand feedstocks like Jatropha, karanja, and jojoba in agricultural lands because of the lower plant yields of these feedstocks in non-agricultural lands. This has a direct influence on the food production and economy of society. Secondgeneration biofuel conversion technologies are also energy-intensive. Besides, the additional requirement of alcohol for biodiesel production from second-generation feedstocks is another drawback associated with it. Therefore, to maintain the balance between socioeconomics and biodiesel demand, researchers are paying attention to new alternate solutions, which are more economical and easily accessible at larger extents. The shortcomings associated with first- and second-generation feedstocks for biodiesel production were addressed with the development of the third-generation feedstocks. The biodiesel produced from microalgae is termed as third-generation biodiesel and the respective feedstocks termed as third-generation feedstocks [8, 14, 15]. The lesser greenhouse effect, excellent growth rate and productivity, lesser requirement of farming land, high lipid content, and lesser influence on food supply are some of the important merits of the biodiesel produced from microalgae. Because of their autotropic nature, algae have a strong mitigation potential against CO2 emissions [25]. Furthermore, due to two specific characteristics, algae also provide various valuable substrates for producing diverse fuels [25].

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Biodiesel Production, Storage, and Applications  443

The first characteristic is that algal oil can be easily converted into diesel fuel, or even gasoline components; the second characteristic is that the special fermentative bacteria can degrade the biomass for biobutanol production and also can be genetically manipulated to biobutanol, biomethane, bioethanol, vegetable oil, and jet fuel [26]. Biodiesel production from algae is still under the research stage, while technological knowledge for largescale production of biodiesel from algae is in the infancy stage. Therefore, the large-scale, economical, and sustainable production of algal biomass is still a bottleneck in its use. This is the major constraint for the commercial production of algal biodiesel. In addition, animal fats, pork lard, beef tallow, and waste cooking oils also come under the potential feedstocks for third-generation biodiesel production [3, 9, 15]. Among these waste oils and fats, animal fat is the most widely used feedstock for biodiesel production and is preferred over first- and second-generation feedstocks because the biodiesel produced from animal fats have high-octane number, non-corrosive nature, and greater sustainability [8, 26]. However, the major drawback associated with these waste oil-based feedstocks is the lack of sustainable technology for the commercial production of biodiesel. Furthermore, most of the animal fats possess a high concentration of saturated fatty acid, which increases the transesterification complexity [20]. Most recently, biodiesel can also be produced from genetically modified algae, yeast, fungi, cyanobacteria, and the related photobiological processes. It is considered as fourth-generation biodiesel. Genetically modified algae are used to enhance biodiesel production. This is achieved by using some common strategies such as improving the photosynthetic efficiency, increasing light penetration, and reducing photoinhibition [12, 14]. The ability of these genetically modified microorganisms to convert CO2 to fuel through significantly improved the photosynthetic process, as a result providing a much stronger mitigation potential against CO2 emissions and the reduction of GHGs as compared to third-generation feedstocks. The biodiesel produced through fourth-generation feedstocks also strives to have the lowest environmental impact compared to the other generations. However, this study is still in the early stages of development [14]. The commercial-scale production of biodiesel from fourth-generation feedstock is still under the early development stage due to the insufficient biomass production and high production costs [12]. However, the introduction of genetically modified algae has emerged as a promising feedstock to obtain customized characteristics of the desired algae, but the major consequence will be the uncertainty associated with the species and the unknown threats that they pose to the ecosystem [26]. Although numerous feedstocks have been used for the biodiesel production (Table 18.1), their availability in any region depends

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444  Clean and Renewable Energy Production

upon various factors such as the geographical location, regional climatic conditions, type of soil, and the agricultural practices prevalent there. In addition, complete life cycle analysis of an individual feedstock should be performed to assess the direct economic value of the feedstock, its environmental impacts, energy economics, land availability, employment creation, and the logistic and production costs [27, 28]. The production costs of biodiesel are also dependent on the end use of the other products formed, like the upgradation of glycerol [29].

18.3 Biodiesel Conversion Methods The success of biodiesel production technology using different feedstocks depends upon the fatty acid composition of the respective feedstock. The fatty acid composition is one of the most important parameters that ensure the sustainability of the biodiesel produced. The oil/fat sources used for biodiesel production are a mixture of saturated and mono- or polyunsaturated long-chain fatty acids. The respective proportions of these saturated and unsaturated fatty acids also affect the quality of biodiesel. The greater percentage of unsaturated fatty acids lowers the fuel characteristics of the biodiesel obtained. However, more than 350 feedstock sources have been reported in different scientific reports for the production of biodiesel [30]. It is quite impossible to summarize all in a single manuscript; however, some of the representative and commonly used feedstocks for biodiesel production are listed here. Table 18.2 displays the fatty acid composition of the representative feedstocks used for biodiesel production. Although there are various sources available for biodiesel production, the direct use of raw oil as fuel in diesel engines is not possible because of its high free fatty acid content, high viscosity, low volatility, auto-oxidation, and gum formation during storage and combustion [5, 16]. Therefore, the oils obtained from these feedstocks and animal fats need to be subjected to appropriate treatment to convert them into engine-­compatible fuel, i.e., biodiesel. Biodiesel can be prepared by three methods, namely, thermal cracking, micro-emulsion, and transesterification [7, 8]. Among these, the transesterification method is the most widely explored to convert these oils into biodiesel. It is defined as the reaction of a triglyceride (present in oil or fat) and alcohol (usually methanol or ethanol) with or without a catalyst to form biodiesel (i.e., fatty acid methyl esters, FAMEs) and glycerol (Scheme 18.1). The catalysts used may be alkaline, acidic, or enzymatic. Depending on the solubility of the catalyst in the solvent, both homogeneous and heterogeneous catalysts can be used for the transesterification reaction. Table 18.3 includes the various catalysts used

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Biodiesel Production, Storage, and Applications  445

Table 18.2  Fatty acid composition of various feedstocks for biodiesel production [31–34].

Feedstock

C14:0

C16:0

C16:1

C18:0

C18:1

C18:2

C18:3

0.0

6.5–10.58

0.0

Others

Edible oils Sunflower oil Soybean oil

Palm oil

1.0

Canola oil

4.76–5.8

22.5–27.0

8.19

8.19

10.4–24.8

2.6–4.7

16.5–24.8

51.8–53.0

6.5–7.0

37.8–43.8

2.7–4.8

39.9–42.6

5.6–12.2

0.2–0.55

5.6

2.5

72.98

18.16

Cottonseed oil

23.2

2.0-8.0

17.4

54.7

–

Rice bran oil

12.0-25.4

1.8–8.32

27.8–44.7

29.5–39.5

1.9–13.4

0.7–1.0

0.16–1.9

2.8–3.5

3.8–4.4

0.2 1.8–8.25

Non-edible oils Castor oil

0.01

Rapeseed oil

3.5–4.0

0.5–2.3

62.0–78.0

1.8–8.25

Jatropha oil

14.1–17.6

0.7

8.1

41.8

31.5

0.3

Karanja oil

2.2

–

4.8

61.2

25.2

6.6 (Continued)

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446  Clean and Renewable Energy Production

Table 18.2  Fatty acid composition of various feedstocks for biodiesel production [31–34]. (Continued) Feedstock

C14:0

C16:0

C16:1

C18:0

C18:1

C18:2

C18:3

Others

Chlorella protothecoides oil

4.72

0.55

1.78

62.4

20.64

6.85

9.2

Chlorella vulgaris oil

44.99

5.86

1.06

1.7

25.4

12.5

8.7

Spirulina oil

24.8

3.7

6.3

9.8

12.2

4.46

9.8

Microalgae oil

Waste oils Waste cooking oil

8.8

4.2

45.15

39.74

0.20

1.7

Waste sunflower oil

6.1

12.99

41.92

39.1

0.2

–

Waste animal fat Waste chicken fat

19.82

3.06

6.09

37.62

31.59

1.45

0.37

Waste tallow

3.10

23.8

2.6

27.7

47.2

2.6

0.80

5.10

Waste lard

1.3

23.7

2.2

12.9

41.4

15.0

1.0

2.4

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Biodiesel Production, Storage, and Applications  447

Table 18.3  Representative feedstocks, catalysts, reaction conditions, and biodiesel yield for biodiesel production. Feedstock

Catalyst (wt.%)

Alcohol-to-oil molar ratio

Temperature (°C)

Reaction time (h)

Biodiesel yield (%)

Reference

Sunflower

NaOH (1.0)

6:1

60

2

97.1

[29]

NaOH (0.6)

6:1

60

1

76–97

[35]

CaO (2.0)

12:1

60

2

99.6

[36]

CaO-based/gold nanoparticle (3.0)

9:1

n.a

3

94–97

[37]

Mg/La (5.0)

53:1

65

0.5

100

[38]

Mg/La (5.0)

53:1

R.T.

2.2

100

[38]

Pseudomonas fluorescens (10.0)

4.5:1

40

48

91

[39]

WO3/ZrO3 (3.0)

20:1

200

5

97

[40]

Zeolite-X (4.2)

6:1

60

7

95

[40] (Continued)

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448  Clean and Renewable Energy Production

Table 18.3  Representative feedstocks, catalysts, reaction conditions, and biodiesel yield for biodiesel production. (Continued) Feedstock

Catalyst (wt.%)

Alcohol-to-oil molar ratio

Temperature (°C)

Reaction time (h)

Biodiesel yield (%)

Reference

Soybean

HCl (10.0)

20:1

70

45

65

[41]

H2SO4 (3.0)

6:1

120

1

95

[42]

H2SO4 (0.5)

9:1

100

8

99

[43]

H2SO4 (1.0)

30:1

65

69

>90

[44]

CaO (8.0)

12:1

65

3

95

[45]

CaO–K2O (15.0)

4.6:1

70

4

99

[46]

6:1

70

8

63

[48]

Ca(OC2H5)2 (3.0) Eu2O3/Al2O3 (10.0)

[47]

KI/Al2O3 (2.5)

15:1

65

8

96

[49]

KNO3/Al2O3 (6.5)

15:1

65

7

87

[50]

S–ZrO2 sulfated zirconia (5.0)

20:1

120

1

98.6

[51]

KOH/NaX zeolite (3.0)

10:1

65

8

85.6

[52]

Ca–Na2ZrO3 (1.0)

30:1

65

0.25

98.8

[53] (Continued)

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Biodiesel Production, Storage, and Applications  449

Table 18.3  Representative feedstocks, catalysts, reaction conditions, and biodiesel yield for biodiesel production. (Continued) Feedstock

Catalyst (wt.%)

Alcohol-to-oil molar ratio

Temperature (°C)

Reaction time (h)

Biodiesel yield (%)

Reference

Mg-Al hydrotalcite (7.5)

15:1

65

9

67

[54]

CalleraTM Trans L lipase (1.45)

4.5:1

35

24

96.9

[55]

LipozymeTL silica gel (0.06)

1:1

40

n.a.

90

[56]

LipozymeTL (0.04)

1:1

40

n.a.

66

[56] [57]

LipozymeRMIM (7.0)

3:1

4

50

60

Thermomyces lanuginosus (15)

7.5:1

31.5

7

96

[58]

NaOH (1.0)a

6:1

45

10 min

99

[59]

Ti(Pr)4Al(Pr)3 (3.0)a

6:1

60

2

64

[60]

KOH (0.5)a

6:1

26–45

0.5

90

[61]

Na or K (0.15)

6:1

45

1

100

[62]

CaO (7.0)a

10:1

62

1

90

[63]

NaOH (1.0)b

6:1

30

1 min

97.7

[64]

CaO (3.0)b

7:1

65

1

96.6

[64]

a

(Continued)

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450  Clean and Renewable Energy Production

Table 18.3  Representative feedstocks, catalysts, reaction conditions, and biodiesel yield for biodiesel production. (Continued) Feedstock

Catalyst (wt.%)

Alcohol-to-oil molar ratio

Temperature (°C)

Reaction time (h)

Biodiesel yield (%)

Reference

Palm

KOH (1.0)

6:1

60

1

96

[65]

NaOH (1.0)

6:1

60

0.5

95

[66]

CaO (9.0)

12:1

60

2

94–97

[67]

CaO functionalized with Sr (5.0)

9:1

65

0.5

98.4

[68]

Pseudomonas fluorescens (20.0)

18:1

58

24

98

[69]

KOH (n.a.)a

6:1

40

20 min

95

[70]

KOH (1.5–1.7)

11:1

35-40

n.a.

92

[71]

CaO (8.0)a

9:1

60

1

92.7

[72]

a

[HSO3-bmim]H2SO4 (9.17)

11:1

108

6.34 min

98.8

[73]

KOH (1.0)

6:1

65

2

96

[74]

KF/Eu2O3 (3.0)

12:1

65

1

92.5

[75]

Cellulose-derived sulfonated C (20.0)

20:1

65

6

93.4

[76]

b

Rapeseed oil

(Continued)

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Biodiesel Production, Storage, and Applications  451

Table 18.3  Representative feedstocks, catalysts, reaction conditions, and biodiesel yield for biodiesel production. (Continued) Feedstock

Cottonseed oil

Rice bran

Catalyst (wt.%)

Alcohol-to-oil molar ratio

Temperature (°C)

Reaction time (h)

Biodiesel yield (%)

Reference

Candida antartica (3.0)

4:1

35

12

95

[77]

KOH (1.0)b

6:1

50

5 min

93.7

[78]

CH3Ona (0.75)

6:1

65

1.5

96.9

[79]

TiO2/SO4−2 (2.0)

12:1

230

8

>90

[80]

KF-Al2O3 (3.0)

12:1

65

3

>90

[81]

Candida antartica (1.6)

4:1

50

24

95

[82]

KOH (1.5)b

6:1

60

7 min

92.4

[83]

CH3Ona (0.88)

6:1

55

1

83.3

[79]

HCl (10)

20:1

70

6

>90

[41] (Continued)

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452  Clean and Renewable Energy Production

Table 18.3  Representative feedstocks, catalysts, reaction conditions, and biodiesel yield for biodiesel production. (Continued) Feedstock

Catalyst (wt.%)

Alcohol-to-oil molar ratio

Temperature (°C)

Reaction time (h)

Biodiesel yield (%)

Reference

Castor oil

H2SO4 (0.2)

6:1

80

8

80

[84]

H2SO4 (1.0)

20:1

50

1

90.83

[85]

CH3Ona (1.0)

16:1

30

0.5

93.1

[86]

H2SO4 (1.0)

15:1

50

2.1

73.27

[87]

Ni-doped ZnO nanoparticles (11.0)

8:1

60

1

95.20

[88]

Liquid lipase Eversa® Transform (5.0)

6:1

35

>8

94

[58]

SiO2/50% H2SO4 (1.0)b

6:1

n.a.

