Green Sustainable Process for Chemical and Environmental Engineering and Science: Carbon Dioxide Capture and Utilization 9780323994293

Green Sustainable Process for Chemical and Environmental Engineering and Science: Carbon Dioxide Capture and Utilization

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Green Sustainable Process for Chemical and Environmental Engineering and Science: Carbon Dioxide Capture and Utilization
 9780323994293

Table of contents :
Cover
Half Title
Green Sustainable Process for Chemical and Environmental Engineering and Science: Carbon Dioxide Capture and Utilization
Copyright
Contents
Contributors
1. Carbon dioxide capture and its utilization towards efficient biofuels production
1.1 Introduction
1.2 Utilization of captured carbon dioxide for biofuel production
1.2.1 Photosynthesis and photo oxidation of water
1.2.2 Bio-sequestration of CO2
1.3 Conclusion and future perspectives
References
2. Deep eutectic liquids for carbon capturing and fixation
2.1 Carbon dioxide emissions
2.2 Deep eutectic liquids
2.3 Types of deep eutectic liquids
2.4 Preparation of DELs
2.5 Authentication of DELs
2.6 DEL based CO2 absorption
2.7 Carbon capture efficiency of various HBDs
2.7.1 Urea
2.7.2 Glycerol
2.7.3 Glycerol^^c2^^a0 + ^^c2^^a0L-arginine
2.7.4 Natural organic acids
2.7.5 Dihydric alcohols
2.7.6 Amines
2.7.7 Levulinic acid
2.7.8 Guaiacol
2.7.9 Azoles
2.7.10 Miscellaneous HBD
2.8 CO2 absorption in aqueous solution of DELs
2.9 CO2 absorption in ternary DELs
2.9.1 Alkanolamines
2.9.2 Superbases
2.9.3 Hybrid
2.10 Ammonium-Based DELs
2.10.1 Carboxylic acids
2.11 Phosphonium based DELs
2.12 Azole based DELs
2.13 Bio-phenol derived superbase based DELs
2.14 Hydrophobic DELs
2.15 Non-ionic DELs
2.16 DEL supported membranes
2.17 DELs with multiple sites interaction
2.18 Conclusion and future prospects
Acknowledgment
References
3. Cookstoves for biochar production and carbon capture
3.1 Introduction
3.2 Cookstoves designed for biochar production
3.2.1 Top-lit updraft \(TLUD\) stove
3.2.2 Development of TLUD-Akha architecture design
3.2.3 Origins of TLUD-Biochar ^^e2^^80^^98Ecosystem^^e2^^80^^99
3.2.4 Composition of biochar produced from biochar cookstoves
3.2.5 Rural women in carbon capture
3.3 Biochar production and climate-change implications
3.3.1 Biochars and their applications for carbon capture and others
3.3.2 Challenges of biochar cookstoves in rural developing countries
3.4 Conclusion
References
4. Metal support interaction for electrochemical valorization of CO2
4.1 Introduction
4.2 Metal supports for ECR of CO2
4.2.1 Carbon and graphene-based support systems
4.2.2 Titanium nanotubes
4.2.3 Foam electrode
4.2.4 Mesoporous electrode
4.2.5 Hydrogel and aerogel
4.2.6 Gas diffusion electrode
4.3 Conclusion
Acknowledgment
References
5. Utilization of carbon dioxide as a building block in synthesis of active pharmaceutical ingredients
5.1 Introduction
5.2 NNucleophile-triggered CO2-incorporated carboxylation to form C^^e2^^80^^93N bonds
5.2.1 Synthesis of carisoprodol
5.2.2 Synthesis of felbamate
5.2.3 Synthesis of furaltadone
5.2.4 Synthesis of oxadiazon
5.2.5 Synthesis of oxazolidinone
5.2.6 Synthesis of toloxatone
5.2.7 Synthesis of doxazosin, bunazosin, and prazosin
5.2.8 Synthesis of zenarestat and KF-31327
5.2.9 Synthesis of tipifarnib
5.2.10 Synthesis of MAO-B inhibitor
5.2.11 Synthesis of URB602
5.2.12 Synthesis of alpha-alanine
5.3 NNucleophile-triggered CO2-incorporated methylation to form C^^e2^^80^^93N bonds
5.3.1 Synthesis of butenafine
5.3.2 Synthesis of methylephedrine
5.3.3 Synthesis of naftifine
5.4 ONucleophile-triggered CO2-incorporated carboxylation to form C^^e2^^80^^93O bonds
5.4.1 Synthesis of atorvastatin
5.5 CO2-catalyzed oxidation of alcohols to form C^^e2^^80^^93O bonds
5.5.1 Synthesis of DMU-212 and combretastatin A-4
5.6 C-Nucleophile-triggered CO2-incorporated reductive carboxylation to form C^^e2^^80^^93C bonds
5.6.1 Synthesis of methionine hydroxy analog
5.6.2 Synthesis of naproxen
5.7 C-nucleophile-triggered CO2-incorporated direct C^^e2^^80^^93H carboxylation to form C^^e2^^80^^93C bond
5.7.1 Synthesis of aspirin
5.7.2 Synthesis of 4-aminosalicylic acid
5.7.3 Synthesis of diflunisal
5.7.4 Synthesis of gentisic acid
5.8 C-nucleophile-triggered CO2-incorporated organozinc-mediated carboxylation to form C^^e2^^80^^93C bonds
5.8.1 Synthesis of tamoxifen
5.8.2 Synthesis of \(E\)^^e2^^88^^923-Benzylidene-2-indolinone
5.8.3 Synthesis of ibuprofen
5.9 C-nucleophile-triggered CO2-incorporated organolithium-mediated carboxylation to form a C^^e2^^80^^93C bond
5.9.1 Synthesis of repaglinide
5.9.2 Synthesis of flurbiprofen
5.9.3 Synthesis of epristeride
5.9.4 Synthesis of mefloquine
5.9.5 Synthesis of amitriptyline
5.9.6 Synthesis of methantheline bromide
5.9.7 Synthesis of garenoxacin
5.9.8 Synthesis of englitazone
5.10 C-Nucleophile-triggered CO2-incorporated organomagnesium-mediated carboxylation to form a C^^e2^^80^^93C bond
5.10.1 Synthesis of enadoline
5.10.2 Synthesis of loxoprofen
5.10.3 Synthesis of lamotrigine
5.10.4 Synthesis of felbinac
5.10.5 Synthesis of spironolactone
5.10.6 Synthesis of finafloxacin
5.11 Conclusion
References
6. Electrochemical Carbon Dioxide Detection
6.1 Introduction
6.2 Capture technologies of CO2
6.2.1 Adsorption
6.2.2 Absorption
6.2.3 Separation by membranes
6.2.4 Chemical capture
6.2.5 CO2 sensors
6.3 Fundamentals of electrochemistry
6.3.1 Voltammetry
6.3.2 Potentiometric methods
6.4 Direct potentiometric methods
6.4.1 Potentiometric titrations
6.4.2 Amperometric methods
6.4.3 Conductometric methods
6.4.4 Coulometric analysis methods
6.4.5 Electrodes
6.4.6 Reference electrode
6.4.7 Auxiliary electrode
6.4.8 Potentiometric electrodes
6.4.9 Indicator electrodes
6.4.10 Electrochemical gas sensors
6.4.11 Potentiometric gas sensors
6.4.12 Electrochemical applications
6.5 Summary and conclusion
References
7. Carbon dioxide injection for enhanced oil recovery and underground storage to reduce greenhouse gas
7.1 Introduction
7.1.1 Global carbon management concerns
7.1.2 CO2 availability
7.1.3 Options available for CO2 storage
7.1.4 Comparison of available storage methods
7.2 Oil recovery using CO2
7.2.1 Hydrocarbon miscibility
7.2.2 CO2 miscible injection method
7.2.3 Injection and storage facilities required
7.2.4 Storage capacity calculations
7.2.5 Impact on economics and tax incentives
7.3 Underground storage of CO2 in unconventional reservoirs
7.4 Current status, challenges and future directions
7.5 Conclusions
Acknowledgment
References
8. Ionic liquids as potential materials for carbon dioxide capture and utilization
8.1 Introduction
8.2 Types of ILs
8.2.1 Conventional ionic liquids \(CILs\)
8.2.2 Functionalized ionic liquids \(FILs\)
8.2.3 Reversible ionic liquids \(RILs\)
8.2.4 Polymeric ionic liquids \(PILs\)
8.2.5 Supported ionic liquids \(SILs\)
8.2.6 Magnetic ionic liquids \(MILs\)
8.2.7 Task specific ionic liquids \(TSILs\)
8.2.8 Multiphasic ionic liquids \(MILs\)
8.2.9 Switchable polarity ionic liquids \(S-Polymeric ionic liquids\)
8.2.10 Thermoregulated ionic liquids \(TRILs\)
8.2.11 Ionic liquids gel
8.3 Future applications of IL and GR-based IL
8.4 Conclusion
References
9. Recent advances in carbon dioxide utilization as renewable energy
9.1 Introduction
9.2 CO2 utilization technologies
9.2.1 Mineralization
9.2.2 Beverage and food processing
9.2.3 Biological utilization
9.2.4 Oil recovery enhancement, coal bed methane and fracking of CO2
9.2.5 Fuels and chemicals
9.2.6 Principal and favorable utilization technologies
9.3 Developments in worldwide CO2 utilization projects
9.3.1 United states
9.3.2 China
9.3.3 Germany
9.3.4 Australia
9.4 Market scale and value
9.5 Regulation and policy
9.6 Conclusion and future prospects
References
10. Metal Organic Frameworks as an Efficient Method for Carbon dioxide capture
10.1 Introduction
10.2 Metal organic framework \(MOF\)
10.2.1 Conventional synthesis route
10.2.2 Microwave synthesis technique
10.2.3 Sonochemical synthesis
10.2.4 Mechanochemical synthesis
10.2.5 Electrochemical synthesis
10.3 Synthesis of some MOFS
10.4 Properties of MOFs
10.4.1 Chemical and thermal
10.4.2 Mechanical
10.4.3 Thermal conductivity
10.5 CO2 capture using MOF
10.6 Adsorption of carbon dioxide in metal organic frameworks
10.7 Methods to enhance CO2 adsorption
10.8 Methods to enhance MOF stability
10.8.1 Chemical stabilities
10.8.2 Thermal stabilities
10.8.3 Mechanical stability
10.9 Conclusion
References
11. Industrial carbon dioxide capture and utilization
11.1 Introduction
11.1.1 Commercial capturing processes of carbon dioxide gas
11.2 CO2 collection systems based on liquid
11.2.1 Amine-type liquid solvents for capturing CO2 gas
11.2.2 Basic working principle of absorbents based on liquid amines
11.2.3 Advances in amine-type liquid absorbent materials
11.2.4 Mixtures of amine solvents
11.2.5 Overview and prospects for liquid amine-based absorbents
11.3 CO2 capturing with ionic liquid solvents
11.3.1 Working principle of ionic liquid-based absorbents
11.3.2 Advancement in ionic solvents
11.3.3 Overview and prospects of ionic liquid-based solvents
11.4 Applications, implementation and challenges
11.5 Solid CO2 adsorbents for low-temperature applications
11.5.1 Impact of impurities
11.5.2 Solid amine-based adsorbents: introduction and future prospects
11.6 Carbon adsorbents
11.6.1 Tuning of carbon textural properties
11.6.2 Carbon surfaces with chemical modification
11.6.3 Carbon-based hybrid composites fabrication
11.7 Zeolite adsorbents
11.7.1 Adaptations through cation exchange
11.7.2 Amine impregnation
11.7.3 Fabrication of zeolite-based hybrid materials
11.7.4 Overview and prospects for zeolite-based adsorbents
11.8 Adsorbents of the MOF \(metal^^e2^^80^^93organic framework\) type
11.8.1 Functional component integration
11.8.2 Regulation of intrinsic properties
11.8.3 Overview and prospects for MOF-based adsorbents
11.9 Adsorbents predicated on carbonate-based alkalis
11.9.1 Post-combustion applications, difficulties and implementation
11.9.2 Solid CO2 adsorbents for intermediate temperature applications
11.10 Layered double hydroxides \(LDHs\)-based adsorbents
11.10.1 The influence of LDHs' chemical composition and manufacturing methods
11.11 Adsorbents made of magnesium oxide \(MgO\)
11.11.1 Mesoporous structure fabrication
11.11.2 Transformation of molten salts
11.11.3 Overview and prospects for MgO type adsorbent materials
11.12 Solid CO2 sorbents for high-temperature applications
11.12.1 Calcium oxide \(CaO\) sorbents
11.12.2 Improvements in CO2 collecting efficiency
11.12.3 Modifications in sintering-resistance
11.12.4 CaO generated from discarded materials
11.12.5 Granulation of powder
11.12.6 Overview and future prospects for CaO adsorbents
11.13 Pre-combustion applications, implementation and problems
11.14 The utilisation of CO2 in industrial processes
11.14.1 Conversion of CO2 to energy
11.14.2 Thermochemical method for CO2 methanation
11.14.3 The thermochemical method for dry CO2 and methane reforming
11.14.4 RWGS \(reverse water-to-gas shift\) reaction thermo -- chemical methodology
11.14.5 Methanol is produced by the thermochemical electrolysis of water of carbon dioxide
11.14.6 hydrogenation of CO2 to hydrocarbons through a thermochemical process
11.14.7 Carbon dioxide \(CO2\) photochemical conversion
11.14.8 Photocatalytic CO2 reduction perspectives and prospects
11.14.9 A sorting oxidant: CO2
11.5 Conclusions and prospects
References
12. Ionic liquids for carbon capturing and storage
12.1 Introduction
12.2 CO2 capture technologies
12.3 Ionic liquids \(ILs\)
12.4 Features of ILs
12.5 IL as absorbents for CO2 capture
12.5.1 Conventional ionic liquids
12.5.2 ILs based hybridized solvents
12.6 IL hybrids as adsorbents for CO2 capture
12.7 IL hybrids with membranes for CO2 capture
12.8 Ionic liquid supported membrane
12.9 Poly ILs membrane
12.10 Composite membranes
12.11 Conclusion and future insights
References
13. Advances in utilization of carbon-dioxide for food preservation and storage
13.1 Introduction
13.2 Utilization of carbon-dioxide in food preservation
13.2.1 Beverage drink preservation
13.2.2 Drying of vegetables and fruits
13.2.3 Food preservation using dry ice
13.2.4 Animal stunning procedure
13.2.5 Tanning of animal skin
13.3 Utilization of carbon-dioxide in food storage
13.3.1 Control of storage microsphere
13.3.2 Storage equipment disinfection
13.4 Prospects and conclusion
References
14. An insight into the recent developments in membrane-based carbon dioxide capture and utilization
14.1 Introduction
14.2 Carbon dioxide capture technologies
14.3 A brief about membrane technology
14.4 CO2 separation using membranes
14.4.1 Pre-combustion CO2 capture using membranes
14.4.2 Oxy-fuel combustion CO2 capture using membranes
14.4.3 Post-combustion CO2 capture using membranes
14.4.4 Future considerations for membrane-based CO2 capture
14.5 CO2 utilization using membranes
14.6 Conclusions
References
15. Carbon dioxide to fuel using solar energy
15.1 Introduction
15.2 CO2 reduction onto semiconductor surface
15.3 Major bottleneck for CO2 reduction
15.4 Different types of photo catalyst
15.4.1 Homogeneous photo-catalysts
15.4.2 Cu based photo-catalysts
15.5 Reduction of CO2 to methanol using Cu2O as photo catalyst
15.6 Reduction of CO2 to methanol using Cu2O as electro catalyst
15.6.1 Reduced graphene-oxide, Cu2O and amine compounds composite photo catalysts for CO2 reduction
15.7 Benefits of using RGOin the composite catalyst
15.8 Conclusions
Acknowledgment
References
16. Adsorbents for carbon capture
16.1 Introduction
16.2 Carbon capture processes
16.2.1 Pre-combustion carbon capture
16.2.2 Post-combustion carbon capture
16.3 Adsorbents for CO2 capture
16.3.1 Materials derived from biomass
16.3.2 Clays
16.3.3 Zeolites
16.3.4 Metal-organic frameworks \(MOFs\)
16.3.5 Covalent-organic frameworks \(COFs\)
16.4 Future perspective and conclusion
References
17. Carbon dioxide capture and utilization in ionic liquids
17.1 Introduction
17.2 Capture of CO2 in ILs
17.2.1 Conventional ionic liquids
17.2.2 CO2 capture by functionalized ionic liquids
17.2.3 Capture CO2 by metal coordination-based \(chelate-based\) ionic liquids
17.2.4 CO2 capture by ILs based mixtures
17.2.5 Polyionic liquid membranes
17.2.6 CO2 captures by supported ionic liquid membranes
17.3 Electroreduction of CO2 in ILs
17.3.1 Electrochemical reduction of CO2 to CO
17.3.2 Electrochemical reduction of CO2 to HCOOH
17.3.3 Electroreduction of CO2 to CH3OH
17.3.4 Electrochemical reduction of CO2 to cyclic carbonate
17.3.5 Electrochemical reduction of CO2 to ketone compounds
17.3.6 Electroreduction of CO2 to urea
17.3.7 Electroreduction of CO2 to carbamate
17.3.8 Electroreduction of CO2 to amides and methylamines
17.3.9 Electrochemical reduction of CO2 to other compounds
17.4 Conclusions
Acknowledgments
References
18. Hydrothermal carbonization of sewage sludge for carbon negative energy production
18.1 Introduction
18.2 Sludge as a potential source of alternate energy
18.3 Hydrothermal \(HT\) treatments for the production of fuel
18.3.1 Thermal hydrolysis
18.3.2 Hydrothermal carbonization
18.3.3 Hydrothermal liquefaction
18.3.4 Hydrothermal gasification \(HTG\)
18.4 Hydrothermal carbonization^^c2^^a0+^^c2^^a0gasification^^c2^^a0+^^c2^^a0ccs
18.5 Conclusion
Acknowledgement
References
19. Utilization of supercritical CO2 for drying and production of starch and cellulose aerogels
19.1 Introduction
19.2 CO2 application -- Supercritical drying
19.2.1 How does supercritical drying work?
19.3 Starch aerogel and CO2 utilization
19.3.1 Starch specific aerogels
19.3.2 Hybrid starch aerogels
19.3.3 Mechanical properties of starch aerogels
19.3.4 Topology and morphology of starch aerogels
19.4 Cellulose aerogels and CO2 utilization
19.4.1 Cellulose specific aerogels
19.4.2 Cellulose aerogels as thermal insulators
19.4.3 Hybrid cellulose aerogels
19.5 Conclusions
Author contributions
Ethical approval
Declaration of competing interest
Acknowledgment
References
20. Advances in carbon bio-sequestration
20.1 Introduction
20.2 Carbon sequestration methods
20.3 Limitations of carbon sequestration methods
20.4 Overview of biological sequestration \(Cycle/Mechanism\)
20.5 Bioresources for carbon bio-sequestration
20.6 Cyanobacteria
20.7 Microalgae
20.8 Plants
20.9 Bacteria
20.10 Nanomaterials in carbon sequestration
20.11 Future perspectives
20.12 Conclusion
References
21. Photosynthetic cell factories, a new paradigm for carbon dioxide \(CO2\) valorization
21.1 Introduction
21.2 Carbon capture, utilization and storage mechanism
21.2.1 Pre-combustion capture
21.2.2 Post-combustion capture
21.2.3 Oxy-fuel combustion
21.2.4 Carbon capture by microalgae
21.3 Biological mechanism of carbon capture
21.4 Products from CCU
21.5 Challenges and opportunities
21.5.1 Pre-Combustion technology
21.5.2 Post-Combustion capture
21.5.3 Oxy-fuel combustion
21.5.4 Bio-carbon capture by microalgae
21.6 Future perspectives and conclusions
Funding information
References
22. Carbon dioxide capture and sequestration technologies ^^e2^^80^^93 current perspective, challenges and prospects
22.1 Introduction
22.2 Carbon capture and sequestration \(CCS\) technologies
22.2.1 Carbon capture strategies
22.2.2 Carbon capture technologies
22.3 CO2 transportation, storage and opportunities/applications for CCS technologies
22.3.1 Transportation
22.3.2 Carbon storage
22.4 Current perspective and policies of CSS technologies in various countries throughout the world
22.4.1 Review of CCS policies
22.4.2 Artificial intelligence \(AI\) applications in carbon capture
22.5 Challenges and socio-economic implications of CCS technologies
22.5.1 Post-combustion capture challenges
22.5.2 Geologic storage challenges
22.5.3 Gasification challenges
22.5.4 Environmental impact of CCS technologies
22.5.5 Socio-economic impact of CCS technologies
22.6 Applications and opportunities for CCS techniques
22.6.1 Electricity power generation
22.6.2 Industrial application
22.6.3 Application of CCS techniques in CO2 capture from exhaust gases capture
22.6.4 Application of CCS techniques in CO2 capture from natural gas
22.7 Prospects and future work considerations for CCS approaches
22.8 Conclusion
References
23. Microbial carbon dioxide fixation for the production of biopolymers
23.1 Introduction
23.2 Sources of CO2 emission
23.3 Sequestration methods of CO2
23.4 Carbon concentrating mechanisms
23.5 Advancements in carbon capture and storage & carbon capture utilization
23.6 Carbon dioxide fixation pathways
23.6.1 Calvin cycle
23.6.2 Reductive TCA cycle
23.6.3 Wood-Ljungdahl pathway
23.6.4 Dicarboxylate^^e2^^80^^914-hydroxybutyrate cycle
23.6.5 Malyl Co-A/3-hydroxypropionate pathway \(3-hydroxypropionate bicycle\)
23.6.6 Hydroxy propionate-hydroxybutyrate cycle
23.7 Factors affecting the carbon dioxide biofixation
23.8 Production of biopolymers/bioplastics
23.9 Conclusion
References
24. Carbon dioxide capture and its enhanced utilization using microalgae
24.1 Introduction
24.2 Photosynthesis and CO2 fixation using microalgae
24.2.1 Photosynthesis
24.2.2 CO2 fixation
24.3 Cultivation systems for carbon dioxide capture by microalgae
24.3.1 Physico-chemical properties and carbon dioxide sources
24.3.2 CO2 capture prospects for microalgae cultivation
24.3.3 The impact of cultivation methods on biomass production
24.3.4 Microalgae culture system for CO2 capture
24.4 CO2 capture improvement strategies
24.4.1 CO2 capture can be improved by genetic engineering and metabolic changes
24.5 Conclusion
References
25. Supported single-atom catalysts in carbon dioxide electrochemical activation and reduction
25.1 Introduction
25.2 CO2ERR products
25.3 Single-Atom catalysts efficiency descriptors
25.4 Single-Atom catalyst supports
25.4.1 Two-dimensional \(2D\) metal oxides
25.4.2 Two-dimensional \(2D\) metal chalcogenides
25.4.3 Metal carbides, nitrides \(MXenes\)
25.4.4 Metal-Organic frameworks
25.5 Mechanisms for CO2ERR on single-atom catalysts
25.6 Conclusion
References
26. Organic matter and mineralogical acumens in CO2 sequestration
Abbreviations
26.1 Overview
26.2 Introduction
26.3 Geo-sequestration
26.4 Bio-sequestration
26.5 Mechanisms of carbon capture
26.5.1 Pre-combustion
26.5.2 Post-combustion
26.5.3 Oxyfuel combustion
26.6 Transport of carbon dioxide
26.7 Mechanism of carbon accommodation
26.8 Carbon dioxide sequestration in organic matter
26.8.1 Carbon dioxide sequestration in coal
26.8.2 Carbon dioxide sequestration in shale
26.9 Mineralogical acumen of carbon sequestration
26.9.1 An overview
26.9.2 Clay minerals
26.9.3 Swelling properties of clay minerals
26.9.4 Carbon protection capacity of clay minerals
26.9.5 Methods of organic carbon protection by clays
26.9.6 Adsorption of carbon dioxide on clays
26.9.7 Supercritical carbon dioxide sequestration in clays: an additional chronicle
26.9.8 Adverse influences of carbon dioxide sequestration in clays
26.10 A note on CO2 disposal in basalt formations
26.11 Summary
References
Index

Citation preview

GREEN SUSTAINABLE PROCESS FOR CHEMICAL AND ENVIRONMENTAL ENGINEERING AND SCIENCE

GREEN SUSTAINABLE PROCESS FOR CHEMICAL AND ENVIRONMENTAL ENGINEERING AND SCIENCE Carbon Dioxide Capture and Utilization Edited by

Inamuddin Department of Applied Chemistry, Zakir Husain College of Engineering and Technology, Faculty of Engineering and Technology, Aligarh Muslim University, Aligarh, Uttar Pradesh, India

Tariq Altalhi Department of Chemistry, College of Science, Taif University, Taif, Saudi Arabia

Elsevier Radarweg 29, PO Box 211, 1000 AE Amsterdam, Netherlands The Boulevard, Langford Lane, Kidlington, Oxford OX5 1GB, United Kingdom 50 Hampshire Street, 5th Floor, Cambridge, MA 02139, United States Copyright © 2023 Elsevier Inc. All rights reserved. No part of this publication may be reproduced or transmitted in any form or by any means, electronic or mechanical, including photocopying, recording, or any information storage and retrieval system, without permission in writing from the publisher. Details on how to seek permission, further information about the Publisher’s permissions policies and our arrangements with organizations such as the Copyright Clearance Center and the Copyright Licensing Agency, can be found at our website: www.elsevier.com/permissions. This book and the individual contributions contained in it are protected under copyright by the Publisher (other than as may be noted herein). Notices Knowledge and best practice in this field are constantly changing. As new research and experience broaden our understanding, changes in research methods, professional practices, or medical treatment may become necessary. Practitioners and researchers must always rely on their own experience and knowledge in evaluating and using any information, methods, compounds, or experiments described herein. In using such information or methods they should be mindful of their own safety and the safety of others, including parties for whom they have a professional responsibility. To the fullest extent of the law, neither the Publisher nor the authors, contributors, or editors, assume any liability for any injury and/or damage to persons or property as a matter of products liability, negligence or otherwise, or from any use or operation of any methods, products, instructions, or ideas contained in the material herein. ISBN: 978-0-323-99429-3 For Information on all Elsevier publications visit our website at https://www.elsevier.com/books-and-journals Publisher: Susan Dennis Acquisitions Editor: Anita Koch Editorial Project Manager: Franchezca A. Cabural Production Project Manager: Swapna Srinivasan Cover Designer: Christian J. Bilbow Typeset by Aptara, New Delhi, India

Contents Contributors

xi

Acknowledgment References

Chapter 1 Carbon dioxide capture and its utilization towards efficient biofuels production 1

Chapter 3 Cookstoves for biochar production and carbon capture 53 Mashura Shammi, Julien Winter, Md. Mahbubul Islam, Beauty Akter, and Nazmul Hasan

Abhinay Thakur, and Ashish Kumar

1.1 Introduction 1.2 Utilization of captured carbon dioxide for biofuel production 1.3 Conclusion and future perspectives References

1

3.1 Introduction 3.2 Cookstoves designed for biochar production 3.3 Biochar production and climate-change implications 3.4 Conclusion References

5 13 13

Chapter 2 Deep eutectic liquids for carbon capturing and fixation 17

2.8 2.9 2.10 2.11 2.12 2.13 2.14 2.15 2.16 2.17 2.18

Carbon dioxide emissions Deep eutectic liquids Types of deep eutectic liquids Preparation of DELs Authentication of DELs DEL based CO2 absorption Carbon capture efficiency of various HBDs CO2 absorption in aqueous solution of DELs CO2 absorption in ternary DELs Ammonium-Based DELs Phosphonium based DELs Azole based DELs Bio-phenol derived superbase based DELs Hydrophobic DELs Non-ionic DELs DEL supported membranes DELs with multiple sites interaction Conclusion and future prospects

53 54 62 64 65

Chapter 4 Metal support interaction for electrochemical valorization of CO2 69

Zainab Liaqat, Sumia Akram, Hafiz Muhammad Athar, and Muhammad Mushtaq

2.1 2.2 2.3 2.4 2.5 2.6 2.7

49 49

17 19 19 20 21 22

Abinaya Stalinraja, and Keerthiga Gopalram

4.1 Introduction 4.2 Metal supports for ECR of CO2 4.3 Conclusion Acknowledgment References

24

69 70 80 80 81

Chapter 5 Utilization of carbon dioxide as a building block in synthesis of active pharmaceutical ingredients 85

40 41 42 44 44 45 45 46 46 47 48

Muhammad Faisal

5.1 Introduction 5.2 N–Nucleophile-triggered CO2 -incorporated carboxylation to form C–N bonds 5.3 N–Nucleophile-triggered CO2 -incorporated methylation to form C–N bonds

v

85

87

95

vi

Contents

5.4 O–Nucleophile-triggered CO2 -incorporated carboxylation to form C–O bonds 96 5.5 CO2 -catalyzed oxidation of alcohols to form C–O bonds 97 5.6 C-Nucleophile-triggered CO2 -incorporated reductive carboxylation to form C–C bonds 97 5.7 C-nucleophile-triggered CO2 -incorporated direct C–H carboxylation to form C–C bond 99 5.8 C-nucleophile-triggered CO2 -incorporated organozinc-mediated carboxylation to form C–C bonds 101 5.9 C-nucleophile-triggered CO2 -incorporated organolithium-mediated carboxylation to form a C–C bond 102 5.10 C-Nucleophile-triggered CO2 -incorporated organomagnesium-mediated carboxylation to form a C–C bond 108 5.11 Conclusion 111 References 113

Chapter 6 Electrochemical Carbon Dioxide Detection 119 S. Aslan, C. I¸sık, and A.E. Mamuk

6.1 Introduction 6.2 Capture technologies of CO2 6.3 Fundamentals of electrochemistry 6.4 Direct potentiometric methods 6.5 Summary and conclusion References

119 121 126 128 139 141

Chapter 7 Carbon dioxide injection for enhanced oil recovery and underground storage to reduce greenhouse gas 149 Shubham Saraf, and Achinta Bera

7.1 Introduction 7.2 Oil recovery using CO2 7.3 Underground storage of CO2 in unconventional reservoirs 7.4 Current status, challenges and future directions 7.5 Conclusions Acknowledgment References

149 156 167 169 170 172 172

Chapter 8 Ionic liquids as potential materials for carbon dioxide capture and utilization 177 Md Abu Shahyn Islam, Mohd Arham Khan, Nimra Shakeel, Mohd Imran Ahamed, and Naushad Anwar

8.1 Introduction 8.2 Types of ILs 8.3 Future applications of IL and GR-based IL 8.4 Conclusion References

178 179 191 192 193

Chapter 9 Recent advances in carbon dioxide utilization as renewable energy 197 Muhammad Hussnain Siddique, Fareeha Maqbool, Tanvir Shahzad, Muhammad Waseem, Ijaz Rasul, Sumreen Hayat, Muhammad Afzal, Muhammad Faisal, and Saima Muzammil

9.1 Introduction 9.2 CO2 utilization technologies 9.3 Developments in worldwide CO2 utilization projects 9.4 Market scale and value 9.5 Regulation and policy 9.6 Conclusion and future prospects References

197 198 204 205 205 206 206

Chapter 10 Metal Organic Frameworks as an Efficient Method for Carbon dioxide capture 211 Bharti Kataria, and Christine Jeyaseelan

10.1 10.2 10.3 10.4 10.5 10.6

Introduction Metal organic framework (MOF) Synthesis of some MOFS Properties of MOFs CO2 capture using MOF Adsorption of carbon dioxide in metal organic frameworks 10.7 Methods to enhance CO2 adsorption 10.8 Methods to enhance MOF stability 10.9 Conclusion References

211 212 215 217 217 219 219 222 227 227

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Contents

Chapter 11 Industrial carbon dioxide capture and utilization 231

12.11 Conclusion and future insights References

Uzma Hira, Ahmed Kamal, and Javeria Tahir

11.1 11.2 11.3 11.4

Introduction CO2 collection systems based on liquid CO2 capturing with ionic liquid solvents Applications, implementation and challenges 11.5 Solid CO2 adsorbents for low-temperature applications 11.6 Carbon adsorbents 11.7 Zeolite adsorbents 11.8 Adsorbents of the MOF (metal–organic framework) type 11.9 Adsorbents predicated on carbonate-based alkalis 11.10 Layered double hydroxides (LDHs)-based adsorbents 11.11 Adsorbents made of magnesium oxide (MgO) 11.12 Solid CO2 sorbents for high-temperature applications 11.13 Pre-combustion applications, implementation and problems 11.14 The utilisation of CO2 in industrial processes 11.15 Conclusions and prospects References

231 233 242 244 245 246 248 250 252 254 255 257 260 262 268 270

12.7 12.8 12.9 12.10

Adeshina Fadeyibi

13.1 Introduction 13.2 Utilization of carbon-dioxide in food preservation 13.3 Utilization of carbon-dioxide in food storage 13.4 Prospects and conclusion References

297 298 302 305 305

Chapter 14 An insight into the recent developments in membrane-based carbon dioxide capture and utilization 311 Pritam Dey, Pritam Singh, and Mitali Saha

14.1 Introduction 14.2 Carbon dioxide capture technologies 14.3 A brief about membrane technology 14.4 CO2 separation using membranes 14.5 CO2 utilization using membranes 14.6 Conclusions References

311 312 314 316 321 322 323

Srijita Basumallick

Faizan Waseem Butt, Hafiz Muhammad Athar, Sumia Akram, Zainab Liaqat, and Muhammad Mushtaq

Introduction CO2 capture technologies Ionic liquids (ILs) Features of ILs IL as absorbents for CO2 capture IL hybrids as adsorbents for CO2 capture IL hybrids with membranes for CO2 capture Ionic liquid supported membrane Poly ILs membrane Composite membranes

Chapter 13 Advances in utilization of carbon-dioxide for food preservation and storage 297

Chapter 15 Carbon dioxide to fuel using solar energy 327

Chapter 12 Ionic liquids for carbon capturing and storage 279

12.1 12.2 12.3 12.4 12.5 12.6

291 291

279 280 281 281 283 289 289 290 290 290

15.1 Introduction 15.2 CO2 reduction onto semiconductor surface 15.3 Major bottleneck for CO2 reduction 15.4 Different types of photo catalyst 15.5 Reduction of CO2 to methanol using Cu2 O as photo catalyst 15.6 Reduction of CO2 to methanol using Cu2 O as electro catalyst 15.7 Benefits of using RGOin the composite catalyst 15.8 Conclusions

327 327 328 329 330 330 331 333

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Contents

Acknowledgment References

333 333

Chapter 16 Adsorbents for carbon capture 337 Vijay Vaishampayan, Mukesh Kumar, Muthamilselvi Ponnuchamy, and Ashish Kapoor

16.1 Introduction 16.2 Carbon capture processes 16.3 Adsorbents for CO2 capture 16.4 Future perspective and conclusion References

337 338 338 342 342

Chapter 17 Carbon dioxide capture and utilization in ionic liquids 345 Guocai Tian

17.1 Introduction 17.2 Capture of CO2 in ILs 17.3 Electroreduction of CO2 in ILs 17.4 Conclusions Acknowledgments References

345 349 391 406 407 407

Chapter 18 Hydrothermal carbonization of sewage sludge for carbon negative energy production 427 Milan Malhotra, Anusha Sathyanadh, and Khanh-Quang Tran

18.1 Introduction 18.2 Sludge as a potential source of alternate energy 18.3 Hydrothermal (HT) treatments for the production of fuel 18.4 Hydrothermal carbonization + gasification + ccs 18.5 Conclusion Acknowledgement References

427 431 432 437 437 438 438

Chapter 19 Utilization of supercritical CO2 for drying and production of starch and cellulose aerogels 441 Jeieli Wendel Gaspar Lima, Clara Prestes Ferreira, Jhonatas Rodrigues Barbosa, and Raul Nunes de Carvalho Junior

19.1 Introduction 19.2 CO2 application – Supercritical drying 19.3 Starch aerogel and CO2 utilization 19.4 Cellulose aerogels and CO2 utilization 19.5 Conclusions Author contributions Ethical approval Declaration of competing interest Acknowledgment References

441 442 445 447 448 449 449 449 449 449

Chapter 20 Advances in carbon bio-sequestration 451 Nigel Twi-Yeboah, Dacosta Osei, and Michael K. Danquah

20.1 Introduction 20.2 Carbon sequestration methods 20.3 Limitations of carbon sequestration methods 20.4 Overview of biological sequestration (Cycle/Mechanism) 20.5 Bioresources for carbon bio-sequestration 20.6 Cyanobacteria 20.7 Microalgae 20.8 Plants 20.9 Bacteria 20.10 Nanomaterials in carbon sequestration 20.11 Future perspectives 20.12 Conclusion References

451 452 453 454 455 456 457 457 458 458 459 459 460

Chapter 21 Photosynthetic cell factories, a new paradigm for carbon dioxide 463 (CO2 ) valorization Bijaya Nag, Abdalah Makaranga, Mukul Suresh Kareya, Asha Arumugam Nesamma, and Pannaga Pavan Jutur

21.1 Introduction 21.2 Carbon capture, utilization and storage mechanism 21.3 Biological mechanism of carbon capture 21.4 Products from CCU 21.5 Challenges and opportunities 21.6 Future perspectives and conclusions Funding information References

463 465 469 470 472 475 476 476

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Contents

Chapter 24 Carbon dioxide capture and its enhanced utilization using microalgae 531

Chapter 22 Carbon dioxide capture and sequestration technologies – current perspective, challenges and prospects 481 Ifeanyi Michael Smarte Anekwe, Emmanuel Kweinor Tetteh, Stephen Akpasi, Samaila Joel Atuman, Edward Kwaku Armah, and Yusuf Makarfi Isa

22.1 Introduction 22.2 Carbon capture and sequestration (CCS) technologies 22.3 CO2 transportation, storage and opportunities/applications for CCS technologies 22.4 Current perspective and policies of CSS technologies in various countries throughout the world 22.5 Challenges and socio-economic implications of CCS technologies 22.6 Applications and opportunities for CCS techniques 22.7 Prospects and future work considerations for CCS approaches 22.8 Conclusion References

481 484

493

497 501 504

Tuba Saleem, Ijaz Rasul, Muhammad Asif, and Habibullah Nadeem

Introduction Sources of CO2 emission Sequestration methods of CO2 Carbon concentrating mechanisms Advancements in carbon capture and storage & carbon capture utilization 23.6 Carbon dioxide fixation pathways 23.7 Factors affecting the carbon dioxide biofixation 23.8 Production of biopolymers/bioplastics 23.9 Conclusion References

24.1 Introduction 24.2 Photosynthesis and CO2 fixation using microalgae 24.3 Cultivation systems for carbon dioxide capture by microalgae 24.4 CO2 capture improvement strategies 24.5 Conclusion References

531 532 533 541 541 541

Chapter 25 Supported single-atom catalysts in carbon dioxide electrochemical activation and reduction 547 Amos Afugu, Caroline R. Kwawu, Elliot Menkah, and Evans Adei

507 508 509

Chapter 23 Microbial carbon dioxide fixation for the production of biopolymers 517 23.1 23.2 23.3 23.4 23.5

Pinku Chandra Nath, Biswanath Bhunia, and Tarun Kanti Bandyopadhyay

25.1 Introduction 25.2 CO2 ERR products 25.3 Single-Atom catalysts efficiency descriptors 25.4 Single-Atom catalyst supports 25.5 Mechanisms for CO2 ERR on single-atom catalysts 25.6 Conclusion References

517 519 519 520

549 551 554 556 557

Chapter 26 Organic matter and mineralogical acumens in CO2 sequestration 561

521 521 527 527 529 529

547 549

Santanu Ghosh, Tushar Adsul, and Atul Kumar Varma

26.1 26.2 26.3 26.4

Overview Introduction Geo-sequestration Bio-sequestration

562 562 563 563

x 26.5 26.6 26.7 26.8

Mechanisms of carbon capture Transport of carbon dioxide Mechanism of carbon accommodation Carbon dioxide sequestration in organic matter 26.9 Mineralogical acumen of carbon sequestration

Contents

564 566 566

26.10 A note on CO2 disposal in basalt formations 26.11 Summary References

587 587 588

566 573

Index

595

Contributors Evans Adei Department of Chemistry, Kwame Nkrumah University of Science and Technology, Kumasi, Ghana

Muhammad Asif Department of Bioinformatics and Biotechnology, Government College University Faisalabad, Faisalabad, Pakistan S. Aslan Department of Chemistry, Faculty of Science, Mugla Sitki Kocman University, Mugla, Turkey Hafiz Muhammad Athar Department of Chemistry, Government College University, Lahore, Pakistan Samaila Joel Atuman School of Chemical and Metallurgical Engineering, University of the Witwatersrand, Johannesburg, South Africa; Department of Chemical Engineering, Faculty of Engineering, Abubakar Tafawa Balewa University Bauchi, Nigeria Tarun Kanti Bandyopadhyay Department of Chemical Engineering, National Institute of Technology Agartala, Jirania, Tripura, India Jhonatas Rodrigues Barbosa Institute of Technology (ITEC), Faculty of Food Engineering (FEA), Federal University of Para (UFPA), Rua Augusto Corrêa S/N, Guamá, Belém, PA, Brazil Srijita Basumallick Asutosh College, University of Calcutta, Kolkata, India Achinta Bera Department of Petroleum Engineering, School of Energy Technology, Pandit Deendayal Energy University, Gandhinagar, Gujarat, India Biswanath Bhunia Department of Bio Engineering, National Institute of Technology Agartala, Jirania, Tripura, India Faizan Waseem Butt Department of Chemistry, Government College University, Lahore, Pakistan Michael K. Danquah Department of Chemical Engineering, University of Tennessee, Chattanooga TN, United States of America Pritam Dey Department of Chemistry, National Institute of Technology Agartala, Tripura, India

Tushar Adsul Coal Geology and Organic Petrology Laboratory, Department of Applied Geology, Indian Institute of Technology (Indian School of Mines) Dhanbad, Jharkhand, India Amos Afugu Department of Chemistry, Kwame Nkrumah University of Science and Technology, Kumasi, Ghana Muhammad Afzal Department of Bioinformatics and Biotechnology, Government College University Faisalabad, Faisalabad, Pakistan Mohd Imran Ahamed Department of Chemistry, Faculty of Science, Aligarh Muslim University, Aligarh, UP, India Stephen Akpasi Green Engineering Research Group, Department of Chemical Engineering, Faculty of Engineering and the Built Environment, Durban University of Technology, Durban, South Africa Sumia Akram Division of Science and Technology, University of Education Lahore, Pakistan Beauty Akter Department of Environmental Sciences, Jahangirnagar University, Dhaka, Bangladesh Ifeanyi Michael Smarte Anekwe School of Chemical and Metallurgical Engineering, University of the Witwatersrand, Johannesburg, South Africa Naushad Anwar Department of Chemistry, Faculty of Science, Aligarh Muslim University, Aligarh, UP, India Edward Kwaku Armah School of Chemical and Biochemical Sciences, Department of Applied Chemistry, C. K. Tedam University of Technology and Applied Sciences, Navrongo, Upper East Region, Ghana

xi

xii

Contributors

Adeshina Fadeyibi Department of Food and Agricultural Engineering, Faculty of Engineering and Technology, Kwara State University, Ilorin, Kwara State, Nigeria Muhammad Faisal Creative Research Center for Brain Science, Brain Science Institute (BSI), Korea Institute of Science and Technology (KIST), Seoul, Republic of Korea; Division of BioMedical Science & Technology, KIST School, Korea University of Science and Technology (UST), Seoul, Republic of Korea; Department of Chemistry, Quaid-i-Azam University, Islamabad, Pakistan; Institute of Plant Breeding and Biotechnology, MNS-University of Agriculture, Multan, Pakistan Clara Prestes Ferreira Institute of Technology (ITEC), Faculty of Food Engineering (FEA), Federal University of Para (UFPA), Rua Augusto Corrêa S/N, Guamá, Belém, PA, Brazil Santanu Ghosh Coal Geology and Organic Petrology Laboratory, Department of Applied Geology, Indian Institute of Technology (Indian School of Mines) Dhanbad, Jharkhand, India; Organic Geochemistry Laboratory, Department of Earth Sciences, Indian Institute of Technology Bombay, Mumbai, Maharashtra, India; Department of Geology, Mizoram University, Aizwal, Mizoram, India Keerthiga Gopalram Department of Chemical Engineering, SRM Institute of Science & Technology, Kancheepuram, Tamil Nadu, India Sumreen Hayat Departmant of Microbiology, Government College University Faisalabad, Faisalabad, Pakistan Nazmul Hasan The United Graduate School of Agricultural Sciences, Kagoshima University, Kagoshima, Japan; Fruit Science Laboratory, Saga University, Saga, Japan Uzma Hira School of Physical Sciences (SPS), University of the Punjab, Lahore, Pakistan Yusuf Makarfi Isa School of Chemical and Metallurgical Engineering, University of the Witwatersrand, Johannesburg, South Africa Md. Mahbubul Islam Bangladesh Biochar Initiative, Dhaka, Bangladesh

Md Abu Shahyn Islam Interdisciplinary Nanotechnology Centre, ZHCET, Aligarh Muslim University, Aligarh, UP, India C. I¸sık Department of Chemistry, Faculty of Science, Mugla Sitki Kocman University, Mugla, Turkey Christine Jeyaseelan Department of Chemistry, Amity Institute of Applied Sciences, Amity University, Noida, Uttar Pradesh, India Raul Nunes de Carvalho Junior Institute of Technology (ITEC), Faculty of Food Engineering (FEA), Federal University of Para (UFPA), Rua Augusto Corrêa S/N, Guamá, Belém, PA, Brazil Pannaga Pavan Jutur Omics of Algae Group, Industrial Biotechnology, International Centre for Genetic Engineering and Biotechnology, New Delhi, India Ahmed Kamal School of Physical Sciences (SPS), University of the Punjab, Lahore, Pakistan Ashish Kapoor Department of Chemical Engineering, Harcourt Butler Technical University, Kanpur, Uttar Pradesh, India Mukul Suresh Kareya Omics of Algae Group, Industrial Biotechnology, International Centre for Genetic Engineering and Biotechnology, New Delhi, India Bharti Kataria Department of Chemistry, Amity Institute of Applied Sciences, Amity University, Noida, Uttar Pradesh, India Mohd Arham Khan Interdisciplinary Nanotechnology Centre, ZHCET, Aligarh Muslim University, Aligarh, UP, India Ashish Kumar NCE, Department of Science and Technology, Government of Bihar, India Mukesh Kumar Discipline of Chemistry, Indian Institute of Technology, Gandhinagar, Gujarat, India Caroline R. Kwawu Department of Chemistry, Kwame Nkrumah University of Science and Technology, Kumasi, Ghana Zainab Liaqat Department of Chemistry, Government College University, Lahore, Pakistan Jeieli Wendel Gaspar Lima Institute of Technology (ITEC), Faculty of Food Engineering

Contributors

xiii

(FEA), Federal University of Para (UFPA), Rua Augusto Corrêa S/N, Guamá, Belém, PA, Brazil

Technology, Potheri, Kattankulathur, Tamil Nadu, India

Abdalah Makaranga Omics of Algae Group, Industrial Biotechnology, International Centre for Genetic Engineering and Biotechnology, New Delhi, India

Ijaz Rasul Department of Bioinformatics and Biotechnology, Government College University Faisalabad, Faisalabad, Pakistan Mitali Saha Department of Chemistry, National Institute of Technology Agartala, Tripura, India

Milan Malhotra Department of Energy and Process Engineering, Norwegian University of Science and Technology, Trondheim, Norway A.E. Mamuk Department of Physics, Faculty of Science, Mugla Sitki Kocman University, Mugla, Turkey Fareeha Maqbool Department of Bioinformatics and Biotechnology, Government College University Faisalabad, Faisalabad, Pakistan Elliot Menkah Department of Chemistry, Kwame Nkrumah University of Science and Technology, Kumasi, Ghana Muhammad Mushtaq Department of Chemistry, Government College University, Lahore, Pakistan

Tuba Saleem Department of Bioinformatics and Biotechnology, Government College University Faisalabad, Faisalabad, Pakistan Shubham Saraf Department of Petroleum Engineering, School of Energy Technology, Pandit Deendayal Energy University, Gandhinagar, Gujarat, India Anusha Sathyanadh Department of Energy and Process Engineering, Norwegian University of Science and Technology, Trondheim, Norway Nimra Shakeel Department of Chemistry, Faculty of Science, Aligarh Muslim University, Aligarh, UP, India

Saima Muzammil Departmant of Microbiology, Government College University Faisalabad, Faisalabad, Pakistan

Mashura Shammi Hydrobiogeochemistry and Pollution Control Laboratory, Department of Environmental Sciences, Jahangirnagar University, Dhaka, Bangladesh

Habibullah Nadeem Department of Bioinformatics and Biotechnology, Government College University Faisalabad, Faisalabad, Pakistan

Tanvir Shahzad Departmant of Environmental Sciences and Engineering, Government College University Faisalabad, Faisalabad, Pakistan

Bijaya Nag Omics of Algae Group, Industrial Biotechnology, International Centre for Genetic Engineering and Biotechnology, New Delhi, India

Muhammad Hussnain Siddique Department of Bioinformatics and Biotechnology, Government College University Faisalabad, Faisalabad, Pakistan

Pinku Chandra Nath Department of Bio Engineering, National Institute of Technology Agartala, Jirania, Tripura, India

Pritam Singh Department of Chemistry, National Institute of Technology Agartala, Tripura, India

Asha Arumugam Nesamma Omics of Algae Group, Industrial Biotechnology, International Centre for Genetic Engineering and Biotechnology, New Delhi, India

Abinaya Stalinraja Department of Chemical Engineering, SRM Institute of Science & Technology, Kancheepuram, Tamil Nadu, India

Dacosta Osei Chemical and Petroleum Engineering Department, University of Kansas, KS, United States of America Muthamilselvi Ponnuchamy Department of Chemical Engineering, College of Engineering and Technology, SRM Institute of Science and

Javeria Tahir School of Physical Sciences (SPS), University of the Punjab, Lahore, Pakistan Emmanuel Kweinor Tetteh Green Engineering Research Group, Department of Chemical Engineering, Faculty of Engineering and the Built Environment, Durban University of Technology, Durban, South Africa

xiv

Contributors

Abhinay Thakur Department of Chemistry, Faculty of Technology and Science, Lovely Professional University, Phagwara, Punjab, India

Vijay Vaishampayan Department of Chemical Engineering, Indian Institute of Technology, Ropar, Punjab, India

Guocai Tian State Key Laboratory of Complex Nonferrous Metal Resources Clean Utilization, Faculty of Metallurgical and Energy Engineering, Kunming University of Science and Technology, Kunming, Yunnan Province, China

Atul Kumar Varma Coal Geology and Organic Petrology Laboratory, Department of Applied Geology, Indian Institute of Technology (Indian School of Mines) Dhanbad, Jharkhand, India

Khanh-Quang Tran Department of Energy and Process Engineering, Norwegian University of Science and Technology, Trondheim, Norway

Muhammad Waseem Departmant of Microbiology, Government College University Faisalabad, Faisalabad, Pakistan

Nigel Twi-Yeboah Operations Department, Ghana National Gas Company, Western Region, Ghana

Julien Winter Private consultant, Cobourg, ON, Canada

C H A P T E R

1 Carbon dioxide capture and its utilization towards efficient biofuels production Abhinay Thakur a and Ashish Kumar b a

Department of Chemistry, Faculty of Technology and Science, Lovely Professional University, Phagwara, Punjab, India b NCE, Department of Science and Technology, Government of Bihar, India

1.1 Introduction When released into the atmosphere, carbon dioxide (CO2 ), a foremost greenhouse gas, retains heat by reflecting infrared light back to the Earth’s surface. As a result, increased CO2 emissions are a worldwide problem because they are one of the primary causes of climate disruption [1–4]. Furthermore, worldwide CO2 emission patterns indicate an annually rise, which is accompanied by an annually rise in overall warming. The rise in CO2 concentration was 2.46 0.26 ppm y−1 in October 2021, as per current statistics, but the temperature has enhanced at an annualized level of 0.08 C per decade since 1980, as per National Oceanic and Atmospheric Administration (NOAA) 2020 annual climate disclose. The result is progressive warming and withering of the environment, which, among other things, is creating enormous and disastrous wildfires around the world, which in turn emit enormous volumes of CO2 into the environment, making carbon releases even more of a problem [5–7]. In actuality, rising CO2 levels in the environment have a variety of other environmental consequences, including adjustments in the hydrogeological process, the enhanced incidence of numerous severe climate occurrences, sea-level rise, speciation migratory, harvest losses, and enhanced events that occurred of infectious diseases, and so on. From 2010 to 2040, consumption for fossil fuels is expected to increase by 40 percent. As a result, alternate energy sources have been and continue to be investigated in order to meet our energy requirements. Renewable energy resources include sunlight, air, and biomass. In the last several years, biomass, which is formed through a physiological origin, has been exploited to generate biofuels and bio-products. There are 4 phases of biofuels, based on the sort of biomass. Biodiesel, bioethanol, bioethanol,

Green Sustainable Process for Chemical and Environmental Engineering and Science: Carbon Dioxide Capture and Utilization DOI: https://doi.org/10.1016/B978-0-323-99429-3.00008-4

1

c 2023 Elsevier Inc. All rights reserved. Copyright 

2

1. Carbon dioxide capture and its utilization towards efficient biofuels production

biohydrogen, and bioethers are examples of biofuels. Bioethanol and biodiesel, which both constitute the first generation of biofuel technologies, are the most common biofuels, as per the Department of Energy. The United States of America, Australia, and the European Union have all financed biofuel experiments. The United States provided financing to New Mexico (2009), Arizona (2008), Florida (2013), and Massachusetts (2011) while the European Union provided funds for four experimental initiatives, three of these operated during 2011 to 2015/16 and the remaining between 2012 and 2017. Biomass is considered as diametrically opposed to the usage of fossil fuels, and hence prevents the release of fresh CO2 into the environment. Utilizing biomass (and biofuels produced from it) is regarded an operation that does not add CO2 to the environment from fossil fuels. Although though it isn’t precisely so, burning biomass or biofuels is regarded a zero-emission solution for power generation and consumption. Despite contrast, comprehensive life cycle analysis investigations demonstrate that, in the existing production–utilization–accounting framework, the usage of biofuels is a carbon transmission through subsurface subsoil to the environment, equivalent to the usage of fossil fuels, albeit considerably less intensively. In truth, biomass is made up of CO2 from the environment, and when burnt, it is thought to restore the equivalent quantity of CO2 to the environment, as if the process were a component of the biological process. In reality, unlike in reality, the cycle is not truly ended. In essence, in contrast to the carbon dioxide produced by combustion processes, one must also evaluate the quantity of CO2 released by numerous human actions that precede biomass generation and processing, as well as the soil carbon depletion induced by agricultural methods [8–15]. By combining telmisartan and a suitable tin(IV) chloride, Hadi et al. [16] was able to create unique, permeable, extremely aromatic organotin(IV) structures. The surface area of the produced mesoporous organotin(IV) complexes was 32.3–130.4 m−2 g−1 , the pore capacity was 0.046–0.162 cm−3 g−1 , and the pore diameter was roughly 2.4 nm, according to Brunauer– Emmett–Teller (BET) calculations. Tin complexes with a butyl group were found to be more effective as carbon dioxide storage devices than those with a phenyl group. At a regulated temperature (323 K) and compression, the dibutyltin(IV) molecule offer the greatest BET interface region (128.871 m−2 g−1 ), the highest quantity (0.162 cm−3 g−1 ), and termed to be effective for CO2 retention (8.3 wt percent) (50 bars). The sorption of compounds was investigated under a specified temperature (323 K) and strain. The H2 and CO2 adsorption isotherms in the presence of compounds are shown in Fig. 1.1. Complexes absorbed a lot of CO2 , which might own because of intense van der Waals contact among them and CO2 . For complexes, the amount of absorbed CO2 was 17.9, 21.2, 15.7, and 34.9 cm−3 g−1 . Evidently, these structures have the maximum Co2 absorption aperture (6.9 wt percent) of the organotin(IV) compound, that could be due to the fact that they have the biggest BET interface region (128.871 m−2 g−1 ). Furthermore, within the organotin(IV) complexes, significant dipole-quadrupole encounters in CO2 or H2 bonding and heteroatoms may occur. When compared to other gases like nitrogen and methane, highly permeable organic polymers having nitrogen, oxygen or sulphur atoms are efficient at preferentially absorbing CO2 . Furthermore, in similar circumstances as those employed for CO2 absorption, complexes display very little H2 adsorption (0.5–1.1 cm−3 g−1 ). It’s possible that this behavior is owing to minimal contact. Similarly, Nasir et al. [17] used the partial pressures of methane and CO2 , as well as the proportions of several membrane materials (polymer, amine, and filler), to link three optimal results in a unified model: CO2 permeance, CH4 permeance, and CO2 /CH4 selectivity.

1.1 Introduction

3

FIGURE 1.1 CO2 and H2 adsorption isotherms for complex (Adapted from Ref. [16]) MDPI 2019. Published in accordance with Creative Common attribution License CCBY 4.0.

These variables aided in forecasting membrane efficiency and influencing secondary variables including membrane life, effectiveness, and product quality. For CO2 permeability, CH4 permeability, and CO2 /CH4 selectivity, the model findings accord with experimental data having an relative deviation of 5.9 percent, 3.8 percent, and 4.1 percent, approximately. The findings suggest that the model could forecast values under a variety of membrane formation configurations. Scholes et al. [18] investigated the capacity of a covalently linked polyether-polyamide block copolymer (PEBAX 2533) and polyethylene glycol diacrylate to extract carbon dioxide through N2 and CH4 in a basic and integrated gas circumstances, as well as when 500 ppm H2 S was involved. The Lennard Jones well depth was found to be a stronger predictor of gas solubility within these polymers than essential temperature. Due to competing sorption from CH4 or N2 , CO2 penetration was decreased in dry mixed gas circumstances relative to single gas measurements. Both polymers, though, maintained CO2 selectivity. Water in the feed caused the PEG membrane to expand, leading in a considerable improvement in CO2 penetration as compared to the gas (dry) environment. Interestingly, the sensitivity was maintained even when the supply gas was moist. The inclusion of H2 S reduces CO2 penetration via both membranes merely slightly. Jiang et al. [19] conducted extensive research on the effects of calcination degrees upon the system architectures of organosilica films. The precursor Bis(triethoxysilyl)acetylene (BTESA) was chosen for membrane manufacturing using the sol-gel method. Calcination degrees influenced film porous width and silanol density, as indicated by TG, FT-IR, N2 adsorption, and molecule tunable gas permeation measurements. The disintegrated acetylene bridges resulted in a loose architecture in the BTESA membrane, which had an extreme high CO2 permeation of 15,531 GPU but a limited CO2 /N2 sensitivity of 4.1. BTESA membranes showed remarkable potential for CO2 extraction applications when they were calcined at 100 °C, with a CO2 permeability of 3434 GPU and a N2 /CO2 sensitivity of 21. FE-SEM was used to analyse BTESA composite membranes that had been calcined at 100 °C in order to learn more about their chemistry, as shown in Fig. 1.2.

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1. Carbon dioxide capture and its utilization towards efficient biofuels production

FIGURE 1.2 SEM images of the BTESA-100 porous film. (Adapted from Ref. [19]) MDPI 2022. Published in accordance with Creative Common attribution License CCBY 4.0.

The BTESA-100 membrane was used to separate CO2 /N2 mixtures for analytical purposes. A study for the long-term operating durability of binary CO2 /N2 (14/79) segregation conducted at 323K to demonstrate its durability of its extraction efficiency, and the findings are presented in Fig. 3. In a constant operation lasting up to 26 h, negligible discernible loss in CO2 /N2 extraction efficiency for CO2 /N2 sensitivity and CO2 permeability. During a long extraction experiment, the BTESA-100 membrane was proven to be dependable, and it has a lot of possibilities in CO2 collection applications. However, owing to the presence of moisture in the operational CO2 /N2 separation procedure, the membrane stability in humidified conditions must also be evaluated. Furthermore, Su et al. [20] investigated the effect of pollutants in the flue gaseous, like H2 O vapor, O2 and SO2 for the sorption of CO2 /N2 integration in carboxyl doped CNT matrix and carbon nanotubes (CNTs) using a large canonical Monte Carlo simulation. The most effective inhibitor of CO2 adsorption when a solitary unclean gas SO2 was introduced, while water only had a significant impact at low pressures (0.1 psi), when a 1D lattice of H2 -bonded monomers formed. Furthermore, O2 was discovered to have no effect on CO2 purification and segregation. With three contaminants in flue gas, SO2 performed a key function in suppressing CO2 adsorption by drastically lowering the adsorption quantity. This was due to the fact that SO2 exhibited a greater affinity with carbon walls than CO2 . Because of correlations among distinct entities, the inclusion of three contaminants in flue gas increased the adsorption intricacy. The CNT matrix’ external adsorption region was heavily dominated by H2 O, which hydrophilic carboxyl groups modified, and SO2 effectively adsorbs CO2 inside the duct. These two impacts restricted CO2 adsorption while increasing CO2 /N2 selectivity, and the contest among them controlled the CO2 adsorption pattern within and without the tube. Furthermore, it was discovered that in the existence of impurity gas, carbon nanotube consistently retained the optimum CO2 /N2 sorption and segregation efficiency, in both single CNT and CNT array situations. A considerable amount of water molecules are absorbed and accumulated among tubes to create chain formations, as per the molecular image of water molecules deposited in (7, 7)

1.2 Utilization of captured carbon dioxide for biofuel production

5

CNT array in Fig. 4, although water molecule adsorption in tubes is scarcely detected. At the same time, as tube radius increases, the adsorption rate of water molecules reduces. Measuring the weight fraction of interfering carboxyl reveals that carboxyl concentration has a significant impact on water molecule adsorption capability. The mass percentage of carboxyl group drops as the width of the tube increases, resulting in a reduction in the adsorption capability of water molecules. The absorption of SO2 in small-diameter nanotube arrays was aided by the existence of water molecules.

1.2 Utilization of captured carbon dioxide for biofuel production Worldwide climate warming and rising green-house gas emissions, and the exhaustion of traditional fuel sources, have become an increasing source of concern in recent decades. Coal, oil, and natural gas burning release upwards of 6 billion tonnes of CO2 into the environment each year [5,21–29]. In this context, physiological CO2 reduction is increasing interest since it results in the production of energy through biomass generated by CO2 fixation via photosynthesis. Because it is energy economical, durable, and ecologically friendly, photosynthetic CO2 fixation is regarded to be a viable technique. Green plants may capture CO2 via photosynthesis, which is a natural process. Furthermore, due to the mitigated rates of growth of traditional land plants, CO2 collection through sustainable natural sources predicted to be just 4–7 percent of fossil fuel outputs [12,30–33]. Microalgae, on either hand, could present a possibility because to its quantity and rapid development proportion. Rapidly maturing single celled microbes called microalgae have a 10–50 percent greater capacity to absorb photovoltaic radiation over bryophytes simultaneously fixing CO2 . Carbonic anhydrase (CA), an extracellular zinc metalloenzyme, aids in the absorption of CO2 from the environment by microalgal cells. CA catalyzes the transformation of CO2 to bicarbonates, that are absorbed by microalgal cells via transporter. The CO2 collected by microalgae is retained as carbohydrates, lipids, or proteins, based on the genus. It may be possible to extract CO2 from microalgae lipid stores and use it as a biofuel. One of the least studied methods for capturing CO2 is the biological pathway via microalgae, in which CO2 is instantly converted to biomass via single source discharges in specially designed platforms like photobioreactors. Phototrophic algae’s carbon fixation has the ability to reduce CO2 emissions into the environment, hence reducing global warming. Microalgal CO2 biofixation in photobioreactors is a potential method for producing more biomass and ethanol. The usage of photobioreactors for CO2 capture by microalgae has several benefits, including increased microalgal production owing to regulated atmospheric factors and enhanced area or volumetric utilization, resulting in more effective utilization of expensive land. Microalgae might thus serve a dual purpose by lowering greenhouse gases through CO2 sequestration and supplying cleaner energy to meet the expanding need for energy.

1.2.1 Photosynthesis and photo oxidation of water Photosynthesis is known to be a biological activity that is performed out by bacteria, algae, and elevated plants. It relates to the process through which species turn light energy to the chemical energy through gathering light and using it for fuel by CO2 adsorption.

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FIGURE 1.3 At 50 °Celsius, a extended durability experiment of CO2 /N2 (14/79) mixture segregation for the BTESA-100 porous film was performed. (Adapted from Ref. [19]) MDPI 2022. Published in accordance with Creative Common attribution License CCBY 4.0.

(A)

(B)

FIGURE 1.4 At 1.0 bar, 300 K, a molecular image of the (7, 7) CNT array in cross-sections (A) and axial axis (B). (Adapted from Ref. [20]) MDPI 2022. Published in accordance with Creative Common attribution License CCBY 4.0.

Carbon gets transferred from the environment into biomass in this manner. The watersplitting process, which results in the creation of oxygen, is a bonus element of algae’s photosynthesis. The photosynthesis reaction occurred in chloroplasts, which are specialized organelles. The physicochemical and biological processes are the two series of steps that make up photosynthesis. The biophysical processes take occur in the chloroplasts’ thylakoid discs [34–39]. The absorbing of light photons by essential pigments such as like xanthophylls and carotenes is referred to as photon absorption. The water is oxidized, releasing oxygen (Fig. 1.3). The reduction of nicotinamide adenine dinucleotide phosphate and production of adenosine triphosphate (ATP) are both aided by the electrons released from water molecules

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FIGURE 1.5 Photosynthesis and photolysis pathways of photoautotrophic bacteria are depicted schematically. (Adapted from Ref. [40]) Springer 2017. Published in accordance with Creative Common attribution License CCBY 4.0.

(NADPH). The energy produced while NADPH and ATP are in their active states is used in the dark processes to bind CO2 . The stroma is where the metabolic response occurs, and the end metabolites are primarily sugar molecules and a few other chemical compounds required for metabolic activity and cell function.

1.2.2 Bio-sequestration of CO2 CO2 from the environment is absorbed during the photosynthetic cycle, that is carried out by microalgae to produce feed. The C3 and C4 routes are the two processes through which green plants assimilate CO2 from the environment. Around 250,000 species of C3 plants and 7500 kinds of C4 plants have been identified. For CO2 fixation, many algae utilize the C3 pathway (Calvin Cycle). CO2 is mixed using a 5-carbon molecule to produce dual 3-carbon chemicals in this process. Ribulose-1,5-bisphosphate carboxylase/oxygenase (RuBisCo) is referred to be an enzyme which catalyzes this process. Most algae are photoautotrophs, which means they can obtain all of their energy from photosynthesis and most of their carbon through carbon dioxide absorption. Diatoms are categorised as C4 plants because it could absorb CO2 in a different way than terrestrial agricultural plants like corn, cotton, and wheat. C4 plants combine CO2 using a tri-carbon molecule to create a tetra-carbon molecule instead using

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RuBisCo to create dual three-carbon molecules, limiting photorespiration loss and improving the efficiency of CO2 fixation. C4 plants are believed to possess double the photosynthetic rate of C3 plants, though that this advantage has become fewer noticeable when CO2 levels are sufficient. The absorbed CO2 is retained as carbohydrates and lipids in the algal cells. The Hatch Slack phase is used by C4 plants in complement to the Benson Calvin process. In this additional cycle, the phosphoenolpyruvate carboxylase (PEPcase) enzyme achieves a pre-acquisition of carbon dioxide in the form of a tetra-carbon molecule. The byproducts of this process are employed to increase the level of CO2 at the location wherein RuBisCO (the carboxylation enzyme of the Benson Calvin cycle) is active, preventing photorespiration. The extracellular carbonic anhydrase (CA) enzyme aids in the absorption of CO2 by microalgal cells. It’s thought to be the carbon concentrating mechanism’s likely main enzyme. The enzyme is involved in a broad variety of macro and microalgal organisms. It aids in CO2 absorption by catalysing the interaction between HCO3 and CO2 . It has been discovered that intracellular CA can happen in the identical cell. The genes code for the CA isoforms are controlled by the inorganic carbon in the media. As a result, the action of CA rises as the amount of inorganic carbon in the media decreases. In order to convert CO2 into HCO3 in the cytosol during C4 photosynthesis and furnish substrates for PEP carboxylase, CA is required. The information gathered from the research conducted with CA inhibitors has proved the presence of CA. Although CA activity has been studied in a variety of micro and macroalgae, investigations of the standard green alga Chlamydomonas reinhardtii have provided the majority of the present knowledge of the function of CA in algae.

r Enhancing passive and active carbon absorption from the atmosphere. r Reducing CO2 escape from high-CO2 -concentration areas within the cell. Montazersadgh et al. [41] decided to generate a novel electrochemical system for producing low-carbon e-biofuels using multipurpose electrosynthesis and integrating CO2 covalorization of biomass resources. Drop-in fuels were produced by reducing CO2 near the cathode, whereas value-enhanced chemicals were produced near the anode. In this study, a mathematical analysis of a continuous-flow architecture was established to evaluate the most technoeconomically viable combinations based on energy effectiveness, environmental effect, and economical ideals. After then, the reactor architecture was tweaked using parametric study. A constant electrolytic cell was designed and confirmed analytically. The algorithm was then utilized in combination with multiple cell kinetics to estimate the optimal cell architecture for distinct e scenarios. A selection of organic compounds with at least one interaction from each group were used to generate the kinetics. The most current developments in biomass oxidation for biofuel generation and CO2 electroreduction dynamics and are also covered in this research. The overall performance of the cell is improved by using a non-water solvent because HER was not predominant at the cathode. Whereas the energy content of the primary commodity primarily determines the energy effectiveness of the cell, properly choosing the reactor kinetics could significantly increase the efficiency of CO2 conversion. When contrasted to certain other manufacturing applications, the cumulative environmental impact (E-factor) is considerable. This is owing to the solvent’s huge quantity in comparison to the output, and it could be minimized by cycling the solvent through the process. The byproducts at the anode for the specified reaction mechanism influence the cell’s economically additional value one of the most. Because both compounds possess a relatively high Gibbs energy output,

1.2 Utilization of captured carbon dioxide for biofuel production

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FIGURE 1.6 For several half-cell reactions, (A) CO2 capture ratio and (B) E-factor. (Adapted from Ref. [41]) Springer 2021. Published in accordance with Creative Common attribution License CCBY 4.0.

the increased cellular energy performance was enhanced to 340 percent. CO2 transformation frequency of 69.3 percent, present efficacy of 56.7 percent with E-factor of 704 are some of the other cell effectiveness parameters. The CO2 conversion rate is also another crucial productivity component that could be improved (see Fig. 1.6). Because the HER was not present at the cathode, DMF was presumed to be the solvent. Similarly, Zdeb et al. [42] discussed the empirical findings of incorporating carbon dioxide as a reagent in the valorization process in coal gasification. Three basic setups featuring varied modeled waste heat use situations were tested on a batch process moving bed gasifier. CO2 , O2 , and a combination of 30 percent CO2 in O2 were utilized as gasification reagents at

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(A)

(B)

FIGURE 1.7 Configuration on a lab scale with a rolling bed reactor and a gasification reagent pre-heating system: (A) a perspective and (B) a graphic illustration. (Adapted with Ref. [42]) MDPI 2019. Published in accordance with Creative Common attribution License CCBY 4.0.

temperatures of 700, 800, and 900 °Celsius. The cumulative influence of processing parameters on coal treatment efficiency of gas productivity, content, and calorific range was investigated, and the empirical value was analyzed utilizing Principal Component Assessment. In the controlled situations used, the trials confirmed the possibility of producing gas with a calorie content of 4–6 MJ/m3 by pyrolysis with a carbon dioxide-containing gasifying agent. Even though encouraging in the development of energy-efficient and low-carbon footprint processes, the concept of carbon dioxide valorization and waste heat utilization in coal gasification requires much further breakthroughs in relation to working assimilation as well as cost-competitiveness metrics until it can be regarded for widespread application. Similarly, Ahmad et al. [43] created a system of data-based soft sensors that uses an ensemble technique called boosting to forecast the content, amount, and grade of fatty acid methyl esters (FAME) in the biofuel synthesis procedure using the oil of several vegetables. The non-intrusive polynomial chaos expansion (PCE) technique was added into the sensitive detectors design to evaluate how ambiguity affected the results. In each of the elements, flow rate and cetane, a unique model (soft sensor) was created. The anticipated results of Methyl-Li, -O, -M, -P, -S, FAME transmission rate, and cetane frequency were 0.27479, 0.32227, 2.41208, 0.1651, 0.82135, 0.96546, and 0.97013 with 1 percent variation in all supply parameters of the sensitive detectors were 0.27479, 0.32227, 2.41208, 0.1651, The sensors are extremely precise at predicting and quantifying ambiguity, making them ideal for practical uses. Zhang et al. [44] focused on the technical and economical configuration of solid-oxide electrolysis for the manufacture of green methanol by Hydrogenation of carbon dioxide. System unification, technical and economical analysis, and multi-objective management are carried out successfully for a research project. The results show a trade-off between energy efficiency and the cost of generating CH3OH. The assessed example’s annual methanol production was 100 kton, with a quality of 98.6 percent weight and a carbon dioxide usage of 150 kton,

1.2 Utilization of captured carbon dioxide for biofuel production

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offering it an annual retention capacity of 800 GWh sustainable energy. Methanol production costs approach 560 $/ton having an electric cost of 74.26 $/MWh, making it commercially unworkable with an usable life of over 13 years, despite the performance being about 70 percent and varying within a small range. When the price of energy is reduced to 47 dollars per megawatt hour and subsequently to 24 dollars per megawatt hour, the cost of producing methanol falls to 365 and 172 dollars per ton, respectively, with a 4.6 and 2.8-year economic success. The cost of power has a considerable influence on project execution. The cost of power varies by country, resulting in varied payback times in various places. Esteves et al. [45] examined at the effects of different light frequencies on biomass production, carbon dioxide reduction, and nutrient removal through a synthetic discharge in Tetradesmus obliquus, Chlorella vulgaris and Neochloris oleoabundans. Light-emitting diodes (LEDs) having varied wavelengths were used in the experimentations: 620–750 nm (red), 380–750 nm (white) and 450–495 nm (blue). N. oleoabundans with white LEDs had the highest specific growth rate (0.264 0.005 d−1 ), while C. vulgaris had the highest biomass output (14 4 mg CO2 L−1 d−1 ) and CO2 fixation rates (12.5 mg CO2 L−1 d−1 ). The three microalgae investigated had the greatest nitrogen and phosphorus extraction efficiency when exposed to white light. Molino et al. [46] developed Scenedesmus almeriensis into a green microalga on a benchscale to trap CO2 and produce lutein. In a vertically hydrodynamic cavitation photo-bioreactor with a steady stream of a mixture of gases of N2 , O2 and CO2 with the former having a concentration of 0.0–3.0 percent v/v, heterotrophic growth of S. almeriensis was carried successfully. Batching was used in the liquid phase. The development of S. almeriensis was optimized. Furthermore, lutein separation was conducted out at 59 °C and 9 MPa utilizing rapid solvent separation using C2 H5 OH to be a Generally Recognized as Safe (GRAS) substrate. Utilizing a carbon dioxide concentration of 2.9 percent v/v, the highest biofuel productivity of 129.24 mgL−1 d−1 was attained during in the development, allowing for a lutein concentration of 8.54 mgg−1 , that was 5.6-fold greater than the similar procedure performed with out CO2 . The ion chemistry analysis of the growing medium revealed that rising CO2 concentration progressively boosted nutrient intake throughout the growth stage. Because it focuses on pigment creation from a natural origin while also capturing CO2 , this research could be of relevance for lutein harvesting at an industrial level. Fig. 1.8 shows the influence of CO2 concentration on nutrient absorption as assessed at the conclusion of S. almeriensis’ development. The results revealed a full phosphate ion consumption, that would impede cellular proliferation. The efficiency of nutrient intake improved as CO2 level raised. The extended culture periods (i.e., 20 days for CO2 = 0.5 percent v/v; 16 days for CO2 = 1.5 percent v/v; 13 days for CO2 = 3.0 percent v/v) did, though, help to increase nutritional intake. During in the development period, nitrate and phosphate were the most heavily absorbed nutrients. A proposed reason for this phenomena is that protein production requires a nitrogen supply, and lutein occurs in microalgae as a nitrogenous macromolecule. The current investigation showed that NO3 and PO4 −3 ions are the most essential nutrient for cell growth in microalgae development. Furthermore, with CO2 levels of 0.0, 0.5, 1.5, and 3.0 percent v/v, the absorption of NO3 ions was 5.0, 59.88, 77.26, and 87.22 percent, correspondingly, throughout development. This finding could be explained by a restricted carbon source, that causes strain in microalgae growth cells, resulting in reduced biological nutrient absorption. In contrast to the intake of other nutrients, there was a reduced intake of both Na+ and Cl ions at the conclusion of the

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FIGURE 1.8 Throughout the development of S. almeriensis, the impact of CO2 levels on nutrient consumption effectiveness was investigated. (Adapted from Ref. [46]). MDPI 2022. Published in accordance with Creative Common attribution License CCBY 4.0.

growth, with an intake under 25 percent. When CO2 level was increased from 0.5 percent v/v to 3.0 percent v/v, the intake of Cl ions reduced, which might be accounted by a shorter cultivation period. Following the growth of Chlorella vulgaris and production of high yield biofuel after successive CO2 capture, the similar findings were reported. Valdovinos-García et al. [47] goal was to assess the techno-economics of microalgae biomass generation whereas only examining methods that could be scaled up to industrial levels. The criterion for the assessment are energy usage and operational costs. Furthermore, the absorption of CO2 by a thermoelectric system was investigated to be a feedstock of carbon for microalgae production. 24 scenarios were created by combining raceway pond cultivars, the primary extract with 3 distinct coagulants, the intermediate extract using samples centrifuged and 3 different filtration technologies, and finally rinsing using Mist and Drum Dryers. The cultivated area was estimated to absorb 102.13 tonnes of CO2 /year with a moderate biomass production of 12.7 g/m2 /day. The situations that featured spinning and vacuum filtering were the ones that used the most energy. The operational costs per kilogram of dry biomass ranging from $4.75 to $6.55 USD. The ideal situation is determined by the final usage of biomass. Ye et al. [48] developed computer simulation algorithms to examine efficient energy and predict manufacturing costs depending on their innovative technique, which catalytically converts glycerol into acrylic acid (C3 H4 O2 ) in a dual-phase method using CO2 as a reactive substrate. The research was carried out using publicly available data from a conventional, intermediate-sized biodiesel plant, with the goal of determining the viability of manufacturing C3 H4 O2 in real time scenario of a regenerative financial system. Variables assessment in reaction to glycerol conventional price, carbon dioxide recycling supply and price, and variations in process scalability and circumstances are also reported. The findings revealed

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it to be an eco-benign CO2 source to the C3 H4 O2 factory is critical for future exploration and advancement.

1.3 Conclusion and future perspectives The majority of the investigations that have been published so far have been carried out on laboratory-scale production under well-regulated circumstances. Several aspects, including as the availability of sufficient CO2 , fertilizers, and light, must be explored and improved in order to apply the optimal parameterization circumstances in the commercial generation of biofuels on a wide level. Technological viability has been demonstrated on a limited level, and tiny quantities of usable biofuel have been generated, but economical viability has yet to be determined. Microalgal-based biofuels should be price competitive with petroleumbased fuels in order to be commercially viable. The process could be made more affordable by incorporating the use of CO2 via direct origin exhaust gas outputs, sewage treatment, or the separation of essential components for use in various industries. Several studies on CO2 biosequestration and biofuel synthesis using organic elements have been conducted, but more investigation is warranted to satisfy the growing utilization of energy. Researchers predict that throughout the future, biofuel would mostly replace fossil fuels, reducing atmospheric CO2 amounts and averting global warming. As a result, a significant effort in the advancement of this technology, as well as technical skills in this field, are still essential until biofuel could become an actuality. The expansion of biofuel companies will undoubtedly be financially and ecologically advantageous, while also creating a great amount of employees at various levels.

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[33] KH Kim, EY Lee, Environmentally-benign dimethyl carbonate-mediated production of chemicals and biofuels from renewable bio-oil, Energies. 10 (2017) 1–15. https://doi.org/10.3390/en10111790. [34] Zhu J, Qu Z, Liang S, Li B, Du T, Wang H. Macroscopic and Microscopic Properties of Cement Paste with Carbon Dioxide Curing. Materials (Basel) 2022;15. https://doi.org/10.3390/ma15041578. [35] García AC, Moral-Vico J, Markeb AA, Sánchez A. Conversion of Carbon Dioxide into Methanol Using Cu–Zn Nanostructured Materials as Catalysts. Nanomaterials 2022:12. https://doi.org/10.3390/nano12060999. [36] Arun J, Gopinath KP, Sivaramakrishnan R, SundarRajan PS, Malolan R, Pugazhendhi A. Technical insights into the production of green fuel from CO2 sequestered algal biomass: a conceptual review on green energy. Sci Total Environ 2021;755:142636. https://doi.org/10.1016/j.scitotenv.2020.142636. [37] Kassim MA, Meng TK. Carbon dioxide (CO2 ) biofixation by microalgae and its potential for biorefinery and biofuel production. Sci Total Environ 2017;584–585:1121–9. https://doi.org/10.1016/j.scitotenv.2017.01.172. [38] Maheshwari N, Kumar M, Thakur IS, Srivastava S. Carbon dioxide biofixation by free air CO2 enriched (FACE) bacterium for biodiesel production. J CO2 Util 2018;27:423–32. https://doi.org/10.1016/j.jcou.2018.08.010. [39] Meylan FD, Moreau V, Erkman S. CO2 utilization in the perspective of industrial ecology, an overview. J CO2 Util 2015;12:101–8. https://doi.org/10.1016/j.jcou.2015.05.003. [40] M Mondal, S Goswami, A Ghosh, G Oinam, ON Tiwari, P Das et al., Production of biodiesel from microalgae through biological carbon capture: a review, 3 Biotech 2017;7:121. https://doi.org/10.1007/s13205-017-0727-4. [41] Montazersadgh F, Zhang H, Alkayal A, Buckley B, Kolosz BW, Xu B, et al. Electrolytic cell engineering and device optimization for electrosynthesis of e-biofuels via co-valorisation of bio-feedstocks and captured CO2 , Front. Chem Sci Eng 2021;15:208–19. https://doi.org/10.1007/s11705-020-1945-6. ´ [42] J Zdeb, N Howaniec, A Smolinski, Utilization of carbon dioxide in coal gasification - An experimental study, Energies. 12 (2019). https://doi.org/10.3390/en12010140. [43] Ahmad I, Ayub A, Ibrahim U, Khattak MK, Kano M. Data-based sensing and stochastic analysis of biodiesel production process. Energies 2019;12:1–13. https://doi.org/10.3390/en12010063. [44] Zhang H, Wang L, van Herle J, Maréchal F, Desideri U. Techno-economic optimization of CO2 -to-methanol with solid-oxide electrolyzer. Energies 2019:12. https://doi.org/10.3390/en12193742. [45] AF Esteves, OSGP Soares, VJP Vilar, JCM Pires, AL Gonçalves, The effect of light wavelength on CO2 capture, biomass production and nutrient uptake by green microalgae: a step forward on process integration and optimisation, Energies. 13 (2020). https://doi.org/10.3390/en13020333. [46] Molino A, Mehariya S, Karatza D, Chianese S, Iovine A, Casella P, et al. Bench-scale cultivation of microalgae scenedesmus almeriensis for CO2 capture and lutein production. Energies 2019;12:1–14. https://doi.org/ 10.3390/en12142806. [47] Valdovinos-García EM, Barajas-Fernández J, de los Ángeles Olán-Acosta M, Petriz-Prieto MA, Guzmán-López A, Bravo-Sánchez M G. Techno-Economic Study of CO2 Capture of a Thermoelectric Plant Using Microalgae (Chlorella vulgaris) for Production of Feedstock for Bioenergy. Energies 2020;13:1–19. [48] XP Ye, S Ren, Coproduction of acrylic acid with a biodiesel plant using CO2 as reaction medium: process modeling and production cost estimation, Energies. 13 (2020). https://doi.org/10.3390/en13226089.

C H A P T E R

2 Deep eutectic liquids for carbon capturing and fixation Zainab Liaqat a, Sumia Akram b, Hafiz Muhammad Athar a and Muhammad Mushtaq a a b

Department of Chemistry, Government College University, Lahore, Pakistan Division of Science and Technology, University of Education Lahore, Pakistan

2.1 Carbon dioxide emissions The emission of various greenhouse gases (carbon dioxide, methane, nitrous oxide, water vapor, and fluorinated gases) has a very substantial effect on our environment. Among all gases, CO2 stands as the most emitted gas due to human activities [1]. High emissions of CO2 cause numerous environmental problems, particularly global warming due to the rise in global temperature. Global warming causes serious problems like, snow clads melting, glaciers melting rise in sea levels, and severe weather conditions. Therefore, it has become a worldwide challenge to reduce CO2 and other greenhouse gases (GHGs) and control global warming [2]. The combustion of fossil fuels (coal, natural gas, and oil) ranks as the most challenging and indispensable emission source of CO2 and other GHGs. Fig. 2.1 further elaborate the contribution of the various sectors toward the global CO2 burden. It is obvious that around 25 percent of CO2 emissions are produced worldwide during the production of electricity and heat for other uses [3]. Recently, CO2 capture has gained globally among researchers. A lot of technologies are already in practice to reduce the combustion of fossil fuels or minimize the emissions of GHGs [4]. Intergovernmental Panel on Climate Change-IPCC has declared Carbon-dioxide Capture & Storage (CCS) as the most impactful method to reduce the post-combustion CO2 burden. CCS depends on the efficiency of the employed process, materials and design, and overall cost [5]. The technologies explored for CO2 capture fall into three categories i.e., pre-combustion, post-combustion, and oxyfuel-combustion.

Green Sustainable Process for Chemical and Environmental Engineering and Science: Carbon Dioxide Capture and Utilization DOI: https://doi.org/10.1016/B978-0-323-99429-3.00007-2

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c 2023 Elsevier Inc. All rights reserved. Copyright 

18

2. Deep eutectic liquids for carbon capturing and fixation

FIGURE 2.1 Sectoral Contribution (percent) of Greenhouse CO2 Emission in United States due to fossil fuels (https://www. epa.gov/ghgemissions/inventory-usgreenhouse-gas-emissions-and-sinks).

i. In the pre-combustion methods, CO2 is captured from oxidized fuel gas, i.e., synthesis gas/syngas, which consists of CO and H2 . This in turn reacts with steam and converts CO into CO2 and H2 from where it is captured. ii. In the post-combustion methods, after the combustion of fossil-fuel, CO2 is captured from the flue gases in a nitrogen-rich environment. iii. In oxy-fuel combustion, fossil fuel is burnt in an oxygen-rich environment. The resulting flue gas consists of CO2 and vapors which are condensed and pure CO2 is captured through the outlet. Most of the commercial plants employ pre-combustion and post-combustion technologies, but oxy-fuel technology is still under process [1]. Among all these technologies, postcombustion capturing has been widely employed due to its flexibility [4]. A variety of catalysts, liquid/solid adsorbents, and membranes are utilized for CO2 removal [6]. The predominant methods for CO2 capture are absorption, adsorption, and membrane-based separation. Captured CO2 is further stored and consumed for various purposes [7]. Out of three methods, adsorption is the most employed method due to its versatility, as this is suitable for both, pre and post-combustion techniques. Adsorption involves a high rate of heat and mass transfer and can be used either physically or chemically based on different reaction factors [8]. Solvents selection is one of the key points in absorption/adsorption methods [9]. According to the fifth rule of “Green Chemistry”, the use of safe solvents and auxiliaries should be emphasized to reduce the by-products [10]. Henceforth, the use of green solvents for desired applications and with least or zero environmental impact has gained the attention of researchers during last couple of decades [11]. For the sake of CO2 capture, many attempts

2.3 Types of deep eutectic liquids

19

have been made to achieve high efficiency [12]. Recently, a novel class of solvents similar to ionic liquids (ILs), called Deep Eutectic Liquids (DELs), has gathered much attention from scientists as a promising liquid for CO2 capture, particularly from an industrial point of view [13]. The present chapter covers the key features of deep eutectic liquids and opurtunities regarding the use of these liquids in carbon dioxide capturing. The chapter also contains the case-studies regarding the use of deep eutectic liquids and conditions for their application as CO2 absorber and capacitor. Finally, readers interested in challenges regarding the use of deep eutectic liquids for CO2 capturing and conversion may get useful information.

2.2 Deep eutectic liquids The term “deep eutectic solvent” has been initially notified in 2001 [14], and finally coined in 2003 [15], for the liquids that melt below their original melting points. The title eutectic actually originsfrom the Greek word “ευτ ηκτ ος ” which meansfacile melting [16]. Deep eutectic liquids (DELs) are not pure compounds rather these exist as combinations of various elements that come from a hydrogen bond donor (HBD) and a hydrogen bond acceptor (HBA). The mixture prepared under a specific stoichiometric ratio may have freezing points lower than either of the two components. The presence of strong hydrogen bonding and other intermolecular interaction renders the majority of these solvents non-volatile, nonflammable, and in certain cases liquid at room temperature. The principles of green chemistry [17] categorize these liquids as green for their non-volatile character. These liquids have become potential candidates to replace toxic conventional organic solvents and expensive ionic liquids (IL) for analytical, synthesis, and electrolytic solutions. Besides, their low cost, ease of raw material availability, biodegradability, and biocompatibility make them more viable as compared to ionic liquids. Another cite-worthy opportunity regarding DELs rises when we change the HBA/HBD ratios (more than 1 million different possible combinations) [18,19]. These liquids have the potential to revolutionize the fields of environmental, polymer, biological and material science. DELs may rank as one of the most important discoveries of the 21st century. Before we proceed towards the utilization of DELs for CO2 capturing, it is important to highlight various types of DELs and the fundamental mechanism involved in their formation or existence. Once becoming familiar with the molecular interactions present in DELs, we can easily customize the various physicochemical features of these liquids for their uses as adsorber or solvent for CO2 dissolution.

2.3 Types of deep eutectic liquids The deep eutectic liquids fall into five major classes based on HBD and HBA involved (Fig. 2.2) in their formation. The most frequently reported and the first generation deep eutectic liquids (labeled as type-I) are prepared by the combination of quaternary ammonium salts (HBA) and metal chlorides (HBD). The next generation (Type II) compose of similar HBD and HBA yet metal chlorides are hydrated which increases the scope and range of produced combinations. Another perspective aspect of type II liquids rises due to the ease of

20

2. Deep eutectic liquids for carbon capturing and fixation

FIGURE 2.2 Types of Deep Eutectic Liquids (DELs).

preparation as metal chlorides coupled with their inherent air/moisture can be used. The third type of deep eutectic liquids also contain similar quarternary ammonium compounds like choline chloride as HBA but here HBD may be alcohol, amine, or carboxylic acid. These low melting liquids are easy to prepare, economical, and non-reactive to biomolecules. Besides, the presence of a large number of organic hydrogen bond donors offers a wide range of combinations, adaptability, and application of this class of liquids. Another interesting class of low melting liquids (type IV) have been prepared by the direct combination of metal chlorides with hydrogen bond donors like urea. It had been generally believed that transition metal salts will not ionize in organic solvents until 2001 Abbott, Capper [14] found that ZnCl2 can form a eutectic mixture with urea, ethylene glycol, acetamide, and 1,6 hexanediol. Some fellow researchers also prepared type IV liquids by mixing HBD and hydrated metal chlorides [20]. Such low melting liquids generally stands as hydrophilic (because of the ionic components) which restricts their application in hydrated samples. The interesting features of non-ionic or hydrophobic DELs emerged as a feasible cure in this concern which have strong interactions among the components of type V of deep eutectic liquids [21]. Commonly, exclusive hydrophobic mixtures utilize long chain fatty acids, alcohols, and monoterpenes which work well for the preparation of these liquids. Recently, Choi et al. prepared natural deep eutectic liquids from natural HBD and HBA and claimed that many of such combinations already exist in living cells and provide a natural medium to various physiological phenomena [22]. A growing trend has appeared regarding the preparation and utilization of natural deep eutectic liquids for a large number of available combinations. Natural deep eutectic liquids possess extremely good solvation capacity along with low volatility and melting point [23]. Besides, the natural deep eutectic liquids prepared by mixing organic acid and glucose (1:1) have been found to be non-toxic, and biocompatible.

2.4 Preparation of DELs As stated earlier, deep eutectic solvents are customized molecular liquids, so their preparation may vary with the nature (melting and boiling points, and stabilities) of HBD and HBA, personal preference, and end-use applications. In general, the formation of deep-eutectic solvent involves the development of intermolecular interactions between HDB and HBA so the

2.5 Authentication of DELs

21

word synthesis misfit for their productions rather than “preparation or formation” are more suitable terminologies. Moreover, prolonged and abrupt heating may degrade the constituents of the solution to limit the effectiveness of the end-user application. In General, deep eutectic liquids have been prepared via three common procedures i.e. (i) thoughly heating the compounds with specific molar ratio in a properly sealed flask at 323–363 K with continuous stirring for 30–90 min till the production of a homogenous transparent solution [23], (ii) vacuum drying the compounds in a rotary evaporator at 323 K followed by addition of water, afterwards, drying the resultant mixture in a desiccator with silica or silica gel [24]. The vacuum drying approach seems to be more suitable for the preparation of natural deep eutectic solvents. Freeze-drying is another way (iii) to prepare low melting liquids which involves the mixing of HBD and HBA in a stoichiometric ratio, followed by dilution with distilled water to get transparent solutions which are subsequently freeze-dried for 2–24h [25]. The liquids prepared via the freeze-drying approach often contain micelle, vehicles, or nonreactor capsules which render them more suitable for biological applications. In the majority of mechanical methods, the HBD and HBA are either dried under vacuum until there is no further weight loss and then subjected to grinding or extrusion to get a clear low melting solution [26,27]. This strategy seems to be more suitable for thermally labile HBD and HBA components. Gomez et al. have applied microwave heating for the formation of low melting liquids and noted that microwaves can reduce energy and time consumption[28]. Likewise, Santana et al. have applied ultrasound waves to facilitate the formation of required liquids [29].

2.5 Authentication of DELs A set of fundamental molecular characterization approaches have been employed to authenticate the formation of DELs [30]. For example, Nuclear Magnetic Resonance (NMR) Spectroscopy works well to monitor the hydrogen bond transfers and determine the composition and structure of DELs [31]. In NMR or H–NMR, the proton environm of the DEL is compared with that of constituents HBDs and HBAs, however in combination with other techniques, it can provides the information about what is present in the mixture, water content, and impurities. Fourier Transform-Infrared (FT-IR) can also identify the shifts and adjustments in molecular structure of DELs in various molar ratios and compositions. Another important spectroscopy associated with molecular vibrations and rotation is Raman Spectroscopy and in this techniquethe observed transitionsare further analyzed through various techniques for detection of “what is present” and “how it is present” in various deep eutectic liquids. These all techniques are often applied to prove DEL formation or composition and purity of studied liquids with high accuracy. Beside spectroscopic characterization, thermogravimetric analysis (TGA) and differential scanning colorimetery (DSC) can help us to study the behavior of DELs in various applications. TGA is widely utilized to gain baseline data quickly for any unknown deep eutectic system, especially volatility. This technique delivers more detailed insights into physicochemical properties. DSC regulate the required heat for any change in temperature particularly latent heat transformation (like phase change or glass transition). Different thermodynamic parameters

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2. Deep eutectic liquids for carbon capturing and fixation

such as melting point, entropies and enthalpies of fusion, thermal stability, and heat capacity of both the pure components and their resultant mixture, thus making it suitable for identifying anomalous behavior of DELs [32].

2.6 DEL based CO2 absorption The polar nature of DELs raises an opurtunity for these liquids to be used as absorbents in CO2. Besides, the physico-chemical features of these liquids are tunable. During last couple of decades, a great deal of deep eutectic liquids has been explored for their potential in CO2 capturing and absorbption. HBA has more significant impact on CO2 solubility. Interestingly, the widely used HBAs in DEL formation have been also found to be suitable in CO2 capturing experiments. Moreover, the solvents formed economical, easily available, and eco-friendly in their nature [33]. The high thermal stability and vapor pressure these liquids are the features of high importance for their application in CO2 capturing devices at variable temperature. For example, monoethanolamine (MEA), a commonly used absorbent, has an absorption capacity of almost 0.5 mol CO2 /mol MEA, but its vapor pressure is quite high which causes degradation on exposure to heat and oxygen. The degradation of MEA is the main disadvantage in terms of absorbent reusability. Comparatively, ChCl:urea based DELs having low vapor pressure and high thermal stability remain stable over the similar temperature range. The amine functional group is advantageous regarding CO2 capture; however, it is impossible to attach this functional group with any conventional solvent/absorbent. Above all, these liquids can be tuned by selecting various HBA and HBD to find out more suitable absorbent. Regardless of extenses associated with these liquids, they face a drawback of having high viscosity which can be solved by dilution. Dilution not only lowers the viscosity of DELs but improves the polarity and conductivity which results in increased CO2 uptake [34]. Intermolecular interactions in deep eutectic liquids after capturing CO2 were very first time reported by Shukla and Mikkola [35] through gravimetric analysis of ammoniumbased eutectic liquids composed of various HBA (monoethanolammonium chloride, 1methylimidazolium chloride, and tetra butyl ammonium bromide) and amine and aminoalcohol based HBD in different molar ratios at 298.15 K. The prepared liquids were checked in terms of polarity, viscosity and absorption. It was observed that the absorption of CO2 doesn’t only dependent on HBD basicity but also affected by the strength of interaction between HBA and HBD. In most of the DELs, an increase in the intermolecular forces increased the CO2 absorption but at the same time stronger intermolecular may increase the visocosity and reduce the mass transfer rate. The FT-IR and 1 H & 13 C NMR results reveal the formation of carbamte by showing peaks at 1558, 1292 cm−1 and at 3.12, >164 ppm, respectively. In addition, a peak at 1350–1505 cm−1 and below 160 ppm confirms the formation of carbonate/bicarbonate groups. The addition of water in studied deep eutectic liquids may reduce CO2 uptake due to increase in acidity and/or decrease in basicity. Another important point regarding the utilization of DELs is to understand how CO2 gets absorbed/adsorbed or dissolve in deep eutectic liquids. Many studies in this regard [36, 37] confirm that CO2 intract physically with the DEL. For example, Ullah, Atilhan [37] report the CO2 absorption mechanism in ChCl-levulinic acid-based deep eutectic liquids which don’t show a significant change in intramolecular interaction after absorption. This reveals

2.6 DEL based CO2 absorption

23

FIGURE 2.3 CO2 Absorption Mechanism in DELs made up of Amine based HBAs. (courtesy to Wibowo, Susanto [36]).

that the CO2 is absorbed physically and not chemically. In physical absorption, molecules of CO2 reside on the liquid surface for some period and then move towards the bulk phase. Wang et al. [38] described the effect of molar ratios and type of HBA and HBD on CO2 solubility. It was observed that HBA cation plays an important role in CO2 absroption and retention. The CO2 molecules are clustered around the molecules of HBA in spatial distribution function isosurfaces. To check the visualization of interactions between CO2 and HBA/HBD, Reduced Density Gradient-RDG, isosurfaces were utilized, which reveal strong van der Waals interactions. These interactions usually turn out in reversible type of sorption. In amine-based DELs, chemisorption may also takes place along with physical sorption, if it happens it can offer more CO2 solubility. In physical absorption, the van der waals interactions and H-bonding between different HBA and HBD also control the solubility of CO2 . While chemsorption take place due to the formation of carbamates as shown in Fig 2.3 [39], in which carbamate formation also occurs along with van der Waals forces between CO2 and HBA. Thus, it is assumed that amine-based deep eutectic liquids are highly efficient in CO2 capturing but the regeneration process can be complicated [36]. In another study, Cheng, Wu [40] projected the mechanism for CO2 absorption by protic ionic liquid-based DEL made up of monoethanolamine + imidazole-ethylene glycol in a 1:3 molar ratio at 298.15 K and 1 atm pressure. It was found that CO2 molecules bind with the amine group of monoethanolamine (carbamate formation) and deprotonate ethylene glycol (carbonate formation). It was supposed that either deprotonation of protonated monoethanolamine cation by imidazole anion results in the formation of neutral monoethanolamine, which in turn reacts with CO2 forming carbamate or EG is deprotonated by imidazole, which then reacts with CO2 to form carbonate. Ishaq, Gilani [41] evaluated the performance of synthesized poly deep eutectic liquidsbased on supported liquid membranes (PDEL-SLM) for pure gases. It was observed that the solution-diffusion mechanism controls CO2 transport across the membrane. Solutiondiffusion is a three-step process, in the first step CO2 is dissolved in DELs, in the second step it is diffused through the bulk phase, and in the last step it is desorbed towards the permeate side

24

2. Deep eutectic liquids for carbon capturing and fixation

FIGURE 2.4 The pathway for carbonate formation during Carbon Capturing by ternary DELs.

of the membrane, to form a concentration gradient. In SLM, only CO2 molecules permeate into the membrane, mostly liquids couldn’t pass from the pores because of the hydrophobicity of the membrane [42]. Recently, Wang, Wang [43] noted that DELs formed by bio-phenol derived ionic liquid and ethylene glycol can capture up to 1.0 mol of CO2 /mol of DEL. The mechanism of CO2 capture in superbase-derived phenol-based DELs is quite different and occurs in two stages (Fig. 2.4). In first stage, anion (Car− ) deprotonate the EG in an acid-base reaction, which results in the formation of HO–CH2-CH2-O− . In the second stage, the anion formed of EG further reacts with CO2 molecules to form carbonate .

2.7 Carbon capture efficiency of various HBDs In general the carbon atom in the vicinity of a more electronegative atom (like O in the case of CO2 ) tends to develop van der waal’s attractions or Hydrogen bond for the formation of Carbonic Acid (Fig. 2.5). In this context, it can be predicted that liquids containing O, N, S, and halogens (X) can offer good platform for the absorption or capturing of CO2 . The similar

2.7 Carbon capture efficiency of various HBDs

25

FIGURE 2.5 The Molecular Orientation CO2 undergo during Dissolution/Absorbtion.

kind of behavior has been observed by the researchers who undertaken the capture of CO2 by DELs or ILs. Besides, the presence of electronegative atom in the neighbourhood of C makes it more electropositive that turn into strong interaction between the carbon and Cl of ChCl (a universal HBA in DELs). The subsequent section highlight the research work undertaken where C of CO2 works as HBA.

2.7.1 Urea Recently, Li, Hou [44] explored the CO2 absorption capacity of deep eutectic liquids consisting of ChCl:Urea in 1:1.5, 1:2, and 1:2.5 molar ratios at various temperatures and pressures. The temperature was studied in the range of 313–333 K with 10 K intervals and pressure was applied upto 13MPa. It was observed that temperature, pressure, and mole ratios significantly (p ≤ 0.05) affected the solubility of CO2 in ChCl:Urea. The solubility of CO2 in these liquids varied abruptly in the low-pressure range and usually increased with increasing pressure. At high temperatures, solubility decreases regardless of the pressure. For the molar ratio of ChCl:Urea mixtures, 1:2 molar ratio exhibited the highest solubility (0.27 mol/kg) than the other two mixtures at 11.1 MPa pressure and 323 K temperature. Likewise, Xie, Dong [45] also studied the CO2 solubility in ChCl:Urea based DELs at different temperatures (308–328 K) with 10 K interval, and at a pressure of up to 45 bars. It was noted that the solubility of CO2 , within the investigated ranges, increases at high pressure and low temperature. The highest solubility of CO2 was 0.195 molar at 308 K and 44 bars. The CO2 solubility was further estimated in dry and aqueous ChCl-urea mixtures. It was noted that solubility increases in an aqueous mixture up to Wwater < 0.5 molar and then it becomes constant. An aqueous mixture will reduce the required solvent amount and viscosity, hence lowering the energy and cost of the process.

2.7.2 Glycerol Leron and Li [46] measured the CO2 solubility in ChCl:Glycerol based DEL in a 1:2 molar ratio at temperature 303–343 K, with 10 K interval, and at the pressure of up to 63 bars. It was again noted that CO2 solubility in ChCl-Glycerol based DEL mixture increases with increasing pressure and decreases with increasing temperature. The highest captured mole fraction of CO2 was observed up to 3.126 mol/kg at 303 K and 58 bars. The solubility data was validated

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2. Deep eutectic liquids for carbon capturing and fixation

by Henry’s law (CO2 solubility as a function of pressure and temperature) with a 1.61 percent absolute deviation. Overall, glycerol based HBD when combined with ChCl offered the carbon capturing capacity comparable with sugar based DELs (Table 2.1). Alok, Dawn [47] reported the absorption of CO2 by preparing crude glycerol and choline chloride-based deep eutectic liquids in 1:1, 1:2, 2:1, 1:3, 3:1, 1:4, and 4:1 molar ratios. This mixture chemically absorbs the CO2 and forms carbamate, from the reaction between CO2 and their HBD units. Out of various crude Gly-ChCl ratios, the highest CO2 solubility (0.377 wt percent) was observed in 2:1 molar ratio after 24hrs. The 2:1 molar ratio was observed further for optimization of temperature, time, and water for CO2 absorption. At 343.15 K, maximum absorption was observed (0.331 wt percent). The optimized time for maximum CO2 absorption (0.123 wt percent) was found to be 20 mins. The absorption of CO2 increases with moisture content up to 10mL (0.381 wt percent) and then become reduces with the addition of water. the FT-IR analysis shows the peak at 2927 cm−1 , which indicates the formation of carbamate. The TGA-DSC analysis indicates the degradation of the respective mixture at 318 °C. The authors found crude glycerol-based solvent systems worth exploring in the future.

2.7.3 Glycerol + L-arginine Chemat, Gnanasundaram [48] evaluated the CO2 solubility in ChCl-glycerol-l-arginine based ternary deep eutectic liquids mixed with l-arginine at 303.15 K and 6–20 bar in different molar ratios. The ChCl-glycerol + L-arginine (1:2:0.1 molar ratio) showed the highest CO2 solubility (5.23 mol CO2 /kg DEL), which was further evaluated on a temperature range of 303–323 with 70 bar pressure. The results show that the uptake of CO2 increases when pressure increases and temperature decreases. l-arginine has a significant effect on CO2 solubility. The higher CO2 solubility is might be due to the presence of amine groups in l-arginine which interact with CO2 . At a high ratio of l-arginine, CO2 solubility decreases due to the high viscosity of deep eutectic liquids. Haider, Jha [49] observed the CO2 solubility in both amine and glycol-based deep eutectic liquids at 303.15 K temperature and 0.1–2 MPa pressure. Choline chloride (ChCl) and tetra butyl ammonium bromide (TBAB) were used as HBA and ethylene glycol (EG), diethylene glycol (DEG), methyldiethanolamine (MDEA), and diethanolamine (DEA) as HBDs. Overall, amine-based systems exhibited higher solubility than glycol-based systems due to the more interactions between the amine group and CO2 molecules. It was observed that in a glycolbased system, HBD has a very pronounced effect on the solubility of CO2 as it decreased from EG to DEG due to the oversaturation, which caused a reduction in free volume. An increase in the DEG mole ratio results in improved solubility due to a decrease in H-bond strength. In FT-IR after absorption spectra, a peak at 2340 cm−1 is due to asymmetric stretching of O = C = O, other spectra remain unchanged confirming the physical absorption of CO2 in MDEA-based systems. Whereas, in after absorption spectra of DEA, a peak at 1441 cm−1 is associated with C = O vibration of carbamate confirming chemisorption. DEA forms carbamate due to the availability of one hydrogen bond to be replaced with CO2 , while there is no hydrogen bond available in MDEA.

TABLE 2.1 A Comparison of Carbon Capturing Potential of different Deep Eutectic Liquids under different conditions. Thermodynamic Conditions (K)/(MPa)∗

Solubility (mol kg−1 )

Remarks

References [44,45]

HBD

Choline Chloride

Urea

1:1.5

1. 398

0.20

Economical

1:2

2. 1

0.27

Low CO2 solubility

1:2.5

1. 308

0.20

Thermally unstable

1:2

2. 4.5

0.19

Not easily recycleable

1:2

1. 303

3.12

Economical

Glycerol

2. 5

[46]

Low CO2 solubility Thermally stable Not easily recycleable

Crude glycerol

1:1

1. 353

0.22

Economical

1:2

1. 368

0.10

Low CO2 solubility

0.10

Thermally unstable

0.34

Not easily recycleable the addition of water enhance CO2 solubility

1:3 1:4

1. 343

2:1

0.38

3:1

1. 313

0.14

4:1

1. 368

0.10

[47]

2.7 Carbon capture efficiency of various HBDs

HBA

Molar ratio HBA:HBD

(continued on next page)

27

28

TABLE 2.1 A Comparison of Carbon Capturing Potential of different Deep Eutectic Liquids under different conditions—cont’d

HBA

Thermodynamic Conditions (K)/(MPa)∗

Solubility (mol kg−1 )

Remarks

References

Fructose

1:1

1. 298

4.24

Economical, non-toxic

[38]

2. 5.0

4.52

High CO2 solubility

4.22

Thermally unstable

Lactic acid Malic acid

Not easily recycleable Solubility increases with the bulkier group on HBA 1,2-propanediol

1,4-butanediol

2,3-butanediol

Monoethanolamine

1:3

1. 293

0.16

Low CO2 solubility

1:4

2. 0.5

0.15

Thermally unstable

1:3

1. 293

0.15

Not easily recycleable

1:4

2. 0.5

020

1:3

1. 293

0.18

High molar ratio and pressure can show higher solubility

1:4

2. 0.50

0.18

1:5

1. 333

0.32

Economical

1:6

2. 1.5

0.31 g/g

Good CO2 solubility

1:8

1. 313

0.33 g/g

Thermally unstable

1:10

2. 0.02

0.34 g/g

Not easily recycleable

[50]

[52]

(continued on next page)

2. Deep eutectic liquids for carbon capturing and fixation

HBD

Molar ratio HBA:HBD

Diethanolamine

Methyldiethanolamine

0.14 g/g

1:8

0.15 g/g

1:10

0.16 g/g

1:6

0.02 g/g

1:8

0.02 g/g

1:10

0.02 g/g

High temperature and pressure

[51]

1:2

1. 293

2.316

Economical, non-toxic

1:3

2. 3.0

0.25

Good CO2 solubility

1:4

1. 303

0.27

Thermally unstable

1:5

2. 0.57

0.28

Not easily recycleable

Phenol

1:2

1. 293.15

0.20

Toxic

Diethylene glycol

1:3

2. 0.50

0.20

Low CO2 solubility

Triethylene glycol

1:4

1. 293

0.21

Thermally more stable

1:3

2. 0.50

0.16

1:4

1. 293.15

0.18

Not easily recycleable An increase in pressur and mole ratio improves CO2 solubility

[37,56]

[59]

2.7 Carbon capture efficiency of various HBDs

Levulinic acid

1:6

(continued on next page)

29

30

TABLE 2.1 A Comparison of Carbon Capturing Potential of different Deep Eutectic Liquids under different conditions—cont’d

HBA

HBD

Molar ratio HBA:HBD

Thermodynamic Conditions (K)/(MPa)∗

Solubility (mol kg−1 )

1:3

2. 0.50

0.19

1:4

References

Solubility decreases from EG to DEG due to oversaturation, both chemical & physical absorption occurs

[49]

Functionalization with amines results in improved absorption, difficult regeneration

[54]

0.19

1:2

1. 303

0.045 mol−1

Diethylene glycol

1:3

2. 1.0

0.037 mol−1

1:4

0.038 mol−1

Diethanolamine

1:6

0.098 mol−1

Methyldiethanolamine

1:6

0.180 mol−1

1:7

0.195 mol−1

1:7:1

1. 298

1:7:5

2. 2.0, 2.2

0.22

Ethanolamine/Amino ethyl piperazine

0.26

Ethanolamine/ Piperazine

0.360

Ethanolamine/ Methyldieth-anolamine

0.259 0.250 (continued on next page)

2. Deep eutectic liquids for carbon capturing and fixation

Ethylene Glycol

Ethanolamine/ Diethanolamine

Remarks

Monoethanolamine/ Diethanolamine

1:2

1. 298

2.67

Glyceline/ Diethanolamine

0.86

Piperazine activated glyceline/ Diethanolamine

1.53

1:2:0.1

1. 303

5.23

Economical, non-toxic

1:2:0.2

2. 2.0

4.01

High CO2 solubility

1:3:0.1

3.99

1:3:0.2

3.75

High ratio of l-arginine can decrease CO2 solubility due to high viscosity

1:4:0.1

3.76

1:4:0.2

3.40

Urea + 20 percent water

1:2:9.97

1. 313

0.342

Low cost

Ethylene glycol + 20 percent water

1:2:12.64

2. 0.10

0.289

Non-toxic

1:2:10.14

0.249

Addition of water reduces solubility, low viscosity

Glycerol + 20 percent water

1:2:14.65

0.246

1:1:10.76

0.219

[48]

[33]

2.7 Carbon capture efficiency of various HBDs

Glycerol/L-arginine

[34]

Levulinic acid + 20 percent water DL-Malic acid + 20 percent water (continued on next page)

31

32

TABLE 2.1 A Comparison of Carbon Capturing Potential of different Deep Eutectic Liquids under different conditions—cont’d

HBA

HBD Monoethanolamine + 50 percent water

Molar ratio HBA:HBD

Thermodynamic Conditions (K)/(MPa)∗

Solubility (mol kg−1 )

1:5

1. 293

0.461

2. 1.5

References

Thermally stable, highly selective, efficient

[52]

High solubility than ILs, efficient, regeneration at high temperature

[63]

0.612 1. 323.15

0.51 mol−1

Glycerol/1,5diazabicyclo[4.3.0]-non5-ene

1:2:3

Glycerol/1,5diazabicyclo[4.3.0]-non5-ene

1:2:6

0.42 mol−1

Glycerol/1,5diazabicyclo[4.3.0]-non5-ene

1:2:7

0.41 mol−1

Glycerol/1,5diazabicyclo[4.3.0]-non5-ene

1:2:8

0.39 mol−1

Glycerol/1,5diazabicyclo[4.3.0]-non5-ene

1:2:10

0.39 mol−1

Glycerol/1,8diazabicyclo[5.4.0] undec–7-ene

1:2:6

0.14 mol−1

(continued on next page)

2. Deep eutectic liquids for carbon capturing and fixation

Monoethanolamine + 75 percent water

Remarks

1:2:6

Urea/ Monoethanolamine

1:2

0.40 mol−1

1. 301

0.70 mol−1

2. 0.10

0.58 mol−1

Urea/Triethanolamine

0.22 mol−1

Urea/2methylaminoethanol

0.95 mol−1

Urea/2-amino-2methyl-1-propanol

1.00 mol−1

Imidazole

1:3

1. 293

0.17

Low CO2 Solubility

1:4

2. 0.516

0.17

1:5

0.18

High levels of guaiacol increases solubility, low dissolution enthalpy

1:3

0.21

Easy Desorption

1:4

0.22

1:5

0.23

1:3

0.18

1:4

0.19

1:5

0.19

1:2

1. 303

[62]

Functionalization with amines enhances the CO2 good recyclability

Urea/Diethanolamine

Guaiacol

Good CO2 solubility

0.2607

Difficult to handle

[57]

2.7 Carbon capture efficiency of various HBDs

Diethylamine hydrochloride Acetylcholine chloride

Glycerol/7-methyl1,5,7-triazabicyclo [4.4.0]dec–5-ene

[58] (continued on next page)

33

34

TABLE 2.1 A Comparison of Carbon Capturing Potential of different Deep Eutectic Liquids under different conditions—cont’d

HBA

HBD

Molar ratio HBA:HBD

Thermodynamic Conditions (K)/(MPa)∗

Solubility (mol kg−1 )

1:3

2. 57, 567, 572, 587

0.2940 0.22

1,2,4-triazole

1:1

0.21

Levulinic acid

1:3

1. 303

0.30

Tetraethylammonium bromide

1:3

2. 0.54

0.27

Tetrabutylammonium chloride

1:3

0.24

1:3

0.30

Tetraethylammonium chloride

Tetrabutylammonium bromide

Ethylene glycol

1:3

1. 303

0.26

1:2

2. 1.0–2.0

0.05 mol−1

1:3

0.05 mol−1

1:4

0.05 mol−1

References

High imidazole content has a positive impact on solubility, thermally stable Bulkier cations show high solubility, exothermic

[65]

Solubility decreases from EG to DEG due to oversaturation, both chemical & physical absorption occurs, amines show higher solubility

[49]

(continued on next page)

2. Deep eutectic liquids for carbon capturing and fixation

2:3

Remarks

0.11 mol−1

1:3

0.09 mol−1

1:4

0.09 mol−1

1:3

0.25 mol−1

1:4

0.29 mol−1

Diethanolamine

1:6

0.10 mol−1

Octanoic acid

1:2

Methyldiethanolamine

Decanoic acid DL-menthol

Dodecanoic acid

2:1

Tetraethylenepentamine chloride

Thymol

1:3

Triethylenetetramine chloride

Diethylene glycol

Methyltriphenylphosphonium Bromide

1. 293

0.59

2. 6.0, 6.6, 3.56

0.75

[68]

Low volatility, synergism of physical and chemical absorption, efficient at high thymol content

[73]

Basic, efficient, good regeneratability

[67]

DEG show reasonable CO2 solubility due to low viscocity, good regeneration, pressurised absorption

[4]

0.39 1. 313

1.355 mol−1

2. 0.10

1.298 mol−1

1:2

1. 313

1.42 mol−1

Ethylene glycol

1:3

2. 0.10

1.46 mol−1

Diethylene glycol

1:4

1. 303

0.053

Glycerol

1:4

2. 10.19, 9.21, 10.39

0.062

1:3

Hydrophobic, good solubility

2.7 Carbon capture efficiency of various HBDs

1:2

Diethylene glycol

0.059 (continued on next page)

35

36

TABLE 2.1 A Comparison of Carbon Capturing Potential of different Deep Eutectic Liquids under different conditions—cont’d

HBA

HBD

Molar ratio HBA:HBD

Monoethanolamine hydrochloride

Methyldiethanolamine

1:3

Solubility (mol kg−1 )

1. 298

0.1158 g/g

2. 0.10

0.1082 g/g

Methyldiethanolamine hydrochloride Imidazole

1,5-diazabicyclo[4.3.0]non-5-ene N-methylthiourea

References

Efficient, dilution lowers viscosity and improve solubility, good recycability

[55]

High pressure and imidazole content show high solubility, non-spontaneous, Recycleable

[72]

Improved absorption on higher mole ratio of EU, high viscosity of DMLU based system, good recyability

[64]

Increased absorption in [DBNH]2 [DTU]:EG due to multiple site interaction, thermally stable, chemisorption results in carbamate and carbonate formation

[76]

0.0594 g/g p-toulene sulfonic acid

3:1

1. 303

1.0059

3.5:1

2. 1.44, 1.49, 1.48

1.0642

4:1 1,5-Diazabicyclo [4.3.0]non-5-ene

Remarks

Ethylene urea

2:1 3:1

1.0959 1. 318

1.75 mol−1

2. 0.1

mol−1

2.01

1,3-dimethylurea

2:1

1.32 mol−1

Dimethylolurea

2:1

0.38 mol−1

Ethylene glycol

1:1

1. 313 2. 0.10

0.145 g/g

(continued on next page)

2. Deep eutectic liquids for carbon capturing and fixation

Diethanolamine hydrochloride

Thermodynamic Conditions (K)/(MPa)∗

TABLE 2.1 A Comparison of Carbon Capturing Potential of different Deep Eutectic Liquids under different conditions—cont’d

HBA

HBD

Molar ratio HBA:HBD

Thermodynamic Conditions (K)/(MPa)∗

1:2

1,5-diazabicyclo[4.3.0]non-5-ene N-dimethylthiourea Malic acid

Betaine

Lactic acid

1:1

Remarks

References

Solubility increases with bulkier group on HBA, non-toxic, ease of availability

[38]

Low cost, excellent regeneration, good absorption, heat resistant

[74]

Comparatively low solubility than other DELs, PAA show highest solubility due to π -π interactions among these, low regeneration

[69]

0.173 g/g

1. 298

4.14 mmol/g

2. 5.0

4.30 mmol/g 4.26 mmol/g

Carvone

Thymol

Cineole

Menthol

1:1

1. 298

0.48

2. 4.0

0.50

Thymol

0.51 0.50

N,N,N-trimethylglycine

Oxalic acid dihydrate

1:2

1. 333

1.72 mg/g

2. 4.0



Glycolic acid

1.68 mg/g

Phenylacetic acid

32.0 mg/g

2.7 Carbon capture efficiency of various HBDs

β-alanine

Solubility (mol kg−1 )

1. Temperature in Kelvin rounded off to 3 significant figure, 2. Pressure (mPa or state) round off to 3 significant figures.

37

38

2. Deep eutectic liquids for carbon capturing and fixation

2.7.4 Natural organic acids Altamash, Amhamed [38] investigated the effect of HBD and HBA on CO2 in natural deep eutectic liquids. The tested HBAs included ChCl, betaine, and β-alanine, whereas HBDs applied comprise Fructose (Fr), Citric acid (CA), Malic acid (MA) and Lactic acid (LA). It was noticed that the no. of hydroxyl groups in HBD controlled the solubility of CO2 . In general, higher the number of hydroxyl groups in HDB the more will be the solubility. This is due to the inter and intramolecular H-bonding between HBD and CO2 . There are 5, 4, 3, and 2 hydroxyl groups in Fr, CA, MA, and LA, respectively. In the case of HBA, an increase in the polarity or size of groups attached to the N atom can increase the solubility of CO2 in resultant DEL. The results of the subject study confirms that natural deep eutectic liquids made up of amino acids (HBA) and sugars/organic acids (HBD) offer more fascinating opurtunities. However, nature of interactions in natural deep eutectic liquids are more complex and are still undisclosed. Untill now, the development of strong van der Waals interactions can be speculated between molecules of CO2 and natural DEL.

2.7.5 Dihydric alcohols The various combinations of ChCl with dihydric alcohols like 1,2-propanediol, 1,4butanediol, and 2,3-butanediol were prepared and tested for their CO2 capturing potential by Chen, Ai [50]. The solubility of CO2 was monitored at different temperatures (293–323 K) with 10 K interval and 6 bars pressure under the isochoric conditions. The solubility of CO2 in dihydric alcohols based DEL mixtures increases as the applied pressure increases and the temperature decreases. It has been observed that DEL contain ChCl and 2,3-butanediol in a 1:4 molar ratio shows the highest solubility of CO2 among all others. The highest mole fraction of absorbed CO2 was observed up to 0.1915 mol/kg at 293.2 K and 508.5 kPa. The enthalpies of all solutions were observed as negative in all conditions.

2.7.6 Amines Three different amine-based DELs were employed in three different molar ratios using ChCl as HBA. The amine based deep eutectic liquids have the advantage of high solubility for CO2 over conventional eutectic liquids and aqueous amine solutions. The highest solubility of CO2 (0.150 g CO2 /g of solvent) was observed in ChCl-monoethanolamine in 1:8 molar ratio. With increasing concentration of monoethanolamine (MEA), CO2 solubility also increases. This higher solubility can be attributed to the simultaneous presence of two electronegative functional group i.e. NH2 and OH. The N–H stretching and O–H broadening in the FT-IR spectrum indicate the formation of H-bonds between these two before absorption. The peaks at 1950 and 2200 cm−1 due to carbamate formation confirmed the chemical absorption in these liquids [51]. Yan, Huan [52] and Wibowo, Liao [53] also undertaken the CO2 capturing from biogas by using ChCl-MEA based DELs comprising 1:5 molar ratio of HBA and HBD. The effect of temperature, pressure, and water content on the absorption capacity and selectivity of CO2 was evaluated by ANOVA and response surface methodology (RSM). The highest absorption was recorded in ChCl-MEA with 75 percent water i.e., 0.609 mol CO2 /mol liquid at 293.15 K temperature and 1.50 MPa pressure. Whereas, pure ChCl-MEA based system showed highest capacity at higher temperature of 333.15 K temperature due to high viscosity. The

2.7 Carbon capture efficiency of various HBDs

39

average absorption capacity of this system was 0.481 mol CO2 /mol solvent. With increasing pressure and water content, the selectivity and absorption capacity increases, while at higher temperature, both the parameter decrease. As the temperature has less influence on the absorption rate than pressure and water content, it confirms the physical absorption in this system. ChCl-MEA based liquids and its aqueous solutions showed pronounced effect on CO2 solubility from biogas, hence, provided potential system for future research. Sarmad, Nikjoo [54] investigated the effect of novel ternary DEL ChCl-ethanolamine (EA) in 1:7 molar ratio functionalized with amine type 1, 2, 2, and 3, as 1-(2- aminoethyl) piperazine (AEP), piperazine (Pz), and diethanolamine (DEA), methyldiethanolamine (MDEA), respectively. These liquids were prepared at 29.15 K temperature and 2 MPa pressure and have their melting points in the range of 264–275 K. The FT-IR and 13 C NMR confirm the carbamate formation due to the chemisorption. The association model was used to explain the thermodynamic characteristics and the categories of chemical bonding set were AB2, and AB (A = DEL, B=CO2 ). The results further revealed that the solubility of CO2 in ChCl-EA-amine based system increases in the order of Pz > AEP > MDEA > DEA. The piperazine (Pz) containing DEL system exhibited the CO2 solubility equivalent to 0.360 mol CO2 /kg DEL. The CO2 capturing efficiency of methyldiethanolamine based DELS was checked along with regeneration capability. Three different DEL with methyldiethanolamine (MDEA) as HBD and different HBA [Monoethanolamine hydrochloride (MEAHCl), Diethanolamine hydrochloride (DEAHCl), and Methyldiethanolamine hydrochloride (MDEAHCl)] were prepared in 1:3 molar ratio at 298.15 K and at CO2 flow rate of 10.1 mL/min. Density Functional Theory and Molecular Dynamics were utilized to evaluate the characteristics of these liquids and their interaction with CO2 molecules. The absorption of CO2 is mainly concerned with HBA. MEAHCl-MDEA based DEL exhibited the highest CO2 absorption (0.115 g CO2 /g of DEL) which was further improved (0.145 g CO2 /g of DEL) by adding 13.50 wt percent of MEA at same temperature in 1:2:0.5 molar ratio. DFT and Molecular Dynamics showed that the interaction of MEAHCl-MDEA with CO2 is through amine group and hydroxyl group in MEAH and MDEA, respectively, also approved by NMR and FT-IR. Addition of primary or secondary amine to aqueous solution of tertiary amine improves the CO2 uptake efficiency. Ternary DEL is cost effective and efficient system which has low desorption energy and shows tremendous regeneration capacity of about five cycles [55].

2.7.7 Levulinic acid The CO2 absorption capacity DEL comprising ChCl and levulinic acid in a molar ratio of 1:2 was estimated at 293 K, 298 K, 308 K, 318 K, and 323 K, and at the pressure up to 30 bars. The highest CO2 solubility (2.316 mmol/gram of DEL) was observed at 293 K temperature and 50 bar pressure [37]. In another report, choline chloride was combined with levulinic acid and furfuryl alcohol in 1:3, 1:4, and 1:5 molar ratios and applied for CO2 absorption in the range of 303.2–222.2 K and 6 bars under isochoric-saturation condition. The obtained results show that CO2 has higher solubility in levulinic acid-based DEL than in furfuryl alcohol-based one. The highest solubility was observed as 0.33 mol CO2 /kg of DEL. Likewise other system described above, the solubility of CO2 in these DELs was found to be function of temperature, pressure, and molar ratio [56].

40

2. Deep eutectic liquids for carbon capturing and fixation

2.7.8 Guaiacol The presence of the benzene ring and –C–O-C- group in guaiacol makes it an efficient candidate for CO2 capture. Liu, Gao [57] prepared guaiacol-based DELs using quaternary ammonium salts like ChCl, acetyl ChCl, and DEA/Cl as HBA and guaiacol as HBD in 1:3, 1:4, and 1:5 molar ratio. The subject DELs were tested for CO2 absorption at 293.15–323.15 K temperature and 0.6 MPa pressure by isochoric saturation method. With the increasing molar ratio of guaiacol, the solubility of CO2 increased. The absorption of CO2 in the studied system was declared to be physical dissolution. DEA/Cl- guaiacol based system in 1:5 molar ratio outperformed the best solubility of CO2 (0.2321mol CO2 /kg DEL) at 293.15 K and 0.522 MPa. Low dissolution enthalpy is required for desorption of CO2 .

2.7.9 Azoles Recently, various azole-based DELs were utilized by Li, Liu [58] to capture CO2 efficiently in isochoric-saturation method. Acetyl ChCl as HBA was mixed with imidazole (Im) and 1,2,4triazole (Tri) as HBD in 1:2, 1:3, and 2:3 molar ratios at 303.15–333.15 K and pressure up to 6 MPa. Solubility of CO2 increases with increasing pressure and decreasing temperature i.e., CO2 is absorbed by physical dissolution. Henry’s law was used to correlate solubility data and thermodynamic properties. Acetyl ChCl-Im system in 1:3 molar ratio showed the highest solubility of CO2 (0.2940 mol CO2 /kg DEL), while Acetyl ChCl-Tri in 1:1 molar ratio had the least CO2 solubility (0.2190 mol CO2 /kg DEL) at 303.15 K and 0.567 and 0.587 MPa pressure, respectively. It is confirmed from the results that high imidazole (Im) content has a positive impact on the solubility of CO2 . Henry’s constant of solubility increases with an increase in temperature.

2.7.10 Miscellaneous HBD Choline chloride was combined with different hydrogen bond donors like phenol, diethylene glycol, and triethylene glycol in 1:2, 1:3, and 1:4 molar ratios. The solubility of CO2 was measured at a temperature range of 293.2–323.2 K, with a 10 K interval and 6 bars pressure. The results showed that the solubility of CO2 increases as the pressure increases and decreases with the increase in temperature. The enthalpies of all solutions were observed as negative in all conditions. Furthermore, choline chloride-triethylene glycol-based liquid mixture in 1:4 molar ratio shows the highest CO2 solubility (0.1941 mol/kg) among others [59].

2.8 CO2 absorption in aqueous solution of DELs Reline-based eutectic liquids, consisting of ChCl: Urea mixture in a 1:2 molar ratio, has the lowest known melting point among known DELs. Reline is hygroscopic as most of the ChCl-based liquids must contain water in trace amounts. This water affects the H-bonding interactions and subsequently their physical/chemical properties. Most of the eutectic liquids and their aqueous mixtures have a low density at high temperatures and high densities at high pressure (1–500 bars) in 1:2 molar ratios. This behavior of density is due to the dependence of

2.9 CO2 absorption in ternary DELs

41

H-bonding on the temperature. It also reduces the molecular distance and hence free volume. In eutectic liquids, water molecules act as an anti-solvent which blocks the absorption of CO2 . Therefore, the hygroscopic behavior of DEL can significantly affect the CO2 solubility at lower pressure [60]. Sun, et al. studied the effect of water on CO2 solubility in reline solution. He investigated that CO2 absorption becomes exothermic with water concentration of less than 0.231 molar ratio. Above this ratio the absorption process becomes endothermic. This outcome is only concerned when the swing-absorption stripping process is considered for CO2 capture. Hsu et al. investigated the solubility of CO2 in a binary solution of aqueous reline (ChClurea) and ternary solution (ChCl-urea-monoethanolamine) in 1:2 molar ratio. The obtained results demonstrated that the solubility of CO2 in binary aqueous solution can be enhanced by combining it with monoethanolamine [61]. Aravena, Lee [33] studied the absorption of CO2 in aqueous deep eutectic liquids based on ChCl as HBA and urea, ethylene glycol, glycerol, malic acid, levulinic acid as HBD, and diluted in 20 percent wt water to improve mass transfer. ChCl-urea-water system was proved to be an efficient system for CO2 solubility in place of alkanolamine based absorbents. At high temperatures, solubility decreases due to the dominant desorption phenomenon. Due to the addition of water, the surface tension of the prepared liquids was increased while the viscosity and density were decreased. The rate of absorption decreases with the addition of water. FT-IR and NMR results revealed that both chemisorption and physical absorption occur in the ChCl-urea-water system, with the former due to the amino groups in urea.

2.9 CO2 absorption in ternary DELs 2.9.1 Alkanolamines The absorption capacity of CO2 in numerous alkanolamines was assessed in deep eutectic liquids and an aqueous medium by Muthu et al. The amines used were monoethanolamine (MEA), diethanolamine (DEA), triethanolamine (TEA), 2-methylaminoethanol (MAE), and 2-amino-2-methyl-1-propanol (AMP). These amines were employed in ChCl:urea medium in optimized molar ratio. The solubility of CO2 in these amines-based eutectic liquids was higher as compared to the aqueous medium. 2-amino-2-methyl-1-propanol-based liquids exhibited higher solubility of CO2 among all the solvents [62].

2.9.2 Superbases Sze, Pandey [63] investigated the effect of different superbases i.e., 1,5-diazabicyclo[4.3.0]non-5-ene (DBN), 1,8-diazabicyclo[5.4.0]undec–7-ene (DBU), and 7-methyl-1,5,7-triazabicyclo [4.4.0]dec–5-ene (MTBD) on the solubility of CO2 . These superbases, when combined with ChCl-Gly-based DEL in different molar ratios can deprotonate the OH groups of ChCl and Gly. The 13 C NMR before and after mixing with CO2 indicates the phenomenon of chemical absorption of. The DBN (an economically avialble base) containing DEL offered an exceptional results. Different molar ratios (ChCl-Gly-DBN 1:2:x, whereas x = 3,6,7 or 8) of DBN-DELs were studied for CO2 solubility and it was observed that 1:2:7 molar ratio gave the highest solubility of CO2 i.e., 105mg/g DEL. These modified liquids have higher solubility values

42

2. Deep eutectic liquids for carbon capturing and fixation

even to those of ILs. Another advantage of these mixtures is that they can be regenerated within 35 mins of heating at 333.15 K in a nitrogen-rich environment. Functionalized DELs (or ternary DELs) are proved as a promising alternatives to conventional solvents or other low melting liquids. In this regard, Jiang, Ma [64] prepared a novel class based on acylamidesuperbase in 1:2 molar ratio. 2-imidazolidone/ethyleneurea (EU)−1,5-Diazabicyclo[4.3.0]non5-ene (DBN) based system exhibited the highest CO2 solubility of 1.751 mol CO2 /mol DEL (upto 23.03 percent wt) at 318.15 K temperature and 0.1 MPa pressure. The absorption capacity of EU-DBN is due to its ring structure, which causes low steric hindrance. When the molar ratio of DBN is increased from 1:2 to 1:3, absorption capacity increases from 1.80 to 2.01 mol CO2 /mol DEL. The absorption capacity increases upto 318.15 K temperature, after that it starts decreasing. Acylamide-superbase-based system showed good recyclability after five successive absorption/desorption cycles. FT-IR and 13 C NMR analysis revealed strong multiple site interactions due to chemisorption between the nitrogen atom of 2-imidazolidone and CO2 resulting in carbamate formation. This is an excellent method to optimize acylamidesuperbase-based DEL to achieve high CO2 capturing efficiency.

2.9.3 Hybrid Choline chloride was combined with monoethanolamine, glycerine and piperazineactivated glyceline in 1:2 molar ratio. All these prepared deep eutectic liquids were added to a diethanolamine solution of 10–30 wt percent. The solubility of CO2 was studied according to the mass transfer. The addition of eutectic liquids in diethanolamine solution increases the conc. of electrolyte resulting in reduced bubble diameter and improved gas holdups. The replacement of water with ChCl-MEA or ChCl-Gly/Pz mixtures results in improved CO2 solubility, mass transfer and thermal stability. While ChCl-glyceline based liquids can negatively affect the solubility of CO2 . The lower stability of ChCl-glyceline and ChCl-Gly/Pz after CO2 absorption provides easy separation of CO2 [34].

2.10 Ammonium-Based DELs Five different deep eutectic liquids were synthesized from levulinic acid as HBD and various ammonium salts (acetylene choline chloride, tetraethylammonium chloride, tetraethylammonium bromide, tetrabutylammonium chloride, and tetrabutylammonium bromide) as HBA in 3:1 molar ratio. The absorption of CO2 in these liquids was studied at 303.2, 313.2, 323.2, and 333.2 K with pressure up to 6 bars. The results indicated the increase in solubility with decreasing temperature and increasing pressure. The cations in ammonium salts play a key role in CO2 absorption, the larger the cation, the more the solubility. Tetrabutylammonium bromide-levulinic acid mixture shows higher solubility (0.043 mol/kg) in 1:3 molar ratio at 303.2 K and 5.6 bars. The enthalpies were exothermic [65]. A comprehensive evaluation of various eutectic liquids for CO2 capture was performed by Luo, Liu [66] through both, experimental and simulation. At first, a hydrophobic low melting liquid comprising of TBAB as HBA and DA as HBD with 1:2 molar ratio was checked by COSMO-SAC model. After that, quantum chemistry models were utilized to screen the interactions between DEL and CO2 molecules. The results revealed that these

2.10 Ammonium-Based DELs

43

interactions are mainly based on weak H-bonding and van der Waals forces. Then, the liquidgas equilibrium method was carried out to check the effect of the pressure and temperature, molar ratios of HBA and HBD, and the type of HBA and HBD, on the absorption of CO2 . The results reveal that the absorption of CO2 follows the Henry’s law which approves the reliability of the applied model. With the decrease in temperature and increase in pressure, CO2 solubility increases. The values of entropy and enthalpy are negative indicating the exothermicity of the process. While positive values of Gibbs free energy indicate that the absorption process is non-spontaneous and requires high pressure. Finally, for low melting liquid-based post-combustion capture of CO2 , a rigorous rate model (RRM) was simulated. RRM was applied to check the environmental sustainability and the life cycle of the studied liquids. Ammonium based DELs have been found to be more efficient for CO2 absorption. Triethylenetetraamine hydrochloride ([TETA]Cl) has been utilized as HBA and EG and DEG as HBD at various mole ratios. Among all the designed liquids, [TETA]Cl-EG based system in 1:3 molar ratio exhibited the highest absorption capacity of 1.457 mol CO2 /mol solvent (17.50 percent wt) at 313.15 K temperature and 0.01 MPa pressure. The molar ratio of HBA:HBD and partial pressure positively affects the solubility while temperature and chloride ion has a negative effect. These liquids showed good renewability even after five successive absorption-desorption cycles as the absorption capacity is not affected. Both the HBD, EG and DEG, improves the basicity of studied liquids by activating –NH/NH2 group on [TETA]Cl. FT-IR results confirmed the presence of carboxylate which is due to chemical absorption between [TETA]Cl and CO2 molecules [67].

2.10.1 Carboxylic acids The CO2 solubility DELs containing carboxylic acids as HBD was studied by Rabhi, Mutelet [68], who used tetrabutylammonium bromide (TBAB) and DL-menthol as HBA and Octanoic acid (OA), Decanoic acid (DA), and Dodecanoic acid (DDA) as HBD in 1:2 and 2:1 molar ratio. The CO2 solubility has been studied under different thermodynamic conditions, i.e. 293–373 K temperature and 12.29 MPa pressure. The DEL comprising TBAB-DA in 1:2 molar ratio exhibited the highest CO2 solubility (2.529 mol CO2 /kg DEL) at 313.15 K temperature and 4 MPa pressure. It was noticed that carboxylic acid (CA) based eutectic liquids have lower efficiency than phosphonium-based DEL but more than ILs. The effect of various zwitter-ion containing natural deep eutectic liquids (NADELs) comprising of N,N,N-trimethylglycine (TMG), and carboxylic acids like oxalic acid (OA), glycolic acids acid (GA), and phenylacetic acid (PAA) were studied by Siani, Tiecco [69]. The solubility of CO2 was estimated gravimetrically at 29–333 K temperatures and pressure upto 4 MPa. The highest CO2 uptake equal to 45.5 mg CO2 /g NADES was observed in PAA-TMG based system in 2:1 molar ratio at 313.15 K temperature and 4 MPa pressure. The presence of π -π interactions in these DELs was accounted for the absorption of CO2 . As the studied NADELs are all acidic in nature and CO2 shows more affinity for basic solvent system, so, CO2 solubility is comparatively lower in these liquids. PAA being less acidic among all the studied NADELs, shows more affinity for CO2 which results in high physical absorption of CO2 . Physical absorption of CO2 was confirmed by FT-IR results which show no difference in spectrum

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2. Deep eutectic liquids for carbon capturing and fixation

before and after absorption. The regeneration ability of studied NADELs was also less than other DELs.

2.11 Phosphonium based DELs Haider, Maheshwari [4] reported three different deep eutectic liquids based on methyltriphenylphosphonium bromide (MTPPB) as HBA and glycerol (Gly), ethylene glycol (EG) and diethylene glycol (DEG) as HBD, for CO2 solubility. The absorption of CO2 in these liquids was studied at 303, 313, and 323 K with pressure upto 1200 kPa. The highest CO2 solubility (0.062 mol CO2 /mole of solvent) was exhibited by MTPPB-DEG based mixture due to its low viscosity. These liquids can be regenerated at higher temperatures, during the decarbonization, for reuse. The solubility of CO2 increases with increased pressure. Phosphonium and ammonium based deep eutectic liquids were designed with different HBD in specific molar ratio and their viscosity and capability of CO2 absorption was checked by Sarmad, Xie [70]. Both the solubility and viscosity are the key factors while designing efficient absorbents. The CO2 solubility was measured on a vapor-liquid setup at 29.15K temperature and upto 2.0 MPa pressure. With the increase in pressure, CO2 solubility also increases as it follows Henry law according to which solubility and partial pressure are proportional to each other. The type of HBD also effects the solubility of CO2 due to interactions between them. It follows the order Triethylmethylammonium chloride-Lactic acid > Triethylmethylammonium chloride-Levulinic acid > Triethylmethylammonium chlorideacetic acid. Due to strong interactions between TEMA-LA, it is difficult for them to interact with molecules of CO2 , hence results in lower solubility. While H-bond interactions are weakest in TEMA-AC, therefore, molecules of AA interact more easily with CO2 molecules resulting in highest solubility. In case of HBA, the length of alkyl chain also effects the CO2 solubility in positive direction. As the viscosity increases with CO2 absorption, this problem was coped by addition of water as a coordinating solvent. The viscosity is decreased by addition of 0.11 mol of water resulting in more pronounced solubility. However, the addition of water can negatively reduce the CO2 solubility and similar are the cases with an increase in temperature to reduce the viscosity. These liquids can further be functionalized in future to improve the absorption capacity.

2.12 Azole based DELs A new class of deep eutectic liquids was reported by Cui, Lv [71] based on azole as HBA [(P2222 )(Im), (P2222 )(Triz), (N2222 )(Im), and (N2222 )(Triz)] and EG as HBD in 1:2 molar ratio at 298.15 K temperature and 0.1 MPa pressure. [N2222 ][Im]-EG in 1:2 molar ratio showed the highest solubility i.e., 0.129 g CO2 /g DEL, while [P2222 ][Triz]–EG and [P2222 ][Im]–EG had the least solubility (0.118 g CO2 /g DEL). FT-IR results indicated the formation of carbonate through the hydroxyl group of EG. Regeneration capability of [P2222 ][Triz]–EG was evaluated as regeneration of any solvent is a key point for industrial/practical applications. Results revealed that this system can be completely recycled at 343.15 K temperature in nitrogen enriched environment.

2.14 Hydrophobic DELs

45

Imidazole based deep eutectic liquids were employed by Qin, Song [72] to cope the problem of global warming by capturing CO2 . Imidazole was mixed with p-toulene sulfonic acid; PTSA in 3:1, 3.5:1, and 4:1 molar ratios at 303.15–333.15 K temperature and 0.11–1.5 MPa pressure. COSMO-RS and Jou-Mather model was used to predict the solubility of CO2 in studied DELs. Results reveal that improving the pressure and Imidazole content can improve the solubility while the temperature has the opposite effect. The lower values of enthalpy of dissolution suggest their easy regeneration capacity, while positive Gibb’s free energy of dissolution reveals non-spontaneity of process. Jou-Mather model predicted the results more accurately (5.1 percent deviation) than COSMO-RS, which predicts qualitative results more accurately than quantitative.

2.13 Bio-phenol derived superbase based DELs Bio-phenols can be derived from plants and follow the principles of “green chemistry”. A unique combination of bio-phenols like thymol (Thy) and carvacrol (Car) functionalized with superbases (1,8-diazabicyclo [5,4,0]undec–7-ene; DBUH) was mixed with EG in 1:2, 1:3, 1:4 molar ratios at 298.15 K and 0.01 MPa to check their performance for CO2 solubilities. [DBUH][Thy]-EG exhibited the highest CO2 capacity of 1.0 mol CO2 /mol DEL in 1:4 molar ratio at room temperature and atmospheric pressure. The DBUH based ILs exhibited much lower capacity for CO2 due to their high viscosity than the studied DELs. Studied DELs show much higher capacities as the addition of EG lower their viscosities. Interestingly, EG molecules only interact with CO2 molecules through H-bonding and not with anions (CAR− , Thy− ). FT-IR and NMR analysis reveal the chemisorption of CO2 . The appearance of signals at 3.49, 3.77 ppm and 61.2, 65.9, 157 ppm in after absorption spectra of 1 H and 13 C NMR, respectively, indicates the formation of carbonate. HMBC also confirms the observed results. In FT-IR spectra the peaks at 1640 and 1282 cm−1 in after absorption spectra are also due to the carbonate formation. These liquids can be desorbed in nitrogen rich environment at 343.15 K and showed good recyclability [43].

2.14 Hydrophobic DELs Gu, Y. et al. reported a class of hydrophobic deep eutectic liquids composed of functional polyamine-hydrochloride as hydrogen bond acceptor and monoterpene (thymol) as hydrogen bond donor to check the solubility of CO2 from flue gases. These liquids showed hydrophobic behavior even after CO2 absorption. The increased conc. of monoterpene results in decreased density and viscosity. The key advantage of these liquids is their low volatility due to the H-bonding between HBA and HBD groups. Monoterpene based deep eutectic liquids could even capture CO2 at low pressure, and the highest CO2 solubility (1.36 mol CO2 /mol DEL) was observed for [TEPA] Cl and thymol in 1:3 molar ratio at 313.2 K and 103 kPa. The solubility of CO2 increases with decreasing temperature and increasing pressure. The terpene based eutectic liquids can be used more than five times, which indicates their high stability. The FT-IR analysis showed that high solubility of CO2 is due to its interaction with amine resulting in the formation of carboxylate. Both chemical and physical absorption put up the overall CO2

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2. Deep eutectic liquids for carbon capturing and fixation

absorption. It was found that these polyamine-terpene based deep eutectic liquids exhibited much higher absorption capacities than hydrophobic ILs (0.020 mol CO2 /mol) [73]. Al-Bodour, Alomari [74] investigated the effect of hydrophobic NADELs on CO2 solubility through isochoric saturation process. The NADELs were prepared by mixing HBA like carvone (CAR), and cineole (CIN) and HBD including thymol (THY), and menthol (MEN) in different molar ratios at 298 and 308 K temperatures and upto 4 MPa pressure. Hydrophobic terpenes based NADELs exhibited high physical absorption on high pressure and low temperature. CIN-MEN system showed the highest solubility of CO2 (0.51 and 0.48 mol/kg), while CAR-THY system had the least CO2 solubility (0.45 and 0.43 mol/kg) at 298 K and 308 K temperature, respectively. Absorption capacity of CIN-MEN system is 6.50 percent higher at 298 K and 10.50 higher at 308.15 K than CAR-THY system. Regeneration capacity of these systems is also excellent thus reducing the energy and operating cost. These solvents can be proved as best candidates for carbon management in future.

2.15 Non-ionic DELs The non-ionic low melting liquids comprising of phenolic alcohols were prepared by Alhadid, Safarov [75] in preselected molar ratios and applied CO2 capturing application. It was revealed that phenolic alcohol structure/symmetry positively effect the CO2 solubility. Hence, high molar ratio of phenolic alcohol accelerates the CO2 solubility. The choice and molar ratio of constituents was strictly limited by melting temperature of these liquids, which was maintained by the addition of l-menthol to lower the melting point. The absorption of CO2 was evaluated in l-menthol-thymol and 2,6-xylenol-thymol based DEL in 1:2 and 1:1 molar ratio, respectively. The CO2 solubility in preselected liquids was also measured experimentally by isochoric method at different temperature and pressure. l-menthol-thymol based liquids exhibited the highest solubility in both COSMO-RS and experimental (0.308 mol CO2 /kg). In these systems, CO2 solubility is higher as compared to ionic deep eutectic liquids or IL, which makes them an excellent, cost effective and simple solvent for CO2 absorption.

2.16 DEL supported membranes The different combinations of the well known DEL system comprising choline chloride and urea, when infused into the micro pores of membrane composed of polyvinylidene-fluoride (PVDF) can work more effectively for gases absorption and purification. The deep eutectic liquid-supported liquid membranes (DEL-SLM) were employed to check the pure and mixed CO2 gas (N2 /CO2 & CH4 /CO2 ) solubilities along with separation. The solubility was found to be function of H-bonding and basicity of DEL. The interaction energies (Ei ) of reported liquids for CO2 , CH4 and N2 were −29.4, −13.01, −9–91kJ/mol, respectively. These energy values of CO2 indicates its strong interaction with DEL-SLM than others which was counter confirmed by DFT results. The DEL-SLM consisting of ChCl:urea in 2:1 molar ratio exhibited the highest permeability for CO2 (45.6 barrer). DEL-SLM showed the same effect of temperature as that of SILM, permeability of CO2 increases with decreasing temperature due to low density. Another advantage of DEL-SLM is their mechanical stability and reusability [5].

2.17 DELs with multiple sites interaction

47

Due to the high efficiency of amine based deep eutectic liquids, Ishaq, Gilani [39] incorporated these into the microporous PVDF membrane. ChCl as HBA was mixed with different HBD such as MEA, DEA, and TEA in 1:6 and 1:8 molar ratios. Resulting DELs were confirmed by FT-IR along with their physiochemical properties. Consequently, prepared liquids were incorporated in membrane (SLM) to check its absorption capability. This novel system exhibited tremendous CO2 selectivity in CO2 /N2 and CO2 /CH4 as 78.87 and 70.46, respectively. CO2 shows chemical absorption and high selectivity over N2 and CH4, which is due to the basic nature of these liquids. The transport of CO2 gas through membrane is based on solution-diffusion mechanism. The CO2 permeability increases upto 9 barrer with increase in temperature from 298 to 338 K due to low viscosity. At higher conc. of CO2 , selectivity is decreased from 7.87 to 68.1 due to saturation of SLMs which resulted in low transport. These SLM showed excellent CO2 capturing performance when compared to ILs based SLM due to low viscosity and can be used at industrial level. Another class of designer liquids based on ChCl as HBA, and polyacrylic acid (PAA) & polyacrylamide (PAM) as HBD were prepared in 15:1 and 20:1 molar ratio and impregnated in micropourous membrane PVDF for CO2 capture. Ishaq, Gilani [41] screened the performance of the synthesized PDEL-SLM with pure and mixed gases. It exhibited the highest selectivity for CO2 /N2 and CO2 /CH4 as 60 and 55.4 barrer, respectively due to small kinetic diameter of CO2 , basic character, strong H-bonding and molar free volume of PDELs. The permeability of CO2 is increased with increasing temperature due to low viscosity, activation energy and more free volume of PDELs. FT-IR results confirm the presence of H-bonding between ChCl and HBD. These green, low cost, and efficient solvents are the best replacement of PILs in CO2 capture which can be further modified into task specific liquids.

2.17 DELs with multiple sites interaction Deep eutectic liquids having multiple sites for interaction play a key role in improved CO2 absorption efficiency. Keeping this fact in view, Fu, Sang [76] prepared such DELs comprising of superbase ILs (1,5-diazabicyclo[4.3.0]-non-5-ene N-methylthiourea [DBNH][MTU]) as HBA and EG as HBD. [DBNH][MTU]:EG showed absorption capacity of 0.142 g CO2 /g DEL with single site interaction while [DBNH]2 [DTU]:EG exhibited absorption of 0.173 g CO2 /g DEL with double site interactions at 313.15 K which were higher than their respective ILs. This high CO2 absorption is attributed to the synergistic interactions between DEL and CO2 , resulting in carbonate and carbamate formation. EG plays significant role in CO2 absorption as DBNH+ activate the EG then both capture the CO2 through their imino and –OH groups, respectively. The viscosity of single site interaction system decreases with increase in temperature and EG content. While, in double site interaction system, it is independent of temperature but increases with increase in EG content. Activation energies also have impact on solubility as single site system had lower activation energies. The solubility of CO2 increases upto 313.15 K, after then desorption occurs in both systems. Addition of water in both systems results in decrease of CO2 absorption as water molecules form H-bonds with DEL which in turn reduces the interaction sites for CO2 .

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2.18 Conclusion and future prospects An increase in the atmospheric concentration of CO2 and other green house gases is believed to cause various disasters and severe climate changes. Therefore, it has been the biggest challenge of 21st century to reduce the emission of CO2 through switching towards energy efficient technologies and environmental friendly energy source. However, the relentless increase in CO2 can be exclusively managed by pre-combustion technologies, rather there is an urgent need of post-combustion carbon dioxide conversion or reduction. In this context, amine scrubbing technology which utilizes an aqueous solution of alkanolamines has been already in practice, but these methods are associated with the certain drawbacks like solvent evaporation, equipment corrosion, and toxic effluents. Recently, deep eutectic liquids (DELs) have captured much attention due to their incredible properties i.e., non-volatile and nontoxic character, tunable density and viscosity, and above all biodegradability, and recyclability. Deep eutectic liquids have been also proved to be an efficient solvent than ionic liquids in terms of CO2 capturing. Various combinations of HBA and HBD were evaluated to check their performance for CO2 absorption/solubility. Table 8.1 provides a comparison of CO2 sorption potential and green or thermodynamic credential of various DEL system tested so far. A critical review of collected data infers that DEL system made up of nitrogen and oxygen containing hydrogen bond donors work more efficienly as compared to others. Overall, amine based DELs are found to be most efficient ones due to their synergistic (both physical and chemical) CO2 absorption. The chemical absorption gives the best value of solubility as compared to physical absorption because the later involves the formation of H-bonding between HBA and HBD which reduces the available sites for CO2 molecules. The desorption behavior in chemical absorption is challenging in terms of solvent recyclability and degradation, as high temperature is required along with nitrogen rich environment. In amine based DELs, high CO2 solubility (up to 2.67 mol CO2 /kg DEL) is due to formation of carbamate. High viscosity of DELs is their biggest limitation which can be coped by diluting with water or any other solvent in specific molar ratio (upto 30 wt percent). Dilution not only decreases the viscosity but also improves its conduction and polarity. Increased level of dilutions can affect negatively as it reduces the available sites for CO2 interaction and desorption occurs. The highest solubility is observed at high pressure and low temperature as at high temperature kinetic energy of DEL molecules dominates the binding energy. After amine based DELs, EG based systems also showed good efficiency, as EG absorb CO2 molecules through chemical absorption resulting in carbonate formation. DELs can be functionalized into ternary DELs to improve the absorption efficiency. The functionalization with super-bases results in increased CO2 solubility when compared with other DELs. Acylmide-superbase based DELs show highest CO2 absorption capacity upto 2.01 mol CO2 /kg DEL. A novel method of CO2 absorption is DEL supported liquid membranes with amine based DEL impregnated in microporous PVDF membrane. SLMs exhibits highest absorption, selectivity and regeneration. Finally, DELs have the potential to become the most versatile and prominent solvents for CO2 capture at industrial level due to their low cost, tunability and other characteristics. These can surely replace the other solvents including ionic liquids by careful selection of HBA and HBD. Further research can be focused on the novel methods to lower the viscosities of DELs in order to enhance its efficiency.

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Acknowledgment The first author wants to acknowledge the moral and financial support of her parents Mr. and Mrs. Liaqat Ali.

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[53] Wibowo H, et al. Study on the effect of operating parameters towards CO2 absorption behavior of choline chloride – Monoethanolamine deep eutectic solvent and its aqueous solutions. Chem Eng Process. Process Intensif 2020;157:108142. [54] Sarmad S, Nikjoo D, Mikkola J-P. Amine functionalized deep eutectic solvent for CO2 capture: measurements and modeling. J Mol Liq 2020;309:113159. [55] Ahmad N, et al. Understanding the CO2 capture performance by MDEA-based deep eutectics solvents with excellent cyclic capacity. Fuel 2021;293:120466. [56] Lu M, et al. Solubilities of carbon dioxide in the eutectic mixture of levulinic acid (or furfuryl alcohol) and choline chloride. J Chem Thermodyn 2015;88:72–7. [57] Liu X, et al. Solubilities and Thermodynamic Properties of Carbon Dioxide in Guaiacol-Based Deep Eutectic Solvents. J Chem Eng Data 2017;62(4):1448–55. [58] Li X, Liu X, Deng D. Solubilities and Thermodynamic Properties of CO2 in Four Azole-Based Deep Eutectic Solvents. J Chem Eng Data 2018;63(6):2091–6. [59] Li G, et al. Solubilities and thermodynamic properties of CO2 in choline-chloride based deep eutectic solvents. J Chem Thermodyn 2014;75:58–62. [60] García G, et al. Deep Eutectic Solvents: Physicochemical Properties and Gas Separation Applications. Energy Fuels 2015;29(4):2616–44. [61] Sarmad S, Mikkola J-P, Ji X. Carbon Dioxide Capture with Ionic Liquids and Deep Eutectic Solvents: a New Generation of Sorbents. ChemSusChem 2017;10(2):324–52. [62] Muthu A, Maheswari U, Palanivelu K. National Conference on Green Engineering and Technologies for Sustainable Future-2014 Absorption of carbon dioxide in alkanolamines in deep eutectic solvent medium for CO2 gas separation. J Chem Pharmaceut Sci 2014:6–8. [63] Sze LL, et al. Ternary Deep Eutectic Solvents Tasked for Carbon Dioxide Capture. ACS Sustain Chem Eng 2014;2(9):2117–23. [64] Jiang B, et al. Superbase/Acylamido-Based Deep Eutectic Solvents for Multiple-Site Efficient CO2 Absorption. Energy Fuels 2019;33(8):7569–77. [65] Deng D, et al. Investigation of solubilities of carbon dioxide in five levulinic acid-based deep eutectic solvents and their thermodynamic properties. J Chem Thermodyn 2016;103:212–17. [66] Luo F, et al. Comprehensive Evaluation of a Deep Eutectic Solvent Based CO2 Capture Process through Experiment and Simulation. ACS Sustain Chem Eng 2021;9(30):10250–65. [67] Zhang K, et al. Efficient and Reversible Absorption of CO2 by Functional Deep Eutectic Solvents. Energy Fuels 2018;32(7):7727–33. [68] Rabhi F, Mutelet F, Sifaoui H. Solubility of Carbon Dioxide in Carboxylic Acid-Based Deep Eutectic Solvents. J Chem Eng Data 2021;66(1):702–11. [69] Siani G, et al. Physical absorption of CO2 in betaine/carboxylic acid-based Natural Deep Eutectic Solvents. J Mol Liq 2020;315:113708. [70] Sarmad S, et al. Screening of deep eutectic solvents (DESs) as green CO2 sorbents: from solubility to viscosity. New J Chem 2017;41(1):290–301. [71] Cui G, Lv M, Yang D. Efficient CO2 absorption by azolide-based deep eutectic solvents. Chem Commun 2019;55(10):1426–9. [72] Qin H, et al. Physical absorption of carbon dioxide in imidazole-PTSA based deep eutectic solvents. J Mol Liq 2021;326:115292. [73] Gu Y, et al. Hydrophobic Functional Deep Eutectic Solvents Used for Efficient and Reversible Capture of CO2 . ACS Omega 2020;5(12):6809–16. [74] Al-Bodour A, et al. High-Pressure Carbon Dioxide Solubility in Terpene Based Deep Eutectic Solvents. SSRN Electron J 2022. [75] Alhadid A, et al. Carbon Dioxide Solubility in Nonionic Deep Eutectic Solvents Containing Phenolic Alcohols. Front Chem 2022;10. [76] Fu H, et al. Bicyclic amidine-based deep eutectic solvents for efficient CO2 capture by multiple sites interaction. J Environ Chem Eng 2021;9(5):106248.

C H A P T E R

3 Cookstoves for biochar production and carbon capture Mashura Shammi a , Julien Winter b, Md. Mahbubul Islam c, Beauty Akter d and Nazmul Hasan e,f a

Hydrobiogeochemistry and Pollution Control Laboratory, Department of Environmental Sciences, Jahangirnagar University, Dhaka, Bangladesh b Private consultant, Cobourg, ON, Canada c Bangladesh Biochar Initiative, Dhaka, Bangladesh d Department of Environmental Sciences, Jahangirnagar University, Dhaka, Bangladesh e The United Graduate School of Agricultural Sciences, Kagoshima University, Kagoshima, Japan f Fruit Science Laboratory, Saga University, Saga, Japan

3.1 Introduction Traditional biomass burning is the only energy source for food-preparation in developing nations that consume most household energy. Near about 40 percent of global homes use conventional biomass fuel and cooking equipment which is not clean energy [1,2]. Biomass fuel sources in rural developing countries are usually agricultural crop residues such as rice straws, husks, sugarcane, other cereals, cow dung, litter, other manure, and biomass crops agroforestry products [3,4]. Most consumers want cookstoves that cook rapidly and effectively while using as little fuel as feasible [1]. The most common biomass cookstoves are three-stone fires (TSF) [5]. However, in waste biomass fuels, the high nitrogen content is usually correlated with high nitric oxide (NO) emissions, while fast-cooking is linked with carbon monoxide (CO) emissions for a given cooking task [1]. Consequently, particulate matter and gaseous emissions, as well as poor indoor air quality, are the main contributors to the serious health issue from biomass burning. [6,7]. Improved cookstoves have aided in reducing adverse environmental and health consequences in rural areas [8]. Still, they also had drawbacks in terms of labor for fuel preparation, lighting, and

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replenishing [9,10]. Therefore, changing the design and architecture of cookstoves was shown to reduce smoke, fuelwood savings, and char generation. Cookstoves’ thermal and physicochemical operating parameters can significantly control the selected gaseous emissions of unburned products such as CO, NO, VOC, soot, and particulate matter [1,2]. Nonetheless, worldwide attention has addressed environmental challenges by improving energy efficiency and lowering carbon emissions in these countries. In many developing countries, a simple and efficient cookstove design can be an essential item in reducing the amount of domestic energy and indoor pollution [10]. Biochar-bioenergy can help solve various pervasive economic, public health, and environmental issues that must be addressed [11]. For thousands of years, pyrolysis has been the traditional method that produces char or charcoal from biomass [12]. However, ’biochar’ is a comparatively current research topic [13]. Biochar is derived from the pyrolysis or thermal conversion (>350 °C) of organic biomass such as plant or animal-based waste under limited or oxygen-deficient conditions [11,13-16]. So the final biochar product is a pyrogenous organic material with aromatized carbon structure [17]. Biochar is a steady carbon enriched natural product [13,16]. From modest home cook burners to bigger commercial pyrolysis facilities, biocharbioenergy systems come in a variety of sizes [18]. However, biochar has a high probability of scaling up as a sustainable cooking technology using alternative fuels (clean solid energy for cookstove) in developing countries [12]. Biochar cookstoves also offer other advantages to sustainable development, such as directly enhancing yields in tropical agriculture [9]. Additional applications for it include air filtration, water treatment, activator for biogas generation, carbon storage, and reducing environmental effects [12]. Because of these reasons, cookstoves that pyrolyze or gasify their fuels have gotten a lot of interest in developing countries. Biochar cookstoves are modest devices designed to provide clean, affordable, and renewable energy in these regions. It is important to remember that the seventh sustainable development goal (SDG7) calls for ensuring that everyone has access to cheap, dependable, sustainable, and modern energy. Moreover, the thirteenth sustainable goal (SDG 13) is about immediate action to fight climate change and its impacts. Biochar cookstoves can complement these both goals simultaneously by providing clean and affordable fuel while capturing carbon for climate action. This chapter, therefore, aims to review the role of cookstoves (SDG 7) in carbon sequestration or carbon capture (SDG 13) and simultaneously contribute to climate change mitigation.