0.5

95

[89]

SiO2/50% H2SO4 (1.0)

6:1

n.a.

25 min

95

[89]

Al2O3/50% KOH (1.0)

6:1

n.a.

5 min

95

[89]

H2SO4/C (5.0)b

12:1

65

1

94

[90]

AlCl3 (5.0)

24:1

100

18

98

[91]

Dolomite (calcined)

7.6:1

60

2.5

96.6

[92]

b b

Canola oil

(Continued)

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Biodiesel Production, Storage, and Applications  453

Table 18.3  Representative feedstocks, catalysts, reaction conditions, and biodiesel yield for biodiesel production. (Continued) Feedstock

Jatropha

Catalyst (wt.%)

Alcohol-to-oil molar ratio

Temperature (°C)

Reaction time (h)

Biodiesel yield (%)

Reference

Li/TiO2 (5.0)

24:1

65

3

98

[93]

CaO (5.3)a

7.5:1

60

2.5

99.4

[92]

KOH (1.0)

6:1

50

2

97.1

[94]

KOH (2.0)

6:1

60

1

80.5

[95]

NaOH (1.0)

6:1

60

1

98

[96]

NaOH (3.3)

0.7:1

65

2

55

[97]

NaOH (0.8)

9:1

40

0.5

96.3

[98]

CaO (1.5)

9:1

70

2.5

93

[99]

CaMgO (4.0)

15:1

65

6

83

[100]

KNO3/Al2O3 (6.0)

12:1

70

6

84

[101]

Sr2+–CaO/MgO (5.0)

9:1

65

2

99.6

[102]

Pseudomonas cepacia (5.0)

4:1

50

8

98

[103]

CaO (5.5)a

11:1

64

n.a.

95

[104] (Continued)

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454  Clean and Renewable Energy Production

Table 18.3  Representative feedstocks, catalysts, reaction conditions, and biodiesel yield for biodiesel production. (Continued) Feedstock

Catalyst (wt.%)

Alcohol-to-oil molar ratio

Temperature (°C)

Reaction time (h)

Biodiesel yield (%)

Reference

KOH (0.5)a

5:1

Ambient temperature

7 min

97.6

[105]

Activated C-supported heteropoly acid (20.0)a

20:1

60

40 min

87.3

[106]

NaOH (4.0)b

30:1

55

7 min

86.3

[107]

KOH (1.5)

7.5:1

65

2 min

97.4

[108]

KOH (1.0)b

6:1

65

10 s

90

[109]

b

CaO (3.0)

10:1

65

6 min

78.1

[23]

Al2O3/CaO (3.0)b

10:1

65

6 min

85.7

[23]

b

Fe2O3/CaO (3.0)

10:1

65

6 min

86.8

[23]

MnO2/CaO (3.0)b

10:1

65

6 min

93.4

[23]

b

ZnO/CaO (3.0)

10:1

65

6 min

99.1

[23]

CaO/P2O5 (4.0)b

18:1

n.a.

5 min

94

[110]

b

(Continued)

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Biodiesel Production, Storage, and Applications  455

Table 18.3  Representative feedstocks, catalysts, reaction conditions, and biodiesel yield for biodiesel production. (Continued) Feedstock

Catalyst (wt.%)

Alcohol-to-oil molar ratio

Temperature (°C)

Reaction time (h)

Biodiesel yield (%)

Reference

Karanja (Pomgamia pinnata)

KOH (1.0)

6:1

65

2

98

[111]

KOH (1.0)

10:1

60

1.5

92

[112]

Li/CaO (2.0)

12:1

65

8

94.8

[113]

H2SO4 (1.5)

6:1

55

1

87.2

[114]

ZnO–methanol/C

10:1

105

1.5

CaO (3.0)b

10:1

65

6 min

74.1

[23]

Al2O3/CaO (3.0)b

10:1

65

6 min

85.4

[23]

Fe2O3/CaO (3.0)

10:1

65

6 min

87.1

[23]

MnO2/CaO (3.0)b

10:1

65

6 min

93

[23]

b

ZnO/CaO (3.0)

10:1

65

6 min

97.8

[23]

KOH (0.75)

6:1

55

1

95.7

[114]

KOH (0.70)

6:1

60

0.5

98

[116]

KOH (1.0)

6:1

45

3

95

[117]

b

Mahua

[115]

(Continued)

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456  Clean and Renewable Energy Production

Table 18.3  Representative feedstocks, catalysts, reaction conditions, and biodiesel yield for biodiesel production. (Continued) Feedstock

Catalyst (wt.%)

Alcohol-to-oil molar ratio

Temperature (°C)

Reaction time (h)

Biodiesel yield (%)

Reference

Algae

NaOH (3.5)

8:1

50

1.22

87.42

[118]

H2SO4 (3.36)

8:1

50

1

89.58

[118]

H2SO4 (100)

56:1

30

4

60

[119]

Sulfonated biochar (5.0)

10:1

100

1

98.2

[120]

H2SO4 (1.5)b

10:1

60

40 min

91.8

[121]

CaO (3.0)b

10:1

65

6 min

80.1

[23]

Al2O3/CaO (3.0)b

10:1

65

6 min

86.3

[23]

Fe2O3/CaO (3.0)

10:1

65

6 min

88.2

[23]

MnO2/CaO (3.0)b

10:1

65

6 min

96.7

[23]

ZnO/CaO (3.0)

10:1

65

6 min

99.8

[23]

b

b

(Continued)

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Biodiesel Production, Storage, and Applications  457

Table 18.3  Representative feedstocks, catalysts, reaction conditions, and biodiesel yield for biodiesel production. (Continued)

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458  Clean and Renewable Energy Production

Feedstock

Catalyst (wt.%)

Alcohol-to-oil molar ratio

Temperature (°C)

Reaction time (h)

Biodiesel yield (%)

Reference

Waste cooking oil

KOH (1.2)

6:1

60

2

95.8

[35]

KOH (1.0)

3:1

60

1

94

[19]

NaOH (0.6)

4.8:1

60

0.6

98

[122]

H2SO4 (5.0)

12:1

60

3

95.36

[19]

H2SO4 (4.0)

14.7:1

60

1

93.32

[123]

H2SO4 (1.0)

20:1

95

10

>90

[124]

Xylose-derived sulfonated C catalyst (10.0)

10:1

110

4

89.6

[125]

Zinc stearate immobilized on silica gel (3.0)

18:1

200

10

98.0

[126]

Novozym 435 (15.0)

3.8:1

12

44.5

100

[127]

Novozyme 435 (4.0)

3:1

50

30

90.9

[128]

(Continued)

Table 18.3  Representative feedstocks, catalysts, reaction conditions, and biodiesel yield for biodiesel production. (Continued) Feedstock

Catalyst (wt.%)

Alcohol-to-oil molar ratio

Temperature (°C)

Reaction time (h)

Biodiesel yield (%)

Reference

KOH (1.0)b

6:1

65

1

95.79

[129]

NaOH (3.0)

12:1

70

0.5 min

97

[130]

KOH (1.0)b

7:1

65

3 min

97.2

[129]

Sulfonated biochar-BS140 (10.0)b

10:1

140

10 min

72

[131]

Zr0.7H0.2PW12O40 (2.1)

20:1

65

24

87.5

[40]

Fe/Mn-doped tungstate/ molybdena (6)

25:1

200

8

92.3

[40]

Carbon based from starch (10)

30:1

180

6

92

[40]

b

n.a., not applicable. a Reaction carried out under ultrasonication. b Reactions carried out under microwave irradiation.

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Biodiesel Production, Storage, and Applications  459

for biodiesel production along with the optimized reaction parameters and respective biodiesel yields.

18.3.1 Homogeneous Catalysis The reactants and catalysts are in the same phase under homogeneous catalysis. Homogeneous transesterification is the most conventional method for biodiesel production. Both homogeneous alkaline and acid catalysts are used for the transesterification of fatty acids [132]. Homogeneous alkaline catalysts mainly include the alkali hydroxides or alkoxides. Ambient temperature and pressure conditions, faster conversion rate, and the cost-effectiveness of the process are the important advantages of the homogeneous transesterification of oils and fats using alkaline catalysts. However, non-recyclability, tedious separation of these homogeneous alkaline catalysts, and saponification are the major disadvantages associated with this method [19, 35]. It involves additional steps in the overall process and consequently increases the total cost of the production of biodiesel. In addition, the formation of water using hydroxides increases the total water content in biodiesel, thus reducing its performance as a fuel. However, this problem could be avoided to some extent by using the methoxides of sodium or potassium as homogeneous catalyst. Thus, careful removal of water via evaporation and chemical drying are the additional steps involved in biodiesel production. Homogeneous alkaline catalysts are only useful for the transesterification of oils or fats having free fatty acid (FFA) value less than 5%; above this limit of FFA content, saponification takes place, which causes separation problems [40]. The reaction mechanism for base-catalyzed reaction mechanism for the transesterification of triglycerides is shown in Figure 18.3. The transesterification of oils and fats is also investigated using homogeneous acid catalysts. The most common catalysts under this category include hydrochloric acid (HCl), sulfuric acid (H2SO4), sulfonic acid (H2SO3), boron trifluoride (BF3), and phosphoric acid (H3PO4) [19, 40, 41, 87]. In comparison to the alkaline catalysts, these acid catalysts are more lenient to the presence of water or moisture. Generally, during the two-step transesterification of oils and fats having higher FFA values, prior to completing transesterification by using alkali catalysts, the acid catalysts are often used to lower the FFA value in order to obtain better results. The acid-catalyzed transesterification process has several drawbacks, such as slow reaction rate, need of a high oil-to-alcohol ratio, high temperature requirement, and the corrosive nature of acids, which are the major constraints in its commercial application. Sometimes, the

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460  Clean and Renewable Energy Production

+

R'OH

RO-

B

+

O O R3

O R2 O

O

BH

R1

RO-

+

R3

O

O

OR R2 R1 O

O O O

O O

O +

OR'

R2

O

R3 O

BH

R1

O

- B

O OH

R1

O

O

R3 O

O

Figure 18.3  Homogeneous base (:B)-catalyzed reaction mechanism for the transesterification of triglycerides [40].

protonation of carbonyl carbon of the ester group may also cause the formation of carbocation that leads to the formation of new esters as a side reaction (Figure 18.4) [40]. In spite of its several disadvantages, this method has some merits as well, such as direct biodiesel production with OH

O O R3

R2 O

O O

Triglyceride

R3

R1

R3

R2 O

O O

O

O O

O

H+

H HO O R' O R2 R1 O

R'OH

R1 O

-H+

O

R3

H O O R' O R2 R1 O

O

O

O

OH R3

O

R1

O

O

O +

R2

O Diglyceride

OR'

Fatty acid ester

Figure 18.4  Homogeneous acid (H+)-catalyzed reaction mechanism for the transesterification of triglycerides [40].

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Biodiesel Production, Storage, and Applications  461

feedstock oils having low FFA values, its ability of perform the esterification and transesterification simultaneously, which results in high yields of biodiesel, and greater tolerance to the water present during the reaction. Table 8.2 summarizes the most common homogeneous acid and base catalysts used for biodiesel production.

18.3.2 Heterogeneous Catalysis In heterogeneous catalysis, the reactants and the catalysts are in different phases. Generally, the catalysts used in this category are in solid state; therefore, the transesterification reaction takes place at the surface of the catalyst used. Similar to homogeneous catalysts, heterogeneous catalysts are also categorized into acid and base heterogeneous catalysts. Heterogeneous catalysts have significant merits over homogeneous catalysts, as the former avoids the formation of soap, release of toxic effluents, and the problem of corrosion of the reactor material; the most important is that these catalysts can be reusable as well. These merits of heterogeneous catalysts make the overall process less energy-intensive, cost-effective, and more efficient [40, 132]. Homogeneous acid catalysts have been shown as effective for transesterification processes; however, some serious issues are associated with them, such as contamination with reactants, product recovery, and reactor damage due to their corrosive nature [19, 40, 87]. These constraints significantly raise the overall cost of production of biodiesel. However, heterogeneous acid catalysts are very stable, less sensitive to free fatty acids, able to perform the transesterification and esterification processed together, offer relatively easier purification and separation steps, are eco-friendly, and they can be recovered and reused for multiple cycles. These catalysts mainly include the metal oxides such as silica, alumina, oxides of tungsten, titanium, zirconium, molybdenum, etc., zeolites, heteropoly acids, metal sulfides, and cation exchange resins [40, 49, 51, 80, 132]. As stated above, the transesterification process takes place at the surface of heterogeneous catalysts; therefore, heterogeneous acid catalysts must have a large number of active sites to offer a large surface area. They also have moderate acidity, good water repellent property, and porosity in order to minimize diffusion problems [40, 132]. Similar to homogeneous acid catalysts, transesterification using heterogeneous acid catalysts also requires higher temperature and longer reaction time in order to obtain good conversion. The general reaction mechanism for heterogeneous acid-catalyzed transesterification is shown in Figure 18.5.

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462  Clean and Renewable Energy Production

O O R2

O Si

O O

O Si O

OR'

O M

O

R2

O

O Y

O O Si O O

Fatty acid ester +

YOH R2 R'

O

O Si

O O

O Si O

O M

O O O

O

Si O O

O

R1

* Y=

O

R3 O

O

O O

H O

Y

O Si

O O

O Si O

O M

O

O O O

R2 O Y

Si O O

R'OH

M = Zr/Hf

Figure 18.5  Heterogeneous acid (MO2+SiO2)-catalyzed reaction mechanism for the transesterification of triglycerides [40].

Among all the types of homogeneous and heterogeneous catalysts developed so far for transesterification reactions, the heterogeneous base catalysts have been extensively studied for transesterification across the globe. Their relatively lower solubility in alcohol, high catalytic activity, high basic strength, easy availability, simplified process, easy separation, low wastewater generation, relatively lower equipment expenditures, and reduced environmental impacts are the important reasons behind the wide acceptance and use of these heterogeneous base catalysts. The most commonly used heterogeneous base catalysts for transesterification include oxides of alkaline earth metals (CaO, MgO, SrO, etc.) and their various derivatives, mixed metal oxides of Ca and Mg, and alumina-­supported CaO and MgO. The hydrotelcite, K/γ-alumina, KF/Ca–Al, basic zeolites, alkali metal-loaded alumina, transition metal oxides (e.g., ZnO, TiO2, TiO2/SO4-2, ZnO and ZrO, and Na2MoO4) and their derivatives, and biomass-derived heterogeneous base catalysts have also been extensively studied recently [133, 134]. Catalyst leaching and moisture sensitivity are the

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Biodiesel Production, Storage, and Applications  463

major disadvantages associated with these heterogeneous base catalysts. The general reaction mechanism for heterogeneous acid-catalyzed transesterification is shown in Figure 18.6. Heterogeneous acid and base catalysts have provided a commercially efficient route for transesterification reactions as they complete the reaction in a shorter reaction time; however, the active molecules in heterogeneous catalysts are not completely accessible in the homogeneous system; as a result, the catalytic activity of the catalyst is reduced. These heterogeneous catalysts could not completely avoid the formation of undesirable products and the saponification of glycerides and methyl esters [30]. In addition to this, the surface active sites of the solid support further suppress the catalytic activity of the catalyst. These issues are addressed with the development of nanostructured heterogeneous catalysts. These nanocatalysts are preferred because of their large surface area and very high catalytic activity. These nanocatalysts have not only shown their high catalytic activity and selectivity but have also retained the catalyst separation and regeneration. They are also able to prevent the saponification and other side reactions during transesterification. These nanocatalysts act as a junction between heterogeneous and homogeneous catalysts; thus, these catalysts provide the desirable characteristics of both systems

R'OH M O

OH R3

O O R2

R1

O

+ O

O

R'

OR'

Fatty acid ester O R3

O O

O

R2 O R1

O

H

M

O O O R2 R3 O O R1 O O

O H M O

Figure 18.6  Heterogeneous base-catalyzed reaction mechanism for the transesterification of triglycerides [40].

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464  Clean and Renewable Energy Production

[132]. Nanozeolites, nano-hydrotalcites, calcium oxide nanocatalysts, magnesium oxide nanocatalysts, titanium nanocatalysts, and zirconium nanocatalysts are some of the representative nanocatalysts used in biofuel production. Various solid nanocatalysts have been reported for the efficient transesterification of oils and fats from different origins. These include the amorphous alumina nanocatalyst, mixed oxide SiO2/ZrO2, TiO2–ZnO nanocatalyst, Mn–ZnO nanocatalyst, heteropoly acid-based nanocatalyst, KF/CaO–Fe3O4, magnesium-doped magnesium aluminate (MgO/MgAl2O4), MgO–La2O3 nanocatalyst, ZrO2-loaded C4H4O6HK nanocatalyst, K2O/c-Al2O3 nanocatalyst, hydrotalcite nanocatalyst, and Ca/Al/Fe3O4 [40, 132].

18.3.3 Enzymatic Catalysis More recently, the use of biocatalysts (e.g., enzymes) in place of chemical catalysts has emerged as a newer and efficient approach for transesterification. In comparison to the conventional acid–base and chemocatalytic routes, the enzymatic route for biodiesel production has some significant advantages. The catalytic activity of enzymes remains almost unaffected by the free fatty acids and water present during the transesterification process. The enzymatic route also requires relatively milder reaction conditions and lower alcohol-to-oil ratio; more importantly, this route is the most ­environment-friendly among all routes [132, 135]. Lipase (i.e., triacylglycerol acyl hydrolases obtained from plants, animals, and microorganisms) is one of the most widely explored biocatalysts for enzymatic transesterification. Aspergillus niger, Burkholderia cepacia, Candida antarctica, Candida rugosa, Mucor miehei, Pseudomonas cepacia, Pseudomonas fluorescens, Rhizopus oryzae, Rhizomucor miehei, and Thermomyces lanuginosus are some of the commonly named microorganisms used as the lipase source [136, 137]. Although the enzymatic route has several advantages over conventional chemocatalytic routes, the use of free enzymes as catalysts has some problems regarding their stability under the reaction conditions, the product separation, and the catalyst recovery. These issues raise the economics associated with the enzymatic route, thus becoming the major constraints in the large-scale application of enzymatic methods [137]. To overcome these issues, the alternative is the use of the immobilization of enzymes on the solid support. The immobilization of enzymes on solid support provides greater thermochemical stability, easy separation and recovery of catalyst, and restricts the enzyme molecules from denaturation.

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Biodiesel Production, Storage, and Applications  465

However, the possibility of change in the enzyme shape during immobilization and the limited support material availability are some of the concerns associated with this method [136, 137].

18.4 Physicochemical Properties of Biodiesel Since biodiesel has diesel-like fuel characteristics, prior to its use (directly or in blended form) as fuel in combustion engines, it needs to be characterized to ensure that it meets the fuel standards/specifications issued by various regulatory agencies (Table 18.4). The physical properties of a fuel, such as the density, viscosity, flash point, cloud point, pour point, and oxidation behavior, are affected by the environmental or climatic conditions of the different geographical regions. Thus, these fuel standards/specifications are set by authorized agencies keeping in mind the environmental or climatic conditions of the geographical regions where the biodiesel fuel or any fuel will be utilized. Thus, biodiesel must retain its physicochemical properties during its storage and application in combustion engine. Any changes in the physicochemical properties of biodiesel hinder its use as fuel. The important physical properties of biodiesel obtained from various feedstocks, along with the recommended fuel specifications, are summarized in Table 18.5.

18.5 Storage Stability of Biodiesel The thermal and storage stability of biodiesel is one of the important criteria concerning its fuel properties. Due to the presence of unsaturated fatty acid(s) in biodiesel (irrespective of the feedstock and methods used for biodiesel preparation) (Table 18.2), the stability of biodiesel is lower than that of common diesel fuel. The presence of these unsaturated fatty acids leads to the formation of deposits and the darkening of fuels as a result of the formation of contaminants, such as alcohols, aldehydes, acids, peroxides, which occurs during long-term storage of biodiesel fuel. Various processes such as auto-oxidation, photo-oxidation, hydrolysis, thermal decomposition, contamination of impurities, storage tank material, presence of trace metals, and exposure to light are primarily responsible for these side reactions or by-product formation that change the fuel properties considerably during long-term storage of biodiesel [138] (and references therein).

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466  Clean and Renewable Energy Production

Table 18.4  Fuel standards for biodiesel and diesel [138]. Biodiesel Europe

Germany

USA

India

Petroleum diesel

EN 14214:2003

DIN V 51606

ASTM D 6751-07b

BIS (P)

EN 590:1999

0.86–0.90

0.875–0.90

0.85–0.90

0.87–0.90

0.82–0.845

Viscosity 40°C (mm2/s)

3.5–5.0

3.5–5.0

1.9–6.0

3.5–5.0

2.0–4.5

Flashpoint (°C)

120 min

110 min

93 min

>100

55 min

CFPP (°C)

*Country specific

Summer, 0 Spring/autumn, −10 Winter, −20

–

–

*Country specific

Cloud point (°C)

–

–

*Report

–

–

Sulfur (mg/kg)

10 max

10 max

15 max

0.035

350 max

Water (mg/kg)

500 max

300 max

500 max

500 max

200 max

Oxidation stability (h, 110°C)

6 h

–

3 h

6 h

N/A (25 g/m3)

Cetane number

51 min

49 min

47 min

>51

51 min

Acid value (mg KOH/g)

0.5 max

0.5 max

0.5 max

 oleic acid esters. The auto-oxidation of biodiesel is a free radical chain reaction that involves the three common steps of chain reaction, i.e., chain initiation step, chain propagation step, and chain termination step [143]. In the chain initiation step, the initiator decomposes into free radicals, which interact with the active molecule and transform them into reactive radicals. These reactive radicals under the propagation step combine with various other molecules to form different stable products and other reactive radicals. These reactive O O

OH

OH 9Z

12Z

Oleic acid

9Z

Linoleic acid

O

15Z

OH 12Z 9Z

Linolenic acid

Figure 18.7  Active allylic and bis-allylic positions in the unsaturated fatty acids present in biodiesel.

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470  Clean and Renewable Energy Production

radicals are converted into respective stable products in the termination step. The general mechanism of the radical chain reaction is shown below [143, 144]. 1) Chain Initiation RH

+

In

R

+

InH

2) Chain Propagation R

+

O2

ROO

ROO

+

R1H

ROOH

+

R1

RO

+

OH

ROOH ROO

+

H2 C C C C C H H H2 H2

H C C H2

H C C C C C H2 H H H2

C C C H H H2 O2

H C C H2 O H C C H2 O

C C C H H H2 O

+

H C C C C C H2 H H O H2 O

C C C H H H2

+

O

+ ROOH H C C C C C H2 H H O H2 O

R 1H H C C H2 O

C C C H H H2 OH

+

H C C C C C H2 H H O H2 HO

3) Chain Termination ROO

+

R1

ROO

+

R1OO

RO

+

R1

ROOR1 Carbonyls

RO R

+

R1

+

Alcohols +

O2

ROR1 +

R'CHO R

R

R1

R = unsaturated fatty acid R and R1 may be similar of different

In the case of the auto-oxidation of FAEs, the highly active hydrogen of the methylene group at the allylic and bis-allylic positions is abstracted by the radical initiator and generates resonance-stabilized carbon ­radicals— this corresponds to the chain initiation step. In the propagation step, the carbon radicals formed by the initiator combine with the oxygen molecules, resulting in the formation of peroxides. These peroxides further abstract the active methylene hydrogen, which leads to the formation of hydroperoxides and generates fresh stabilized carbon radicals and continues the

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Biodiesel Production, Storage, and Applications  471

propagation step until its termination. The termination step leads to the formation stable products. In addition, some other parallel reactions (such as addition–elimination reactions, rearrangement reactions, fragmentation reactions, and disproportionation reactions) also take place during the auto-oxidation of FAEs [145].

18.5.1 Addition–Elimination Reaction ROO

H2 C C C C C H2 H H H2

+

-ROOH

H C C H2

C C C H H H2

C C H2 H

H C C C H H2

(allylic radical of FAE)

H C C H2

C C C H H H2 + H2 C C C C C H2 H H H2

H C C H2

C C C H H H2 H2 C C H2

H C C C H2 H

new radical formed

These new radicals may also undergo cyclization and polymerization reactions. The allylic radicals formed during the addition–­elimination reaction may react with the O2 molecules, leading to the formation of ­peroxide radicals. These peroxy radicals can further react with double bonds of unsaturated fatty acids, which results in the formation of respective peroxide-linked dimers [145]. H C C H2

C C C H H H2 +

O

C C C H H H2

O

O O H C C H2 O

H C C H2 O

C C C H H H2

H C C H2 O

C C C H H H2

O

+

C C C H2 H H

peroxide radical formed

H2 C C H2

C C H2

C H

H2 C C H2

peroxide dimer

Thus, it is necessary to restrict these oxidative processes in biodiesel for its application as fuel. Therefore, the oxidation stability of biodiesel is a

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472  Clean and Renewable Energy Production

parameter of great importance for its commercialization and application as fuel. It is an inherent capacity of the biodiesel to resist the various chemical changes that occur during the long storage and deteriorates its fuel characteristics. It is noticeable from Table 18.5 that neat biodiesel does not meet the minimum prescribed value for the induction period (i.e., 6 h as per the ASTM). The poor oxidation stability of biodiesel can be improved by the addition of natural or synthetic chemical additives into the biodiesel [146, 147]. These antioxidants retard, control, or inhibit the auto-oxidation processes of fatty acid alkyl esters and reduce the formation of oxidized side products. Depending upon their oxidation inhibition characteristics, the antioxidants can be classified into two categories: primary antioxidants (or chain-breaking antioxidants) and secondary antioxidants (or hydroperoxide decomposer antioxidants). Primary antioxidants do not inhibit the radical initiation reaction of biodiesel degradation; however, they act as free radical scavengers that inhibit the oxidation during the propagation step. The allylic or bis-allylic carbon radicals formed after the initiation steps are highly reactive and react with O2 molecules, resulting in the formation of reactive peroxy radicals, which, on subsequent abstraction of the active proton from bis-allylic carbon, results in the formation of hydroperoxide radicals. The antioxidants react with these peroxy and hydroperoxide radicals and discontinue the further propagation processes by forming stable molecules [148]. The general mechanism of the retardation of oxidation processes in biodiesel can be shown as: ROO

+

AH

ROOH

+

A

RO

+

AH

ROH

+

A

ROOH

+

ROOH

+

H

ROH

+

A A

ROA

+

H

Phenolic and substituted phenolic compounds, secondary aromatic amines, thiophenols, and natural antioxidants (tocopherols and flavonoids) are the commonly used primary antioxidants as biodiesel stability enhancers due to their low cost and easy availability. Pyrogallol, propyl gallate, tert-butyl hydroquinone (TBHQ), butylated hydroxy anisole (BHA), butylated hydroxy toluene (BHT), diphenylamine (DPA), and dodecyl gallate (DG) (Figure 18.8) are some of the most commonly used synthetic antioxidants studied for the improvement of biodiesel storage stability [24, 147, 149]. These additives can be used individually or in various proportions of their binary mixtures [24, 147, 149]. Figure 18.9 presents the mechanism

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Biodiesel Production, Storage, and Applications  473

HO

OH

OH

OH

OH

OH

HO O

HO

O Propylgallate

Pyrogallol

O

OH (TBHQ)

OH

O HO

2,6-di-tert-butyl-4methylphenol (BHT)

2-tert-butyl-4methoxyphenol (BHA)

N H diphenylamine

OH

HO OH

dodecylgallate

Figure 18.8  Commonly used synthetic antioxidants.

OH

OH

OH + ROO OH Pyrogallol (PY)

O

O ROOH

H O

OH I

OH II

Radical Stabilization

O

+

O

ROO ROOH

OH

3-hydroxycyclohexa3,5-diene-1,2-dione

ROO ROO

O

H O

OH

Figure 18.9  Mechanistic representation of the antioxidant behavior of pyrogallol [24].

for the inhibition of auto-oxidation of unsaturated fatty acids in the propagation step using pyrogallol as an antioxidant. Rawat et al. reported that, in comparison to the individual antioxidants, the binary combinations of antioxidants not only have shown their greater effectiveness to slow down the rate of auto-oxidation but also, due to the effective synergism between the antioxidants used, they improved the longterm storage stability of biodiesel significantly [24, 147, 149]. The general mechanism of the synergistic relationship between the binary antioxidant systems has also been discussed in these reports (Figure 18.10). The effectiveness of synthetic antioxidants toward biodiesel stabilization is also dependent upon their solubility in the biodiesel in which they are tested. It has been observed that those antioxidants that are completely

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474  Clean and Renewable Energy Production

OH

O HO

ROOH

OH

H HO

OH

OH

O

H OH

ROO

HO

O O

HO

OH

O

O

Figure 18.10  Mechanistic representation of the synergistic relation between antioxidants (pyrogallol and propyl gallate) [24].

soluble in FAEs are found relatively less effective in comparison to partially soluble antioxidants. This may be because, due to their lower solubility, these antioxidants are concentrated gradually from top to bottom in the biodiesel, thus preventing the oxidation process at the initiation stage in the surface and reducing the rate of propagation to the inner part of biodiesel [150]. Another method to improve the oxidation stability is the blending of biodiesel of different induction periods. In this method, the oxidation stability of the biodiesel with a low induction period could be improved without the addition of any antioxidant [151].