3.2 Cookstoves designed for biochar production Around the world, 2.9 billion people lack access to technology and secure, inexpensive, clean and efficient fuels. Numerous research and development projects have tried to device and implement efficient cookstoves. Unfortunately, several attempts typically fail because the cook’s requirements or preferences are not satisfied due to issues with the stove’s architecture, availability to fuels, or management problems [19]. This situation usually happens when the cook, usually woman, is left out of the participation. A common traditional cooking appliance that uses charcoal, wood chips, and biomass briquettes is the charcoal stove and its modified variant [4]. It is well known that conventional biochar-making technologies such as clay, brick, and steel kilns typically release lots of VOCs. So changes in stove design can minimize pyrolysis fuel usage or enhance airflow rate, lowering

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CO emissions. Boosting natural convection, increasing stove height, insulating the furnace or chimney to raise internal gas temperature can also increase airflow and reduce CO emissions. Another way to lower fuel use is to alter the construction or geometry of the pyrolysis chamber [1]. The traditional pyrolysis process is usually the sluggish one characterized by low temperature (∼300 °C), a long retention period (about 10–30 min to 25–35 h) with a slow heating rate (0.1–0.8 °C/S) [12]. According to research conducted in Kenya, the gasification burner was mostly utilized to prepare food items that required quick cooking. Fifty households were given free gasifier stoves and monitored for 2–3 months of use. 96 percent of the households used the stove at varying frequencies, while 40 percent used it daily. It was wellreceived by all users since it saved fuels, made fewer smokes and provided chars for soil amendment [20]. Typically, the feedstock is carefully selected based on factors such particle size, lignocellulose composition, moisture content, etc. The biochar yield is then measured by a variety of different parameters, including temperatures, heating time, inert gas flow rate, residence duration, etc. [12]. The biochar cookstoves are generally made of steel, metal sheet, structural steel, etc. They are lightweight, portable, and transportable in isolated regions [21]. A combination of locally resourced materials such as clay, brick, and steel can be used to make the structure of the stoves which can have a tinier carbon footprint. For example, Howell and colleagues produced biochar from two agricultural wastes, cottonseed and pecan shells, using simple and low control top-lit updraft (TLUD)-microgasifiers made from paint cans [22].

3.2.1 Top-lit updraft (TLUD) stove A question may arise on what is a top-lit updraft method? A fan for air supply is a feature of the top-lit updraft (TLUD) cookstove, which is an improved version of the biomass cookstove [2,4]. Compared to traditional stoves, this gasifier stove delivers better energyexergy efficiency. The TLUD cookstove’s efficiency is credited to the primary and secondary funnel-shaped central air-inlet that takes airflow into the combustion chamber for burning and results in high combustion temperatures [4]. Because of higher energy-exergy efficiency, TLUD cookstoves require less woody biomass consumption and consequently less harmful emissions. In operation, the top cover (28 cm diameter) of TLUD supports the cooking pot. Usually, the chosen biomass is filled into the combustion chamber (40 cm long) from the top and fired. The top cover is positioned back, and a steady fire is allowed for cooking. During refueling, the stove cover is removed and refilled with biomass fuel [4]. As fuel feedstock for TLUD stoves, wood chips, rice husk briquette and coconut shell performed well [5]. However, it is essential to remember that the locally modified TLUD method commonly has a low biochar yield than industrial pyrolysis reactors. In the TLUDs temperature reaches above 450 °C, and it is frequently difficult to maintain precise temperatures in the devices [22]. The biochar is highly microporous at this temperature, with a larger surface area and fewer functional groups. Higher ash content is found in the more carbonized biochar and has lower residual cellulose crystallinity. TLUD gasifiers are vertical, cylindrical stoves that are filled with a ‘batch’ small piece of wood or compressed biomass. The fuel is ignited on top, and the combustion proceeds downward to the bottom of the cylinder. A grate at the base of the cylinder acts as a conduit for "primary air," which supports the combustion above. We call the downward movement

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of the combustion an ‘ignition front’. It is also known as a ‘migrating flaming pyrolysis front’ (MFPF). At the MFPF there is not enough primary air to burn the fuel to completion, so as the MFPF moves downward, it leaves unburned char above. At the MFPF, heat is generated that causes thermal degradation of the fuel, known as ‘pyrolysis’. Pyrolysis creats two classes of products; char and volatiles. Char is a carbon-rich organic complex that is low in hydrogen and oxygen. It is chemically quite stable (i.e. biochar), so requires high temperatures burn (>1000 C°), and a steady supply of oxygen (because it is mostly carbon). Think of hot charcoal fires. The temperature at the MFPF can range from 550 to 1200 °C in relation to the primary air velocity. Below 550 °C flaming pyrolysis tends to fail, and we have only smoldering combustion (Winter, unpublished data). The volatiles, on the other hand, are quite flammable. However, once the MFPF consumes all of the oxygen in the main air, the volatiles ascend through the unburned char as a white smoke. Volatiles are combined with secondary air entering at the top of the reactor, and are mixed together in a gas burner. This creates most of the heat for cooking. Volatiles are composed of gases (CO, H2 , and light hydrocarbons such as methane), droplets of non-gaseous tars, and fine particles of soot. The volatiles are also known as ‘wood gas.’ Heat generated at the MFPF radiates downwards and raises the temperature of unburned fuel below to its ignition temperature. There are two modes of supplying the primary air; forced draft and natural draft. Forced draft TLUDs (FD-TLUD) use a fan to increase the velocity of air flow. Compared to natural draft stoves, the secondary air can be driven through the burner’s tiny apertures at a considerably faster velocity since it is under pressure. The high momentum of secondary air entrains and mixes with the volatiles into a well-mixed efficient flame. As the velocity of the primary air increases, the downward velocity of the MFPF will increase. Too much primar air will cool the MFPF and slow its downward velocity. FD-TLUD stoves often burn pelleted fuel (5–6 mm diameter and 1–3 cm long). The fan is power by a battery or a thermal-electric generator (that uses heat from the hot surface of the stove). Air movement in natural draft TLUD (ND-TLUD) is driven solely by the buoyancy of gasses that are hotter than the ambient air in the room. Buoyancy is generated both at the MFPF and in the gas burner. Buoyancy forces are usually much smaller that with forced air. Consequently, the fuel burns slower, but the results for cooking are perfectly acceptable. ND-TLUDs are typically used to burn chunks of wood, chips, and briquettes, and their reactors are tallers and wider than FD-TLUDs. ND-TLUDs can burn pellets, but they would require a shorter or modified reactor (because it only takes a fuel bed of pellets half as high or less to burn as long as wood pieces). In order to generate enough draft in a ND-TLUD, there has to be a ‘riser’ or cylinder for the gas flame to pass through before hot gases reach the bottom of the cooking pot. The height of the riser, or vertical distance between the point where the secondary air enters above the reactor, to the top of the riser should be at least 15 cm. If the riser is too short, there will not be sufficient mixing between the secondary air and the volatiles. The gasification rate is controlled by restricting the flow of primary air through a small orifice. It takes very little primary air for gasification, so the orifice should close down to only 2–5 percent of the cross-sectional area of the rector. The orifice can be opened up for more complete combustion of woody fuel and charcoal. It is important not restrict the primary air too much in a NDTLUD, because if the flaming pyrolysis stops, and the gas flame goes out, it is hard to get it flaming pyrolusys started again. It is easier to re-start a FD-TLUD, because you just turn up

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the fan; you are not dependent on natural draft. If the household is not burning pellets, then a ND-TLUD is fine, and you are not reliant on a working fan. Fuels make a difference to the performance of TLUDs, especially ND-TLUDs. Pellets are an ideal fuel, because a very narrow, well defined MFPF froms in the fuel bed, and moves downward as a flat, uniform front regardless of the velocity of primary air. Wood chips burn well if the velocity of primar air is moderate to high, but when primary air is restricted, the MFPF channels down the sidewalls of the reactor. When the fuel are small sticks or chunks of wood, a clear MFPF will not form, and the flameing pyrolysis may occur throughout most of the reactor at the same time. It is best that the fuel is less than 15 percent moisture. Since pellets are only 5–6 mm in diameter, they pryolize to completion as the MFPF moves down. With thicker chunks of wood, it can take several minutes to the center of the fuel to reach pyrolysis temperatures (ca. 400 °C), which is also why a cleay MFPF does not form. Vertical stems of coarse grass or jute sticks will burn in a TLUD (but because of low density don’t burn for long). Loose biomass such as straw and leaves do not burn properly in a TLUD. Wet wood will not burn in a TLUD

3.2.2 Development of TLUD-Akha architecture design The mechanism of the Akha TLUD followed design principles pioneered in the 1990s by Paal Wendelbo in Norway and independently by Dr Tom Reed and Dr Paul Anderson in the USA. Their novel idea was to create a gasification reactor out of a vertical metal cylinder by placing a grate at the bottom to feed a little quantity of “primary” air. The cylinder was loaded with a batch of fuel and ignited on top. The primary air below supported flaming pyrolysis but was insufficient for the combustion of most of the volatiles (white smoke) and char. Volatiles released by gasification rose upwards and were combined with secondary’ air forming a gas flame above the fuel at the top of the cylinder and passing that flame through a circular aperture called a concentrator ring [23]. Their stoves were made entirely of metal. The reaction cylinder was contained within an outer cylinder. Secondary air was preheated by passing upwards through the annular space between the two cylinders. The concentrator ring was a type of gas burner. Other more efficient gas burners exist, but they are more complicated to make. The outer cylinder is concrete in the Akha and forms the stove body. TLUD technology is not very difficult for stove designers to understand, and TLUD stoves can be adapted and scaled for specific uses. The Akha’ Chula’ was designed for rural Bangladesh and its plans are free for the general public to copy, modify and improve as they please as an open-access patent by Winter and Islam [24]. However, specific architectural guidelines should be followed so that the stoves perform cleanly (Fig. 3.1(A)). Commercial variations should be tested for emissions at certified stove-testing laboratories. Certain architectural guidelines should be followed so that the stoves perform cleanly. (1) The base of the stove should be close to air-tight so primary air can be regulated through an orifice that closes down to about 0–3 percent of the crosssectional area of the reactor (Fig. 3.1(B-C)), and (2) the gas burner and riser should be 15 cm tall to provide sufficient velocity of secondary air (Fig. 3.1(D)). Finally, (3) the burner should not restrict the flame or else the flame will pulse and emit soot. Bangladesh has a history of using concrete for combustion cookstoves. The Akha Chula used that experience and a wise strategy to decentralize stove-making by using existing

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FIGURE 3.1 (A) The Akha Chula is composed of several functional modules. It is a prototype still under development. (B) The base module serves as the stove’s supporting base. It is constructed of reinforced, clay-coated, heatresistant concrete. It also functions to receive char dumped from the reactor through a hinged grate, and to regulates “primary air” flow into the stove. Char is cleaned out through a side door. Primary air is regulated by cracking the side door open. (C) On top of the base sits a metal reactor cylinder. Around the reactor are concrete rings that form the stove body. The reactor is held in place by loose sand around its base in the space between the reactor and the lower stove body ring. Through openings in the bottom stove body, secondary air enters and is heated as it flows upward toward the reactor. There are multiple tiny holes in the reactor’s sidewall that control the quantity of air that enters the reactor to prevent the gasification process from stopping. They also control the gas flame so that it doesn’t extinguish (which would create a lot of smoke). (D) The concentrator ring burner is made of reinforced concrete coated with clay. Secondary air moved up and over the top of the reactor cylinder and under the concentrator ring burner. The flame exits through the concentrator orifice. In order to prevent the flow of burning gas from being impeded, the nozzle orifice’s aperture needs to be appropriately large. Laminar flames should therefore fill around 34 of the aperture diameter. The flame will show a prolonged pulse in height at a low frequency between 1–3 Hz if the aperture is too tiny. This results from releases of pressure that have built up beneath the burner. Usually, the pulsation may be heard. The height of the burner module should be at least 15 cm so that the secondary air has sufficient momentum to mix with the volatiles. This burner is based on the original metal burners of the ‘Peko Pe’ and ‘Champion’ Stoves (Diagram source: authors).

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businesses that cast concrete for sanitary installations to make concrete components for stoves. Artisans who work in metal and concrete can be found in most market towns. Dr Md. Kalequzzammen and E. Otto Gomm of the Deutsche Gesellschaft für Internationale Zusammenarbeit (GIZ), Dhaka, created the “Bondhu Chula,” a concrete combustion burner, in 2009. A concrete combination of sand, clay brick fragments, and Portland cement (3:2:1 by volume), reinforced with wire netting, and water cured for seven days, was suggested (Gomm, pers. com., 2020). If (when) the concrete cracks, reinforcing keeps the structure intact (even refractory concrete can crack with uneven heating and cooling.) After assembly, clay was applied to the concrete parts to shield them from extreme heat. The Akha Chula used the same mixture ratio.

3.2.3 Origins of TLUD-Biochar ‘Ecosystem’ The momentum for biochar and TLUD research in Bangladesh got a boost in 2013 with the "Colloquium on Biochar in Bangladesh" hosted by Mr Joyanta Adhikari (Executive Director) of the Christian Commission for Development in Bangladesh (CCDB). CCDB invited three Canadian scientists (Dr Jugesh Vig (agronomist), Dr Sunal Mustafa (economist), Dr Julien Winter (soil scientist) to tour the countryside, observe cooking practices and the availability of biomass, and discuss the potential for biochar with academics and extension agronomists. Afterward, the participants were invited to a colloquium at the CCDB, Dhaka, to discuss their impressions. From the Colloquium came several recommendations: 1. Since many Bangladeshi soils are low in soil organic matter [25-28], biochar could significantly increase soil quality and agricultural productivity. Yields will increase and/or inputs of commercial fertilizers will fall. This will help Bangladesh buffer the impact of climate change and land lost to rising sea levels. 2. However, the practical problem was not how to use biochar but how to make it. Rural households were under energy stress because the demand for wood as cooking fuel was much greater than the supply [29,30]. Although wood is an excellent feedstock for biochar, any method for making biochar in Bangladesh should in no way jeopardize the energy security of households. 3. TLUD stoves may be the solution for making biochar because they will make it a byproduct of cooking. Even when char is collected from the TLUD stoves, TLUDs still use half as much fuel as traditional stoves and reduce women’s exposure to smoky flue emissions. Biochar made in a stove is placed directly into the hands of households. 4. TLUD stoves and biochar are synergistic technologies, so they must be introduced to villages simultaneously rather than separately. For over forty years, the adoption of improved cookstoves by Bangladeshi households has been slow. The game will change when a stove is more than just a cooking device; when a stove makes biochar, and the biochar increases household income. Thus, for TLUD acceptance by households, villagers must have first-hand of experience of biochar effects on soil productivity. In villages target for an intervention, ‘TLUD-biochar ecosystems’ should be established. 5. Developing TLUD-biochar ecosystems will be a multidisciplinary intervention. Villagers will have to learn how to use and prepare fuel for a new type of stove, and use biochar in gardening, crop, and livestock agriculture. Consequently (a) the collaboration of various

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professions and organizations will be needed, and (b) to ensure that the technologies become appropriately established, efforts should be focused on building the knowledge capacity of villagers in selected rural communities rather than diffusely over a broad area. Once established, nodal villages with practical wisdom can help spread the technologies to the surrounding countryside. Introducing TLUDs and biochar to rural villages should be a reciprocal process where researchers and villagers learn from each other. Locations differ in climate, vegetation, crops, livestock, soil, access to urban markets, and cultural conditions. Villagers have detailed, historical, and practical knowledge of their environment. Since there are many uses for biochar, the technologies can be adapted accordingly. TLUD stoves should be manufactured within Bangladesh rather than imported because imported goods are expensive for rural households. In addition, importing will increase the carbon footprint. That includes minimizing the use of imported raw materials such as metal or electrical components. Some metal components can be replaced with concrete and clay. However, in India, the all-metal ‘Champion Stove,’ invented by Dr Paul Anderson [23], has been successfully manufactured and accepted by households. Natural draft (NDTLUD) stoves are preferred to forced draft TLUDs because they don’t use an electric fan to move air. Local manufacturing makes it possible to tailor TLUD stoves to consumer preferences and employ artisans found in most market towns. They can manufacture TLUD components and provide spare parts. ATLUD-biochar ecosystem combats climate change because TLUD biochar contains about 35 percent of the original carbon in fuelwood. Biochar added to soil sequesters the carbon in soil organic matter. It was recommended that CCDB facilitate the formation of a ‘Bangladesh Biochar Initiative’ (similar to the US Biochar Initiative) as a association of research, extension education, and industry professionals for networking, exchanging ideas and as a source of educational material for the public.

Following the Colloquium, CCDB was provided with a 200-L TLUD reactor to make biochar for agronomic trials, plans for small agricultural trials, and instructions on how to make TLUDs. The Akha Chula was developed over the next two years. In 2016, Kerk in Actie (Netherlands) began funding the Akha-Biochar Project at CCDB [31]. With advice from agricultural universities and the Bangladesh Agricultural Research Institute, CCDB established ‘TLUD-biochar ecosystems’ in small clusters of villages in the Manikganj, Naogaon, and Dinajpur Districts. A survey of 111 households in 2018 showed that enthusiasm for biochar became a strong incentive for using the Akha Chula (beyond the other benefits of saving fuel and clean cooking).

3.2.4 Composition of biochar produced from biochar cookstoves The conversion of biomass to biochar (carbon-rich materials) using cookstoves is an inexpensive way to remove atmospheric C by incorporating it into the land. Carbon sequestration is related to the slow-release of carbon dioxide (CO2 ) from the soil and storing CO2 in the soil for a long time, or C in any other forms that help reduce CO2 concentration [32]. Biochar

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cookstoves have the potential to sequester carbon and provide other benefits for sustainable development, containing the establishment of energy security and improving agricultural yields [9]. Biomass is abundantly available and considered a green energy source [12]. It is essential to determine the composition of biochar to get the maximum benefits through the customization of biochar from different substances. Biomass materials and production conditions are mainly responsible for the varying composition of biochar [32]. International Biochar Initiative (IBI), a platform for fostering biochar standards over many years of research and industry collaboration, published Biochar Standards Version 2.1 in 2015. It reported that the minimum requirement for organic carbon (OC) should be 10 percent [33,34]. The biochar is also classified into three types of which, Class 1 biochar containing ≥60 percent OC, Class 2 biochar ≥30 percent to 7: 1.

5.3.3 Synthesis of naftifine Naftifine 69, an API used in Exoderil, is an allylamine antifungal medicine that is used for treating tinea corporis, tinea cruris, and tinea pedis. This compound exhibits anti-inflammatory, antibacterial, and antifungal properties [59]. Dyson et al., synthesized 69 in 58 percent overall yield in two catalytic steps (Scheme 5.15) [60]. (E)-N-(Naphthalen-1ylmethyl)−3-phenylprop-2-en-1-amine 68 was prepared in good yield (70 percent) from the

SCHEME 5.14 One-pot synthesis of methylephedrine starting from 2-(methylamino)−1-phenylpropan-1-ol.

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SCHEME 5.15 Two-step synthesis of naftifine starting from naphthalen-1-ylmethanamine.

reaction of cinnamyl alcohol 67 with naphthalen-1-ylmethanamine 66 in the presence of bis[(2-diphenylphosphino)phenyl] ether (DPEphos) and dichloro(cycloocta-1,5-diene) platinum(II) [Pt(cod)Cl2 ]. Then, the obtained amine 68 was N-methylated using CO2 as a C1 source combined with hydrosilane as the reducing agent and N-heterocyclic carbene 70 to obtain 69 in 83 percent yield.

5.4 O–Nucleophile-triggered CO2 -incorporated carboxylation to form C–O bonds 5.4.1 Synthesis of atorvastatin Atorvastatin 79 is an API in Lipitor, an HMG CoA reductase inhibitor, and belongs to a class of inhibitors called “statins” or HMG CoA reductase inhibitors. It decreases the levels of triglycerides and LDLs (low-density lipoproteins), sometimes called “bad” cholesterol in the blood, whereas it increases the levels of HDLs (high-density lipoproteins), sometimes called “good” cholesterol. Rádl et al., described a multistep synthesis of ester intermediate 77, a key precursor for the formation of 79 [61] The treatment of heptadienol 71 with nbutyllithium, CO2 , and iodine in tetrahydrofuran provided ketal 72, which was reacted with p-toluenesulfonic acid in acetone to afford acetonide 73 (Scheme 5.16). The treatment of 73 with potassium cyanide in hot DMSO provided the cyano compound 74, which was

SCHEME 5.16 Synthesis of atorvastatin starting from hepta-1,6–dien-4-ol.

5.6 C-Nucleophile-triggered CO2 -incorporated reductive carboxylation to form C–C bonds

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SCHEME 5.17 Two-step synthesis of DMU-212 and combretastatin A-4 starting from (3,4,5-trimethoxyphenyl) methanol.

functionalized at the terminal double bond with Me2 S and O3 , or NaIO4 and OsO4 , to afford aldehyde 75; this was then oxidized by the Jones reagent to afford carboxylic acid 76. Following this, the acid was esterified with tert–butanol using 4-dimethylaminopyridine and N,N-dicyclohexylcarbodidimide (DCC) in methylene chloride, affording the required ester intermediate 77. According to the report by Alcantara et al., precursor 77 can be easily transformed into 79 using a three-step reaction protocol [62].

5.5 CO2 -catalyzed oxidation of alcohols to form C–O bonds 5.5.1 Synthesis of DMU-212 and combretastatin A-4 DMU-212 84 is a methoxylated resveratrol analog and an API in certain anti-cancer formulations. This compound has significant anti-cancer activity and selectively targets tumor cells. Moreover, combretastatin A-4 85 is a powerful vascular-damaging and microtubuletargeting agent that targets tumor vasculature to inhibit angiogenesis. Das et al., reported a CO2 -mediated transition-metal-free oxidative approach to synthesize of 84 and 85 from (3,4,5-trimethoxyphenyl)methanol 80 (Scheme 5.17) [63]. That is to say, (3,4,5trimethoxyphenyl)methanol 80 was oxidized to the respective aldehyde 81 in 84 percent yield using CO2 in the presence of K2 PO4 and DMSO. For 84 (96 percent), the obtained aldehyde 81 was treated with 1-(bromomethyl)−4-methoxybenzene 82 in the presence of triethylphosphine in aqueous NaOH, while for 85 (90 percent), aldehyde 81 was treated with hydroxy 83 in the presence of KOH in EtOH.

5.6 C-Nucleophile-triggered CO2 -incorporated reductive carboxylation to form C–C bonds 5.6.1 Synthesis of methionine hydroxy analog Methionine hydroxy analog 87 (MHA) is an API in Microquel Pig Starter often named 2–hydroxy-4-methylsulfanylbutyric acid. MHA represents a significant technical product

98

5. Utilization of carbon dioxide as a building block in synthesis of active pharmaceutical ingredients

SCHEME 5.18 Reductive carboxylation of 3-(methylthio)propanal to methionine hydroxy analog.

largely employed to feed animals. Additionally, MHA displays a higher bioavailability than the essential amino acid methionine. Moreover, MHA reduces urolithiasis and avian kidney damage caused by excess dietary calcium [64]. The preparative electroorganic synthesis of MHA 87 is illustrated in Scheme 5.18. Polycrystalline boron-doped diamond (BDD) is used for the reductive carboxylation of aldehyde 86 to 87 in the presence of a CO2 atmosphere [65]. In the electrochemical approach, a Mg sacrificial anode and a BDD cathode can be used (conversion 66 percent and current efficiency, CE, 22 percent). However, one drawback of this reaction is the formation of impurity by direct reduction of aldehyde 86 to alcohol 88 (Scheme 5.18).

5.6.2 Synthesis of naproxen Naproxen 94, an API used in Naprosyn, is a non-steroidal anti-inflammatory medication used for the treatment of fever and inflammatory diseases such as rheumatoid arthritis, menstrual cramps, and pain. The multistep approach for the synthesis of 94 is illustrated in Scheme 5.19. Methylation of naphthalen-2-ol 89 using Me2 SO4 , followed by the Friedel-Crafts acylation of 90 afforded 2-acetyl-6-methoxynaphthalene 91, which was subjected to electrochemical carboxylation and subsequent treatment with acid to afford acid 92 [3,66]. In the next step, acid 92 was dehydrated using a suspension of fused potassium acid sulfate, dilauryl thiodipropionate (DLTDP) and 2,6-di–tert–butyl–p-cresol (DBPC) in chlorobenzene to produce the corresponding α-arylpropenoic acid 93. Then, 93 was asymmetrically hydrogenated using an asymmetric hydrogenation catalyst (ruthenium complex of chiral phosphine) at low temperatures to furnish 94.

SCHEME 5.19 Synthesis of naproxen starting from naphthalen-2-ol.

5.7 C-nucleophile-triggered CO2 -incorporated direct C–H carboxylation to form C–C bond

99

SCHEME 5.20 Industrial synthesis of aspirin.

5.7 C-nucleophile-triggered CO2 -incorporated direct C–H carboxylation to form C–C bond 5.7.1 Synthesis of aspirin Acetylsalicylic acid 98, commonly known as aspirin, is an API of various commercial drugs such as Bayer Aspirin, Ecotrin, and Aspir 81, and it is one of the most widely used medications worldwide. Aspirin is a popular medicine utilized for treating inflammation, fever, or pain. Specific inflammatory conditions in which acetylsalicylic acid is employed include rheumatic fever, pericarditis, and Kawasaki disease [67]. The industrial synthesis of 98 is illustrated in Scheme 5.20. Sodium hydroxide is used to deprotonate phenol 95, forming the expected sodium phenoxide 96, which reacts with electrophilic CO2 at 125 °C to furnish sodium salicylate through the Kolbe-Schmitt process. This is followed by acid treatment to afford salicylic acid 97. Ultimately, 97 is treated with acetic anhydride to furnish 98. This synthetic approach is being used in the industries for the synthesis of 98 since 1874 [68]. When CO2 is introduced under pressure (5–7 bars), the yield increases from approximately 50 percent to 90 percent [69].

5.7.2 Synthesis of 4-aminosalicylic acid 4-Aminosalicylic acid 100, also known as para-aminosalicylic acid is an API in Paser, which is an antibiotic primarily used to treat drug-resistant tuberculosis [70]. The one-step industrial formation of 100 is illustrated in Scheme 5.21. Treatment of 4-aminophenol 99 with CO2 in a gas phase under high pressure and temperature affords 100 in 80 percent yield [71]. This process is short and environmentally friendly.

SCHEME 5.21 Industrial synthesis of 4-aminosalicylic acid.

100

5. Utilization of carbon dioxide as a building block in synthesis of active pharmaceutical ingredients

SCHEME 5.22 Synthesis of diflunisal starting from 2,4-difluoroaniline.

5.7.3 Synthesis of diflunisal Diflunisal 106 is an API in Dolobid and a popular non-steroidal anti-inflammatory drug (NSAID) with pharmacological properties comparable to other prototypical NSAIDs. Additionally, this compound possesses antipyretic, analgesic, and anti-inflammatory activities and is utilized for short and short-lasting symptomatic relief of moderate to low pain in rheumatoid arthritis and osteoarthritis [72]. Jones et al. synthesized 106 in five steps with an overall yield of 70.4 percent (Scheme 5.22) [73]. The synthesis was initiated by the reaction of 2,4difluoroaniline 101 with a diazotizing reagent (isoamyl nitrite) to afford 2,4-difluorobiphenyl 102, which was then acylated via a Friedel-Crafts reaction to furnish ketone 103. Subsequently, ketone 103 was oxidized to ester 104 using maleic anhydride. The ester product was then hydrolyzed via standard alkaline saponification or acid hydrolysis, followed by acidification to afford alcohol 105. Ultimately, alcohol 105 was carboxylated under the Kolbe process for 4–8 h at 200–260 °C and 1400–1100 psi of CO2 , in the presence of K2 CO3 to afford 106.

5.7.4 Synthesis of gentisic acid Gentisic acid 109 is an API used in Codopalm that exhibits antioxidant, anti-inflammatory, and antibiotic activities. This compound is produced by carboxylation of hydroquinone 107 using CO2 and K2 CO3 , followed by acid treatment of the obtained salt 108 (Scheme 5.23) [74].

SCHEME 5.23 Two-step synthesis of gentisic acid starting from hydroquinone.

5.8 C-nucleophile-triggered CO2 -incorporated organozinc-mediated carboxylation to form C–C bonds

101

SCHEME 5.24 Synthesis of tamoxifen starting from 4-iodophenol.

5.8 C-nucleophile-triggered CO2 -incorporated organozinc-mediated carboxylation to form C–C bonds 5.8.1 Synthesis of tamoxifen Tamoxifen 115, an API used in Soltamox and Nolvadex, is employed to cure breast cancer in men and women, and to prevent breast cancer in women [75]. The multistep synthetic sequence leading to 115 starts from the alkylation of 4-iodophenol 110, followed by condensation of the obtained 111 with phenylacetylene using a palladium catalyst, which leads to 112 (Scheme 5.24) [76]. Then, 112 is subjected to bis(cyclooctadiene)nickel-catalyzed arylative carboxylation using, followed by reaction with acid and then with diazomethane to afford 113. Treatment of 113 with DIBAL-H (diisobutylaluminum hydride) affords alcohol 114. Ultimately, the Dess–Martin reaction, followed by Wittig reaction and subsequent hydrogenation afford 115.

5.8.2 Synthesis of (E)−3-Benzylidene-2-indolinone (E)−3-Benzylidene-2-indolinone 120 is a potent anti-proliferative drug; it is broadly studied for its chemopreventive effects in inducing NQO1 potency [77]. The multistep synthesis initiates with the Sonogashira reaction between 1-amino-2-iodobenzene 116 and ethynylbenzene, affording 117 in excellent yield (95 percent) (Scheme 5.25) [78]. Then, the amino group is protected with TTFA (trifluoroacetic anhydride) to deliver 118 in 79 percent yield. Subsequently, the bis(1,5-cyclooctadiene)nickel-catalyzed carboxylation under 1 atm of CO2 proceeds smoothly to provide acrylic acid 119 in 96 percent yield. Ultimately, 120 is obtained in an overall yield of 56 percent after the removal of the protecting moiety, viz., COCF3 on the amino group of 119, and the reaction of the unprotected intermediate with EDCl.

5.8.3 Synthesis of ibuprofen Ibuprofen 124 is an API in the most common NSAIDs, such as Nurofen, Motrin, Advil, and Brufen, and it is utilized treating inflammation or pain induced by many conditions, such as

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SCHEME 5.25 Synthesis of (E)−3-benzylidene-2-indolinone starting from 2-iodoaniline.

SCHEME 5.26 Synthesis of ibuprofen starting from 1-(4-isopropylphenyl)ethanone.

minor injury, menstrual cramps, arthritis, back pain, toothache, and headache. Ibuprofen operates by reducing hormones that cause pain and inflammation in the body [79]. Knochel et al., disclosed a novel four-step approach for the synthesis of 124 with an overall yield of 59 percent through improvement by the addition of MgCl2 (Scheme 5.26) [80]. Briefly, the reduction of commercially available ketone 121 with sodium borohydride and subsequent chlorination using SOCl2 affords 1-(1-chloroethyl)−4-isopropylbenzene 122 in excellent overall yield (94 percent). The corresponding mineral-salts-based complex 123 (Zn species complexed with MgCl2 species) is readily obtained in 70 percent yield via the treatment of chloride 122 with Mg/ZnCl2 /LiCl. Reagent 123 is appropriately reactive to afford 124 in excellent yield (89 percent) by the addition of CO2 .

5.9 C-nucleophile-triggered CO2 -incorporated organolithium-mediated carboxylation to form a C–C bond 5.9.1 Synthesis of repaglinide Repaglinide 130 is an API in Prandin, an oral anti-hyperglycemic drug used to treat type 2 diabetes mellitus. This compound helps to regulate the levels of blood sugar by causing the pancreas (digestive juices) to produce insulin. The multistep synthesis of 130 is shown in Scheme 5.27. The reaction of 2–hydroxy-4-methylbenzoic acid 125 with 1-bromopropane in the presence of K2 CO3 in dimethyl sulfoxide affords 2-ethoxy-4-methylbenzoic acid ethyl ester 126, which is carboxylated by a reaction with LDA (lithium diisopropylamide) and CO2

5.9 C-nucleophile-triggered CO2 -incorporated organolithium-mediated carboxylation to form a C–C bond

103

SCHEME 5.27 Synthesis of repaglinide starting from 2-hydroxy-4-methylbenzoic acid.

in THF/1,3-dimethylperhydropyrimidin-2-one to furnish the key intermediate [3-ethoxy-4(ethoxycarbonyl)phenyl]acetic acid 127 [81]. Then, condensation of phenyl acetic acid derivative 127 with enantiomerically pure amine analog 128 in the presence of DCC, followed by saponification of the resulting amide derivative 129 affords 130 [82].

5.9.2 Synthesis of flurbiprofen Flurbiprofen 135 is an API of many non-steroidal anti-inflammatory formulations such as Ansaid. This compound has analgesic and anti-pyretic potencies and is employed to reduce joint stiffness from arthritis, swelling, and pain [83]. The synthesis of flurbiprofen 135 starts with the deprotonation of 1-fluoro-3-methylbenzene 131 by a Schlosser’s base (Scheme 5.28). When a blend of potassium t-butoxide and t-butyllithium is employed as the mixed-metal mixture, the selectivity increases considerably. The deprotonation of complex 132 takes place at the position adjacent to fluorine because it is the least-hindered position. The trapping of the organolithium complex with fluorodimethoxyborane-diethyl etherate followed by hydrolysis provides phenylboronic acid, which is subjected to the Suzuki–Miyaura cross-coupling reaction to produce 133 [84,85]. Another superbase metalation of 133 using a mixture of potassium tert-butoxide and lithium diisopropylamide and subsequent carboxylation with CO2 and acid

SCHEME 5.28 Synthesis of flurbiprofen starting from 1-fluoro-3-methylbenzene.

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SCHEME 5.29 Total synthesis of epristeride starting from methyl 3-oxo-4-androstene-17β-carboxylate.

treatment furnishes acid 134. A second metalation, followed by a reaction with iodomethane affords flurbiprofen 135.

5.9.3 Synthesis of epristeride Epristeride 141, an API used in Chuanliu and Aipuliete, is used to treat enlarged prostate in china. This compound is a potent human dihydrotestosterone (DHT) blocker (5-ARI) and operates by reducing the formation of DHT, an androgen sex hormone, in certain areas of the body such as the prostate gland [86]. Baine et al., reported an improved synthetic pathway of 141 in four steps with an overall yield of 44 percent using 136 (methyl 3-oxo-4-androstene17β-carboxylate) as a starting material (Scheme 5.29) [87]. Briefly, ketone 136 was converted to bromide 137 in good yield (85 percent) via a reaction with phosphorous(III) bromide in glacial ethanoic acid. Saponification of bromide 137 with KOH in MeOH afforded acid 138, which was transformed to the main precursor amide 139 in good yield (75 percent) by acid chloride. The latter was in situ generated by the reaction between tert–butylamine and oxalyl chloride and quenching into excess tert–butylamine. The reaction of amide 139 required an organomagnesium reagent (EtMgCl) to exchange the halide at P-3 and produce ethyl chloride. Then, the introduction of s-BuLi resulted in the formation of the desired lithio analog 140 [88]. Ultimately, carbonation at P-3 occurred by a reaction with CO2 , resulting in 141.

5.9.4 Synthesis of mefloquine Mefloquine 147 is an API in Lariam used for the treatment of malaria and the protection of travelers who visit zones where malaria is present. Thus, this drug belongs to the family of antimalarials [89]. The multistep synthetic route to 147, starting from 2-trifluoromethylaniline 142, is outlined in Scheme 5.30 [90]. Treatment of 147 with ethyl trifluoroacetylacetate (TFAAE), followed by bromination of 143 with POBr3 furnishes bromide 144. Acid 145 is obtained by lithiation and carboxylation with CO2 . The reaction of acid 145 with 2-pyridyllithium, generated from n-butyllithium and 2-bromopyridine, affords 146, which is converted into 147 by hydrogenation with a platinum catalyst.

5.9 C-nucleophile-triggered CO2 -incorporated organolithium-mediated carboxylation to form a C–C bond

105

SCHEME 5.30 Synthesis of mefloquine starting from 2-(trifluoromethyl)aniline.

SCHEME 5.31 Synthesis of amitriptyline starting from 1–bromo-2-(bromomethyl)benzene.

5.9.5 Synthesis of amitriptyline Amitriptyline 155, an API used in Elavil, is a tricyclic antidepressant normally employed in the treatment of depression and anxiety; however, low concentrations of it can stop or reduce pain. Kirschning and Kupracz proposed a multistep synthesis of 155 using a flow reactor system, which included three consecutive halogen-lithium exchange reactions (Scheme 5.31) [91]. The Li-Br exchange of 2-bromobenzyl bromide 148 with n-butyllithium affords o-bromobenzyllithium 149, which couples with the unchanged substrate 148 to afford 1–bromo-2-[2-(2-bromophenyl)ethyl]benzene 150. Another Li-Br exchange provides bromide 151. Treatment with CO2 , followed by a third Li-Br exchange furnishes ketone 153 in 76 percent overall yield. Then, the reaction of [3-(dimethylamino)propyl] magnesium chloride 154 with ketone 153 and subsequent acid treatment affords 155.

5.9.6 Synthesis of methantheline bromide Methantheline bromide 160 is an API in the most common antispasmodic drugs, such as Vagantin, and it is used for the treatment of stomach ulcers, intestinal ulcers, pancreatitis,

106

5. Utilization of carbon dioxide as a building block in synthesis of active pharmaceutical ingredients

SCHEME 5.32 Synthesis of methantheline bromide starting from 2-phenoxybenzoic acid.

gastritis, biliary dyskinesia, intestinal problems, pylorospasm, and urinary problems [92]. A multistep synthetic approach for 160 is illustrated in Scheme 5.32. Briefly, a Friedel–Crafts cyclization of acid 156 using concentrated H2 SO4 results in the formation of 9H-xanthen-9one 157 [93]. The reaction of ketone 157 with metallic Na in EtOH affords the intermediate benzhydrol. The OH unit of this intermediate is further reduced to afford 9H-xanthene 158. The reaction of CO2 with the anion of precursor 158 provides 9H-xanthene-9-carboxylic acid 159 after acid treatment. Ultimately, the carboxylate salt of acid 159 is alkylated with 2–chloroN,N-dimethylethanamine, and treated with bromomethane to afford 160.

5.9.7 Synthesis of garenoxacin Garenoxacin 170 is a quinolone antibiotic used as an API in Geninax to treat respiratory tract infections, for instance tonsillitis, pneumonia, pharyngitis, bronchitis, and pharyngitis [94]. The synthesis of Garenoxacin 170 initiates with the methylation of 161, followed by carbonation with CO2 and conversion of the obtained acid to a methyl ether with diazoniomethanide to afford ester 162. Then, the cleavage of the methyl ether using tribromoboron furnishes phenol 163, which is treated with chlorofluromethane in the presence of K2 CO3 to afford 164. The obtained ester 164 reacts with NaN3 , followed by catalytic hydrogenation and saponification to yield acid 165. Subsequently, the amine unit of 165 is diazotized using copper(I) bromide and sodium nitrite, and the diazonium salt is treated with HBr to obtain bromide 166. The condensation reaction of bromide 166 with the Mg salt from ethylpropanedioate and subsequent treatment with DMF-DMA (dimethylformamid-dimethylacetal) and cyclopropylamine affords ketone 167. The reaction of ketone 167 with potassium carbonate closes the ring to give quinolone 168, which is subjected to a Suzuki cross-coupling reaction with the boronic acid from dihydroisoindole 169, leading to the formation of the coupling entity (Scheme 5.33). Ultimately, treatment with HCl removes the trityl protecting group from the isoindole nitrogen atom to afford garenoxacin 170 [95,96].

5.9.8 Synthesis of englitazone Englitazone sodium is the sodium salt-form of Englitazone 176, an agent belonging to the glitazone class of anti-diabetic agents with anti-hyperglycemic activity. Englitazone 176

5.9 C-nucleophile-triggered CO2 -incorporated organolithium-mediated carboxylation to form a C–C bond

107

SCHEME 5.33 Synthesis of garenoxacin starting from 2,6-difluorophenol.

also appears to decrease triacylglycerol levels in animal studies [97]. Clark et al., proposed a multistep synthetic sequence leading to Englitazone 176, which starts from the reaction of reality available chromanol 171 with benzylchloromagnesium; this reaction results in an addition to the latent aldehyde and the development of intermediate dialcohol 172 (Scheme 5.34) [98]. Treatment of the crude product 172 with toluenesulfonic acid affords chroman 173. Then, the organolithium substrate from the halogen-metal exchange reaction of chroman 173 with n-BuLi reacts with CO2 to afford acid 174. Following this, acid 174 is resolved by isolating the diastereomeric salts produced with a chiral base. The reduction of the acid provides aldehyde 175 as a single enantiomer. Ultimately, aldol condensation with 2-thioxo-4-thiazolidinone and subsequent reduction using H2 and Pd/C affords 176 [99].

SCHEME 5.34 Synthesis of englitazone starting from 6-bromochroman-2-ol.

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5. Utilization of carbon dioxide as a building block in synthesis of active pharmaceutical ingredients

SCHEME 5.35 Synthesis of enadoline starting from 1–methoxy-2,3-dimethylbenzene.

5.10 C-Nucleophile-triggered CO2 -incorporated organomagnesium-mediated carboxylation to form a C–C bond 5.10.1 Synthesis of enadoline Enadoline 184 is a medicine that behaves as a highly potent and selective κ-opioid receptor agonist, and it exhibits anti-allodynic and anti-hyperalgesic properties [100]. Huang et al., synthesized 184 in seven steps from 2,3-dimethylanisole 177 (Scheme 5.35) [101]. 2-Methoxy-6-methylbenzaldehyde was obtained by refluxing 2,3-dimethylanisole 177 in a suspension of copper sulfate and potassium persulfate. Subsequently, the obtained alcohol was transformed into the respective aldehyde using manganese dioxide. De-O-methylation was performed with tribromoboron in dichloromethane to afford 6-methylsalicylaldehyde 178. Ethyl 4-methylcoumarilate 179 was obtained in the next step via the treatment of aldehyde 178 with ethyl bromomalonate in potassium carbonate and butanone. Then, the reaction of ester 179 with NBS (N-bromosuccinimide) in the presence of dichloroethane and AIBN (azobisisobutyronitrile) afforded ethyl 4-bromomethylcoumarilate, which was subjected to saponification using K2 CO3 , leading to the formation of acid 180. Heating of acid 180 in leucoline led to a decarboxylation product, which was then stirred with triphenylphosphine and N-chlorosuccinimide in THF to afford 4-chloromethylbenzofuran 181. Following this, 181 was gradually introduced to a stirred magnesium-anthracene mixture at −45 °C, and the solution was bubbled with CO2. Afterward, thionyl chloride and 183 were added to the mixture, which resulted in 184.

5.10.2 Synthesis of loxoprofen Loxoprofen 191, an API used in Loxonin, is an NSAID; its tablets are widely used as painkillers or anti-inflammatory agents. The multistep synthesis of loxoprofen 191 initiates with the reaction of 1-(1-chloroethyl)−4-methylbenzene 185 with magnesium turnings and then with gas CO2 (Scheme 5.36) [102]. After being carboxylated, the obtained acid 186 is treated with NBS (N-bromosuccinimide) in the presence of azobisisobutyronitrile or benzoyl peroxide to afford bromide 187, which is then subjected to methoxylation towards ester

5.10 C-Nucleophile-triggered CO2 -incorporated organomagnesium-mediated carboxylation to form a C–C bond

109

SCHEME 5.36 Synthesis of loxoprofen starting from 1-(1-chloroethyl)−4-methylbenzene.

SCHEME 5.37 Synthesis of lamotrigine starting from 1,2-dichloro-3-iodobenzene.

188 [103]. Next, ester 188 is treated with NaIO4 to construct aldehyde 189. Subsequently, the reaction of aldehyde 189 with 4-(cyclopent-1-en-1-yl)morpholine in HCl, followed by treatment with hydrogen furnishes 191.

5.10.3 Synthesis of lamotrigine Lamotrigine 195, an API used in Lamictal, is an anticonvulsant drug used to treat bipolar disorder and epilepsy. A multistep process described in the patent for preparing 195 is illustrated in Scheme 5.37 [104]. Carboxylation of 1,2-dichloro-3-iodobenzene 192 using CO2 affords acid 193, which is treated with SOCl2 and then with CuCN to produce 194. Then, the reaction of compound 194 with aminoguanidine, followed by saponification furnishes 195.

5.10.4 Synthesis of felbinac Felbinac 198, an API in Traxam and Nabolin, is an NSAID widely used to cure arthritis and muscle inflammation. The two-step synthetic route to 198 starting from 1,1 biphenyl 196 is outlined in Scheme 5.38. Chloromethylation of 1,1 -biphenyl 196 affords 4(chloromethyl)−1,1 -biphenyl 197. Subsequently, the Grignard reagent of 197 is formed and subjected to carboxylation towards 198 [105].

5.10.5 Synthesis of spironolactone Spironolactone 206 is an API in Aldactone, i.e., the drug used to treat fluid build-up owing to kidney disease, liver scarring, or heart failure [106]. The industrial synthesis of 206 consists

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5. Utilization of carbon dioxide as a building block in synthesis of active pharmaceutical ingredients

SCHEME 5.38 Two-step synthesis of felbinac starting from 1,1 -biphenyl.

SCHEME 5.39 Industrial synthesis of spironolactone.

of seven linear steps, starting from dehydroepiandrosterone 199 (Scheme 5.39). The reaction of the Grignard reagent of diol 200, which is obtained from 199, with CO2 affords an alkyne 201. Then, the triple bond of alkyne 201 is hydrogenated using Lindlar’s catalyst in pyridine and dioxane. The reaction of acid 202 with tosylic acid furnishes unsaturated lactone, which is hydrogenated to saturated lactone 203 using H2 over palladium on carbon. Following this, the Oppenauer oxidation delivers 204. Afterward, carbon-6 is unsaturated via a reaction with chloranil as an oxidizing agent. Ultimately, the resulting diene 205 reacts with thiacetic acid, providing 206 in a total yield of 40 percent (Scheme 5.39) [107,108].

5.10.6 Synthesis of finafloxacin Finafloxacin 215 is an API in the fluoroquinolone-based antibiotic marketed by Novartis under the trademark Xtoro. This drug is used to treat acute otitis externa (swimmer’s ear) induced by the bacteria Staphylococcus aureus and Pseudomonas aeruginosa [109]. A multistep synthetic route to 215, starting from 2-trifluoromethylaniline 207, is outlined in Scheme 5.40.

5.11 Conclusion

111

SCHEME 5.40 Synthesis of finafloxacin starting from 2,6-dichloro-3-fluorobenzonitrile.

Treatment of fluoride 207 with a brominating agent in concentrated sulfuric acid affords bromide 208, which, in the next step, is treated with i-PrMgCl to generate a Grignard reagent. This Grignard reagent is further subjected to carboxylation by CO2 , and subsequent acidification to furnish acid 209 with a good yield of 60 percent [110]. Subsequently, treatment with SOCl2 delivers acid chloride 210 in excellent yield (95 percent). Treatment of this acid chloride 210 with ethyl 3-(dimethylamino)prop–2-enoate in the presence of Et3 N in toluene furnishes the acrylate precursor 211 in good yield (80 percent) [109]. The introduction of cyclopropylamine leads to the β-ketoacrylate ester 212, which is readily cyclized to quinolone product 213 using K2 CO3 (Scheme 5.40). Ultimately, 213 bonds with chiral N-Boc pyrrolidine 214 to form an ester. Hydrolysis of this ester and subsequent Boc-deprotection affords the desired 215.

5.11 Conclusion The book chapter highlights advances on the incorporation of carbon dioxide as both an oxygen and carbon source through carboxylation, methylation, and oxidation in the production of important APIs and key intermediates of APIs. Summarily, the last three decades have seen tremendous advances in carbon dioxide capture and its in situ transformation (Fig. 5.2). Such achievements on the transformation of carbon dioxide are of great importance in the development of alternative schemes to APIs because the present academic organic syntheses, as well as industrial chemical formation, rely mostly on the application of fossil-mediated carbon sources. Additionally, carbon dioxide is an environmentally benign, renewable, inexpensive, and abundant source of oxygen and carbon and offers numerous technological schemes for the processing of pharmaceuticals that could afford contaminant-free APIs; this could lead to a considerably reduced usage of conventional liquid and solid reagents and the development of sustainable chemical industry. However, establishing a chemical industry

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5. Utilization of carbon dioxide as a building block in synthesis of active pharmaceutical ingredients

FIGURE 5.2 Potential applications of CO2 as a building block (carbon and oxygen source) in the production of APIs by constructing new C–C, C–O, and C–N bonds.

mediated on carbon dioxide as a raw material (building block) in the production of APIs is a long-standing challenge because of the following issues and demands: (a) some catalytic transformations of carbon dioxide in a homogeneous phase discussed in this book chapter involve harsh conditions (such as high pressure of CO2 , i.e., 3400 psi in the K2 CO3 -based approach, and application of organomagnesium and organolithium at −78 °C); therefore, the development of novel approaches that operate under mild reaction conditions, for instance room temperature or low pressure of CO2 , is a significant objective; (b) the current loading of catalysts and ligands is too high for large-scale implementation. Also, the requirement of more than 1 equiv. of organometallic reagents is undesirable concerning both the economy and the environment. Consequently, the development of more efficient reagents and catalytic systems constitutes a demanding goal; (c) some reactions contain highly moisture- and airsensitive compounds; hence, research on alternative stable synthetic approaches is essential; (d) in few cases, the product distribution is not selective; thus, research on the improvement of the chemo- and regioselectivity of APIs is mandatory; (e) the elucidation of CO2 -based reaction mechanisms is vital to further construct cost-effective catalytic systems for the formation of APIs. Computational approaches have assisted in understanding the mechanisms of numerous organic reactions. This method will play an increasingly significant part in understanding the reactions; consequently, it can promote the formation of new catalytic systems. Therefore, computational chemistry must be employed for mechanistic findings; (f) fundamental knowledge on the thermophysical processes is vital for rational scale-up and

References

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design; (g) the development of highly recyclable catalysts, such as nanomagnetic catalytic systems, and the optimization of the stability of catalysts for their long-term performance are required; (h) challenges facing effective implementation of the technology also involve the continuous formation of particles with a required and reproducible drug quality; and (i) currently, in many processes for the formation of APIs, a huge number of steps are included, which increase the quantity of waste and the manufacturing costs. Therefore, the current objective is to reduce the number of steps and improve the productivity of the reaction steps. The construction of eco-friendly synthetic procedures for the transformation of CO2 is necessary to accomplish this goal. Particularly, chemists must work on microwave-assisted, ionic-liquid-catalyzed, ultrasonic-promoted, and enzyme-catalyzed synthetic approaches to transform CO2 into value-added chemicals. With this book chapter, we aim to inspire extensive research on CO2 capture and its in situ conversion to APIs.

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C H A P T E R

6 Electrochemical Carbon Dioxide Detection S. Aslan a, C. I¸sık a and A.E. Mamuk b a

Department of Chemistry, Faculty of Science, Mugla Sitki Kocman University, Mugla, Turkey b Department of Physics, Faculty of Science, Mugla Sitki Kocman University, Mugla, Turkey

6.1 Introduction Since life on the planet depends on the carbon element, the carbon dioxide (CO2 ) cycle is among the principal biochemical cycles on the earth [1]. In the cycle, plants use CO2 and water in the atmosphere during the photosynthesis process and convert them into sugars such as glucose because of CO2 fixation [2]. Decomposition of organic matter, cellular respiration, and combustion return CO2 to the atmosphere, unlike photosynthesis. For this reason, it is extremely important to keep the quantity of CO2 in the inspired air in balance with the CO2 cycle for life on Earth to continue [3]. CO2 is a type of gas whose existence is vital with both advantages and disadvantages. Since it is one of the adjuvant greenhouse gas that significantly affects climate change by the increase in emissions into Earth’s atmosphere, recently, CO2 has become a crucial global warming factor in nature [4–7]. The utilizing fossil fuels has risen significantly in the 1900s due to the increase in population and the increasing need for energy as a consequence of technological developments [8]. By the rising of utilizing fossil fuels, the quantity of CO2 in the Earth’s atmosphere has increased tremendously. As a result of this situation, the quantity of CO2 in the air has come dimensions that cannot be kept in balance with the CO2 cycle [9,10]. The excessive CO2 emission has caused negative effects in many areas, especially on human health, energy security, life cycle, air quality, and global climate change [11]. The contribution of the CO2 to the increase in global warming is specified as 76 percent, also because of the human-induced CO2 emissions, the CO2 amount in the atmosphere has been increasing by nearly 1.5 ppm per year for the last two centuries. It was specified that

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the concentration of CO2 was about 280 ppm and 370 ppm at the beginning of the Industrial Age and in 2000, respectively. The present amount is approximately 412 ppm. As a result of CO2 being categorized as the major heat-trapping gas, the increment of CO2 amount in the air increases territorial and nautical temperature, which has been determined as the highest in June 2019 since 1880, also causing ocean acidification [12–14]. For all mentioned reasons, the increment of CO2 amount in the air becomes one of the major climate change boosters. Hence, because of the concerns about global warming and greenhouse effects, the research on sensing, capturing, and monitoring CO2 has very excessively come into prominence. Moreover, apart from important concerns about the CO2 rate in the outdoor environment, the existence of high CO2 concentration is possibly fatal or may cause some unhealths such as headache, tiredness, respiratory problems, loss of consciousness, etc. for most the creatures especially humans in the atmosphere, as well. In pursuant of the American Society of Heating, Refrigerating and Air Conditioning Engineers (ASHRAE) Standard, 1000 ppm of the CO2 concentration should be the upper limit in enclosed buildings. The main source of CO2 concentration in enclosed places is human breathing whose level is generally quite more than approximately 450 ppm of the average CO2 level in an outdoor atmosphere. Once again according to ASHRAE standards, 350 to 1000 ppm of the CO2 concentration in closed places is considered a healthy environment. Besides, the existence of CO2 is a fundamental agent for photosynthesis, thus, plants and algae can convert CO2 into glucose and O2 . Therefore, determination and monitoring of the CO2 level, which causes substantial cost, also is quite momentous for both healthcare and organizing life in closed places [13,15]. Alongside harmful effects of CO2 gas on human and environmental health, a part of the atmosphere, CO2 gas, can become a beneficial substance. One of the most known CO2 -using industries is food packaging in a modified atmosphere. The main scope of this field is the prohibit food spoilage and extend the shelf life of packaged food products. The freshness of packaged food can be specified by monitoring the CO2 level, and if there is a decrease in its concentration it is considered that is probably proof of a symptom of leakage in a food package [16,17]. Also, with intrinsic properties, CO2 gas can be used in many industries such as biotechnological processes, producing some chemicals, and also the fabrication of carbonated liquids, cooling and welding systems, fire-extinguishers, and water treatment systems [5,15,18]. Thus, it is due to occupy an important place in daily life, monitoring and sensing the CO2 gas takes an important place in the manufacturing process of such materials. In recent years, more renewable energy technologies such as photovoltaics and wind power have been used instead of fossil fuels in transportation, energy generation, and industry to prevent climate change and reduce its effects. Despite this situation, the Energy Information Administration (EIA) states that fossil fuels will continue to become the fundamental part of useable energy in the near future and the amount of CO2 in the air will maintain to increase [19]. Therefore, it is necessary to develop alternative methods besides renewable energy systems such as wind and photovoltaics in order to reduce CO2 emissions [20–22]. It is a quite effective approach proposed to diminish the amount of CO2 in the air in recent years is carbon capture technology [23]. This technology is divided into two categories, Carbon Capture and Storage (CCS) and Carbon Capture and Use (CCU). CCS means to the capture of refuse CO2 using several technologies and its transport and storage to mineral, geological and oceanic sequestrations. CCS is not preferred because energy is required to extricate, convey, and reservoir CO2 in the air and this energy is supplied from fossil fuels, and also because of limitations such as uncertainty regarding the permeability of CO2 on the storage source

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after storage [24–26]. The CCU method is more advantageous than the CCS method because it can be recycled for later uses instead of storage immediately after the CO2 is captured in the atmosphere. While both methods diminish the quantity of CO2 in the air, CCU uses CO2 as a renewable resource, providing an additional benefit for resource and potential energy recovery [27,28]. It is stated that CCU is a quite suitable method to diminish the quantity of CO2 by taking the natural carbon cycle as an example to generate complex using CO2 in the air [29]. Beyond the CCU methods, electrochemical ways are outstanding. Electrochemistry basically studies the electrons formed due to a chemical change. Electrochemical methods are used to determine the presence or amount of a chemical that causes a change depending on electron exchange, current, concentration, or voltage difference [30]. Electrochemical methods basically include potentiometric, amperometric, voltammetric, conductometric, and coulometric methods. Many sensors developed using these methods find a wide application area [31]. Electrochemical gas sensors are one of those fields [32]. There is a chemical reaction that occurs between the ambient gas and a part of the sensor for an electrochemical gas sensor. At the end of the reaction, electrons are released. The liberated electrons create a current, allowing a current value to be read in the output. Thus, the amount of gas in the environment can be measured according to the flow at the outlet [33]. In the present chapter the former, a bunch of the most used general methods, the latter, electrochemical detection, and reduction of CO2 have been detailed and exampled by the studies reported by divergent groups in the manner of catalysis or electrode development.

6.2 Capture technologies of CO2 CO2 , which is the most important reason for global warming, is one of the topics of great interest both industrial and academic. It is stated that the amount of this gas in the atmosphere is increasing day by day owing to human activities and that the efforts of countries with large economies are not sufficient to prevent global warming, and it is expected that be possible with environmental policies to reduce CO2 emissions of each country [34,35]. It has been stated that the amount of CO2 in the atmosphere can be reduced by using methods such as traditional use (e.g., solvent), fuel generating (e.g. raw materials for diesel and gasoline), biological imposition (e.g., food of carbon for microalgae culture) and chemical production (e.g., raw material for carbonates and polymers) [36]. These methods for reducing the amount of CO2 have an environmentally friendly and economical approach, as methods contribute to the formation of innovative materials and products since CO2 is used as a raw material in industrial processes [34,36,37]. The capture of CO2 from gas flows is carried out using a great variety of technologies. Although these technologies could be adapted to many industrial fields, the technologies are not still appropriate for large-scale production applications. These technologies can be divided into adsorption, absorption, separation by membrane, and chemical capture [38].

6.2.1 Adsorption Adsorption is the process of binding a substance to a solid substance by shifting it from the gas phase with the help of electrostatic or van der Waals forces. Adsorption is the process of linking material to solid material by changing it from the gas state with the help of electrostatic

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or van der Waals forces [39]. The carbon capture process with the adsorption method takes place by attaching CO2 from a gas flow to an adsorbent with supreme CO2 selectivity. The adsorbent is then desorbed (reproduced) by pressure or thermal fluctuations or by applying a potential difference to the adsorbent [40]. These procedures cause the links between the solid material and the gas phase to break, allowing for continuous reuse of the adsorbent [41]. The performance of solid adsorbents is determined by the form and range of the pores, their magnitude, surface area, and interaction between the surface and the CO2 molecules [42]. The adsorption process as a CO2 capture technology has some limitations as it involves complex processes, low efficiency, and requires a big deal of energy to sustain the procedure [43].

6.2.2 Absorption The absorption process takes place in the presence of material that can absorb this gas after CO2 has been captured and transport it from one phase to another. In the process, when the CO2 in the gas phase comes into contact with the solution in the liquid phase, it dissolves into the liquid phase and allows it to be separated from the other components [44,45]. Also, temperature change is very important as it affects the solubility of the gas in the solution. Therefore, the energy requirement during the process to control temperature changes is also quite high. Absorption technologies are one of the most interesting and studied technologies by researchers due to their advantages [46,47].

6.2.3 Separation by membranes In the capture process by the membranes, the CO2 passes through the membranes and is separated from the other compounds. The basis of this method is based on the selectivity of gases against the materials that make up the membrane [48]. The success of this method depends on variables for instance grain size, pore volume, permeability, and selectivity of the membranes. However, since these parameters are difficult to optimize during the capture process, this is considered to be the biggest challenge in the development of studies aimed at capturing CO2 with membranes [44–49].

6.2.4 Chemical capture Among the currently developed CO2 capture technologies, the chemical capture method stands out due to its features such as providing added value to industrial applications and offering more sustainable production systems. This method is based on the principle of obtaining a final output as a consequence of the reaction of CO2 in the atmosphere with organic or inorganic chemicals [50,51]. There is a great interest in the technology because the organic or inorganic chemicals used in this method are biodegradable, have low toxicity, and have high boiling points [40]. The most important factors limiting chemical capture technology are the stability of the chemicals used against oxidation and reduction during repeated cycles and the cost of the process [52,53].

6.2.5 CO2 sensors The sensor means that an apparatus detects or monitors the change in a physical/chemical quantity in the target environment and, though not always, converts the information using

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software and control electronics. Fundamentally, depending on being electronic or nonelectronic, the sensors may contain some important members such as a sensing unit, a transducer, data processing electronics, and a display for giving outcomes [16,54]. A gas sensor works, basically, by relying on specifying the molecules of the target gas and converting that information into beneficial and considerable information. That converting can take place with and without an electronic network. Non-electronic sensors generally give the sensing information with the change in optical visualization. In electronic sensors, on the other hand, a sensing unit generates a change in a physical quantity such as conductivity, capacitance, resistance, etc. of the sensed material in accordance with the chemical reaction between the analyte gas and sensing unit. Plenty of studies have been carried out related to sensors or materials that can be used as sensors with different working principles for the measurement of CO2 change in a certain environment [16,54]. Gas chromatography (GC) and Mass Spectrometer (MS) are one of the common detecting systems for CO2 gas. GC enables the division and specification of the ingredients of a mixture. It consists of a chromatograph with several columns and detectors [55]. The running of GC is based on selective adsorption and the driving of the analyte gas molecules in the column of the system. Choosing the right column and detector leads to good detection of analyte gas. GC consists of various fragments, e.g. thermal conductivity detector (TCD), and electron capture detector (ECD) which are quite beneficial for detecting the CO2 gas [55–57]. The main advantage of GC is being cost-effective. However, analyzing the analyte, for instance, CO2 , takes a long time in GC, thus it is the main disadvantage of the system. The running of MS, besides, relies on the principle that the analyte gas is exposed to high-energy electron beams and thus the gas molecules are split. The split molecules are motioned benefitting from the having charge of them, thus, the molecules can be separated through their charge and mass. However, MS enables to analysis of CO2 gas in an almost instant, it is a quite pricey system. Due to mentioned disadvantages of both GC and MS, using them is not advisable and the methods need to be solved the drawbacks such as miniaturization, sampling issues, the price [4,16,55]. Severinghaus electrode which is a type of CO2 sensor a glass electrode. This electrode is covered by a thin membrane that is selective-permeable, namely, however it enables the transition of CO2 molecules, it prevents the transition of electrolytes. On the other hand, the glass electrode contains a dilute bicarbonate solution. The Severinghaus electrode sensor is based on a working principle that carbonic acid, which is resulted from CO2 gas decomposed into HCO3 − and a p+ , thus, due to the case, the pH of the electrolyte changes. In this method, CO2 gas cannot directly be sensed, however, it can be determined while it forms carbonic acid in an electrolyte, so this case builds the main disadvantage of the system. Besides, while measuring the CO2 , other volatile compounds and gases exist in the measuring environment can affect the pH of the electrolyte [16,17,58]. Infrared detectors are the members of the CO2 detectors that generally possess less response time, portable size, and low-cost. Nondispersive infrared detectors are the most preferred detectors among infrared detectors and exhibit long-term determination, high fidelity, and great gas specificity. Because gases, of course also, CO2 , absorb infrared light energy depending on the quantized vibrating energy of relevant gas, the running principle of the infrared detectors relies on the energy absorption characteristics of analyte gas. Also, the narrow bands of the wavelength of infrared radiation of CO2 are 2700, 4300, and 15,000 nm, thus, it means that

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most of the heat-producing radiation escapes CO2 [16,59–61]. In infrared CO2 detectors, the analyte gas, which is CO2 here, is detected by comparing it with another reference (control) gas that does not absorb infrared. The radiation from the infrared source is let to penetrate both the CO2 and the control gas to reach a radiation sensor. The amount of CO2 is determined in regard to the infrared absorption of the analyte gas compared to the control gas. The main disadvantage of non-dispersive infrared detectors is that non-target gases such as water vapor and carbon monoxide (CO), which are in the environment to be measured and have absorption in the infrared region, may affect the CO2 measurement results [16,17,60,62]. Nanomaterials which can involve organic, inorganic fragments or merging them are a good alternative to sense CO2 gas. Although organic materials have some beneficial features such as mass transport, chemical reactivity, etc. as regards CO2 sensing, inorganic materials have different advantages such as mechanical stability, conductivity, and optical properties as well. Since metal oxides have some outstanding features such as taking small space, simply generating, high stability and sensitivity, although taking high working energy and show low selectivity, metal oxide gas detectors are preferable sensors for sensing and monitoring the CO2 gas as a nanomaterial-based sensor [7,15,63,64]. Due to being a producible large surface area, which increases the adsorption of gas molecules and contributes to surface reaction with the gas phase, various metal oxide materials such as La2 O3 [7], CdO [65], Y-doped ZnO: CdO [66], SnO2 [67] are some of the favorable sensing materials for the manufacture of gas sensors. Metal-oxide gas detectors had the main disadvantage owing to generating process conditions that exhibit impurity during the generating films [7,15,68]. Other crucial nanomaterials for generating a CO2 sensor are carbon-based semiconductors. Carbon-based semiconductors are interesting and utilizable materials for sensing systems with their important features such as being tough, high carrier mobility, etc. Carbon nanotubes (CNTs) are one of the members of carbon-based semiconductors and CNTs are preferred sensing carbon-based semiconductor materials for gas sensing systems owing to possessing a large surface area to sense the gas molecules. Depending on the aligning form of CNTs, the response time of the sensor is significantly changed [13,69]. It is reported that at room temperature, horizontally aligned CNT-based CO2 sensor shows a faster response time, which may be related to the lacking of intertube links, while randomly aligned CNT-based CO2 sensor has a slower response time, which may be also due to existence of bending of CNTs [70]. Another member of carbon-based semiconductors is graphene. Pure graphene, graphene oxide, and reduced graphene oxide, which are derivatives of graphene are favorable nanomaterials for generating a gas sensor. While a graphene absorbs the analyte gas molecules, however, the amount of electrons in the graphene is a trace of change, there is a significant change in the conductance of graphene, thus, graphene becomes a quite suitable sensing material of a gas. A graphene-based CO2 sensor shows quite a short response time in comparison with CNTbased CO2 sensors at room temperature and also at over room temperature [13,71]. While the analyte gas, namely CO2 , is detected, the other gas/gases can affect the right measurement, therefore this case reveals the main disadvantage of graphene-based CO2 sensors. Apart from the nanomaterials, which are given above, various nanomaterial structures such as semiconductors, and polymers such composite structures can be used for sensing CO2 . In recent years liquid crystals (LCs) have been strong prospective photonic structures with simple adaptable, low energy consumption for being a gas sensor. Liquid crystals (LCs) are

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materials that exhibit both rheologic features of isotropic liquids, namely ordinary liquids, and features of molecular order of solid crystals. This unique feature for LCs reveals at a specific temperature interval which is called mesophase [72,73]. To open a new door for the technology of capturing and storing carbon or carbon-based materials, scientists have focused on CO2 sorption in LCs. It is reported that LC could absorb fundamental gasses such as CO2 , and N2 , and it was especially shown that CO was the best solute among the gasses used [74]. As is known, however, CO2 weakly dissolves in ordered liquids such as LCs, it is well dissolved in isotropic liquids which do not show any molecular order [75–78]. It is possibly done that CO2 gas is solved in an LC material at isotropic phase then decreasing the temperature of the LC a few degrees at constant pressure, thus, the LC changes its phase to mesophase and due to that new state, CO2 is released. This CO2 capturing and releasing process needs very less energy than other known CO2 capturing systems because a few degrees change in temperature of an LC material is enough to trigger the phase transition [79]. De Groen and co-workers reported the change in phase behavior of LC+CO2 [75,76] and LC mixture+CO2 [78] in nematic mesophase and separated the CO2 gas by considering a three-phase equilibrium. Moreover, some amphiphilic block copolymers consist of blocks such as poly(propylene oxide) (PPO), and poly(ethylene oxide) (PEO), and such blocks can be potentially used for CO2 capture [80]. A copolymer based on PPO, and PEO self-assemble and change their form as a lyotropic LC in a dilute solution. Lyotropic LCs are a type of LC whose features can be changed with the change in temperature and concentration [72]. Rodriguez-Fabia et al. studied on CO2 absorption of lyotropic LCs which consisted of PEO-PPO blocks and exhibited lamellar and hexagonal phases, depending on the viscosity of the LCs, and it was showed that the ionic strength of the LC solutions could affect the CO2 absorption [80]. In addition, cholesteric (Ch) LCs have the potential to be used as an optical sensors so as to detect gases [81–83]. (Ch LCs are more symmetrical than nematic LCs. The centroids of the molecules and the n director, which characterizes the orientations of the molecules, lie in a plane. The orientation of the director is not constant and changes as it moves from one plane to the other. Thus, a spiral step which is generally called as the pitch is formed. The pitch can be changed by an external stimuli such as temperature, electric, and magnetic fields. The helical orientation direction of Ch LC molecules is determined by the right- or left-handed chiral dopant depending on its helical twisting power (HTP) [72,84,85] If the light coming into the Ch LC has the same wavelength as the length of the pitch and is circularly polarized in the same direction as the pitch, the light beam is held by Ch. On the contrary, if the light is oppositely polarized, Ch allows it to pass through the structure, thus Ch LCs is identified as selective transparent photonic material. The helical pitch can be varied by stimuli such as CO2 gas, therefore the color of transmitted light changes compared to its non-CO2 -exposed state. So, the HTP of the chiral is changed and the presence of CO2 can be specified according to the change in color of transmitted light which can be observed with necked eyes [82]. It was reported the real-time monitoring of CO2 using an E7 nematic mixture doped with a high HTP chiral [81]. Effect of CO2 in the chiral structure revealed in both optical observations and structural analyses. In the IR spectra of chiral dopant, stretching vibrations of the N–H which belongs to the amino group (3377 and 3355 cm−1 ) was not observed after exposing it with CO2 , while a carbonyl group stretching band was obvious at 1650 cm−1 [81]. As a new approach to detecting volatile organic compounds, electrospun LC fibers are a substantial prospective structures with the ability which is based on varying scattering of transmitted light while the electrospun fiber

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is exposed to volatiles. Electrospinning is one of the versatile and cost-effective methods to obtain phase-separated fiber, [86–92]. Lagerwall and co-workers stated that electrospun coresheath LC/polymer fibers with various morphologies could sense the toluene in the gas phase as a non-electronic gas sensor [93]. In the beaded (non-homogenous) LC/polymer fibers, exposed to toluene, the scattering degree of the LC decreased since the toluene vapor reached the LC and reduced the phase transition temperature of LC due to behaving as an impurity. So, the isotropic liquid-nematic phase transition temperature of the LC decreases up to room temperature depending on the concentration amount of vapor. Thus, the LC inside the fiber as a core formed isotropic liquid, and the disappearance of light scattering could be observed with necked eyes without the need for any polarizer. When closing the exposing toluene, toluene molecules left from the LC and LC formed an anisotropic phase again. By benefiting from the effect of volatile organic compounds on LC birefringence, a similar study was taken place for detecting toluene, cyclohexane, and isopropanol with electrospun fibers involving LC mixture [94]. It was stated that the detecting process was reversible and repeatable, Also, the response time was quite short (a few seconds). Lagerwall et al. reported such kind of LC/polymer core-sheath fibers might be used for detecting hazardous gases and would be potentially useful materials for wearable sensor [93].

6.3 Fundamentals of electrochemistry Electrochemistry is a branch of chemistry that studies the electrical behavior of substances and the relationships between electrical energy and chemical reactions between conductive interfaces [95]. The methods used to analyze the electrochemical properties of substances are also called electroanalytical methods. Electroanalytical methods have many advantages over other analytical methods [33,96]. Among them, the simultaneous detection of species with different oxidation levels is easy, and the equipment and software that enable the application of the methods are much cheaper and more useful than chromatographs and spectrophotometers [97]. Moreover, there are multi-purpose ones that enable the applicability of many electroanalytical methods in the same device [98]. A collective representation of the electroanalytical methods is given in Table 6.1.

6.3.1 Voltammetry Voltammetry is an electroanalytical method that examines the relationship between the measurement of different current values at varying potential values of a polarized working electrode with a small surface area (usually less than 1 cm2 ) and the analyte concentration [99]. In voltammetry, different types of working electrodes are used, as well as different types of voltage sources. Voltammetric methods are named according to the types of current used and the working electrode [100]. Such as direct current voltammetry, direct current polarography, alternating current voltammetry, alternating current polarography, square wave current voltammetry, pulse voltammetry, differential pulse voltammetry, and cyclic voltammetry [101]. Two or three-electrode systems can be used in voltammetric measurements, threeelectrode systems are commonly used. A simple representation of a three-electrode system is given in Fig. 6.1.

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TABLE 6.1 A collective representation of electroanalytical methods. Electroanalytical Methods Methods throughout the analysis environment

Interface Methods Static methods (I = 0)

Dynamic methods (I ˃ 0)

Potentiometry Potentiometric Controlled potential titrations

Conductometry

Conductometric titrations

Constant current

Fixed electrode Coulometric titrations potential coulometry Voltammetry Amperometric titrations

Electrogravimetry

Electrogravimetry

FIGURE 6.1 A simple illustration of a three-electrode system.

Different voltages can be applied separately to the E1, E2, and E3 input resistors, or superimposed voltages can be obtained by applying different voltages to each end. The three fundamental quantities that characterize a voltammogram are residual current, limit current, and half-wave potential [102]. As seen in Fig. 6.2, each voltammogram has two digits. The first step is called the residual current (ia) step. The current value of the second digit is also called the limit current (il). Residual current is the sum of currents due to two reasons. The first is the capacitance current resulting from the double layer formed between the electrode and the solution. The second is the faraday current resulting from small levels of electroactive impurities that can be found in the supporting electrolyte apart from the analyte. The limit

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FIGURE 6.2 A voltammogram and its components.

current is the current value between the first digit and the second digit of the voltammogram. This current is the current value when the concentration of the electroactive sort on the electrode surface goes to zero and is almost independent of the potential. The half-wave potential is the potential value corresponding to half of the limit current (il/2 ) and is denoted by E1/2 . Techniques to eliminate residual current have been developed to increase sensitivity (e.g. normal pulse voltammetry/polarography, voltammetry of square wave, pulse voltammetry, differential pulse voltammetry, cyclic voltammetry). In these methods, pulse-shaped voltages are used [103].

6.3.2 Potentiometric methods In potentiometric measurements, a reference electrode, an indicator electrode, and a potential measuring device are required. In the process, the potential of the electrochemical cells is measured without drawing a significant amount of current (Fig. 6.3). Potentiometric methods can be defined into two groups [104].

6.4 Direct potentiometric methods Direct potentiometric measurements can be made with an indicator electrode. The method is simple, the potential generated at an indicator electrode inserted into the sample precursor is compared with the potential generated when the same electrode is inserted into a standard precursor. Since the ion to be detected by the electrode is special, no pre-separation is required. Direct potentiometric measurements also allow continuous and automatic monitoring of analytical parameters [105]. In addition to the great convenience of direct potentiometric measurements, some obligatory errors in the structure of the method should also be known and considered. The most important of these is the "liquid coupling" potential found in many potentiometric measurements. The coupling potential imposes a limitation on the accuracy of the measured values [106].

6.4.1 Potentiometric titrations The equivalence point of a potentiometric titration is determined by the potential of a suitable indicator electrode. In a potentiometric titration, different information is obtained than in direct potentiometric measurements. For example, direct potentiometric measurements of acetic acid of 0.100 M and hydrochloric acid of 0.100 M solutions with a pH-sensitive electrode

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FIGURE 6.3 A general illustration of a potentiometric cell.

give very different pH values, because hydrochloric acid is completely dissociated while acetic acid is partially dissociated in solution. However, for the neutralization of equal volumes of solutions of these two acids, equal amounts of the standard bases are used. The endpoint determination method with potentiometric titration gives much more accurate results than the endpoint determination with the indicator. The method is particularly successful in working with colored and turbid solutions and in the determination of known ions in the solution. However, it takes more time than with the indicator [107].

6.4.2 Amperometric methods Amperometric methods are used to determine the equivalent points of titrations. It is essential here that at least one of the substances leaving the reaction is oxidized or reduced in a microelectrode. In the method, the current at a constant potential is measured as a function of the volume of the titrant (or time if the substance is created by a constant-current coulometric process). The results are analyzed by graphing. Data on either side of the equivalence point give the slopes a different line; The turning point is found by extrapolating the point where these lines intersect (Fig. 6.4) [108].

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(A)

(B)

(C)

FIGURE 6.4 Typical amperometric titration curves.

An amperometric titration is more sensitive than voltammetric titrations and is less dependent on the properties of the microelectrode and supporting electrolyte. It is desirable that the temperature be constant, but tight control is not required. Also, the substance to be determined does not have to be electroactive; It is also sufficient for the titrant or product to be active on the electrode [105].

6.4.3 Conductometric methods In an electrolyte solution, basically, the positively charged particles and the negatively charged particles migrate to the cathode and anode electrodes, respectively. This process is defined as electrical conduction. Even conductivity is identified as a measure of current and it is known that it is linearly related to the amount of charged particles in the solution. Depending on the mobility talent of a particle and its concentration in the media, the current can be produced [109]. Peculiarities of the particles restrict the carrying out of the analyzes which relied on direct conductivity measurements. In a solution that involves blends of ions, direct conductivity measurement is not selective because all the ions in the solution, which promote conductivity, affect the whole solution’s conductivity. Although, the method is significant for some applications owing to its sensitivity being high. One of the most applications of this method is the controlling of the refinement of deionized water [110]. Conductivity measurements are applied to determine the concentrations of solutions containing only one strong electrolyte (such as alkalis or acids). Calibration curves are used in this type of analysis. The measurement can be made in solutions containing up to 20 percent by weight of the substance. The salinity of seawater can also be determined by conductivity measurements. With conductivity measurements, information can be obtained about the association and dissociation properties of aqueous solutions containing one or more ionic particle [111]. Utilizing the method for aqueous solutions and systems in which the reaction is outstanding is the most significant benefit of the method. For example, however, carrying out the analysis of dilute phenol (Ka »10−10 ) solution is impossible by using methods which are the potentiometric or indicator endpoint, it could be carried out with the method. While the whole electrolyte concentration rises, the precision of

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TABLE 6.2 A general classification of voltammetric working electrodes. Mercury based electrodes

r r r

Dropping mercury: Gravity forced, Mechanical Hanging mercury Mercury film

Solid electrodes

r r r

r

Platinum Gold Carbon: Graphite, Carbon paste, Glassy carbon or carbon paste, Carbon felt, Carbon fiber, etc.… Bismuth

Modified electrodes

r r

Composite Chemically modified: Polymer membrane coated, Surface adsorption, Covalent bonding, etc.…

Rotating electrodes

r r

Disc Ring-disc

the method diminishes. The change in current when titrant is added is observed when the concentration of salt of solution is rich [112].

6.4.4 Coulometric analysis methods The coulometer encompasses a group of analytical methods that measure the electricity (in coulons) required to quantitatively switch the analyte to another oxidation state. There is a proportionality constant, subtracted from known physical constants, between the weight of the measurand and the analyte; therefore, there is no need for a calibration and standardization step. Coulometric methods are as accurate as gravimetric or volumetric processes; it is also faster and more useful than gravimetric determinations [113]. Two general techniques are applied in the coulometric analysis. In the first technique, the potential of the working electrode is kept at a level that does not affect the less reactive particles in the solution during the quantitative oxidation or reduction of the analyte. Here, the current is initially high, but drops rapidly and decreases to zero as the analyte leaves the solution. The energy required is measured with a chemical coulometer. In the second technique, a constant current is applied until the indicator signal indicates that the reaction is complete. When the equivalence point is attained, the amount of electricity is calculated from the amount of current. This second technique is called “coulometric titration”, its application area is wider than the first method [114].