18.6 Combustion Characteristics of Biodiesel Combustion characteristics are another most important parameter for the commercialization and sustainable use of any fuel. Due to adverse impacts on the environment from harmful emissions and the strict environmental protection regulations, it has become highly essential for a fuel to pass the prescribed emission tests prior to its commercial application. The major emission gases from fossil diesel include carbon monoxide (CO), carbon dioxide (CO2), nitrogen oxide (NOx), unburned hydrocarbon (UBHC), and particulate matter (PM). These gases are primarily responsible for both environmental pollution and human health hazards [144, 152]. Among the various alternative fuels known so far, biodiesel is one of the most compatible fuels for existing diesel engines and can be used without any engine modifications. In comparison to fossil diesel, biodiesel has a higher cetane number (essential for better ignition quality), absence of sulfur and aromatic contents, excellent lubricity, excellent

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Biodiesel Production, Storage, and Applications  475

miscibility with diesel, comparatively more cleaner combustion profile due to its oxygenated nature, and has significantly lower GHG emission (except NOx emission), making it more acceptable than fossil diesel [153]. Several reports are available on the study of the combustion characteristics of biodiesel, most of them describing how much emission is reduced under the various engine operating conditions (such as the type of engine, cylinder pressure, start of combustion ignition delay, heat release, combustion duration, and mass burning) [152–155]. The results obtained from the above analysis were then compared with the emission characteristics of fossil diesel. Studies are also available on highlighting the effects of the different biodiesel–diesel blends on the emission characteristics, which are very helpful to understand the effects of engine operating conditions and feedstock types on the emission patterns. However, it is very difficult to state clearly the relationship between the feedstock type and the emission properties because, besides the feedstock type, the emission composition also depends on the various other parameters of the engine and its operating conditions. Therefore, to understand the relationship between the feedstock type and emission characteristics of biodiesel, it is essential to conduct the studies under similar or almost identical conditions and the results fairly compared [152, 155].

18.7 Conclusions and Future Perspectives of Biodiesel The increasing demand for alternatives to conventional fossil fuel fortified academics, researchers, and investors across the globe to seriously admit the potential of biodiesel as a promising renewable source of energy. This is due not only to its diesel-like fuel characteristics but also to its environmentally benign nature. The present chapter highlighted the diversity of feedstocks available, the various technological developments, advantages, constraints, and the future perspectives for biodiesel production and its potential application as fuel. Although significant development in the biodiesel production technologies, such as exploration of newer feedstocks, technological progress in biodiesel conversion and processing, and its commercialization, has already been done, many gray areas still need to be focused on to make biodiesel commercialization more economic and sustainable. Less availability and the higher cost of feedstock are the major challenges primarily faced by the biodiesel industry. The higher cost of feedstock accounts for most of the cost of biodiesel production, irrespective of the technologies used for its production. The selection of non-edible oils, microbial oils,

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476  Clean and Renewable Energy Production

waste oils and waste animal fats as biodiesel feedstocks has somewhat addressed the cost issue. However, the presence of a higher amount of impurities and the high FFA and water contents in these low-cost feedstocks demand the use of additional pretreatment, product separation, and purification steps during biodiesel production, thus increasing the overall biodiesel production cost. The fluctuating feedstock market is yet another constraint responsible for irregular biodiesel costs. Thus, to ensure the continuity in feedstock availability and thus biodiesel production, there is a need to identify potential feedstocks that are locally available throughout the year. In addition, many technical constraints are also responsible for the economic commercial production of biodiesel, such as efficient and reusable catalysts, downstream processing, and effective utilization of the by-products formed. Since the biodiesel technologies are still under the research and development stage, the continuous introduction of newer technologies obsoletes all the instruments and prior investment. Therefore, such hidden financial risks are also associated with biodiesel production. Biodiesel production from microbial oils is emerging with excellent future perspectives in comparison to many of the first- and second-generation terrestrial feedstocks. There are many other potential renewable fuels, such as methane and bio-hydrogen, which can be produced with these microbial oil feedstocks with minimal environmental footprint. However, these technologies are yet to be further developed for their commercial production. Moreover, the success of sustainable biodiesel production at the commercial level could not be achieved without the active participation and support of the government for the improvement and advancement of these technologies. Biodiesel industries must collaborate with the leading research institutions to address the technological gray areas in this section. Finally, the future of the biodiesel industry will be impacted by the price of crude oil and the availability of alternative fuels.

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Biodiesel Production, Storage, and Applications  477

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478  Clean and Renewable Energy Production

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Biodiesel Production, Storage, and Applications  487

1 45. Frankel, E.N., Lipid oxidation, 2nd Edn, A volume in Oily Press Lipid Library Series, Woodhead Publishing Limited, Cambridge, UK, 2005, ISBN: 9780953194988. 146. Knothe, G., Structure indices in FA chemistry. How relevant is the iodine value? J. Am. Oil Chem. Soc., 79, 847–854, 2002. 147. Rawat, D.S., Joshi, G., Pandey, J.K., Lamba, B.Y., Kumar, P., Algal biodiesel stabilization with lower concentration of 1:3 ratios of binary antioxidants – key factors to achieve the best synergy for maximum stabilization. Fuel, 214, 471–479, 2018. 148. Varatharajan, K. and Pushparani, D.S., Screening of antioxidant additives for biodiesel fuels. Renew. Sustain. Energy Rev., 82, 3, 2017–2028, 2018. 149. Chen, Y.-H. and Luo, Y.-M., Oxidation stability of biodiesel derived from free fatty acids associated with kinetics of antioxidants. Fuel Process. Technol., 92, 7, 1387–1393, 2018. 150. Romola, C.V.J., Meganaharshini, M., Rigby, S.P., Moorthy, I.G., Kumar, R.S., Karthikumar, S., A comprehensive review of the selection of natural and synthetic antioxidants to enhance the oxidative stability of biodiesel. Renew. Sustain. Energy Rev., 145, 111109, 2021. 151. Karavalakis, G., Hilari, D., Givalou, L., Karonis, D., Stournas, S., Storage stability and ageing effect of biodiesel blends treated with different antioxidants. Energy, 36, 1, 369–374, 2011. 152. Palani, Y., Devarajan, C., Manickam, D., Thanikodi, S., Performance and emission characteristics of biodiesel-blend in diesel engine: A review. Environ. Eng. Res., 27, 1, 200338, 2022. 153. Tamilselvan, P., Nallusamy, N., Rajkumar, S., A comprehensive review on performance, combustion and emission characteristics of biodiesel fuelled diesel engines. Renew. Sustain. Energy Rev., 79, 1134–1159, 2017. 154. Kim, D.S., Hanifzadeh, M., Kumar, A., Trend of biodiesel feedstock and its impact on biodiesel emission characteristics. Environ. Prog. Sustain. Energy, 37, 7–19, 2018. 155. Mohamed, M., Tan, C.-K., Fouda, A., Gad, M.S., Abu-Elyazeed, O., Hashem, A.-F., Diesel engine performance, emissions and combustion characteristics of biodiesel and its blends derived from catalytic pyrolysis of waste cooking oil. Energies, 13, 5708, 2020.

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488  Clean and Renewable Energy Production

Biomass Energy and Its Conversion Naval V. Koralkar1*, Mohit Kumar2, Raj Kumar1 and Praveen Kumar Ghodke3 Department of Chemical Engineering, ITM (SLS) Baroda University, Vadodara, Gujarat, India 2 University of Nebraska Medical Center, Omaha, USA 3 Department of Chemical Engineering, National Institute of Technology Calicut, Kozhikode, Kerala, India 1

Abstract

Biomass has evolved as a sustainable and renewable energy source due to its wide variety of sources and easy accessibility throughout the world. For the sustainable generation of power, fuels, and chemicals, biomass resources present a very potential alternative to fossil fuels. However, choosing the optimal use for biomass is a difficult decision because there are numerous alternative feedstocks and conversion paths, each of which has a unique economic and environmental performance. The adoption of conventional biomass-to-energy technologies has benefited nearby populations. This strategy, nevertheless, results in high pollution levels, degraded forests, and deforestation. Recent technological advancements and increased availability have made it possible to use biomass as a renewable energy source with little negative environmental effects. Fuels made from biomass might take the form of biogas, bioliquid, or biosolid fuels. It can take the place of fossil fuels in the transportation and electricity industries. The present chapter critically discusses the major biomass conversion technologies that are in use today and those that may be important in the future. This would enable important personnel from governments, legislators, and others involved in power generation to focus on the problem of increased energy demand. It is believed that the daily energy consumption growth is being accompanied by the expansion of the world economy. The energy produced using biomass has the capacity of replacing the expensive fuel used in nearby industries. Keywords:  Biomass, renewable energy, conversion techniques, modeling *Corresponding author: [email protected] Surajit Mondal, Adesh Kumar, Rupendra Kumar Pachauri, Amit Kumar Mondal, Vishal Kumar Singh and Amit Kumar Sharma (eds.) Clean and Renewable Energy Production, (489–504) © 2024 Scrivener Publishing LLC

489

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19

19.1 Introduction Nowadays, energy consumption is enormous and a crucial component of a country’s progress, and a lack of energy has turned into a threat to the economic development of countries all over the world [1, 2]. However, not everyone has access to contemporary energy services despite their importance [3, 4]. Due to global population increase, continued economic development, and technological improvement, today’s energy needs are on the rise [4]. Humans have used biomass as a source of energy for several years, primarily in the form of wood. Direct combustion has historically been used to utilize biomass, and it is still widely employed in many regions of the world. Historically, biomass has been a distributed, labor- and land-­intensive energy source. Therefore, more convenient and concentrated sources of energy have replaced biomass as industrial activity has grown in many nations. The world’s fourth largest energy source is biomass [5]. Worldwide renewable energy targets are summarized in Table 19.1. The electric utility, the timber and wood products, and the pulp and paper industries all use energy derived from biomass fuels. A renewable energy source, wood fuel will become more significant in the future. There are three primary factors that affect how much it costs to build and operate a wood-fired power plant of a certain scale. They are the cost and delivery

Table 19.1  Worldwide renewable energy targets [6]. Source of renewable energy

1994 PJ

2000 PJ

2007 PJ

2020 PJ

Wind energy

2.06

16

33

45

Photovoltaic solar

0.01

1

2

10

Thermal solar

0.16

2

5

10

Geothermal

0

0

0

2

Cold/hot storage

0.02

2

8

15

Heat pumps

0.25

7

50

65

Hydropower

0.90

1

3

3

Biomass and waste

35.2

54

85

120

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490  Clean and Renewable Energy Production

of the fuel, the availability of the necessary fuel, and the finance and building of the needed power plant [6].

19.2 Sources of Biomass The global population is growing exponentially, and so is the demand for energy. This suggests that the energy supply in the future must come from renewable sources of energy due to the widespread depletion of fossil fuels and the steadily growing concern about environmental deterioration. One of the earliest and most sustainable energy sources is biomass. Organic waste is burned to produce it. In a dedicated waste-to-energy facility, it is burned to produce electricity. Wood and wood wastes, agricultural crops and their waste by-products, municipal solid trash, animal waste, food processing waste, aquatic plants, and algae are all examples of biomass resources. Wood and wood waste typically account for the majority of biomass energy production (64%), followed by MSW (24%), farm waste (5%), and landfill gases (5%) [7]. Our ecology, economy, and energy security may all be significantly improved by using biomass as a clean, renewable energy source [7]. In contrast to other alternative energy sources, biomass is a diverse resource that may be transformed into energy in a variety of ways. Plant matter, such as trees, grass, agricultural crops, or other living material, is referred to as biomass. It can be used as a solid fuel or transformed into liquid or gaseous forms to create fuels, chemicals, heat, or electricity [8]. Resources made from biomass can be classified as wastes, standing forest, and energy crops. Figure 19.1 shows the resources of biomass energy. Biomass Energy Resources

Wastes: 1. Agricultural production waste 2. Agricultural processing waste 3. Crop residues 4. Mill wood waste 5. Urban wood wastes 6. Urban organic wastes

Forest Products: 1. Wood 2. logging residue 3. trees, shrubs and wood residues 4. saw dust, bark etc. from forest clearings

Figure 19.1  Resources of biomass energy.

Energy crops: 1. short rotation woody crops 2. herbaceous woody crop 3. grasses 4. starch crops 5. sugar crops 6. forage crops 7. Oilseed crops

Aquatic plants: 1. algae 2. water weeds 3. water hyacinth 4. reeds and rushes

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Biomass Energy and Its Conversion  491

19.3 Techniques for Converting Biomass Into Energy The physical, thermal, and biological processes used to transform biomass into energy are considered conventional methods. Different kinds of biomass waste can be used as feedstock for these energy conversion processes. Figure 19.2 shows a brief description about techniques used for the generation of biomass energy.

Biomass Conversion Techniques

Heat/Electricity/Chemicals/Fuels Figure 19.2  Biomass energy generation techniques [9].

Briquetting

Cooking Stove

Gas

Biogas Plant

Physical Conversion

Engine

Distillation and Dehydration

Fermentation

Biological Conversion

Bio-ethanol

Steam Cycle

Gasification Fuel Cell

Combustion Engine

Gas Turbine Gas Turbine

Combustion

Thermal Conversion

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492  Clean and Renewable Energy Production

19.3.1 Thermochemical Conversion Thermochemical conversion, which involves carefully controlling the heating or oxidation of biomass, is a viable alternative method of producing bioenergy [10, 11]. The phrase refers to a number of processes, including pyrolysis, gasification, and combustion, which can be set up to generate heat, power, or gaseous or liquid precursors for conversion into liquid fuels or chemical feedstocks [12–16]. Utilizing thermochemical conversion techniques, the main goal is to produce fuels with increased calorific values. Raw rice husk, which is transformed into energy, is frequently utilized as a feedstock in this method. Figure 19.3 shows an outline of the conversion of biomass by thermal means. Pyrolysis, gasification, and liquefaction are all examples of thermochemical processes. Increased oxygen availability occurs during the reactions of pyrolysis, gasification, and combustion [17].