6.4.5 Electrodes 6.4.5.1 Working electrodes Both the chemical and electrochemical properties of the electrodes used in voltammetry are important. Therefore, a limited number of polarizable electrodes are used in voltammetry. These are mercury liquid, platinum, gold, bismuth, and carbon-based solid electrodes and modified electrodes grouped in Table 6.2. The potential working range (working window) of each of these electrodes, which can be used as stationary or rotated, is different. This range depends on many parameters such as electrode type, solvent, type of electrolyte used, and pH. The formation of hydrogen or the reduction of the supporting electrolyte determines the cathodic limit, while the oxidation of the electrode material or solvent determines the anodic limit [115].

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6.4.5.2 Carbon-based electrodes Carbon-based electrodes are fast-responsive, economical, and easily formed electrodes in different configurations and diameters. Carbon is an ideal electrode material in terms of many properties such as having a large anodic potential interval, weak electrical resistance, low electrical resistance, low residual current, and renewable surface structure. Various forms such as carbon fiber, glassy carbon, graphite paste, and carbon film can be used in electrochemical applications [116]. Glassy carbon (GC) and carbon paste (CP) are the most used carbon electrodes. CPE has advantages such as very low ground current, and composite nature with ease of regeneration and modification, while GC electrode has significant electrochemical reactivity, good mechanical stiffness, and negligible porosity. These important properties of carbon electrodes are of great importance in the development of carbon-based electrochemical sensors. GC electrodes, one of the carbon electrode types, are obtained by reducing the pore size with a special method. GC is formed because of the thermal decomposition (degradation) of some polymers at approximately 1800 °C. Since these materials are hard, the surface of the GC electrodes must be polished before each trial. The GCs get ready for use by applying a pre-polarization process at +0.65 V. The working potential limits of the GC electrodes are approximately +1.00 V and −0.75 V. GC electrodes are generally available as stationary and rotating discs. In addition, these electrodes are widely used as detectors in high performance liquid chromatography and fluid systems [117]. 6.4.5.3 Composite carbon electrodes CP electrodes are prepared by mixing powdered graphite with an organic liquid such as mineral oil. After the cake is prepared, it is filled by squeezing into a tube (eg Teflon tube) [118]. A platinum or copper wire is used for the electrical connection. CP electrodes, which have a wide potential range, are short and easy to make and replace and have a sufficiently low ground current [119]. CP electrodes are frequently used in the production of modified composite electrodes. Electrodes can be prepared by adding and mixing the modifying chemical directly to the conductive electrode material. These electrodes are called composite electrodes. For example, the modifier (complexing agent, adsorbent, catalyst) is used by making a paste together with carbon powder and nujol. In addition, electrodes can be made by compressing with carbon and turning it into pellets [120].

6.4.6 Reference electrode For this purpose, non-polarized metal-metal ion electrodes of the second class which are mentioned in the following potentiometric electrodes section, are used. These electrodes are also non-polarized only at small current intensities. As the current intensity increases, the electrodes deviate from the ideal position. The most used ones are calomel and Ag/AgCl electrodes [121].

6.4.7 Auxiliary electrode The non-polarized electrode becomes over-polarized at high currents because current flows along the above mentioned electrodes in two-electrode systems. In addition, if the solution resistance is high, the potential (iR) required to overcome this resistance increases to

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FIGURE 6.5 The potentiometric electrodes applied in the field of the gas sensing.

a significant level. For these two reasons, the polarization potential of the working electrode is perceived incorrectly. As a result, the i = f (E) curves become flat, and the steps or peaks disappear after a certain point. This issue is resolved by using a third electrode in the system. The current is passed through the working electrode and the auxiliary electrode pair, and the potential of the working electrode is determined under zero current against the comparison electrode. Since the current passes through the auxiliary electrode, these electrodes must be noble metals [122].

6.4.8 Potentiometric electrodes The most preferable potentiometric electrode is the pH electrode. Ion-selective electrodes are commonly preferred over the redox electrodes to selectively measure certain ions. For example, while the fluoride measurements, in dental care products, ion-selective electrodes are extensively useable in applications since fluoride cannot be simply determined or else. Using ion-selective electrodes, the electrolytes sodium, potassium, lithium, and calcium in the blood are determined by clinical analyzers [123]. Such an electrode has a metal in contact with a solution involving the cation of the mentioned metal. One of the leading example is the silver electrode which is inserted into a solution of silver nitrate (Fig. 6.5).

6.4.9 Indicator electrodes In potentiometric measurements, a reference electrode, an indicator electrode, and a potential measuring device are required. In the process, the potential of the electrochemical cells is measured without drawing a significant amount of current. Application areas include

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TABLE 6.3 A brief of the potentiometric electrodes. Metallic electrodes

Membrane electrodes (special or ion-selective)

First order electrodes: Used for cations Second order electrodes: Used for anions 1)Ag/AgI, 2)Ag/AgCl, 3)Mercury Inert redox electrodes: Fe2+/3+ and Ce4+

Glass membrane pH electrodes Liquid-membrane electrodes Solid state-precipitation electrodes Gas-sensitive membrane electrodes: CO2 , NH3 , O2

FIGURE 6.6 General working principle of an electrochemical gas sensor.

titrations based on endpoint determination, ion determinations with ion selective membrane electrodes, pH measurement and determination of thermodynamic equilibrium constants such as Ka, Kb, and Ksp [124]. Indicator electrodes are electrodes that are selected in the appropriate response according to the analyte and detect analyte activity. The salt bridge is used to prevent the components in the analyte solution from blending with the reference electrode; A potential arises along the fluid connection at both ends. An ideal electrolyte for salt bridge is potassium chloride, since the motions of K+ and Cl- ions are almost equal [125]. Indicator electrodes used in potentiometric measurements are collected in Table 6.3.

6.4.10 Electrochemical gas sensors Electrochemistry studies the electrons formed due to a chemical change. Electrochemical methods, on the other hand, determine the chemical that causes this change depending on electron exchange, current, concentration, or voltage difference. Electrochemical methods include potentiometric, amperometric, voltammetric, conductometric, and coulometric methods. Many sensors developed using these methods find a wide application area. Electrochemical gas sensors are one of them. In the working principle of an electrochemical gas sensors, a chemical reaction occurs between the ambient gas and the active centre in the sensor. At the end of this reaction, electrons are released. The liberated electrons create a current, allowing a current value to be read at the output. Thus, the amount of gas in the environment can be measured according to the flow at the outlet [126]. Electrochemical sensors are generally used to detect toxic gases and oxygen, especially CO, ammonia, and chlorine (Fig. 6.6). Briefly, there are two or three electrodes in the structure of electrochemical sensors. CO gas in the environment passes through the membrane and reaches the electrodes. Electrodes react chemically with CO gas and an electron current is formed. The amount of the gas concentration

6.4 Direct potentiometric methods

(A)

135

(B)

FIGURE 6.7 Schematic view of two gas-sensing electrodes.

is linearly proportional to the amount of the current. The detector sends an alarm signal according to the level of current generated in the sensor [127].

6.4.11 Potentiometric gas sensors Potentiometric gas sensors have been improved relied on the potential difference of different gases under different physical conditions. Generally, zirconium-based sensors based on measurement at high temperatures are well-developed examples in this field. It is widely used in the measurement of environmentally harmful nitrogen oxides and similar gases in the automotive industry [128]. A schematic view of a well-known gas-sensing electrode is given in Fig. 6.7. The electrode composes of three parts; a reference electrode, a special ion electrode, and an electrolyte solution contained in a cylindrical plastic tube. A thin gaspermeable membrane is attached (replaceable) to one end of the tube to separate the inner electrolyte solution from the outer sample solution. The membrane is a thin microporous film made from a hydrophobic plastic; Due to its water-repellent property, water and electrolyte are prevented from entering and leaving the pores of the film. The pores only allow air or other gases with which the membrane is in contact to pass. If the solution in which the membrane is immersed contains a gas, for example, CO2 passes from the solution to the pores of the membrane, as seen in the following reaction. CO2(aq) outer solution



CO2(g) Member pores

Since the number of pores is very large, the equilibrium position is reached quickly. The CO2 in the pores is also in contact with the inner solution and a second equilibrium reaction

136

6. Electrochemical Carbon Dioxide Detection

easily occurs. CO2(g) Member pores

↔ CO2(aq) Inner solution

A glass-reference electrode pair immersed in the inner solution film detects the pH change. The total reaction of the described process is found by adding up the three chemical Eqs. CO2(aq) + 2H2 O ↔ H3 O+ +HCO3 − outer solution

Inner solution

The reaction’s equilibrium constant is represented by K,    H3 O+ HCO− 3  K=  CO2(aq) outer

(6.1)

The HCO3 − concentration in the inner solution is not significantly affected by the HCO3 − concentration that is formed by the CO2 passing through the pores from the outer solution if the initial concentration is kept very high; thus, Kg, K  Ka =  HCO3 − aq   H3 O+  Ka =  CO2(aq) outer and A1 the hydrogen ion activity in the inner solution is written.     A1 = H3 O+ = Kg CO2(aq) outer

(6.2) (6.3)

(6.4)

The potential of the electrode system in the inner solution is dependent on A1 according to Eq. (6.4). Substituting Eq. (6.4) in Nernst’s Eq., the following Eq. is derived.   E = L + 0.0592.logKg. CO2(aq) outer (6.5) or

  E = L + 0.0592.logKg. CO2(aq) outer 

L = L + 0.0592.logKg

(6.6) (6.7)

Accordingly, the potential of a cell containing an internal reference and indicator electrode is determined by the CO2 concentration in the outer solution. Here, none of the electrodes meet the sample solution; therefore, it would be more accurate to call the system a gas-sensing “cell” rather than a gas-sensing electrode. Substances that prevent measurement are other gases dissolved in the sample that can pass through the membrane and affect the pH of the inner solution. The selectivity of gas-sensitive electrodes can be increased by using an inner electrode that is sensitive to some ions other than the hydrogen ion; For example, a nitrate-sensitive electrode should be used to prepare a nitrogen dioxide-sensitive cell. Here the equilibrium reaction is as follows. 2NO2(aq) + H2 O ↔ NO2 − + NO3 − + 2H+ outer solution

Inner solution

6.4 Direct potentiometric methods

137

FIGURE 6.8 Field effect transistors and gas detection mechanism.

This electrode allows NO2 determination in the existence of gases e.g. SO2 , CO2 , and NH3 , which can raise the pH of the inner solution [33,105].

6.4.12 Electrochemical applications Kelvin probes are also devices based on work function measurement. Species that create a charge change on the electrode surface shows a physical capacitance vibration effect by changing the dielectric value. These measurements, especially made using field effect transistors, are interesting in terms of adapting to small-scale studies in analytical chemistry. FET-based gas sensors (Fig. 6.8), which are effective and have a wide range of selectivity, contain a metallic sensing surface [129]. In one of the studies, a FET sensor developed using a mixture of platinum and gold was used to detect ozone at ppb level at high temperature. [130]. In recent studies, it has been reported that sensors used at room temperature are more useful and preferred. For example, a screen-printed electrode (SPE) imprinted with barium carbonate was used as a Kelvin probe for CO2 determination [131]. Although it works at room conditions, its sensitivity to humidity besides CO2 emerges as the sides that need to be developed. It has been reported that porphyrin film was used in other FET-based studies. In these studies, the fact that the porphyrin is a single layer has shown that it is a suitable ground as a gas sensor, but it is a subject that is open to development. There are also studies to identify toluene using conductive polymer-containing FETs [132,133]. Porous and membranecontaining electrodes, where metal, electrolyte, and gas are in contact, providing direct oxidation of the gas, were used as amperometric gas sensors. In another example, peak separations of CO2 , O2 and N2 O gases could be easily seen using gold microdisk electrodes [134]. In general, the peaks obtained from the gases in the studies performed in blood gas analysis overlap. Therefore, economical electrodes such as vitreous carbon or metal electrodes with the

138

6. Electrochemical Carbon Dioxide Detection

high surface area are being developed [135]. But gold, silver or platinum electrodes possess better sensitivity and selectivity performances. Apart from this, different alternatives can be used as electrolyte medium. In a study using a gold working electrode and a solid polymer electrolyte membrane, it was reported that CO2 was determined, and alternative studies with Nafion and poly(benzimidazole) for the use of polymer electrolyte were also successfully applied [136–138] Similar electrochemical systems, in which O2 and aromatic gases are determined apart from CO2 , allowing the gasses to be determined by adsorbing them to the surface and are known as all-solid-state sensors [139]. Here the indicator stage is the desorption of gases individually according to their electrochemical desorption potentials. Clark electrode can be utilized for gas-sensing gas mixtures in this type of medium achieving minimized Faradaic currents [137]. Electronic noses are a developing area in the analytical chemistry, generally, polymer modified composite detectors are used to capture gases [140]. Aromatic gases which have different odors can be identified near to the human senses. This type of a sensor gives a better result by using modified electrodes because of combining more than one detector. In particular, chemiresistive sensors combined with quartz crystals have been reported [141]. Although these devices are for multiple determination, studies for the determination of individual gases are also continuing. Detection of nerve gases is one of them and can be detected up to 0.05–0.2 mg/m3 LOD values. Also, other chemiresistive gas-sensing semiconductive materials including SnO2 metal-oxide are reported widely Thus, changes can be made to increase the sensitivity of the measurement [142]. Especially atmospheric gases are reported in this detection method. Electrochemical determination was made with ceramic-type sensors containing Na2 SO4 and aluminum composites for the determination of CO2 in an inert atmosphere containing CO2 and O2 . In this study, it has been reported that a sensor that can be used continuously for weeks at high temperatures such as 300 to 600 °C has been developed [143]. Sometimes ionic liquids are used to support electrode structure to enhance the catalytic performance of CO2 detection. In such study, bismuth electrodes were combined with various ILs to reduce CO2 electrochemically [144]. Copper based electrodes are maintaining a significant contribution to this field and several modifications are reported to enhance catalytic CO2 reduction ability. In the same manner, the effect of the O2 on the catalytic CO2 reduction of Cu-based electrode was examined. Because of the selectivity and the hindrance effects due to the O2 affinity to Cu two main problems are studied in detail by [145]. The authors reached certain findings such as subsurface O2 presence facilitates the CO2 conversion in different ways with additional supports like intermediate binding and optimization of the adsorption way [145]. The advantage of catalytic activity obtained using noble metals creates a great disadvantage as they are not economical at the same time. For this reason, studies on the use of semi-noble metals in the field have accelerated, as in Cu. In general, metal-based catalysts used in CO2 determination and reduction are divided into types such as metals, partially oxidized metals, metal oxides, metal sulfides, frameworks, and metal-loaded carbons. In electrochemical CO2 determination and reduction studies using these metals and their derivatives, it has been observed that the final and intermediate products vary greatly according to the electrode material used, the medium, the method, and the applied potential. It has been reported that some semi-metal oxides such as Sn, Bi, and Co perform better in the composite form [146].

6.5 Summary and conclusion

139

Starting from the point of economy, the choice of electrode material mostly tends towards carbon-based materials. The use of carbon-based electrodes modified with the mentioned metals rather than metal electrodes is also preferred because of their long life. In addition, carbonbased electrodes provide high overpotential for hydrogen generation, which facilitates CO2 reduction. Metal modification can be done by physical, chemical, or electrochemical methods. While electrochemical and physical methods are economical and fast methods, the chemical method creates more stable structures. It is a disadvantage that the chemical method requires more research in multi-step and synthesis steps. In general, an electrochemical reduction is preferred for the modification of electrodes with metals, unless a simpler chemical method is available. Sometimes a combination of these methods can be used. Activation of the electrode surface is done electrochemically, and the metal modification can be physical or chemical (Table 6.4).

6.5 Summary and conclusion Keeping the CO2 cycle in balance is a very important issue for life. With the increase in the use of fossil fuels, this balance has deteriorated significantly, and its negative effects are felt at a serious level in many areas such as health, energy, air quality, global warming, and climate change. Therefore, determination and monitoring of the CO2 level, which cause substantially cost, also is quite momentous for both healthcare and organizing life [13,15] In recent years, more renewable energy technologies e.g. photovoltaics and pinwheels have been used instead of fossil fuels in transportation, energy production and industry to prevent climate change and reduce its effects. The most significant and beneficial method proposed to diminish CO2 emissions in recent years is carbon capture technology [23]. These technologies can be divided into adsorption, absorption, separation by membrane, and chemical capture [38]. However, the technologies show some disadvantages. The adsorption process as a CO2 capture technology has some limitations as it involves complex processes, low efficiency, and requires large amounts of energy to sustain the process [43]. Absorption technologies are one of the most interesting and studied technologies by researchers, but temperature change is very important as it affects the solubility of the gas in the solution. Therefore, the energy requirement during the process to control temperature changes is also quite high [46,47]. Since the particle size, pore volume, permeability, and selectivity parameters are difficult to optimize during the capture process, the membrane usage is also challenging in capturing CO2 [44–49] The most important factors limiting chemical capture technology are the stability of the chemicals used against oxidation and reduction during repeated cycles and the cost of the process [52,53]. Beyond the CCU methods, electrochemical ways are outstanding. Electrochemistry studies the electrons formed due to a chemical change [32]. In the working principle of an electrochemical gas sensor, a chemical reaction occurs between the ambient gas and the active center in the sensor which can be developed by the addition of different nanomaterial, metal, metal oxide, carbon-based materials, and so on [33]. Until now, nondispersive infrared detectors, nanomaterials which can involve organic, inorganic fragments, gas chromatography, and mass spectrometers are utilized in CO2 detection and determination or as sensor detectors. Although taking high working energy and showing a low selectivity, due to the features such as taking small space, simple generating, high stability and sensitivity

140

6. Electrochemical Carbon Dioxide Detection

TABLE 6.4 Electrochemical CO2 detection and reduction studies. Utilized material

Method

Electrolyte

Purpose

Ref.

BaTiO3 –CuO thin-film

Impedance



Detection

[147]

SnO2 thin films

Conductometry



Detection

[148]

Cu NPs on Glassy carbon plate electrode

Voltammetry

0.1 M KHCO3

Catalysis/Reduction

[149]

Zn dendrite on Zn foil

Potentiometry

0.5 M NaHCO3

Catalysis/Reduction

[150]

nano-SnO2 /graphene on GC electrode

Voltammetry

0.1 M NaHCO3

Catalysis/Reduction

[151]

Zn–BTC MOFs on carbon paper

Controlled potential electrolysis

Ionic liquid

Catalysis/Reduction

[152]

Polyethylenimine/ Nitrogen-doped carbon nanotubes on GC electrode

Controlled potential electrolysis

0.1 M KHCO3 /CO2 -saturated water

Catalysis/Reduction

[153]

Cu modified boron doped diamond electrode

Linear Sweep voltammetry

0.5 MKOH

Catalysis/Reduction

[154]

Ag NP and MWCNTs with Gas diffusion electrode

Impedance

1 MKOH

Catalysis/Reduction

[155]

Au NPs on mesoporous carbon

Controlled potential electrolysis

0.5 M KHCO3

Catalysis/Reduction

[156]

PdCu/C on carbon paper electrode

Controlled potential electrolysis

0.1 M KHCO3

Catalysis/Reduction

[157]

SnO2 /MWCNT on carbon paper

Linear Sweep Voltammetry (LSV) and Chronoamperometry (CA)

0.5 M NaHCO3

Catalysis/Reduction

[158]

NiO on MWCNT with carbon paper

Linear Sweep Voltammetry (LSV) and Chronoamperometry (CA)

0.5 M NaHCO3

Catalysis/Reduction

[159]

metal oxide gas detectors are preferable sensors for sensing and monitoring the CO2 gas as a nanomaterial-based sensor [7,15,63,64]. On the other hand, CNTs are the most popular member of carbon-based semiconductors and pure graphene, graphene oxide, and reduced graphene oxide which are derivatives of graphene are favorable nanomaterials for generating a gas sensor [13,69]. CO2 sensors are not only designed as solid-state platforms but also an electrolyte including, gas sensors, Clark type sensors, solid carbon transducers, and FET sensors that use divergent modification materials. In the recent years LCs have been strong prospective photonic structures with simple adaptable, low energy consumption for being a gas sensor. Electroanalytical methods have many advantages over other analytical methods [33,94]. Among them, the simultaneous detection of species with different oxidation levels is easy,

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141

and the equipment and software that enable the application of the methods are much cheaper and more useful than chromatographs and spectrophotometers [95]. Electrochemical sensors are generally used to detect toxic gases and oxygen, especially CO, ammonia, and chlorine. Besides CO2 detecting and reducing electrochemical sensors occupy an important place. Especially modified electrodes possess enhanced advantages on the catalytic activity obtained using noble metals. However, the electrodes show a great disadvantage as the electrodes are not economical. For this reason, studies on the use of semi-noble metals in the field have accelerated, as in Cu. In general, metal-based catalysts used in CO2 determination and reduction are divided into types such as metals, relatively oxidized metals, metal oxides, metal sulfides, frameworks, and metal-loaded carbons. In electrochemical CO2 determination and reduction studies using these metals and their derivatives, it has been observed that the final and intermediate products vary greatly according to the electrode material used, the medium, the method, and the applied potential. It has been reported that some semi-metal oxides such as Sn, Bi, and Co perform better in the composite form [144]. In conclusion, no matter which type of electrode or method is used there is no edge for the sustainable development of electroanalytical sensor devices. The selectivity, sensitivity, and detection limits can be modified as the researchers’ demands.

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[155] Ma S, Luo R, Gold JI, Yu AZ, Kim B, Kenis PJA. Carbon nanotube containing Ag catalyst layers for efficient and selective reduction of carbon dioxide. J Mater Chem A 2016;4:8573–8. https://doi.org/10.1039/c6ta00427j. [156] Miola M, Hu XM, Brandiele R, Bjerglund ET, Grønseth DK, Durante C, et al. Ligand-free gold nanoparticles supported on mesoporous carbon as electrocatalysts for CO2 reduction. J CO2 Util 2018;28:50–8. https://doi.org/10.1016/j.jcou.2018.09.009. [157] Yin Z, Gao D, Yao S, Zhao B, Cai F, Lin L, et al. Highly selective palladium-copper bimetallic electrocatalysts for the electrochemical reduction of CO2 to CO. Nano Energy 2016;27:35–43. https://doi.org/10.1016/ j.nanoen.2016.06.035. [158] Bashir S, Hossain SS, Rahman SU, Ahmed S, Al-Ahmed A, Hossain MM. Electrocatalytic reduction of carbon dioxide on SnO2/MWCNT in aqueous electrolyte solution. J CO2 Util 2016;16:346–53. https://doi.org/ 10.1016/j.jcou.2016.09.002. [159] Bashir SM, Hossain SS, ur Rahman S, Ahmed S, Hossain MM. NiO/MWCNT Catalysts for Electrochemical Reduction of CO2 . Electrocatalysis 2015;6:544–53. https://doi.org/10.1007/s12678-015-0270-1.

C H A P T E R

7 Carbon dioxide injection for enhanced oil recovery and underground storage to reduce greenhouse gas Shubham Saraf and Achinta Bera Department of Petroleum Engineering, School of Energy Technology, Pandit Deendayal Energy University, Gandhinagar, Gujarat, India

7.1 Introduction Changes in the energy balance of the Earth can lead to global warming. This is called “climate forcing.” Also, greenhouse gas emissions are increasing, which leads to climate change. The term “greenhouse effect” refers to substances that absorb and radiate infrared energy in the same wavelength range as the Earth [1]. Almost 0.1 percent of the Earth’s atmosphere is made up of greenhouse gases such as carbon dioxide (CO2 ) (0.04 percent), methane (0.012 percent), nitrous oxide (0.08 percent), and ozone (0.012 percent) [2]. Fig. 7.1 shows how these gases and the contribution of carbon dioxide emissions in the atmosphere from different countries interact. For a large percentage of carbon dioxide emissions, natural gas, oil, and coal are the primary sources, whereas other contributions come from deforestation, cement, other land-use changes, and fertilizer [3]. Greenhouse gases affect the environment and health by generating smog, trapping heat, and causing lung disease in humans from air pollution. Furthermore, food shortages, wildfires, and extreme weather are caused by greenhouse gas emissions [4]. From 1990 to 2019, the effects of greenhouse gases that humans put into the air grew by more than 40 percent [5]. Moreover, oil production around the world is decreasing, and massive oil resources are not being found quickly enough to compensate. Thus, the tertiary recovery technique must be used to maintain and develop existing oil fields worldwide. Fig. 7.2 shows how top countries’

Green Sustainable Process for Chemical and Environmental Engineering and Science: Carbon Dioxide Capture and Utilization DOI: https://doi.org/10.1016/B978-0-323-99429-3.00002-3

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c 2023 Elsevier Inc. All rights reserved. Copyright 

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7. Carbon dioxide injection for enhanced oil recovery and underground storage to reduce greenhouse gas

(A)

(B)

Worldwide Greenhouse Gases Emission by Different Gas Nitrous oxide 6%

Top CO2 Emitting Countries, 2020

Flue gases 2%

Methane 16%

India 3% Carbon Dioxide by Fossil fuel and Industria l process 65%

Carbon Dioxide by Forestry and other land use 11%

Rest of the countries 16%

United States 34%

Japan 5% United Kingdom 6% Germany 8%

China 19%

Russia 9%

FIGURE 7.1 (A) Worldwide greenhouse gas emission percentage and (B) higher rate of CO2 emitting countries in 2020 [102].

Worldwide Oil Produce, Export, and Consume (in percentage) by Different Countries in 2021 Crude oil producing 20

Crude oil exporting

Crude oil consuming

20.48 12 6.6 2.85

United State

3.19

Saudi Arabia

13.5

13.07

11 4.6 3.6

Russia

6 3.04 2.53

Canada

5

4 1.3

China

2.1 3.23

Brazil

5

4.84 2

0.5

India

1.5

Rest of the countries

FIGURE 7.2 Top countries’ oil production, exports, and consumption in 2021 [103].

oil production, exports, and consumption were distributed in 2021. Tertiary recovery techniques can increase oil recovery by 40 to 50 percent [6]. Tertiary recovery strategies are known as enhanced oil recovery (EOR) methods. Over the past ten years, nitrogen gas, natural gas, and carbon dioxide gas injections have been used as part of an enhanced oil recovery strategy to reduce miscibility pressure, improve displacement efficiency, and lessen the effects of global warming. Furthermore, re-pressurizing oil reserves using CO2 gas infusion and displacing residual oil with long-term storage has been utilized to minimize CO2 emissions [7]. With CO2 gas

7.1 Introduction

151

injection, most oil is recovered [8]. Because CO2 mixes with oil, the oil floats and becomes less dense [9]. As a result, CO2 gas injection has been one of the most effective strategies for improving oil recovery and storing greenhouse gases in geological contexts for a long time, thereby helping to mitigate the effects of global warming.

7.1.1 Global carbon management concerns Nowadays, human progress would be impossible without energy. So, improving human growth and industrial development while addressing the global climate disaster is the greatest challenge of the 21st century [10]. As industries move towards a low-carbon future, the changeover will be difficult. Therefore, the worldwide need for energy will necessitate a large amount of time and ongoing investment in alternative energy sources. In the current policy scenario, global CO2 emissions and economic development remain strongly linked [11]. Fig. 7.3 depicts how emissions will continue to rise to around 36 Gt of CO2 in 2040 as primary energy demand rises. In addition, there will be a rise in the cost of power generation without government subsidies. Government initiatives that encourage sustainable growth can reduce the global energy demand from 19 Gtoe (giga tonne oil equivalent) to 14 Gtoe in 20 years [12]. In addition, direct CO2 emissions from industry and transportation will rise by about 20 percent by 2040. As a result, carbon capture and storage (CCS) is an essential low-carbon strategic tool used to reduce CO2 emissions in order to improve oil recovery. According to Adu et al. [13], oil and gas companies tend to prefer CO2 -EOR in depleted oil and gas reservoirs as a strategy of CO2 sequestration and to enhance oil production. Furthermore, capturing,

FIGURE 7.3 Worldwide energy demands related to CO2 emissions by New Policies, Current Policies, and Sustainable Development Scenarios [11].

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transporting, and storing excess CO2 due to increased oil production can be mitigated to some extent if multiple techniques for capturing CO2 are used in CO2 -EOR operations. Therefore, CCS with CO2 -EOR supports a strategy that improves oil recovery and mitigates climate change problem [13]. CO2 has many different effects on oil production, such as the mechanisms used to inject CO2 into a depleted oil reservoir to increase production rate by oil swelling and viscosity reducing for the infusion of immiscible fluids (at low pressures) to entirely miscible displacement in high-pressure operations [14]. Furthermore, some of the CO2 injected comes with the oil and is frequently separated and re-injected back into the reservoir in order to reduce operational expenses. For instance, CO2 -based EOR projects are still ongoing in Brazil, Canada, Croatia, Hungary, Trinidad, and Turkey, and CO2 -based EOR increases the amount of oil that can be extracted from a well by an average of 13.2 percent in the United States [15]. Thus, planning and allocating CO2 are crucial in maximizing the economic benefits via EOR strategies and minimizing environmental damage through this process.

7.1.2 CO2 availability Carbon dioxide levels in Earth’s atmosphere are presently around 412 parts per million (ppm) and going up [16]. Fig. 7.4 shows the percentages of different gases present in the air on the Earth. So, many CO2 capture and storage systems have been developed. For example, Marchetti [17] mentioned many options for CO2 capture from power stations and heat exchangers and recommended storing the CO2 in the sea. In addition, Fu and Gundersen [18] stated that CO2 be separated from fuel or exhaust gas before or after combustion by using membranes, adsorption, hybrid applications, cryogenic separation, and absorption. Therefore, there are three main methods considered to capture CO2 during combustion: oxyfuel combustion, post-combustion capture, and pre-combustion capture. Firstly, post-combustion capture (PCC) traps and separates CO2 from flue gases after burning natural gas, coal, or oil in the atmosphere, but primarily charcoal [13]. A post-combustion

FIGURE 7.4 Different gases with their percentage present in the atmosphere [16].

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TABLE 7.1 Differences between CO2 capturing methods (post, pre, and oxy-fuel combustion capture) [13]. Capture methods

Strategy

Advantages

Disadvantages

Application

Post combustion

Using air to separate CO2 from exhaust gas

Technique is easily retrofittable

CO2 levels are extremely low, at less than 15 percent

Mostly coal-fired power plants

Pre-combustion

Air, steam, or oxygen can be used to separate CO2 from fuel.

CO2 range 15–60 %

Additional capturing equipment costs

Power plants IGCC

Oxy-fuel combustion

To separate CO2 , fuel is burned with pure oxygen

CO2 concentration over 80 %

Technique is costly due to its high oxygen demand

Oxygen-combusting power plant

capture method was used to absorb CO2 at the Boundary Dam CCS Project, which started operating in 2014 [19]. Secondly, pre-combustion capture extracts CO2 before combustion, and this method is typically used in integrated gasifier combined cycle (IGCC) coal power plants. Also, Blomen et al. [20] stated that pre-combustion with IGCC could make controlling pollutant emissions more efficient and less expensive. Thirdly, an oxy-fuel combustion method uses an air separation unit (ASU) to separate the oxygen flow from the gasoline channel, which is then used in a furnace to combust [13]. After combustion, flue gas contains carbon dioxide, water vapour, and extra oxygen. Then, CO2 congregation in the oxygen-blown combustion exhaust gas is about 80 percent, which simplifies CO2 separation [21]. There have been recent advancements in oxy-combustion that make it an extremely efficient solution for coal power plant CO2 capture, both in terms of customizing ancillary equipment, boilers, and ASU to existing facilities as well as its large CO2 purity of greater than 99 percent [22]. Thus, absorption systems remove CO2 from flue gases at a lower cost and require less energy than PCC. Table 7.1 summarizes the differences between post, pre, and oxy-fuel combustion capture. Finally, gas pipelines are used to transfer the captured CO2 from power plants and manufacturing plants to the sequestration location, where it will either be injected into subsurface formations or used for EOR. In addition, anthropogenic CO2 must be transported under various compositional controls to ensure its safety [23]. But transporting CO2 made by humans through pipelines might not be a big problem. In fact, CO2 pipelines can be structured and work properly within certain limits [24]. Also, pure CO2 is delivered through pipes in a supercritical gas state at a pressure of 7.38 MPa and a temperature of 31.18 ºC, well above its critical point due to the need to increase density while reducing pressure gradients and eliminating multiple flows [25]. A phase diagram of CO2 can be described in Fig. 7.5 to understand the phase behaviour of CO2 at different pressures and temperatures.

7.1.3 Options available for CO2 storage Significantly, the aim of CCS projects is the successful and long-term storage of captured and transported CO2 , in order to reduce the greenhouse effect. There are three major CO2

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7. Carbon dioxide injection for enhanced oil recovery and underground storage to reduce greenhouse gas

FIGURE 7.5 The CO2 supercritical fluid region as depicted in the temperature-pressure phase diagram [104].

FIGURE 7.6 Various methods for storing carbon dioxide [9].

storage concepts: ocean storage, mineralization, and geological storage [26]. Fig. 7.6 illustrates different types of CO2 storage methods in the underground. Firstly, geological CO2 storage sites need to be found across the territory. So, CO2 can be stored in a plethora of geological contexts, including deep coal seams, saline aquifers, and depleted oil and gas fields [27]. Mohamed et al. [28] also stated that saline aquifers had the maximum storage capacity of any

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7.1 Introduction

type of subsurface storage reservoir. Secondly, mineralization is the process of transforming CO2 from a soluble phase into a solid mineral phase through chemical reactions with minerals and natural materials [29]. For instance, the formation of carbonates as a reaction of aluminosilicate minerals can be a crucial storage process, but the time scale is in the hundreds to thousands of years [30]. Thirdly, it is possible to store CO2 in the oceans for hundreds of years by injecting CO2 into the subsurface of seawater, which then forms hydrates under the ocean’s subsurface or deep within the ocean’s layers [13]. As a result of the ocean acidification caused by the interaction between the leaked CO2 and salty water, the quality of seawater changes, and marine life is impacted [31]. Furthermore, when compared to other methods of storing energy, mineral carbonation has two key advantages: First, the amount of metal oxides in Earth’s silicate rocks exceeds the amount needed to fix all the CO2 created by fossil fuel combustion [32]. Second, there is almost no practical limit on how long CO2 can be stored [14]. However, mineral carbonation is associated with significant constraints. Thus, the huge amounts of CO2 make handling the gas difficult.

7.1.4 Comparison of available storage methods Here, several technologies have been proposed to enable and expand CO2 storage to ameliorate climate change’s effects. Table 7.2 summarises the comparison between ocean storage, mineral carbonation, and geological storage of CO2 for the long term. Theoretically, injected CO2 in a geological formation will be trapped by many mechanisms, including residual, structural/stratigraphic, mineral, and solubility. It is shown in Fig. 7.7 that TABLE 7.2 Summary of the comparison of several CO2 storage strategies [14]. CO2 Storage Methods

Methodology

Merits

Demerits

Applications

Ocean storage

Injection of captured CO2 into the deep ocean

Store more CO2 than terrestrial vegetation

Leakage of CO2 can harm marine organisms

Anthropogenic CO2 has no physical limit

Mineral Carbonation

Storage fixes CO2 as inorganic carbonate minerals

No practical limitation in storage time (Long-term storage)

Expensive and energy intensive resulting

Low temperatures systems are more favorable

Geological storage: Depleted oil and gas reservoir

Miscible and/or Immiscible CO2 -EOR method

Re-pressurize oil fields and displace residual oil

CO2 Transportation rises exploration costs

To enhance oil recovery and mitigate greenhouse gas effect

Geological storage: Deep saline aquifer

Super-critically injected CO2 as a gas or a heavy fluid

There would be an extremely low leakage rate

Process is very time consuming

Store CO2 for long-time period

Geological storage: Coal-bed methane

Injected CO2 binds to the coal

Sequestered CO2 permanently



Extract methane gas

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7. Carbon dioxide injection for enhanced oil recovery and underground storage to reduce greenhouse gas

FIGURE 7.7 The level of CO2 storage security over time by various CO2 trapping methods [9].

CO2 storage security is increasing with time due to different CO2 trapping techniques. Firstly, the structural/stratigraphic trapping mechanism refers to the capture of supercritical CO2 beneath low-permeability cap-rock [33]. Depending on the rock type, this trapping technique may take 20–40 years. Secondly, the relative permeability and capillary force impacts of residual trapping also play a significant role in the transition of the CO2 injected into an immobile state [29]. In addition, depending on the type of rock, this sequestration mechanism might not take action for hundreds of years after the injection. Thirdly, solubility trapping occurs when CO2 dissolves in brine and sinks to the formation’s bottom over time, enhancing the security of the CO2 trap [34]. Finally, mineral trapping is the process of converting CO2 into a solid mineral component through chemical processes that take place in the production of minerals and organic matter [30]. However, CO2 -EOR could be used to store CO2 underground in depleted oil reservoirs as residual trapping, which can increase oil production too.

7.2 Oil recovery using CO2 CO2 injection for oil recovery can be a miscible or immiscible displacement process. Kamali et al. [35] determined that CO2 -EOR is one of the most effective EOR technologies because of the chemical and physical properties of CO2 , the CO2 oil system, and technological progress. The viscosity, density, and interfacial tension of oil in a reservoir can be lowered by adding CO2 . Also, CO2 injection makes heavy to medium hydrocarbon oil more viscous. In conditions

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157

FIGURE 7.8 Continuous injection of CO2 during the CO2 -EOR procedure.

of miscibility, the manifestation of these effects is more prominent than in conditions of immiscibility [36]. Furthermore, single-phase flow occurs at pressures between the minimal miscibility pressures (MMP) and fracture pressures. So, when the pressure in the reservoir is below MMP, immiscible flooding is used [37]. It is also important to mention that Moghanloo et al. [38] conducted experiment on CCS for reducing CO2 emissions and continuous injection of CO2 -EOR for improving oil recovery and reducing carbon footprints as shown in Fig. 7.8. Different computational and experimental techniques exist for determining the MMP. Many laboratory experiments use one of these three methods: the rising bubble strategy, the slim tube test, or the vanishing interfacial tension technique [39]. In addition, according to Ekundayo and Ghedan [40], the slim tube test is the most effective method for determining MMP because it models the 1-D displacement of reserve crude oil by CO2 injection, ultimately accounting for thermodynamic processes in the CO2 -oil system within a slim tube coil. Furthermore, the literature recommends long coil lengths and slow injection rates to standardized slim tube studies by avoiding component fluctuations, fingering, and ensuring a constant thermodynamic front [41]. Fig. 7.9 shows an MMP measurement apparatus utilizing slim tubing. The coil in that setup is 60 to 80 ft long since the researchers suggested using a coil with a length greater than 40 ft to obtain a consistent displacement [42]. Consequently, it takes at least five weeks to determine MMP using the slim tubing approach when the recovery factor is obtained at just four different pressures [43]. A lower rate of CO2 injection is used to displace the oil when the pressure and temperature have been stabilized in the system. To estimate the recovery factor, discharges are monitored throughout the experiment. For each pressure, two zones are recognized: the “immiscible” region (where recovery variables are strongly dependent on pressure) and the “miscible” region (where recovery factors are less dependent on pressure) [43]. Fig. 7.10 depicts the MMP as the junction of these two regions.

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7. Carbon dioxide injection for enhanced oil recovery and underground storage to reduce greenhouse gas

FIGURE 7.9 Schematic of the MMP measurement equipment setup utilizing a slim tube [42].

FIGURE 7.10 A plot for determination of MMP at various pressures using a 60 ft coil [43].

Several CO2 -EOR systems, namely CO2 water alternating gas (WAG), continuous CO2 flooding, and huff-and-puff, have been implemented and developed [44]. In Table 7.3, a comparison and contrast of the benefits and drawbacks of different methods to inject CO2 into hydrocarbon reservoirs is depicted. However, continuous CO2 flooding has disadvantages such as early breakthrough due to viscous fingering effects, gravity override, and poor volumetric sweep efficiency, although field cases demonstrate its efficacy [45]. In addition,

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7.2 Oil recovery using CO2

TABLE 7.3 Positives and negatives sides of a variety of CO2 injection methods [107]. Method

Methodology

Advantages

Disadvantages

Continuous gaseous CO2 injection

It is applied on a large scale to displace residual oil in a reservoir with continuous CO2 injection.

It is possible to get a larger oil displacement ratio with this technology than the other CO2 injection methods.

Gravitational separation and a considerable decrease in sweep efficiency are possible.

Injection wells with CO2 in a sequence

Low-permeability, heterogeneous reservoirs may be developed through the cyclic injection of CO2 .

Increased oil displacement by CO2 and reservoir sweep, and reduce gas breakthrough in producing wells may be possible.

This method is inefficient, expensive, and impractical.

Injecting CO2 and water alternately

Better CO2 -EOR efficiency can be obtained by injecting the appropriate amount in small portions, alternatively or concurrently with water.

It is an efficient method for increasing oil recovery with limited permeability.

Injection rates are limited in some reservoirs due to low permeability and inadequate pore-space connectivity.

Injection of CO2 -foam

These approaches employ foams to control the movement of CO2 .

Foam displaces oil in a better way than the water-flooding or CO2 injection.

CO2 -foam technique is time-consuming.

continuous CO2 flooding in several field applications requires considerable capital and operational expenses [46]. Furthermore, it is possible to significantly enhance the production of oil and extraction from some reservoirs using CO2 -EOR. Also, there are financial benefits to using CO2 -EOR, such as the minimal cost of CO2 , and the fact that it makes good-quality oil that can be supplied and recycled [47]. However, CO2 -EOR has been used for a long time in the United States [48]. Since the 1980s, it is the only oil recovery method that has grown. It is estimated that 50 Mt per annum of CO2 is being used for oil recovery in North America, which accounts for more than 5 percent of the country’s oil production [49]. Fig. 7.11 shows how much of the current demand for CO2 is required by different ways of extracting energy. In addition, oilfields may be extended for decades, and millions of barrels of oil can be recovered with the CO2 -EOR method. Oil extraction from these reservoirs can also be improved by 4–15 percent, which means a small percentage of the trapped oil may be recovered using CO2 -EOR techniques, while a larger portion cannot be recovered at all. Even then, developers are still interested in the CO2 -EOR [50]. Hydrocarbon industries have generated substantial economic returns due to the huge majority of EOR projects depending on low-cost CO2 sources. Fig. 7.12 shows how CO2 -EOR advancements have increased oil recovery around all the reservoirs. Approximately 50 percent of the CO2 injected into the reservoir can be retained at the CO2 breakthrough if reinjection is not considered [51]. However, EOR and the storage of expensive anthropogenic CO2 are constrained economically, despite the widespread recognition that there are no significant technical difficulties.

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7. Carbon dioxide injection for enhanced oil recovery and underground storage to reduce greenhouse gas

FIGURE 7.11 The percentage of current CO2 demand in the different applications [49].

Different EOR Methods for Oil Recovery 60.00%

15.00%

CO2 Miscible

CO2 Immiscible

12.00%

Steam

8.00%

5.00%

HCCombustion Immiscible

3.00%

Micellar

FIGURE 7.12 Performances of most efficient CO2 -EOR approaches for oil production [105].

7.2.1 Hydrocarbon miscibility The extraction of crude oil from a rock’s pores by a solvent action that prevents the creation of interfaces between the driven and driving fluids is known as miscible displacement [52]. Thus, to establish whether a displacement process is miscible flooding or not under reservoir circumstances, the MMP, which determines the lowest pressure at which a miscible phase may be generated, is an essential quantity [53]. An empirical calculation is preferable to the time-consuming and complex laboratory measurement of MMP for engineering design of CO2 flooding, particularly during the feasibility study phase. Furthermore, first-contact miscibility operations at reservoir pressures greater than the MMP are required to produce oil through CO2 miscibility. It is possible to achieve multiple contact miscibility by freezing and vaporising gas drive mechanisms when infused fluid and reserve oil come into contact at a relatively greater reservoir pressure than MMP [54]. But injecting CO2 at a high pressure above the fracture pressure of the reservoir will cause fractures, so this cannot be done forever [37].

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161

Moreover, miscibility in petroleum reservoirs is the physical condition of two or more fluids that allows them to mix in any proportion without forming an interface [52]. For example, if two fluid phases occur after adding a little amount of one fluid to another, the fluids are deemed immiscible [55]. Thus, there are two ways to obtain miscibility during CO2 flooding: the first-contact approach and the frequent contact method. The circumstances of first and multiple contact miscibility at a given pressure are determined by the temperature of the infused gas and oil [56]. But because of the limits on injection pressure, it is hard to get CO2 and reservoir oil to mix on first contact. Instead, multiple contact miscibility processes are common in the field [37].

7.2.2 CO2 miscible injection method Miscible CO2 -EOR is the most common type of gas injection-based EOR method. In addition, injected CO2 and reservoir oil combine in any proportion to form a single-phase [57]. The injection must be done at a high pressure to ensure that the injected gas is compatible with the reservoir crude oil. MMP refers to the pressure at which miscibility occurs [58]. MMP is a critical element during miscible CO2 flooding since displacement efficiency is heavily reliant on it. Hence, a process known as multiple-contact or dynamic miscibility is used when reservoir pressure exceeds the MMP, causing intermediate and larger molecular weight asphaltenes in the reservoir oil to vaporise into CO2 (the vaporised gas-drive method) and some of the injected CO2 to volatilise into the oil (the condensed gas-drive technique) [59]. This movement of molecules between oil and CO2 helps to create an oil-and-CO2 -miscible transition zone [60] by making it possible for the two phases to mix without a boundary. Moreover, when miscible solvents are mixed with reserve oil in full proportions, the combination remains in one phase. While multiple contacts are made, the amount of oil that can be recovered is significantly increased [61]. So, inserting CO2 into the oil in the reservoir causes the intermediate-molecular-weight petroleum to evaporate in place, which makes the oil dynamically miscible [62]. Holm [63] noted that dynamic miscibility can be achieved by condensing hydrocarbons of moderate molecular weight from a thick solvent into a thin reservoir of oil. Therefore, CO2 injection can be miscible or immiscible with oil, depending on the composition, pressure, and temperature of the reservoir. Since miscible and immiscible CO2 -EOR methods are used in advanced CO2 -EOR utilization, the two methods are shown in Table 7.4 [64]. Furthermore, a high-pressure core flooding device is utilized to conduct CO2 -EOR flood experiments at the laboratory, which is schematically depicted in Fig. 7.13. A continuous flow pump is operated to inject brine, crude oil, and CO2 via a core plug contained within a high-pressure core holder. In addition, a syringe pump is applied to maintain a pressure of 2–3 MPa greater than the infusion pressure on the core plug [110]. The components listed above have been warmed in an air bath. The temperature of the air bath is maintained at the reservoir temperature by way of a temperature controller. A backpressure regulator is deployed during the core flooding test to set the appropriate production pressure. The volume of produced oil is measured using a measuring cylinder, and the volume of generated gas is measured with a gas flow meter. During each test, low-rate CO2 is injected to move the crude oil at a specific reservoir temperature and insertion pressure [9]. The injection and production pressures are continually observed and recorded during the experiment. It is possible to evaluate and record

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7. Carbon dioxide injection for enhanced oil recovery and underground storage to reduce greenhouse gas

TABLE 7.4 Comparison between miscible and immiscible CO2 -EOR technique [64]. Miscible flooding

Immiscible flooding

It is applicable in deep reservoirs with heavy oil and a pressure greater than the MMP for mixing of oil and CO2 .

In this method, oil and CO2 are not mixed (shallow reservoirs with heavy oil or low reservoir pressure).

In presence of CO2 , oil condenses into a single liquid phase.

It is related to the partial dissolution of CO2 in petroleum.

It can utilize the water-injection infrastructure.

After long-term CO2 injection, oil output rises.

It is a high economically efficient process.

It is not an economically feasible process in some cases.

This method can be used on a small reservoir.

This method is only used on large reservoirs (part of the reservoir).

FIGURE 7.13 The schematic of core flooding apparatus demonstrating the high-pressure CO2 injection process [9].

the total volume of oil and gas generated using a camera and a gas flow meter. Each core flooding test collects the oil and gas generated, and gas chromatography is used to look at the oil and gas components. The determined oil recovery factor (ORF) in the core flooding test at various injection pressures and reservoir temperatures is shown in Fig. 7.14 as a function of injected CO2 vol [110]. When high concentrations of CO2 are added, the ORF increases until no further oil can be

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7.2 Oil recovery using CO2

FIGURE 7.14 Effects of CO2 injection

Oil recovery factor (%)

100

pressure on oil recovery factor [110].

80 60 Injection Pressure 13.5 Mpa

40

Injection Pressure 16.2 Mpa 20 0

Injection Pressure 19.5 Mpa Injection Pressure 22.1 Mpa 0

0.5

1 PV of injected CO2

1.5

2

extracted. In the early stages of the operation, the ORF of lower infusion pressure is higher than that of high pump pressure. Due to the reduced solubility, a smaller fraction of the inserted CO2 is absorbed into the light crude oil at a lower injection pressure, and a moderate fraction of the injected CO2 plays a key role in dispersing the crude oil [110]. Then, since CO2 and crude oil have a higher interaction as injection pressure rises, the eventual ORF at medium pore volume increased. Additionally, the interfacial tension between the oil and gas-phase disappears as miscibility occurs between the injected CO2 and residual oil [58]. As a result, the mixture is pushed as a single-phase from porous rock to oil wells. When using miscible displacement, efficiency is increased, and IFT is reduced, while residual oil saturation is reduced and overall production is increased [58]. But the only problem with the miscible displacement method is that it costs a lot to run.

7.2.3 Injection and storage facilities required Surface facilities at the infusion site include storage capabilities, a distribution manifold at the end of the transportation pipeline, transmission pipelines to wellheads, further compression facilities, monitoring and control systems, and insertion wells [65]. So, CCS and CO2 -EOR projects require significant investments in infrastructure. For financial reasons, it is important to have a reliable, continuous source of CO2 . Therefore, depleted oil and gas reserves offer a potential location for the storage of carbon dioxide [66]. Due to phase-behaviour difficulties, low reservoir pressure will pose a considerable obstacle for CO2 injection. This tendency will make CO2 injection settings much more difficult to change at the beginning [66]. 7.2.3.1 Onshore facilities The facilities needed for onshore CO2 -EOR are almost the same as those required for water-flooding. These are also essential for developing the systems for CO2 -EOR operations, including gas-phase gathering pipelines, CO2 meters, and distribution systems [67]. However, there are three critical differences between the two procedures. These are [68]:-

r An innovation in producing wells has made CO2 separator gas more abundant, making the extraction of CO2 gas easier.

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FIGURE 7.15 Progression of onshore CO2 -EOR facilities [106].

r Once CO2 has been taken out of the separator gas and dried out before being compressed, it must be processed for infused uses.

r As a result of compression, CO2 is given a higher injection pressure. Also, onshore CO2 -EOR facilities should plan to add flue gas CO2 restoration facilities, a CO2 contraction unit, CO2 pipelines, CO2 insertion wells, and a facility for separating CO2 from associated gas [68]. Fig. 7.15 illustrates the development of CO2 -EOR onshore facilities. 7.2.3.2 Offshore facilities The offshore facility upgrade and modification activities required for CO2 -EOR do not differ much from onshore designs. Because of the increase in reservoir pressure, the initial CO2 capture pressure of about seventy to eighty bars will not be enough to keep the required injection rate steady [66]. Pumps are needed for higher discharge pressures from the trunk line to be transferred to an injection facility [66]. Fig. 7.16 depicts the development of CO2 EOR offshore facilities. During the CO2 -EOR method, the current crude launcher, which was created to deliver crude from an offshore platform to the oil terminal, will be transformed into a water injection receiver [69]. The mixer obtained from the onshore plant will be injected straight into the platform’s water injection facilities through coarse filters. The objective is to collect pipeline-produced suspended particles larger than eighty microns [69]. Furthermore, it may be necessary to use an offshore pressure enhancer in cases where the onshore compressed air station’s pressure drops too early to allow direct injection into the reservoir [70]. Therefore, the pressure discharge of an offshore pumping system must be greater than the bubble point in order to avoid serious damage and cavitations [71].

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7.2 Oil recovery using CO2

FIGURE 7.16 CO2 -EOR offshore facilities development [69].

7.2.4 Storage capacity calculations In a CO2 -EOR project, the CO2 storage potential is linked to the planned incremental oil recovery. According to the initial assumption, the potential amount of CO2 that can be stored in oil reservoirs is equal to the volume of the generated oil and water. Therefore, more precise estimations can be made by using accurate mathematical reservoir simulations, which can correspond to the gravity segregation, impacts of water intrusion, reservoir heterogeneity, and CO2 dissolving in the formation water during the simulation process [72]. Then, to figure out how much CO2 is trapped in the reservoir, researchers need the following content composition (mole): Inj

produced

brine residual + Mmobile + Mmineral + MCO2 MCO2 = Moil CO2 + MCO2 + MCO2 CO2 CO2

(7.1)

residual is where, Moil CO2 represents the proportion of CO2 that has been dissolved in oil, MCO2 brine the volume of CO2 stored due to hysteresis in relative conductivity, MCO2 defined as the quantity of CO2 that’s been dissolved in brine, Mmobile refers to the quantity of CO2 that has CO2 produced

relates to the quantity of CO2 also been fundamentally trapped in the subsurface, MCO2 generated, Mmineral applies to the amounts of CO stored as a result of crystalline admixture, 2 CO2 Inj

brine and MCO2 refers to the quantity of CO2 injected [73]. Moil CO2 and MCO2 can be transported from the simulator specifically, but Mresidual and Mmobile should be measured based on residual gas CO2 CO2

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7. Carbon dioxide injection for enhanced oil recovery and underground storage to reduce greenhouse gas

saturation due to hysteresis on each grid block as follows: n   = Vmg (i)∗ fCO2 (i)∗ Sg (i) − Sgr (i) ∗PV (i) Mmobile CO2 i=1  n Mresidual = VmCO2 (i)∗ fCO2 (i)∗ SCO2 ,r (i)∗PV (i) CO2 i=1

(7.2) (7.3)

In this case, fCO2 the CO2 mole fraction, Vm ,g denotes the gas-phase molar mass, Sg the gas saturation, PV the net porous volume, Sgr the residual gas saturation, and n the total number of grid frames. In the short term, Mmineral is insignificant [74,75]. CO2 Recently, only light oil and gas fields are considered for CO2 storage in research study. The following sources can be used to estimate a gas field’s CO2 storage capacity [76,77]: mCO2 = ρCO2 × OGIP × Bg × R

(7.4)

where, mCO2 is the mass of the CO2 stored in kg; ρCO2 is the CO2 density at reservoir conditions in kg/m3 ; OGIP is the original gas-in place at standard conditions in m3 ; Bg is the gas formation volume factor in fraction; R is the primary recovery factor in percentage. If a gas field includes gas condensate, the remaining condensate in the reservoir after primary depletion can be recovered by means of CO2 – enhanced gas recovery [78]. By adding an extra CO2 – enhanced gas recovery factor, it can be estimated how much CO2 can be stored (Asia Pacific Economic [79]): mCO2 = ρCO2 × OGIP × Bg × (R + RCO2 )

(7.5)

where, RCO2 is the additional recovery factor by CO2 – enhanced gas recovery. Using CO2 EOR on a light oil field is appropriate if the oil has gravity greater than or equal to API 27 [51]. After secondary recovery and more recovery with CO2 -EOR, a recovery factor can be used to estimate the CO2 storage capacity (Asia Pacific Economic [79]): mCO2 = ρCO2 × OOIP × Bo × (R + RCO2 )

(7.6)

where, OOIP is the initial oil-in-place at standard conditions in m3 ; Bo is the oil formation volume factor in rm3 /Sm3 , R is the recovery factor after secondary recovery and RCO2 is the recovery factor for CO2 -EOR. The following Eq. (Asia Pacific Economic [79]) can be used to predict CO2 storage in saline aquifers: mCO2 = ρCO2 × A × h × ∅ × E

(7.7)

where, A is the aquifer size in m2 , h is the net sand thickness in m, ∅ is the formation porosity of in percent, E is the CO2 storage efficiency factor in percent. In order to connect one or more CO2 sources to the closest CO2 sink, researchers execute a source sink mapping effort [80]. For example, long-term CO2 storage capacities in different sites in India are summarised in Table 7.5, which shows the differences between various efficiency parameters.

7.2.5 Impact on economics and tax incentives CO2 capture, transportation, and storage in conjunction with EOR are frequently regarded as a promising technique to ensure cost-effective avoidance of CO2 emissions into the atmosphere [81]. The fact that a reservoir is geologically suitable for CO2 -EOR does not mean that CO2 -EOR will be cost-effective. Generally, the cost of crude, the store tax credit, and

167

7.3 Underground storage of CO2 in unconventional reservoirs

TABLE 7.5 Capacities of CO2 storage in various Indian reservoir fields. CO2 Storage Capacity (Mt) Reservoir Type

Low

Mid

High

Percent (%)

Reference

Ocean

105,226

412,650

1,134,788

99.15

[108]

Depleted Gas Field

1696

1850

1995

0.44

[109]

Depleted Oil Field

1425

1702

1969

0.41

[80]

Total

108,347

416,202

1,138,752

100.00

the price of CO2 are three external factors that affect the cost of a CO2 -EOR operation [82]. However, the most expensive part of an EOR project is the purchase cost of CO2 . In addition, an EOR oil barrel’s production costs can be increased by up to 25–50 percent just by the upfront expenditures of supplying, injecting, and recycling CO2 [48]. Because of the recycling of CO2 , oil exploring industries plan the EOR project in such a way that the most CO2 can be used and the least amount of CO2 is purchased again. Also, achieving economic goals in CO2 EOR reservoirs requires a cutting-edge, more significant CO2 -EOR strategy as well as tax or other government subsidies for storing greenhouse gases [83]. Thus, it has been shown that the utilization of the CO2 displacement mechanism impacts the oil production rate, the CO2 consumption percentage, and the CO2 recycling rate [84]. In general, long-term CO2 storage has not been considered while designing CO2 -EOR activities. A CO2 -EOR site must also go through additional storage-focused activities, known as monitoring programs, before, during, and after CO2 injection to demonstrate and ensure that 99 percent of the CO2 is stored for an extended period of time [85]. As a result, the Intergovernmental Panel on Climate Change (IPCC) desires a well-selected site capable of storing 99 percent of CO2 in a reservoir for a thousand years [86]. However, CO2 -EOR regulatory authorities may not run or allow injection sites to reduce greenhouse gas emissions [87]. This is because monitoring programs add costs to CO2 -EOR operators that, if not offset by compensatory measures, will affect the economics of the project [88].

7.3 Underground storage of CO2 in unconventional reservoirs Conventional reservoirs can be found in separate basins for CO2 storage. Consequently, the hydrocarbons can be easily extracted using conventional exploration methods using vertical or horizontal wells [68]. But there are two types of oil or gas reservoirs: those that require unconventional methods of recovery and those that require conventional methods of recovery [89]. The primary reasons for the increased interest in unconventional reservoirs are the decline of conventional sources of energy and rising energy demand. Unconventional reservoirs for CO2 storage are depicted in Fig. 7.17. Gas and oil shales, tight-gas sands, heavy oil, coalbed methane, gas-hydrate, and tar sands deposits are some of the most anticipated reservoirs [68]. These reservoirs frequently demand complex recovery strategies, such as stimulation or thermal recovery techniques, as well as specialised process facilities. Pilcher et al. [90] stated that these methods need to be technically and, more importantly, financially possible.

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7. Carbon dioxide injection for enhanced oil recovery and underground storage to reduce greenhouse gas

FIGURE 7.17 Some of the most common unconventional reservoirs.

Shale deposits can be discovered all over the world, and traditional assets can be easily obtained. However, the vast change in recent years by operators toward producing unconventional reservoirs has left many such formations available for CO2 sequestration [91]. So, the extremely low permeability of shale reservoirs may appear to be a deficiency, but shale fracture surfaces can absorb a substantial quantity of CO2 . Therefore, shale reservoirs with natural and hydraulic fracture networks are ideal for CO2 storage [92]. Furthermore, some of the greatest oil reserves in the world are found in heavy oil fields. Large oil deposits can be found in more than thirty countries around the world. These deposits have the same amount of oil as the Middle East’s greatest conventional oil reserves, but few of them have been fully developed [68]. Thus, there is a problem with the heavy oil reservoir’s asphaltenic crude precipitation [93]. Due to the big difference in viscosity between heavy oil and CO2 , heavy oil is hard to get out of the reservoirs. Moreover, in these unconventional reservoirs, oil and gas extraction and CO2 sequestration entail a hierarchical network of sophisticated movement and transport of nano-pores, cracks, and micro-fractures. Some of the mechanisms employed include the creation and degradation of hydrates; adsorption and absorption in shale and coal seams; thermal cracking of shale oil; CO2 replacement; and other methods. The following are some of the possible approaches, but these are not comprehensive [94]:

r CO2 can be stored underground in a way that makes it easier to get oil and gas, move gas and liquid, and move through porous media.

7.4 Current status, challenges and future directions

r r r r

169

Gas absorption and desorption in shale gas and coal-bed methane reservoirs. CO2 helps to recover gases from gas hydrates, shale gas, and coal-bed methane. Unconventional oil/gas and CO2 geological storage micro-fluidic technology. Geothermal CO2 Storage

7.4 Current status, challenges and future directions Economically, CO2 -EOR is attractive, but there is disagreement about how much CO2 it reduces because CO2 is released back into the environment when oil products are burned. As a result, calculating the ultimate total feasible storage of CO2 is crucial in order to thoroughly analyze the carbon storage potential of CO2 -EOR [84]. CO2 emitters from various sources can be found, as well as oil reservoirs large enough to store the CO2 produced by these emitters [95]. Additionally, it is a simple way for the general public to learn about the benefits of CO2 -EOR. After that, CO2 -EOR will rise in popularity and gain support from the general population. However, the current status of CO2 -EOR and carbon storage in India can be stated as follows [96]:

r The National Program on Carbon Sequestration (NPCS) Research was created by the Department of Science and Technology (DST) in 2007.

r At Ankleshwar, a depleted oil and gas reservoir, ONGC Ltd has been working to establish a pilot prototype EOR project using CO2 (40 MMSCMD of sour gas per day) from the Hazira gas production site. This CO2 would be recompressed and injected to increase crude oil recovery. r A combined funding scheme for Indian-Norwegian climate research projects, including CCS, has been launched by the DST and the Research Council of Norway (RCN). According to the Agreement on Scientific and Technological Cooperation between the governments of India and Norway, this program is being carried out. To implement CCS, three challenging steps must be accomplished: first, CO2 must be captured from large air pollutants like power plants; second, it must be transported to a storage place; and third, it must be injected into the storage unit, which is frequently a deep geological context [9]. When it comes to CCS systems, there is no unique way to distinguish them from each other [97]. Fig. 7.18 depicts the global capacity and state of CCS in 2020 (Global CCS Institute, 2021). Worldwide, more than a hundred and thirty-five large-scale CCS facilities are currently under construction [98]. These projects can be different types as follows:

r There are currently 27 CCS projects in operation, with an annual capture capacity of 36.6 Mt CO2 , or less than 1 percent of the 5.4 Gt CO2 expected in 2050.

r 4 are still in the planning stages. r 58 projects are in significant progress with a specific front-end structural engineering approach in place (in contrast to only 13 in 2020).

r Early stages of 44 projects are under consideration (compared to 21 in 2020). r Two CCS project initiatives have been put on hold.

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7. Carbon dioxide injection for enhanced oil recovery and underground storage to reduce greenhouse gas

CCS Capacity (Mtpa)

100.00 80.00

Operational

60.00 Planned 40.00 20.00 0.00

FIGURE 7.18 Capacity and status of CCS around the world in 2020 (Global CCS Institute, 2021).

The important criteria considered in technical consideration are usually the residual oil in place, MMP, reservoir depth, formation dip angle, and oil API gravity [99]. However, with offshore areas, additional aspects must be considered. Firstly, if the CO2 source is not close to the field, the best thing is to do the separation of CO2 from the flue gas. When there is a lot of CO2 , it is required to find a suitable place and a way to process the gas [100]. This is due to the fact that CO2 turns the water in the formation into an acidic state as it is injected, which, in turn, leads to the corrosion of coastal equipment. Therefore, facilities must be compatible with acid that may be generated if CO2 -WAG procedures are used in the fields to prevent corrosion in the facilities [101]. Moreover, there will be a need to improve reservoir simulations and modelling studies in the future to develop new strategies for exploration. There is still much work to be done to properly understand such interactions and their impact on the storage reservoir’s quality [95]. Efforts should be made to create new CO2 flooding methods. Mineral dissolution should be addressed as a future CO2 emission control strategy. More research is being conducted to make CO2 monitoring and leakage detection sensors and technologies that are quick, accurate, and extremely sensitive [100]. Finally, optimization studies integrating mathematical simulation, modelling, and programming are needed.

7.5 Conclusions During the first few years of operation, CO2 -EOR has the potential to decarbonize. The timing of the lowering in EOR carbon intensity is an important consideration, given the urgency with which global warming must be halted. Therefore, CO2 -EOR is the only economically established emission utilization option that provides large-scale continuous preservation for captured CO2 . Still, CCS has been the only technique that can decarbonize industries like

7.5 Conclusions

171

metallurgy, cement, and petroleum products. As a result, the summary and conclusions of the current study include a few of the most important points:

r CO2 flooding is more interesting than water flooding, and huff-and-puff supplies N2. As

r r

r

r

r

r

r

r

discovered by the EOR strategy, the only other liquid that may mix with oil is CO2 (a 90 percent mole part with CO2 in the oil stage is possible). As a result, the solubility of CO2 in oil increases and the oil viscosity is reduced. Using CO2 -reinjected petroleum framework MMP data, an optimized CO2 -EOR structure MMP relationship was found to improve the sweep efficiency and CO2 use of the MMP, which is a key part of miscible flooding. For CO2 -EOR projects, the difference between the MMP values produced using the fast slim tube approach and the standard method proved insignificant. An effective mixing region in the movement of light crude oil with CO2 can be accommodated in a 40 ft coil when the displacement velocity is modest enough for transverse dispersion to eliminate viscous fingering. After careful assessment of exploratory tests and prototype simulations, the gas injection method was found to be more practical than water flooding. A CO2 miscible flood must be done with the computational model to validate and store CO2 in an appropriate study of oilfield test parameters such as oil viscosity, depth, reservoir porosity and permeability, API gravity, oil saturation, and gross pay thickness. The results suggest that CO2 injection is the best acceptable EOR approach for 75 percent of the reservoirs examined (60 percent as miscible and 15 percent as immiscible). Based on the MMP requirements, it is also suggested that CO2 injection can be used to increase oil recovery from hydrocarbon reserves by 15 percent after secondary recovery. CO2 -EOR processes with increased injection pressure usually show a greater dependence on the CO2 extraction factor. As a result, CO2 retrieved and extracted more light components, but more heavy components, including asphaltene, were left in the reservoir rock. In addition, the CO2 miscible flooding phase of the asphaltene precipitation in the reservoir rock creates a significant problem. Optimizing the CO2 recycling system can reduce project CAPEX and OPEX by minimizing the need for conversion of surface facilities as well as investing in CO2 -EOR for residual oil zones. It has been found that CO2 -EOR could be used to get a lot more oil out of the remaining oil zones below the oil and water contacts in oil reservoirs. The miscibility impact of CO2 over all other gaseous injections makes CO2 infusion the best for oil and gas production. While gas reinjection can enhance the reservoir’s storage capacity by around 60 percent, it is possible to store CO2 in the reservoir at a CO2 breakthrough. Consequently, India has 420 Gt of CO2 storage capacity in 6 large gas sources, 37 significant oil fields, and saline aquifers in 22 geological formations. Also, CO2 from the electricity and industrial sectors could be stored in these reservoirs for more than 200 years. Finally, one of the most essential strategies for slowing or halting the effects of climate change is the use of carbon capture and storage (CCS). As a result, the CCS chain needs to build an extensive network of pipes with lower transport costs as the amount carried increases. It also needs to expand CCS projects, reduce the energy cost of capturing CO2 from power plants, and do many other things.

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7. Carbon dioxide injection for enhanced oil recovery and underground storage to reduce greenhouse gas

Acknowledgment The authors would like to acknowledge Shell Energy India Private Limited, Hazira, Gujarat for funding the project related to CO2 -EOR and underground storage in the Indian context under the theme of CO2 capture, utilization, and storage (CCUS) and the School of Energy Technology, Pandit Deendayal Energy University, Gandhinagar, Gujarat, India for providing the required facilities to conduct the project.

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C H A P T E R

8 Ionic liquids as potential materials for carbon dioxide capture and utilization Md Abu Shahyn Islam a, Mohd Arham Khan a, Nimra Shakeel b, Mohd Imran Ahamed b and Naushad Anwar b a

Interdisciplinary Nanotechnology Centre, ZHCET, Aligarh Muslim University, Aligarh, UP, India b Department of Chemistry, Faculty of Science, Aligarh Muslim University, Aligarh, UP, India

List of Abbreviations ILs [EMIM][BF4 ] [BMIM][BF4 ] CO2 [HMIM][NTf2 ] [BMIM][PF6 ] [EMIM][NTf2 ] [OMIM][PF6 ] [HMIM][PF6 ] [OMIM][BF4 ] [N-BuPy][BF4 ] [BMIM][NO3 ] [EMIM][EtSO4 ] [EMIM][Ac] [BMIM][DCA] [C4 mim] [CF3 CF2 CF2 CF2 SO3 ] GO SILM [P6,6,6,14] [CoCl4 ] [P6,6,6,14][FeCl4 ] [P6,6,6,14][MnCl4 ]

Ionic liquids 1-ethyl-3-methylimidazolium tetrafluorobarate 1–butyl–3-methylimidazolium tetrafluorobarate Carbon dioxide 1-hexyl-3-methyl imidazolium bis(trifluoromethylsulfonyl)imide 1–butyl–3-methyl imidazolium hexafluorophosphate 1-ethyl-3-methyl imidazolium bis(trifluoromethylsulfonyl)imide 1-octyl-3-methyl imidazolium hexafluorophosphate 1-hexyl-3-methyl imidazolium hexafluorophosphate 1-octyl-3-methyl imidazolium tetrafluorobarate N-butylpyridinium tetrafluorobarate 1–butyl–3-methyl imidazolium nitrate 1-ethyl-3-methyl imidazolium ethylsulfate 1-ethyl-3-methyl imidazolium acetate 1–butyl–3-methyl imidazolium dicynamide 1-n–butyl–3-methylimidazoliumnonafluorobutylsulfonate Graphene oxide Supported ionic liquid membrane Phosphonium tetrachlorocobalt Phosphonium tetrachloroferrate Phosphoniumtetrachloromanganese

Green Sustainable Process for Chemical and Environmental Engineering and Science: Carbon Dioxide Capture and Utilization DOI: https://doi.org/10.1016/B978-0-323-99429-3.00004-7

177

c 2023 Elsevier Inc. All rights reserved. Copyright 

178 [P6,6,6,14] [GdCl6 ] [P6,6,6,14][NTf2 ] [N2224][CH3 COO] [N1111][Gly] [N2222][Gly] [N1111][Lys] [N2222][Lys] [N4444] [Gly] [N1111][Gly] [aN111][Gly] PAMPS

8. Ionic liquids as potential materials for carbon dioxide capture and utilization

Phosphonium hexachlorogadolinium Phosphonium Triethylbutylammonium acetate Tetramethylammonium glycinate Tetraethylammonium glycinate Tetramethylammoniumlysinate Tetraethylammonium lysinate Tetrabutylammonium glycinate Tetramethylammonium glycinate 1,1,1-trimethylhydrazinium glycinate Poly(2-acrylamido-2-methyl-1-propanesulfonic acid)

8.1 Introduction Ionic liquids (ILs) are low melting point ( propylene > propane > CO2 according to their decreasing value of Henry’ s constant. Table 8.1 [19,36,46–49] represents the specific ILs and their solubility at different temperature and pressure.

8.2.7 Task specific ionic liquids (TSILs) TSILs is such type of ILs which has imidazole-based compound which help in selective adsorption of different gases specially CO2 . 8.2.7.1 CO2 capture by only TSILs TSILs is the most attractive approach of for the separation of target compound from a mixture of in a gas stream is selective absorption into a liquid. It has both synthetic and separation application [38,51,52]. Cation of TSILs consists of an imidazole ion to which a primary amine ion moiety is covalently bonded and we bifluoride ion very basic bicarbonate ion from CO2 and water. The solubility of CO2 in pyridinium and imidazolium liquids which are ionic in nature was reported by Brennecke et al. and Xie et al. [52,53]. It was observed by them that the CO2 solubility improves in the case of ILs which contains chains of fluoroalkyl either on anion or on the cation in comparison to ILs which are less fluorinated. These Ionic Liquids which are

187

8.2 Types of ILs

TABLE 8.1 ILs and their solubility at different temperature and pressure. ILs

Mol fraction

gCO2 /g

Pressure/Temperature (bar/K)

Reference

[BMIM][BF6 ]

0.36

0.087

29.5/313

[19]

[NBuPy][BF4 ]

0.243

0.063

28.6/313

[19]

[BMIM][NO3 ]

0.276

0.052

12.8/298

[19]

[EMIM][EtSO4 ]

0.192

0.032

20/313

[19]

[BMIM][DCA]

0.1582

0.04

28.3/313

[20]

[BMIM][BF4 ]

0.137

0.031

12.7/313

[46]

[EMIM][BF4 ]

0.160

0.026

8.8/298

[47]

[P(14,6,6,6)][NTf2 ]

0.6309

0.098

14.2/313

[48]

[EMIM][Ac]

0.39

0.165

20/323

[50]

[BMIM][Ac]

0.373

0.132

[BMIM][NTf2 ]

0.4

0.07

28.3/298

[50]

[HMIM][NTf2 ]

0.2535

0.033

27.4/313

[50]

[EMIM][NTf2 ]

0.26

0.0395

22/313

[49]

[DMIM][NTf2 ]

0.562

0.112

13.7/313

[51]

[50]

fluorinated have low reactivity and high stability and hence render them several outstanding properties. The CO2 solubility in Task Specific Ionic Liquids [N2224][CH3 COO] was studied by Wang et al. [54] and the hydrated complexes which are derived from it. For dried TSILs, the mechanism of CO2 capture involves mainly the interactions between Lewis’s acids and bases, in case of the CO2 , hydrated complexes, the acetate component and H2 O reacted to form the acetic acid and bicarbonate ion. At 1 bar pressure and room temperature, the reported mole fractions range from 0.05 to 0.39. 8.2.7.2 CO2 capture by TSILs based nanomaterials In this case of TSILs based nanomaterials, authors have use 1-butylimidazoliumion and 2-bromopropylaminehydrobromide in ethanol for the cationic part. Brennecke and his coworkers [55] have been observed that intrinsic solubility of CILs phase [HMIM][PF6 ] increase the mass transfer rate on the exposure of CO2 . The mechanism involving Task Specific ILs-amine which is functionalized with carbon dioxide was designed by Bates et al. [56]. The mechanism of the reaction results in the maximum concentration of 0.5 mol of carbon dioxide captured with TSILs being 1 mol (1:2 mechanism).

8.2.8 Multiphasic ionic liquids (MILs) MILs are basically ionic liquids which has primary amine group and different type of gases are adsorb on the ILs surface by a phenomenon called liquid or gas adsorption.

188

8. Ionic liquids as potential materials for carbon dioxide capture and utilization

8.2.8.1 CO2 capture only by MILs In case of MILs four ILs, [N1111][Gly], [N2222][Gly], [N2222] [Lys]and [N1111] [Lys]were studied and it is mixed with N-methyl diethanolamine (MDEA) or water for the capture of CO2 [57]; the result of the experiment showed that ILs–MDEA in aqueous media shows a greater rate of absorption and higher capacity of uptake than MDEA solutions in aqueous media, which means that when an ILs is added, it can boost the capacity of absorption of CO2 . Same kind of results were observed for the MDEA mixture with three kinds of ILs [BMIM][DCA], [BMIM][Ac] and [BMIM][BF4 ], respectively [46]. In case of these three types ILs [BMIM][BF4 ] has the highest capability to adsorb CO2 .ThoughCO2 solubility in [BMIM][BF4 ] at 8.8 bar and 298 K is 0.026 gCO2 /g in case of [BMIM][Ac] at 20 bar and 323 K is 0.132 gCO2 /g [58] and in case of [BMIM][DCA], it is 0.04 gCO2 /g at 14.2 and 313 K [46]. 8.2.8.2 CO2 capture by MILs based nanomaterials In case of MILs base nanomaterials two different phases consist of liquid and gas are separated by gas adsorption technique. Liquid flow nanotechnologies play an important role in nanotechnologies, ranging from graphene oxide membrane for gas separation [55] and supercapacitor for energy storage [59,60]. In the practical application the materials which are two dimensional like sheets of GO and graphene which self-assemble in the structure which is like a paper with intra layer or inter layer at nanometer range, liquids are in relative order layer in the system [61].

8.2.9 Switchable polarity ionic liquids (S-Polymeric ionic liquids) Switchable ILs is such type of ILs which are activated on the presence of some special type of gases and it work as on off phenomena of switch so it is called switchable polar ionic liquid when gases are present near the IL it activates and adsorb the gases on the surface. 8.2.9.1 CO2 capture only by S-Polymeric ILs S-Polymeric ILs are triggered and activated by CO2 , COS or CS2 with a very smaller concentration and under very light condition. Such triggers which are on molecular make it easier to solve the problem of recycling the conventional ILs and hence, help in the solute’s preparation. For the preparation of the solution the equimolar mixture of 1-hexanol and 1,8 triazabicyclo(5,4,0)–undec-7-ene may be used as the solvents with switchable polarity. Using carbon dioxide as a trigger by charging the polarity Decane was elucidated from the SPS. It was reported by Jessop et al. [62] and Feng et al. [63] that the mixture of 1-hexanol and 1,8-di aza-bi-cyclo [5.4.0]–undec-7-ene (DBU) which is equimolar in nature can be employed as an SPS. SPILscan be developed by using phenol, fluoro alcohol, pyrrolidone or imidazole to neutralize 7-methyl-1,5,7-triazabicyclo[4,4,0] dec–5-ene (MTBD) by Wang et al. [64]. 8.2.9.2 CO2 capture by S-Polymeric ILs based nanomaterials In the case of S-Polymeric ILs based graphene nanomaterials, authors have been electrochemical switchable CO2 capture scheme has been proposed as highly selective and reversible CO2 for bare h-Bn nanomaterial. Especially CO2 is weakly absorbed on neutral h-Bn material [65]. By the process of Density functional theory and ejecting an extra electron there can be

8.2 Types of ILs

189

huge increment in the adsorption by using chemisorption system which is charge induced. It all depends on the band gap between the layer of the h-Bn and due to its insulating character. The capture of CO2 which is switchable is possible by taking into the account the g-C4 N3 nanosheets which are conductive in nature, of which there is a scope of modification experimentally in the charge states due to large mobility of electron and higher electrical conductivity. It was observed by using the first principal calculations that the CO2 adsorption energy on g-C4 N3 nanosheets can be significantly increased from 0.24 to 2.52 eV by injection of some extra electrons into the adsorbent. When capture coverage of CO2 reaches its saturation, the negatively charged g-C4 N3 nanosheets accomplish the capture capacities of CO2 up to 73.9 × 1013 cm−2 or 42.3 wt. percent.

8.2.10 Thermoregulated ionic liquids (TRILs) TRILs are such type of ILs which are activate on a very high temperature and it conserve energy and work at an optimum temperature and CO2 and some other gases selectively adsorb on the surface. Fig. 8.7 [48] [EMIM][NTf2 ], [BMIM][NTf2 ], [HMIM][NTf2 ] based ILs, how react when increase in the temperature and how it affects CO2 absorption. It is observed that the absorption rate of [EMIM][NTf2 ] based ILs has higher CO2 absorption rate at lower temperature and when we increase temperature absorption of CO2 decrease and in case of [BMIM][NTf2 ] it is also first increase then decrease the rate of CO2 absorption with increase in temperature. 8.2.10.1 CO2 capture only by TRILs TRILs used in lowers the electrical and thermal energy costs and several ILs used in selective capturing liquids used in purpose of separation of CO2 separation and purification from gas mixtures [66]. Albo et al. have been reported that [HMIM][PF6 ] has a strong has a strong dissolving ability for CO2 . After many experiments it can be seen that the smaller ratio of water is favorable for CO2 solvation. In contrast CO2 solubility lowers in the presence of high concentration of water [67]. Solubility measurements of CO2 in the novel ILs [C4 MIM] [CF3 CF2 CF2 CF2 SO3 ] were performed with a high-pressure view-cell technique in the temperature range from 293.15 to 343.15 K and pressures up to about 4.2 MPa whereas, solubilities of H2 , N2 , and O2 in the ILs were also measured at 323.15 K via the same procedure. The mole fraction solubility of a single gas in [C4 MIM][CF3 CF2 CF2 CF2 SO3 ] was expressed as Henry’s constant, as deduced from the Krichevsky-Kasarnovsky equation. 8.2.10.2 CO2 capturing by TRILs based nanomaterials In the case of thermoregulated ILs based nanomaterials we use C4 N3 and C3 N4 type of 2D sheet in which carbon nitride nanosheets with attractive bandgaps and surface engineered application in both energy and environment related topics, catalysis for water splitting [64,67], Hydrogen evolution [68], CO2 reduction [69], organo-synthesis [70] and two kinds of nanosheets used by cross linking nitride containing anions in ILs[76]. By switching on and off the voltage and providing voltage we can initiate the reaction. OS-based carbon was able to adsorbs 4.8, 3.0, and 0.7 mmol CO2 g − 1 at the temperatures of 0, 25, and 100 °C, respectively. Generally, CO2 solubility in [EMIM][NTf2 ] at 12.8 bar and 298 K is 0.0395 gCO2 /g [49] and CO2 solubility in [BMIM][NTf2 ] at 22 bar and 313 K is 0.07 gCO2 /g [46] and in case

190

8. Ionic liquids as potential materials for carbon dioxide capture and utilization

FIGURE 8.7 Absorption of CO2 in the presence of different ILs in different temperature [48].

8.3 Future applications of IL and GR-based IL

191

of [DMIM][[NTf2 ], CO2 solubility at 28.3 bar and 298 K is 0.112 gCO2 /g [36] (highest among all) and in case of [HMIM][NTf2 ], CO2 solubility is 0.033 gCO2 /g [46] at 13.7 bar and 313 K.

8.2.11 Ionic liquids gel ILs gel is a composite material which consists of inorganic material or polymer matrix with ILs. ILs gel used to capture CO2 and other gases in the mixture like H2 , O2 , N2 and CO2 . ILs gel has a stationary solid phase and mobile liquid phase. 8.2.11.1 CO2 capture by only ILs gel To capture CO2, we use Amino acid based Ionic liquids AAILs based facilitated transport mechanism [53]. To resolve the problem of CO2 capturing a large amount of Amino acid ILs (AAILs) must be added into AAILs gel membranes which help in decreasing the mechanical strength as well as pressure resistance of AAILs gel membrane. In order to capture CO2, authors create DN gel network. As well as the molecular size of AAIL decreases, by changing the substituents in the ammonium-based cation, and by reducing the fractional free volume, CO2 absorption increases. The increase of the humidity up to 20 percent caused the decrease of the AAIL viscosity of about 2 mPa s after the CO2 absorption which was related to the loosely formed hydrogen bond network in the AAIL [62]. Kasahara et al. [70] investigated AAILs containing [N4444][Gly], [N1111][Gly] and [aN111][Gly] for CO2 adsorption. 8.2.11.2 CO2 capture by ILs gel-based nanomaterials In case of ILs gel-based nanomaterials, researchers have been used two layered double network (DN) [55] gel matrix that increases the resistance of pressure and gel membrane containing a large amount of AAILs help in fabrication of a thin membrane with high CO2 permeability. First report on the AAILs fabrication based polymeric gel membrane showiing excellent CO2 permeability and CO2 /N2 ratio selectivity as well as outstanding stability under pressurized condition. By the experimental result we found that poly vinyl pyrrolidine and poly dimethylacrylamide have good compatibility with phosphonium based ionic liquid gel. First network of the DN gel, PAMPS, is a rigid polyelectrolyte, was used because it provides high osmotic pressure inside the gel during immersion of it in water. AAIL-based DN ion gel membranes were prepared by 3-step process as follows: Firstly, preparation of DN hydro-gel, and impregnated it on AAILs/water mixture of the DN matrix, and finally, removal of water from the gel using evaporation techniques. Marr and co-workers combine to for the metal nanoparticles in ILs to prepare catalytic gel. Pd(OAc)2 and PPh3 were heated in [BMIM][NTf2 ] to form a suspension of nanoparticles.

8.3 Future applications of IL and GR-based IL In recent times due to global warming concentration of CO2 rises and to minimize the global warming, capturing of CO2 using nanotechnology is a trending topic now mostly we used graphene-based structure which is formed in multilayer and CO2 stored in the interfacial surface of graphene structure [71]. The more the thickness of graphene structure increases less the absorption and when the thickness decreases it increase the CO2 absorption [72]. Mainly

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we capture the CO2 using ILs like [EMIM][BF4 ] or [BMIM][PF4 ]. Due to their low melting point we use these types of ILs [73]. With the help of simulation technique and umbrella sampling [74], with a proper set of desirable traits like Canonical, grand canonical and micro canonical structure we can form the experimental setup. With a set of variables and constant in different types of system in canonical system like N, V,E and N,V,T in grand canonical system μ,V,T in micro canonical structure we can form the desirable structure to study how the reaction is proceed and set up is monitored computationally. ILs are used extensively in the adsorption of CO2 and some other harmful gases because it is cost effective, eco-friendly, less harmful and no harmful side products obtained after the CO2 adsorption, ILs are used in association with graphene because it is extremely important for the reduction of viscosity between the different layer of graphene or graphene like polymeric layer system. Nanotechnology is used in CO2 capturing extensively and it has a vast use in the absorption of harmful gases in atmosphere. Generally, we use multilayer like structure like graphene and graphene oxide which can absorb CO2 in its cage or interfacial surface of different graphene layer [75]. Sometimes GO absorbs CO2 directly. Different kind of nanomaterial is also used to absorb CO2 . In the place of single layer graphene functional nano porous graphene with high porosity can selectively permeable gas molecule [15]. The space occurs between the plane of GO and the composition of intercalated H2 O during the membrane facilitate the process of gas permeation. The GO planes are mainly composed of oxygen rich functional groups which mainly absorb CO2 and carbonyl group and carboxyl group present in the edge plane. Oxygen atom which is highly polarized in the carboxylic group plays as negative center which helps in the stacking of GO sheets [68,76]. Most of the GO polymer mixed matrix membrane polymer needs to be soluble and miscible with aqueous GO solution. ILs mixed with GO are very selective layer [77]. The absorption rate of gas increases by the selectivity of ILs by the addition GO nano-sheet with molecular sieving channel. Among all the type of absorbing component graphene oxide has the highest rate of absorption capacity is of 1.52 mmol·g−1 at 273 K and 1 bar [76]. In the case of nanomaterial supported graphene base structure we use PAN supported membrane.

8.4 Conclusion In modern day due to global warming the atmospheric CO2 increases the temperature of the environment and to tackle the problem we use the CO2 capturing technique using ILs with the help of graphene-based structure and in that case, graphene helps to capture CO2 in the interfacial surfaces and ILs lowers the viscosity between the two surfaces. CO2 absorption ability mainly depends on the interfacial distances between the two-layers and its thickness. When thickness decreases more quantity of CO2 adsorb in the interfacial surfaces. Many functional groups mainly amine based functional group like mono ethanolamine help as a functional ILs and in different type of ILs we use mainly [BMIM][BF4 ], [EMIM][BF4 ], [BMIM][Ac], [EMIM][Ac] and [BMIM][PF6 ], [EMIM][PF6 ] type of ILs because they are very reactive than others and CO2 absorption is also dependent on temperature if we increase or decrease the temperature rate of CO2 absorption also affected mainly CO2 absorption decrease when we increase the temperature. In recent years, PILs, SILs, TRILs and ILs gel extensively are extensively used for CO2 capturing.

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C H A P T E R

9 Recent advances in carbon dioxide utilization as renewable energy Muhammad Hussnain Siddique a, Fareeha Maqbool a, Tanvir Shahzad b, Muhammad Waseem c, Ijaz Rasul a, Sumreen Hayat c, Muhammad Afzal a, Muhammad Faisal d and Saima Muzammil c a

Departmant of Bioinformatics and Biotechnology, Government College University Faisalabad, Faisalabad, Pakistan b Departmant of Environmental Sciences and Engineering, Government College University Faisalabad, Faisalabad, Pakistan c Departmant of Microbiology, Government College University Faisalabad, Faisalabad, Pakistan d Institute of Plant Breeding and Biotechnology, MNS-University of Agriculture, Multan, Pakistan

9.1 Introduction Environment and energy are two most important issues of the present era. Rapid economic growth in many countries has a negative impact on pollution and environment and this problem is becoming more severe worldwide. Therefore, there is a need to find out the novel techniques so that survival of present and future generations could be ensured. One of the major problems facing the environment today is the production of greenhouse gases (GHG) at a high rate and other air pollutants. Major part of our energy comes from the combustion of fossil fuels. The combustion of fossil fuels produce the greenhouse gases [1]. Around about 56 percent of CO2 emits from the industrial sectors while burning fossil fuels. CO2 is the most anthropogenic greenhouse gas leading towards serious environmental issues. The increase of carbon dioxide release by the consumption of fossil fuels lead towards the climate change and global warming. In 2018 other sources of CO2 emission are power generator sectors, transportation vehicles and industries. While in 2019 the increase emission

Green Sustainable Process for Chemical and Environmental Engineering and Science: Carbon Dioxide Capture and Utilization DOI: https://doi.org/10.1016/B978-0-323-99429-3.00032-1

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of CO2 is due to the sustainable use of natural gas and oil. According to Earth System Research Laboratory concentration of CO2 in atmosphere has reached to 411 ppm that is a high record while the 350 ppm is the safe level of CO2 concentration. It is noticed that the increase in temperature will continue in the future because of economic growth and industrial development. In the past CO2 is removed from the environment through plants and crops which absorb the CO2 and sunlight in a process of photosynthesis and release the oxygen. While today due to increase in population, industrialization is increasing steadily that’s why the concentration of CO2 is increasing with a high rate. So plants are not able to remove such a sufficient amount of CO2 naturally [2]. Therefore, Intergovernmental Panel on Climate Change (IPCC) recognized that there is a need to reduce CO2 concentration and relevant policies and regulations should be introduced. Following measures can reduce the carbon emissions: a) b) c) d)

improvement of fuel energy efficiency CO2 capture carbon storage CO2 conversion

Furthermore, the creation of fresh processes, products, and industries could be aided by the introduction of new technologies for converting CO2 to valuable items, hence reducing global warming [3–5]. In CCUS (carbon capture and sequestration), CO2 is the seized from the exhausted gases which are released during the burning of fossil fuels and later on filtered to attain better quality of CO2 . This purified CO2 gas is used to produce valuable products that are economically, socially and environmentally beneficial. CO2 is also used in various fields of biological, chemical and food industries. Although all these efforts are made to reduce the GHG but unfortunately we are failed to do that. In this chapter we discuss carbon dioxide utilization technologies including energy storage, biological usage, mineralization, drinks and food utilization and chemical synthesis. Likewise, we discuss existing CDU research and development projects around the world. Finally, we talk about the CDU market, policy, and difficulties.

9.2 CO2 utilization technologies CO2 is used in different ways especially in mineralization, beverage and food industries, fuel and chemical production etc.

9.2.1 Mineralization In Mineralization processes also known as accelerated carbonation, CO2 emissions through industries is used to form the valuable products. CO2 mineralization processes involves the use of feedstock, natural silicates ores [6] and natural alkaline solid waste [7,8]. Mineralization process in which alkaline residues are used to decrease CO2 emissions from industries and power plants become more effective [9,10]. Mineralization has two main advantages 1) having high capture capacity using natural ores 2) low feedstock cost when alkaline solid waste is used. Alkaline solid residues used for mineralization include mineral and mining processing

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waste [11,12], cement and concrete waste [13], fossil fuel residues [14,15] and paper industry waste [16,17]. These residues contain large amount of calcium and magnesium that’s why considered as best feedstock for CO2 mineralization. Mineralization is achieved by using 4 main approaches [18]. 1) carbonation curing: a process in which CO2 is used to enhance the durability and strength of cement based products 2) electrochemical mineralization: a process in which CO2 is mineralized through electrochemical cell and electricity is produced 3) Indirect carbonation: a process in which different ions are extracted to produce highly purified chemicals 4) direct carbonation: a process in which CO2 and alkaline slurry are mixed together in same step Mineralization of CO2 through alkaline solid waste is also useful to control air pollution for several industries and power plants. Pei et al. [18]. were used fly ash to control the pollutants from petrochemical industries and results showed the successful removal of CO2 was 96 percent, for NOx it was 99 percent, and for particulate matter it was 83 percent. The products obtained from CO2 mineralization can also have a variety of environmental applications [7]. Additional mineralization methods (indirect carbonation) can yield high-value minerals e.g., abiotic catalysts, geopolymers, soil conditioners and calcium carbonate precipitates as well as glass ceramics. Furthermore, electrochemical mineralization technology can be used to restore gaseous CO2 from a different industrial processes whereas also producing electrical energy [19]. The amount of mineralized carbon dioxide is little as compared to global CO2 emissions, it is advantageous in terms of alkaline solid waste remediation and the production of high-value products.

9.2.2 Beverage and food processing CO2 is consumed as acidifying agent in beverages and food industries [20]. CO2 purity is considered as main factor during the gasification processes because contamination occur from benzene, COS and H2 S. CO2 is especially used in producing carbonated drinks, water which is deoxygenated, products made from milk and food preservatives. A large quantity of liquid CO2 is used in making sparkling wines, beer and soft drinks so it is necessary CO2 come from renewable resources. For food preservation, mechanical refrigerators are used for CO2 storages and transportation. Liquid CO2 and dry ice (solid form CO2 ) are used for food that require freeze drying. For the production of flavors, essentials oil and coffee decaffeination, CO2 is utilized through supercritical fluid extraction method which is important in removal of volatile, heat subtle and oxidizing compounds. In this technology agents used for extraction have following advantages [21–23]. a) non-toxic b) non-corrosive c) stable chemically d) better permeability e) reused after decompression in sense to save energy (Fig. 9.1). In 1978, Germany introduced the first SFE technology at industrial scale by converting the coffee beans into caffeine [24]. Nowadays this technology is routinely used for daily life purposes as described in Fig. 9.2 [25]. The considerable applications of SFE technology includes fat and oil extraction [26–30], cholesterol and lipids [31,32], production of natural colors [33], antioxidants [34,35], hops [36] as well as decaffeination of coffee and tea [37–39]. A lot of essential oils are extensively consumed in cosmetics and food industries. Importantly, SCE have

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FIGURE 9.1 Represent the CO2 mineralization process through alkaline residues.

better extraction capacity when compared with other removal equipment. Conde-Hernandez et al. [40] compared the SCE technology with steam and hydro distillation approaches and found that SCE technology had better antioxidant activity and oil yield. Nowadays SFE techniques in combination with other methods like enzymes [41], ultrasound [42] and microwave [43–45] have been widely reported. However, there are a lot of hurdles in the development of SCE technology because of high costs at large scale production, sophisticated equipment is required and difficulties in continuous production which make low use of this technology (Fig. 9.3, Table 9.1).

9.2.3 Biological utilization CO2 is naturally fixed by plants and autotrophic microorganisms through a process of photosynthesis. This fixation is safe and cost effective. The use of microorganism is advantageous because of rapid production rate, high photosynthetic activity, require small volume, easily adaptable to any environment and easily integrated with other technology. Microalgae attain a great attention of researchers because it can easily replace the fossil fuels and used as an alternative energy source. Moreover, 1kg biomass of microalgae can fix the 1.83 kg of CO2 [46–48]. The sources of carbon obtain from microalgae are inorganic carbon that is [49,50] dissolved in water. The type of microalgae used depends on the application, such as CO2 fixation from flu gas. Microalgae not only need to be able to fix CO2 efficiently, but they also need to be able to withstand high temperatures, high concentrations of CO2, NOx and

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FIGURE 9.2 Represent the daily used food obtained through supercritical fluid extraction.

FIGURE 9.3 Represent the process of CO2 -EOR. TABLE 9.1 Represent the CO2 fixation using different algae. Algae sp

Temperature (K scale)

% level of CO2

CO2 fixation rate g/(L d)

References

Anabaena sp.

309

11

1.02

[57]

Botryococcus braunii

291

6

0.496

[58]

Chlorella vulgari

297

5.1

0.251

[58]

Dunaliella tertiolecta

292

5.2

0.271

[58]

Botryococcus sp.

302

10.4

0.258

[59]

Chlorella pyrenoidosa

293

10.1

0.25

[60]

Chlorella sorokiniana

297

4.2

0.252

[61]

202

9. Recent advances in carbon dioxide utilization as renewable energy

SOx. [49,50]. Following physiochemical parameters should be considered during the fixation of CO2 : 1) Culture temperature is a considerable parameter for the photosynthetic bio-fixation of CO2 assisted by microalgae. Microalgae can grow at 291–298k temperature. Fluctuations in temperature can hinder the growth of microalgae by dropping the Rubisco enzyme activity level that is important for CO2 fixation [20]. 2) Light is another important parameter that play significant role in the growth of microalgae, system operation and reactor design and provide the energy for activation and assimilation of some enzymes that play important role in the process of photosynthesis [51]. 3) Without the addition of CO2 , the pH can reach a very high level of 10 during high-density production. As a result, such an environment has a negative impact on the photosynthetic reaction process and nutritional salt absorption in cells, resulting in a drop in microalgae biomass output. As a result, during algae cultivation, the pH should be kept neutral [52]. 4) CO2 concentration is very critical parameter that seriously affect the microalgae growth rate. Concentration of CO2 should be kept between 10–20 percent [53]. It is feasible to directly utilize flue gas from fossil fuels. Microalgae can also thrive in higher CO2 environments. Chlorococcum littorale and Synechocystis aquatilis, for example, grow well at a concentration of 40 percent. The fixation of CO2 by different algae has been reported in Table 9.1. These findings might aid in the development of microalgae tolerance to high CO2 concentrations from fossil fuel combustion exhaust gas [54–56].

9.2.4 Oil recovery enhancement, coal bed methane and fracking of CO2 Carbon dioxide storage of earth is accomplished by introducing collected CO2 into subterranean pools under appropriate conditions, where it is kept for more than 10,000 years [62]. However, by injecting CO2 in gas and oil reservoirs, it is feasible to boost fossil fuel output. CO2 injections into depleted oil reservoirs improve oil recovery (EOR), shale formations improve shale gas recovery (ESGR), and un-mineable coal seams improve coal bed methane recovery. It is believed that CO2 will be used as a fracturing fluid in the future, potentially replacing water [63]. The EOR method is utilized for collection of crude oil from oilfields that has been moderately removed by principal and subordinate recovery methods. Chemical, heat and gas injections are the most common procedures utilized for EOR [64–66]. CO2 -EOR projects are mostly active in the United States and Canada, where there are also available CO2 sources. More than 90 percent of the world’s oil reserves may be eligible for CO2 EOR technology [67]. The following key considerations should be kept in mind for the ongoing deployment of CO2 -EOR technology: 1) checking of subterranean and released discharges 2) enhancing on site risk management 3) Refining the usage of unrestrained fields.

9.2.5 Fuels and chemicals CO2 can be used for the fuels and chemicals production. The commonly used products obtained from CO2 are salicylic acid, methanol, formic acid, cyclic carbonates and urea [68]. Formic acid play great role in the CO2 emission reduction [69].

9.2 CO2 utilization technologies

203

9.2.5.1 Electrocatalytic conversion Different types of pathways are used for CO2 conversion into fuels and chemicals e.g. biochemical, photochemical, electrochemical and thermochemical [70]. Different types of electrochemical methods are used to convert the CO2 to valuable products such as methanol [71], methane, carbon monoxide [72] and hydrocarbons [73]. Although a lot of studies are reported which focused on the electro-reduction of CO2 on different catalytic sites but still there are many challenges that limits the use of this technology [74–76]. 9.2.5.2 Plastics Polymers used for the synthesis of plastics are mostly CO2 based and they are environmental friendly. Plastics are synthesized through a process known as copolymerization in which hydrocarbons and CO2 (31–50 percent) are used and the use of petrochemical is reduced [77,78]. In 1969 Inoue et al. [79] first time used the CO2 with epoxide in a polymerization process. Copolymerization process is catalyzed by the catalyst. So, the production of cost efficient and highly reactive catalyst is necessary to future development. CO2 is used to form the fabricated polyoxymethylene (POM) through polycondensation process [80].

9.2.6 Principal and favorable utilization technologies In order to enhance oil recovery CO2 injection method is working in different areas. However, following problems are associated with the conventional methods including leakage and acidification of water supply and the energy used for the transportation of CO2 . So to encourage this technology issues associated with the transportation and corrosion of CO2 should be solved [81]. However, different energy inputs are required for CO2 conversion while the renewable energy resources like solar and wind power, are the favorable sources for this process, and the energy from these processes cannot be directly used for electricity generation. However, if the charges of renewable energy resources down continuously in this manner, the usage of renewable energy for CO2 conversion will increase. Microalgae is one of the finest options for producing liquid fuels and reducing CO2 emissions [82]. The quick rise in lipid content with low energy usage and minimal CO2 emission during biofuel conversion are major hurdles for such technology. It is also critical to recognize that such technologies are spatially specialized for early production and are tailored to local resources and circumstances. To summarize, the synthesis of basic industrial chemicals in huge quantities will be more beneficial if the objective of these processes is to diminish the released anthropogenic CO2 . The combined systems are utilizing various usage methods for example the methanol production is linked with the increased gas retrieval, are potentially interesting solutions [83,84]. Before the commercialization of CO2 utilization techniques, it is necessary to identify optimal use routes, which is accomplished through the use of Life Cycle Assessment (LCA) or Techno-Economic Analysis (TEA). According to von der Assen et al. [85], Even at the early stages of development, LCA can suggest environmentally advantageous avenues for CDU. Several extensive evaluations, on the other hand, have concentrated on reviewing the environmental consequences of several CDU technologies in depth, which will aid in the future in making appropriate CO2 utilization paths in certain cases. As a result, the optimum

204

9. Recent advances in carbon dioxide utilization as renewable energy

CO2 utilization technique has the following properties. a) little extra energy requirement b) simple methods c) large size and worth of future market.

9.3 Developments in worldwide CO2 utilization projects In the following countries the CO2 utilization technologies are operated and constructed at different stages:

9.3.1 United states The united states are working in EOR technology. In the United States three following technologies are working on the CO2 utilization technology which focused on increasing commodity market including 1) mineralization 2) chemicals 3) polycarbonate plastics. It is expected that in 2030 these methods will work on large scale with a lot of application. Initially in United States carbon tax was $10/t in 2008, which will increased to $50/t for saline storage and $35/t for EOR use by 2026 [86].

9.3.2 China CO2 usage in China is mostly subsidized by the government and carried out by enterprises backed by universities or research organizations [87]. China National Petroleum Company operates the first large-scale CO2 utilization technology in 2018 [88]. Furthermore, the participation of Chinese government in the major Clen Energy conference, other international structures and Carbon Sequestration Leadership Forum as well as secondary national research companies and institutes are involved in mutual cooperation projects. China now has the most carbon storage, sequestration and experimental facilities in procedures, structure, or development [87].

9.3.3 Germany Ever since 2002, German government decided to decrease the GHG emission by 40 percent upto 2020 and 80 percent upto 2050 so that change in climate can be combat [89]. In 2015 they set a target as “New High Tech Approach” that describe the upcoming direction. 33 Carbon dioxide utilization projects were granted in Germany from 2010–16. Government paid €100 million and different universities paid €50 million for research projects [90].

9.3.4 Australia The government of Australia is included in several international forums that work on promoting the development and construction of CO2 reduction technologies. These forums includes Australia-China Combined Organization Assembly and others inside and elsewhere in Asian region [91].

9.5 Regulation and policy

205

9.4 Market scale and value The market for CO2 consumption differs across countries which affect the environment benefits obtained the CO2 utilization methods. The demand of the yields obtained by using CO2 is increasing day by day. The market for CO2 show a great growth rate >13 percent/year by 2022. CO2 is not used an alternate for storage because a large volume of CO2 is required for storage. CO2 assisted EOR market is mainly funded through gas and oil industries. Four points should be kept in mind about the CO2 utilization market: 1) 2) 3) 4)

Building materials (concrete, carbonate aggregates) Chemical intermediate (formic acid, methanol etc.) Fuels (methane) Polymers

Methane contributed 3–4 trillion cubic meter per year to current market that is expected to be 4–5 trillion cubic meter per year in 2030. Following obstacles are associated with this technology 1) low cost catalyst 2) merged process for carbon conversion, storage and renewable energy. High cost of this technology limit the market growth rate [92]. The methods involved in the utilization of CO2 require more expansion on vast scale by enhancing the size of market and producing ability in experimental to viable plants.

9.5 Regulation and policy There are still failure risks in the present CCS industry. As a result, in the absence of a well-made strategy, the private division will not invest in carbon release and storage at the scale which is required to accomplish climate change alleviation goals. A solid monitoring framework is required to reduce and evade the destructive consequences of failure while also maximizing economic profit on investment. As a result, well-thought-out CO2 use laws are crucial for creating and expanding markets. In many circumstances, products must fulfil current industry standards in order to be accepted. These standards are usually produced by consensus-based and voluntary groups under the supervision of government and industry members. There are currently little incentives to update or amend existing standards. Even where there is a willingness to change, regulatory frameworks move slowly and to minimize the CO2 release [93]. Development and investment is a major problem today due to shortage of information, the self-motivated market and technology, and a unstable government landscape. Discrete approaches regarding CO2 consumption techniques are usually optimistic, owing to the superficial objective of minimizing CO2 emissions. To foster public interest and confidence, governments must make suitable information available to the public. Governments should interact with principles backgrounds to minimize intervals in the market release of these items and to broaden a creative agenda for CO2 consumption. Only a few countries, most notably Norway, UK, US, China, Japan and Canada have specific policies in place to assist CCS deployment [94]. In the time-consuming track, the guidelines of government are crucial to enhance the technologies organization, without them, CO2 consumption will not contribute much to attaining climate objectives. We must match CO2 product purchases with climate policy if we are serious about meeting the objectives.

206

9. Recent advances in carbon dioxide utilization as renewable energy

9.6 Conclusion and future prospects Rising CO2 levels in the atmosphere are considered to worsen climate change. Despite the fact that CO2 collecting technologies are fairly advanced, using captured CO2 remains a big challenge that will necessitate more future study. There are currently several restrictions to emerging CDU, including as water and energy usage, the use of costly chemical agents, and gas substructure concerns. Economical CO2 consumption technologies are especially needed, also commercial adoption requires trials on larger scale. It is obvious that a detailed understanding of various CO2 usage methods is useful in understanding processes and selecting appropriate ways for CO2 capture. For bridging gaps in present industrial applications, potential integrated technologies are preferred. Furthermore, displaying CDU R&D projects and assessing CO2 consumption markets can help determine the viability of full-scale adoption of these technologies. Economic viability is critical for the industrial practicality of CDU technology, whether accomplished via technological improvement or regulatory reforms. As a result, future significant research objectives should focus on CDU and CCS guidelines, policies, and evaluations, as well as the incorporation of CO2 consumption with other measures to decrease energy depletion and expenses, particularly on a pilot scale. In the meantime, public education and exposure of CCUS should be prioritized, and international partnerships should be expanded to promote public knowledge of the environmental consequences. It is also worth mentioning that CDU is not a replacement for CCS, but rather a supplement to it, and that without CCS, we would fall short of our environment goals. Governments should boost their commitment to CCUS and play a vital role in assisting its implementation in order to limit the global mean temperature increase below 1.5 °Celsius. Encourage private sector participation in larger-scale demonstration programs, as well as in the commercialization of CDU technology. CO2 may become a resource sought after by numerous sectors of the global economy in the near future, influencing regulation and policy in the market for CO2 -based products.

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[86] Edwards RWJ, Celia MA. Infrastructure to enable deployment of carbon capture, utilization, and storage in the United States. Proc Natl Acad Sci USA 2018;115:E8815–24. [87] Xie H, Li X, Fang Z, Wang Y, Li Q, Shi L, et al. Carbon geological utilization and storage in China: current status and perspectives. Acta Geotech 2014;9:7–27. [88] Andrews-Speed P. China’s efforts to constrain its fossil fuel consumption. Palgrave Handbook Manage Fossil Fuels Energy Transit 2019:109–37. [89] Marcu, A, Zachmann, G. Developing the EU Long Term Climate Strategy. 2017. indiaenvironmentportal.org.in. [90] Mennicken L, Janz A, Roth S. The German R&D Program for CO2 Utilization—Innovations for a Green Economy. Environ Sci Pollut Res 2016;23:11386–92. [91] Gaurina-Međimurec N, Novak Mavar K. Carbon Capture and Storage (CCS): geological Sequestration of CO2 . CO2 Sequestration 2020. [92] Zhang Z, Pan SY, Li H, Cai J, Olabi AG, Anthony EJ, et al. Recent advances in carbon dioxide utilization. Renew Sustain Energy Rev 2020:125. [93] IPCC: Global warming of 1.5°C. Summary for policymakers - Google Scholar Available online: https:// scholar.google.com/scholar_lookup?title=GlobalWarmingof1.5°C&author=IPCC&publication_year=2018 (accessed on May 26, 2022). [94] Havercroft I, Consoli C. Is the World Ready for Carbon Capture and Storage ? Glob CCS Inst 2018.

C H A P T E R

10 Metal Organic Frameworks as an Efficient Method for Carbon dioxide capture Bharti Kataria and Christine Jeyaseelan Department of Chemistry, Amity Institute of Applied Sciences, Amity University, Noida, Uttar Pradesh, India

10.1 Introduction Elevation in industrialization and population leads to excessive energy consumption. Due to advanced technology and ready availability of non-renewable fossils more than three fourth of energy needs are pillared by burning these fuels as a corollary of which the rate of greenhouse gases majorly carbon dioxide is increasing at high pace [1]. On the basis of previous studies the concentration of CO2 has shown a steep escalation and reached 408 ppm in 2019 which eventually will have adverse impact on the climate [2]. Increased level of CO2 will proliferate the earth’s temperature therefore, implementation of carbon dioxide capture and storage (CCS) techniques might help to reduce its emission to some extent [3]. CCS is an efficient way to mitigate the concentration of CO2 in atmosphere. Out of the steps involved in the above mention technique capturing of carbon dioxide gas is the most difficult task and to achieve this new advanced materials are produced for the same. Metal-Organic Frameworks are latest materials that will reliably serve the purpose of providing a platform for evolution of next generation materials possessing benignant properties like high gas adsorption capacity and their chemical and structural tenability [7]. The selection of the components of the framework depends upon the attraction potential of the internal pore surface with regards to carbon dioxide gas. Many technologies have been invented which works on the principle of adsorption, absorption or membrane separation [8]. Out of all methods amine scrubbing is found to be most effective as it can mitigate CO2 levels by 98 percent but it has some major demerits which includes high energy usage, corrosive nature and the huge amounts of absorber used [9]. In the past few decades various studies have been carried out and published explaining applications of different MOFs. In this review, the studies focus on various techniques used by

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MOFs to capture carbon dioxide gas selectively [9]. Different synthesis methods for preparing metal organic frameworks have been discussed. Besides all the properties [10] showed by MOF, modification in frameworks via ligand functionalization is attracting more and more scientists, they provide- one with the advantage of synthesizing desired pore size MOF for various applications. The synthesis methods involve conventional routes, microwave synthesis, sonochemical routes, electrochemical and mechanochemical routes, out of all the conventional method which includes generation of frameworks via Solvothermal methods are the most readily used one. Synthesis of some MOFs for CO2 selective adsorption are also discussed which involves MOFs like Mg-MOF-74, MOF-801-Zr, MIL-608(In)NH2 . Some basic properties of MOFs are also explained. Principles and methods involved in gas separation are studied, four mechanisms- thermodynamic equilibrium separation, kinetic effect, molecular sieving effect, and quantum sieving effect are explained in detail. Selection of adsorbent plays important role in designing frameworks, the selection procedure involves two major methods that is adsorption process and nature of pores of the adsorbent. Among various factors enthalpy of adsorption and adsorption capacity are two most considerable factors while explaining capturing of this gas on frameworks via adsorption. Various methods like opening pore sites, pre synthetic and post synthetic procedure and size tenability are some methods to proliferate adsorption capacity for carbon dioxide gas which are briefed in this chapter. Along with that stability of metal organic frameworks also plays crucial character in amelioration of its properties, hence in this chapter we reported various methods which can be used for both existing frameworks and unknown frameworks respectively. These methods includes stabilities in terms of chemical, mechanical and thermal aspects.

10.2 Metal organic framework (MOF) Metal Organic Framework are compounds formed by combining inorganic metal ions or nodes connected via organic linkers hence classified under porous organic-inorganic hybrid constituents. They are crystalline coordinate compounds having 1D, 2D, 3D structures. They show various unique properties like low density, uniform channels, adjustable chemical functionalities, internal surface area [11], high porosity [12] and many more. They have attracted attention due to their applications in various fields like separation and capturing gases, drug delivery, medical imaging, sensors, biomedical applications, heterogeneous catalysis.

10.2.1 Conventional synthesis route It is among the most popular route for synthesizing MOFs and the needed energy is produced by conventional methods only. Solvothermal reactions are generally carried out in sealed reactors at very high temperature between the ranges 80 to 260 °C which is more than the boiling point of the solvent being used at autogenous pressure conditions. On the other hand, non-Solvothermal reactions are carried out at normal temperature which is either under or around the solvent’s boiling point being used [13]. The major pros attached to these reactions is that many frameworks can be prepared by just mixing the primer materials at room temperature hence precipitation take place in very small time gap therefore it is also known

10.2 Metal organic framework (MOF)

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FIGURE 10.1 Solvothermal synthesis process.

FIGURE 10.2 Microwave synthesis technique.

as direct preparation method which saves reaction time as many reactions are recorded to be completed in days or weeks [14] (Fig. 10.1).

10.2.2 Microwave synthesis technique It is a renowned method for the synthesis of MOF materials. The method depends upon the interaction of electromagnetic wave with the electric charge produced by ions or electrons present in the solution and in case of solids electric current is produced by the electric resistance offered by solid materials. The reactions were carried out in an oven by maintaining the reaction with respect to temperature and pressure [15]. The reaction time is usually less than one hour and the reaction is usually achieved at 100 °C. This method results in the formation of highly crystalline material with nano size which makes it more adaptable and useful than conventional method. Using this method, we can mitigate synthesis time and alter the shape and size of the crystals accordingly [16] (Fig. 10.2).

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FIGURE 10.3 Sonochemical synthesis process.

10.2.3 Sonochemical synthesis The synthesis reaction in this type of method initiates in presence of high ultrasonic waves and the frequency used for the waves is higher than hearing range of humans that is 20 kHz to 10 MHz. The process begins by passing ultrasonic waves into the solution which will creates variable pressure zones inside the solution say rarefaction or compression which leads to the formation of bubbles also refer as alternate cyclic regions as a corollary of which the pressure in the lower region starts mitigating towards reactants and solvent vapor pressure which results in formation of small size cavities. The bubbles tends to achieve their critical size which is not stable, leads to failure. The whole process of synthesis, maturing and collapsing occurs in very short span of time but high attention needs to be paid for selecting synthesis materials vapor pressure, viscosity and the equipment temperature, frequency along with majorly considering the selection of solvent for the process because organic solvents did not prove themselves to be useful as they impact the collision cavities intensity which will directly affect the temperature and pressure [17] of the reaction. In case of solid particles cavitation is not the preferable phenomenon hence microjet is considered suitable in which whenever the bubbles come in contact with the particle, bubble’s erosion takes place which results in activated particle surface. This method is used specifically for generation of organic substances and nano range materials [18]. This method possesses various advantages over and above the mentioned methods because it environment friendly, very fast [19] and most important being energy efficient (Fig. 10.3).

10.3 Synthesis of some MOFS

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FIGURE 10.4 Mechanochemical synthesis.

10.2.4 Mechanochemical synthesis This method does not fall with all other methods because in this there is no use of solvent, it is a solvent free method. Process initiates with normal mixing of organic linkers with metal salt by ball mining process. Among all the above methods, it is the most convenient and had many merits being environment harmless, less reaction time, solvent free reaction [20], size of particles obtained is small. In some cases, when metal is replaced by metal oxides in this process it will produce water molecule as side product of the reaction [21]. Reactivity of the reaction can be enhanced by choosing organic linker with low melting point and metals which release salt during the reaction due to which the movement of reactants become easy which will speed up the rate of reaction [21] hence metal carbonates and oxides are highly used for the same. The outside addition of small volume of solvent, the process called liquid-assisted grinding (LAG) was found to be impactful in proliferating mobility of reactants [22] (Fig. 10.4).

10.2.5 Electrochemical synthesis Reaction in this method is carried out by flow of electric current produced by electric transfer of molecules. Cell construction involves cathode, anode, and electrolyte solution made up of conducting salt and linker molecules dissolved in it. Instead of using direct metal salts into the reaction, metals ions were added occasionally to avoid deposition of metal ion on cathode, to avoid protic compounds like acrylonitrile, acrylic, and maleic esters were used. This method is usually used for large scale production of materials because of high end point yield offered and used by researchers for producing zinc and copper metal organic frameworks [23] (Fig. 10.5).

10.3 Synthesis of some MOFS I. Mg-MOF-74 This material is synthesized using Solvothermal method which initiates with reaction between magnesium nitrate with DOT (2,5-dihydroxyterepthalic acid) in presence of

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FIGURE 10.5 Electrochemical synthesis process.

deionized water and DMF (N,N–diethylformaide) and ethanol [24]. The procedure followed was reported in literature is as follows: 0.712 g of magnesium nitrate was mixed with 0.167 g DOT via sonication and then it is dissolved in a mixture of DMF (67.5 ml), ethanol (4.5 ml), and deionized water (4.5 ml) in the (v/v/v) ratio 15:1:1. The prepared solution is then transferred to an autoclave which is made up of stainless steel with a Teflon lining inside it. It is then heated at autogeneous pressure and 125 °C temperature for 26 h then taken out and cooled to RT. The mother liquor is then poured out and replaced with methanol followed by removal of guest molecules in vacuum for 15 h at 250 °C which results in the preparation of dark yellow crystals of Mg-MOF-74. II. MOF-801-Zr 0.06 g of zirconium chloride (ZrCl4 ) and (0.36 g) fumaric acid were dissolved in 45 ml DMF solution followed by addition of extra 20 ml [25] of fumaric acid and stirring of the mixture for 10 min. The mixture was then transferred to an autoclave, which is then sealed and heated in an oven for 16 h at 403 k temperature. The precipitates obtained after cooling and filtering the mixture were dipped in DMF (30 ml) for one more day then washed with methanol various times and after drying it at 333 k in vacuum white powder of MOF-801-Zr was obtained. III. MIL-68(In)-NH2 The procedure followed has some variation in comparison to published literature in [26], 1.92 mmol of In(NO3 )3 .xH2 O and 0.645 mmol of NH2 -BDCH2 were dipped in 6.2 ml DMF in Teflon autoclave. The mixture was then stirred for 15 min after addition of pyridine, the autoclave was sealed and heated at 125 °C for 5 h The obtained yellow powder was then washed with DMF and dried.

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10.4 Properties of MOFs 10.4.1 Chemical and thermal In comparison to other zeolites and inorganic porous solids their thermal and chemical stability is shorter because of the weak bond of coordination which is holding the metal and ligands together. Most of them are moisture or air sensitive hence need extra care and generally used under inert atmospheric conditions. To illustrate, MOF-5 is highly sensitive to air and leads to quick degradation of crystal structure of the material and mitigation of surface area due to hydrolysis of the present bonds of Zn-O, [27] whenever they came in contact with the same.

10.4.2 Mechanical For application like capturing gases the mechanical stability of material should be considerably high so that it can permit the heavy packaging of adsorbent bed without overlooking the structure. To elucidate, in case of Cu3 (BTC)2 when large pressure is applied it results in decrease of lattice volume by 10 percent [28].

10.4.3 Thermal conductivity This parameter is important in identifying heating efficiency of the adsorption bed and the time required to regenerate temperature swing adsorption based capture process. According to published work by Yaghi [29] the thermal conductivity of MOF-5 declines when temperature is low in the range (20 k–100 k) but remain almost stable above 100 k.

10.5 CO2 capture using MOF MOF as Adsorbent M M organic frameworks, MOFs due to their porosity, 3D structure and modular nature are able to sustain their framework with minimum damage. They showcase many attractive properties like excellent surface area and their functionality [30], variability in size of pores [31]. These functional groups allow MOF to modify [32] the sizes of the pores. Due to these numerous properties, they attract the attention of researchers and are being used for a number of applications including biosensors, biomedical applications, catalysis, separation and storage of gases [32] and many more. The role of MOFs as an adsorbent to capture carbon dioxide has been discussed. 5.1. Methods for gas separation: Separation is a procedure of differentiating components of any mixtures, which usually needs large amount of energy [33]. Separation can be achieved by various separation methods like separation adsorption in which the components present on the adsorbent surface have different affinity towards the guest molecules. Gas separation methods involves adsorption and absorption-based technologies [34], cryogenic distillation, and membrane based technologies but out of all adsorption separation is the most convenient because of the advantages it provides in comparison to the above mentioned methods which includes being eco-friendly [34], low energy

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consumption, and easy maintenance. The whole process consist of two main steps which includes adsorption followed by desorption. In the former step the gaseous mixture is allowed to pass through a column filled with adsorbents. Then desorption is carried out to replace all the components which get struck on the adsorbent bed for reusable purpose. There are mainly four methods which are generally used for gas separation like vacuum swing adsorption (VSA), electric swing adsorption (ESA), temperature swing adsorption (TSA) and pressure swing adsorption (PSA). Out of above-mentioned methods TSA and PSA are most commonly used ones. In TSA the deposition starts with heating the adsorbent. Due to heating or cooling it lasts up to few hours or sometimes up to a day. While in PSA the rejuvenation takes place by decreasing the pressure of the adsorbent. It is usually more preferable over TSA due to short time periods which varied from seconds to minutes and its non-temperature dependent process. VSA is also attracting the interests of researchers because it works in range of ambient pressure, as the stream pressure of many flue gases is close to atmospheric one [35]. 5.2. Mechanism for specific adsorption: There are basically four types of mechanisms for selective gas adsorption separation for porous materials5.2.1. Thermodynamic equilibrium separation: Also known as dynamic separation. In this method the size of the adsorbent pores needs to be big enough as a corollary of which the constituents of the gaseous amalgam can easily sweep into the adsorbent. In this situation the extent of reaction between the adsorbate molecules and the surface of adsorbent play crucial role in selective adsorption quality. This interaction strength is directly proportional to dipole moment, polarizability, magnetic susceptibility and quadrupole moment [36]. 5.2.2. Quantum sieving effect: This is mainly used for separation of isotopes like D2 /H2 [37]. The adsorption is achieved on the basis of rate of diffusion of the guest molecules and pore diameter compatibility with de-Broglie wavelength. 5.2.3. Molecular sieving effect: Also known as shape and size exclusion. In this adsorption depends upon cross sectional size that is kinetic diameter (the minimum distance between two molecules with null kinetic energy and they have a collision) and shape of the adsorbate [37]. 5.2.4. Kinetic effect: This decoupling is implied when equilibrium dissociation is not achievable. The major problem faced while using this method is maintenance of pore size of the adsorbent between the kinetic diameters of the molecules that needs to be separated. Example includes separation of carbon dioxide and methane gas using this effect [36]. 5.3. Adsorbent selection and criterion: This is one of the most important step for separation process. Adsorbents having high adsorbing capacity and selectivity for selective molecules are considered to be ideal for use, therefore, the following things need to consider while choosing adsorbent: r Adsorption process r Nature of pores of the adsorbent The separation of large amount of gas, in case of detachment process, the adsorbents are sorted out on the basis of how quickly desorption can occur. While when we are not considering the selection process then the factor which should be considered is nature of adsorbent including the shape and size of its molecules, polarizability, and dipole moment

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along with quadruple moment. To elucidate, if the targeted molecule possesses higher quadrupole moment then adsorbent with high electric field gradient and high surface area is suitable for separation. Similarly, if molecules possess high dipole moment then adsorbent molecules must contain high polarized surface [37].

10.6 Adsorption of carbon dioxide in metal organic frameworks This section explains the most important aspects required to be considered during adsorption of CO2 within metal organic frameworks. 6.1. Adsorptive capacity for CO2 : This is one of the critical factors for adsorption technology and is based on surface area of the adsorbent molecules. Because of ultra-high surface area, MOFs are capable enough to capture carbon dioxide in comparison to zeolites and other compounds of activated carbon. Other than surface area, there are some factors like adsorption, pressure, temperature, and interaction between the adsorbent and adsorbate molecules which plays vital role in CO2 grasp capacity [38] of adsorbent material. Many researches have been published in this context but the main focus in most of them is on gravimetric capacity which relies upon the weight percent of grasped gas over total system’s weight [39]. According to the study carried out by Yaghi and group [40], they used 9 different metal frameworks with distinct geometries (MOF-177, MOF-505, Cu3 (BTC)2 , IRMOF-11, MOF-2, IRMOFs-3, MOF-74, IRMOF-6, IRMOF-1) to find the relation between surface area of MOFs and the adsorption capacity of CO2 at temperature-298 k and pressure-35 bar The results conclude that out of all MOFs mentioned above MOF-177 found to have higher surface area hence higher carbon dioxide adsorptive capacity. When pressure is increased from 35 bar to 50 bar then another MOF called MOF-210 showed best CO2 uptake capacity as reported by another group. It was found out that by increasing the size of organic linker this capacity can be enhanced, as reported when the organic linker in case of MOF-177 is changed to BBC 4,4’,4’-(benzene-1,3,5-triyl-tris(benzene-4,1-iyl)) from BTB: 1,3,5 benzenetribenzoate, MOF-200 was obtained with proliferation in adsorptive capacity. Enhancement of surface area along with volume of pores can also be used to boost the capacity, this can be obtained by expanding the structure of the material during synthesis or by using huge organic ligands [40]. 6.2. Enthalpy for adsorption: Another important factor which impact the broadband of MOF application in gas capturing is enthalpy of adsorption also referred as isoelectric or adsorption heat. The magnitude of isoelectric heat indicates the extent of interaction between the CO2 and pore surface which in turn explains the amount of heat needed for desorption and details of adsorption selection [41].

10.7 Methods to enhance CO2 adsorption Various methods have been designed to proliferate the adsorption of carbon dioxide gas. This chapter provides a detailed explanation of all the methods follows: 7.1. OMS-open metal sites: metal sites possess significant role in elevating selectivity and captivity of carbon dioxide gas over all other gases. During preparation of MOF some metal ions get involved with solvent molecules leading to mitigating adsorption capacity

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of MOF towards guest CO2 . This can be reduced by varying temperature conditions which leads to remove all the extra solvent molecules and the created vacant space known as open metal sites, which will result in increased adsorption of gas. These open metal sites hold on the binding between the guest and the host molecules hence, creation of more active sites results in more trapping of guest gas [42]. Most of the d-block elements can be used for preparing MOFs as they have vacant d-orbitals which are used for interaction with other molecules and atoms. In order to generate metal frameworks with excellent separation and adsorption properties it is essential to understand the nature of interaction between the host and the guest entity. Transition metals play vital role in interaction between open metal sites and the guest molecule, as they maintain the balance between various important factors like van der Waals forces, hybridization of orbitals, Pauli repulsions and electrostatics. According to the results published in literature [43] it is found that MOF-74 shows highest binding enthalpy with vanadium forming V-MOF-74 which resulted in enhancing the bonding interactions between gas molecules and OMS. 7.2. Pre-synthetic procedure: MOF and separating gas (CO2 ) can be improved by implying ligand functionalization. Variety of various functional groups and the ease of modification makes this most suitable and applicable for gas storage purpose. CO2 molecules exert quadrupole moment, hence when the framework contain polar groups it will show higher interaction towards guest gas molecules carbon dioxide over other gases. There are many ways for ligand functionalization mentioned below: 7.2.1. Nitrogen site opening: Usually presence of ONS i.e. open nitrogen sites goes in favor of enhancing MOF properties of selection and adsorption of carbon based gases, examples include tetrazole. When CPF-6 MOF is coordinated, the tetrazole ligand having high amount of uncoordinated nitrogen sites, formed a compound that possess high adsorption for CO2 [44] even in absence of OMS (open metal sites). The adsorption ratio varies with different open nitrogen sites, in some cases their presence enhances adsorption while sometimes decreases the same. To elucidate, MOFUTSA-49 [Zn(mtz)2 ], the tetrazolate ligand that is attached to it contains open nitrogen sites via (5-methyl-1H-tetrazole) and CH3 groups. The interaction between zinc metal and mtz− ligand leads to formation of 2 free nitrogen which are present adjacent to the methyl groups hence the remaining uncoordinated nitrogen on the pores of surface will help in efficient capturing of CO2 that is found to be 13.6 weight percent at 1bar and 298 k [45]. Another class of ligands involve adenine groups because of number of nitrogen groups presents at various positions allow variety in MOF structure; also, adenine groups are coplanar hence leads to π –π interaction between ligands [46]. Furthermore, another study reported the effects of size of chain length of ligand attached to the MOFs for carbon dioxide capture, results states that larger the size of chain lower will be the adsorption due to chain entanglement leading to less OMS [47]. 7.2.2. Functionalization via amine groups: High affinity of amine ligands for carbon dioxide ligands make them the first method to opt for CO2 selectivity and adsorption. It is evident that amines fall in category of Lewis bases while carbon dioxide act as Lewis acid [48]. According to the results published by Pachfule [49] he discovered two amine functionalized MOFs i.e. Cd-ANIC-1 and Ca-ANIC-2 where ANIC stands for 2-amino-isonicotinic acid. The capacity for capturing CO2 gas in each case is very high that is found to be 4.72 mmol/g and 4.22 mmol/g respectively.

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It has been found that along with merits possessed by amine groups in capturing of gases there are some demerits as well, according to which whenever a high amine group containing ligand is attached to the metal framework the excessive cluster of these ligands will cause interlaces on the surface of framework leading to reduction in adsorption capacity. Also, chain length of amine groups needs to be considered in context to the same research team [50]. Experiments by using different chain lengths, the results suggested that groups with shorter length shows greater adsorption in comparison to the other with larger chains. 7.2.3. Sulfonates and phosphates functionalization: With relation to adsorption enhancement along with stability of frameworks the above mentioned two groups need to be taken into account. They enhance framework stability towards water at a considerable rate [51]. It has been found out that presence of water in MOFs impact their stability towards adsorption of gases [52]. According to the first study carried out by marco, he synthesized two phosphate ligand coordinated MOF, [(Cu3 (H2 L2 ) (bipy)2 ·11H2 O), H2 L2 and [N,N,N΄,N΄tetrakis(phosphonomethyl) hexamethylenediamine]. The results explained that the above MOF showed high carbon dioxide absorptivity over N2 gas i.e. 77 cm3 /g at 10 bar Reasons stated for selectivity includes quadrupole moment of CO2 causing attraction to ligand molecules and no vacant pores were left to absorb N2 . On the basis of other publications, CALF-30 and CALF-25 [53] are two MOF which have shown no structural changes even when exposed to water conditions (90 percent) humidity at 298 k and 273 k respectively, this may be due to hydrophobic framework which is generatesd due to steric groups present on the ligand. According to another recent study [54], MOFCALF-33 found to proliferate water stability and adsorption due to the ester groups present on the ligand which increases the active sites for trapping of gas. 7.2.4. Functionalization using other groups: groups like hydroxyl, carbolic, alkyls and many more can be used for enhancement of adsorption of gases on the surface of MOFs. Examples from the studies include functionalization of ligand [Zn3 (bpdc)3 (bpy)].(DMF)4 .(H2 O) and produced [Zn3 (bpdc)3 (2,2’ -dmbpy). (DMF)x (H2 O)y and [Zn3 (bpdc)3 (3,3’ dmbpy)].(DMF)4(H2 O) 1 . In both the cases the volume of pores 2 and the surface area decreases in comparison to the non-functionalized MOF while the adsorption is higher in first and lower in second. This is due to the fact that, if the thrust of carbon dioxide affinity is controlled on space losses, it leads to decrease in adsorption and in second one the reason can be the elevation in affinity for CO2 is not up to the mark for surface loss and volume of pores [55]. 7.3. Post synthetic procedure: Another method for altering the adsorption capacity of metal organic frameworks for adsorption of greenhouse gas carbon dioxide is post synthetic method. The principle followed behind this method is to modify MOF with high selectivity and adsorptive coefficient with minimum energy usage. It differs from presynthetic procedure as in pre-synthetic we usually insert functionalized ligands into the already existing frameworks while in post-synthesis method there is chance of reactions between pre-existed metal sites and ligands functional groups which will make some changes in crystal structure followed by the product. Other drawbacks of pre-synthesis methods involve high attention during Solvothermal process especially due to behavior of function groups in varying reaction conditions; also, solubility of functional groups in used solvent along with hindrances caused by them leads to production of reaction side

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products hence, post synthesis methods [56] has proved useful in comparison to a certain extent. The most exclusive functionalized group used for post synthetic treatment is ethylenediamine symbolized as en. One example is synthesis of en-MOF-74 which shows good adsorption towards CO2 , Moreover it shows remarkable stability in various humid conditions [56]. The first method for post synthetic procedure was introduced by Gadipelli and Guo that is thermal annealing for synthesizing MOF-5 (Zn4 O[BDC]3 ). In this the framework is treated in temperature conditions which are below the decomposition temperature of the framework results in removal of solvent molecules from pore surfaces. Results shows double adsorption in context to unmodified MOF [57]. 7.4. Tuning pore size: As already explained size of pores of metal organic frameworks impact their adsorption capacity and this phenomenon is termed as size exclusion effect. The adsorption capacity of MOF depends upon the kinetic diameter of CO2 molecules and pores of surface of frameworks. Generally, molecules with diminished size can pass through the pores while others cannot. The idea diameter range for CO2 over N2 and methane is 3.3A0 – 3.6A0 . The relative size can be obtained via metal and ligand exchange. According to publications, short length ligands, small molecules of metal, heavy linker are perfect for the same [58]. This effect can be achieved via PS-exchange process. To exemplify, the exchange of metal ion in MOF UiO-66(Zr) to UiO-66(Ti) was discovered by Kim [59] and its carbon dioxide adsorption properties were evaluated by Lau [60]. The outcomes stated that due to small size of Ti than Zr the size of the pores of framework reduces which is more harmonious with the kinetic diameter of carbon dioxide gas, hence capturing enhanced two times along with increase in isoelectric heat. Another way to mitigate pore size of MOF is interlinking between different frameworks by using bulky ligands, also called as interweaving or interpenetration networking [61]. What actually happens in this case is self -assembly [62] of frameworks causing networks hence overall stability will proliferate which ultimate leads to pore size reduction hence capturing capacity will increase for adsorption of gases. When this theory was tested with some MOFs it was found that at high pressure due to reduction of pore size, adsorption capacity decreases while at lower pressure it increases due to availability of open sites. According to publications, a new 2-folded Cd-MOF was synthesized by Qin and his team who found out that this framework shows great selectivity of carbon dioxide [63] gas over methane. Furthermore, Geo and coworkers represented another 4-fold interpenetrated network framework i.e. MMPF-18. This MOF at ambient temperature showed good adsorption selectivity for CO2 [64].

10.8 Methods to enhance MOF stability As the practical applications of MOFs is burgeoning, the most important factor is stability of MOFs. There are different ways to improve the MOF stability i.e. by modifying ligand configuration, coordinate bond property, and metal node characteristics. The methods which will be discussed in this section are: 1. Chemical stabilities 2. Thermal stabilities 3. Mechanical stabilities

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FIGURE 10.6 Chemical stabilities of MOFs.

10.8.1 Chemical stabilities Despite the fact that many MOFs are sensitive to medium atmospheric environment which leads to structural degradation because of the coordination bonds between ligands and metal ions. There are two approaches to improve the chemical stabilities. First is to improve the stability of unknown MOFs and second one is to enhance the stability of known or existing MOFs [65] as shown below in Fig. 10.6. i. Improving the stability of unknown MOFs: It is believed that there are two reasons for destruction of MOFs i.e. breaking of metal ligand bond and formation of more stable product compared to starting MOFs. Factors on which chemical stability of MOFs depends are basicity, internal structure of MOFs, charge density of metal ions, configuration, and connectivity of metal ions and hydrophobicity of ligands.

r High-valent metal containing MOFs: According to hard soft acid base principle, in the similar coordinate environments, hard acids also known as high-oxidation states metals which have high density of charge such as Cr3+ , Fe3+ , Zr4+ , Al3+ etc., [65] which form the coordinate bond ligand and act as donor ligands known as hard bases which form MOFs with good coordination bonding and resulting in chemical stability. To balance the pKa value (carboxylate linkers have low pKa value) high oxidation states metal ions coordinate with great attachment to stabilize the charges. It results into a large amount of connections of metal clusters which also improve the chemical stableness of metal organic framework. r Low-valent metal containing MOFs: Except from the high oxidation states metal ions, soft acids also known as low valent metal ions such as Ni2+ , Zn2+ , Ag+ , Co2+ ,Fe2+ etc., form the

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balanced magnetic organic framework with N-containing linkers considered as soft bases. Azoles large value of pKa and high coordination bonds represent the stability of MOFs in basic solutions. There is directly proportional relation between the pKa value of N-donor ligand and stability of MOFs under the humid conditions. Example – zeolite imidazolate framework (ZIF)−8 also known as MAF-4. r Mixed metal MOFs: A new strategy for enhancement of the chemical balanced metal organic frameworks (MOFs) is to introduce the more than two different metal ions into the MOFs. These MOFs are more stable as compared to single metal MOFs [65]. Different reasons can be considered for this like resulting in strong coordination bonds, increasing the metal clusters inertness and improve the surface hydrophobicity [66]. Its main principle is to replace the existing metal ions to inert species. For example, in MOF-5 the Zn2+ metal ion was replaced by Ni2+ to improve the hydro stability. r Hydrophobic ligand: Hydrophobic groups are attached or created near the metal nodes so that hydrophobic interaction properties of metal MOFs are improved by reducing the affinity of MOFs towards the water or any moisture [65]. The fragile coordinate covalent bonds from the strike of hydro molecules are protected by the hydrophobic functional groups by placing near the metal clusters and it improves the stability of MOFs in water. r Interpenetrated framework: Term interpenetration also known as framework catenation is an alternative method to enhance the MOFs stability. The presence of free spaces in a larger amount in extended porous frameworks leads to high energy which results in instability of MOFs. Interpenetration is defined as the entanglement or interweaving of the two or more frameworks which can be identical or independent [65]. Interpenetration reduces the pore size and increases the wall thickness of the framework. Interpenetration does not allow the movement of the ligand by fixing it on one place within the framework which leads to more stable MOFs structures formation [66]. ii. Improving the chemical stability of existing MOFs: The method used for improving the chemical stability using unknown MOFs has some limitations so another strategy were introduced i.e. enhancing the chemical stableness of already known MOFs. This has major four approaches which includes, post synthetic modification, post synthetic exchange, composite fabrication and hydrophobic surface treatment [65].

r Post-synthetic modification (PSM): PSM is an important technique for the formation of new MOFs from the existing MOFs to better the chemical properties of the parent metal organic frameworks. Combination of metal clusters and organic linkers in MOFs offers major chances to a wide scope of chemical modifications. It states that inserting a specific functional groups through the (PSM) method can change the pore conditions of MOFs [67]. PSM is further classified into four parts i.e. metal based modification of MOFs, ligand based, metal and ligand based and guest based [70]. Metal based modification of MOFs includes the metal exchange where breaking of the coordinate bonds and formation of new bonds takes place, epitaxial growth on the surface, metal incorporation or also known as metal doping. Ligand based modification of MOFs includes ligand exchange in MOFs, ligand installation and ligand labialization or ligand removal [70].

r Post- synthetic exchange (PSE): It is the method which can improve both chemical and physical properties of MOFs through linker exchange in which the replacement takes place

10.8 Methods to enhance MOF stability

225

of counter ions present in MOFs and metal ion metathesis. The process PSE has the ability to expand the toughness of bonds of unstable SBUs coordinate covalent bonds and adjust the MOFs water protection without disorganizing the framework structure [65]. r Hydrophobic surface treatment: The introduction of functional groups in MOFs, the adsorption and porosities properties gets reduced. Hydrophobic surface treatment technology was created to solve this issue. To prevent the MOFs from water this technique is used on the exterior plane of MOFs that leads to protection of porosity to a greater extent. Hydrophobic surface treatment included three processes, post synthetic annealing, post synthetic surface moderation and surface coating. Surface water repellent coating protect from the attack of water for example (PDMS) polydimethylsiloxane coating improve the stability of MOFs [65]. r Composite: the compatibility and porosity of MOFs are the two factors which allows the hybridization of MOFs with different materials like graphite oxide, polymers, carbon nanotubes etc. [68] by inserting the MOFs on the pores exterior either inside the holes or by inserting different substances into the left out space of MOFs resulting in MOF composites. MOF composites can be prepared with merged property or show new outcomes, hydrostability, hydrophobicity, mechanical properties etc.

10.8.2 Thermal stabilities Breakage of node and linker bond resulting in thermal deterioration of MOFs is the most common cause which is followed by linker combustion. As a result, number of linkers and bond strength of node-linker are both related to thermal stability. Melting, amorphization, graphitization or linker de-hydrogenation (anaerobic), node-cluster dehydration are all example of thermal degradation. The degradation products are useful materials in the linkergraphitization process. The majority of MOFs contains divalent cations for example: Cd(II), Co(II), Zn(II), Cu(II) and N-donating linkers or carboxylate. Higher valency metal centres for example Ti(IV), Zr(IV), Al(III), Ln(III) [69] with the presence of oxyanion terminated linkers improves thermal stability as we increases the metal ligand bond strength. Changing the composition of linker pendent groups is another technique to enhance thermal stability, increasing bond strength. Framework catenation or interweaving or interpenetration of networks can improve the thermal stability fostering positive framework-framework interactions. As we increase the crystal density the absolute energy of polymorphs decreases according to computational results [69]. By applying mechanical stress more stable compounds can be form by changing MOFs phase. Catenation process can also be used but not all the time. It is useful for limited application. Catenation can improve the intriguing properties of MOFs for example huge pore columns. Despite the fact that this has yet to be investigated, by changing the MOF node structure, thermally driven dehydration occurs at temperatures below those for framework disintegration and it affect directly on the MOFs structures catalytic activity. Direct loss of water ligands or by deflating the hydro ligands into molecular water and oxo ligands can both cause dehydration [69]. There are two types of techniques which can measure the thermal stability of MOFs i.e. in situ PXRD and thermogravimatric analysis (TGA). PXRD gives the more detached information, but TGA is used for screening.

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10. Metal Organic Frameworks as an Efficient Method for Carbon dioxide capture

TABLE 10.1 Some MOFs used for CO2 capture. Name Of MOFs

CO2 Uptake

Pressure

Temperature

References

MIL-102

3.4

3 MPa

298 k

[74]

Zn2 (ndc)2 (dpni)

4.3 mmol/g

1750 KPa

298 k

[74]

MIL-96

3.7 mmol/g

3.5 bar

303 k

[75]

MIL-53-Al, Cr

10 mmol/g

30 bar

304 k

[76]

ZIF-20

70 ml/g

760 torr

273 k

[77]

Cu(fam)(4–4’-bpe)0.5

100 ml/g

760 torr

195 k

[78]

MIL-53

7.5 mmol/g

20 bar

304 k

[79]

Cu(dhbc)2 (4–4’-bpy)

70 ml/g

.4–8 atm

298 k

[80]

Ni2 (cyclan)2 (mtb)

57 ml/g

1 atm

195 k

[81]

Ni-MIL-74

1 percent

1 bar

298 k

[82]

UiO(bpdc)

8 percent

1 bar

303 k

[83]

CPM-33b

1 percent

1 bar

298 k

[84]

DGC-MIL-101

1 percent

1 bar

298 k

[85]

Co/DOBDC

2 percent

1 bar

298 k

[86]

HKUST-1

1 percent

1 bar

313 k

[87]

ZIF-7-R

8 percent

1 bar

303 k

[88]

10.8.3 Mechanical stability Another important factor is mechanical stability of MOFs for industry and practical applications. Under vacuum, MOF pore structure changes its phase or partial collapse of pores occurs which leads to the instability [71]. To avoid these kinds of problems two methods were introduced i.e. solvent evacuation and solvent exchanges. By exchanging the solvents of higher surface tension with the lower surface tension ones which includes n-hexane, CH2 Cl2 , and liquid CO2 followed by solvent removals helps in activating the MOFs [73]. Under mechanical pressure, MOFs show low stability. Another way to improve the mechanical stability is based on the connectivity of the bonding topology. A major role play in mechanical stability is stiffness/hardness of the materials which can be defined by the non-bonded interactions and introducing functional groups which leads to extra framework connectivity through non-bonded interactions [72]. Non-bonded secondary network interactions can improve the mechanical stability of MOF. According to the researcher’s, mechanical stability of MOF (nano porous material) can be improve by two strategies i.e. by modifying the secondary and primary network. Table 10.1 summarizes the various MOF’s used for CO2 capture.

References

227

10.9 Conclusion Research from last 20 years proved to be useful in alleviating the concentration of harmful greenhouse gas carbon dioxide with the help of metal organic frameworks. They are the best opted option till now for the same due to their functionalities which includes excellent surface areas, tunable size of pores, disparity in structures, and their eco-friendly synthesis methods. MOFs proved to be the excellent material for capturing of gases over other zeolites and active carbon compounds due to the possibility of changing its properties via making alteration in the metal ions and organic ligands. Functionalization of frameworks via altering ligand properties by changing attached groups proved to enhance the carbon capturing capacity of MOFs to a considerable value and also enhance their selectivity towards the same. Various research has been going on how to augment the open metal sites by reducing the entanglement caused by large chains to burgeon the adsorption capacity of these frameworks. This area of study needs to be explored more because of its existing potential applications in order to find the solutions of various problems in field of adsorption of gases, sensors, batteries, and many more.

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C H A P T E R

11 Industrial carbon dioxide capture and utilization Uzma Hira, Ahmed Kamal and Javeria Tahir School of Physical Sciences (SPS), University of the Punjab, Lahore, Pakistan

11.1 Introduction Despite the rapid growth of alternative and unconventional energy sources, fossil fuels remain the world’s principal energy source, and their replacement seems unlikely in the future decades [1,2]. CO2 emissions are steadily increasing as a result of increased nonrenewable fossil fuel use and their industrial uses and are considered a major contributor to the escalating challenge of climate change [3]. According to Earth’s CO2 , the average amount of atmospheric CO2 has increased intensely, from 172–300 (parts per million) before the industrial revolution to 416.47 parts per million on 30th May 2020 [4,5]. The disastrous implications of ever-increasing CO2 emissions, such as global warming, climate change disasters, as well as the associated energy and environmental issues, have been a source of significant concern in recent decades. As a result, many investigations on capturing and utilization (CCU) of the carbon dioxide concept are encouraged and suggested. The capturing and utilization (CCU) of carbon dioxide case study is widely recognized as a viable approach to reducing anthropogenic carbon emissions. Capturing carbon dioxide is one of the cheapest methods to decrease the amount of carbon which is being emitted from the chemical industries. The useful compounds and oil recovery can be done by the conversion of raw substances using this captured CO2 through successive utilization processes [6]. Hence, CCU technologies are crucial for solving global emission challenges and carbon-intensive industry in general. During the last few years, substantial improvement has been made in the area of possible industrial carbon dioxide capturing and utilization (CCU) materials and their use in CO2 emission reduction (See Fig. 11.1). Due to the shortage of an appropriate assessment of the progress of favorable CCU methods, particularly from the 2017 to the present, providing a satisfactory and a brief overview of these sophisticated approaches with a thorough understanding is critical. This study seeks to offer a detailed, authoritative, and critical assessment of important CCU achievements, which has gotten a lot of attention due to its great risk of speeding up global warming. The properties and all features of solid and liquid type carbon

Green Sustainable Process for Chemical and Environmental Engineering and Science: Carbon Dioxide Capture and Utilization DOI: https://doi.org/10.1016/B978-0-323-99429-3.00023-0

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11. Industrial carbon dioxide capture and utilization

FIGURE 11.1 Industrial CO2 capturing and utilization scheme.

dioxide capturing substances were studied briefly under various operational settings, as well as prospective orders were also suggested for the improvement of their ability to capture CO2 and CO2 utilization developments in various domains.

11.1.1 Commercial capturing processes of carbon dioxide gas Carbon dioxide capture is excessively acknowledged as an important step in reducing carbon emissions from fossil fuel use [7]. To keep atmospheric CO2 levels at 350 ppm, by the end of the century, at least 550 giga tones (Gt) of CO2 will have been eliminated [8]. CO2 can be trapped in a variety of ways, for example, pre, oxy-fuel and post-combustion [9]. After burning of fossil fuels, CO2 emitted from carbon-containing materials is adsorbed during the post-combustion process. CO2 is separated from fossil fuels before they are burned in precombustion technology [10]. The oxy-fuel combustion method minimizes the amount of N2 used in the combustion process and replaces it with pure O2 [11]. Post-combustion carbon (PCC) capture needs the least amount of modification of existing facilities, making it the most efficient method for reducing carbon emissions. The low temperature based solid CO2 capturing systems and the liquid CO2 capture material system are the most often used CO2 capture systems for PCC. Meanwhile, in some sectors, hightemperature solid CO2 capture materials systems might be utilized. Liquid amine- and ionic liquid-based CO2 capture systems are the two most common types of liquid-based CO2 capture systems. Carbon, solid-amine, zeolite, alkali carbonate-based compounds are common low-temperature solid CO2 capture adsorbents. However, the low CO2 partial pressure in flue gas remains a significant separation problem, resulting in insufficient driving power for CO2 collection and a large amount of gas to be handled [12].

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The pre-combustion process may be used for a variety of industrial process like in the hydrogen power plant, and coal-fired station. The generally used solid CO2 capturing compounds can be separated into high temperature-based CO2 sorbents and medium-temperature adsorbents depending on the temperature at which certain industrial processes operate. However, the most pressing issues for present pre- and post-combustion CO2 collection include optimizing high regenerability, high CO2 reversible uptake, kinetics optimization and moisture effect.

11.2 CO2 collection systems based on liquid Given the seriousness of the worldwide heating problem, it is critical to advance costeffective and practical CO2 collection methods at the commercial level. CO2 collection Process is usually linked with CO2 /N2 separation in fossil fuel combustion exhaust flue gas. Chemical absorption, solid adsorption, and membrane separation are the three basic methods used in PCC. Chemical absorption takes advantage of CO2 ’s high reactivity to provide a high collection efficiency and rapid absorption rate. Furthermore, the use of a solvent/absorbent based on liquid in the absorption process might be simply incorporated into existing fuel-fired power stations, making it a very promising short-to-medium-term CO2 capture method. According to statistics, absorption-based procedures account for over 60 percent of PCC technologies [13]. Because of their high rate of absorption, huge CO2 capacity, and chemical/thermal durability, low viscosity, solvents based on amines, such as methylethanolamine (MEA), are the most commonly used absorbents [14]. Despite this, amine-based CO2 absorption systems have high restoration energy requirements, amine decomposition and equipment corrosion during operation. The development of innovative liquid-based CO2 absorbents has sparked a lot of attention in the scientific community. From the point of molecular engineering, a full overview of recent advancements in CO2 capture processes based on liquids, including ionic liquids and solvents based on liquid amines, materials should be provided.

11.2.1 Amine-type liquid solvents for capturing CO2 gas Most commonly used liquid absorbents for carbon dioxide capturing and utilization (CCU) are liquid amines because of their large absorption rate, low viscosity, and large CO2 potential, and thermal/chemical stability [14]. Despite this, amine-based CO2 absorption systems have high restoration energy requirements, amine decomposition and equipment corrosion during operation. The filtered gas exits the absorber with a CO2 removal effectiveness of ∼ 90 percent in most cases. Thermal fluctuation process is then used to liberate the trapped CO2 from the enriched CO2 solution at an elevated heat range between 100 and 120°C. Chemical absorption’s great selectivity allows for an almost pure CO2 as a product at the stripping exit. Amine-based absorbents have a significant advantage in CO2 absorbing at reduced pressure and dilute flue gas cascade, to make scrubbing of amine an appropriate method on a wide view, CO2 emission sources with a fixed point of emission. Therefore, due to high desorption energy consumption, chemical absorption’s reactivity offers resistance behavior. The energy generally utilized in the CO2 inclusion/exclusion process (See Fig. 11.2) covers reboiler renewal energy, electrical energy is provided to the pumps and compressor for CO2 collection process. The considerable regeneration heat required in the reboiler is the

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FIGURE 11.2 The characteristic absorption/desorption procedure for industrial CO2 capturing through using liquid solution and solvents, which is favorable for low energy consumption [15].

greatest impediment to utilizing this “wet-scrubbing” technology. There are three sources which regenerate the energy: (1) Energy absorbed or released is used for providing heat to the solvent, (2) Energy produced during reaction used for CO2 capturing, and (3) latent heat used for solvent evaporation step, in a particular example, water is used for an aqueous amine solvents. The inherent features of amine solvents are represented by these three sections. Low regeneration energy consumption is a benefit of the solution’s qualities. Low stripping volume, high cycle capacity and low heat capacity are the first three requirements. A solvent with a high cycle capacity usually has an enlarged assimilation potential capacity for the assimilation process and a high dissimilation rate potential for dissimilation process. Secondly, for the reduced reaction energy, a reduced enthalpy rate for CO2 desorption is advantageous. The low value of reaction enthalpy, on the other hand, may be linked to a high stripping-steam needed and a high value of latent heat. Thirdly, getting low latent heat requires a small amount of stripping-steam and low evaporation enthalpy. When researching new solvents, various factors such as equipment corrosion, amine decomposition, reaction kinetics, cost, viscosity, and environmental friendly options should be considered [15] (Fig. 11.3).

11.2.2 Basic working principle of absorbents based on liquid amines Methylethanolamine (MEA) has been used commercially as the most robust amine absorbent, to capture carbon for over 50 years. Moreover, many other liquid amines, such as N-MDEA and DEA, are also commonly used and studied. These materials use a reversible process to absorb and desorb CO2 . The CO2 absorption performance is mostly determined by the chemical structure of the chosen amines. The quantity of hydrogen atoms bound to nitrogen atom in amines are divided into the three categories: PA (Primary Amine) with –NH2 ligand. SA (Secondary Amine) with the –NH ligand TA (Tertiary Amine) with the –N ligand

11.2 CO2 collection systems based on liquid

235 FIGURE 11.3 Representation of the probable reactions happening in the molten alkalibased metal nitrates-covered magnesium oxide.

In the given situation, binding energy of certain liquid based-amines differs depending on their basicity. The following is the order of binding energy between CO2 and amines: PA < SA < TA

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The net reactions of different amines with CO2 are as follows: a) For primary amines/secondary amines: CO2 + 2R1 R2 NH  R1 R2 NH2 + + R1 R2 NCOO– b) For tertiary amines: CO2 + H2 O+R1 R2 R3 N  2R1 R2 R3 NH+ + HCO3 – R1 and R3 represent to the alkyl/alkanol group whereas for primary amines, R2 denotes the hydrogen atom, whereas for secondary and tertiary amines, R2 denotes the alkanol/alkyl substituent. The zwitterion reaction mechanism is widely assumed to govern CO2 absorption in primary amines and secondary amines [16,17]. Following the CO2 reaction, these amines create a carbamate, due to a strong C–N bond formed in the carbamate, it has a quick absorption rate but a high regenerative energy [18]. The enthalpy value of absorption reaction of the CO2 for PA is typically 80.0–90.0 kJ/mol CO2 and 70.0–75.0 kJ/mol CO2 in secondary amines. A base-catalyzed hydration process absorbs CO2 into tertiary amines, in which tertiary-amines increase CO2 hydrolysis to bicarbonate production, as a consequence, the CO2 capability is large and the regenerative heat is low, but the absorption rate is very sluggish. Furthermore, the value of enthalpy of CO2 absorption rate in tertiary-amines ranges from 40 kJ/mol to 55 kJ/mol. As a result, there is a barter in rate of absorption and regeneration energy for CO2 collection with help of single amine. Absorption of CO2 by a single amine is plainly insufficient to produce all of the desired outcomes. One of the most successful approaches for CO2 extraction from energy plants that ignite natural gas or coal is the absorption process employing liquid amine solvents. Nonetheless, amine-scrubbing techniques encounter a number of difficulties. Due to demand of high energy for the regeneration of solvent, most significant disadvantage is the high running cost, regardless of the fact that it is the cheapest PCC technology available [19]. During carbon capture, the energy-intensive regeneration process has 60.0 percent higher consumption of the total energy. MEAs renewal energy (almost 4.0 GJ t1 CO2 ), in instance, far surpasses both the theoretical and tolerable limits (0.40 and 0.72 GJ t1 CO2 , respectively). Second, amine degradation is seen as a significant impediment to CO2 collection utilizing absorbents based on amines, because it increases the overall CO2 collection cost by 10 percent of total and creates possible secondary pollutants, it is not recommended. Furthermore, several decompositions of the products have been demonstrated to enhance corrosion in stainless steel and carbon steel systems. Some of the amines and amine intermixes with high degree resistance of disintegration have recently been explored to reduce operational costs and amine loss caused by amine decomposition. Several other inhibitors can also be utilized as oxygen scavengers to slow down the breakdown of amines. Third, the corrosion of the equipment is a problem in the absorption process of CO2 because an electrochemical reaction is involved with wet CO2 , which limits life expectancy of machinery and even creates unplanned plant downtime and safety mishaps. Amine-scrubbing apparatuses, which are often composed of carbon based-steel, are easily corroded, especially in high-temperature locations like the regenerator and heat exchanger. CO2 concentration,

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temperature, specific breakdown of the products, the amine utilized, and the oxygen content all influence corrosion rates. Furthermore, heat stable salts (HSS) are typically generated when amines react irreversibly with degradation of the materials or the other contaminants in the input gas [20]. They are unable to soak up CO2 or disintegrate along with the heating solvent renewal process. The accumulation of HSS in the mechanism of absorption can cause a variety of operational concerns, including a loss in CO2 capacity, excessive corrosion, foaming, and fouling [21]. In general, the most common procedures for removing blended HSS from used weak amine absorbents are thermochemical reclamation (distillation), electro-dialysis (ED), and ion exchange. Thermal reclamation is the distillation process of the separated amine which is away from the bottoms that contain HSS. ED uses a DC electric field to separate HSS that requires no extra substances. Thus, it is an energy-saving technique having a tiny imprint [22]. Nonetheless, in the DC field, the ED process suffers from significant amine loss. HSS anions can be changed into hydroxide ions using ion (basic) exchange resins that contain OH– from KOH or NaOH. This maintains the lost amines’ capacity to absorb CO2 . However, this procedure uses a lot of hydroxides of sodium or potassium (NaOH or KOH), and the resulting useless water that is alkaline, pollutes the environment severely [23]. As a result, these restrictions encourage more research into chemical absorption for CO2 capture.

11.2.3 Advances in amine-type liquid absorbent materials The principal disadvantages of the amine-exfoliating method, namely high renewable energy, amine disintegration, and machinery erosion, are induced by intrinsic properties of the particular amines, including poor thermal permanency, destructive character, and more CO2 desorption enthalpy value. As a result of these factors, there has been a lot of research into finding alternative solvents to conventional amines. The development of absorbents based on liquid amines have received the most consideration due to the good CO2 absorption capability of amine solvents. Several absorbents based on liquid amines, such as solvents of mixed amines, solvents based on non-aqueous amines, and bi-phasic solvents, have been developed to improve amine scrubbing’s carbon capture ability and eliminate the downsides. Additionally, catalyst-assisted regeneration is offered as a feasible method for lowering CO2 desorption below 100 o C while also reducing energy demand. As a result, the next section of this chapter contains a full status report on these four types of absorbents based on liquid amines.