19.3.1.1 Pyrolysis The generation of liquid products, solid charcoal, and gaseous chemicals from biomass, or “bio-oil”, is known as pyrolysis. In chemists’ terminology, the pyrolysis procedure is referred to as an endothermic reaction and uses energy. The pyrolysis process, which includes all chemical alterations that take place when heat is applied to a substance without oxygen, forms the basis of thermochemical conversion. Water, charcoal (or, more accurately, a carbonaceous solid), oils or tars, and stable gases including methane, hydrogen, carbon monoxide, and carbon dioxide are all by-products of biomass pyrolysis. Pyrolysis, which is simply described as the chemical Thermal Conversion

Combustion

Gasification

Pyrolysis

Heat

Fuel Gases (CO+H2)

Liquids

Figure 19.3  Biomass conversion using thermal conversion.

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Biomass Energy and Its Conversion  493

changes that take place when heat is applied to a material in the absence of oxygen, is the basic chemical reaction mechanism that is the precursor of both the gasification and the combustion of solid fuels. The type of changes that occur during pyrolysis depends on the substance being pyrolyzed, the process’ final temperature, and the rate at which it is heated. Due to the poor heat conductivity of typical lignocellulosic biomass materials like wood, straws, and stalks, controlling the rate of heating necessitates that the particles being heated be fairly small. The yield of pyrolysis products is determined by the heating rate, which is otherwise very sluggish in huge materials like logs [18]. Pyrolysis will produce mostly char at low temperatures, less than 450°C, when the heating rate is fairly slow, and mostly gases at high temperatures, greater than 800°C, with rapid heating rates, depending on the thermal environment and the final temperature. The primary end-product is a liquid bio-oil, a relatively recent finding that is just now being used to commercial applications. It is produced at an intermediate temperature and under quite high heating rates [19]. Fast pyrolysis and slow pyrolysis (which includes torrefaction) are thermochemical processes where biomass is transformed mostly into a liquid or solid. Fast pyrolysis is typically used to maximize the liquid bio-oil product yield since the liquid bio-oil has a higher calorific value than ordinary biomass and can be handled more easily. The bio-oil can either be burned directly or modified so that it can be used as a fuel for vehicles. Another method for valuing the outcomes of quick pyrolysis is the extraction of special compounds from the bio-oil. The majority of the volatiles are removed from the biomass during slow pyrolysis to produce charcoal, a smokeless fuel that is still used extensively for cooking and heating. The yield of the solid product is maximized through the use of slow pyrolysis techniques. Charcoal producers have been utilizing the slow pyrolysis of wood at temperatures as high as 450°C for thousands of years. Torrefaction is a relatively mild kind of pyrolysis that occurs at temperatures of around 300°C. Here pyrolysis is only intended to eliminate a tiny fraction of the volatiles, specifically those produced when hemicellulose degrades. The solids produced have higher energy densities, are more hydrophobic, are grindable, and have lower biodegradability than the original biomass. Compared with biomass, these features enable better handling, transportation, and usage of the torrefied biomass inside the existing coal-based processes.

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494  Clean and Renewable Energy Production

19.3.1.2 Biomass Gasification Gasification is a process that turns biomass into a mixture of gases at a high temperature through a series of chemical reactions. In addition to hydrogen, carbon dioxide, carbon monoxide, and methane, this gas is flammable by nature. Gasification is a thermochemical process that results in the production of syngas, sometimes referred to as producer gas, product gas, synthetic gas, or synthesis gas. The major components of syngas are CO, H2, N2, CO2, and a few hydrocarbons (CH4, C2H4, C2H6, etc.). Tar, NH3, and extremely minute levels of H2S may also be present [20, 21]. In general, biomass gasification is the thermochemical conversion of organic (waste) feedstock in a high-temperature environment. Through this process, biomass can be converted to chemicals such as methane, ethylene, adhesives, fatty acids, surfactants, detergents, and plasticizers in addition to syngas for energy production [22]. Biomass gasification processes can be classified into air gasification (using air), oxygen gasification (using oxygen), steam gasification (using steam), carbon dioxide gasification (using carbon dioxide), and supercritical water gasification (using supercritical water), among others, depending on the gasification agents used. In general, higher HHVs of syngas are produced by oxygen gasification, steam gasification, carbon dioxide gasification, and supercritical water gasification than by air gasification. A gasifier is the location where the gasification reactions occur. A gasifier has a significant impact on the gasification reactions, procedures, and end products. Fixed bed gasifiers (also known as moving bed gasifiers), fluidized bed gasifiers, and entrained flow gasifiers are the three main categories into which gasifiers can be divided [20]. A few examples of the fixed bed gasifiers are updraft, downdraft, and horizontal draft. There are various types of fluidized bed gasifiers, including bubbling, circulated, double-circulated, etc. Details about the different types of gasification mentioned above can be found in literature [20].

19.3.1.3 Combustion Combustion is the oldest method of using biomass because it was discovered when civilization first emerged. Humans first learned how to cook and stay warm by burning wild wood. Combustion is a chemical process between oxygen and biomass’ hydrocarbons that produces heat. Here the biomass undergoes oxidation, resulting in the two principal stable

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Biomass Energy and Its Conversion  495

Thermochemical conversion Combustion

Steam

Steam Turbine

Gasification

Gas

Gas Turbine, Methanol/ combined engine Hydrocarbons

Fuel Cell

Heat

Biochemical conversion

Pyrolysis Liquefaction HTU

Gas

Oil

Charcoal

Upgrading

Diesel

Digestion

Fermentation

Extraction (Oilseeds)

Biogas

Gas engine

Distillation

Estrification

Ethanol

Bio-diesel

Electricity

Fuels

Figure 19.4  Principle methods for converting biomass to secondary energy sources [25]. Some categories represent a variety of technological ideas as well as the deployment capacities of those ideas.

molecules—H2O and CO2. With more than 90% of the energy from biomass coming from the reaction heat generated, it is currently the biggest energy consumer [22]. Figure 19.4 shows the principle methods for biomass conversion to secondary energy sources. The two primary sources of energy obtained from biomass are heat and electricity. Even in remote places, biomass still supplies heat for heating and cooking. Steam produced in biomass-fired boilers is frequently used for district or industrial heating. In many nations with frigid climates, direct sources of warming include fireplaces and stoves that burn wood. Using biomass combustion, electricity, the backbone of all contemporary economic activity, may be produced. The most popular method involves using a steam turbine to create power and burning biomass in a boiler to create steam. In a boiler, biomass is utilized either as a substitute for fossil fuels or in addition to them. The latter method is gaining popularity because it is the quickest and least expensive way to reduce carbon dioxide emissions from an existing fossil fuel plant [23].

19.4 Biochemical/Biological Conversion Biochemical conversion is the breakdown of biomass through anaerobic digestion, fermentation, or composting processes using the enzymes of bacteria or other microbes. The technologies for converting biomass into matching products by specific physical, chemical, and biological pretreatments

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496  Clean and Renewable Energy Production

are referred to as “biomass biochemical conversion.” The key distinction between the aforementioned physical and chemical conversion of biomass is that pretreatments in the biochemical conversion technologies of biomass are focused on assisting in achieving optimal conversion effects rather than producing final products. Additionally, compared with the other two biomass conversion processes, biochemical conversion is milder. By choosing different microorganisms in the process of biochemical conversion, biomass can be transformed into a variety of products, including hydrogen, biogas, ethanol, acetone, butanol, organic acids (pyruvate, lactate, oxalic acid, levulinic acid, and citric acid), 2,3-butanediol, isobutanol, xylitol, mannitol, and xanthan gum [23, 24]. On the one hand, such products can create synthetic alternatives to goods with a petroleum base. On the other side, the goods can take the place of goods made from grains, such ethanol. Biomass conversion technologies are mild, pure, clean, and effective when compared with other conversion methods. Additionally, using biochemical conversion methods, biomass can be converted into a variety of intermediates by testing various enzymes or microbes, offering a wide range of platform materials for the synthesis of renewable resources into fuels, chemicals, and other products. Due to these advantages, biomass conversion by means of biochemical technology has been widely used.

19.5 Physical Conversion In the physical method of conversion, the biomass is compressed into small briquettes. Physical route is used for making the biomass and waste suitable in usable form for its application in reactor or thermal application. Biomass and waste have less density, and it is difficult to handle in a reactive system. Physical process helps to make it harder to give some particular strength, making it easy to use in conversion processes like incineration, gasification, etc. The physical conversion of biomass and waste for energy use involves the process of densification of biomass and wastes. Densification is the process of increasing the density of something (in this case, biomass). It makes a fuel denser and gives more uniform properties with respect to its raw form. Densification can be carried out by means of compaction, compression, concretion, and concentration. The advantages of densification are as follows: 1. simplified mechanical handling and feeding 2. uniform combustion in boilers

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Biomass Energy and Its Conversion  497

3. reduced dust production 4. reduced possibility of spontaneous combustion in storage 5. simplified storage and handling infrastructure—lowering capital requirements at the combustion plant 6. reduced cost of transportation due to increased energy density The major disadvantage to biomass densification technologies is the high cost associated with some of the densification process. The details about the densification process can be found in literature [24, 26].

19.6 Power Plant Dynamic Modeling and Simulation Using Biomass as Fuel The following is how biomass is described by the United Nations Framework Convention on Climate Change [27]: “A non-fossilized and biodegradable organic material originating from plants, animals and micro-organisms. This shall also include products, by-products, residues and waste from agriculture, forestry and related industries as well as the non-fossilized and biodegradable organic fractions of industrial and municipal wastes”.

The use of biomass as fuel for the production of electric and thermal power has significantly risen during the past few decades [28]. The problems with the environment, energy, and labor policy are the sources of the reasons for this. Future energy planning must consider climate change mitigation in great detail. Carbon dioxide-neutral biomass-based fuels are an effective technique to hold back the increase of CO2 concentration in the atmosphere. The emissions of greenhouse gases should be decreased. Over 90% of the world’s contribution to bio-energy comes from burning biomass [28]. The design of a biomass combustion system is primarily influenced by the properties of the fuel that is readily available, regional environmental regulations, the cost and efficiency of the necessary equipment, and the required energy and capacity (heat and electricity). It takes an expensive fuel-feeding system, modern combustion technology, and a flue gas cleaning system to use low-quality fuels with inhomogeneous fuel properties, such as moisture content, particle size, and heating value, effectively and sustainably. Only in large-scale factories is this practically feasible.

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498  Clean and Renewable Energy Production

Typically, biomass is a domestic fuel that is grown close to the power station where it will be consumed. That is as a result of biomasses having a low energy density. Biomass cannot be transported over long distances economically for energy usage. For this reason, a study of the available biomass resources is crucial to the viability of an investment in a biomass-fired power plant. Up to 20 times more jobs are needed to harvest, transport, and prepare biomass for use as energy than, say, coal and oil [29]. Traditionally, simulation has been used to create processes, automate tasks, and train operators. Real-time process control and monitoring have expanded as a result of advances in computers and software engineering. Examples include tracking simulators, predictive simulators for operators’ decision support systems (what-if simulations), and simulators as a component of optimal process control. The three main advantages of simulation are as follows [30]: 1. test runs that cannot be carried out on a real plant due to financial or safety concerns, 2. tests conducted before the actual physical plant is finished, and 3. enabling the discovery and correction of design and configuration issues early during the factory acceptance tests before installations and test runs on the site. This reduces the effort and time needed for commissioning of the plant. Various software tools are used in research and development initiatives to generate data regarding the system under development’s attributes. The steady states of the process variables at various operating points are revealed by balance calculations based on static process models. The thermal power of the boiler, cooling water temperature, and ambient temperature are typical boundary conditions for a power plant process. Calculations of balances provide answers to queries concerning the impact of various process configurations and operational points on the plant’s capacity and efficiency. Because of the component’s geometric design, computational fluid dynamics (CFD) techniques can show how mass and thermal flows behave inside the process. In order to achieve the best combustion efficiency and necessary heat transfer capacity, CFD tools can be used to design the best structure, such as a boiler for a power plant. In order to describe the unique properties of the process, such as combustion, heat transfer, and emissions, boiler manufacturers typically use their own design tools, which include

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Biomass Energy and Its Conversion  499

computation routines for mass and heat transfer and numerous experimental equations.

19.6.1 Biomass Combustion Modeling In this section, focus is laid on the combustion properties of biomass and its implementation in the dynamic combustion model. Typically, during simulations, general issues of modeling heat transfer and other phenomena are ignored for all types of power plant. Different forms of combustion process and technical characteristics are a result of the properties of biomass. The variety of qualities in biomass is one of its key characteristics. Due to its component composition, heating value, and bulk characteristics like density, particle size, particle shape, etc., biomass is often a relatively inhomogeneous fuel. A fluidized bed or a moving grate is an example of modern applied technology for biomass combustion on the scale of power plants. Due to varying volumes of flue gases and the kinetics of the combustion process, the dimensions of the furnace and the distribution of combustion air are also different from coal combustion. The study done to identify the mechanics and distinctive characteristics of biomass combustion has allowed for the increased usage of biomass as a fuel [29–35]. The thermodynamic behavior of biomass during the three stages (warming, drying, and pyrolysis) of combustion must be characterized in order to be able to predict the combustion process. Parameters such as thermodynamic properties, thermal conductivity, specific heat and heat of formation, heat of reaction, and ignition temperature are the important properties of biomass which serve as the input parameters during modeling of the combustion. These models replicate the behavior of different types of biomasses.

19.7 Summary The present chapter provides a brief description of the different conversion techniques of biomass to energy. These includes thermochemical, biochemical, and physical means of conversion of biomass into useful energy. A detailed description about the conversion technology has been discussed, and based on the previous studies, it is suggested that thermochemical conversion techniques have been significantly used for converting biomass into useful fuels. Combustion and gasification processes are typically harder to arrange or manage. In general, a biomass can be gasified using any of the gasification processes. However, because the qualities of

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500  Clean and Renewable Energy Production

the feedstock vary, the procedures and outcomes could be very different. Future development of new technologies, process optimization for gasification, and feedstock characteristics research are all crucial. We currently have a significant economic and national security problem with the world’s energy dependence. The international trade of biomass and energy carriers derived from biomass is expanding, and biomass markets are becoming global marketplaces. The utilization of biomass as a source of raw materials for the production of bioenergy has drawn significant attention for the creation of environmentally friendly methods for energy production. The majority of research on biomass conversion technologies focuses on finding more sophisticated ways to make energy fuels in order to address the global shortage that exists now. The investigations also attempt to lessen greenhouse gases and other negative environmental effects caused by fossil fuels. The wide variation in the properties of the fuels used in actual plants is a crucial problem in the modeling and simulation of biomass-fired power plants. This should be kept in mind while we examine the simulation’s findings. The study claims that the utilization of biomass energy has significantly increased in the last decade. Appropriate conversion techniques should be utilized based on the efficiency of the process. The foundation of a low-risk, low-cost, and low-carbon-emission energy supply system for large-scale fuel and power delivery as well as providing a framework for the evolution of large-scale biomass raw material supply systems might be flexible energy systems that combine biomass and fossil fuels. To achieve the abovementioned targets, it will take years of R&D work, the growth of the biomass market, persistent regulatory backing, and international cooperation.

References 1. Mofijur, M., Masjuki, H., Kalam, M., Atabani, A., Shahabuddin, M., Palash, S., Hazrat, M., Effect of biodiesel from various feedstocks on combustion characteristics, engine durability and materials compatibility: A review. Renew. Sustain. Energy Rev., 28, 441–455, 2013. 2. Kusumo, F., Silitonga, A.S., Ong, H.C., Masjuki, H.H., Mahlia, T.M.I., A comparative study of ultrasound and infrared transesterification of sterculia foetida oil for biodiesel production. Energy Sources Part A Recovery Util. Environ. Eff., 39, 1339–1346, 2017.

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Biomass Energy and Its Conversion  501

3. Islam, M., Challenges of adopting strategic procurement policies: A case study of infrastructure Development Company Limited, Ph.D. Thesis, BRAC University, Dhaka, Bangladesh, 2017. 4. Bass, S. and Dalal-Clayton, B., Sustainable development strategies: A resource book, Routledge, Abingdon-on-Thames, UK, 2012. 5. Demirbas, A., Recent advances in biomass conversion technologies. Energy Educ. Sci. Tech., 6, 19–41, 2000. 6. Joutz, F.L., Biomass fuel supply: A methodology for determining marginal costs. Bioresour. Technol., 39, 179–183, 1992. 7. Demirbas, A., Biomass resources for energy and chemical industry. Energy Educ. Sci. Tech., 5, 21–45, 2000. 8. Richard, L.B., An introduction to biomass thermochemical conversion. DOE/NASLUGC Biomass and Solar Energy Workshops, August 3-4, 2004. 9. Masud, M.H., Ananno, A.A., Arefin, A.M.E., Ahamed, R., Das, P., Joardder, M.U.H., Perspective of biomass energy conversion in Bangladesh. Clean Technol. Environ. Policy, 21, 719–731, 2019. 10. Demirbas, A., Combustion characteristics of different biomass fuels. Prog. Energy Combust. Sci., 30, 219–230, 2004. 11. Goyal, H.B., Seal, D., Saxena, R.C., Bio-fuels from thermochemical conversion of renewable resources: A review. Renew. Sustain. Energy Rev., 12, 504– 517, 2008. 12. Butler, E., Devlin, G., Meier, D., McDonnell, K., A review of recent laboratory research and commercial developments in fast pyrolysis and upgrading. Renew. Sustain. Energy Rev., 15, 4171–4186, 2011. 13. Wang, M.Q., Han, J., Haq, Z., Tyner, W.E., Wu, M., Elgowainy, A., Energy and greenhouse gas emission effects of corn and cellulosic ethanol with technology improvements and land use changes. Biomass Bioenergy, 35, 1885–1896, 2011. 14. Brar, J.S., Singh, K., Wang, J., Kumar, S., Cogasification of coal and biomass: A review. Int. J. For. Res., 2012, 1–10, 2012. 15. Bridgwater, A.V., Review of fast pyrolysis of biomass and product upgrading. Biomass Bioenergy, 38, 68–94, 2012. 16. Solantausta, Y., Oasmaa, A., Sipilä, K., Lindfors, C., Lehto, J., Autio, J. et al., Bio-oil production from biomass: Steps toward demonstration. Energy Fuels, 26, 233–240, 2012. 17. Singh, V. and Debabrata, D., Potential of hydrogen production from biomass, in: Science and Engineering of Hydrogen-Based Energy Technologies, 2019. 18. Overend, R.P., Thermochemical conversion of biomass, combustion, 1999. 19. Jayasinghe, P. and Hawboldt, K., A review of bio-oils from waste biomass: Focus on fish processing waste. Renewable Sustain. Energy Rev., 16, 798–821, 2012. 20. Zhang, Y., Zhao, Y., Gao, X., Li, B., Huang, J., Energy and exergy analyses of syngas produced from rice husk gasification in an entrained flow reactor. J. Cleaner Prod., 95, 273–280, 2015.

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21. Lozano, F.J. and Lozano, R., Assessing the potential sustainability benefits of agricultural residues; biomass conversion to syngas for energy generation or to chemicals production. J. Cleaner Prod., 172, 4162–4169, 2018. 22. Chen, H. and Wang, L., Introduction, in: Technologies for Biochemical Conversion of Biomass, pp. 1–10, 2017. 23. Chen, H.Z., Process engineering of bio-based products, Chemical Industrial Press, Beijing, 2010. 24. Victor, V.M., Jogdand, S.V., Chandraker, A.K., Biomass densification technologies to obtain briquettes for energy application – A review. Int. J. Eng. Res. Technol., 3, 20, 1–4, 2015. 25. Turkenburg, W.C., Renewable energy technologies, world energy assessment: Part-I Energy and major global issues, pp. 219–267, 2000. 26. Manickam, I.N., Ravindran, D., Subramanian, P., Biomass densification methods and mechanism. Cogener. Distrib. Gener. J., 21, 4, 33–45, 2006. 26. UNFCCC: Clarifications of definitions of biomass and consideration of changes in carbon pools due to a CDM project activity. Framework convention on climate change – Secretariat. CDM-EB-20, Appendix 8, July 8, 2005. 27. International Energy Agency, Statistics, 2012, http://www.iea.org/stats/ index.asp/ (accessed March 2012). 28. van Loo, S. and Koppejanm, J. (Eds.), The Handbook of Biomass Combustion & Co-firing, Earthscan, London, UK, 2008. 29. Basu, P., Combustion and gasification in fluidized beds, CRC Press, Boca Raton, FL, 2006. 30. Galgano, A., Salatino, P., Crescitelli, S., Scala, F., Maffettone, P.L., A model of the dynamics of a fluidized bed combustor burning biomass. Combust. Flame, 140, 4, 271–284, 2005. 31. Leckner, B., Hansson, K.M., Tullin, C., Borodulya, A.V., Dikalenko, V.I., Palchonok, G.I., Kinetics of fluidized bed combustion of wood pellets. Proceedings of the 15th International Conference on Fluidized Bed Combustion, 15–19 May 1999, The American Society of Mechanical Engineers, CD-rom, Savannah, 1999. 32. Raiko, R., Saastamoinen, J., Hupa, M., Kurki-Suonio, I., Combustion and burning (in Finnish), Gummerus Oy, Jyväskylä, Finland, 2002. 33. Saastamoinen, J.J., Modelling of dynamics of combustion of biomass in fluidized beds. Therm. Sci., 8, 2, 107–126, 2004. 34. Tourunen, A., Häsä, H., Pitsinki, J., Jegoroff, M., Saastamoinen, J., Hämäläinen, J.J., Effects of bio mass on dynamics of combustion in CFB. Therm. Sci., 8, 2, 93–105, 2004. 35. Joronen, T., Kovács, J., Majanne, Y. (Eds.), Power Plant Automation (in Finnish). SAS Publication Series 33, The Finnish Society of Automation, Helsinki, Finland, 2007.

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Biomass Energy and Its Conversion  503

Co-Gasification of Coal and Waste Biomass for Power Generation Naval V. Koralkar1*, Mohit Kumar2, Raj Kumar1 and Praveen Kumar Ghodke3 Department of Chemical Engineering, ITM (SLS) Baroda University, Vadodara, Gujarat, India 2 University of Nebraska Medical Center, Omaha, NE, USA 3 Department of Chemical Engineering, National Institute of Technology Calicut, Kozhikode, Kerala, India 1

Abstract

A prospective clean fuel technology that could achieve great thermodynamic efficiency with just moderate CO2 emissions is co-gasification of coal and biomass. For more than a century, gasification of coal and biomass has been the only method used to produce gas–liquid fuels and create chemicals. Because biomass contains cellulose, hemicellulose, and lignin, which aid to ignite and speed up gasification, co-gasification is more efficient than isolated coal gasification. If carbon is caught and sequestered, using biomass as a feedstock to produce fuels or power has the advantage of being carbon-neutral or even becoming carbon-negative. However, there are obstacles to the efficient use of biomass wastes: (a) the supply of biomass is constrained and varies with the seasons; (b) the density of biomass is low and costly for long-distance transportation; and (c)  because there is a scarcity of feedstock, biomass plants are typically small, which results in higher capital and production costs. The co-combustion or co-gasification of biomass wastes with coal is more economically appealing and less technically difficult when these issues are taken into account. The current chapter analyzes the potential of co-gasification technology in light of the variety of coal and biomass that are readily available. The research highlights and

*Corresponding author: [email protected] Surajit Mondal, Adesh Kumar, Rupendra Kumar Pachauri, Amit Kumar Mondal, Vishal Kumar Singh and Amit Kumar Sharma (eds.) Clean and Renewable Energy Production, (505–522) © 2024 Scrivener Publishing LLC

505

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20

developments in coal and biomass co-gasification, a new clean energy technology, are reviewed in this chapter. The difficulties, roadblocks, limitations, and technological interventions that must be overcome for co-gasification options to be developed successfully are also discussed. Keywords:  Co-gasification, biomass, coal, energy

20.1 Introduction Due to the expansion of several nations, the global energy demand is rising. According to the U.S. Energy Information Administration (EIA), the demand for energy would keep rising quickly through 2025. The majority of this rise is anticipated to take place in Asia’s developing nations, particularly China and India [1]. In order to address the challenges of climate change, the rising energy demand must be balanced with lowered pollution levels and greenhouse gas emissions. There is not a single energy source that can supply all of the world’s energy needs at this time. Due to its advantageous operational characteristics, co-gasification of coal and biomass in fluidized bed gasification systems has recently attracted a lot of interest. Numerous researchers from across the world have studied the co-processing of all waste types, which indicates that co-gasification appears to be a more appealing alternative than co-liquefaction or co-pyrolysis [2]. Since the 1800s, when coal gasification first started, there have been numerous advancements that have led to the potential use of coal as a feedstock for the gasification process that creates syngas and liquid fuel [3]. Biomass has an advantage over the other renewable sources since it is more widely scattered around the planet [4–7]. After coal, oil, and natural gas, biomass is the fourth most significant source of energy and currently supplies more than 10% of the world’s energy needs. By 2050, it is predicted that waste from different sources and biomass might supply one-third of the world’s primary energy needs [4, 8, 10]. Due to its inherent characteristics, such as high moisture content, low calorific value, high hydrogen content, hygroscopic nature, and low density, biomass gasification does have some limitations, which makes it more important during transportation, storage, and preparation for gasification [9, 11]. Despite the fact that coal gasification is an established technology, relatively little is known about the co-gasification of coal and biomass. The production of heat, power, liquid, and gaseous biofuels utilizing synthesis gas appears to be made possible by the co-gasification of coal and biomass [12].

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20.1.1 Combined Usage of Biomass and Coal Green plants create biomass, which includes all land and water-based vegetation and all organic waste, and it is frequently seen as a renewable energy source [13]. Due to the high costs of collecting and delivery, it has not been extensively utilized. Currently, producer gas has been produced from biomass by either direct burning or gasification [14, 15]. Due to the unique characteristics of biomass and its availability, the latter situation (gasification) is a viable method for biomass-derived energy [16]. In the process of gasification, a gas mixture primarily composed of H2, CO, CO2, and CH4 is created. This mixture, known as producer gas, can be used to make hydrogen fuel (by separating it from the producer gas) [17–19], as a substitute for some crude oil products like methanol [20, 21], or for the generation of heat and electricity. Figure 20.1 shows the reported world energy consumption trend and projection over the next century in the literature by Zerta et al. [22]. Figure 20.2 displays the percentages of each energy kind [23]. These numbers show that liquid biofuels and biomass energy currently account for 14% of the global energy consumption. The three main factors driving the increased interest in biomass energy and liquid biofuels are as follows: (1) political advantages, such as reducing reliance on imported oil, (2) job creation, and (3) environmental friendliness, such as lowering greenhouse gas emissions and other polluting elements. As shown in Figure 20.1, typical gasification systems include fixed bed (updraft and downdraft), fluidized bed, and entrained flow reactors. Currently, biomass is primarily burned directly to provide heat and power. Although biomass gasification has the potential to produce liquid 50 Oil Coal Gas Biomass Nuclear Other Renewables Hydro

Percentage (%)

40 30 20 10 0 1980

1990

2000

Figure 20.1  Percentage of energy kind [23].

2010 Year

2020

2030

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Co-gasification of Coal and Biomass  507

fuel, it is not currently economically feasible due to the high processing costs of the low-energy-density biomass feedstock. Another conventional fossil fuel that has been used for the production of heat and electricity is coal [24]. Coal is typically used as a feedstock for the manufacturing of coke and coal gas or through direct burning for the creation of electricity. Through gasification and liquefaction, coal might also be transformed into materials that could replace petroleum or natural gas. German scientists developed the Fischer–Tropsch (F–T) synthesis process in 1932, which uses coal gasification producer gas as the feedstock gas to create liquid gasoline from CO and H2. Germany produced 590,000 tonnes of F–T liquid fuel annually as of 1938. However, the widespread manufacture of liquid fuel from coal was discontinued due to the fast exploitation of crude oil and natural gas in the 1940s and 1950s, and during that time, coal’s share of global energy consumption fell from 65% to 27%. Given the current pace of consumption, the world’s coal reserves, which are thought to be over 1 trillion tonnes, may last for about 180 years. Both biomass and coal are carbonaceous substances that are derived from plants and share the same fundamental chemical elements. Direct co-combustion or co-gasification are two methods that can be used to combine the use of biomass and coal. In the latter scenario, it is possible to manufacture liquid fuel using F–T synthesis with producer gas, which presents a fantastic chance to subsidize liquid fuels made from crude oil. Since they can outweigh each other’s drawbacks, the combined usage of coal and biomass has a lot of advantages [25]. These are as follows: 1. Economically, a large-scale energy plant can operate more adaptably and consistently by using a blend of coal and biomass. When there is a shortage of biomass feedstock, for instance, a biomass energy plant located close to a forestry or wood processing industrial region can use the extra cheap coal instead of paying a high delivery fee to transport biomass from a distance. On the other hand, if lowcost biomass from a nearby source can be blended into the feedstock, the operational costs for the coal-fired electricity plant can be decreased. 2. Densification of the feedstock’s energy content: Adding coal to biomass can raise the product’s specific energy content or decrease the need for auxiliary energy inputs because biomass generally has a lower carbon fraction and lower energy content.