11.2.4 Mixtures of amine solvents A mixture of all types of amines have been created to solve the constraints of employing a single amine for CO2 capture. The advantages of different amines include their rapid absorption rates (originating from primary/secondary amines), low extrusion reaction enthalpies (originating from tertiary/sterically-hindered amines), and high absorption capacities, can be reconciled by blended amine solvents, resulting in a novel amine-based regeneration CO2 astringents. A bi-amine mix is created by combining specific primary/secondary amines with dissolved tertiary amines to achieve optimal efficiency. Blending a little amount of MEA with aqueous MDEA, for example, increased CO2 absorption accelerates MDEA while lowering

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heat recovery as compared to solo MEA. Furthermore, raising the MEA/MDEA ratio can improve kinetics of reaction and mass transit rates. Increasing the number of components to generate tri/quad-amine integrates may aid to maximize CO2 intake/release efficiency while reducing regeneration heat. The overall performance of blended amine solvents incorporating multi-components has shown considerable increases in reaction kinetics, Stability, solubility of CO2 , corrosion problems, mass transfer issue, and regenerative heat. CO2 absorption response mechanism is complicated because of the intricate constituents of mixed amine absorbents. Liu, et al., applied the concept of mixed amines based on non-aqueous solutions and used 13 C NMR to compare the reaction mechanisms of (TETA–AMP) in both non-aqueous solvents and aqueous solvents [24]. During CO2 absorption, carbamate was produced initially, followed by CO3 –2 /HCO3 – ions. As a result, CO3 –2 /HCO3 – was absorbed subsequent to desorption of carbamate. In contrast, the non-aqueous counterpart generated carbamate and C2 H5 OCO2 . 11.2.4.1 Amine-based solvents that are non-aqueous The deionized water in a conventional aqueous amine absorbent causes a number of issues. Its large heat capacity and vaporization heat make energy-efficient regeneration difficult. Furthermore, aqueous conditions are undoubtedly linked to equipment corrosion. Novel possible non-aqueous absorbents have recently received a lot of scientific attention. Several organic compounds, such as EG (ethylene glycol) and di-EG, can be used as water substitutes because of their poor heat potential, stripping-temperature value and enthalpy of evaporation [24]. Because of the comparatively poor heat potential and the value of enthalpy of evaporation for organic solvents, the majority of the needed regenerative energy is utilized to decompose the CO2 -related materials, whereas sensible-heat value for solvents and heat of vaporization for solvents are greatly reduced. As a result, non-aqueous amine solvents allow for lower energy use while keeping aqueous amines’ CO2 absorption reactivity [25]. Furthermore, low range of stripping-temperatures can decrease losses of amines, oxidative and thermal decomposition, and corrosion of machinery when compared to typical aqueous solvents [26]. New non-aqueous absorbents with higher performance have recently been the focus of intense research efforts. The non-aqueous solvent AMP–AEEA–NMP, for example, was produced with an influx of 1.65 mmolg–1 for CO2 [26]. With a total regenerative heat of 2.09 giga-Joule per tones of CO2 , or roughly half that of the aqueous 5 molar MEA solution, NMPs poor heat potential was appropriate for its low value of heat and its low value of enthalpy of evaporation was appropriate for its lower latent heat. Through the production of carbonate species, 2-piperidineethanol–ethylene glycol a non-aqueous solvent recently achieved potential of 0.97 mol of CO2 mol–1 and CO2 desorption occurred at 50 °C, presenting a possible replacement for conventional amine solvents [27]. The CO2 absorption feature of many absorbents, which were non-aqueous and aqueous, was compared by Barzagli et al., [28]. In the amine/CO2 /solvent systems, 13 C NMR spectroscopy was found to be a useful approach for determining reaction mechanisms and distribution of species. In the aqueous solution, There was the creation of carbamate and bicarbonate Only carbamate has been produced in non-aqueous conditions. In non-aqueous conditions, the absorption rate was higher and the CO2 loading was lower. in place of water, two different types of glycol-ether have recently been used to dilute methyl ethanolamine [29]. Therefore, the solvents which were non-aqueous, only carbamate was formed, while 13 C NMR revealed both carbamate and bicarbonate. Non-aqueous solvents outperformed

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aqueous 5 M MEA in terms of desorption effectiveness, vaporization heat, and cyclic capability of 1.45 mmol g–1 . As a result, when matched to the aqueous 5 molar methylethanolamine classification, the non-aqueous solvents low value of regenerative energy by 55 percent. The viscosity of amines which was non-aqueous, however, showed a dramatic increase in value when CO2 is added. The quick increase in viscosity during absorption of CO2 in non-aqueous absorbents based on amines has been identified as a critical parameter for commercial use, as it impairs mass transfer and liquid transportation. Liu et al., [30] projected a new technique to minimize the Carbon- dioxide mixed in non-aqueous solution viscosity based on the structural correlation. As non-aqueous CO2 capture solvents, a series of ethylene di-amine derivatives were developed. Lower viscosities and high regeneration characteristic were achieved in range of 50–80 °C. Furthermore, using organic-diluent having high volatility alcohols might result in significant solvent loss [31]. Some non-aqueous solvents based on amines have also been found to have poor regeneration ability without N2 sweeping. Various small-scale experiments are needed to evaluate amazing total carbon sequestration capability before utilizing non-aqueous solvents based on amines in industrial applications. 11.2.4.2 Biphasic solvents Biphasic solvents have caught a lot of attention because of their low stripping volume and low regeneration energy consumption [32]. They are classified as: liquid & solid and liquid & liquid biphasic-based solvents that depend on the CO2 -rich transition state. The homogenousabsorbents may be divided into two separate layers by CO2 absorption or temperature change. The CO2 -lean layer is one, and the CO2 -rich layer, contains the large quantity of the captured carbon dioxide gas. Only the CO2 -rich transition state, which is related with a flow of restricted volume and very high concentrated CO2 , requires a stripping-process, allowing for lower heat of vaporization, value of sensible heat, and CO2 pressure. As a result, a much more effective regenerating procedure, and less CO2 work on compression might be achievable [33]. Using the thermomorphic biphasic solvent DMXTM , IFP Nouvelles Sources of power initially created a DMX-process. The desorption heat is only 2.1 GJt–1 CO2 , whereas the reproduced heating for the traditional 5 molar MEA material is up to 4.0 GJ t–1 CO2 [34,35]. Mixed amine-based biphasic solvents, which typically contain all types of amine, have recently received a lot of attention. The absorption accelerator in the CO2 absorption reaction is a primary/secondary amine-based –NH2 or –NH groups, such as MEA and DETA, which forms protonated-amine and carbamate with high value of ionic strength. Liquid–liquid phase separation is aided by unreacted tertiary amines with a high hydrophobicity, for example diethylenthanolamine (DEEA), N,N-dimethylcyclohexylamine. Blended-amine solvents such as DEEA/DETA, TETA [36], and pentamethyldiethylenetriamine/ DETA, for example, showed change in transition state after CO2 absorption. The MEA–DEEA and AEEA–DEEA blended amine-based biphasic solvents have a large cyclic potential (∼ 0.64 mol of CO2 mol–1 ), a quick split time of transition state, and a low value of regenerative energy (2.56 gigajoule per tones of CO2 ). Higher value of the viscosity is frequently linked with CO2 mixed in biphasic solvents, particularly because the CO2 -rich phase is highly concentrated. With the use of AMP, the excessive viscosity might be reduced [37]. Furthermore, the mixed amine biphasic solvent had an abnormal strong CO2 injection and a good value of phase volume ratio, which was harmful

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to lowering regeneration energy usage [38]. Later, (1-methyl-2-pyrrolidinone) chemical was utilized to partially replace H2 O in the mixed amine biphasic solvent to improve the phasesplitting property [39]. Some organic solvents, for example 1-propanol and sufolane, have recently been observed to cause amine absorbent phase separation because of hydrophilicity differences [40,41]. The mechanism/procedure of carbon dioxide absorption in the biphasic solvent methyethanolamine–sulfolane is depicted. Sulfolane facilitated phase splitting of the methyethanolamine solvent during CO2 absorption, producing a hydrophilic CO2 -enriched stage and a hydrophobic CO2 -depleted phase. The CO2 absorption rate increased due to the significant interaction between sulfolane and CO2 . Furthermore, the regeneration energy needed to remove such a CO2 -rich stage was restricted to ∼ 2.67 GJ/t CO2 . Sulfolane was also used to fine-tune the DEEA–TETA solvent’s phase-splitting characteristics [42]. The addition of sulfolane to the absorbent increased the hydrophobic composition, lowering the percent volume of the hydrophilic CO2 -enriched state[42]. The quantity of energy prerequisite to regenerate the CO2 -enriched stage was decreased to 1.81 gigajoule per ton of CO2 . Developing innovative low regenerative heat biphasic solvents, quick rate of absorption, big CO2 absorption potential, low value of viscosity, higher stability, and lower value of volatility has remained a key problem to date. Furthermore, existing CO2 absorption systems utilizing biphasic solvents must be optimized in order to decrease energy intake and operational budgets for CO2 arrest. 11.2.4.3 Regeneration with catalysts Catalyst-assisted regeneration is currently in its early stages of development as a new technique. Catalysts for solid acids, such as metal-oxide compounds and molecular sieves with functional properties, have been added into absorbents based on amines in this scenario to enhance carbamate degradation and at that time eject the absorbed CO2 at lower temperature [43]. As a result, solvent regeneration at lower temperatures was possible, resulting in significant reductions in stripping steam and regeneration energy. Furthermore, some disadvantages linked with higher temperatures, including corrosion and decomposition, would be alleviated. Various solid- acids have been designed and tested for their catalytic desorption capability CO2 at lower temperature values and decrease the energy intake in energy recovery. The γ -Al2 O3 and solid-acid (HZSM-5) have been shown to successfully maximize CO2 rate of desorption and reduce regenerative energy. For solid catalysts to enable CO2 desorption, acid power, and the Bronsted to Lewis-acid ratio are also crucial. The TiO(OH)2 nano-catalyst has recently been shown to improve the rate of carbon dioxide desorption from the absorbent methyenthanolamine by more than 45,00 percent, allowing for desorption at a lower value of temperature [41]. The CO2 desorption efficiency, cyclic capacity, and desorption rate were reported to improve by 32 percent, 56 percent, and 54 percent, respectively, with ZrO2 and ZnO [43]. At 80 °C, Ag2 O–Ag2 CO3 showed better catalytic activity in solvent regeneration, increasing CO2 desorption rate by 1000 percent [44]. Metal-oxide compounds and molecular sieves with metal modifications are among the solid acid catalysts produced by Liang and Tontiwachwuthikul’s group. The energy required for regeneration was lowered by up to 40 percent [45–48]. The basic and acidic sites, mesopore shape, and more surface area to volume ratio are the essential catalyst characteristics that impact CO2 desorption performance. Strong basic and acidic sites, in particular, could

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considerably improve the catalytic mechanism. The catalytic process benefits from a higher value of Bronsted to Lewis acid ratio. The massive mesoporous SSA also boosts the active site availability for catalytic reactions. Furthermore, catalytic activity has been found for catalysts with two sites containing both basic and acidic sites, for example SZMF [45–48]. The SZMF catalyst has been presented as a potential desorption pathway. The MEA regeneration process was controlled by the zwitterion mechanism, which consisted of two steps: carbamate breakdown and protonated amine deprotonation. The metal atoms such as Fe, Zr and acidsites, on the other hand, assisted the transition of MEA-carbamate to MEA and CO2 . Lowtemperature CO2 desorption was made possible by the innovative method, which was energyefficient. The catalyst-assisted regeneration method has a lot of promise for lowering the necessary regeneration heat duty. However, being a newly created strategy during early stages of progress, catalyzed regeneration research area is confined to a few different types of catalyst compounds, certain of them are costly, hard to detached, and unstable, making catalyzed CO2 desorption a pipe dream. Designing solid acid catalyst compounds with good catalytic activity, higher stability, cheap, and facile fragmentation is critical. Furthermore, future industrialization will require the development of a viable the absorption–desorption cycle using solid-acid catalysts.

11.2.5 Overview and prospects for liquid amine-based absorbents CO2 capture through liquid amines, finding new effective absorbents and designing a CO2 capture method with adequate heat integration remain important problems. Blended amine solvents, which are among the promising solvents based on amines under study, are maintaining good CO2 adsorption capability, including quick absorbing speed and low regenerate heat, they are viable for utilization in commercial application in the coming future. Furthermore, the classic amine absorption procedure may be employed virtually straight without modification. Blended amine solvents have been validated as viable alternatives to conventional single amines in lab and pilot plant research. To investigate blended amine solvents on an industrial scale, not only performance-limited aspects like cyclic potential, desorption, Kinetics of absorption, value of enthalpy should be considered, but also various additional factors like volatility, viscosity, corrosion, toxicity, decomposition, and market value. Screening analysis on biphasic solvent systems have been carried out frequently in the last decade. They have the ability to reduce low regeneration heat without losing CO2 capacity or rate of absorption. However, the issues of higher regenerative temperature and high viscosity in combination with biphasic solvents must be further investigated. For further scale-up pilot experiments, biphasic-solvents that operate well overall, such as lower regenerative heat, lower degradation, fast absorption rate, high CO2 absorption potential, lower corrosivity, low value of viscosity, and lower volatility, are urgently needed. Furthermore, process development and optimization are critical for achieving industrial-scale low-energy CO2 capture. Conditions that are not aqueous We are still in the early stages of developing better amine absorbents & catalyst-aid production. Prior to industrial use, their viability should be assessed. Non-aqueous amine absorbents offer excellent chances to strip CO2 at lower temperatures with less regeneration heat, minimizing amine loss and equipment corrosion.

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The investigation of the CO2 absorption/desorption mechanism and solvent screening are still ongoing. The quick increase in viscosity during CO2 absorption, significant volatility while using alcohol as an organic-diluent, as well as low restoration efficiency without N2 sweeping, should also be considered. Production through catalysts is still being studied in the lab for the layout of effective catalysts and the process of catalytic desorption, but it could be industrialized in the near future. A few solid-acid catalyst materials have been suggested so far for the use only. Designing efficient solid acid catalysts with outstanding stability and cheap cost for low-energy CO2 desorption is very desirable. Furthermore, customized methods for each technological choice should be developed in order to drastically decrease energy intake and operational price.

11.3 CO2 capturing with ionic liquid solvents Various absorbents for classic solvents based on amines have been the subject of extensive investigation. ILs are organic salts with a designable organic cation and anion. They have intrinsic structural adaptability, lower corrosion, good thermal stability, low volatility, and higher solubility of CO2 [49] making them prospective applicants for CO2 collection with low value of volatility, lower corrosivity, higher degree of stability, low degradation, and low regenerative energy. The primary benefit of ionic liquids is CO2 capturing, that is why they have good potential to absorb CO2 while using less regeneration heat than solvents based on different amines.

11.3.1 Working principle of ionic liquid-based absorbents Physical absorption of functional ionic liquid is commonly differentiated based on the structural properties and the interaction between ionic liquid Atmospheric CO2 absorption through absorbents & chemical processes. Imidazolium-based ionic liquids, for example, were initially proposed as a method of capturing CO2 emissions. The fluorination of the anionic part and an increase in the alkyl group chain lengths could increase CO2 solubility in physical ILs. The interaction between ILs and CO2 (van der Waals forces) is usually minimal, resulting in lower regenerative energy but restricted absorption speed of CO2 , selectivity, and potential. Absorption process of CO2 through ionic liquids is also found to be restricted by restricted mass transfer instead of solubility of CO2 , because of their high viscosity [50]. Physical ILs have a number of disadvantages that make large-scale industrial application difficult. In physical ionic liquids, mass transfer might be solved by changing suitable anions like [DCN]−1 dicyanamide, or [TCM]−1 tri-cyanomethanide, [50]. Functional ionic liquids, on the other hand, have been anticipated as a system to advance CO2 collection efficiency by adding different active groups for a synthetic absorption. Because of the functional tenacity of polymer electrolytes, it’s indeed possible to customize anion groups to achieve specific features like low value of viscosity, low value of reaction enthalpy, and higher capacity for CO2 . Their absorption enthalpy, in particular, may be easily controlled by the anion that influences the regeneration heat of ionic liquids. As a result, these chemisorption sites of functional ionic liquids showed increased CO2 absorption performance, making them suitable amine absorbent replacements. Furthermore, ILs may directly absorb

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CO2 without the use of a water as diluent agent, and the regenerative portion was streamlined as a result of the ionic liquid’s lower vapour pressure, which reduced regeneration energy even more when compared to the traditional amine-scrubbing procedure [51].

11.3.2 Advancement in ionic solvents To solve the difficulties with physical ILs stated above, certain structural alterations can be made by providing functional groupings for certain tasks. The first functionalized IL was created by substituting a primary amine moiety on the imidazolium cation [52]. IL absorbed CO2 in a stoichiometry ratio of 1: 2, just like MEA, and generated ammonium-carbamate salts. Based on carboxylate- or acetate pioneering ionic liquids for CO2 chemisorption were suggested and extensively researched. When generating novel ILs, the benchmark is frequently [Bmim][acetate]. With the carboxylate reaction product, it has a large CO2 capacity and a low reaction enthalpy. The high temperature deterioration problem and inadequate high viscosity for mass transfer, however, linger unaddressed. Amino acid-Ionic liquids have recently grabbed a lot of attention because of their nontoxic biodegradability and significant CO2 capacity. According to the findings, functional AA-ionic liquids with amino acid or an amine can enhance solubility for CO2 [53]. The long side chain chains of the amino-acid influenced CO2 potential, which was highly connected to reactive amine groups [54]. However, the CO2 -mixed in Amino acid-Ionic liquid solution has a hydrogen bond network that causes significant viscosity that may be reduced through separating the amino–based group in the anion, lowering hydrogen bonding probabilities. [55]. Higher CO2 solubility with stoichiometric ratio of 1:1, higher stability, higher rate of reaction, and AHA-Ionic liquids, which primarily have ([CNPyr]) 2-cyanopyrrole anions, are promising options for CO2 chemisorption [56]. The planned ILs’ viscosity was very low. The reaction processes between [DETAH][AHA] and CO2 are simple to comprehend, with [DETAH]+ enabling rapid CO2 absorption and [AHA] ensuring huge absorption capacity and minimal regeneration heat. The deprotonation of the alkyl chain, which was found by the basic character of the anion along with the lengthy alkyl chains, was confirmed to be a major determinant in CO2 absorption. Despite their promising CO2 collection capabilities, functional ILs are limited in their industrial application due to their low mass transfer for gas and liquid, and expensive price caused by their high value of viscosity. Co-solvent support, encapsulation, and use, in addition to changing the composition of ionic-liquid, are recommended as ways to lower viscosity and alleviate transport problems. 1-propanol–water co-solvent with Dilute double-functional ionic liquids such as ([DETAH][Tz]) resulted in the creation of a biphasic solvent [57]. The massive cost and viscosity of Ionic liquids, as well as their significant value of volatility and energy penalty, severely restrict their usage in carbon collection. The performance of amines and ionic liquids can be effectively preserved by combining ordinary amine solutions with functional ILs as activators. This technique provides a potential absorbent with lower regeneration costs than the traditional amine process along with good economics and higher absorption rates of CO2 than ionic liquids. Liang and co-workers [58] recently investigated CO2 absorption in low viscous binary-absorbents containing imidazoline ionic-liquid and amines. The blended absorbent such as MDEA–[BEIM][BF4 ] had a higher CO2 capability, low viscosity,

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and strong reproduction. Furthermore, when compared to the traditional methylethanolamine with 30 percent by weight of the solvent, the [bpy][BF4]–MEA binary solvent was observed to save 15 percent energy and 7.44 percent money. Furthermore, increasing the concentration of [bpy][BF4] would lower total energy and operational costs even more. Overall, ILs and amine mixes are attractive options for CO2 capture that saves energy and money.

11.3.3 Overview and prospects of ionic liquid-based solvents Because of their low value of volatility, higher stability, lower corrosivity, minimal decomposition, and low regenerative heat, ILs are potential candidates for CO2 absorption. However, various barriers, such as high price and higher viscosity, prevent them from being widely used. The high viscosity would generate a mass transmission delinquent and additional drive exertion for liquid transmission. To maximize the viscosity, reaction enthalpy, and cost of the ionic-liquids, task-specific ILs must be designed. To filter ionic-liquids and examine the effect of various anions and cations, molecular modelling can be utilized. Pure ionic-liquids are currently finding it challenging to compete with traditional amine solvents. By mixing the ionic-liquids with the amine solution or co-solvent, the viscosity can be reduced, and the price problem can be offset by the abridged restoration of heat. Before ionic-liquids can be used on a large scale, a thorough feasibility and economic analysis is required.

11.4 Applications, implementation and challenges At the small scale, a wide range of absorption methods based on amines have been examined. Some topologies and process integration, such as split-flow of solvent, absorber intercooling, stripper inter-heating, and flash-stripper have been thoroughly researched to enhance performance in absorption and lower demand of energy of CO2 collection from power plant exhausts [59,60]. Though the integration process would result in greater plant efficiency, the additional cost is unavoidable because of augmented intricacy of the procedure, [61] It should be technologically and economically assessed before commercialization. A promising alternative for CO2 absorption is the mixture of a solvent with a membrane. CO2 solvent placed on the permeate side can absorb permeating CO2 instantly; after the CO2 molecules have diffused over the membrane, high CO2 removal rates result. Many universities and businesses have recently conducted pilot plant tests and achieved CO2 absorption capacities of up to 80 t CO2 per day [62]. The energy penalty for regeneration is substantially smaller for URCASOLTM (DOW and ALSTOM), IHI, and RS2TM solvents than for MEA [63]. Demonstration scale experiments have recently been carried out in order to offer references for future commercial deployment. Two major technology providers such as Shell CansolvTM and MHI for large-scale CO2 capture based on amines among other PCC technology providers. At the commercial demonstration scale, the liquid-amine based CO2 capture technique has been used in the Petra-Nova and Boundary-Dam projects. Since 2014, the Boundary-Dam project in Saskatchewan, A 160 MW petroleum power plant in Canada has already been established to capture CO2 emissions. As of 2017, a 240 MW petroleum power station in Houston, USA, has been generating 1.4 million tons of Carbon dioxide per year through the Petra Nova project. Unlike the traditional CO2 capture procedure that uses an absorbent based

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on monophasic amine, few absorption procedures for recently found biphasic solvents have been created. A blending unit, such as a decanter unit, is deployed before to the stripper unit in the demixing process of the solvent (DMXTM , IFP Nouvelles Energies).The CO2 rich and CO2 lean different stages are detached in this unit, and the CO2 rich phase is revived thermally [64]. In general, liquid-based carbon capturing and storage (CCS) technology is intended to absorb CO2 from fossil-fuel-related plants. According to CO2 emission reduction targets, the demand for industrial scale carbon capturing and storage technology is increasing. By 2050, carbon capturing and storage technologies are predicted to reduce 30 percent of overall CO2 emission reductions. Despite the fact that the There is still a long way to go before CCS technology can be commercialised. constrained by economic and technical issues. The significant energy consumption related to CO2 capture is the biggest roadblock. For example, when the cutting-edge amine unit is deployed, the power station’s thermal efficiency will be lowered by 18 to 30 percent and electricity costs would climb by 45 to 70 percent, providing a substantial hurdle to CCS technology progress [64,65]. To reduce energy costs and attain a commercially viable price, liquid-based CO2 capture technology still requires significant advancements in solvent chemistry and design of the process. Furthermore, given the current high cost of CCS, its complete deployment will be impossible without appropriate governmental initiatives, for example carbon cost, an acceptable exhausts trading system, a global carbon pricing tax, performance requirements, and CO2 storage restrictions [63].

11.5 Solid CO2 adsorbents for low-temperature applications Solid amine-type adsorbent compounds are good CO2 capture materials, with good capacity at lower CO2 partial pressure ∼ 10–15%percent, low restoration temperature ( Mg > Na sequence. The greater energy of sorption of this chemical revealed that it aids in the carbonation of CaO. CO2 chemisorption, surface reactivity with O2– to generate CO3 2– , and lastly the formation of CaCO3 are all part of the CaO carbonation process. CO2 diffusion and O2– mobility are important elements in CO2 capture. Guo et al. [163] proposed a Zr–Ce-additive with improved CO2 capture of the CaO-based sorbent based on these findings. Oxygen vacancies were formed as a result of the synthesis of Ce2 Zr2 O7 , allowing CO2 and O–2 diffusion and mobility to be facilitated. Huang et al. [164] created an (oxysalt) eutectic doped CaO with a low melting point. At the initial carbonation procedure, loading Calcium oxide with alkali carbonate molten salt increased its CO2 uptake from 3.26 to 10.94×103 mol g–1 , which can be associated with the molten salts high O2– concentration and O2– conductivity.

11.12.3 Modifications in sintering-resistance For CaO-based sorbents, capacity loss is acknowledged as the most critical issue. In this sense, a great effort has gone into reducing sintering and boosting cycle stability. Incorporating CaO particles with inert materials is one of the most feasible options. Supporting materials such as Al2 O3 , MgO, Y2 O3 , CuO, CeO2 , TiO2 , KMnO4 , SiO2 , Cex Zry Oz , La2 O3 , LaAlx Mgy O3 , and CaZrO3 have been completely explored and reviewed in previous studies, but all the good works still need to be highlighted in order to disclose some new edges. According to prior studies, the performance and economy of CaO-based materials are more important. Due to the excellent stability of their derivatives such as Ca12 Al14 O33 , Ca9 Al6 O18 , MgAl2 O4 , and CaZrO3 , additives such as Al2 O3 , MgO, ZrO2 , and their combinations are chosen. Sintering resistance of stabilized CaO sorbents is determined by the degree of dispersion of inert supports. As a result, the study focus is on adopting multiple synthetic methods, such as sol–gel, co-precipitation, hydrothermal, freeze/spray drying, flame spray pyrolysis and milling, to ensure effective and efficient dispersion of the supporting components in the CaO or Ca precursors. Using various precursors synthesized using the aforementioned procedures, stabilized Calcium oxide with particular structure, shape and mixing degree can be obtained. Armutlulu et al. [165] also described an ALD technique for making shell-comprising nanoparticles having an Al2 O3 coating on CaO nanoparticles. Sintering among the particles was efficiently prohibited by enclosing hollow Calcium oxide in a thin Al2 O3 film (< 3 nm). After 30 cycles, CaO with 10 ALD cycles had a CO2 absorption of 55 wt percent (80.50 percent capacity retention), which is greater than untreated manufactured Calcium oxide (40.0 wt percent with 53.40 percent capacity retention); both samples had considerably excellent uptake as compared to limestone’s performance (11.0 wt percent with about 20.30 percent capacity retention). The good morphological properties of Al2 O3 -stabilized CaO were related to its

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great cyclic stability, and the hollow (spherical) structure was widely retained during the cyclic process. The structure and morphology of CaO, particularly the porous structure created by the calcination of organic precursors, have been hypothesized to be affected by calcium precursors. As a result, in many mixing procedures, such as calcium acetate, organic calcium has been used as the CaO precursor. Huang et al. [166] used calcium acetate as a precursor and used a simple non-solvent/solvent approach to make CaO/MgO. The CaO/MgO composite was made at a nm mixing level and showed a CO2 uptake of 59.20 wt percent after 7 cycles (with 95.30 percent of its (initial) capacity retained).

11.12.4 CaO generated from discarded materials Despite the fact that synthetic stabilized CaO has a higher CO2 uptake and is more stable, Because of its high price, it can’t be used in more constructive ways. A growing number of calcium byproducts or inert additions are being made from solid waste or minerals, both of which are economically advantageous. Metallurgical slag, eggshell, seashell, and limestone are all reasonably priced calcium wellsprings. Good example of additives that includes Si, Al, and Mg include Sepiolite, bauxite gravels, ash, fruit bunch, and cement. As a result of the use of these low-cost scrap/raw materials, solid waste management becomes much more feasible. Unlike the chemical reagent-based direct synthesis of stabilised calcium oxide, the extraction of a Ca doped and source is required prior to the formation of sorbent. Mechanical grinding, drying, and mixing are typical procedures for preparing Ca supplies and dopant precursors.

11.12.5 Granulation of powder The studies outlined above are primarily focused on the production and characterization of powdered calcium oxide sorbents. Particles in white powder cannot be used directly for implementation due to elutriation from heat exchanger and carbonator. CaO sorbents are fixed using granulation and resource that enables in the manufacture of moulding materials. While low CaO loading significantly reduces sorption capacity, the converse is also true. Another method is to extrude or spheronize calcium oxide into granules, use the mechanical forces to shape the granules into pellets. The porous structural properties of powder materials are always destroyed when using this method, however [167]. In order to increase the pore size of CaO-based pellets, cellulose [168], hemicellulose [167], plastic wastes [169], lignin [169] and urea [170] were commonly used as pore-forming templates. Polymer is the most commonly used template among these. Calcium oxide pellets were mixed with 30.0 percent microcrystalline cellulose for 20 cycles, and uptake (34.0 wt percent) was increased by 48.0 percent as compared to the untreated materials/pellets, as according Li and colleagues [168]. Porosity promoter’s burning resulted in a significant increase in the number of cavities and gas channels formed by the release of gas and removal of (microcrystalline) cellulose. In recent years, researchers have focused on improving the properties of calcium oxide (CaO), such as CaL, and reducing production costs by developing inexpensive precursors. CaL had already been tested in aircraft and bench plants in the power sector as an outlay choice for scrubbing amine for post-combustion capture or as a catalyst for IGCC pre-combustion. Ca looping for CO2 capture from power systems was tested on a pilot plant by Hanak et al. [159].

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Because of the better penetration for clean energy H2 , more calcium oxide is being used for adsorptive of enhanced H2 production, such as glycerol radical reform, methane reforming [171], ethanol and tar reforming, and gasification of biomass [172]. It is common to use reversible processes like WGS and SR in these hydrogen production reactions. When CO2 is removed from the mixture, a larger amount of H2 is produced, pushing the equilibrium to the right. CO2 capture helps the endothermic reaction because calcium oxide cementation is an exothermic process. The SEMR becomes an exothermic process as a result of this modification, as well. CaO-supported catalysts (bi-functional) such as Nickel/CaO have been developed for sorption-enhanced hydrogen production. Although sintering reduces Bioavailability in bulk CaO, the most common solution is to add additional support, as initially noted. Addition of a Cao carrier and immobile substances (amphoteric oxides) to Ni-based motivators blocks the development of coke, and is the most significant thing with Ni-based catalysts because it makes rapid activity decay. Transition metals, like Ni, have a greater catalytic activity than Pd, Rh, and Pt [173]. Despite this, transition metals are thought to have a greater research trend. Catalysts for simultaneous steam reforming of glycerol and CO2 removal have been characterised by Charisiou et cetera. [171]. Increasing the scattering and grain size of nickel lifeforms resulted in greater resistance to coke formation and calcium oxide sintering in modAl, resulting in more effective glycerol conversion and higher purity H2 production.

11.12.6 Overview and future prospects for CaO adsorbents Before CaO-based sorbents can be used in industrial applications, their costing, activity, stability, anti-crush strength, and shape must all be considered. Because of their higher cost but also lack of stability, chemically synthesized CaOs CO2 sorption capacity and long cycle life have improved significantly. After granulation, CaOs ability to absorb CO2 is significantly reduced, making its activity unsatisfactory, and more importantly. Future research should therefore concentrate on the following areas: 1) preparation of Calcium oxide technology on a large scale from mineral/solid waste, with greater capacity and stability for sorption-enhanced hydrogen production, along with catalyst loading techniques; 2) separation and purification of carbon dioxide and material regeneration; 3) direct conversion/utilization of Calcium oxide sorbents to fix CO2 .

11.13 Pre-combustion applications, implementation and problems The pre-combustion photographing CO2 process extracts CO2 from syngas or gas restructured at high energies (2.0–7.0 MPa) and medium air temperature (200.0–450.0 °C). Carbon monoxide is enzymatically converted to CO2 and H2 in the capture facility, which is site construction after the WGS reactor. However, it can also be consolidated with WGS to change this same equilibration. It is possible to use high-temperature CO2 adsorbents like CaO and Li2 SiO3 to improve H2 production by capturing CO2 in situ during the process of reforming at elevated heat (4450 1C). The PSA technique is preferred for pre-combustion CO2 capture because this can take benefit of great CO2 concentrations (e.g. 15 percent to 60 percent). Precombustion low-temperature classification technique are still confined to laboratory experiments because of the complex processes, expensive tools costs, and energy requirements

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(TRL3). When compared to WGC, which removes CO2 from shifted gas immediately at high temps without or before [174], it has received considerable attention. Weak chemisorbents with reversible CO2 capture work well with WGC systems. Sulfur removal, WGS catalysis, and CO2 capture all take place in one stage in SEWGS technology. This is a pretty standard WGC pre-combustion CO2 capture method. Using commercialised K2 CO3 supported hydrotalcites as CO2 adsorbents, the ECN has been working to expand SEWGS since 2005. The technical validity of SEWGS must have been confirmed in during two-year CCP [175]. Following feed, a co-current CO2 rinse and counter-current vapour purge step were added to the six, ten-step PSA process to reduce loss of H2 in the product gas. A steam rinse was used instead of CO2 rinsing in the successive European FP6 construction CACHET [176] because it reduced productivity and consumed CO2 compression energy. A European FP7 operation CAESAR sought to reduce steam consumption during the rinsing as well as purging stages through implementation parameter optimization [177]. A significant reduction in steam intake could be achieved by accounting for H2 O co-adsorption during flow and rinse processes [178]. According to ECN, the SEWGS innovation was ready to be scaled up in 2013. As of now, SEWGS is used in the Systematic project to capture CO2 from BFG, with the aim of reaching an 85 percent CCR with 60 percent less energy consumption or a 25 percent lower collect cost. TDA developed another PSA-based WGC method for pre-combustion CO2 capture at 190–260 °C using functionalized mesoporous carbon. No degradation in performance was observed after 1500 cycles of adsorption and desorption at the United Nations Carbon Sequestration Core [179–182]. For example, a 10-step PSA predicated on adsorbents patented by TDA can make maximum CCR (>90 percent) and CP (>99 percent) and with little fuel (0.34 MJe kg1), according to recent virtual environment research. The State - owned oil Yangzi Petrochemical Plant in China is where TDA plans to build a pilot-scale PSA facility. On a smaller scale (10 kg CO2 h1), TDA is also developing a poor WGS–PSA consolidated PSA technique [183]. When compared to a single PSA process, the integrated WGS–PSA process improved performance of the system by 0.5 percent. A preliminary study by Tsinghua University found that the ET–PSA method uses 20.3– 26.6 cents less fuel than the Selexol mechanism [184]. Over the course of a five-year project (2011AA050601), an ET–PSA prototype capable of handling 6Nm3 h1 of CO2 /H2 /H2 S mixed gas at 400 1C but also 30 bar was developed [185]. After 75 h of total operation and a total of 1089 working days of cumulative operation, the lab-scale proposed system achieves a CCR of 95,7–98,6 percent and an H2 S elimination ratio of more than 99 percent. Since 2016, researchers have been focusing on high Vapour synthesis with in-situ CO2 separation. Hydrogen sanctity (HP, 99.9994 percent) and hydrogen restoration ratio (HRR, 97.51 percent) from shifted gas have recently been improved in a 2-train Sameera reflux structures [186]. Even by end of 2020, a Shanxi Treasury project aims to construct an ET–PSA component with the a computational power of 5000 N m3 h-1 for the production of high-purity H2 from a petroleum plant (MH2 01506). High-temperature CO2 adsorbents can be used to capture CO2 from methane, biomass, glycerol and bio-oil [187] in a cost-effective manner. It eliminates need for a distinct WGS fission and H2 purification process by absorbing CO2 at the production point. Endothermic reforming activities can be supplied with thermal energy via the linked carbonation process. Other than traditional fixed-bed structures, the DFB reactor was used for regeneration of

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saturated adsorbents, where excess heat from combustion is used. Pure O2 and repurposed flue gas are needed to cool the CO2 calcination process. In the last few years, SER pilot farms have already been successfully built. In reality, the vast bulk of pilot-scale initiatives have relied on SER technology primarily to control the H2 -to-CO ratio for upstream synthesis methods and to lessen reforming power consumption, with the harvested CO2 being released back into flue gas without really being concentrated. The IFK Stuttgart’s SER tests with pine biogas as the fuel supplier for oxyfuel combustion in a 200 kWth DFB reactor are an excellent example. When the calcination mode was changed from air to O2 combustion, the CO2 level in the flue gas rose from 26.7 vol cents to up to 95 vol percent. Finally, the PSA-based WGC procedure is a promising pre-combustion CO2 collection method. A number of pilot-scale WGC plants (TRL 6) are currently being built around the globe. Pre-combustion CO2 collection through the use of adsorption is described in research papers. In addition, a number of issues have been discovered at the adsorbent, nuclear power plant, and overall system levels. Post-combustion CO2 capture is still a challenge for intermediate and high-temperature CO2 adsorbents, despite significant progress in their development over the past few years. For pre-combustion CO2 collection, molten salt endorsed MgO has incredible capacities that can only be tested through prototypes. Current WGC devices still use a number of excess steam to get high purity and recovery. However, multitrain PSA can reduce energy consumption while increasing operational complexity but rather capital expenditure. The separation of contaminants at extreme heat, such like H2 S, COS, HCl, and metals, must also be taken into consideration in addition to the CO2 requirement. It is possible to use WGC procedures in not only IGCC, but also in other high-pressure, hightemperature processes, like NGCC, biomass gasification energy plants, inclusive steelworks, and diesel fuel chemical industries. SER hydrogen manufacturing processes based on hightemperature CO2 adsorbents with pure O2 generated by an actual air separating funnel for the calcination are feasible for pre-combustion CO2 capture; however, a thorough technoeconomic assessment should be undertaken to assess the capture cost. As a result of comparing different CO2 capture technologies, this paper provides an indepth look at how well different technologies absorb and desorb CO2 , as well as the enthalpy and capacity of each technology’s absorption and adsorption processes. There is a wide range of applications for liquid solvent filtration systems in post-combustion processes. Capture materials with high adsorption performance and excellent regenerability are essential for the pre-combustion process. Pilot-scale demonstrations for real world applications should be included in future research priorities.

11.14 The utilisation of CO2 in industrial processes One of the most important strategies in combating climate change is to close the anthropogenic carbon cycle. This requires the effectual coupling of Carbon dioxide capture with subsequent conversion [188–190]. The net cost of releasing Carbon dioxide and reducing emissions could be reduced if CO2 was used to produce meaningful products [191]. Looking to diversify their power production and increasing their energy security could be achieved through the use of CO2 -based fuels in countries that do not have access to fossil fuel production [192–194]. Diluting and NOx pollution from fuels could also be mitigated by CCU

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products [195–197]. Traditional chemical production methods must be compared to CO2 based production, as well as the impact on the environment. Hydrocracking reactions have emerged as perhaps the most good potential conversion technologies for trying to mitigate the effects of global warming on the life cycle of polyol and formic acid production [199]. For the fuels sector, the CO2 utilisation potential is 10 percent, while the chemical products sector’s is between 1 and 7 percent, according to recent numbers Chemical compounds such as urine (70 Mt CO2 per a Mt product, annualised demand 100 Mt), methanol (14 Mt CO2 used per Mt device, annual market clamour 40 Mt per year), and organometallic trace elements (over 110 Mt CO2 used per Mt brand, annualised mandate 40 Mt every year) (30 Mt CO2 or per Mt product, annualised clamour 80 Mt per year) have been made from CO2 . It is possible to reduce annual Emissions of carbon dioxide by v3.7 Gt, — roughly 10 percent of the current annual CO2 emissions, by implementing a variety of CO2 utilisation methods. Aside from a few materials, the market would be overwhelmed if they were implemented on a large scale [198]. CO2 utilisation hot topics include: thermochemical CO2 , photochemical CO2 , electrical electrochemical CO2 , photoelectrochemical CO2 , thermal photothermal CO2 , and CO2 as soft superoxide anion for dehydrogenation, all of which are systematically summarised in this section.

11.14.1 Conversion of CO2 to energy This method of CO2 utilisation, thermo-catalytic CO2 conversion into chemicals, is a promising strategy for CO2 utilisation which not only helps reduce environmental issues characterized by excessive Dioxide (CO2 ) emissions, but it also delivers a long-term alternative for producing essential substances or materials. This means that CO2 to console fuels and contaminants could be rapidly industrialised on a world basis, accelerating human efforts to reduce CO2 emissions. In order to significantly reduce CO2 molecules, large-scale clean fuel conversion plants will be built. Because of the recent spike in oil barrel price levels, or at least the uncertainty that has accompanied it, many scientists are focussed on the photochemical, electrical conduction, catalytic, or genetical conversion of CO2 . Another important driver for the conversion of CO2 to fuels is the ongoing energy transition, which aims to change the way power is generated by using techniques that emit less CO2 . Power-to-X processes, which first store excess electricity as hydrogen and then combine it with CO2 to form chemicals or fuels, allow the decarbonized sources inside the energy mix to expand. This has a major effect on the reduction of CO2 emissions as a result. When it comes to making valuable compounds, activating CO2 is the most important step because it is both stable thermodynamically and kinetically. Due to the high energy content of CO2 , another useful reactant is often reacted to it. When it comes to the most commonly used reducing agent, H2 is the most widely used because it can be developed utilising renewable energy and also the well before water electrolysis technology [200]. However, due to the "apparent inertness" of chemical compounds, extremely harsh conditions (such as high temperature and pressure) are absolutely essential to quicken increase the rate of chemical or alter chemical equilibrium. A viable option would therefore appear to be CO2 hydrogenation processes to start producing methanogenesis products like CO2 , methanol and other hydrocarbons, as discussed in the following section. It is important to consider the long history of chemical reactions as well as the numerous publications that have addressed these topics when summarising the various technologies and methods that will be

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used to fully explain reaction mechanisms and catalyst synthesis strategies. Supplementary importance is attached to the use of transition metals such as Fe, Ni, Cu, and Co, which are less expensive than noble metals. A global assessment of industrial CO2 emissions will also be conducted.

11.14.2 Thermochemical method for CO2 methanation Methane, the primary component of natural gas, is used not only in industrial activities but also as a primary source of cooking and heating throughout Europe. Methane may also be simply liquefied and safely stored in huge amounts. The presence of several existing infrastructures makes transportation and storage of this high energy density alkane extremely convenient. Therefore, the Sabatier–Senderens reaction, which is also known as the methanation of CO2 (CO2 + 4H2 CH4 + 2H2 O), is critical for both industrial and consumer applications. To help astronauts survive and provide energy on Mars, NASA has studied the possibility of using a reduction agent (H2 ) produced by splitting water to convert CO2 in the Atmospher into CH4 and H2 O. The dehydrogenation of CO2 takes place in the Tremp procedure at low pressures (5.0– 20.0 bar) and high temperatures (200–500 °C to 800 °C). When operating CO2 methanation reactors, controlling the exothermicity of the reaction is critical to maintaining favourable conditions and avoiding the deactivation of the catalyst due to sintering under hydrothermal conditions. A wide range of catalytic systems for the Sabatier reaction have been developed, including those based on Rh and Ru endorsed on traditional oxide telcos (Al2 , SiO3 , ZrO2 , TiO2 , but also CeO2 ), but also their mixtures. In terms of sensitivity, exercise, and stability, nickel-based catalysts have now been identified as being the most popular materials for methanogenesis of CO2 at a low cost. The addition of activators at binding sites and the modification of the support by tinkering with metal–support interactions have both been used to increase levels or improve methane specificity [201–205]. Electrochemical interactions between support and its materials, which are motivated by changes in the toughness of covalent bonding of the chemisorbed species, have a significant impact on the performance of the catalyst As a result of the vacancies of oxygen being created during the process of reduction, reducible supports are recommended to provide suitable active sites for CO2 activation.

11.14.3 The thermochemical method for dry CO2 and methane reforming Dry Methane, the primary component of natural gas, is used not only in industrial activities but also as a primary source of cooking and heating throughout Europe. Methane may also be simply liquefied and safely stored in huge amounts. The presence of several existing infrastructures makes transportation and storage of this high energy density alkane extremely convenient. Therefore, the Sabatier–Senderens reaction, which is also known as the methanation of CO2 (CO2 + 4H2 CH4 + 2H2 O), is critical for both industrial and consumer applications. To help astronauts survive and provide energy on Mars, NASA has studied the possibility of using a reduction agent (H2 ) produced by splitting water to convert CO2 in the Atmospher into CH4 and H2 O. The transformation of CO2 takes place in the Tremp method at low pressures (5.0–20.0 bar) and high temperatures (200–500 °C to 800 °C). When operating CO2 methanation reactors,

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controlling the exothermicity of the reaction is critical to maintaining favourable conditions and avoiding the deactivation of the catalyst due to sintering under hydrothermal conditions. A wide range of catalytic systems for the Sabatier reaction have been developed, including those based on Rh and Ru maintained on traditional oxide bearers (Al2 , SiO3 , ZrO2 , TiO2 , etc. CeO2 ), but also respective mixtures. In terms of selective, activity, and stability, nickel-based catalysts have already been identified as perhaps the most popular materials for methanation of CO2 at a low cost. The addition of activators at catalytic activity and the modification of the support by tinkering with metal–support interactions have both been used to increase participation or improve methane selection [202,203]. Electrochemical interaction between support and also its elements, which are controlled by variations as in strong of covalent bonding of the adsorbed species, have a significant impact on the performance of the catalyst As a result of the vacancies of oxygen being created during the process of reduction, reducible supports are recommended to provide suitable active sites for CO2 activation.

11.14.4 RWGS (reverse water-to-gas shift) reaction thermo – chemical methodology This method of converting CO2 to CO2 has long been considered a viable option because the resulting CO is a chemically active compound and considered as an essential intermediate in numerous chemical industrial processes, such as carbonylation and upgrading, as well as the synthesis of acids such as acetic acid and methanol, hydrocarbons, and dimethylether. RRM and AM are two of the most widely accepted mechanisms for the RWGS reaction. Without used in the intermediate, H2 serves as a corrosion inhibitor in RRM [206]. Because CO2 has the potential to completely oxidise all of the partially reduced financial backing, RRM position is dependent on this possibility. CO is created by the break – down of a base – catalyzed intermediate formed when H2 and CO2 react, according to AM [207]. Another theory put forth by scientists was that the RWGS reaction is mediated by carbonates. They are most commonly used because of their rising activity and selectivity in this catalyzed reaction. A high selectivity for CO is achieved by using noble iron metal carbides [208]. Aside from these active metals (Ni, Co and Fe), the RWGS reaction has a good performance when other metals are tuned. A common active metal in the methanation procedures is Ni. Bimetallic Ni–Cu compositions have been used by Reina et al. in order to reduce methanation [209].

11.14.5 Methanol is produced by the thermochemical electrolysis of water of carbon dioxide Methanol is a major chemical product that is utilized as a solvent, fuel or fuel additive for fuel cells. Methanol is also a necessary component in the synthesis of high-value-added compounds including acetic acid, anhydrides, formaldehyde, monomers like methyl methacrylate and methyl esters. Global consumption is steadily increasing, from over 40 million tonnes in 2007 to nearly 100 million tonne in 2019 [210]. For its first industrial methanol plant, BASF used liquid fuels as the biodiesel in 1923. With Zn metal acting like a physical spacer, Cu/Zn-based

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precursors or chemistries have been thoroughly examined in the production of CH3 OH from hydrogen evolution Reaction. A motivator for the process has been proposed to use the metal of Cu, Cu–ZnOx contact, or CuZn alloys, while the concern of “in what life forms operates as the exact and authentic active sites” remains open.

11.14.6 hydrogenation of CO2 to hydrocarbons through a thermochemical process Hydrocarbons are critical components in bulk chemistry and include light (C2 –C4 ) olefins, fresh herbs, and liquid alkyl and alkenes. There are a variety of other solvents can be used to power engines and vehicles, such as gasoline, jet fuel, and diesel (C5–C20). Fischer–Tropsch synthesis, catalysed by Fe, Co, and Ru, has been used for decades to produce hydrocarbons from syngas [211–213]. CO and H2 dissociation and C–C chain formation are greatly facilitated by the metallic nanoparticle surface. However, selectivity management is a major challenge because product distribution generally follows the ASF rule. Metal oxide and zeolite bifunctional catalysts have recently been examined, and their unique properties of willfully violating the ASF distribution, a problem for decades, attracted considerable attention. Because of this, an oxide-zeolite catalytic system was developed with the goal of bypassing the traditional Fischer–Tropsch synthesis’s hydrocarbon selectivity limitations Chemical coupling was carried out by the acid sites (derived from MSAPO) in this ZnCrOx/MSAPO catalyst by Bao et al. [214], resulting in an 80 percent preference for C2 – C4 olefins. Using a Zr–Zn/SAPO-34 hybrid catalyst, Wang et al. [215] generated 70 percent selectivity for C2 –C4 olefins. It is possible to activate CO2 through the RWGS reaction and then convert it to hydrocarbons through the use of the ASF distribution, but these are two separate processes. Direct conversion of CO2 into gasoline was achieved by Sun et al. [216] using a cross catalyst with three different catalytic activity (Fe3 O4 , Fe5C2, but also acid sites). After CO2 was converted into a-olefins by RWGS at Fe3 O4 sites, it was reduced to CO again at Fe5C2 sites by the FT synthesis. This second route requires CO2 hydrogenation to benzene or DME, accompanied by C–C coupling catalysed by Bronsted acid sites, and the electrophilic required to produce diffused forward towards the porous acid sites. With a selectivity of 79 percent for gasoline range hydrocarbons, the Zhong et al. [217,218] bifunctional catalyst for CO2 hydrogenation was developed. As CO2 as well as H2 were activated on the oxygen - containing functional groups of In2 O3 , methanol was produced, followed by C–C coupling reactions in the zeolite pores. When using the bifunctional launching pad, several copper alloys have been investigated for their potential use in the CO2 to methanol/DME conversion process, which would include Zn–Cr oxide [218] and Cu–Zn–Zr [219] as well as iron-zinc oxide (Fe–Zn–Zr) and zinc oxide (ZnO–ZrO2 ). In all these oxide–zeolite catalysed systems, the length between the oxide and nanoclay particles remains a critical factor in the targeted product selectivity. For example, poisoning of the Halide acid sites due to close communication between two features could lead to the production of CH4 as the primary end product.

11.14.7 Carbon dioxide (CO2 ) photochemical conversion The use of solar energy for photolysis CO2 conversion is one of the most practical and widely available renewable sources, and it is both clean and beneficial to the environment.

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FIGURE 11.4 Presentation of three basic charge kinetic steps during conversion of carbon dioxide.

photochemical

CO2 conversion bolstered by an endless photovoltaic fuel source is enriched by the simple structure and economic viability of an electrocatalytic array, which is promoting the tech’s ongoing development. In order to overcome the fluctuation of sunlight whereas the generating energy, chemical fuels can be stored and used on sales, thanks to the highly endothermic process of CO2 reduction by water [220,221]. The growth of long-term CO2 transformation systems feedstock has gained considerable traction by moving away from use of fossil fuels [122,124].

11.14.8 Photocatalytic CO2 reduction perspectives and prospects The use of solar energy for CO2 photocatalytic conversion into precious chemical fuels is particularly enticing because it makes use of renewable resources. When compared to other methods, photochemical conversion uses less heat and energy because it can be done at or near room temperature and pressure. Several approaches have been devised to resolve the major challenges of developing CO2 reduction portrait with high kinetics potentials. A heterogeneous system, which includes a heterogeneous photo-catalyst with a combined effect of complexes, is more exciting in terms of scaling up. A few key characteristics should be present in a photo catalyst for chemiluminescence CO2 conversion. To begin, a narrow band with a high percentage should be utilised. Fig. 11.4 shows an example of this. Good charge intrinsic properties that increase charging migration while reducing charging recombination are also important. Ultimately, the system must have all the good features of ground that lead to specific interactions between surfaces. High adsorption capacity for Molecules and adequate band potentials reduce competition only with H2 evolution reaction, among other things (water reduction reaction). There are many ways to increase CO2 and H2 O transformation after lighting, but product accuracy must also be taken into account. There has been little control over control devices and tunability due to the possibility of a wide selection (CH4 , CO, C2 H4 , C2 H5 OH, and CH3 OH) and a lack of perception of awareness of reaction

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pathways and processes. A definitive understanding of photochemical CO2 conversion’s reaction pathways and product distributions has been achieved as a result. Because of lower power in comparison to the conventional, there is still an urgent the need investigate and develop new photo-catalytic materials for greater CO2 photo-conversion efficiency. In their current state, photocatalytic CO2 reduction’s low production of solar incites energy is unfeasible. There is a need for extensive mechanistic investigation, both experimental and predicated upon the first principles, in order to discover new photo precursors and gain an understanding of when to capture the entire range of sunlight. Photo-thermal catalysis (detailed in the previous section) could benefit from this new understanding, which could be applied to other types of catalysis.

11.14.9 A sorting oxidant: CO2 CO2 has primarily been employed in conjunction with a reducing agent, primarily H2 . Though, the present main source of H2 depends heavily on co-production of CO from the reforming of methane, naphtha, and low carbon alcohols and oxygenates like dimethyl ether. If renewable H2 is not utilized, the conversion of CO2 into chemicals and fuels becomes uneconomical. It has been suggested that CO2 reduction could be performed utilizing various saturated hydrocarbons such as alkyl aromatics and light paraffin, rather than just hydrogen. At the same time, these hydrocarbons can changed into olefin compounds like ethylene, butenes (including butadiene), propylene and styrene which are main industrial chemicals and can be made through simple dehydrogenation, cracking and oxidative dehydrogenation with molecular oxygen. These olefins, on the other hand, have been reported to be formed by using oxidative dehydrogenation with CO2 , in which CO2 acts as an oxidative agent which directly remove H2 from the saturated bond and/or capture H2 molecules, which are produced via dehydrogenation as follows: Cn H2n+2 + CO2 → Cn H2n + CO + H2 O Cn H2n+2 → Cn H2n + H2 CO2 + H2 → H2 O + CO CO2 use, as a soft oxidative, accelerates all the catalytic oxidative changes and is experiencing significant expansion in different industries. It has the potential to contribute to C emission reduction ,energy-efficient and cost-effective chemical manufacture [225,226].

11.5 Conclusions and prospects Carbon collection and utilization offers a lot of promise when it comes to lowering carbon releases. This chapter provided a complete assessment of long-term growth of enhanced CO2 capture and usage, which has gotten a lot of consideration since its significant prospective to exacerbate worldwide increasing temperature. The processes before and after ignition/combustion have gained global consideration and developed as a two primary strategies for CO2 capture. CO2 -EOR and CO2 hydrate are both effective CO2 utilization strategies. In 2030, CCU has the technical capacity to reduce annual CO2 discharges about 3.5 Gt. CO2 -eq [195,227,228]. The administration of all countries should frame targeted funding schemes for CO2 usage [229]. Despite the enormous difference concerning the little carbon recognition rate and extraordinary CO2 reduction price, incorporating a power plant using

11.5 Conclusions and prospects

269

CCU technological features into discharge transaction structure might significantly reduce economic funding burden [230]. The national carbon market is set to go live in 2020, conferring to a scheme released in public (through the China administration, not just the global opinion or illustrations), with first stage focusing primarily on power generation industries, such as cogeneration source of electrical and heat power plants. The process of CO2 hydrogenation might be proceed in oil refineries via electrolytic procedure of hydrogenation or through coking plants via the use of residual gas. It could also combine with renewable sources without producing waste hydrogen. The excess energy could be used for electrocatalytic CO2 conversion and hydrogen production via water electrolysis. The hydrogen energy created from renewable sources could be used in other ways. The carbon resources market value and their movement have developed as a dynamic field for engineers and researchers throw-out the globe in order to achieve tremendous minimization of active carbon release. The significance of carbon budgets as a direct prize for ecofriendly businesses has been established through the investigation of carbon allowances as a straight incentive for a good little-carbon financial enlargement. Corporations that have received a carbon recognition prizes are required to provide specified allocations on everyday base for jumble sale of the carbon market in order to increase market liquidity. The cost-effective development of carbon-free hydrogen generating technology is critical in the context of resourceful CO2 consumption, particularly CO2 hydrogenation process for the manufacture of useful chemical compounds. Aside from the high-rate H2 synthesis by water electrolysis, additional present manufacturing H2 fabrication technologies, for example H2 fabrication from natural resources such as (coal & natural gas), generate a significant quantity of CO2 . Recent research has concentrated on solar photocatalytic hydrogen generation through hydrolytic process, and breakdown of hydrogen sulphide (H2 S) for H2 fabrication, among other things, in order to develop inexpensive, carbon-free hydrogen sources. CO2 -ECBM and CO2 -EOR are the two most common methods for exploiting CO2 , indicating the critical relevance of maintaining and increasing the output of most oilfields, as well as increasing the extraction and usage capacity of coal-bed methane. The widespread use of CO2 -EOR might result in significant carbon storing capacity and increased oil fabrication, which would be beneficial to the gas and oil engineering’s economic benefits in addition to mitigating the energy security threat posed by expanding foreign dependency on the oil [231]. The rate of the demonstration of CCUS scheme is comparatively significant, which stymies the CCUS process’s expansion. The demonstration of the present CCUS scheme is expected to cost too much, and carbon capturing might add an additional 140–600 RMB per (CO2 ) to the operation cost. Given existing CCUS technologies, implementing CCUS would raise primary energy utilization by 10 to 20 percent while sacrificing productivity, which is a main roadblocks to widespread CCUS adoption. CCUS technology’s comprehensive method flow, incorporation, and ascendable skill development might be implemented in phases and technology demonstrations in a range of industries. The cumulative expertise gained through several tests and the identification of important methodologies will gradually speed up the standardization and rate discount of CCUS expertise, which is critical for attaining longstanding profitable positioning of the CCUS. For coal chemical companies, demonstration projects combining low rate carbon capturing with EOR are advised to be broadly adopted. Oil and gas companies are urged to take the lead in launching a CO2 -EOR demonstration in order to broaden their engineering skills. The CCUSs relevant premeditated design and system scheme should be reinforced in order to boost governmental support and economic motivation,

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laying a firm groundwork for the CCUS to perform a vital part in long-standing carbon release drop. Controlling overall carbon emissions should be stepped up, and quantification of restricted aims for numerous productions should be defined and recommended in order to raise awareness of little quantity carbon growth and the need for CCUS distribution for businesses. Ground-breaking inducement strategies that assist the development of CCUS, such as tax exemptions and differential subsidies, are urged to be investigated and implemented. The CCUS demonstration project is well supported by the commercialized speculation and bankrolling procedure with incorporation of the administration and the marketplace, with optimistic exploitation of several means like green economics, environment bond, low-carbon funds, and so on. Overall, the impending research and growth in the CCU area are discussed.

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C H A P T E R

12 Ionic liquids for carbon capturing and storage Faizan Waseem Butt a, Hafiz Muhammad Athar a, Sumia Akram b, Zainab Liaqat a and Muhammad Mushtaq a a b

Department of Chemistry, Government College University, Lahore, Pakistan Division of Science and Technology, University of Education Lahore, Pakistan

12.1 Introduction The rapid increase in population and urbanization has not only declined the worldwide CO2 sinks (landscapes, forests, and soil) but also increased the consumption of fossil fuels. The most concerned outcome is the exponential increase in levels of carbon dioxide which makes up nearly 86% of the green-house gases responsible for global warming, extreme heat episode, and other climate crisis [1]. A report “Global warming of 1.5 °C” (2018), stated “the worldwide temperatures were 1.0 °C more than the pre-industrial levels and predictions are that it will reach 1.5 °C by 2030” [2]. The mandatory initiative to eradicate the effect of global warming is to reduce the emissions of greenhouse gases most importantly CO2 . The signing of Kyoto Protocol has offered initiatives to researchers to reduce CO2 emissions especially from fossil fuels. Carbon capture and storage (CCS) is a great initiative that has revolutionized the field of environmental chemistry as an effective pathway to reduce CO2 atmospheric concentration on a large scale [3]. CCS is concerned with lowering of CO2 emissions from various processes like cement manufacturing, ammonia production, and fossil fuel plants (the main contributor) etc. [4]. A report suggests that an approximate amount of 236 billion tons of CO2 can be captured and stored if CCS is executed to its full potential probably by the end of 2050 [5]. The best approach towards CO2 capturing is its separation from coal beds, saline deposits, depleted oil, and gas reservoirs and other suitable sedimentary formations of this sort [6,7,8,9]. The keygoal is to introduce a technology which will help us in fulfilling the assigned task in a well efficient way while keeping a check on environmental impact as there is a huge risk

Green Sustainable Process for Chemical and Environmental Engineering and Science: Carbon Dioxide Capture and Utilization DOI: https://doi.org/10.1016/B978-0-323-99429-3.00018-7

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FIGURE 12.1 The Generic layout of Pre, Post, and Oxyfuel-combustion capture technologies.

of leaking of stored CO2 [10-12]. Manchao et al. [13] evaluated the risk assessment of stored CO2 in geological features with focal emphasis on dumped coal seams as well as mines. An alternate and safe mainstream approach would be conversion of CO2 into another product of high value which is termed as carbon capture and usage (CCU) [14,15].

12.2 CO2 capture technologies The materials that interact with CO2 can be utilized for capturing and requirement of other materials depend entirely on the processes in which the gas is constrained (Fig. 12.1). The three common processes adopted for large scale CO2 capturing are (i) pre-combustion and (ii) the post-combustion. The first involves the conversion of hydrocarbon fuels into CO and H2 . The CO is then converted into CO2 utilizing water shift conversion followed by separation from H2 [16,17]. The post-combustion process involves sequestration of CO2 after the combustion of hydrocarbon fuels utilizing air as an oxidant [16,17]. It is one of the most commonly used process for CO2 capture and storage. In another strategy, the Oxyfuel-Combustion utilizes pure O2 as an oxidant to convert hydrocarbon fuels into CO2 and steam followed by separation of CO2 [16,17]. Before we proceed towards the application of Ionic Liquids in carbon capturing and storage it is necessary to review certain terms. Some of the techniques that capture CO2 may use cryogenic separation, bio-fixation, absorption, adsorption, membrane separation, and chemical looping [18]. Absorption utilizes physical interaction or chemical bonding to interact and react with CO2 . Chemical absorbents form covalent bonds while physical absorbents form Van der Waals interactions with CO2 obeying Henry’s law (which states that the solubility of the gas has direct relation with the partial pressure of gas at constant temperature). The solvent thus formed can be regenerated and CO2 can be released. The regeneration process is carried out using high temperature and low pressure [19]. Adsorption utilizes only the surface of the material for the interaction (either chemical or physical). A bed of adsorbers placed in the path of flue gas capture CO2 only while flue gas is sent to a clean bed followed by regeneration of the saturated bed [20]. However, the limited selectivity of adsorbents has restricted the usage of adsorption technique for a large-scale application. Membrane separation involves the physical or chemical interaction of gases with a permeable membrane. An advantage of this process is that the membranes can easily be modified according to need and conditions

12.4 Features of ILs

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and can widely be used on large scale industrial processes. The best approach is to couple membrane separator with a liquid that imparts selective retention and/or capturing of CO2 [21]. Cryogenic Separation involves cooling and condensation to produce liquid CO2 which helps a lot in transportation. High concentration gases as in pre-combustion and oxyfuelcombustion are better suited for this process as low concentration gases require high amounts of energy for cooling process [22].

12.3 Ionic liquids (ILs) The previous decade has seen many classes of novel materials that are synthesized specifically to increase the efficiency of CO2 capture and storage. One such promising class in this regard is Ionic Liquids (ILs). Ionic liquids are molten salts comprising of cations and anions [23]. Ionic liquids may contain very large number of ions and neutral molecule and show remarkable ionic interaction additionally to van der Waals interaction which is present in many liquid states. These remarkable ionic interactions develop very low vapor pressures, thermal stability, miscibility, and high viscosity. The word ionic liquid firstly used by Walden for Ethylammonium nitrate which have very low melting point below 50°C. The ionic liquid which are liquid at room temperature or have very low melting point often consist of large size organic cations for example 1-alkyl-3-methylimidazolium, 1-alkylpyridinium [24]. Cations of ionic liquid are generally very large size organic compounds (Fig. 12.2) whereas anion may have smaller size as compared to cation and thus the final structure formed may be of inorganic nature. The difference between the size of cation and anion might be responsible for the development of weak interaction in ILs. The general final structure of ILs is very similar to salt but in salt there are strong interaction between cation and anion responsible of crystalline structure and very high melting point (Fig. 12.3).

12.4 Features of ILs The major advantages of these liquids over others are that they have extremely low vapor pressure, high chemical and thermal stability, and a large electrochemical window. In addition to that, ILs are highly modifiable having flexible functional groups leading to creation of green functional solvents [25,26]. The ionic liquids usually comes in with higher densities as compared to water and organic solvents, however, tetraalkylborates having shorter alkyl chain length are lighter in density. In general, the density of IL changes with the size and nature of alkyl chain length and similar might the case with anion [27]. The ionic liquids are good conductor and polar in nature, their polarity may fall closer to the alcohols with short alkyl chain [28]. Recently, scientists have coupled ILs with membranes and various membrane processes to modify their use in numerous purposes. The most useful modification is the immobilization of ILs on membrane, which deliver excellent recovery and reusability of ILs along with minimum loss of these liquids out of the system. Furthermore, immobilization of ILs establishes the minimal use of active phase needed for carbon capture or retention. Besides, the matrix used for immobilization of ILs may act as a barrier between both the phases (receiving phase and feeding phase). Membrane based ILs can be employed on industrial level

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FIGURE 12.2 The Generic structure of well-known cations and anions used for the preparation of ionic liquids.

for the absorption of CO2 . The ionic liquids come in good solvation power and higher ionic conductivity [29–32]. Finally, the ionic liquids may comprise of what has been termed as “ionic cluster” and “hydrogen bond” and viscosity of ILs changes with the strength of hydrogen bond. The nature and size of cluster in addition to viscosity and density affects the features of these solvent like dissolution, alkalinity, acidity [33,34]. Overall, ionic liquids can be prepared from bulky organic cations and relentless number of anions and these combinations can have countless number of arrangements, that is why these liquids are also known as ‘Designer Solvents’ [29,35,36]. The key barriers towards the use of ILs in various application and specifically carbon capturing are higher density, viscosity, and synthesis cost of these liquids. However, opportunities are available regarding cost-effective synthesis, density, and viscosity tuning. For example, tetraalkylborates containing ILs are lighter and less viscous. Besides, the cation-alkyl chain length can be altered to adjust the density/viscosity, same is the case with the nature and

12.5 IL as absorbents for CO2 capture

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FIGURE 12.3 The reaction mechanism CO2 follow during its absorption by Amine group containing Ionic Liquids.

alkyl chain length of anions [27]. Another opportunity involves the hybridization of ILs with other solvents. Likewise, modification of ILs with various membranes and processes, and immobilization can resolve the density and cost challenges. The immobilization of ILs on solid supports (supported ILs) not only improve their reusability and recycling but also minimize the loss of these liquids out of the system [29-32].

12.5 IL as absorbents for CO2 capture The traditional ammonia alcohol solutions like monoethanolamine (MEA) that are used as absorbents for CO2 capture face challenges in terms of large solvent loss and high energy consumption. According to the experimental data, the reaction between CO2 and amine are associated with larger enthalpy changes, which simply mean larger amount of heat energy will be consumed during the liberation of captured carbon. For example, 90% absorption of one ton CO2 by 30% aqueous MEA is associated with 2.5–3.6 Gigajoule energy [37-39]. Therefore, it is necessary to introduce alternative substitutes with strong absorption capacity and little to no solvent loss/energy loss. Several generations of ILs offer similar properties with promising results, some of these have been cited in the subsequent sections.

12.5.1 Conventional ionic liquids It was reported in 1999, that CO2 is highly soluble in a hydrophobic IL 1-Butyl-3methylimidazolium hexafluorophosphate BMIM-BF6 [40]. A lot of studies have been conducted since then to investigate the role of these designer liquids in CO2 capture. The properties of ILs can be easily fine-tuned by modifying functional-groups and resulting “task

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12. Ionic liquids for carbon capturing and storage

specific” can be applied for CO2 absorption. It has been reported that ILs based on pyridine and imidazole have been used for carbon capture and storage (CCS) [39]. Bates et al. [37] designed imidazolium ion containing primary amine group based ILs which showed CO2 capture level of 0.5 mol CO2 /mol for a 3 hrs exposure. The special chemical structure of amino acids has shown to provide great attachment sites and thus they have been incorporated in the preparation of ILs [41]. It was proven by Sistla and Khanna [42] that ILs that have multiple attachment sites (amino acid based ILs) show much higher CO2 absorption as compared to other absorbents. Lv et al. [43] comprehensively investigated the mechanism involved in carbon dioxide absorption by amine containing ILS. It has been noticed that initially CO2 reacts with [APmim]/[Gly] exothermally to form carbamate, the CO2 first react with anion (Gly−1 ) and then with cation (APmim+1 ). There were no evidences of the formation of zwitterions. Meanwhile, the concentration of carbamate increases initially, then decreases due to decrease in pH. In the subsequent stage, the concentration of HCO3 −1 /CO3 −2 due to the hydration of CO2 . The presence of amine functional-groups in ILs combination resulted in CO2 capture level of 1.23 mol CO2 /mol. Bhattacharya et al. [44] also formulated a novel IL absorbent based on choline-amino acid that had low viscosity with a remarkable CO2 capture level of 1.62 mol CO2 /mol. The density functional theory (DFT) analysis also verifies the mechanism of action of interaction among CO2 and amine groups. In addition to amines, several super-bases have been used for formulation of novel ILs and it was reported that the basicity led to increased CO2 capturing. A new class of ILs based on imidazole anions and 1,8-diazbicyclo[5.4.0]–undec-7-ene (DBU) cations was developed by Zhu et al. [45]. It was reported that the addition of super-base resulted in CO2 capture level of 1 mol CO2 /mol. Xu et al. [46] referred the highly absorption of CO2 to increased basicity of ILs due of addition of DBU. Moreover, the CO2 absorption can also be increased significantly by tuning the alkyl chain length and anions. Aki et al. [47] demonstrated a remarkable increase in CO2 absorption by changing the alkyl chain length from butyl to a longer octyl chain. Sharma et al. [48,49] evaluated the efficacy of various anions on CO2 absorption and listed them in the following order: BF4 − < DCA− < PF6 − < TfO− < Tf2 N− . It has been reported that a CO2 capture level of more than 2 mol CO2 /mol can be achieved by introduction of particular anions on various reaction sites [50]. The economic value and feasibility of ILs over traditional absorbents is the key concern to declare them superior in addition to other properties. Ma et al. [51] found that carbon capture and storage process from a power plant based on ILs and traditional organic solvents (based on alcohol) and evaluated that the process based on IL absorbent was 30.01% more cost effective in terms of energy consumption. In another report, Ma et al. [52] have also found that ILs based on ([Bmim][PF6 ]) and ([Bmim][BF4 ]) showed remarkably less energy consumption by 24.8 and 26.7% respectively as compared to alcohol ammonia solutions. De rivaet et al. [53] optimized the process and reported a remarkable reduction in overall energy consumption to 1.4 Gigajoule/ton CO2 .

12.5.2 ILs based hybridized solvents Another promising approach towards carbon capture is formulation of novel biphasic solvents consisting of two or more solvents hybridized together in a fuse. Table 12.1 compare

TABLE 12.1 Summary of frequently used Ils for carbon capturing.

Ionic liquids (Ils)

Acronym

3-(n-aminoalkyl)−1,2-dimethyl imida- [aamim][MtF3 SO2 ][NH2 ] zoliumbis((trifluoromethyl)sulfony)

Conditions1 T(K) P(mP) 298.15

Capture capacity XCO2 /mol of IL2

References

0.348 mmol/g Water miscible, solubility increases with increasing chain length, IL with BF4 1.18 mmol/g anion is more efficient

[66]

[67]

[aamim][BF4 ]

298.15

1-butyl-3-methylimidazolium tetrafluoroborate

[bmim][BF4 ]

320, 330 43, 49

0.60

1-hexyl-3-methylimidazolium tetrafluoroborate

[hmim][BF4 ]

330 35

0.67

1-butyl-3-methylimidazolium hexafluorophosphate

[bmim][PF6 ]

298

0.20

1-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide

[bmim][Tf2 N]

298

0.19

1-n-octyl-3-methylimidazolium hexafluorophosphate

[C8 -mim][PF6 ]

313 9.26

0.75

1-n-octyl-3-methylimidazolium tetrafluoroborate

[C8 -mim][BF4 ]

313 9.29

0.70

323 9.26

0.53

1-ethyl-3-methylimidazolium ethyl sulfate

[emim][EtSO4 ]

333 9.46

0.46

N-butylpyridinium tetrafluoroborate

[N-bupy][BF4 ]

323 9.23

0.58

Good solubility with bulkier alkyl group at low pressure, hydrophobic

Absorption capacity decreases [68] with BF4 as anion, quaternary ammonium based IL was found efficient, hydrophobic Solubility changes with both cations and anions, less soluble in water

[69]

285

(continued on next page)

12.5 IL as absorbents for CO2 capture

3-(n-aminoalkyl)−1,2-dimethyl imidazoliumtetrafluoroborate

1-n-butyl-3-methylimidazolium nitrate [bmim][NO3 ]

Remarks

Conditions1 T(K) P(mP)

286

TABLE 12.1 Summary of frequently used Ils for carbon capturing—cont’d Capture capacity XCO2 /mol of IL2

Remarks

References [70]

Acronym

1-hexyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide

[hmim][Tf2 N]

298 1.30

0.58

Low water miscible

bis(trifluoromethylsulfonyl)imide

[C6 H4 F9 mim][Tf2 N]

298 1.30

0.35

hydrophobic

1-butyl-3-methylimidazolium dicyanamide

[bmim][DCA]

313, 333 11.8, 11.2

0.58 0.52

1-butyl-3-methylimidazolium nitrate

[bmim][NO3 ]

313, 333 9.80, 9.20

0.50 0.43

DC and Tf2 N anion based IL are [71] insoluble in water, CO2 absorption reduces with increasing temperature and decreasing pressure, fluorinated anions exhibited good absorption capacity

1-butyl-3-methylimidazolium trifuoromethanesulfonate

[bmim][TfO]

313, 333 15.0 11.6

0.64 0.55

1-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide

[bmim][Tf2 N]

313, 333 13.2, 13.0

0.74 0.72

Methyltrioctylammonium nicotinate

[N8881 ][NIA]

303

0.53

Methyltrioctylammonium formate

[N8881 ][For]

1.02, 1.02, 1.03

0.35

Methyltrioctylammonium acetate

[N8881 ][Ac]

Polyurethane-imide tetrabutylammonium bromide

HPIL-02-TBA

303

33.1 mg/g

Polyurethane-imide 1-Butyl-3-methylimidazolium

HPIL-06-BMIM

0.02

27.8 mg/g

Polyurethane-imide tetrabutylphosphonium

HPIL-06-TBP

28.7 mg/g

Polyurethane-imide 1-butyl-1-methylpyrrolidinium chloride

HPIL-06-BMPYRR

26.4 mg/g

0.31

[N8881 [NIA] has lowest viscocity [72] and higher absorption, also it showed good regeneration capacity, functionalization improves efficiency TBA and TBP cations were most [73] efficient, improved mechanical properties

(continued on next page)

12. Ionic liquids for carbon capturing and storage

Ionic liquids (Ils)

[BTMA][Tf2 N]

298

0.19

Methyltrioctylammonium trifluoromethanesulfonate

[MTOA][OTf]

1.0

0.27

Diethylmethylammonium methanesulfonate

[DEMA][METS]

0.15

Diethylmethylammonium trifluoromethanesulfonate

[DEMA][OTf]

0.10

ButyltrimethylammoniumMethyltrioctylammonium bis[(trifluoromethyl)sulfonyl]imide trifluoromethanesulfonate

[BTMA][MTOA][Tf2 N][OTf]

0.27

ButyltrimethylammoniumDiethylmethylammonium bis[(trifluoromethyl)sulfonyl]imide methanesulfonate

[BTMA][DEMA][Tf2 N][METS]

0.15

ButyltrimethylammoniumDiethylmethylammonium bis[(trifluoromethyl)sulfonyl]imide trifluoromethanesulfonate

[BTMA][DEMA][Tf2 N][OTf]

0.15

MethyltrioctylammoniumDiethylmethylammonium trifluoromethanesulfonate methanesulfonate

[MTOA][DEMA][OTf][METS]

0.23

MethyltrioctylammoniumDiethylmethylammonium trifluoromethanesulfonate

[MTOA][DEMA][OTf]

0.24

Diethylmethylammonium methanesulfonate trifluoromethanesulfonate

[DEMA][METS][OTf]

0.12

Physical absorption, absorption [74] capacity reduced minimally with low cost regeneration

12.5 IL as absorbents for CO2 capture

Butyltrimethylammonium bis[(trifluoromethyl)sulfonyl]imide

287

(continued on next page)

288

TABLE 12.1 Summary of frequently used Ils for carbon capturing—cont’d

Ionic liquids (Ils)

Acronym

Conditions1 T(K) P(mP)

Capture capacity XCO2 /mol of IL2

Remarks

References

IL based Hybrid Solvent for Carbon Capturing [Hopmim][NO3 ] + H2 O

318 2.33 bar

0.09

Low carbon capturing capacity [75]

(tri-isobutyl(rnethyl)phosphonium tosylate) + H2 O (4:96)

[iBu3 MeP][TOS] + H2 O

289 4.5 bar

0.03

Low carbon capturing capacity [76]

triethylbutylammonium acetate + H2 O (1:2)

[N2224][CH3 COO] + H2 O

298 0.1 bar

0.19

Low carbon capturing capacity [77]

trihexyl(tetradecyl)phosphonium prolinate + H2 O (95.5:4.5)

[P66614][2-CNPyr] + H2 O

295 0.1 bar

0.91

Highest carbon capturing capacity

1-hexyl-3-methyl-imidazolium bis(trifluoromethylsulfonyl) imide + MEA (1:1)

[Hmim][NTf2] + MEA

313 0.1 bar

0.50

Good carbon capturing capacity [79]

1-ethyl-3-methylimidazolium acetate + [Emim][Ac] + [Emim] [TFA] + MEA 1-ethyl-3-methylimidazolium trifluoroacetate + MEA(49.98:50.02)

323 0.1 bar

0.12

[80]

hydroxyl imidazolium ionic liquids [Cl] + MEA (1:2)

308 0.1 bar

0.40

[81]

imidazolium-based poly(ionic liquid) Grafting on Titanium nanotubes 298 0.2 bar

2.43 mmol g − 1 Efficient and recyclable

[61]

tetramethylammonium glycinate ([N1111][Gly]) + MDEA (1:1)

[N1111][Gly] + MDEA

298 0.1 bar

0.56

tetraethylammonium lysinate ([N2222][Lys])+MDEA (1:1)

[N2222][Lys] + MDEA

298 0.1 bar

0.74mol

“1” Denotes temperature in Kelvin and 2.

[C3 OHmim][Cl] + MEA

[78]

Good carbon capturing capacity [82]

12. Ionic liquids for carbon capturing and storage

hydroxypropylmethylimidazolium nitrate + H2 O (95.89:4.11)

12.7 IL hybrids with membranes for CO2 capture

289

the carbon capturing potential of various solvents in combination with ILs. The crux of this process is that there will be two distinct phases after liquid absorption: one with a high CO2 level and the other one with poor CO2 levels. The regeneration process will be very economical using these hybrid solvents as there would be no need for desorption in CO2 poor phase. Hasib ur Rahman et al. [54] formulated a biphasic solvent based on diethanolamine and 1alkyl-3-methylimidazoliumbis imide with high levels of CO2 absorption. It was reported that the separation was made easier as CO2 interacted with DEA to form a carbonate. Zhang et al. [55] prepared a novel solvent based on DMEE and ([N1111] [Gly]) and reported the formation of two separate phases. Huang et al. [50] blended amine group containing ILs with ethanol and water to prepare a hybrid solvent that separated into two distinct phases after CO2 absorption.

12.6 IL hybrids as adsorbents for CO2 capture The adsorption process for CO2 capture has some advantages: The adsorbent consumes less energy than absorbing liquid and is much easy to regenerate. The cost of utilizing IL hybrids as adsorbents is much less as compared to absorbing liquids. The potential of adsorbent is greatly enhanced using ILs. The high viscosity disadvantage of ILs is eradicated when it is hybridized with the adsorbent. There are two methods for preparation of IL hybrids that can be used as powerful adsorbents. First is the impregnation of these liquids into the adsorbents. Uehara et al. [56] utilized impregnation method for CO2 capture through a porous silica material and amino acid-based IL ([EMIM][Lys]). A CO2 capture capacity of 1.2 mmol/g was observed using this IL hybrid. Zhang et al. [57] impregnated various mesoporous materials on a variety of IL combinations and reported that the MCM/ILs showed the superior results in terms of CO2 capture capacity. Cheng et al. [58] demonstrated that hybridized ILs impregnated onto various sieves had significant advantages over unsupported ILs. The second method for the preparation of IL hybrids is grafting. Nkinahamira et al. [59] reported that the adsorption selectivity of the adsorbent can be increased greatly by the introduction of ILs onto mesoporous materials. Zhu et al. [60] evaluated that grafting imparts stable functionality to the ILs leading to great retention and effective adsorption. Yuan et al. [61] demonstrated that grafting of amine based ILs onto titanate nanotubes improved the adsorption capability of the adsorbent up to 2.46 mmol/g.

12.7 IL hybrids with membranes for CO2 capture A widely used technology for separation and capturing of CO2 is membrane technology. The two fundamental factors related to this technology are selectivity and permeability [62]. These two factors working antagonistically have a trade-off effect and thus the main focus in this technology is on improving selectivity by modifying materials leading to effective permeability [63]. It has been reported that the CO2 capturing ability of ILs is much superior [64] and provides a viable root to introduce CO2 separation membranes [65]. Three different types of ILs hybrid membranes exist which are: (i) ionic liquids supported membranes, (ii) poly ionic liquids membrane, and (iii) composite membrane.

290

12. Ionic liquids for carbon capturing and storage

12.8 Ionic liquid supported membrane A membrane technology based on incorporation of ILs on a solid inorganic support to achieve CO2 separation is termed is supporting ionic liquid membrane (SILM). The separation process involves absorption of gas molecules by the layer of absorbing liquid followed by diffusion of captured gas inside the liquid and desorption of the gas. The overall process is time saving and the solvent usage is reduced to a great extent as well [83]. The introduction of ILs lead to a wide operating temperature due to their greater thermal stability [84]. Karunakaran et al. [85] formulated novel membranes based on graphene oxide and [EMIM][BF4 ] ILs for CO2 separation which showed remarkable results as compared to traditional methods. The immobilization of ILs into the pores is a difficult task which is carried out either via vacuum filtration [86] or with the help of an autoclave [87]. Lan et al. [88] stabilized hollow fiber membranes with vacuum treatment which showed significantly improved results in terms of CO2 capturing. Zhang et al. [55] demonstrated that introduction of water serves as an additional support in transport mechanism for CO2 suggesting that the selectivity can be improved under humid conditions. Liu et al. [89] introduced 2D nanosheets for additional delivery channels for CO2 transport leading to high-pressure and temperature resistant membrane with long term durability. Hwang et al. [90] reported that the application of electric fields can increasing the overall performance of the membranes by 2–5 times. Jie et al. [91] demonstrated that the membranes can be modified using grafting amine groups which makes use of the fact that amine groups show great affinity with CO2 .

12.9 Poly ILs membrane The large-scale application of SILM is restricted due to poor mechanical properties and pressure stability of IL membranes [92]. One way to stabilize ILs in the membranes is to prepare poly ILs membranes which will impart mechanical strength to the layer owing to the mechanical properties of the polymeric substance [93]. The formation of poly IL membranes involve addition of poly-ILs in a volatile solvent followed by assembly of ILs molecules after the solvent is removed [94]. Tang et al. [95] studied the effect of poly-ILs on CO2 absorption and reported very promising superior results in terms of absorption capacity and desorption rates. Vollas et al. [94] formulated a composite membrane based on PILs-ILs and reported that this membrane was much efficient as compared to ILs monomers. Nellepalli et al. [96] studied the efficacy of PILs based polymers in terms of stability and reported superior results as compared to pure membranes.

12.10 Composite membranes Using polymer as a matrix and ILs as an additive, a novel composite membrane can be prepared with unique mechanical and separation properties. The first choice to formulate such membranes is to crosslink ILs and polymers. The second option is to mix inorganic porous material, polymer, and ILs leading to a mixed matrix membrane (MMM). Halder et al. [97] demonstrated that composite membranes based on [C2 mim] [Tf2 N] and a copolymer

References

291

showed significantly improved CO2 absorption results. Lu et al. [98] reported a relatively high affinity between CO2 and ILs in a ([Bmim][TFSI]) based membrane with a very good performance for CO2 capturing. The blended of ILs with other polymers to create a composite can result in improved the selectivity of membranes [99]. Dai et al. [100] reported that humidification significantly improves the absorption capacity of membranes formed by mixing polymers with ILs. Hao et al. [101] formed a ILs/zeolite based MMM for CO2 capture and reported high perm selectivity of CO2 due to introduction of inorganic porous materials providing better membrane separation effect. Huang et al. [102] utilized graphene oxide customized with ILs as a filler and paired it with a polymer matrix i.e., poly(ether-blockamide), for the formulation of a new MMM. A uniform system with great hydrogen bonding between filler and polymer matrix was reported as a result. Ahmad et al. [103,104] evaluated that the introduction of ILs in the composite membranes lead to enhanced permeability and selectivity by strengthening the affinity among the polymer matrix and the filler. Vu et al. [105] prepared MMMs utilizing ILs-coated ZIF particles and reported that the interface defects were significantly reduced by the introduction of hydrogen bonding of ILs.

12.11 Conclusion and future insights Large scale global warming due to increased CO2 concentration by anthropogenic activities has led to undesired air pollution. A very popular option to eradicate the amount of this greenhouse gas is carbon capture and storage (CCS) which is hindered by various economical and environmental prospects along with the solvents used in the process. A wide range of solvents have gained momentum is that regard having certain advantages and pitfalls and ILs have evidenced to be the excellent candidate at present. The non-volatile and flexible nature of ILs impart an appealing benefit yet their application on a large scale is not implemented as of now due to their non-biodegradable nature and cytotoxic profile. The conventional ILs comprising of 1-n-octyl-3-methylimidazolium cations and hexafluorophosphate and tetrafluoroborate offered good carbon capturing capacities. The mixing of IL trihexyl(tetradecyl)phosphonium prolinate with water further improved the effectiveness of the subject liquids as CO2 adsorbent. The grafting of amine based ILs onto titanate nanotubes also can improve the adsorption capability of the ILs. The experimental conditions and parameters also need significant improvements overall. The key barriers regarding the use of ILs as adsorbent i.e. high cost, difficult density, and more viscosity, can only be handled via integrating ILs into solid supports, membranes or other solvents.

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C H A P T E R

13 Advances in utilization of carbon-dioxide for food preservation and storage Adeshina Fadeyibi Department of Food and Agricultural Engineering, Faculty of Engineering and Technology, Kwara State University, Ilorin, Kwara State, Nigeria

13.1 Introduction Quality control is an integral part of food preservation and storage [1]. Different approaches have been used to maintain product quality and extend shelf-life by inhibiting microbial magnification [2–5], maintain physiological conditions such as moisture and temperature, and modifying the storage atmosphere [6,7]. The bottom line is to ensure microorganisms, like the bacteria and yeast, are prevented from multiplying to such a level that can cause deterioration or affects shelf-life [6–8]. By this, wastages can be minimized, and the costs of materials and resources will be reduced thereby enhancing efficiency of the system for environmental sustainability [9,10]. Typically, the CO2 and other acid oxides are commonly used as preservatives or additive agents because of their ability to retard the magnification of bacteria and yeast in stored products [11–13]. Current and future applications of the CO2 gas in post-harvest value chain were discussed in this study. For example, the solid CO2 gas, also referred to dry-ice, is an important refrigerant and abrasive agent useful in food equipment cleaning [14–17]. It is a robust industrial substance especially applied in stunning, tanning, decaffeination of coffee, chemical feedstock, and solvent for controlled drying of food [18]. The gas is added to beer, wine, soft-drink, and drinking water to aid effervescence and prevent short-term spoilage [19]. It is also an effective material in the CSA storage of grains and horticultural crops [20–22]. Also, it was suggested to investigate the influence of the dry ice pretreatment on microstructural properties, vibration loadings and rheological stability of the stored foods as a way-forward for further studies. Besides, the CSA technology maybe limited in application during transportation and retail storage of the food due the involvement of big and sophisticated equipment. Thus, this study

Green Sustainable Process for Chemical and Environmental Engineering and Science: Carbon Dioxide Capture and Utilization DOI: https://doi.org/10.1016/B978-0-323-99429-3.00029-1

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proposed the use of simplified equipment to advance the potential of the CO2 technology in the design of CSA storage facilities. This will help advance development and management of the food products during their storage and preservation.

13.2 Utilization of carbon-dioxide in food preservation 13.2.1 Beverage drink preservation The ability of the CO2 gas to be absorbed easily into a liquid to form tiny bubbles is an advantage for the beverage industries [19]. This provides protection against the activities of microorganisms thereby retaining the beverage quality and extending its shelf-life [23]. The gas is also effective in inactivating enzymes such as pectin methylesterase, polyphenol oxidase, and lipoxygenase, which cause undesirable chemical and physical changes in the food [24,25]. Lima et al. [26] reported an effective preservation of a coconut water and acerola fruit juice beverage drink for 6 months at ambient air temperature. The authors reported acceptable microbiological, color and taste stabilities during period of storage. Also, according to Campos et al. [27], the CO2 has been used to inactivate the enzyme activities in the coconut water beverage thereby effectively reducing the carbonic acid pH and extending the shelf-life of the product. A high-pressure- CO2 technique has been used to inactivate the enzymes without heating that may otherwise cause nutrient denaturing by exerting a minimal impact on the quality but extends shelf-life and inactivates the enzymes activities [11,24,28–30]. A typical flow process for beverage drinks pretreatment using a continuous dense-phase CO2 system can be described in Fig. 13.1 [31]. The system was able to pasteurize the beverage by causing the heating of the product through electrostatic effects. Unlike the actual pasteurization the heat is supplied directly via external sources, this technology obtains its heat by temperature build-up as current passes through an electric conductor. In fact, Porto et al. [31] concluded that the process can minimize quality loss of the beverages even at low pressure CO2 concentration.

13.2.2 Drying of vegetables and fruits Drying is a convenient way of extending the shelf-life of vegetables and fruits by removing excess moisture through mass and heat transfer [32,33]. But this is often associated with a loss in nutrients and structure thereby affecting the physical nature of the food. By using a pressurized CO2 drying technology, the physical nature of the food products can be regulated by maintaining its color and shape, so they appear natural and fresh. However, only few research demonstrates the ability of this technique for preserving the physical and biochemical characteristics or preventing the quality degradation of the dried samples of the vegetables and fruits. A high pressure micronization technique, which uses the high-pressure CO2 drying processes, was reported by Weidner [34] for the drying and particle size reduction of the vegetables and fruits. The system was able to preserve the quality thereby adding value to the product and enhancing its shelf-life. A combination of the high-pressure CO2 pretreatment and drying can control the quality degradation of the food. Wei et al. [13] reported the effectiveness of this technology for controlling the activities of pathogenic microorganisms in the food system. During this process, Balaban et al. [13] reported that Listeria monocytogenes

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FIGURE 13.1 Typical flow process for beverage drinks pretreatment using a continuous dense-phase CO2 system [31].

and other microorganisms, for example, are destroyed when the food was treated with the CO2 at 6.18 MPa at 35°C for 2h, and the nutritional and other chemical quality parameters of the product are preserved after drying. Although the CO2 application pretreatment alone is effective for quality control during food drying, combining the process with novel ultrasound, magnetic field, electric field, nonionizing effects and so on, can better enhance the system performance. For example, the quality and microstructure of fresh honeydew melon can be preserved by freeze drying the product after it has been pretreated with a combination of the CO2 and ultrasound technique, as shown in Fig. 13.2 [35]. According to Jiang et al. [35], the melon fruits pretreated with the ultrasound assisted CO2 show an insignificant drip loss during thawing compared to the untreated products. To the best of the writer’s knowledge, there are no reported research on the application of the combination of the CO2 gas and the magnetic field, electric field, and nonionizing radiations as pretreatment effects on the quality the vegetables and fruits. Therefore, there is a need to further research in these areas.

13.2.3 Food preservation using dry ice The dry ice is a solid form of the CO2 and is suitable for maintaining the freshness of such as meat and dairy products during long trips or overnight shipping [36]. The dry ice has its temperature ranging from −78.3°C or −61.1°C and does not melt, but rather sublimates

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FIGURE 13.2 A high-pressure CO2 - ultrasound pretreatment for freeze-drying of vegetables and fruits [35].

into carbon dioxide gas thereby leaving no liquid mess to clean up [18]. It is produced in the solid blocks, slices, pellet, and rice size pieces depending on the customer’s demand [37]. The attribute of many food products including a bovine muscle [38], seer fish [14,16], arctic charr fillets [39], meat [40], and shrimp [41] has been reportedly enhanced by storing them in the dry ice crystals. Also, according to Jo et al. [15], eggs treated with a chitosan coating and stored with the dry ice will have a reduce loads of Salmonella Typhimurium on its surface than those without treatment with the dry ice at ambient temperature. It will also be limited in terms of the moisture loss, CO2 emission, and pH increase, thereby helping to maintain the freshness and shelf-life of the eggs. Thus, the dry ice has great potential to inhibit the quality loss in the food since it can control the activities of the deterioration microorganisms, pH, and the moisture content of the produce. There is however no available information on the effect of the dry ice treatment on the microstructural properties of the stored food. It is therefore necessary to investigate the influence of the dry ice pretreatment on microstructural properties, vibration loadings and rheological stability of the stored foods as a way-forward for further studies.

13.2.4 Animal stunning procedure The CO2 gas is used to induce unconsciousness on farm animals in preparation for slaughtering [42–45]. As the animal inhales the CO2 gas, the oxygen level in the blood decreases resulting in a loss of brain function and eventual brain death. A typical CO2 stunning procedure is presented in Fig. 13.3 [46]. The moment the animal enters the stunning room, the gas is passed to it in cyclic form as it moves via the turn tables, it becomes unconscious as it exits the other end as shown. According to most literatures [47–50], the loss of consciousness or awareness will normally begin after 1 minute inhalation of about 85% CO2 gas by the animal [22]. During this process, Pedro et al. [22] and Macron et al. [51] reported that the animal will experience a decrease in the brain activity which affected the blood flow and concentration. This permits easy preservation since the animal is now unaware of its surrounding. A group

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FIGURE 13.3 A CO2 stunning procedure for pigs [46].

stunning of the animals, with minimal restraint, less handling or stress can also be maintained in the process. The dependance on people and equipment is also minimal with this type of stunning technology. Despite the advantages of using the CO2 for stunning, the procedure is associated with a lot of challenges. A high concentration of the CO2 can cause fear, pain, and distress before the animals become unconscious [50]. Also, as an agent that stimulates the respiratory organ, it can cause irritation of the nasal mucosa membranes and suffocate the animals before losing consciousness. For these reasons, improvement in the application of the CO2 stunning technique or alternative methods are often sought after in the food industry. So far, available research has shown no clear alternative improvement in the application of this stunning technique in animal husbandry. Thus, it is necessary to focus research in this area to find alternative for the CO2 stunning technology or at least improve it.

13.2.5 Tanning of animal skin Tanning refers to the treatment of animal skins to produce leather. The tanning involves a procedure that permanently alters the protein structure of the skin, thereby making it less susceptible to degradation. However, this process is rigorous and takes time to complete. A compressed CO2 can shorten tanning times, to reduce water effluents and pollution and to save leather-finishing-fats. In conventional tanning process, chemicals are applied for cleaning, but this usually leads to the release of toxic substances like the chromium and sulphate into wastewater tanneries. However, according to Hu and Deng [21] who reviewed the application of a supercritical CO2 for the preservation of leather, this technique can be improved by pressurizing the gas to clean the skin product without involving chemicals, as shown in Fig. 13.4. The high amount of the CO2 required in this process has makes it economically unattractive, but it presents the cleanest approach for tanning of the leather products. For this reason, a synergy of both methods is sometimes employed to reduce cost and ensure effective tanning. The findings of Prokein et al. [52] proposed the production of a high-quality lather

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FIGURE 13.4 A high-pressure supercritical CO2 for tanning of leather [21].

using a CO2 -intensified tanning at 60 bars in combination with a 50 wt% of the tanning agent applied at separate stages. This is a better cleaning alternative, but it does not eliminate the problem since there are still traces of chemicals that may affect aquatic life in the receiving water bodies. Hence, it is necessary to further research on the application of the CO2 gas alone for the tanning of the leather and skin products without the chemical addition at low gas concentration and pressure.

13.3 Utilization of carbon-dioxide in food storage 13.3.1 Control of storage microsphere A CSA is a technology that is used to regulate the gaseous atmosphere in a food storage environment to prolong shelf-life and maintain quality [20]. Agricultural materials like the grains, legumes and oilseed can be stored in a CSA primarily to control insect pests [53] since the system could create an unpleasant condition for their survival. The CSA system are normally designed to cause a reduction in the level of atmospheric oxygen and elevates the CO2 gas concentration. This can be achieved by adding pure CO2 or nitrogen to the bulk grains at 25 °C to ensure the concentration is raised above 35 percent and maintained for 15 days [54]. This is sufficient to cause the insects and pests to suffocate and are killed. A CSA storage of different grains species had been described by Kaspersson et al. [55] and Pelhate [56] in their work on the safety and analysis of the microbial loads of stored barley by determining the proportion of the adenosine triphosphates in the grains stored in a silo [57]. The addition of

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FIGURE 13.5 A hematic storage system for grain storage [83].

CO2 to the grains, according to the authors, increases the safe storage time by several months. A combination of the CO2 and nitrogen fillets was reported to improve the performance of unpolished rice grains in storage [58]. This will create a reduce oxygen and rich CO2 atmosphere for respiration and microbial activities thereby enhancing the product’s storability. A hematic CSA system which is based on the depletion of the oxygen concentration and enrichment of the CO2 gas is suitable for controlling the microorganisms, insect, and pests in the storage, as shown in Fig. 13.5 [83]. This scenario is created via a natural process metabolism of the insect present in the storage and the respiration of the microorganisms within the system, especially if the grains contain high amount of moisture content. It is also effective for extending the shelf-life of meat, cheese, and other animal food products by retarding the bacterial and mold magnifications [59,60]. Consequently, this will increase both the lag phase and the generation time of the spoilage microorganisms; but the bacteriostatic effect of the CO2 gas on the magnification of the microbes and the molds has not yet been reported. Moreover, the CSA storage technology is well proven for preserving the quality of the vegetables and fruits [61]. The mechanism involves a careful material selection and special technique to produce a smart system [62–64], which can control the level of the gases in the storage atmosphere like the CSA system of storing grains in the silos. When fruits or vegetables are stored or packaged in these systems [65–67], they utilize the available oxygen gas and exhale the CO2 gas into the micro-atmosphere [68–71]. The excess of this gas can be removed using a CO2 scrubber or the system maybe specially designed using a nanoparticle [72–74], which can help to remove the excess gas, to balance the atmosphere. However, the products stored using the CSA approach may likely deteriorate faster when it is exposed to the

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FIGURE 13.6 A fouling occurring due to overcrowding of microbes [86].

ambient or physiological temperatures [75–78]. Also, the involvement of big and sophisticated equipment in the CSA may limit its application during transportation and retail storage of the products [79–82]. There is therefore the need for a simplified equipment that can advance the potential of this technology for food storage application in small farms and industries.

13.3.2 Storage equipment disinfection The CO2 are also used as disinfectants for animal feed to destroy microorganisms. The substance sublimates on contact and expand to generate the pressure needed to sweep the microorganisms. It can be applied to dissolve hydrocarbon contaminants, especially those found as residues in large storage tanks because of its low temperature. The dry ice crystals can also be forced through contaminated pipes to remove unwanted substances at the temperature rises in the pipes [84]. This is obviously a relatively new area of research requiring urgent attention because of the contaminants can malfunctioning of the equipment and halt operation [85]. In most cases, the food equipment maybe affected by overcrowding of the microorganisms around the metal (Fig. 13.6), thus resulting in a condition called fouling [86]. When this happens, disinfectants like the CO2 can be applied at high pressure to kill the microbes and enable the equipment for further healthy engagement. To the best of the writer’s knowledge, the commercial application of this technology has not been fully harnessed.

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13.4 Prospects and conclusion The commercial and industrial utilization of the CO2 preservation technology is partly dependent on its solubility in water and partly on its biochemical functionalities, which allows it to exhibit a disinfectant property. In food preservation, the substance is applied to perverse quality during drying and inactivate enzymes, such as polyphenol oxidase, and lipoxygenase, which are responsible for loss of color and flavor in beverages. It is also applied for plant and animal management, including facility inspection and control, cleaning of hide and skin products, and protection of grains and horticultural crops against insects, pest, and microbes’ attacks. However, to best of the writer’s knowledge, there are no reported research on the application of the combination of the CO2 gas and the magnetic field, electric field, and nonionizing radiations as pretreatment effects on the quality the vegetables and fruits. There is also no available information on the effect of the dry ice treatment on the microstructural properties of the stored food. Also, it was suggested to investigate the influence of the dry ice pretreatment on microstructural properties, vibration loadings and rheological stability of the stored foods as a way-forward for further studies. So far, available research has shown no clear alternative improvement in the application of this stunning technique in animal husbandry. Thus, it necessary to focus research on the improvement of the CO2 stunning technology to minimize the residual chemical generated into the wastewater bodies for a better cleaning alternative. Finally, the food products stored using the CSA technology may likely deteriorate rapidly when exposed the ambient or physiological temperatures. Also, the involvement of sophisticated facilities in this procedure may limit its application during transportation and retail storage of the products. Therefore, a simplified equipment was recommended to facilitate management of the storage system.

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14 An insight into the recent developments in membrane-based carbon dioxide capture and utilization Pritam Dey, Pritam Singh and Mitali Saha Department of Chemistry, National Institute of Technology Agartala, Tripura, India

14.1 Introduction Carbon dioxide (CO2 ) is the primary greenhouse gas that has the highest contribution toward global warming potential, due to a rise in Earth’s temperature. CO2 is produced when a carbon-rich fuel is completely burnt with the help of oxygen. Fossil fuels are considered the primary sources of energy, amounting to around 80 percent of the total global energy in 2019 [1]. Thus, the burning of fossil fuels is the primary reason behind CO2 production, while industrial and vehicular exhausts are the primary emitters of CO2 in the atmosphere. In the last century, uncontrolled and unrestricted use of such fossil fuels has led to an unprecedented increase in the CO2 levels in the Earth’s atmosphere. In this regard, fossil fuel utilization for energy needs and industrial purposes has resulted in more than 35 gigatons of worldwide CO2 emissions in the last year itself, which is the highest to date [2]. The rise in CO2 levels in the atmosphere is a real concern for our society. Implementation of stricter emission norms, utilization of cleaner energy sources, reduction in the dependency on fossil fuels, and encouragement toward afforestation are a few ways with which the issue of rising CO2 levels can be kept under control [3,4]. With the growing impetus toward the reduction of CO2 concentrations in the atmosphere to thwart the rising problems of global warming and climate change, scientists and researchers have suggested the following three strategies [5]: (1) To reduce energy intensity – which aims at minimal and efficient use of energy (2) To reduce carbon intensity – where the primary energy sources have to be shifted towards non-fossil fuels based and renewable energy

Green Sustainable Process for Chemical and Environmental Engineering and Science: Carbon Dioxide Capture and Utilization DOI: https://doi.org/10.1016/B978-0-323-99429-3.00012-6

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FIGURE 14.1 Carbon dioxide capture strategies.

(3) To enhance CO2 sequestration – which involves technological up-gradation for enhanced CO2 capture and utilization In recent times CO2 has emerged as one of the important gaseous raw materials in several industries. CO2 is generally added in compressed form in soft drinks via a process known as carbonation. CO2 finds application as an important industrial gas in the welding sector [6]. CO2 has immense application in the synthesis of alternative fuels, where it goes through an electrochemical reduction process to produce fuels and polycarbonates [7]. CO2 is the raw material in the production of synthetic gas or syngas and also in Fischer-Tropsch liquid fuel [8]. CO2 can also be used for producing biofuels using CO2 -concentrating bacteria, which utilizes biochemical pathways to synthesize hydrocarbons from CO2 and water [9]. Moreover, other uses of CO2 include enhanced recovery of oil and gas [10], energy storage [11], and chemical industry – for synthesizing methanol [12,13]. Thus, capturing a problematic gaseous emission (CO2 ) and utilizing it for the production of valuable products (chemicals and fuels) is a crucial method to mitigate the high levels of CO2 in the atmosphere which in turn would alleviate the issue of global warming.

14.2 Carbon dioxide capture technologies CO2 capture has become an economically significant and environmentally decisive way to mitigate global warming. In this regard, various CO2 capture technologies have evolved in the last few decades. The CO2 capture process is usually coupled with technology that governs either its storage or utilization (Fig. 14.1). Thus, the two types of CO2 capture technologies fall into the domains of carbon capture and storage (CCS) and carbon capture and utilization (CCU) [14]. In CCS, the carbon is captured as gaseous CO2 emission at the point of generation, compressed, and transported to a storage spot. The storage usually involves placing the compressed CO2 in underground geological formations [15]. The CCS technologies

14.2 Carbon dioxide capture technologies

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mostly target point emissions coming from burning fossil fuels for power generation and transportation, two of the most power-intensive sectors and also major contributors to global CO2 levels [6]. Although technologies to capture CO2 from the flue gas of coal-fired power plants can cut emissions, these technologies still cannot reduce the threat posed by the CO2 that has been already added to the air. In contrast to the mitigation of CO2 from industrial flue gas, CCS is advantageous, as not all the CO2 needs to be removed from the air [16]. On the other hand, CO2 capture and utilization (CCU) is considered a significant mitigation strategy to utilize CO2 as a source for the production of biofuels or other hydrocarbon compounds [8,17]. In CCU, the captured CO2 undergoes chemical or bio-chemical modifications which upgrade the CO2 into hydrocarbon-based fuels or other valuable chemicals. The CO2 capture can be categorized into three types, depending upon the place and method of CO2 capture. These three processes are pre-combustion CO2 capture, oxy-fuel combustion CO2 capture, and post-combustion CO2 capture [6]. Fig. 14.1 illustrates the three CO2 capture methods. As the name suggests, in pre-combustion CO2 capture, the CO2 gas is captured before the actual combustion of fuel (specifically, coal) takes place. As soon as the coal is gasified, carbon monoxide (CO) is released. A CO2 reformer, causes a steam-based reaction of CO at high pressures to yield hydrogen gas and CO2 . The evolved CO2 is removed using physical scrubbers or chemical solvents, while the hydrogen is used for generating power and electricity in the thermal plant. The removed CO2 is compressed and stored for further use. Physical absorption, adsorption, chemical looping, and non-polymeric membrane-based techniques are used to capture CO2 in the pre-combustion capture process. In oxy-fuel combustion, the fuel is burnt in an oxygen-rich environment (with above 85 percent oxygen saturation in the gas stream) instead of air to enhance the combustion efficiency of the unit. As we know that complete combustion of fuel results in only CO2 release and no formation of CO, thus this method generates a huge quantity of unadulterated CO2 upon combustion of fuel. An air separator unit separates pure oxygen and sends it to the boiler/ combustion unit. After combustion, CO2 remains as the primary flue gas (with a very high concentration in the emitted gas), which can be easily captured, compressed, and stored. An advantage of the oxy-fuel combustion process is that other gaseous emissions like oxides of nitrogen, particulate matter, CO, etc. are emitted at very trace amounts, making CO2 capture convenient [5]. Adsorption, chemical looping, and cryogenic air separation are usually employed for the oxy-fuel combustion CO2 capture. In the post-combustion capture method, CO2 capture takes place after the fuel is burnt in the air. As a result, CO2 , along with other gaseous emissions are liberated from the combustion unit. CO2 is captured from the flue gas after flue gas cleaning or scrubbing, sulfur, and particulate matter reduction, and CO2 separation from the flue gases advanced gas separation technologies [6]. Chemical absorption, adsorption, low-temperature solid-gas reactions, cryogenic CO2 anti-sublimation, calcium looping, and polymeric membrane-based techniques are used for capturing post-combustion CO2 . Physical pre-combustion or chemical post-combustion CO2 capture technologies; like absorption, adsorption, cryogenic separation, chemical looping, etc., with their elaboratelystudied designs and a better understanding of the operational parameters, have led to their wider implementation [18,19]. Chemical absorption using amine solvents is the conventional method to capture post-combustion CO2 . However, hazardous compounds in the atmosphere are due to the high volatility of such amine solvents.to form [20]. As a result, the focus has

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shifted towards novel sorbent materials. Also, cryogenic technologies are very costly, while chemical looping requires excessive amounts of reactive chemicals. Modern technologies are developed with a promise to be sustainable and cost-effective. Likewise, recent innovations in the development and up-gradation of existing CO2 capture technologies should focus on being more efficient, cost-effective, and sustainable for being acceptable in the modern era [21]. A handful of review articles are present in the recent literature which systematically describe the technologies available for CCS and CCU. Conventional technologies like absorption, adsorption, and bio-sequestration are generally highlighted in such reviews. The emergence of membrane technology for CO2 capture is a recent phenomenon, which came into the light only after advancements were made in materials for membrane production and processing. As a result, the niche of CO2 capture using membranes was not exploited to a greater extent. A lack of experimental literature is an implication of that. Hence, this chapter shall prove effective in summarizing the recent developments in membrane technology for CO2 capture, storage, and utilization. The subsequent headings deal with a brief description of the concept of the membrane technology behind CO2 capture, some examples of this technology being used throughout the world, and the advantages and limitations associated with this technology.

14.3 A brief about membrane technology A membrane is a partition (or a thin film) between two different fluid phases through which an active transport of specific solute molecules takes place depending upon the type of gradient which exists between them. Membranes are very much in use for the advanced separation of valuable products (solutes) from a mixed stream (solution). In membrane separation, the target (solute) is selectively permeated from one side of the membrane (packed inside a module) to its other side, while the bulk fluid (retentate) is discarded on the former side. The affinity of a solute molecule toward the membrane and the selectivity of the membrane are two important parameters that govern the separation efficiency of the membrane [6]. Fig. 14.2 provides a simple illustration on the working of a membrane in selective separation of a target molecule. Different types of membrane modules exists, in which membranes are fabricated and placed together in series or parallel formation to yield a membrane system or network. Such membrane networks are designed as per the requirements of an industry or the intent of separation (the purity to be achieved and the rate of separation to be followed) [21]. Earlier naturally-obtained membranes were considered for preparing membrane modules. But, their longevity and purity raised serious questions. As a result, synthetic membranes came into the picture and are now dominating the membrane industry. Synthetic membranes are of two types: polymeric membranes (in which organic membranes as well as organic-inorganic coupled membranes are present), and inorganic membranes. However, both polymeric and inorganic membranes can have either porous or non-porous nature, depending upon the material and method of fabrication. Separation through a porous membrane occurs due to Knudsen diffusion of the target molecules through the membrane structures. Whereas, in an non-porous membrane, separation occurs due to atomic, molecular, or ionic-diffusion mechanism coupled with a facilitated transport of the target molecules from the feed to the

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FIGURE 14.2 Mechanism of membrane separation.

permeate side. As a result, inorganic membranes are usually linked with superior performance and stability. Now-a-days much research and development are focused on developing mixed-matrix and composite membranes. Mixed-matrix membranes (MMM) are fabricated by embedding inorganic fillers into a polymeric matrix to get a combination superior performance of inorganic materials with the facile handling properties of polymeric materials. Composite membranes possess an asymmetric structure with a thin and dense top layer embedded on a thicker but porous support layer. Both the layers can be fabricated separately, which increases the complexity and cost of such membranes [21]. However, both the layers can be optimized separately for improvements in the selectivity, permeability, and stability of the composite membrane. The placement of membrane in a module plays an important role in determining the overall performance and durability of a membrane system. Three most widely used membrane modules are: Plate and frame module, spirally wound module, and Hollow fiber module [22]. The effective membrane area, packing volume, and membrane cost per area are dependent on the material for membrane fabrication and the type of membrane module [21]. The performance of the membrane operation also depends upon the type of feed flow and membrane placement. The two commonly used modes of module operation are: cross-flow and counter-flow modules. For a fixed feed flow rate, feed pressure, retentate composition and permeate pressure, a counter-flow mode requires lesser effective membrane area and power consumption as compared to a cross-flow mode. Also, a higher mass fraction of the target gas molecule can be achieved in the permeate stream by using the counter-flow mode of membrane operation [23]. The classification of membranes and their modules are illustrated in Fig. 14.3. Few benefits of using membranes are: reasonably minor carbon footprint associated with its usage, no change in the phase of the target is requited, not a cumbersome mechanical system to operate, operates generally under steady-state conditions, an ease to scale up, and flexibility in operations [21]. Still, some disadvantages of membranes are: cost of membrane-modules

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FIGURE 14.3 Membrane classification (with examples) and types of membrane modules.

increases with an increase in the selectivity for a particular molecule (target), a compression system is required for generating the required inlet pressure, membrane fouling occurs during continuous operations, and issue of membrane wetting [22]. Much research and innovations are still required to make membrane technology a mature one for thorough industrial use.

14.4 CO2 separation using membranes Gas separation using membranes came into the picture in 1980s, when Cellulose acetate membranes were used to separate CO2 from natural gas stream. During the 1990s selective separation of N2 from air using polymeric membranes became a thrust area in membrane research [23]. However, deployment of membrane systems for gas separation at commercial scales was not successfully carried out in the past. More emphasis was given on research and development of membrane systems for CO2 capture and storage. Only recently, a few industrial applications of gas separation using membrane systems were performed. In 2015, Abanades et al. [21] has listed out a detailed review recent innovations in CO2 capture technologies in which recent developments in membrane modules and systems for CO2 separation were also presented. Very recently, a couple of articles were published which reviewed latest star-of-the-art in research and development as well as industrial applications of CO2 capture, storage, and utilization technologies [6,17,21,24]. However, there is a deficit in the thorough reviews only on membrane processes for CO2 capture and utilization in the recent literature [25,26]. Thus, in this chapter the authors intend to highlight the recent developments in membrane-based CO2 capture and utilization.

14.4.1 Pre-combustion CO2 capture using membranes As mentioned earlier the air with steam is first passed through a CO2 reformer or a coal gasifier, which converts the two into CO2 and H2 , also called syngas, using a water-shift

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reaction. This CO2 is then removed from the mixture of gases, using a membrane system. Membrane-based pre-combustion CO2 capture is the least talked-about and worked-upon CO2 capture technique [23]. Researchers are usually more concerned about capturing the postcombustion CO2 . However, the cost of CO2 capture during pre-combustion is significantly lower than that for post-combustion process. One reason for this is the requisite of adding an extra equipment, like compressor or vacuum pump for pressurizing the feed stream [6]. The membranes for the pre-combustion CO2 capture are usually of two types: H2 -selective membranes and CO2 -selective membranes. The H2 -selective membranes permeates H2 gas, while CO2 is present in the retentate. Whereas, the CO2 -selective membranes have high selectivity for CO2 and preferentially permeates the same. Usually, metallic or inorganic membranes are utilized for CO2 capture from the air before it is sent to the combustion chamber. Metallic membranes are mostly considered for pre-combustion CO2 capture due to their high thermal stabilities. Zeolite-based membranes and membranes involving metalorganic frameworks are also considered for H2 /CO2 separation [27]. Additionally, highly efficient absorbent coupled with a membrane contactor were also investigated for successful H2 or CO2 separation from pre-combustion process. Ionic liquids as absorbent species were reported to have improved the performance of an absorptive membrane separation of precombustion CO2 [28]. Recently, mixed matrix membranes (MMM) and ceramic-composite membranes were tested for pre-combustion CO2 capture [26]. Such membranes were reported to have enhanced CO2 permeability as well as H2 /CO2 selectivity. Table 14.1 presents a few selected recent advancements in pre-combustion CO2 capture using advanced membrane systems. In each case, the feed was H2 and CO2 which came out of the steam reformer. Most of the membrane-based gas separation technique were aimed at permeating H2 from the feed so that high purity CO2 can be collected from the retentate stream. CO2 capture of around 90 percent was reported in most of the recent literature, which indicates superior performance of MMMs and Pd-based composite membranes.

14.4.2 Oxy-fuel combustion CO2 capture using membranes The major issue with post-combustion CO2 capture is the presence of N2 in the flue gas coming out of the combustion chamber. In oxy-fuel combustion process, pure oxygen in suppled for the combustion of fuel, thus there is no N2 present in the exhaust gas. The combustion of fuel results in the liberation of CO2 and water vapor. While water vapor can be condensed out of the exhaust stream, the remaining the CO2 -rich gas can be easily compressed, stored, and utilized. Industrially, in oxy-fuel combustion process, membranes are used for oxygen separation or O2 /N2 separation from air. Thus, O2 -selective membranes are generally employed in oxy-fuel combustion CO2 capture. In general, fluorite-based and perovskite-based membranes are used for selective O2 separation from air [27]. This separation can be performed with polymeric membranes at ambient temperature or with ceramic oxygen transport membranes at elevated temperature [36]. Usually, most of the work in the literature under membrane-based oxy-fuel combustion process had dealt with removing O2 or N2 from the air so that combustion of fuel can near its completion, which can result in the emission of pure CO2 in the exhaust stream. Ji and Zhao [27] and Sunarso et al. [37] have provided extensive literature review on oxy-fuel combustion CO2 capture process using membrane, prior to 2015. Table 14.2 provides a few selected recent

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TABLE 14.1 Selected recent membrane technologies for pre-combustion CO2 capture. % CO2 removal/CO2 flux/ CO2 permeability/H2 /CO2 selectivity

Membrane type

Operating conditions

References

Cu-based organic framework blended with polybenzimidazole to form MMM

Feed = H2 +CO2 Feed pressure = 2–5 bars CO2 membrane adsorption at 308 K, and 333 K Time = 5 h

CO2 permeability = 15.1 Barrers H2 /CO2 selectivity = 29–39

[29]

Pd-porous ceramic composite membrane

Feed = H2 +CO2 with N2 sweep Feed pressure = 2.6 bar Temperature = 673 K Time = 3600 h Counter-current flow

90 percent CO2 capture achieved H2 /CO2 selectivity = 500

[30]

Butyl-3-methlyimidazolium tricyanomethanide as CO2 absorber

Feed = CO2 +He Feed pressure = 20 bar Temperature = 353 K

10.4–24.9 × 10−6 molm−2 s−1

[31]

Pd-(23 percent Ag) alloy composite membrane

Feed = H2 +CO2 with N2 sweep Feed pressure = 15–20 bar Temperature = 573 K Time = 36 h

90 percent CO2 capture achieved

[32]

ZIF-8 nanoparticles in polybenzimidazole MMM

Feed = H2 +CO2 Feed pressure = 6 bar Temperature = 523 K

CO2 permeability 0.765 GPU H2 /CO2 selectivity = 22.3–35.6

[33]

3-stage membrane module with CO2 selective membranes

Feed = H2 +CO2 Feed pressure = 35–110 bar Temperature = 343–423 K

90 percent CO2 capture achieved H2 /CO2 selectivity = 20–50

[34]

Butyl-3-methlyimidazolium tricyanomethanide as CO2 absorber in a shell-and-tube membrane contactor

Feed = CO2 +He Feed pressure = 1–20 bar Temperature = 293–353 K

3.04 × 10−5 molm−2 s−1

[35]

advancements in oxy-fuel combustion CO2 separation using membranes. In recent literature, O2 recovery from air using ion-transport ceramic membranes at high operating temperature (> 1173 K) were mostly presented. Also, O2 recovery of above 90 percent were reported by most authors. The innovations in the field of membranes for O2 /N2 separation in an oxy-fuel combustion process is still at its developmental stage, as no commercialization has been reported till date. Although, lot many literature is already present which showcases the capabilities of such membranes at lab scale. When compared to the cryogenic air separation, the most common CO2 capture technique during oxy-fuel combustion process, membrane-based CO2 capture is still unfavorable owing to high temperature requirement for its operation and requirements of costly membranes for the process [27]. Also, problems of high temperature sealing as well as chemical and mechanical stability of the membrane set-up are still some technical issues that

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TABLE 14.2 Selected recent membrane technologies for oxy-fuel combustion CO2 capture process. % O2 or CO2 recovery/ O2 flux / net efficiency

References

Membrane type

Operating conditions

Ion-transport ceramic, non-porous membrane

Feed = Air Feed pressure = 26.3 bar Temperature = 1173 K

85 percent CO2 recovery Net efficiency = 68 percent

[38]

Ta-doped SrCo0.8 Fe0.2 O3-δ O2 transport membranes in parallel tubes

Feed = Air Temperature = 1223 K Time = 70 h

92 percent O2 recovery Net efficiency = 31.8 percent

[36]

Oxygen transport membrane (non-porous, ceramic)

Feed = Air with water vapor as sweep gas Temperature = 1173 K Pressure = 40 bar

97.5 mol%percent O2 recovery Net efficiency = 85 percent

[39]

La0.6 Sr0.4 CoO3−δ hollow fiber membrane reinforced with stainless steel

Feed = Air Temperature = 1273 K

O2 flux = 2. 29 mlcm−2 min−1

[40]

needs to be addressed before commercializing the oxy-fuel combustion CO2 capture using membrane systems.

14.4.3 Post-combustion CO2 capture using membranes Most membrane operations for carbon capture are primarily linked with the postcombustion CO2 capture condition. CO2 from the industrial flue gases are separated from other components of flue gas, like H2 and N2 , mostly using polymeric membranes. Commonly used polymeric membranes are: cellulose acetate, polysulfone, polyethersulfone, polyvinyl alcohol, polyvinylidene difluoride and polyimide membranes. Polyimides are known to retain the best performance CO2 separation owing to their good thermal, mechanical, and chemical stabilities, and varying CO2 permeability [24]. Whereas, inorganic membranes have higher selectivity, lower CO2 permeability, superior chemical and thermal stability. Recently various mixed matrix membranes (MMM), ceramic porous membranes, metal-organic frameworks, and composite membranes were developed which enhanced the CO2 separation capacities of membrane operations [36] Addition of inorganic filers of micro- or nano-scale into polymeric matrix were found to have increased the thermo-mechanical stability of the membrane. Alami et al. [6], Chao et al. [24], and Kárászová et al. [41] have provided extensive reviews on post-combustion CO2 capture using polymeric membranes. These reviews highlighted the trends in post-combustion CO2 capture using membranes. In recent times, along with the traditional membranes many commercial and advanced polymeric separation membranes like: Pebax® , Matrimid® , PolyActiveTM , PolarisTM , PermSelectTM , PRISMTM , sulfonatedpolyether-ether-ketone (SPEEK), and sulfonated-polystyrene-b-poly(ethylene-r-butylene)-bpolystyrene (S-SEBS) were in great demand for preparing MMMs as well as composite membranes for post-combustion CO2 capture. Moreover, polymer intrinsic microporosity (PIM) films and PolyILs (polymeric membranes infused with ionic liquids) are current materials for

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TABLE 14.3 Selected recent membrane technologies for post-combustion CO2 capture process. % CO2 recovery/ CO2 /N2 selectivity/ CO2 flux / net efficiency

References

Membrane type

Operating conditions

Poly-amine fixed site carrier membrane

Feed = Flue gas from coal-fired plant Temperature = 323 K Pressure = 1.1 bar Counter-current mode

90 percent CO2 recovery CO2 permeance = 3.8 × 10−5 kmolm−2 bar−1 s−1

[20]

Poly(vinylidene fluoride) fibers in Polydimethylsiloxane thin film composite hollow fiber membrane contactor

Feed = CO2 +N2 Temperature = 298 K Pressure = 0.4–1.4 bar Counter-current mode

38 percent CO2 recovery CO2 /N2 selectivity = 27 CO2 permeance = 2049 GPU

[42]

Nano-porous single-layer graphene membrane

Feed = CO2 +N2 +H2 O Two stage cross-flow mode of membrane operation

90 percent CO2 recovery CO2 permeance = 10,000 GPU CO2 /N2 selectivity = 30

[43]

Polyvinylamine-based facilitated transport membranes

Feed = Flue gas Temperature = 313 K Pressure = 1.5 bar 2–3 membrane stages

90 percent CO2 recovery CO2 /N2 selectivity = 30 CO2 /O2 selectivity < 10 CO2 permeance = 2.18 Nm3 m−2 h−1 bar−1

[44]

Polydimethylsiloxane-Trimesoyl chloride-PolydimethylsiloxanePolysulfone multi-layered composite membrane

Feed = CO2 /N2 mixture Temperature = 298 K Pressure = 1.5 bar 2 membrane stages

90 percent CO2 recovery CO2 /N2 selectivity = 13-CO2 permeance = 6000–10,500 GPU

[45]

active research on membrane-based post-combustion CO2 separation. Table 14.3 provides selected recent advancements in last two years in post-combustion CO2 capture using membrane systems. A recent review by Han et al. [46] has discussed the emerging polymeric membranes for post-combustion CO2 separation, with in depth analysis of the theory involved in the working of such polymeric membranes. Also, the advancements in the field of thin film membrane synthesis and their utilization in post-combustion CO2 capture were reviewed by Liu et al. [47], which needs mentioning. Recently, hybrid systems comprising of membranes and other separation process were proposed and developed for increasing the capture efficiency of post-combustion CO2 . Membranes systems coupled with solid adsorbents or with strong absorbents or with chemical looping technique are under research and developmental stage for enhancing CO2 capture [6]. However, the manufacturing as well as operating cost of such hybrid systems are a cause of concern before being commercially utilized in industrial plants for large-scale post-combustion CO2 capture.

14.4.4 Future considerations for membrane-based CO2 capture The advancements in manufacturing membranes and membrane systems for CO2 capture should aim for high CO2 permeability and selectivity. However, a trade-off exists between the

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two in terms of membrane operation which needs to be balanced in the future for enhancing the membrane performance. Membranes used for CO2 enrichment, as well as for N2 , H2 , and O2 separation, should possess long term thermo-mechanical and chemical stability, and should be efficient and cost-effective [41]. Polymeric membranes need to withstand membrane ageing and plasticization, while inorganic membranes need to have enhanced flexibility in operation. Also, with the availability of membrane performance data, developments in the membrane manufacturing can be fast-tracked in the future [21]. All membranes need to be manufactured in a way such that they possess least fabrication complexities, can be easily scaled-up, and are produced from cheapest possible precursors. The cost of membranes and their modules is still an issue, which dictates the overall process economics. Many of the membranes and membrane systems currently under development are likely to decrease in cost over time with technological advancements in production and installation techniques and also a general rise in the market demand and competition [21]. Recent trends of utilizing bio-based “green composite” materials can be looked into for manufacturing of advanced composite membranes for specific gas separation. Green composites are a current thrust area of research for manufacturing of a variety of advanced materials which have lover carbon footprints and are sustainable than most commercially available materials [48].

14.5 CO2 utilization using membranes The concept behind CO2 utilization is to use the emitted CO2 for synthesizing new substances, either as a raw material or as a catalyst. The captured CO2 is linked with reduction in the carbon footprint of the Earth. The captured CO2 can be utilized in many ways. The direct utilization of CO2 is performed in many food-beverage and chemical industries [26]. Microalgae production has recently being considered as a major CO2 sink after a wide variety of applications have been realized. Some of the products of microalgae production include pharmaceuticals, livestock food, and biofuels [7,8]. Other major uses of CO2 are as commercial refrigerant [49], in the synthesis of acetate using molecular H2 gas [50], methanol synthesis [12,13], urea generation [51], electrochemical synthesis of formic acid [52], and enhanced oil recovery by means of CO2 flooding or displacement process [53]. Some interesting CO2 utilization pathways include desalination of seawater [54] and photocatalytic removal of dyes from aqueous solutions [55,56]. Fig. 14.4 illustrates the various utilization pathways for capture CO2 . Among the above-mentioned CO2 utilization pathways, membrane-based CO2 capture and utilization for algal production is a sustainable approach because the captured CO2 is directly utilized by the algae for biomass formation and synthesis of various metabolites [9,16]. The use of membrane-based photo-bioreactor is an example of example of the same. In such bioreactors, the membrane module helps in permeation of pure CO2 from the entering air, which is utilized by micro-algal culture supported behind the membrane module. The micro-algae utilizes this CO2 by cellular sequestration and formation of organic compounds (metabolites) with the release of O2 gas into the environment. Thus, membrane-based algal bioreactors not only sequestrate the ever increasing CO2 in the air, but also releases O2 in the environment. Also, the algal biomass can be easily converted into bio-fuels by various

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FIGURE 14.4 Pathways for CO2 utilization.

processes [9]. Some recent and innovative membrane bioreactors [14] and membrane microalgal reactors [57] were fabricated to capture CO2 from air and utilize it for microbial biomass growth. Such systems can prove very beneficial in the coming future. However, further research and development in this field is imperative to enhance the CO2 permeability of such membranes.

14.6 Conclusions There is an eminent need to mitigate the rising carbon dioxide (CO2 ) concentrations in the Earth’s atmosphere. In this regard, CO2 capture technologies, before and after the combustion of fuel, have become paramount in the modern era. Within the CO2 capture technologies, membrane-based CO2 capture has emerged as an efficient and sustainable alternative. With tremendous advancements in membrane technologies, CO2 capture using membranes has become a hassle-free affair. Metallic or metal-ceramic composite membranes with high N2 /CO2 selectivity are mostly investigated for pre-combustion CO2 separation. Such membranes have high thermo-mechanical stability. During oxy-fuel combustion process, fluoride or perovskite-based membranes have demonstrated high O2 selectivity, thus resulting in a high percent weight CO2 in the exhaust stream. Whereas, polymeric membranes are used for post-combustion CO2 capture. Now-a-days, commercial membranes and multilayered polymeric membranes, having high CO2 permeance and CO2 /N2 selectivity are utilized for CO2 capture from industrial flue gases. Still more advancements and innovations are required for making the membranes more affordable, stable, and high-performing. The captured CO2 can be utilized by different pathways, for material synthesis, enhanced oil

References

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recovery, pharmaceuticals, and bio-fuel production. Membrane-based micro-algal bioreactors are a sustainable technology for CO2 capture and utilization. Such systems not only sequester CO2 and provide O2 to the atmosphere, but also provide valuable bio-materials as well as biofuels. Such systems are also used for water remediation and wastewater treatment. Thus, it can be concluded that membrane-based CO2 capture and utilization can become a sustainable technology in the coming future for global warming abatement.

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[21] Abanades JC, Arias B, Lyngfelt A, Mattisson T, Wiley DE, Li H, et al. Emerging CO2 capture systems. Int J Greenhouse Gas Control 2015;40:126–66. [22] Ibrahim MH, El-Naas MH, Zhang Z, Van der Bruggen B. CO2 capture using hollow fiber membranes: a review of membrane wetting. Energy Fuels 2018;32(2):963–78. [23] Merkel TC, Lin H, Wei X, Baker R. Power plant post-combustion carbon dioxide capture: an opportunity for Membranes. J Memb Sci 2010;359:126–39. [24] Chao C, Deng Y, Dewil R, Baeyens J, Fan X. Post-combustion carbon capture. Renew Sustain Energy Rev 2021;138:110490. [25] Norahim N, Yaisanga P, Faungnawakij K, Charinpanitkul T, Klaysom C. Recent membrane developments for CO2 separation and capture. Chem Eng Technol 2018;41(2):211–23. [26] Shah C, Raut S, Kacha H, Patel H, Shah M. Carbon capture using membrane-based materials and its utilization pathways. Chem Paper 2021;75:4413–29. [27] Ji G, Zhao M. Membrane separation technology n carbon capture. In: Yun Y, editor. Recent Advances in Carbon Capture and Storage. London, United Kingdom: InTech Open Publishers; 2017. p. 59–90. [28] Theo WL, Lim JS, Hashim H, Mustaffa AA, Ho WS. Review of pre-combustion capture and ionic liquid in carbon capture and storage. Appl Energy 2016;183:1633–63. [29] Kang Z, Peng Y, Hu Z, Qian Y, Chi C, Yeo LY, et al. Mixed matrix membranes composed of two-dimensional metal–organic framework nanosheets for pre-combustion CO2 capture: a relationship study of filler morphology versus membrane performance. J Mater Chemist A 2015;3(41):20801–10. [30] Goldbach A, Feng B, Chenchen Q, Chun B, Lingfang Z, Chuanyong H, et al. Evaluation of Pd composite membrane for pre-combustion CO2 capture. Int J Greenhouse Gas Control 2015;33:69–76. [31] Dai Z, Deng L. Membrane absorption using ionic liquid for pre-combustion CO2 capture at elevated pressure and temperature. Int J Greenhouse Gas Control 2016;54:59–69. [32] Peters TA, Rørvik PM, Sunde TO, Stange M, Roness F, Reinertsen TR, et al. Palladium (Pd) membranes as key enabling technology for pre-combustion CO2 capture and hydrogen production. Energy Proce 2017;114: 37–45. [33] Sánchez-Laínez J, Zornoza B, Téllez C, Coronas J. Asymmetric polybenzimidazole membranes with thin selective skin layer containing ZIF-8 for H2 /CO2 separation at pre-combustion capture conditions. J Memb Sci 2018;563:427–34. [34] Giordano L, Gubis J, Bierman G, Kapteijn F. Conceptual design of membrane-based pre-combustion CO2 capture process: role of permeance and selectivity on performance and costs. J Memb Sci 2019;575:229–41. [35] Sohaib Q, Muhammad A, Younas M, Rezakazemi M. Modeling pre-combustion CO2 capture with tubular membrane contactor using ionic liquids at elevated temperatures. Sep Purif, Technol 2020;241:116677. [36] Chen W, van der Ham L, Nijmeijer A, Winnubst L. Membrane-integrated oxy-fuel combustion of coal: process design and simulation. J Memb Sci 2015;492:461–70. [37] Sunarso J, Hashim SS, Zhu N, Zhou W. Perovskite oxides applications in high temperature oxygen separation, solid oxide fuel cell and membrane reactor: a review. Prog Energy Combus Sci 2017;61:57–77. [38] Duan L, Yue L, Qu W, Yang Y. Study on CO2 capture from molten carbonate fuel cell hybrid system integrated with oxygen ion transfer membrane. Energy 2015;93(1):20–30. [39] Vellini M, Gambini M. CO2 capture in advanced power plants fed by coal and equipped with OTM. Int J Greenhouse Gas Control 2015;36:144–52. [40] Wang B, Song J, Tan X, Meng B, Liu J, Liu S. Reinforced perovskite hollow fiber membranes with stainless steel as the reactive sintering aid for oxygen separation. J Memb Sci 2016;502:151–7. ˇ [41] Kárászová M, Zach B, Petrusová Z, Cervenka V, Bobák M, Šyc M, et al. Post-combustion carbon capture by membrane separation. Review, Sep Purify Technol 2020;238:116448. [42] Younas M, Tahir T, Wu C, Farrukh S, Sohaib Q, Muhammad A, et al. Post-combustion CO2 capture with sweep gas in thin film composite (TFC) hollow fiber membrane (HFM) contactor. J CO2 Util 2020;40:101266. [43] Micari M, Dakhchoune M, Agrawal KV. Techno-economic assessment of post-combustion carbon capture using high-performance nanoporous single-layer graphene membranes. J Memb Sci 2021;624:119103. [44] He X. Polyvinylamine-Based Facilitated Transport Membranes for Post-Combustion CO2 Capture: challenges and Perspectives from Materials to Processes. Eng 2020;7(1):124–31. [45] Sheng M, Dong S, Qiao Z, Li Q, Yuan Y, Xing G, et al. Large-scale preparation of multilayer composite membranes for post-combustion CO2 capture. J Memb Sci 2021;636:119595.

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15 Carbon dioxide to fuel using solar energy Srijita Basumallick Asutosh College, University of Calcutta, Kolkata, India

15.1 Introduction Green plants convert CO2 to bio-fuel glucose using sun light and chlorophyll. But the mechanism of photo-synthesis is not yet fully known, it is not yet possible to replicate photosynthesis in laboratory. It is known photolysis of water at light phase and reduction of CO2 in the dark phase are the key processes of photosynthesis. Again, it is known natural photo catalyst NADP plays an important role in Kelvin cycle, where CO2 is reduced. In fact, conversion of CO2 to glucose is thermodynamically unfavourable, a uphill reaction, as free energy change of this reaction if positive, the thermodynamical requirement is fulfilled using solar energy. This reaction is also kinetically slow, because of requirement of high activation energy. Thus, requirement of efficient photo-catalyst is important for conversion of CO2 to simple fuel like methanol, ethanol etc. In the recent years, immense interests are noted [1–10] in development of photo-catalysts and electro-catalysts for carbon dioxide (CO2 ) reduction. It is known CO2 is a greenhouse gas causing global warming. Natural photosynthetic way of reducing CO2 pollution (as stated above) is not enough to restore the ecological CO2 balance because of rapidly increasing global carbon emission (exceeding gig ton, annually). Thus, photo-chemical or electro-chemical reduction [1–10] of CO2 is important to restore CO2 balance.

15.2 CO2 reduction onto semiconductor surface In general, photo reduction of carbon dioxide is carried out using a semiconductor with band gap energy compatible to solar light. Upon irradiation electron is excited to conduction band leaving behind hole in the valence band. This is illustrated by our work on reduction of carbon dioxide and formation of formic acid. We have carried out an experiment where chitosan coated Cu2 O quantum dots were drop casted on boron doped Si-wafer. Chitosan

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FIGURE 15.1 Probable mechanism of CO2 reduction on Chitosan coatedCu2 O dispersed Si-water.

provided stretched film with well separate and exposed Cu2 O quantum dots that helps adhere Si-wafer as confirmed from AFM images. Increased -OH and -C = O peak indicated formic acid formation. The quantum yield was low when catalyst surface was kept inside glass jar containing H2 O which acts as hole scavenger. Formation of formic acid as photo-reduction product of CO2 was also supported from a similar study that was done by Liu et al. [9] using TiO2 catalyst. They reported formation of formic acid as photo-catalytic reduction product of CO2 on to TiO2 surface. In case of chitosan coated Cu2 O quantum dot dispersed Si-wafer we have proposed a probable mechanism of formation of formic acid (shown in Fig. below) [11]. Interestingly, unlike photo synthesis here CO2 reduction occurs in the presence of light (Fig. 15.1). Recently photo electrochemical reduction of carbon dioxide is also been reported, here semiconductor is anchored to an electrochemical cathode surface where photo reduction is enhanced many fold. Thus carbon dioxide reduced onto semiconductor surface accepting this photo excited electron in two different ways, first simple photo-catalytic (PC) reduction and secondly, photo electro-catalytic (PEC) reduction [12]. In both these processes overall action happens through different steps. In case of PEC photo catalyst present in cathode reduce carbon dioxide adsorbed on the surface. Whereas the hole migration takes place at counter electrode [12] or anode side. This hole in anode is scavenged by water or sacrificial electron donors like amine as well as other whole scavenging material. It is important to note that band gap of chosen semiconductor catalyst should straddle reduction and oxidation potentials of carbon dioxide as well as water or sacrificial electron donor or hole scavenging material. Now due to band bending in the interface of semiconductor and electrolyte or vacuum, the band gap of semiconductor catalyst on the surface becomes much less than bulk band gap. As a result net band gap must be greater than the oxidation and reduction potential of carbon dioxide and particular anode reaction as mentioned above [13].

15.3 Major bottleneck for CO2 reduction Among several products of CO2 reduction, methanol, ethanol, methane and ethane formation is favourable. But it is kinetically highly unfavourable as it goes through intermediate radical anion CO2 ◦− formation. Conversion of CO2 to CH3 OH requires 6e- as shown in Eq. (15.1). This makes it even more kinetically unfavourable to reduce. Free energy of formation of CO2 ◦−

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radical anion (1 e- transfer to CO2 ) is higher compared to other products as it requires bending of linear CO2 [14]. CO2 + 6H+ + 6e = CH3 OH + H2 O E0 = −0.38 V vs NHE at pH 7

(15.1)

Another problem of photo-reduction of CO2 onto semi conductor surface is recombination of hole-electron pair. For that rate of electron and hole separation and migration through catalyst should be comparable to the rate determining step of reduction of CO2 . This step may be either rate of mass diffusion of product or reactant. It is probable that water splitting reaction taking place onto hole site and plays an important role. Due to band bending modified and band gap issue water splitting reaction become competent with CO2 reduction. Both of these reactions got same anodic oxidation of O2 − (H2 O) to O2 at +1.23 V and CO2 reduction potential varies from −0.24 V (CH4 formation) to −0.89 V (HCHO formation) vs NHE at pH 7, 1 atm and 25 °C depending on the products, where as in case of water splitting at cathode proton adsorption and hydrogen evolution takes place at −0.41 V vs NHE at pH 7. Not only that CO2 ◦− can form CO2 back. Hole generated in the semiconductor catalyst produce oxygen, OH radical, also hole itself and free proton from water all of which can take back electron from the intermediate species like CO2 ◦− to form CO2 back through a reverse reaction. As already discussed bending of CO2 during adsorption on catalyst surface is a prime step for carbon dioxide reduction reaction. This can be done by several ways like increase in surface area, increasing defect, introducing basic sites or metal co catalysts. It is noted that some crystalline faces facilities CO2 adsorption like 101 of TiO2 . Whereas 001 face of TiO2 has higher active oxygen as a result high photo catalytic activity is seen. At the same time many mesoporous zeolite particles with catalytic sites inside pore surface shows better catalytic activity for selective methanol formation from carbon dioxide reduction. This can be explained due to formation of stable charge transfer complex (Ti3+ -O− )∗ and trapped hole centres on O− sites in TiO2 on zeolite surface. Introduction of basic sites either inorganic or organic like amines or calcium oxide, magnesium oxide works towards better adsorption of carbon dioxide. Wang and co-workers found addition of MgO on TiO2 as well as Pt-TiO2 enhances CO and CH4 formation respectively. Crystal defect play important role in adsorbing carbon dioxide. Thus oxygen and sulphur vacancies introduced in several semiconductors show reduction in activation energy with increase in adsorption of CO2 . Co catalysis of noble metals as Ru play an important role as it can trap electrons and reduce the recombination process as well as desorption of carbon monoxide help reduce poisoning of catalyst surfaces.

15.4 Different types of photo catalyst 15.4.1 Homogeneous photo-catalysts When homogeneous catalyst is used rate of CO2 reduction becomes faster due to less kinetic barrier for electron transfer reaction and formation of easy adduct/complexation. Again heterogeneous catalysts undergo more poisoning compared to homogeneous one [14]. Thus water dispersible catalyst might produce better yield in CO2 reduction due o increase in net surface area or more adsorption of CO2 on to catalyst surface. Some amine compounds are highly soluble in water and enhance CO2 reduction. Since one-electron reduction of

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CO2 requires strong reducing agents that are generally difficult to obtain by photochemical methods [15]. It is known amines enhance solubility of CO2 [15] which can help in better yield too. Sacrificial electron donor amines like TEOA (triethanolamine) or tertiary amine is used [16,17] in combination with another photo sensitizer or alone [16,17]. But after electron donation to CO2 , it undergoes secondary reactions leading to the formation of by-products i.e. oxidized amines [18,19]. Theoretical models for renewable sacrificial electron donor amines have been proposed [17], where once used, by-product can be hydrogenated to return amine for one more CO2 ◦− radical anion generation, there by working as a catalyst. Major problem associated with this approach is that a well divided compartment for CO2 reduction as well as amine regeneration site is essential for practical purpose. Especially they form homogeneous mixture in water and it is difficult to separate amine and products of CO2 reduction. But this remains unsolved. Among all possible heterogeneous photo catalyst semiconductor photo catalysts are most important. There are several semiconductor systems that has band gap fitting to the required potential. Examples are TiO2 , Cu2 O, CdS, ZnO, GaP, SiC, WO3 etc. Among which TiO2 and Cu2 O is most important. In case of semiconductors corrosion is a major issue to be identified.

15.4.2 Cu based photo-catalysts Among different photo- catalysts, Cu2 O is a unique semiconductor catalyst because it absorbs in the visible light (sunlight), its CO2 adsorption efficiency is really high and last but not the least certain crystal faces as well as copper oxygen cluster helps bending CO2 reducing free energy of formation CO2 ◦− . It is known [5–7] Cu2 O is an efficient catalyst for CO2 reduction in sun light or using electrical energy. This is because Cu2 O has compatible crystal structures [20] where CO2 molecules can easily adsorbed. Calculated values of heat of adsorption show favourable interaction [20] of CO2 molecules on Cu2 O catalyst. In spite of several unique features, major problem associated with Cu2 O photo catalyst is that it undergoes photo-corrosion.

15.5 Reduction of CO2 to methanol using Cu2 O as photo catalyst Even though the CH3 OH formation has huge kinetic barrier due to 6e- reduction process but CH3 OH is a better fuel than that of CH4 or C2 H4 . Surprisingly, due to the unique binding of CO2 onto Cu2 O surface as well as its H binding capacity that helps stabilizing the intermediate which is required for methanol production.

15.6 Reduction of CO2 to methanol using Cu2 O as electro catalyst In case of electrochemical reduction current density directly relates to the formation of by products as well as faraday efficiency of CO2 reduction to methanol. But higher current density helps 6 electron transfer reaction on inefficient catalyst surface. Several electro catalysts like Mo [21] and different types of Ru catalyst [22,23] have low current densities (60 percent). But among all other Cu shows best faradaic

15.7 Benefits of using RGOin the composite catalyst

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efficiency 100 percent [22] for current density up to 33 mA cm−2 . Faradaic efficiencies have been calculated on the basis of six-electron transfer reduction of CO2 and efficiencies greater than unity suggest electrochemical-chemical (EC or CE) mechanisms [7,22,24].

15.6.1 Reduced graphene-oxide, Cu2 O and amine compounds composite photo catalysts for CO2 reduction A composite catalyst where a heterogeneous catalyst is grafted with a sacrificial amine is a better choice because catalyst purification from reaction mixture is easy and it leads to recovery of sacrificial amine too. In another approach, H2 O oxidation mediated H2 generation is coupled with CO2 reduction. But amines are protonated at lower pH. Very interestingly this can help reducing hydrogen evolution reaction that can compete with CO2 reduction. Though it compromise its activity as sacrificial electron donor [25]. If Cu2 O is attached to RGO it can act as a hole or electron trap and reduce the rate of hole-electron recombination [26]. Key idea behind this proposed scheme is to combine amine functionalized GO with copper (I)-oxide to make a composites that will be water dispersible and this composites will reduce activation energy of CO2 reduction onto Cu(I)-Oxide surface. In particular Cu2 O grafted reduced graphene oxide can be prepared following literature [27,28]. We envisage the amine fictionalization will help in chelating Cu2+ ions. This will help in better growth in crystalline Cu2 O nano particles [25,29] on top of reduced graphene oxide sheet. Besides this amine can act as sacrificial electron donor [30] to neutralize hole generated in Cu2 O due to photo excitation in semiconductor band gap. Particularly pentane amine derivative of graphene oxide might be interesting. Recently Carpenter et al. [17] has shown γ proton containing amine can act as sacrificial electron donor can be regenerated instead of stoichiometric west generated in reaction medium. Formation of composite photo-catalyst comprising of amino functionalized reduced graphene oxide and Cu2 O is schematically shown below (Fig. 15.2) [31].

15.7 Benefits of using RGOin the composite catalyst Mechanistic study of this catalytic reduction process will definitely provide new insight of photo-reduction mechanism of CO2 onto this catalyst composite system. The objective is to synthesis highly water dispersible amine functionalized graphene oxide (GO) – Cu2 O (AGO–Cux O) nano composite catalyst for CO2 reduction. This is because GO has the ability of forming an ultra thin film [31] of large surface area. Pt loaded GO composites have been successfully prepared and applied in fuel cells. In recent years, GO and partially reduced Graphene Oxide (rGO) have been focused as important catalyst for CO2 reduction due to their large specific surface area having unique graphitized basal plane with excellent electrical, mechanical and thermal properties. Though studies on synthesis of Pt loaded graphene/rGO and their applications in different catalytic reactions are well doccumented, synthesis of Cu2 O loaded GO is limited. Recently, [28] reduced GO (rGO)-Cu(I) oxide composite catalyst has been used in the study of photo- reduction of CO2 . The purpose of this study is to provide a catalyst support with high surface area. But we propose to explore catalytic activity of

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FIGURE 15.2 Scheme of amino-rGO–Cu2 O composite and their photo-catalytic reaction for CO2 reduction.

amino-functionalize GO along with its enhanced water dispensability. Thus, our proposed composite catalysts are expected to have multi functional activities. Very recently, we have reported [25] chitosan-Cu2 O catalyst composite for electro reduction of CO2 and showed that this novel catalyst not only help reducing catalyst loading by its film forming ability, but also retard H2 evaluation reaction at high cathodic potential in aqueous medium, a major problem of CO2 electro reduction in aqueous media. DFT calculations [20,32] on CuO and Cu2 O have shown that Cu2 O is a better catalyst for CO2 reduction than CuO. Our objective is to obtain liquid fuels like methanol and formaldehyde as reduction products, by optimising reaction conditions and catalyst preparation conditions. R&D activities on electro reduction of CO2 to methanol/hydrocarbon have gained tremendous momentum during the recent years.

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Japanese groups, particularly group lead by Hori et al. studied exhaustively electro reduction of CO2 using mainly Cu based catalysts. They have reported different reduction products and concluded that reduction products varies widely from hydrocarbons like methane, ethane etc. to methanol depending on experimental conditions. This group has analyzed reduction products formed underdifferent conditions. These are documented under references [1–5]. In USA different groups are actively engaged in electro-reduction of CO2 using Cu based catalysts, the work of Krishna Rajeswar Rao of Texax A&M may be specially mentioned here, he used Cu based catalysts, prepared by elecro-chemical method to study elecro-reduction of CO2 in aqueous solution and showed that methanol is a major product. Works of John Flake et al. [33,34] on CO2 reduction deserves special mentioned here, Their work is mainly on Cu nano electro-catalysts and they have identified the efficiency of different crystal faces on CO2 reduction reactions. They have shown that with thin catalyst layer, the Faradiac efficiency enhanced to double. In France, Jean-Michel Save´ant group working on electrochemical reduction of CO2 , particularly with iron based catalysts but there work is cited here for their excellent review article on this subject published in chem. Soc review of RSC. Theoretical works [32] on copper oxides catalysts on CO2 reduction are interesting and provide an understanding of mechanism of this reduction reactions, particularly, on the adsorption of CO2 on different surfaces and calculated values of interaction energies. Electrochemical reduction of CO2 to methanol is mentioned here as electricity generation through sunlight is a viable path.

15.8 Conclusions Based on our discussions in this chapter, we conclude that instead of simple semiconductor catalysts, composite catalysts, particularly combined with reduced graphene oxide has a promise in development of future efficient photo-catalyst.

Acknowledgment The author wishes to thank Head of the Department of Chemistry and Principal, Asutosh College under Calcutta University for their cooperation.

References [1] Costentin C, Robert M, Savéant J-M. Catalysis of the electrochemical reduction of carbon dioxide. Chem Soc Rev 2013;42(6):2423–36. [2] Takeda H, Ishitani O. Development of efficient photocatalytic systems for CO2 reduction using mononuclear and multinuclear metal complexes based on mechanistic studies. Coord Chem Rev 2010;254:346–54. [3] Windle CD, Perutz RN. Advances in molecular photocatalytic and electrocatalytic CO2 reduction. Coord Chem Rev 2012;256(21):2562–70. [4] Keith JA, Carter EA. Theoretical Insights into Pyridinium-Based Photoelectrocatalytic Reduction of CO2 . J Am Chem Soc 2012;134(18):7580–3. [5] Yoshio H, Katsuhei K, Shin S. Production of CO and CH4 in electrochemical reduction of CO2 at metal electrodes in aqueous hydrogencarbonate solution. Chem Lett 1985;14(11):1695–8. [6] Yoshio H, Katsuhei K, Akira M. Shin S. production of methane and ethylene in electrochemical reduction of carbon dioxide at copper electrode in aqueous hydrogencarbonate solution. Chem Lett 1986;15(6):897–8.

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[7] Hori Y. Electrochemical CO2 Reduction on Metal Electrodes. In: Vayenas CG, White RE, Gamboa-Aldeco ME, editors. Modern Aspects of Electrochemistry. New York, NY: Springer New York; 2008. p. 89–189. [8] Xiong Z, Zheng M, Liu S, Ma L, Shen W. Silicon nanowire array/Cu2 O crystalline core–shell nanosystem for solar-driven photocatalytic water splitting. Nanotechnology 2013;24(26):265402. [9] Liu D, Fernandez Diez Y, Ola O, Mackintosh S, Maroto-Valer M, Parlett CMA, et al. On the impact of Cu dispersion on CO2 photoreduction over Cu/TiO2 . Catal Commun 2012;25:78–82. [10] Ogura K. Electrochemical reduction of carbon dioxide to ethylene: mechanistic approach. Journal of CO2 Utilization 2013;1:43–9. [11] Basumallick S. Chitosan Coated Copper-Oxide Film onto Si-wafer:a Novel Photo Catalyst for CO2 Reduction. Journal of Multidisciplinary Engineering Science and Technology (JMEST) 2014;1(4):70–2. [12] Chang X, Wang T, Gong J. CO2 photo-reduction: insights into CO2 activation and reaction on surfaces of photocatalysts. Energy Environ Sci 2016;9(7):2177–96. [13] Hisatomi T, Kubota J, Domen K. Recent advances in semiconductors for photocatalytic and photoelectrochemical water splitting. Chem Soc Rev 2014;43(22):7520–35. [14] Fu Z-C, Mi C, Sun Y, Yang Z, Xu Q-Q, Fu W-F. An Unexpected Iron (II)-Based Homogeneous Catalytic System for Highly Efficient CO(2)-to-CO Conversion under Visible-Light Irradiation. Molecules 2019;24(10):1878. [15] Singto S, Supap T, Idem R, Tontiwachwuthikul P, Tantayanon S, Al-Marri MJ, et al. Synthesis of new amines for enhanced carbon dioxide (CO2 ) capture performance: the effect of chemical structure on equilibrium solubility, cyclic capacity, kinetics of absorption and regeneration, and heats of absorption and regeneration. Sep Purif Technol 2016;167:97–107. [16] Reithmeier R, Bruckmeier C, Rieger B. Conversion of CO2 via Visible Light Promoted Homogeneous Redox Catalysis. Catalysts 2012;2(4). [17] Richardson RD, Holland EJ, Carpenter BK. A renewable amine for photochemical reduction of CO(2). Nat Chem 2011;3(4):301–3. [18] Carpenter BK. Computational Study of CO2 Reduction by Amines. J Phys Chem A 2007;111(19):3719–26. [19] Cohen SG, Parola A, Parsons GH. Photoreduction by amines. Chem Rev 1973;73(2):141–61. [20] Le MTH Electrochemical reduction of CO2 to methanol: louisiana State University and Agricultural and Mechanical College; 2011. [21] Summers DP, Leach S, Frese KW. The electrochemical reduction of aqueous carbon dioxide to methanol at molybdenum electrodes with low overpotentials. J Electroanal Chem Interfacial Electrochem 1986;205(1):219– 32. [22] Frese SL W. Electrochemical reduction of carbon dioxide to methane, methanol, and CO on Ru electrodes. J Electrochem Soc 1985;132(1):259–60 23. [23] Bandi A. Electrochemical Reduction of Carbon Dioxide on Conductive Metallic Oxides. J Electrochem Soc 1990;137:2157. [24] Gattrell M, Gupta N, Co A. A review of the aqueous electrochemical reduction of CO2 to hydrocarbons at copper. J Electroanal Chem 2006;594(1):1–19. [25] Basumallick S, Santra S. Chitosan coated copper-oxide nano particles: a novel electro-catalyst for CO2 reduction. RSC Adv 2014;4(109):63685–90. [26] Linsebigler AL, Lu G, Yates JT. Photocatalysis on TiO2 Surfaces: principles, Mechanisms, and Selected Results. Chem Rev 1995;95(3):735–58. [27] Tran PD, Batabyal SK, Pramana SS, Barber J, Wong LH, Loo SCJ. A cuprous oxide–reduced graphene oxide (Cu2 O–rGO) composite photocatalyst for hydrogen generation: employing rGO as an electron acceptor to enhance the photocatalytic activity and stability of Cu2 O. Nanoscale 2012;4(13):3875–8. [28] An X, Li K, Tang J. Cu2 O/reduced graphene oxide composites for the photocatalytic conversion of CO2 . ChemSusChem 2014;7(4):1086–93. [29] Togashi T, Hitaka H, Ohara S, Naka T, Takami S, Adschiri T. Controlled reduction of Cu2 + to Cu+ with an N,O-type chelate under hydrothermal conditions to produce Cu2 O nanoparticles. Mater Lett 2010;64:1049– 1051. [30] Pellegrin Y, Odobel F. Sacrificial electron donor reagents for solar fuel production. CR Chim 2017;20(3):283–95. [31] Basumallick S. Design and Synthetic Scheme of Water Dispersible Graphene Oxide-Coumarin Complex for UltraSensitive Fluorescence Based Detection of Copper (Cu2 +) Ion in Aqueous Environment. Graphene. 2014;03:45– 51.

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16 Adsorbents for carbon capture Vijay Vaishampayan a, Mukesh Kumar b, Muthamilselvi Ponnuchamy c and Ashish Kapoor d a

Department of Chemical Engineering, Indian Institute of Technology, Ropar, Punjab, India b Discipline of Chemistry, Indian Institute of Technology, Gandhinagar, Gujarat, India c Department of Chemical Engineering, College of Engineering and Technology, SRM Institute of Science and Technology, Potheri, Kattankulathur, Tamil Nadu, India d Department of Chemical Engineering, Harcourt Butler Technical University, Kanpur, Uttar Pradesh, India

16.1 Introduction Technological advancement and rapid growth in industrialization paved the way for the global industrial revolution. Developing countries aspire to generate and utilize more energy to match the demand and supply ratio of energy economics. Unfortunately, most developing nations rely on conventional energy sources, leading to enormous atmospheric pollution and release of especially CO2 . The excessive release of greenhouse gases has resulted in climate change [24,26]. Researchers are trying to find solutions through CCS, which could be a viable solution to mitigate the issues that arise due to global climate change. The minimization of CO2 concentrations is now more focused on the research of innovative storage strategies and new materials such as Metal-organic frameworks (MOFs), Covalent-organic frameworks (COFs), highly porous carbonaceous materials, biomass-based materials, and so on. These new methodologies could contribute to achieving the United Nation’s declared sustainable development goals (SDGs) and a healthy future for our mother earth. CCS technologies hope to reduce carbon footprints but host a few techno-economic challenges that must be addressed for more effective implementation. The environmental risk factors, energy utilization, etc., could be addressed before the implementation of CCS projects. High equipment cost, capital expenditure, and less explored highly porous materials make the projects less economically viable to implement in developing countries. [12,27].

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This chapter discusses the various processes and strategies used for the CCS, along with the advantages and disadvantages. Furthermore, the various classes of the materials are discussed and the future perspective for the CCS are provided.

16.2 Carbon capture processes Today, various commercially available technologies already exist to capture CO2 from the mixture of gases. These technologies are majorly implemented in the purification stage of downstream industries, chemical processing units, oil and gas processing plants. The process selection depends on the pollution parameters, chemical, geographical, and physical conditions [20,21]. The carbon capture methods can be categorized into pre-combustion and post-combustion carbon capture.

16.2.1 Pre-combustion carbon capture The initial fuel is partially combusted in the pre-combustion carbon capture process to get H2 and CO/CO2 . Later, the gaseous feed is supplied to the CO2 separator employing physical or chemical adsorption methods. In the last stage, a clean fuel without containing the CO2 is provided for energy conservation. The capital cost of such plants is higher, but it’s a more effective process to reduce CO2 pollution with less efficiency. These processes are also easy to incorporate into the existing processing of the plant.

16.2.2 Post-combustion carbon capture Power generation plants produce flue gases contributing to carbon emissions. The postcombustion carbon capture methodology in the power plants is implemented for CCS. After the combustion process, the energy and flue gases are generated. This generated energy is utilized for the various unit processes in the plant. These flue gases are rich in nitrogen, followed by carbon dioxide. Chemisorption or physisorption processes can capture the CO2 from the mixture of gases to meet the pollution control standards. These processes are easy to accommodate in the matured process plant. Along with these techniques, there are several approaches for CC. Researchers have used adsorption, absorption, membrane separation, etc., for CCS. The selection of these processes depends on various factors such as the type of material used for the CCS, the material’s chemical and physical properties, the number of active sites present in the material, and so on. Various metal oxides, MOFs. COFs, biomass-derived activated carbon materials, zeolites, and clays are used for the CCS as showed in the Fig. 16.1 [5,11,16,25].

16.3 Adsorbents for CO2 capture 16.3.1 Materials derived from biomass The biomass derived materials can be useful sources to manufacture the carbonaceous materials. Further, various chemical modifications could be performed to enhance the functionalities by activating the prepared carbons. Farooq Sher et al. synthesized an activated

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FIGURE 16.1 Various adsorbent materials for carbon capture.

carbon from the three different biomass materials using a single-step chemical activation process followed by heating at 750 °C. Potassium hydroxide was utilized to activate carbonaceous materials in different mass ratios. This strategy was applied to form a high surface area, enhance porosity, and increase the number of active sites, which helped increase CO2 uptakes [23]. Yafei Guo et al. developed a MgO-loaded adsorbent using biomass waste of coffee grounds, rice husk, sugarcane bagasse, and sawdust. The calcination was performed to make the adsorbent. The adsorption behavior of the prepared adsorbent was studied with the MgO loadings using a fixed-bed reactor. The CO2 adsorption performance varied with the different supporting materials due to changes in physicochemical properties. MgO in the nano-crystallized form could provide more active sites for CO2 adsorption and thus improves the utilization of MgO. The CO2 adsorption capacity was decreased in the range of 10–40 wt percent while increasing the MgO loading. The pore blockages caused an increase in the diffusion resistance, thus hampering the performance of the prepared material [12]. Similarly, Zhang et al. developed carbon material from the black locust and activated chemically using KOH with ammonia solution for the adsorption of CO2 . Surface characteristics were studied using the N2 adsorption isotherm. The prepared activated carbon exhibits a high surface area of 2511 m2 /g. As adsorption temperature increased, the CO2 adsorption onto the various activated catalyst decreased. The adsorption results revealed that the activated carbon using KOH material could be one of the ways for CC [4].

16.3.2 Clays The most crucial and expensive step in CCS is CO2 capture. Clay minerals are a good option for CO2 adsorption due to their low cost, high availability, stability, and ease of modification. Pozueloa et al. developed an amine-functionalized clay material for CO2 capture. They have used a series of inexpensive clay materials such as montmorillonite, bentonite, saponite, sepiolite, and palygorskite as support to introduce amine-containing sorbents for CO2 capture.

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Firstly these clay materials were hydrated and then functionalized with a different method - (a) grafting with aminopropyl (AP) and diethylenetriamine (DT) organosilanes; (b) impregnation with polyethyleneimine (PEI); and (c) double functionalization by impregnating previously grafted samples. The maximum uptake of CO2 was observed in the case of grafted and impregnated samples as 61.3 and 67.1 mg CO2 /g. The low adsorption in double functionalization material was probably due to high organic loading, which resulted in pore size reduction [10]. Ahmed Hamza et al. studied sandstone rocks which consist of different amounts and types of clay for CO2 adsorption in the temperature range from 50 to 100 °C and pressure up to 20 bars. Sandstone rocks contain minerals such as Quartz, Illite, Kaolinite, Chlorite, Plagioclase, Feldspar, Calcite, and Dolomite. Maximum CO2 adsorption was observed for sandstone rocks associated with high swellable clay content, such as illite at a pressure of 20 bars and temperature of 50 °C. With an increase in temperature to 75 °C, adsorption uptake of CO2 decreases, but a further increase in temperature to 100 °C improves the CO2 adsorption due to a change in crystallinity. The adsorption of CO2 was monolayer at a lower temperature (50 °C), and multilayer adsorption was observed in the temperature range 75 and 100 °C [13]. Cecilia et al. worked on two inexpensive clay minerals sepiolite and palygorskite, as potential adsorbents for CO2 capture. The microwave-assisted acid treatment was done to enhance the textural properties (surface area and pore volume) of sepiolite and palygorskite, and then they were functionalized by the ammine group using different methods of grafting, impregnation, and double functionalization. The introduction of the amine group to clay minerals increases the interaction of CO2 with the amine group, and adsorption mainly takes on the outer surface of the clay mineral. Since the adsorption of CO2 is purely due to the chemical interaction of amine with CO2 so, the double functionalization leads to the maximum adsorption due to a more number of amine groups [3].