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508  Clean and Renewable Energy Production

3. Due to the high concentration of metal elements in biomass, which have a catalytic influence on the reactivity of coal gasification, the co-gasification of the combined coal and biomass can be improved. As a result, it is possible to increase the rate of carbon conversion to the gaseous phase while reducing the yield of tar and residual char [26]. 4. By varying the biomass-to-coal mixing ratio, the composition of gasification-producing gas might be changed [27]. 5. Utilizing biomass for energy decreases environmental harm compared with using pure coal because it is sustainable and mostly carbon neutral because plants absorb CO2 during growth [28]. Additionally, biomass has substantially lower levels of pollutants than coal. As a result, the combined use of biomass in an energy plant can lower the emission of net CO2 and other toxins while still meeting legal standards. Since coal and biomass have very diverse physical and chemical qualities, each fuel’s gasification characteristics should be different [29, 30]. Although biomass is an excellent source of renewable energy and liquid fuel, its low energy density and scattering feature limit its commercial viability. The downstream processing is greatly impacted by the composition of the producing gas since the gasification process is a crucial stage in the generation of alternative liquid fuel utilizing thermo-chemical technology. Therefore, in order to build and run the future industrial production, it is crucial to fully comprehend and optimize the coal–biomass co-gasification process. The gasification of each separate fuel has been extensively studied in literature. The present chapter bridges the gap between the understanding of the co-gasification of coal and biomass as well as the process optimization.

20.2 Co-Gasification Co-gasification is the gasification of a mixture of waste/biomass and coal, which presents a number of opportunities for utility companies and customers, in particular, to protect the environment by reducing GHG emissions from current process equipment [31]. The co-gasification of biomass and coal has received a lot of attention from researchers recently [32–34] because it offers opportunities for the management of significant amounts of combustible agricultural and wood wastes in the forestry, agricultural, and food processing sectors. In addition, upgrading an existing coal power

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Co-gasification of Coal and Biomass  509

station to co-fire biomass is considerably less expensive than developing brand-new systems just for biomass energy. Direct co-firing is possible with biomass rates in the range of 3–5% on an energy basis. However, when cyclone boilers are employed, this rate could increase to 20% [35, 36]. Co-gasification creates syngas that is high in hydrogen and contains CH4, which can be used in power plants. The volatiles easily break down and produce free radicals during the co-gasification process, which reacts with the organic coal matter and boosts the conversion rate while lowering CO2, SO2, and NOx emissions. It is possible to alter the composition and yield of gaseous products from the co-gasification process by adjusting the quantity and characteristics of the fuel combination and temperature since different types of coal and biomass have varied properties [34, 37]. The results of an experimental study of a coal and biomass mixture (0–100%) revealed a linear relationship between changing fuel ratios and gas components, with high wood ratios producing a gas that was more suitable for F–T synthesis and the production of synthetic natural gas (SNG) due to a higher H2/CO ratio [38]. In two catalytic fixed bed (dolomite- and Ni-based catalysts) reactors, Pinto et al. [39, 40] examined the gas produced by the co-gasification of coal and waste mixes (olive oil bagasse, pine, and polyethylene). Based on their findings, it was able to switch from one type of waste to another without significantly altering the gasifier, although the tar and hydrocarbons that were emitted were different. Wastes in the feedstock caused the gas to contain higher amounts of hydrocarbons and tar. Due to the high alkaline and chlorine concentrations of the biomass, direct co-firing can cause a number of issues. The main issues that have been identified are corrosion, slagging, fouling in the boiler, heat exchanger, and piping, poisoning of catalysts, and electrostatic precipitator performance issues [41]. Table 20.1 shows a summary of research carried out in the field of co-gasification. Indirect and parallel co-firing have been established to address these issues [36, 49]; however, they have greater production costs (CAPEX and OPEX) than direct co-firing. Co-gasification of biomass with plastic wastes, petroleum coke, and tyres has also been researched in addition to co-gasification of biomass with coal [41, 50, 51].

20.2.1 Gasification Technologies During the gasification process, biomass is dried, pyrolyzed, burned, and gasified in a series of processes. As a waste valorization technology, biomass gasification has been developed to produce syngas, H2, CH4, and

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510  Clean and Renewable Energy Production

Table 20.1  Summary of research carried out in the field of co-gasification. Reference

Feedstock

Gasifier type

Operating parameters

Outcomes

[42]

Petroleum coke Pine pellets

Fluidized bed

(i) Gasification agent: steam (ii) Biomass ratio: 50%, 80%, and 100% (iii) Temperature: 800°C and 900°C (iv) Total gasification time: 2.5–3 h

1. As the biomass ratio increased, the activation energy decreased. 2. Higher petcoke conversion and lower tar concentration were caused by higher gasification temperature and oxygen concentration.

[43]

Shinwa coal Pine sawdust

Fluidized bed

(i) Gasification agent: CO2 40% and N2 60% (ii) Biomass ratio: 0%, 25%, 75%, and 100% (iii) Temperature: 900°C, 1,000°C, and 1,100°C (iv) Ratio of fuel/CO2: 0.20, 0.21, 0.21, and 0.23

1. As the biomass content increased, the reactivity of the char increased as well. 2. The data on carbon conversion might be interpreted using the random pore model (RPM).

(Continued)

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Co-gasification of Coal and Biomass  511

Table 20.1  Summary of research carried out in the field of co-gasification. (Continued) Reference

Feedstock

Gasifier type

Operating parameters

Outcomes

[44]

Plastic (PE) Wood pellets

Dual fluidized bed

(i) Gasification agent: steam (ii) Biomass ratio: 0%, 25%, 75%, and 100% (iii) Temperature: 850°C (iv) Steam-to-carbon mass ratio (SCR): 2.3 (v) Heterogeneous catalyst: olivine

1. As contrast to mono-gasification, co-gasification resulted in the successful thermochemical conversion of plastics. 2. Increasing the amount of plastics in the feed led to higher ethane and ethylene fractions and lower CO2 concentrations.

[45]

Hard coal Energy crops

Fixed bed

(i) Gasification agent: steam (ii) Biomass ratio: 0–100% with 20% intervals (iii) Temperature: 700°C, 800°C, and 900°C

1. As the temperature rose, the char became more reactive. 2. Regardless of temperature, fuel blend chars had higher reactivity than biomass chars.

[46]

Bituminous coals Cedar bark

Entrained flow

(i) Gasification agent: CO2 (ii) Biomass ratio: 0–30% (iii) Temperature: 1,200°C and 1,300°C (iv) Pressure: 0.5 MPa (v) Ratio of fuel/CO2: 0.20, 0.21, 0.21, and 0.23

1. At 1,200°C, the mixture’s reactivity was higher than that of a single coal. 2. At 1,400°C, the reactivity was essentially the same. 3. No clearly visible synergy to increase gasification reactivity was seen. (Continued)

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512  Clean and Renewable Energy Production

Table 20.1  Summary of research carried out in the field of co-gasification. (Continued) Reference

Feedstock

Gasifier type

Operating parameters

Outcomes

[47]

Pine saw dust Plastic Coal

Fluidized bed

(i) Gasification agent: air; ER: 0.3–0.46 (ii) Feed blend: 60% coal, 20% pine, and 20% plastic (iii) Temperature: 750–880°C (iv) Catalyst: dolomite

1. The ideal conditions were 850°C for the temperature and ER equivalent ratio of 0.36. 2. The resulting gas had a low tar level and medium hydrogen content (up to 15% dry basis).

[48]

Pine chips Black coal Sabero coal

Fluidized bed

(i) Gasification agent: air–steam (ii) Biomass ratio: 0%, 25%, 40%, and 100% (iii) Temperature: 840–910°C

1. The CO levels grew. 2. H2 first increased up to 25% of biomass before declining. 3. The total level of thermal efficiency rose (40% to 68%). 4. The efficiency of converting carbon rose from 63% to 83.4%.

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Co-gasification of Coal and Biomass  513

chemical feedstocks. As shown in Figure 20.2, typical gasification systems include fixed bed (updraft and downdraft), fluidized bed, and entrained flow reactors. A detailed description of the process can be found in the literature by Farzad et al. [53]. A broader range of innovative gasification technologies, including plasma gasification and wet biomass gasification in supercritical water, has been developed to convert various feedstocks to gas products [48, 54]. Furthermore, process integrations and combinations seek higher process efficiencies, improved gas quality and purity, and cheaper investment costs. As a result, the so-called emerging technologies, such as the integration of gasification and gas cleaning technologies or pyrolysis combined with gasification and combustion, have recently gained more attention. Newer technologies have been adopted for the gasification of biomass. A summary of these modern technology is presented in Table 20.2. Coal and biomass are put into the gasifier after being mixed in the current co-gasification practice. However, due to the density difference between biomass and coal, the two fuels are separated during the fluidization phase, and the coal and biomass are pyrolyzed and gasified separately. This is undesirable because the difference in mean residence time between the two fuels will restrict the co-gasification operation’s robustness. One method for producing co-pyrolyzed char is to pre-mix and press the two fuels into pellets; in this case, the difference in the characteristic of gasification will be due to the intrinsic reaction rate because the internal mass

Updraft

Downdraft

Fuel

Fluidized Bed

Entrained Bed

Fuel

Fuel Gas

Oxygen & Steam

Gas

Drying

Drying

Pyrolysis

Pyrolysis

Reduction Oxidation

Air

Fuel Air Air Gas

Gas

Slag Air

Figure 20.2  Typical gasification technologies.

Ash

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514  Clean and Renewable Energy Production

Table 20.2  New technologies applied for the gasification of biomass. Employed strategy

Advantages

Limitations

Gasification and gas cleaning in a single reactor

1. Stable process design 2. Affordability

More research is needed for large-scale commercial applications

Gasification concept with multiple stages

1. Clean, high-quality syngas 2. Greater process efficiency

Enhanced complexity

Plants for distributed pyrolysis with a central gasification plant

1. Use of low-grade, dispersed biomass 2. Low-cost transportation of char oil slurry

Not an economically viable method for the production of gasoline and olefin

Gasification of plasma

1. Any organic matter decomposition 2. Hazardous waste treatment

1. High investment cost 2. High power requirement 3. Low efficiency

Supercritical water gasification

1. Liquid and biomass with high moisture content are treated 2. No pre-treatment is required

1. High energy requirement 2. Expensive investment

Cogeneration of thermal energy and electricity

Enhanced process efficiency

Only decentralized heat and power production is feasible as heat needs to be produced near consumers

Polygeneration of heat, electricity, and H2/SNG

(i) Enhanced process efficiency (ii) Generation of renewable H2/renewable fuel for transportation

1. Enhanced complexity in process design 2. In the absence of a natural gas distribution system, it is not economically feasible.

Coupled gasification F–T process

Production of clean, carbon-neutral liquid biofuels

Enhanced complexity in process design

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Co-gasification of Coal and Biomass  515

transfer resistance effect will be more pronounced when the dimension of the particle exceeds a certain value [52].

20.3 Biomass Gasification Co-Generation The economic and sustainability aspects of the gasification of biomass can be improved using the approach of co-generation. Co-generation is the process of making two or more products at the same time (called poly-generation) to get the most use out of the energy and materials in the feedstock. As an added benefit, co-generation gives you the freedom to adapt to changing market needs. The CHP process is a great example of a co-generation process [48, 55]. Buildings that are industrial, commercial, or residential can use CHP production units to generate both heat and electricity. Although biomass combustion for CHP is common, gasification offers improved electrical efficiency and a wider range of acceptable feedstock quality [56]. For small-scale CHP, the combination of biomass gasification with a gas engine makes sense since it has a high biomass to power the efficiency potential of 35–40% compared with conventional technology [55, 57]. A plant with a small size (1–10 MW) might be appealing to reduce technical issues [55, 58]. The use of CHP in conjunction with cogeneration to increase electricity production has been studied by numerous researchers. Some researchers have combined enhanced biomass power efficiency with an organic Rankine cycle, which also converts 10–15% of heat into electricity [48, 54]. A different strategy is the integrated gasification combined cycle (IGCC) method, which combines the power of a gas turbine and a steam turbine. Due to the low electrical efficiency of tiny steam turbines, an IGCC process is only worthwhile for larger-scale applications [54, 59]. Different organic compounds, such as methanol, dimethylether, olefins, methane, hydrogen, F–T diesel, etc., can be produced via selective syngas conversion processes with different catalysts [60]. Compared with CHP co-generation, newer technologies seek to combine the production of heat, power, and SNG, hydrogen, or biofuels. SNG made from biomass is regarded as a clean, renewable fuel that can be used in place of fossil fuels in transportation, CHP, and heating systems. In the last decade, several researchers have been looking at the production of SNG from biomass gasification syngas [48, 61].

20.4 Summary The chapter focuses on the present co-conversion of biomass and waste by showcasing the fuels’ complementary properties, minimizing negative

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516  Clean and Renewable Energy Production

effects from individual usages. Different co-generation techniques show more economically feasible situations by producing heat and power alongside other items. In addition, co-gasification of biomass and coal can be used to use waste and biomass more effectively while producing fewer undesirable by-products (such as tar), a greater carbon conversion rate, and a higher gas production than coal/biomass gasification. Future renewable energy scenarios involving co-gasification and co-generation could be promising, but they need more research, especially in light of their impact on the environment. Advancement and expansion of knowledge in order to understand the co-gasification technology is a crucial method of tackling the environmental and sustainability issues.

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Co-gasification of Coal and Biomass  521

Activated carbon 12, 290, 297, 316, 323 Additives 1, 22, 36, 473 Agricultural and forest waste 186 Air Quality 26, 196 Alcohol 2, 180, 381, 442 Algae 59, 157, 198, 461 Algae-Microbial Fuel Cells 159 Alternative fuel 7, 316, 380, 381, 421 Ammonia Fiber Explosion 390 Anion exchange membrane (AEM) 316, 318, 323, 324 Anion exchange membrane water electrolyzers (AEMWEs) 318 Aqua hydrogen 109, 111 Arsenic 421 Artificial intelligence 271, 275, 279, 281, 363, 374 artificial neural network (ANN) 365 ASTM D 471 Auto-oxidation 474, 475 Batch Reactor 183 Battery–electric vehicles (BEVs) 207, 208 Biocatalytic 30 Biochemical 427, 496, 497 Biochemical Conversion 178, 427, 496, 497 Bio-coal 181 Biodegradability 5, 6, 19, 436 Biodegradable 5, 19, 147, 430, 503 Biodiesel 8, 27, 29, 437, 438, 439, 445, 466 Biodiesel Process 28, 29

Biodiesel production technologies, 437, 476 Bioelectricity, 147 Bioenergy 147, 376, 427 Bioethanol economy 395 Bioethanol, 375, 377, 395, 396 Biofuel 1, 27, 400, 442 Biological CO2 57 Biological Carbon Sequestration 57 Biological Conversion 492, 496 Biomass 79, 177, 178, 185, 377, 380, 497, 498, 500, 505, 516 Biomass Combustion Modeling 500 Biomass Conversion Routes 178 Biomass feedstocks 187, 442 Biomass Type 184 Biomaterials 293 Bio-oil yield 185 Bio-oil 186, 192, 494 Bioprocessing, 375, 391 Bio-source 298, 300, 303 Blue hydrogen 109 Bottom simulator reflectance 99 Brake-specific fuel consumption 10 Brunauer–Emmett–Teller (BET) 192 Capacitance 290, 297, 304 Carbon Aerogel 288, 293, 294 Carbon capture and sequestration 55 Carbon capture, utilization, and storage (CCUS) 56 Carbon Content Utilization 184 Carbon dioxide emissions 127, 337, 339, 344, 346, 496

523

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Index

Carbon dioxide equivalent 340, 346 Carbon emissions 88, 131, 145, 146, 157, 335, 337, 338, 339, 340, 341, 342, 343, 344, 345, 346, 347, 351, 352 Carbon emissions, Carbon footprint 9, 88, 335, 340, 341, 342, 343, 346, 347, 349, 350, 353, 356 Carbon nanotube 288, 293, 294, 300 Carbonization 12, 79, 175, 288, 290, 291, 292, 294, 296, 297, 298, 299, 300, 301, 303, 347 Cashew nut 4, 5, 15, 16, 27, 28, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49, 50 Cashew nut shell liquid (CNSL) 15, 16, 17, 27, 28, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49, 50 Catalyst 10, 11, 12, 13, 14, 29, 30, 79, 114, 144, 152, 153, 154, 161, 175, 176, 180, 181, 183, 184, 186, 187, 188, 189, 190, 191, 192, 193, 194, 290, 296, 297, 301, 303, 316, 319, 320, 321, 322, 323, 325, 327, 328, 329, 330, 383, 389, 394, 397, 399, 401, 426, 427, 430, 438, 445, 448, 449, 450, 451, 452, 453, 454, 455, 456, 457, 458, 459, 460, 462, 463, 464, 465, 477, 510, 512, 513, 516 Cellulose 177, 179, 180, 184, 185, 186, 379, 380, 381, 382, 383, 384, 385, 386, 387, 388, 389, 390, 391, 392, 393, 394, 397, 399, 400, 401, 451, 505 Cellulose hydrolysis 398 Cetane number 9, 15, 467, 475 Chemical activation 288, 290, 291, 292, 294, 295, 296, 297, 298, 299, 300 Chemical energy 144, 201 Chemical hydrides 110, 112, 211, 214

Chemical Looping Combustion 55 Chemical oxygen demand (COD) 159, 160, 163, 192 Chemical Pretreatment 384, 387, 390 Clean Energy 114 Clean energy sources 88 Climate Change 16, 53, 54, 55, 56, 58, 81, 88, 115, 124, 126, 127, 131, 202, 226, 330, 335, 336, 337, 338, 341, 345, 346, 347, 348, 349, 413, 414, 416, 498, 506 CNSL Study 35 CO2 enhanced oil recovery 54 CO2 Sequestration 69, 106 CO2 sequestration 54 Coal 14, 55, 60, 69, 70, 74, 89, 109, 124, 127, 128, 181, 182, 191, 226, 227, 229, 295, 296, 298, 302, 314, 336, 338, 339, 413, 414, 415, 494, 499, 500, 505, 506, 507, 508, 509, 510, 511, 512, 513, 514, 517 COD Co-Gasification 505, 506, 508, 509, 510, 511, 512, 513, 514, 517 Coke formation 189 Combustion 7, 17, 55, 71, 72, 74, 79, 89, 112, 145, 146, 178, 201, 207, 208, 209, 210, 314, 330, 331, 339, 345, 376, 379, 424, 425, 427, 428, 429, 430, 433, 438, 445, 466, 475, 476, 490, 492, 493, 494, 495, 496, 497, 498, 499, 500, 500, 505, 508, 514, 516 Combustion characteristics 475, 476, Compressed Gas 110, 111 Compressed hydrogen storage 212 Consolidated bioprocessing (CBP) 390, 391, 392, 397, 398, 399, 400, 401 Continuous Reactor 182, 183, 189 Continuous Stirred Tank Reactor (CSTR) 183, 184

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524  Index

Conversion 11, 29, 53, 57, 67, 75, 76, 79, 80, 113, 130, 144, 176, 177, 178, 179, 180, 181, 182, 184, 190, 191, 193, 194, 227, 237, 240, 288, 289, 305, 376, 386, 388, 390, 398, 418, 419, 424, 426, 427, 428, 429, 443, 445, 460, 462, 476, 489, 491, 492, 493, 495, 496, 497, 500, 501, 509, 510, 511, 512, 516, 517 Current–voltage (I–V) 270, 280, 281, 369 Depressurization process 91 Desalination process 104 Diode array 31 Direct injection 29 Dust accumulation 275 Dynamic Tidal Power 232, 235 Early streamer emission (ESE) 247, 248, 255, 256, 258, 261 Eco-friendly 4, 13, 28, 29, 267, 377, 425, 438, 443, 462 Electric vehicle 201, 202 Electrical energy 57, 58, 144, 161, 202, 208, 230 Electrode Materials 293, 297, 301 Electrolysis 110, 193, 213, 313, 314, 315, 316, 317, 318, 319, 320, 321, 322, 323, 325, 326, 328, 329, 330, 331 Electrolyte 104, 155, 161, 162, 164, 296, 304, 313, 315, 316, 319, 322, 323, 326, 327, 329, 330 Electron impact (EI) mode 31 Emission parameters 29 Energy Energy Balance 8, 190 Energy Balance and Security 8 Energy Content 181, 400, 508 Energy demand 88, 129, 131, 176, 227, 375, 377, 416, 437, 438, 489, 506 Energy Saving 182, 344, 347

Energy Scenario 127 Engine Function 9 Engine operation 1 Environment emissions 1 Environmental conditions 62, 67, 356 Environmental dependence 269 Environment-friendly 3 Enzymatic Catalysis 465 ESE lightning protection 247, 248, 257, 258, 260 Exhaust gas 10, 13, 14, 423 Extended-range electric vehicles (EREVs) 207 Extraction Methodologies 90 FCEVs 209 Flowing mud 101 Fossil fuel 123 FTIR 31 Fuel cell 203 Fatty acid methyl ester 33, 445 Feedstocks 9, 14, 20, 202, 203, 205, 233, 348, 397, 439 Fermentation 29, 79, 178, 213, 375, 376, 377, 379, 380, 383, 385, 388, 390, 402, 492, 496 Fossil fuel Franklin lightning protection 247, 248, 257 Free fatty acids 3, 29, 462, 465 Friction and wear 3 FTIR 13, 14, 15, 16, 17, 27, 28, 31, 32, 36, 37, 51, 191 Fuel Fuel cell-assisted electric vehicles (FCEVs) 203, 204, 207, 209, 210, 214, 215 Fuel cells 58, 59, 60, 112, 113, 143, 144, 148, 150, 161, 163, 191, 203, 315 Fuel properties 11, 466, 498

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Index  525

Gas Exploitation 100 Gas hydrates 61, 87, 88, 89, 90, 91, 92, 93, 95, 96, 97, 98, 99, 100, 101, 102, 103, 115 Gas Separation 87, 89, 102, 107, 108 Gasification 71, 101, 109, 175, 178, 213, 430, 493, 494, 495, 497, 500, 501, 505, 506, 507, 508, 509, 510, 511, 512, 513, 514, 515, 516, 517 Gasification technologies 510, 514 GC-MS 12, 13, 14, 15, 17, 28, 31, 32, 33, 34, 36, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49, 50, 51, 191 Generation of Biofuels 176, 177 Genetic algorithm 135, 268, 271, 279, 280, 281, 282, 362 Global maximum power point 282, 283, 358, 360, 361, 362 Graphene oxide 293, 294 greenhouse gas (GHG) 16, 53, 55, 87, 88, 127, 128, 129, 177, 192, 202, 225, 377, 417, 443, 506, 507 Grid electricity 202 Gas Exchange 92 Gas Exploitation 100 Gas Hydrates 89 Gas replacement 93 Gas Separation 107 Gas volume expansion 96 GCMS 32 Genetic algorithm 279 Geological characteristics 106 Geological Hazards 93 Global carbon capture 54 Gray hydrogen 109 Green Hydrogen 109 Greenhouse warming potential 89 Grid electricity 203 Heating Rate 180, 181, 183, 184, 186, 188, 494 Hemicellulose 379 Heterogeneous catalysts 462 Homogeneous Catalysis 460 HTL Reaction 179

Hybrid electric vehicles (HEVs) 207 Hybrid renewable energy system 130 Hydrocarbons 2, 5, 17, 73 Hydrochar 175 Hydroelectric power 202, 271 Hydrogen Energy 108 Hydrogen evolution reaction (HER) 313 Hydrogen Storage 87 HEVs 210 Hybrid Renewable Energy 123 Hydro Electric power 202 Hydrogen Energy 108, 202 Hydrogen Energy Storage 211 Hydrogen in metal hydrides 212 Hydrogen Storage 87, 110 Incremental Conductance 359 Internal combustion (IC) engines 7 International Energy Agency (IEA) 20, 127, 228, 271, 349 Ionic Liquid 383 IRENA 225 Irradiance levels 280 Life cycle 348 Lightning strike frequency (LSF) 253 Lignin 379 Lignocellulosic biomass 380 Limitations of the HTL 193 Linolenic acid 470 Liquid Hydrogen 111 Lubricants 1 Machine learning 28, 272 Modeling of PV system 277 Maximum power point tracking, MPPT 359 Maintenance Prediction 274 MATLAB/Simulink model 202 Maximum power generation Membranes 109, 322, 325 Metal hydrides 114, 213 Methane 62, 80, 91, 215, 424, 500 Microalgae 159, 179

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526  Index

Microbes 147, 394 Microbial fuel cells 146, 152 Microorganisms 149, 388, 401, 469 Microwave 184, 299, 389 Ministry of New and Renewable Energy (MNRE) 274 Modeling of the PEMFC System 208 Municipal Solid Waste Management 427 Nanoparticles 457 Natural Gas 91, 105 Negative Emission 53 Net zero emission 54 NMR 34 NMR spectroscopy 34 Non-edible oils 443 Ocean Energy 227, 230, 243 Ocean Energy Europe (OEE) 230 Ocean Energy Systems (OES) 230 Operating parameters 352, 516 Operating Temperature 114, 188, 326 Organic compounds 89 Organic waste material 147 Oxygen Content 183, 193 Particle swarm optimization 366 PEMFC 201 Photovoltaic 115 Photovoltaic system 267 Pink hydrogen 110 Power loss 282 Particle swarm optimization (PSO) 370 Photosynthetic microbial fuel cell mechanism 145, 154 Photosynthetic 49, 154 Photovoltaic 77, 117 Photovoltaic (PV) 270, 359 Physical conversion 502 Physico-chemical properties of fuel Plant-Microbial Fuel Cells 163

Plug Flow Reactor 185 Plug-in hybrid electric vehicles (PHEVs) 209 Porous 291, 300 Power enhancement 271 Power Generation 213 Power Plant Dynamic Modeling 503 Power plant 503, 515 Power–voltage (P–V) 273 Pressure 380, 389 Pretreatment 389 Process Yield 182 Product distribution 192 Proton Exchange Membrane Fuel Cell 203 PV power generation 265, 273 Pyrolysis 182, 297, 301, 387 Quick refueling and durability 205 Renewable 227 Renewable energy 236, 243 Residence Time 519 Safety 9 Salinity gradient, 227 Scanning electron microscope (SEM) 193 Seawater Desalination 105 Sedimentation 98 Series-parallel 278 Sewage 147, 425 Simultaneous saccharification and fermentation (SSF) 383 Slurry 390 Solar energy 76, 141, 116, 274 Solar Energy Potential 131 Solar parameter prediction 279 Solar photovoltaic system 360 Solar power 251 Solidified Natural Gas 103 Specific conductance Steam Explosion 389

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Index  527

Storage stability 441 Sulfur dioxide 91, 431 Supercapacitors 290 Sustainability 102 Techno-Economic 196 Temperature 215, 239, 272, 326, 343, 373, 388 The European Marine Energy Centre (EMEC) 230 Thermal Stimulation 91 Thermochemical 469 Thermochemical conversion 498 Thermogravimetric analysis (TGA) 193 Tidal currents 237 Tidal Lagoon 234 Tidal Stream Generator 234 Total nitrogen 194 Total permeability 97 Toxicity 18 Transesterification 29 Transportation 204, 291 Tribological 17 Triglycerides 29 Turquoise hydrogen 109

Underground Hydrogen Storage 111 Unsaturated fatty acids 449 Vegetable Oils 2 Vegetable Seed Oils Vehicles’ batteries 204 Viscosity 449 Volatile 89 Volumetric efficiency 105 Waste 79 waste cooking oil 451 Waste-to-Energy 496 Wastewater 58 Water 62 78 106 Wave energy, 230 Weather forecasting 278 WECANet 230 Wet Oxidation 390 White hydrogen 110 Wind energy 123 Wind Potential 137 Yellow hydrogen 110 Zero emission 129, 205, 334

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528  Index

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