16.3.3 Zeolites Zeolites belong to the category of aluminosilicates which are crystalline and have wide applications in commercial adsorbents and catalysis. They have tetrahedrally coordinated Al and Si, which are joined together by oxygen (O). They are very effective as CO2 adsorbents at temperatures up to 250–300 °C. Murge et al. synthesized a low-cost Y-type zeolite adsorbent from gasified rice husk waste for adsorption of CO2 . The adsorption capacity and performance of the zeolite material were checked in a fixed-bed flow reactor. The material’s adsorption capacity depends upon Si/Al ratio, pore size distribution, adsorption temperature, reactor pressure, and moisture presence. The maximum adsorption capacity was around 114 and 190 mg of CO2 /g of the sorbent at 1 and 5 bar pressure, respectively, at 30 °C [18]. Lithium low silica X type (LiLSX) zeolite as a potential CO2 sorbent for post-combustion carbon system was synthesized by Rasmus Kodasm et al. Sorption study of Li-LSX-zeolite was done with the help of fixedbed configuration and TGA instrument. The maximum adsorption capacity and selectivity (CO2 /N2 ) were observed at 60 °C, which was 4.43 mmol/g and 85.7, respectively. With an increase in the calcination temperature from 60 to 300 °C, the adsorption ability of zeolite for CO2 was decreased by 10 mol percent due to the reduction of the micropore surface. Also, the increase in partial pressure of CO2 enhances the adsorption rate of CO2 because of facilitated CO2 diffusion processes, and the diffusion can be calculated by the rate-limiting step for CO2

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adsorption [15]. Wang et al. synthesized rare earth metal zeolites of La and Ce by ion exchange in X zeolite, which was prepared from rice hull ash (RHA). It was observed that the chemical and crystal structure of the modified zeolites did not change, but the microscopic properties and pore size changed. The maximum amount of CO2 adsorption exhibited by NaX and LaLiX was 6.14 and 4.36 mmol/g, respectively, at atmospheric pressure. The cyclical regeneration performance studies and desorption curve data suggest that it was physical adsorption and easy to regenerate [28]. Farid Akhtar et al. synthesized binderless zeolite NaX laminates using pulsed current processing method for CO2 capture. The thickness of the laminates ranges from 310 to 750 μm. The NaX laminates exhibit very high CO2 adsorption capacity and high selectivity of CO2 -over-N2 and CO2 -over-CH4 . It was observed that with the increase in laminate thickness, the adsorption rate decreased, for the laminate of thickness of 310 μm, 40 percent of maximum uptake reached in only 24 s, and thickness of 750 μm reached 40 percent of maximum uptake in around one minute [1].

16.3.4 Metal-organic frameworks (MOFs) The metal-organic framework is highly used for CO2 capture due to its high porosity and chemical tunability. Many studies support that MOF is a significant material in carbon capture. Like other adsorbents such as silica, zeolites, and activated carbon, the CO2 adsorption in MOF is physisorptive due to weak interaction between CO2 and the pore, but the CO2 uptake in the case of MOF is much higher than other materials due to their ultra-high surface area. Mei-Hui Yu et al. synthesized a novel multistage-based MOF using a mixed-ligands strategy. It was reported that four kinds of cages would selectively adsorb CO2 over other gases based on angle-directed and face-directed strategies. Due to the very high surface area (BET and Langmuir are 2111.2 and 2307.2 m2 /g) of MOF, the large amount of CO2 adsorption 113 cm3 /g is possible, which is comparatively very high as compared with other MOF [31]. Behnam Ghalei et al. prepared a mixed matrix membrane (MMM) by introducing a nanosized metal-organic framework (MOF) to enhance the adsorption of CO2 . Nano sizing the MOF by water modulated synthesis helps in its better dispersion over the matrix, which allows for the reduction of non-selective microvoid formation around the particle. Interaction of MOF with polymer matrix was increased by amination, which also helped rigidification and enhanced the selectivity of the overall composite [9]. Liang et al. synthesized a fluorinated MOF dptzCuTiF6 by interpenetration approach to effectively capture CO2 from flue gas at 298 K. It was reported that MOF dptz-CuTiF6 showed remarkable volumetric and gravimetric CO2 uptakes at 10 percent CO2 and 298 K. It was also reported that the MOF is also required significantly less amount of energy for the regeneration as compared with reference aqueous amine technique (38 kJ/mol versus 105 kJ/mol) and dptz-CuTiF6 achieves complete CO2 desorption at 298 K under inert gas purging. The single-crystal studies revealed high CO2 adsorption capacity, moderate CO2 heat of adsorption, and high CO2 –N2 selectivity because of optimal packing of the CO2 molecules within the MOF and favourable thermodynamics and kinetics from cooperative host-guest interactions [17].

16.3.5 Covalent-organic frameworks (COFs) COFs became one of the most suitable candidates due to their unique properties, such as high porosity, predetermined structure, thermal stability, and structural diversity with a

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lower density [7,30]. Similarly, COFs shared some properties with the organic polymers for the uncomplicated fabrication of thin films, synthesis, tunability in structure and chemicals, growth, and user-friendly functionalization [6]. These properties make COFs useful for applications like chemical sensing, gas adsorption, catalysis, energy storage, etc. [19,22,29]. Y B Apriliyanto et al. designed the 2D COFs for the carbon dioxide and nitrogen gas adsorption by integrating density functional theory (DFT) and force field-based molecular dynamics (MD) simulations. The COF was modeled using a 1,3,5-tris(chloromethyl)benzene-based building unit and p-diaminobenzene and hydrazine as linkers. The adsorption sites and energies were explored, and the capacity to uptake gas, permeability, and adsorption isotherm was studied. The adsorption isotherm suggested a more robust CO2 adsorption than N2 [2]. Bin Han et al. synthesized 2D-COFs using a solvothermal process with the help of phthalocyanine-based building blocks. Tetraanhydrides of 2,3,9,10,16,17,23,24-octacarboxyphthalocyaninato cobalt(II) with 1,4- phenylenediamine and 4,4 -biphenyldiamine were taken as a precursor materials. The synthesized material was highly porous with excellent chemical and thermal stability [14]. Qiang Gao et al. built 2D COFs using a solvent-directed divergent synthesis method. The central core for COF was constructed using tetraphenylethane (TPE). During the process, solvent control formed two separate COF structures, TPE-COF-I and TPE-COF-II. These structural variations were unable to predict via conventional COF synthesis methods. These variations were initiated from solvent-influenced crystallization chemistry. TPE-COF-II exhibits a superior carbon dioxide adsorption performance than TPE-COF-I due to its enhanced surface area and high CO2 uptake capacity. This solvent-influenced modification paved the way for multifunctional tunability during the COF synthesis [8].

16.4 Future perspective and conclusion The sequestration of the produced CO2 would play an essential role in shaping the global ecosystem in the near future. These approaches must adapt and run on a multi watt scale to sequester most of the generated carbon emissions. The utilization of sequestrated CO2 could be utilized for the production of other value-added materials. These processes must be safe, green, and stable for wider acceptance. Compared to an unabated plant, carbon capture plants of almost all designs have a few extra possibilities to hold energy by time-shifting energy-intensive processes. The industrial sector must try decarbonizing to achieve global CO2 emissions targets. Numerous industries such as paper and pulp, iron and steel manufacturing, petroleum refining could be the prime sides to implement the next generation CCS. CCS is regarded to be a viable method for lowering CO2 emissions from industrial activities. Each industrial process has a unique set of physical characteristics, chemical makeup, and gas volume fluxes. On the basis of these stream parameters, such as CO2 concentration and moisture content, the suitability and selection of a CCS system would be determined.

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17 Carbon dioxide capture and utilization in ionic liquids Guocai Tian State Key Laboratory of Complex Nonferrous Metal Resources Clean Utilization, Faculty of Metallurgical and Energy Engineering, Kunming University of Science and Technology, Kunming, Yunnan Province, China

17.1 Introduction With the rapid development of economy and society, people are more and more dependent on natural resources, and the consumption rate is also increasing. As one of the most important primary energy sources, fossil energy consumption is increasing at a very alarming rate in recent years. In 2017, the International Energy Agency (IEA) noted in its annual outlook that the world’s energy structure will still be dominated by traditional fossil energy before 2035. According to preliminary estimates, with the development of economy and society, the total global energy demand will increase by more than 34 percent, and the demand for fossil energy will still account for more than 80 percent of the total energy [1–3]. However, the continuous growth of energy consumption have also brought many negative impacts and pressure to the ecological environment on which human beings depend, and has become the focus of global attention. At the same time, it is considered to be among the most severe challenges for mankind since the 21st century. Since the industrial revolution, the combustion of fossil fuels has continuously increased carbon dioxide emissions, leading to serious greenhouse effect [1,2]. By 2018, global carbon dioxide emissions have increased to 3.71 billion tons [1–3]. In recent years, climate change caused by the greenhouse effect has led to various extreme weather events, which have a more and more serious impact on human production, life and life health. For example, glacier retreat, frozen soil melting, sea level rise, rainfall increase, ocean acidification, biological system disorder, bio-diversity reduction, and even have a negative effect on agricultural production and food security. Tsunami, earthquake and other natural disasters have caused significant harm to human life. This will further aggravate the economic gap and geopolitical conflicts in the whole world [4–8]. In recent years, the content of carbon dioxide in the

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atmosphere has increased at a rate of 2 ppm per year. By 2019, the volume fraction of CO2 in the atmosphere has reached 4.11 × 10−4 [1–3]. In 2020, affected by the 2019 coronavirus epidemic, global CO2 emissions decreased by nearly 2 × 108 tons. However, with the economic recovery, CO2 emissions rise again [6,7]. The global energy-related CO2 emissions in December 2020 increased by 2 percent compared with December 2019. According to BPs energy outlook, carbon dioxide emissions from energy consumption will continue to increase in the coming years. Under the changing transition scenario, it will increase by about 10 percent in 2040 [8]. The rising global carbon dioxide emissions have attracted extensive attention from the business community, the public, the government and academic groups [1–9]. In order to cope with these rapid growth and achieve the 1.5 °C temperature control target proposed by IPCC (Intergovernmental Panel on climate change) [9], it is particularly important to develop reasonable methods in time to solve the CO2 problem. According to IPCC prediction, by 2100, the global temperature is expected to rise by about 1.4–5.8 °C, which greatly exceeds the ecological environment load, causing serious global climate problems. How to reduce the concentration of CO2 in the atmospheric environment is extremely important to deal with global warming. In order to alleviate the pressure brought by CO2, good separation and recovery and effective comprehensive utilization are one of the important topics of current research. Therefore, capturing, fixation and conversion of carbon dioxide is the urgent task. Carbon capture and storage (CCS) is the most direct measure taken by people to control carbon dioxide emissions. CO2 capture mainly includes three aspects: Capture before combustion, capture during combustion and capture after combustion [1–3]. Before combustion, the captured flue gas flow is small, the partial pressure of CO2 is high, the separation difficulty is low, and the cost is low, but the operation is complex, the stability is poor, and the requirements for gas turbines are high. Capture technology in combustion mainly includes oxygen enriched combustion technology and chemical combustion technology. Oxygen enriched combustion carbon capture technology is generally applicable to newly planned coal-fired power plants. It is relatively low-cost and easy to scale. It is considered to be among the CCS technologies that are easiest to be popularized and commercialized on a large-scale. The main problems of this technology are enormous investment and high energy consumption. The advantage of chemical combustion carbon capture technology (CLC) is that it can capture CO2 at the source without adding separation devices [1–3]. Making the fuel burns gradually, and uses the energy step by step. In the process, there is no flame and the temperature is relatively low, which can reduce NOx emissions. Its disadvantage is that the investment of the device is large, and it is not suitable for the transformation of existing thermal power units. The power-generation system based on CLC capture technology is still under continuous development and research. The post combustion capture system is usually installed downstream of the pollutant removal device of the existing power plant, which has no impact on the structure and energy utilization mode of the power plant. It has the characteristics of a mature process and simple principle. The post combustion capture technology can meet the requirements of the existing flue gas characteristics of the system and is not difficult to operate. Because of its small workload, simple operation and no change to the existing mainstream process of the plant, it is considered to be the most feasible CO2 emission reduction method. However, the coal-fired flue gas flow is large, the flue gas composition is complex, the CO2 partial pressure is low, and the energy consumption in the capture process is very high. At present, available post combustion collection technologies mainly include solvent absorption, adsorption, membrane separation

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and low temperature separation. Chemical absorption technology is basically applicable to most large-scale carbon capture projects that have been brought into operation in the world. Among them, amine solvents such as diethanolamine (DEA) and monoethanolamine (MEA) have become one of the most mature and commonly used CO2 capture methods in industry owing to their good solubility and fast CO2 absorption rate. Although amine solvents have outstanding advantages, they have problems such as large solvent volatilization loss and serious equipment corrosion; In addition, due to the large absorption enthalpy of CO2 in amine solvents, the energy consumption of a solvent regeneration process is high [1–3]. Therefore, looking for new green solvents to absorb CO2 and developing related processes has become a research hotspot of carbon capture technology. On the other hand, as a C1 resource, CO2 resource is rich, cheap, accessible, green, non-toxic and renewable. Transforming its chemistry into high value-added chemicals, energy products and material are part of the effective ways to realize its resourcefulness and solve energy and environmental problems, which is of far-reaching significance for sustainable development [1–6]. Utilization of CO2 resources mainly includes two aspects: the direct application of CO2 and the transformation and utilization of CO2 . Carbon dioxide can be directly used in industrial processes, such as soft drinks, food, fire extinguishers, welding and foaming agents. It can also be pressurized to form a new green solvent supercritical CO2 , which can be used for the synthesis and separation of nanoparticles and composites [2]. As a more promising way of CO2 resource utilization, converting CO2 into high value-added chemicals and fuels cannot only effectively reduce its emissions and mitigate the greenhouse effect, but also bring economic benefits and meet energy needs [2]. At present, CO2 conversion technology mainly includes thermal catalytic hydrogenation, biological conversion, photocatalytic conversion and electrochemical reduction. So far, people have conducted extensive research on the resource utilization of CO2 . Various high value-added chemicals and chemical intermediate with CO2 as raw materials, such as urea, formic acid, methanol, formamide, methylamine, carbonate, polycarbonate, polyurea and benzimidazole, have been synthesized by designing efficient catalytic systems or reacting with high-energy substances [1–8]. However, as the highest valence oxide of carbon, CO2 has a high degree of thermodynamic stability and kinetic inertia. CO2 reaction system usually needs to use specific metal catalysts for catalysis under high pressure and/or high-temperature conditions. There are also many challenges in the electrochemical conversion of CO2 . In order to effectively carry out CO2 chemical conversion, CO2 molecules must be activated first, and the key to activate CO2 molecules is to establish an efficient catalytic system. At present, people have developed a variety of suitable systems for catalytic activation and conversion of CO2 , such as metal containing porous materials, metal/organic ligand systems, hindered acid-base pairs, phosphine ylide CO2 adducts, nitrogen heterocyclic carbene systems, ionic liquids (ILs) systems, etc. [2]. In particular, development of ionic liquids provides a new system for efficient and clean CO2 conversion, and important progress has been made in the utilization of CO2 resources under mild conditions. Ionic liquids (ILs) are a kind of substance that are liquid at or near room temperature, which is composed of larger organic cations and smaller inorganic or organic anions [9–12]. Common cations include quaternary phosphate salt ions, pyridine salt ions, quaternary ammonium salt ions, and imidazole salt ions. Anions include halogen ions, hexafluorophosphate ions, tetrafluoroborate ions, etc. Ionic liquids have low melting point, extremely low vapor

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pressure, nonvolatile, wide liquid temperature range, nonflammability, good thermal and chemical stability, strong solubility, wide electrochemical window, adjustable structure and performance, and can be recycled. More importantly, ILs has higher designability. Through the changes of cations and anions, ionic liquids can be equipped with one or more specific functional groups to meet different application needs [10–12]. They have broad application prospects in replacing traditional organic solvents, so they are extremely valued by academia and industry [10–12]. The reason why ionic liquids can become one of the research hotspots in 1 Wide liquid recent years is closely related to their unique physical and chemical properties.  temperature ranges. From near or below room temperature to above 300 °C, it is conducive to kinetic control and has high chemical and thermal stability. Generally, its structure remains 2 small vapor pressure and basically non-volatile, so it will not unchanged within 300 °C.  evaporate during storage and use. It can be utilized in high-vacuum system to eliminate the environmental pollution caused by the volatilization of organic compounds during operation. 3 high conductivity At the same time, it can be recycled by a simple ion exchange method.  and wide electrochemical window. It can be used as an electrolyte in many electrochemical 4 adjustable physical and chemical properties of ionic liquids. The solubility of processes.  inorganic matter, water, organic matter and polymer can be adjusted by selecting different cations or anions. From hydrophobic to hydrophilic, and sensitive to water in the air, when it is an immiscible solvent, it can provide a non-aqueous, polar adjustable two-phase system. Hydrophobic ionic liquids can be used as the immiscible polar phase of water and can adjust 5 good solubility in many inorganic and organic substances, salts, solids and the pH value.  liquids. It has a wide variety and a wide range of choices. Often, ionic liquids have the dual functions of solvent and catalyst, so they can be used as catalyst support or solvent for various reactions. Ionic liquids are generally considered as ideal green solvents due to their unique properties, and are widely used in separation and extraction processes and organic synthesis reactions [10–12]. Ionic liquids have broad application prospects in CO2 capture, fixation and conversion. In recent years, significant progress has been made in related researches [13–40]. In the research field of CO2 capture and fixation, ILs are mainly used as solvents to absorb CO2 , or applied as adsorbents to achieve the purpose of CO2 fixation or separation [13–34]. On the one hand, ILs have a high physical adsorption capacity for CO2 . On the other hand, the basic groups in ILs can also react with CO2 for chemical adsorption. Therefore, the adsorption of CO2 by ILs will be higher than 1:1 (mass ratio of substances). In the field of CO2 conversion, ionic liquids are widely used in the electrochemical reduction of CO2 because of their efficient dissolution and activation of CO2 , precise regulation of products and strong conductivity [35–40]. Among them, the solubility of CO2 in ILs is much higher than that of aqueous solutions. Therefore, ionic liquid electrolytes have high CO2 concentration, which improves mass transfer efficiency and CO2 conversion. In addition, hydrogen bonds, electrostatic and cluster interactions in ionic liquids make it easier to combine with CO2 , thus effectively activating CO2 molecules. Under mild conditions, the electrochemical conversion of CO2 in ionic liquid systems is the frontier and hotspot of CO2 conversion and utilization. In recent years, many valuable achievements have been made in the capture, fixation and conversion of CO2 by ionic liquids [1–40]. In this chapter, we will discuss the progress and prospects of ionic liquids as adsorbents and catalysts for CO2 capture, fixation and conversion. We mainly introduces the advantages and disadvantages of various ionic liquids such as functionalized ionic liquids, supported

17.2 Capture of CO2 in ILs

349

ionic liquids and ionic liquid polymers as CO2 adsorbents and catalysts in the capture and conversion process, and discus the research prospects in related fields, providing a reference for the systematic research of ionic liquids in the capture, fixation and conversion of CO2 in ionic liquids [13–40].

17.2 Capture of CO2 in ILs 17.2.1 Conventional ionic liquids Compared with the traditional organic solvent system, the solubility of CO2 in ILs is very large, although its absorption process is a physical adsorption [41,42]. According to the structural characteristics of ILs and the CO2 fixation or absorption mechanism, ionic liquids that absorb CO2 can be divided into conventional ionic liquids (such as imidazolium salt, pyrrolidine salt, ammonium salt, sulfonate plasma liquid) and functionalized ionic liquids. Among them, the interaction between conventional ionic liquids and CO2 is mainly physical interaction, so compared with other ionic liquids, conventional ionic liquids can absorb or fix CO2 less [41–99]. Table 17.1 displays the relevant data of CO2 absorption by conventional ionic liquids. 17.2.1.1 Imidazolium ionic liquid Imidazole is highly alkaline, easy to salt, and easy to alkylate in an alkaline environment. Conventional imidazole ILs have low viscosity and good fluidity. Therefore, various imidazole based ILs have been extensively applied in CO2 absorption. The most commonly used imidazole ILs for CO2 absorption are formed with imidazole cation and the anions of PF6 - , Ntf2 - and BF4 - , such as [C8 mim]PF6 , [Bmim]PF6 , [Bmim]BF4 , [Hmim]Ntf2 and so on [41–99]. Compared with conventional organic solvents, imidazole ILs have a large absorption capacity for carbon dioxide even a physical absorption process. Blanchard et al. [52] measured the CO2 solubility in a series of imidazolium ILs such as [Bmim]NO3 , [Bmim]PF6 , [Emim]EtSO4 , [C8 mim]BF4 , [C8 mim]PF6 , [n-[Bupy]BF4 within the pressure range of 0.1∼10 MPa. It showed that the order of CO2 solubility is: [Bmim]PF6 /[Omim]PF6 > [Omim]BF4 > [n-Bupy]BF4 > [Bmim]NO3 > [Emim]EtSO4 at 313 K and 0∼9.5 MPa. It was found that the CO2 solubility in ILs with fluoride anions is greater than that in other anion based ILs. The CO2 solubility in ILs is greatly affected by anions, but less by cations. Carvalho et al. [71] studied the solubility of CO2 in phosphonium-based ionic liquids. The gas–liquid equilibrium of trihexyltetradecylphosphonium chloride and trihexyltetradecylphosphonium bis(trifluoromethylsulfonyl)imide, in a wide range of pressures and temperatures. It showed that phosphonium ionic liquids can dissolve even larger amounts of CO2 (on a molar fraction basis) than the corresponding imidazolium-based ILs. Kazarian et al. [75] showed that the bending vibrational spectrum of CO2 in [Bmim]PF6 and [Bmim]BF4 split to vary degrees, which may be due to the Lewis base interaction between F atom in ionic liquid anion and CO2 . Therefore, they speculated that the role of CO2 and ionic liquid anions is that the O–C-O axis is vertically arranged around the P-F and B-F bonds Aki et al. [76,77] studied the solubility of CO2 in ten imidazole based ILs. It is found that solubility of CO2 increases with increasing the pressure, while it decreases with the

350

17. Carbon dioxide capture and utilization in ionic liquids

TABLE 17.1 Adsorption capacity of CO2 in conventional ILs. Entry

System

T(K)/P(bar)

mol CO2 per mol IL

Ref.

1

[Aemim]BF4

303/1

0.41

[43]

2

[Aemim]DCA

303/1

0.42

[43]

3

[Aemim]PF6

303/1

0.46

[43]

4

[Aemim]Ntf2

303/1

0.49

[43]

5

[Aemim]TfO

303/1

0.47

[43]

6

[Amim]Ntf2

313/1

0.1777

[44]

7

[Apbim]BF4

295/1

∼0.5

[45]

8

[Bmim]Ac

323/20

0.373

[46]

9

[Bmim]ATZ

293/0.1

0.1228

[47]

10

[Emim]ATZ

293.15/0.1

0.1150

[47]

11

[Bmim]BF4

313.15/3.161

0.2734

[48]

12

[Bmim]OTf

313.15/0.2441

0.0373

[49]

13

[Hmim]Ntf2

313.15/0.3371

0.0801

[49]

14

[Bmim]SCN

313/16

0.126

[50]

15

[Bmim]DCA

298.2/59.43

0.5149

[51]

16

[Bmim]Met

298.3/61.73

0.741

[51]

17

[Bmim]NO3

298.2/56.21

0.4073

[51]

18

[Bmim]Ntf2

298.2/46.94

0.6491

[51]

19

[Hmim]Ntf2

298.2/60.91

0.7396

[51]

20

[Hmmim]Ntf2

298.2/56.56

0.6845

[51]

21

[Omim]Ntf2

298.2/60.13

0.7516

[51]

22

[Bmim]PF6

313/29.5

0.36

[52]

23

[Omim]BF4

313/28.9

0.319

[52]

24

[Omim]PF6

313/29.5

0.353

[52]

25

[Emim]EtSO4

314/28.1

0.146

[52]

26

[n-Bupy]BF4

313.15/26.8

0.243

[52]

27

[BPy]BF4

323/92.35

0.581

[52]

28

[Bmmim]PF6

298.15/6

0.092

[53]

29

[Emim]Ntf2

298/6

0.15

[53]

30

[Emim]TFA

323/20

0.2

[53]

31

[Emmim]Ntf2

298/6

0.137

[53] (continued on next page)

351

17.2 Capture of CO2 in ILs

TABLE 17.1 Adsorption capacity of CO2 in conventional ILs—cont’d Entry

System

T(K)/P(bar)

mol CO2 per mol IL

Ref.

32

[BMP]Ntf2

313/19.3

0.35

[54]

33

[C12 mim]BF4

333.15/0.94

0.1271

[55]

34

[C12 mim]PF6

333.15/0.99

0.1371

[55]

35

[C12 mim]Ntf2

333.15/0.76

0.1286

[55]

36

[Hmim]BF4

298/9.0

0.163

[56]

37

[Emim]BF4

298/8.8

0.106

[56]

38

[Hmim]PF6

313/25.7

0.299

[57]

39

[C9 mim]PF6

298/19.2

0.357

[58]

40

[DEA]Bu

313/0.926

0.1010

[59]

41

[Dmim]Ntf2

298/28.3

0.562

[60]

42

[EimH]CuCl2

303.2/0.1

0.0050

[61]

43

[Emim]CuCl2

303.2/0.1

0.0177

[61]

44

[Emim]C2 N3

313/28.1

0.9896a

[62]

45

[Emim]DCA

313.2/0.0528

0.0040

[63]

46

[Emim]SCN

313.2/0.0528

0.0023

[63]

47

[Emim]TCM

313.2/0.0497

0.0082

[63]

48

[HOPmim]NO3

315/21.4

0. 100 4

[64]

49

[N1114 ]NTf2

298/0.995

0.1948

[65]

50

[P14,6,6,6 ]Ntf2

313/27.4

0.6309

[66]

51

[Emim]Ac

298/0.994

0.1171

[67]

52

[PMPy]DCA

298/0.994

0.1218

[67]

53

[TBMP]Formate

298/0.99

0.1705

[67]

54

[Bmim]MeSO4

303/10

0.119

[68]

55

[MBPy]BF4

303/10

0.1443

[68]

56

[MBPy]DCA

303/10

0.1436

[68]

57

[MBPy]SCN

303/10

0.0962

[68]

58

[MBPyrr]DCA

303/10

0.1204

[68]

59

[MeBuPyrr]SCN

303/10

0.0971

[68]

60

[MeBuPyrr]TFA

303/10

0.1674

[68]

61

[Emim]TfO

303.85/149

0.626

[69]

62

[Bmim]TfO

303.85/11.5

0.273

[69] (continued on next page)

352

17. Carbon dioxide capture and utilization in ionic liquids

TABLE 17.1 Adsorption capacity of CO2 in conventional ILs—cont’d Entry

System

T(K)/P(bar)

mol CO2 per mol IL

Ref.

63

[Hmim]TfO

303.85/12.5

0.288

[69]

64

[Omim]TfO

303.85/180

0.741

[69]

65

[Hmim]FAP

298.1/19.99

0.493

[70]

66

[Bmim]TFES

298/19.9

0.285

[70]

67

[Bmim]TMA

298/19.9

0.431

[70]

68

[TBP]For

298.1/19.9

0.348

[70]

69

[THTDP]Cl

302.55/149.95

0.8

[71]

70

[THTDP]Ntf2

296.58/721.85

0.879

[71]

71

[BMPyrr]FEP

283.5/18

0.498

[72]

72

[HEA]Ac

298.15/15.15

0.1076

[73]

73

[HHE]MEA

298.15/15.42

0.0761

[73]

74

[BHEA]Lac

298.15/15.12

0.0835

[73]

75

[HHEME]Lac

298.15/15.23

0.0776

[73]

76

[HE]For

303/78.9

0.3083

[74]

77

[HE]Ac

303/90.1

0.4009

[74]

78

[HE]Lac

303/82

0.2422

[74]

79

[THEA]Ac

303/82.5

0.2561

[74]

80

[THEA]Lac

303/70.9

0.4617

[74]

81

[HEA]For

303/72.8

0.1907

[74]

82

[HEA]Ac

303/65.7

0.486

[74]

83

[HEA]Lac

303/73.2

0.264

[74]

84

[HEA]Lac

303/12.4

0.0704

[74]

increase of the temperature. To study the effect of anions, seven ILs fromed by [Bmim]+ and with different anions of NO3 - , trifluoromethanesulfonate (TFO- ), dicyandiamide (DCA- ), bis (trifluoromethylsulfonyl) imide (Ntf2 - ), tetrafluoroborate (BF4 - ), hexafluorophosphate (PF6 - ), and tris (trifluoromethylsulfonyl) formamide) were studied. It is found that the solubility of CO2 strongly relies on the anions. The order of the solubility of CO2 follows NO3 - > DCA- > BF4 - > PF6 - > CF3 SO3 - > Ntf2 - > formamide- . It was shown that the more fluorine atoms in the anion, the higher the CO2 solubility is. The effects of the numbers and lengths of alkyl chains on cations were studied, including 1-hexyl-3-methylimidazole bis (trifluoromethylsulfonyl) imide ([Hmim]Ntf2 ), 1-octyl-3-methylimidazole bis (trifluoromethylsulfonyl) imide ([Omim]Ntf2 ) and 2,3-dimethyl-1-hexyl imidazole bis (trifluoromethylsulfonyl)

17.2 Capture of CO2 in ILs

353

imide ([Hmmim]Ntf2 ). It was shown that the solubility of CO2 would be slightly increased with increasing the length of alkyl chain on cations. The solubility capacity of CO2 in 1,1,3,3-tetramethylguanidine lactic acid ([TMG]L) and 1–butyl–3-methylimidazolium hexafluorophosphoric acid ([C4 mim]PF6 ) at 0 to 11 MPa and 297 K to 328 K was studied by Zhang et al. [78]. The experimental results noted that the CO2 solubility in [TMG]L is slightly larger than that in [C4 mim]PF6 . At 5.73 MPa and 319 K, the CO2 solubility in [TMG]L and [C4 mim]PF6 is 2.77 mol/kg and 2.65 mol/kg, respectively. The selectivity of [TMG]L for CO2 is much better than that of other gases such as O2, N2 , H2, and CH4 . Shariati et al. [79,80] measured the equilibrium relationship between CO2 and [Emim]PF6 , [Bmim]PF6 , [Bmim]BF4 , [Hmim]BF6 and [Hmim]PF6 ionic liquids under high pressure (up to 97 MPa), and analyzed the effects of anions and alkyl chain lengths on the CO2 solubility in ILs. It was showed that the CO2 solubility in ILs increases with increasing the length of alkyl chain at the same pressure. It is showed that the increase of the length of alkyl chain lead to the decrease the point pressure of bubble, which causes to the higher CO2 solubility in ILs. It also shows that the CO2 solubility in ILs with PF6 - is greater than that in ILs with BF4 - , suggesting that the interaction of PF6 - with CO2 is more strong than that of BF4 - . Shiflett et al. [81] measured the CO2 solubility in [Bmim]Ac, [Bmim]PF6 and [Bmim]BF4 at 283 ∼ 384 K and up to 2.0 MPa, and established a state equilibrium theory to correct the experimental data. It was showed that the gas solubility in ILs increases with the increase of the pressure and decreases with increasing the temperature. Kumelan et al. [82,83] measured the CO2 solubility in [Bmim]PF6 , [Bmim]CH3 SO4 , and [Hmim]Ntf2 at 293–393 K and 0–9.7 MPa. By using the generalized Henry’s law to correlate the experimental data, the thermodynamic properties of the system such as dissolution enthalpy, dissolution entropy and dissolution Gibbs free energy, was calculated. Jacek et al. [84] showed that the CO2 solubility in [Hmim]Ntf2 can reach about 4.7 mol/kg at a pressure less than 10 MPa and 293–413K. Schilderman et al. [85] obtained the same conclusion when measuring the CO2 solubility in [Emim]Ntf2 under the conditions of the CO2 mole fractions of 12.3 percent–59.3 percent, at a pressure less than 15 MPa and 310–450 K and. Anderson et al. [86] revealed the effect of cationic fluorination on the CO2 solubility in ionic lqiuids. They found that CO2 solubility in [C8 H4 F13 mim]Ntf2 was larger than that in [C6 H4 F9 mim]Ntf2 , while solubility of CO2 in [C6 mim]Ntf2 was the lowest. The CO2 solubility increases with increasing the amount of fluorine in the side chain of alkyl, but this trend is not obvious. Mark et al. [87] studied the CO2 solubility in [Bmim]Ac under the conditions of pressure less than 2 MPa and 283–384 K. It was found that when CO2 mole fraction reached to 20 percent in the system, there was almost no vapor pressure, indicating that CO2 and ILs formed a nonvolatile or extremely low vapor pressure molecular complex, with strong mutual attraction between molecules and obvious formation of molecular complexes. The formation of the complexes is reversible and the ILs do not degenerate. Kumelan et al. [82] measured solubility of CO2 in [Bmim]PF6 , [Hmim]Ntf2 and [Bmim]CH3 SO4 at 293–393 K and 0–9.7 MPa. They calculated the thermodynamic properties of the system, such as dissolution Gibbs free energy, entropy and enthalpy by using the Henry’s law. Soriano et al. [88,90] measured the solubility of CO2 in [Bmim]PF6 , [Emim]BF4 and

354

17. Carbon dioxide capture and utilization in ionic liquids

[Emim]TFO at 303.2∼343.2 K and medium pressure (within 6.5 MPa) by thermogravimetric microbalance method. Palgunadi et al. [89] studied the CO2 solubility in two dialkyl imidazolium dialkyl phosphate ILs [Emim]Et2 PO4 and [Bmim]Bu2 PO4 near atmospheric pressure and 313 ∼ 333 K. It showed that the dissolution mechanism of CO2 is the same as that of other ILs. Jung et al. [91] synthesized an imidazole methyl sulfonate [Dbim]MeSO3 , and measured the absorption capacity of CO2 together with another three imidazole methyl sulfonates [Emim]MeSO3 , [Bmim]MeSO3 , [Dmim]MeSO3 . It was found that the absorption capacities of CO2 in four ILs from small to large is [Dmim]MeSO3, [Emim]MeSO3 , [Bmim]MeSO3 and [Dbim]MeSO3 . Brennecke et al. [92] measured the absorption capacity of CO2 in 10 imidazolium ILs at 25– 60 °C and the pressure of 1 ∼ 15 MPa. For the same cation ([Bmim]+ ), the absorption capacity of CO2 with different anions at the same temperature and pressure is from small to large as DCA- , NO3 - , PF6 - , BF4 - , Ntf2 - , TFO- and methide- . Shannon [93] and Manic [94] measured the absorption capacity of CO2 in ILs with different lengths of carbon chain. It was found that the increase of the carbon chain was caused to the enhancement of CO2 absorption. When anions of ILs are same, the solubility enhances slightly with increasing the carbon chain of substituents on cations. 17.2.1.2 Pyridine and pyrrolidine ILs Anthony et al. [92] found that the gas solubility in ILs with pyrrolidine cation is larger than that in the ammonium based ILs. The solubility of gas in [C1 C2 im]Ntf2 changes significantly with temperature, but the solubility in ionic liquid [C1C4 Pyrr]Ntf2 changes little. Honga et al. [96] revealed the effect of cation change in ionic liquid on gas solubility. The solubility of CO2 and C2 H6 was measured out in three Ntf2 - containing ILs with cations [C1 C2 im]+ , [C1 C4 Pyrr]+ and [N1132 –OH]+ at 300∼345 K. It was shown that changing cations have a little effect on the CO2 solubility, but it is obvious. The effects of changing cations on the solubility of two gases in ionic liquids are similar, but a more significant effect on the solubility C2 H6 was found than that on CO2 . The order of the effect of ILs on the solubility of CO2 follows [C1 C4 Pyrr]Ntf2 > [C1 C2 im]Ntf2 > [N1132 –OH]Ntf2 , and the solubility reduce with increasing the temperature. Although the effect of changing cations on solubility is smaller than that of changing anions, it is worth noting. Anderson et al. [97] measured the solubility of CH4 , N2 , CO2 and other gases in 1-hexyl3-methylpyridinium bis (trifluoromethyl) amine ([HmPy]Ntf2 ), which was compared and analyzed with the existing solubility data. They proposed many ways to improve the CO2 solubility in ILs. It concluded that the anions in ILs can affect CO2 solubility more than the cations. The solubility of CO2 can be improved by introducing fluorine atoms instead of hydrogen atoms into the anions or changing the types or introducing functional groups of anion. The effect is more obvious when introducing fluorine atoms into anions, and increases with the increase of fluorine substitution degree. The CO2 solubility can also be enhanced by introducing ether groups or long-chain alkyl groups to increase the free volume of ILs or the affinity with CO2 . Moganty et al. [98] studied CO2 solubility of in 1-hexyl-3-methylimidazolium hexafluorophosphate ([Hmpy]BF6 ), 1-butyl-3-methylpyridinium tetrafluoroborate([Bmpy]BF4 ),

17.2 Capture of CO2 in ILs

355

1-octyl-3-methylpyridinium ([Ompy]BF4 ), [Hmim]Ntf2 , [Emim]Ntf2 , 1-ethyl-3methylimidazolium bis(pentafluoroethyl sulfonyl) imino ([Emim]BETI), 1-ethyl3-methylimidazolium trifluoro-acetate ([Emim]TFA), 1-ethyl-3-methylimidazolium trifluoromethanesulfonate ([Emim]TFO) at atmospheric pressure and at 10 °C, 25 °C and 40 °C. They calculated the corresponding Henry’s constants. In combination with the Henry’s constants in the four ILs reported in the literature, the solubility parameters of ILs were calculated according to the viscosity data of ILs. The Henry’s constants in the 12 ILs for CO2 were predicted by RST. The deviation between the experimental results and the predicted results is within ±2.5 percent, which indicates that the prediction method is basically reasonable and reliable. 17.2.1.3 Sulfonate ionic liquids Recently, CO2 solubility in sulfonate ILs have also been studied. Zhang et al. [99] studied the CO2 solubility in sulfonate ILs such as [P66614 ]C12 H25 PhSO3 and [P66614 ]MeSO3 at a pressure of 4∼9 MPa and a temperature of 305∼325 K. It was shown that the CO2 solubility in the two sulfonate ILs varies small, but the CO2 solubility in [P66614 ]MeSO3 is larger than that in [P66614 ]C12 H25 PhSO3 . The CO2 solubility in sulfonate ILs is related to Henry’s constants, which increases with the increase of temperature, which is consistent with Alvaro’s results. It is also showed that the CO2 solubility in sulfonate ILs is generally lower than that in imidazolium ILs.

17.2.2 CO2 capture by functionalized ionic liquids Under ambient temperature and pressure, imidazole type, sulfonate type, ammonium salt type, pyrrole type ILs and other conventional ILs have limited CO2 absorption capacity, so it is necessary to develop new ILs with specific functions for CO2 fixation/conversion. The emergence of functionalized ILs has greatly improved the absorption capacity of CO2 in ILs. Functionalized ionic liquids is an ILs that uses the structural designability of ILs to introduce one or more specific functional groups into the cation and anion ions or the cation and anion ions of ionic liquid have a specific structure and give ionic liquid some special functions or characteristics. Functionalized ILs can obviously break through the limitations of conventional ILs and solve the shortage of commercial absorbents such as amino-based solutions [100–187]. Table 17.2 shows the CO2 absorption in functionalized ILs. Bates et al. [45] reported that the functionalized ionic liquids of [pabim]BF4 was appied to capture CO2 . The saturated CO2 concentration in ILs can reach to 7.4 percent. The capture mechanism was that CO2 molecules attacked the free electron in N atoms to form a new CO–O radical. At the same time, another NH2 radical of [Pabim]+ accepted an H+ and became an NH3 + radical. Zhang et al. [116] successfully prepared tetrabutylphosphonium amino acid ILs ([TBP]amino acids). They also used the ionic liquid as an absorbent for CO2 to conduct CO2 absorption tests. It was found that the quaternary phosphonic amino acid ionic liquid has a high absorption capacity of CO2 with 0.5 mol CO2 /mol IL. However, due to its high viscosity and high cost, it does not have the capacity of large-scale production. Yu et al. [118] synthesized fifteen novel amino acid ionic liquids (AAILs) by the combination of several tetraalkylammonium cations with four amino acid anions ([Gly], [L-Ala], [β-Ala]

356

17. Carbon dioxide capture and utilization in ionic liquids

TABLE 17.2 The capture of CO2 in various functionalized ILs. Systems

T(K)/P(bar)

mol CO2 per mol IL

Ref.

1

[NH2 p-bim]BF4

295/1

∼0.5

[45]

2

[APMim]DCA

303/10

0.29

[68]

4

[APMim]Ntf2

303/10

0.27

[68]

5

[AEMPyrr]BF4

303/10

0.28

[68]

6

[APMim]BF4

303/10

0.32

[68]

7

[MeImNet2 ]BF4

303/4

0.09

[68]

8

[Emim]Ac

313.2/0.1

0.28

[100]

9

[Emim]Ala

313.2/0.1

0.38

[100]

10

[DETAH]Lys

313.15/0.1

2.13

[101]

11

[TETAH]Lys

313.15/0.1

2.59

[101]

12

[DETAH]Gly

313.15/0.1

1.81

[102]

13

[DETAH]Im

313.15/0.1

2.04

[102]

14

[DETAH]Py

313.15/0.1

1.95

[102]

15

[DETAH]Tz

313.15/0.1

1.74

[102]

16

[DMAPAH]2-F-PhO

303.2/0.1

0.67

[103]

17

[DMAPAH]3-F-PhO

303.2/0.1

0.73

[103]

18

[DMAPAH]3,5-F-PhO

303.2/0.1

0.82

[103]

19

[DMAPAH]4-F-PhO

303.2/0.1

0.86

[103]

20

[VBTMA]Ala

298/0.1

0.29

[105]

21

[VBTMA]Arg

298/0.1

0.83

[105]

22

[VBTMA]Gly

298/0.1

0.47

[105]

23

[VBTMA]Hist

298/0.1

0.46

[105]

24

[VBTMA]Lys

298/0.1

0.66

[105]

25

[VBTMA]Pro

298/0.1

0.38

[105]

26

[VBTMA]Ser

298/0.1

0.39

[105]

27

[VBTMA]Tau

298/0.1

0.44

[105]

28

[P2228 ]2-CNPyr

333.15/0.1

0.92

[106]

29

[P2228 ]6-BrBnIm

333.15/0.15

0.88

[106]

30

[P2228 ]BnIm

333.15/0.1

0.97

[106]

31

[P4444 ]Ala

298/1

∼0.67

[106]

32

[P4444 ]Gly

298/1

∼0.6

[106]

Entry

(continued on next page)

357

17.2 Capture of CO2 in ILs

TABLE 17.2 The capture of CO2 in various functionalized ILs—cont’d Systems

T(K)/P(bar)

mol CO2 per mol IL

Ref.

33

[P4444 ]β-Ala

298/1

∼0.6

[106]

34

[DMAPAH]Formate

298.15/0.1

0.2

[111]

35

[DMAPAH]Octanoate

298.15/0.1

0.46

[111]

36

[DMEDAH]Formate

298.15/0.1

0.32

[111]

37

[Emim]Benzoate

333/5.3

0.129

[113]

38

[Emim]Lac

333/5.3

0.113

[113]

39

[Emim]Piv

333/5.3

0.275

[113]

40

[PEG150 MeBu2 NLi]Ntf2

298/1

0.66

[114]

41

[PEG150 MeNH2 Li]Ntf2

298/1

0.45

[114]

42

[PEG150 MeTMGLi]Ntf2

298/1

0.89

[114]

43

[P4442 ]Cy-Suc

293.15/0.1

2.21

[118]

44

[P4442 ]Suc

293.15/0.1

1.85

[118]

45

[P4442 ]pH-Suc

293.15/0.1

1.4

[118]

46

[N2222 ]β-Ala

313

∼0.50

[118]

47

[N2224 ]Ala

313

∼0.48

[118]

48

[TMGH]Im

313.15/0.1

0.64

[122]

49

[TMGH]PhO

313.15/0.1

0.05

[122]

50

[TMGH]Pyrr

313.15/0.1

0.66

[122]

51

[DEEDAH]Ac

293/1

0.3

[122]

52

[DEEDAH]HCOO

293/1

0.47

[122]

53

[DMAPAH]Ac

293.15/1

0.33

[122]

54

[DMAPAH]HCOO

293.15/1

0.28

[122]

55

[DMEDAH]HCOO

293/1

0.38

[122]

56

[P66614 ]Ala

295/1

0.66

[122]

57

[P66614 ]ILe

295/1

0.97

[122]

58

[P66614 ]Sar

295/1

0.91

[122]

59

[P66614 ]Lys

295/1

1.37

[122]

60

[P66614 ]Tau

295/1

∼0.8

[122]

61

[P4442 ]DAA

293.15/0.01

1.25

[123]

62

[P4442 ]Suc

293.15/0.01

1.65

[123]

63

[N2222 ]Ala

313

∼0.45

[123]

Entry

(continued on next page)

358

17. Carbon dioxide capture and utilization in ionic liquids

TABLE 17.2 The capture of CO2 in various functionalized ILs—cont’d Systems

T(K)/P(bar)

mol CO2 per mol IL

Ref.

64

[N66614 ]Asn

295/1

2

[123]

65

[N66614 ]Gln

295/1

1.9

[123]

66

[N66614 ]His

295/1

1.9

[123]

67

[N66614 ]Lys

295/1

2.1

[123]

68

[N66614 ]Met

295/1

1

[123]

69

[Bmim]2-Op

303.15/0.1

1.02

[125]

70

[BMmim]2-Op

303.15/0.1

1.06

[125]

71

[BMPyr]2-Op

303.15/0.1

1.17

[125]

72

[N4442 ]2-Op

303.15/0.1

1.24

[125]

73

[P4442 ]2-OP

303.15/0.1

1.4

[125]

74

[P4442 OH]2-Op

303.15/0.1

0.94

[125]

75

[pH–C8 eim]2-Op

293.15/0.1

1.69

[125]

76

[Bmim]Ala

298/2

0.39

[125]

77

[Bmim]Arg

298/2

0.62

[125]

78

[Bmim]Gly

298/2

0.38

[125]

79

[Bmim]His

298/2

0.45

[125]

80

[Bmim]Leu

298/2

0.38

[125]

81

[Bmim]Lys

298/2

0.48

[125]

82

[Bmim]Met

298/3

0.42

[125]

83

[Bmim]Pro

298/2

0.32

[125]

84

[Bmim]Val

298/2

0.39

[125]

85

[Me2 N(CH2 CH2 OH)2 ] Gly

313/1

0.48

[125]

86

[Me2 N(CH2 CH2 OH)2 ]Pro

313/1

0.54

[125]

87

[Me2 N(CH2 CH2 OH)2 ]Gly

313/1

0.53

[125]

88

[Me2 N(CH2 CH2 OH)2 ]Tau

313/1

0.5

[125]

89

[N1112 ]Pro

313

0.74

[125]

90

[P66614 ]Beta-Ala

303.15/0.1

1.1

[127]

91

[P66614 ]MA-Tetz

303.15/0.1

1.13

[127]

92

[P66614 ]Gly

303.15/0.1

1.2

[127]

93

[P66614 ]2 Asp

303.15/0.1

1.96

[127]

94

[Emim]Arg

313/1

0.52

[127]

Entry

(continued on next page)

359

17.2 Capture of CO2 in ILs

TABLE 17.2 The capture of CO2 in various functionalized ILs—cont’d Systems

T(K)/P(bar)

mol CO2 per mol IL

Ref.

95

[P4444 ]Ala

298/5

1.1

[127]

96

[P4444 ]Bic

298/5

0.44

[127]

97

[P4444 ]dmGly

298/5

0.24

[127]

98

[P4444 ]Gly

298/5

1.02

[127]

99

[P4444 ]ILe

298/5

1.07

[127]

100

[P4444 ]Pro

298/5

1.01

[127]

101

[P4444 ]Val

298/5

1.07

[127]

102

[AP4443 ]Ala

298/1

0.92

[127]

103

[AP4443 ]Gly

298/1

0.94

[127]

104

[N1111 ]Lys

303

0.39

[128]

105

[Cho]Pro

308/1

∼0.6

[128]

106

[P66614 ]o-AA

303/1

0.6

[128]

107

[P66614 ]o-ANA

303/1

0.56

[128]

108

[P66614 ]p-AA

303/1

0.94

[128]

109

[P66614 ]p-ANA

303/1

0.78

[128]

110

[MTBDH]2 HFPD

296/1

2.04

[128]

111

[P66614 ]2-CN-Pyr

295/1

0.9

[129]

112

[P66614 ]3-CF3 -Pyra

295/1

0.9

[129]

113

[P66614 ]2-SCH3 BnIm

295/1

0.73

[130]

114

[P66614 ]6-BrBnIm

295/1

0.9

[130]

115

[P66614 ]BnIm

295/1

0.91

[130]

116

[P22212 ]2-CN-Pyr

295/0,15

0.73

[131]

117

[P2224 ]2-CN-Pyr

295/0.15

0.8

[131]

118

[P44412 ]2-CN-Pyr

295/0.15

0.72

[131]

119

[P44418 ]2-CN-Pyr

295/0.15

0.64

[131]

120

[P66614 ]2-CN-Pyr

295/0.15

0.62

[131]

121

[DBUH]Phth

298/1

0.98

[132]

122

[TMGH]Phth

298/1

0.98

[132]

123

[P66614 ]1-Naph

303/1

0.89

[133]

124

[P66614 ]2,4,6-Cl-PhO

303/1

0.07

[133]

125

[P66614 ]2,4-Cl-PhO

303/1

0.48

[133]

Entry

(continued on next page)

360

17. Carbon dioxide capture and utilization in ionic liquids

TABLE 17.2 The capture of CO2 in various functionalized ILs—cont’d Systems

T(K)/P(bar)

mol CO2 per mol IL

Ref.

126

[P66614 ]2-Cl-PhO

303/1

0.67

[133]

127

[P66614 ]2-Naph

303/1

0.86

[133]

128

[P66614 ]3-Cl-PhO

303/1

0.72

[133]

129

[P66614 ]3-NMe2 -PhO

303/1

0.94

[133]

130

[P66614 ]4-CF3 -PhO

303/1

0.61

[133]

131

[P66614 ]4-Cl-PhO

303/1

0.82

[133]

132

[P66614 ]4-MeO-PhO

303/1

0.92

[133]

133

[P66614 ]4-NO2 -PhO

303/1

0.3

[133]

134

[P66614 ]4-Me-PhO

303/1

0.91

[133]

135

[P66614 ]4-H-PhO

303/1

0.85

[133]

136

[DBUH]TFE

298/1

1.01

[134]

137

[P4444 ]3-F-PhO

313/1

0.74

[135]

138

[P4444 ]PhO

313/1

0.77

[135]

139

[P4444 ]2-F-PhO

313/1

0.67

[135]

140

[P4444 ]4-F-PhO

313/1

0.84

[135]

141

[Bmim](CH3 )2 CHCOO

298/1

0.28

[136]

142

[Bmim](CH3 )3 CCOO

298/1

0.31

[136]

143

[Bmim]CH3 CH2 COO

298/1

0.28

[136]

144

[Eeim]Ac

298/1

0.32

[137]

145

[Apmim]Im

313/1

0.75

[138]

146

[Bis(mim)C2 ]Im2

313/1

0.75

[138]

147

[Bis(mim)C4 ]Im2

313/1

0.95

[138]

148

[Bmim]Im

313/1

∼0.54

[138]

149

[Emim]Im

313.5/1

∼0.54

[138]

150

[HO-emim]Im

313/1

∼0.55

[138]

151

[N1111 ]Gly

298/1

0.17

[139]

152

[C2 (N112 )2 ]Gly2

298/1

0.89

[140]

153

[C2 (N114 )2 ]Gly

298/1

0.81

[140]

154

[Bis(mim)C2 ]Gly2

313/1

∼0.8

[141]

155

[Bis(mim)C2 ]Pro2

313/1

∼0.9

[141]

156

[Bis(mim)C4 ]Gly2

313/1

∼0.9

[141]

Entry

(continued on next page)

361

17.2 Capture of CO2 in ILs

TABLE 17.2 The capture of CO2 in various functionalized ILs—cont’d Systems

T(K)/P(bar)

mol CO2 per mol IL

Ref.

157

[Bis(mim)C4 ]Pro2

313/1

∼0.8

[141]

158

[C1 C4 Pyrro]Ac

353/0.98

0.01

[142]

159

[N2222 ]PhO

323

0.64

[143]

160

[TETA]NO3

288.15/1

1.49

[144]

161

[ApaeP444 ]Ala

298/1

1.14

[145]

162

[ApaeP444 ]Asp

298/1

1.07

[145]

163

[ApaeP444 ]Gly

298/1

1.29

[145]

164

[ApaeP444 ]His

298/1

1.01

[145]

165

[ApaeP444 ]Lys

298/1

1.73

[145]

166

[ApaeP444 ]Ser

298/1

1.19

[145]

167

[AEMP]Ala

298/1

1.57

[146]

168

[AEMP]Gly

298/1

1.5

[146]

169

[AEMP]Leu

298/1

1.47

[146]

170

[AEMP]Pro

298/1

1.54

[146]

171

[OH-emmim]PhO

298/1

1.58

[147]

172

[P66614 ]2-Op

293/1

1.58

[148]

173

[P66614 ]3OCH3 -2-Op

303/1

1.65

[148]

174

[P66614 ]3-Op

303/1

1.38

[148]

175

[P66614 ]4-ABI

303/1

1.6

[148]

176

[P66614 ]4-Op

293/1

1.49

[148]

177

[P66614 ]4-CHO-Im

303/1

1.24

[149]

178

[P66614 ]4-CHO-PhO

303/1

1.01

[149]

179

[P66614 ]4-EF-PhO

303/1

1.03

[149]

180

[P66614 ]4-Kt-PhO

303/1

1.04

[149]

181

[P66614 ]Met

295/1

∼0.9

[150]

182

[P66614 ]Pro

295/1

∼0.9

[150]

183

[Aemmim]Tau

303/1

0.9

[151]

184

[MTBDH]Im

296/1

1.03

[152]

185

[MTBDH]TFE

296/1

1.13

[152]

186

[MTBDH]PhO

296/1

0.49

[152]

187

[MTBDH]Pyrr

296/1

0.92

[152]

Entry

(continued on next page)

362

17. Carbon dioxide capture and utilization in ionic liquids

TABLE 17.2 The capture of CO2 in various functionalized ILs—cont’d Systems

T(K)/P(bar)

mol CO2 per mol IL

Ref.

188

[(P2 -Et)H]Im

296/1

0.96

[152]

189

[MTBDH]TFPA

296/1

0.39

[152]

190

[(P2 -Et)H]Pyrr

296/1

0.86

[152]

191

[(P2 -Et)H]PhO

296/1

0.45

[152]

192

[(P2 -Et)H]TFE

296/1

1.04

[152]

193

[Me2 N(CH2 CH2 OH)2 ]Tau

310/2.5

∼0.4

[153]

194

[Me2 N(CH2 CH2 OH)2 ]Tau

310/4

0.92

[153]

195

[P66614 ]Bentriz

296/1

0.17

[154]

196

[P66614 ]Im

296/1

1

[154]

197

[P66614 ]Ind

296/1

0.98

[154]

198

[P66614 ]Oxa

296/1

0.91

[154]

199

[P66614 ]PhO

296/1

0.5

[154]

200

[P66614 ]Pyr

296/1

1.02

[154]

201

[P66614 ]Tetz

296/1

0.08

[154]

202

[P66614 ]Triz

296/1

0.95

[154]

Entry

and [Val]). The capacity of CO2 absorption was measureed at 40 °C under ambient pressure. It was found that [N2224 ][LAla] (N2224 : triethylbutylammonium) has the lowest viscosity (29 mPa.s/25 °C), and the adsorption of CO2 in this ILs can reach the theoretical equilibrium value (0.5mol CO2 /mole ILs) within 30min. The absorbed CO2 can be completely desorpted at 60 °Cand 0.1 kPa. Gurkan et al. [122] synthesized Trihexyl(tetradecyl)phosphonium Methioninate ([P66614 ]Met) and Trihexyl(tetradecyl)phosphonium Prolinate ([P66614 ]Pro), and studied CO2 absorption in these ionic liquids. It is showed that there is intramolecular proton transfer in ILs, that is, the sterically hindered large phosphonium cation prevents the intermolecular proton transfer process. Then six amine functionalized anionic tethered ILs was synthesized such as Trihexyl(tetradecyl)phosphonium sarcosine ([P6614 ]Sar), Trihexyl(tetradecyl)phosphonium glycinate ([P66614 ]Gly), Trihexyl(tetradecyl)phosphonium alanine ([P66614 ]Ala), Trihexyl(tetradecyl)phosphonium valine ([P66614 ]Val), Trihexyl (tetradecyl)phosphonium leucine ([P66614 ]Leu) and Trihexyl(tetradecyl)phosphonium isoleucine ([P66614 ]Ile) and studied the CO2 absorption in these ionic lqiuids. They found that the capacity of CO2 adsorption in these ILs was higher than 0.5 mol CO2 /mol IL under the pressure less 0.1 MPa. The order of the decomposition temperatures of ionic lqiuid were observed to decrease as Tau- > Gln- > Pro- > Met- > Lys- > Thr- > Asn- . Wang et al. [127] fixed three kinds of amino acid based ILs of [Emim]Ala, [Emim]Gly, and [Emim]Arg on nano-porous material of PMMA, and tested their CO2 adsorption capacity at

17.2 Capture of CO2 in ILs

363

different adsorption temperatures. The results show that the higher the temperature is, the lower the absorption capacity is. The absorption capacities of CO2 in these three ILs were 1.38 mmol/g, 1.53 mmol/g and 1.01 mmol/g at 40 °C, respectively. Li et al. [128] used polyethylene glycol 200 (PEG-200) as a solvent to dissolve [choline]Proto obtain a low viscosity TSILs solution, which was used to capture CO2 near atmospheric pressure. The results show that the addition of inert PEG-200 can greatly shorten the CO2 absorption and desorption time in [choline]Pro (at 323.15k, the CO2 absorption and desorption time in pure [choline]Pro-are 240 and 260 min respectively; when PEG-200 of the same quality as [choline]Pro is added, the CO2 absorption and desorption time is reduced to 50min at 308.15K. In addition, phenolic anion functionalized ILs have also attracted much attention. Hu et al. [135] reported some functionalized ILs with fluorophenol anions. The results showed that these ILs had low viscosity. The order of capacity of CO2 absorption was [P4444 ]4-F-PhO > [P4444 ]3-F-PhO> [P4444 ][2-F-PhO]. Ma et al. [140] designed and synthesized amino acid ILs [C2 (N112 )2 ]Gly2 and [C2 (N114 )2 ]Gly2 , measured the capacity of CO2 absorptionin the two ILs at different concentrations. They mixed the ionic liquid with aqueous solution of MDEA to study the CO2 absorption capacity of the compounded system. It was shown that the amount of CO2 absorbed by ILs is decreased with increasing their concentration. The CO2 absorption capacity of 15 percent [C2 (N112 )2 ]Gly2 +15 percent MDEA mixed solution can reach 1.02 mol CO2 /mol IL,when the ionic liquid is mixed with MDEA aqueous solution, while the pressure at this time is only 0.25 MPa. Zhang et al. [141] synthesized four kinds of amino acid based ILs of [Bis(mim)C4 ]Pro2 [Bis(mim)C2 ]Pro2 , [Bis(mim)C2 ]Gly, [Bis(mim)C4 ]Gly2 , and two dumbbell ILs of [bis(mim)C6 ](Ntf2 )2 and ([N111 –C6 -mim](Ntf2 )2 which contains two groups of anions and anions. The physical properties of the six ILs and their absorption of CO2 were tested. It was found that the CO2 absorption in six ILs increased with increasing the pressure. At 1 MPa and 40 °C, the absorption of CO2 by the four amino acid ILs exceeded 1 mol CO2 /mol IL, and the efficiency of absorption was much larger than that of the other two dumbbell ILs. Peng et al. [146] synthesized four amino acid ILs of [Aemp]Gly, [Aemp]Ala, [Aemp]Leu, [Aemp]Pro-with [Aemp]+ cation. Due to its high viscosity, they dissolved the ionic liquid in water, ethylene glycol and SiO2 gel respectively to test its CO2 absorption capacity. The results show that ionic liquid + SiO2 has higher CO2 absorption capacity than that dissolved in water or ethylene glycol. When m(IL): m (SiO2 ) = 1ࢼ4 (mass ratio), the capacity of CO2 absorption can reach to 1.5 mol CO2 /mol IL When only one amino-group is introduced into the cation, and the increase of the capacity of CO2 absorption is limited. Therefore, some scholars began to introduce multiple amino groups. Zhang et al. [155] synthesized 20 bifunctional ILs by using amino acid as the anion and (3-aminopropyl) tributylphosphonium [AP4443 ]+ as the cation. Four ILs with anions Gly- , Ala- , Aal- and Leu- were selected for atmospheric CO2 capture experiments. It showed that when directly used these ionic liquid for CO2 capture, the CO2 absorption can remain at 0.2 CO2 /mole ILs after 2h, since the viscosity of ILs will rise sharply after absorption of CO2 . However, when supported on porous SiO2 to form a supported ILs liquid film, the resistance formed by high viscosity can be effectively overcome, and the theoretical absorption amount of 1.0 mol CO2 /mole ILs can be reached within 80 min.

364

17. Carbon dioxide capture and utilization in ionic liquids

Wu et al. [156] synthesized an amino containing ILs of 1-(1-aminopropyl)−3methylimidazolium bromide ([NH2 p-mim]Br), and found it can effectively absorb CO2 . At 40 °C and 10.6 MPa, the capacity of CO2 absorption can reach 0.444 mol CO2 /mol IL. Han et al. [157] studied the absorption of CO2 by urea/choline chloride, 1,1,3,3-tetramethylguanidinium perchlorate ([TMG]ClO4 ) and 1-aminoethyl-3-methyl imidazolium tetrafluoroborate ([Aemim]BF4 ), It is found that adding atmospheric CO2 to IL can significantly reduce its alkalinity, and the alkalinity of IL can be easily recovered by bubbling N2 through the solution to remove CO2 . Meindersma et al. [158] measured the CO2 absorption in [Bmim]BF4 amino functionalized 1-(3-aminopropyl)−3-methylimidazolium tetrafluoroborate ([Apmim]BF4 ). It was found that the amount of CO2 absorbed depends on the concentration of [Apmim]BF4 . A new diamino ionic liquids 1-aminoethyl-2,3-dimethylimidazolium taurine([Aemmim] Tau) was synthesized with a dual amino ionic liquid with amino-functionalized imidazolium cation and taurine anion by Zhang et al. [151]. At 303.15 K and 0.1 MPa, the CO2 absorption capacity of this ionic liquid can reach to 0.9 mol CO2 /mol IL at 303.15 K and 0.1 MPa. The dissolved CO2 can be easily deabsorbed under higher temperature or vacuum. They found that [Aemmim]Tau can be recycled, and no significant loss of performance has been observed after six cycles. ILs containing amino groups can greatly improve the absorption capacity of CO2 , and ILs containing amino groups on both anion and cation have better absorption effect. It was shown that when the ionic liquid containing amino group is mixed with conventional imidazole ILs, the effect of imidazole ILs on CO2 absorption can be improved [159], which provide a potential foundation for large-scale application in the future. Natural amino acids and their derivatives in amino-acid ILs can act as both anions and cations of ILs, such as glycine nitrate ([Gly]NO3 ), alanine boron tetrafluoride ([Ala]BF4 ), 1-ethyl-3-methyl-imidazole glycine ([Emim]Gly), 1ethyl-3-methyl-imidazole valine ([Emim]Val), etc. Amino acid ILs have high thermal stability, negligible vapor pressure, and wide liquid stability range. At the same time, amino acid ILs have many unique properties. For example, amino acid ILs have a strong hydrogen-bond network structure and can dissolve many life substances, such as DNA, cellulose, etc. It can replace the traditional organic solvent medium for chemical reaction and realize the greening of the reaction process [159]. Wang et al. [160] used Task-Specific ionic liquids (TSILs) to capture CO2 with (1-(2hydroxyethyl)−3-methylimidazolium bis(trifluoromethylsulfonyl)imide ([Im21 OH][Ntf2 ]) and 2-hydroxyethyl(dimethyl)isopropylammonium bis(trifluoromethylsulfonyl)imide ([Nip,211 OH]Ntf2 ) with hydroxyl groups on the cationic side chains. A new CO2 capture solution is formed by mixturing with equimolar super bases DBU (1,8-diazabicyclo[5.4.0]undec– 7-ene), MTBD (1,3,4,6,7,8-hexahydro-1-methyl-2H-pyrimido[1,2-a]pyrimidine), BEMP(2–tertbutylamino-2-diethylamino-1,3-dimethylperhydro-1,3,2-diazaphosphorine) and ETP2 (DMA) (1-ethyl-2,2,4,4,4-pentakis(dimethyl amino)−2λ5 ,4λ5 -catenadi(phosphazene)) with TSILs. It is found that it can be achieved near equimolar absorption of CO2 under ambient pressure and 20 °C within 30 min. The capture of CO2 by [Im21 OH]Ntf2 –DBU occurs rapidly, and the capacity of CO2 capture is more than 1 mol per mole of superbase, which is superior to those captured by convetional ILs. Sharma et al. [161] combined the amino cation [2-Aemim]+ with six different anions, and studied the CO2 absorption capacity in these six ILs at 30 °C, 50 °C and 0.16 MPa. It showed that the absorption capacity of ILs containing amino groups to CO2 is greatly enhanced under

17.2 Capture of CO2 in ILs

365

ambient pressure, up to 0.49 mol CO2 /mol IL. The the capacity order of CO2 capture from small to large in different anions based ILs follows as BF4 - , PF6 - , DCA- , Ntf2 - , and TfO- . Daiyue et al. [162] designed a series of symmetrical amino acid based ILs and measured the performance of CO2 absorption. It was shown that these ILs had high fast absorption rate, absorption capacity and good repeated absorption performance. At the same time, [N2222 ]Ala, [N111 ]Gly, [N2224 ]CH3 COO, which are functional ILs with low viscosity, short synthetic route and fast absorption rate, was compounded with MDEA aqueous solution to study the absorption properties of the mixed solutions with different proportions. Among them, the absorption capacity of 2.5 percent [N111 ]Gly is the largest, and the amount ratio of substances reaches 1.058 at 0.94 MPa. Amino acids have low cost, excellent biodegradability and bioactivity, a wide variety and stable chiral centers. Amino acid ILs have excellent absorption properties for CO2 , and have high absorption at room temperature and less than 1 MPa. Wang et al. [163] designed various phenolic anion functionalized quaternary ILs with large π -bond structure. It was found that this functionalized ILs have a higher absorption capacity of CO2 and easier desorption than those functionalized by phenol anion (PhO− ). For example, at 20 °C and 1 bar, the absorption capacity of [P66614 ]PhO is 0.73 mol CO2 /mol IL, and the desorption residue is 0.17 mol CO2 /mol IL. Under the same conditions, the CO2 absorption capacity of the functionalized quaternary ionic liquid containing phenolic anions with large π bond structure is greater than 0.9 mol CO2 /mol IL, and desorption residue is less. Because the structure of phenol can be adjusted by substituents, the phenolic functionalized ILs can also be adjusted by substituents of anions, so as to improve the interaction between ILs and CO2 and regulate the CO2 absorption capacity. The phenol anion of short-chain quaternary ammonium ionic liquid [P2222 ]PhO with phenol as anion removes H atom connected to C2 in cation, and then easily interacts with CO2 to produce phosphorus of phenol [164], since its electronegativity, the carboxylic acid radical can also react with CO2 . For example, Tao et al. [165] used formic acid, acetic acid, propionic acid and butyrate as anions and [P4444 ]+ as cations to form quaternary carboxylate ILs, and studied the absorption performance of CO2 in these ILs. It is shown that due to the electron donating property of alkyl group, the CO2 absorption in ILs with butyrate as an anion can reach 0.4 mol CO2 /mol IL Wang et al. [166] measured the CO2 absorption performance of quaternary ILs functionalized with a series of cinnamic acid-based anions, indicating that the capacity of CO2 absorption in these ILs is close to the amount of equivalent substances, and when the substituent on the anion benzene ring is an electron donor substituent, the CO2 absorption capacity of ILs will increase, and the electron withdrawing substituent will lead to the reducing of CO2 absorption capacity. Tao et al. [167] synthesized [P4442 ]2 Ida ionic liquid by removing two protons from iminodiacetic acid Ida2− anions. It was found that the absorption capacity of this ionic liquid for CO2 was 1.69 mol CO2 /mol IL at 40 °C and 1 bar. Zhu et al. [168–170] studied the interaction between substituted [Im]+ and CO2 , indicating that [Im]+ can react to equimolar with CO2 , and the electron withdrawing group and electron pushing a group on the anion reduce the CO2 capture capacity of ILs. Because SO2 is more acidic than CO2 , the basic azolyl anion can interact with both CO2 and SO2 . Cui et al. [171] revealed the selective absorption of SO2 and CO2 gas by substituted imidazole anion functionalized ILs. It is shown that the substituents with

366

17. Carbon dioxide capture and utilization in ionic liquids

electron withdrawing reduced the alkalinity of ILs, thus improving the selectivity of SO2 /CO2 . This shows that low alkaline (or acidic) ILs can effectively separate SO2 from CO2 , and have potential application prospects for the selective separation of acid gases. Wang et al. [172] adjusted the structure of imidazole functionalized ionic liquids by imidazole anion by adding substituents to imidazole cation, reduced the yield of carbene CO2 and improved the CO2 capture capacity of anion. Wang et al. [173] designed a kind of ILs functionalized with imide anions, indicating that the [P4442 ]Suc ILs which containing succinimide anions constructed by pre organization can efficiently absorb low concentration CO2 through three site synergy. For example, at 20 °C, the molar absorption and mass absorption of [P4442 ]Suc reach 1.65 mol CO2 /mol IL and 22 percent (mass fraction), respectively. The viscosity of the system decreases after CO2 absorption. The implantation of electron withdrawing phenyl group in anion decreases the absorption capacity of CO2 in ionic liquid, while the implantation of electron pushing cyclohexyl group increases the absorption capacity of CO2 . The development and application of the above functionalized ionic liquids of azo anions, carboxylate anions and phenol anions have enriched and developed the types of functionalized ionic liquids that can be used to capture CO2 , as well as people’s understanding of the interaction between functionalized ionic liquids and CO2 . In terms of CO2 capture capacity, these ionic liquids are usually similar to that of other substances. How to further improve the capture efficiency and utilization of ionic liquids, so that each mole of ionic liquids can capture multiple moles of CO2 , and ionic liquids are easy to recover, is still one of the important goals of developing functional ionic liquids. Hao et al. [174] found that [P4444 ]2-OP has the advantages of low viscosity of 193 cP, and the absorption capacity of CO2 is 1.2 mol CO2 /mol IL. Macfarlane et al. [175] studied the interaction mechanism between amino functionalized hydroxypyridine anion and CO2 . It showed that the CO2 absorption in ILs was 0.87 ∼ 0.99 mol CO2 /mol IL. The NMR further showed that amino was easy to interact with CO2 , while the interaction between oxygen negative sites and CO2 were secondary. It can be seen that different positions and structures of functional groups on anions will have different effects on their interaction with CO2 . In addition, Liu et al. [176] synthesized [P4444 ]3 2,4-Opym-5-Ac ionic liquid by removing three protons from 2,4-dihydroxypyrimidine-5-carboxylic acid as a 3-valent anion, with a capacity of 1.46 mol CO2 /mol IL for CO2 absorption at ambient temperature and pressure. This result shows that it is limited to using multivalent anions to improve the capacity of CO2 absorption in ILs. Xu et al. [177] used the alkanolamine-based dual functional ILs with multidentate cation coordination and pyrazolide anion in a molar ratio of 2:1 to obtain a chelating ionic liquid containing both amino functionalized cations and pyrazole anions. The capacity of CO2 absorption in this ILs is 0.5 ∼ 0.8 mol CO2 /mol IL at 1 bar and 80 °C. It showed highly efficient CO2 capture at relatively high temperature. Taylor et al. [178] measured the absorption of SO2 and CO2 by benzimidazole anion functionalized ILs, indicating that the ionic liquid can replace CO2 by absorbing SO2 after absorbing CO2 , otherwise it cannot replace SO2 . Two kinds of amido-containing anion-functionalized ionic liquids (ILs) were designed and synthesized to capture CO2 , where the anions of these ILs were selected from deprotonated succinimide (H-Suc) and o-phthalimide (pH-Suc) [179]. The relationship between the structure of this kind of amido anion-functionalized ionic liquid and its CO2 capture performance provides new enlightenment for the development and design of new materials and new

17.2 Capture of CO2 in ILs

367

methods for reversible and efficient CO2 capture and separation. It was shown that these anion-functionalized ILs exhibited high CO2 solubility (up to 0.95 mol CO2 /mol IL) and low energy desorption, and enthalpy change was the main driving force for CO2 capture by using such ILs as absorbents. MacFarlane et al. [180] showed that the proton type ionic liquid synthesized by dimethylaminoethylamine or dimethylaminopropylamine with azolide compounds or fluorophenol compounds in a molar ratio of 1:1, although the cation has tertiary amine functional groups, the amount of CO2 absorbed by such substances occurs on the active site of the anion, not on the tertiary amine or quaternary ammonium functional group of the cation. It shows that tertiary amine has no obvious contribution to CO2 capture by ionic liquid. Wang et al. [181] prepared quaternary ILs with triazolide as anion (Triz- ) and azobenzene group on the cation through acid-base neutralization reaction. It was found that these ILs can contact with CO2 in a molar ratio of 1:1 to form carbamates through the interaction of anions. The in-depth study shows that compared with ILs containing CIS-azo groups, ILs containing trans-azo groups have higher capacity of CO2 absorption. The effect of entropy in the system is the key factor in the interaction between these ILs and CO2 , and the entropy changes greatly when the ILs containing trans-azobenzene interact with CO2 . Brennecke et al. [182] synthesized [Emim]2-CNPyr ionic liquid and studied the interaction between CO2 and ILs. It is found that this ionic liquid can absorb CO2 through two parallel paths of 2-CNPyr-CO2 and carbene-CO2 . Hu et al. [183] found that the carbine-CO2 structure produced by the interaction of [Bmim]PhO and CO2 can be transferred to the anion to form PhO-CO2 . Similarly, umecky et al. [184] showed that ILs with acetylacetone as anion can also absorb CO2 through chemical absorption. Sharma et al. [185] introduced acidic groups (-COOH) into the carbon chain to obtain a series of ILs [Emmim]X, and measured their CO2 absorption capacity at 30 and 50 °C and atmospheric pressure. It showed that these ILs have good absorption capacity at atmospheric pressure, about 1.0 mol CO2 / mol IL, and have excellent regeneration performance, which can be used repeatedly. Mahurin et al. [186] introduced benzyl groups into cations to synthesize a new type of ionic liquid, which showed stronger selectivity for CO2 absorption. Liu et al. [187] added Zn2+ to ionic liquid [Emim]TFSI and mixed it in the amount ratio of 1:1. The absorption capacity of the resulting mixed solution for CO2 was greatly enhanced, reaching 8.2 percent (mass fraction) at 40 °C and 0.1 MPa. Although TSILs has the advantage of large absorption capacity, it also has the inherent disadvantage of high viscosity of ILs. In particular, the formation of new bicarbonate by reacting with CO2 will rapidly increase the viscosity, and the whole system will even change into gel, greatly reducing the mass transfer efficiency and absorption efficiency. At the same time, it is also necessary enhance the energy consumption and temperature in the regeneration stage of ILs. Compared with traditional ILs, the TSILs have the following characteristics. (1) The introduced groups are diverse. There are various groups introduced into functional ILs, which can be designed by scholars, so many different functional ILs have been produced. (2) It has good regeneration. After multiple absorption desorption, the absorption capacity is almost the same as that of the first time, so it can be reused. (3) Higher production cost and higher viscosity. Because the functionalized ILs are designed and synthesized by scholars, the cost and time required are huge, and they do not have the conditions for application. (4) The research is relatively scattered, lacking integrity and systematisms.

368

17. Carbon dioxide capture and utilization in ionic liquids

The reason for the rapid increase of the viscosity of the system after the capture of CO2 by TSILs is pointed out. On the one hand, the TSILs with free amino group has a large density and a small free volume, which will slow down the rotation of ions in the system and increase the viscosity; On the other hand, there is a hydrogen bond between carbonate and amino group after CO2 capture, which is easy to form a complex hydrogen bond network structure, resulting in a sharp increase in the viscosity of the system. To overcome the above difficulties and further improve TSILs, we need to start from the following aspects: (1) look for TSILs with large capture capacity, low viscosity, low desorption temperature and energy consumption, especially the development of aprotic heterocyclic anions with CO2 capture function, which will not produce acidic protons after CO2 capture, and the viscosity of the system will not increase [45]. (2) By mixing TSILs with ordinary ILs or molecular solvents, the carbonate (hydrogen) salt generated in the absorption process is dissolved or extruded into the system to reduce the viscosity of the system. (3) Adopt process enhancement means, including high gravity field, microwave, ultrasound, etc., to enhance mass and heat transfer in the absorption and desorption process and reduce energy consumption.

17.2.3 Capture CO2 by metal coordination-based (chelate-based) ionic liquids Metal coordination-based ionic liquids are molten salts formed by the coordination of metal ions with inorganic or organic ligands at low temperatures. When metal ions and ligands have multiple coordination sites, they are usually called metal-chelated ionic liquids. Metal coordination (chelation) ionic liquids have been widely used in the field of organic catalysis and gas absorption, showing good absorption properties. In recent years, it has been applied to CO2 capture, fixation and conversion, and has made some progress [188–202]. Table 17.3 shows the main progress of CO2 capture by metal-coordinated ionic liquids. In this section, we will summarize the absorption performance and influencing factors of CO2 in this metal ionic liquid. It can be seen from Table 17.3 that the absorption of CO2 in metal ion coordination ionic liquids depend on the type of ligands and metal ions. In general, when the cations are the same, the CO2 absorption of metal anion coordination ionic liquids increases with the increase of the volume of coordination anions. Although the CO2 absorption of metal anion coordination ionic liquids is slightly higher than that of traditional ionic liquids, the CO2 absorption of metal anion coordination ionic liquids at an atmospheric pressure is still relatively small compared with functional ionic liquids, which may be because the physical interaction between metal anion coordination ionic liquids and CO2 is still dominant. The viscosity of metal anion coordination ionic liquids is usually large, which greatly limits its application in carbon capture. Metal coordination-based ILs used for CO2 absorption mainly include metal anioncoordination-based ILs, metal cation-coordination-based ILs and metal anion/cationcoordination-based ILs. Metal-anion-coordination ILs are prepared by the reaction of conventional ILs with metal salts (such as iron salt, aluminum salt, zinc salt, etc.) with the same anion. They have the characteristics of simple synthesis and low raw material cost [187–193]. Compared with the conventional ILs, the metal anion coordination ILs has a certain improvement in CO2 absorption performance. Liu et al. [187–192] compared the CO2 absorption of [Emim]Ntf2 and metal-anion-coordination ILs of [Emim]Zn(Ntf2 )3 at 313.15 K and 0.1 MPa. It was found that the CO2 absorption of [Emim]Ntf2 was 0.0347 mol CO2 /mol IL,

369

17.2 Capture of CO2 in ILs

TABLE 17.3 The capacity of CO2 absorption in metal coordination-based ILs. Entry

Systems

T(K)/P(bar)

mol CO2 per mol IL

Ref.

1

[Li(AEE)]Ntf2

313/1

0.55

[102]

2

[P(C4 )4 ]Gly-SiO2

298/1

0.6

[116]

3

[P(C4 )4 ]Ala]-SiO2

298/1

0.67

[116]

4

[aP4443 ]Gly-SiO2

298/1

1.0

[127]

5

[aP4443 ]Ala]-SiO2

298/1

1.0

[127]

6

K[Sacc]

298/1

0.38

[132]

7

K[Phth]

298/1

0.96

[132]

8

Na[Phth]

298/1

0.96

[132]

9

[Na(MDEA)2 ]Pyr

353.15

0.75

[177]

10

[Emim]Zn(Ntf2 )3

313.15/0.1

1.8953

[187]

11

[Na(CyNH)]Gly

298/1

0.68

[188]

12

[Na(iPrNH)]Ala

298/1

0.73

[188]

13

[Na(iPrNH)]Gly

298/1

0.91

[188]

14

[Na(NH2 )]Gly

298/1

0.43

[188]

15

[Na(nPr2 N)]Gly

298/1

0.48

[188]

16

[Na(nPrNH)]Gly

298/1

0.59

[188]

17

[Na(tBuNH)]Gly

298/1

0.85

[188]

18

[Na(β-iPrNH)]Ala

298/1

0.65

[188]

19

[K(18-crown-6)]Ala

298/1

0.71

[189]

20

[K(18-crown-6)]Gly

298/1

0.75

[189]

21

[K(18-crown-6)]Leu

298/1

0.68

[189]

22

[K(18-crown-6)]Met

298/1

0.75

[189]

23

[K(18-crown-6)]PhO

298/1

0.90

[189]

24

[Li(12-crown-4)]PhO

298/1

0.75

[189]

25

[Na(15-crown-5)]PhO

298/1

0.84

[189]

26

[K(18-crown-6)]Pro

298/1

0.99

[189]

27

[Na(15-crown-5)]Pro

298/1

0.89

[189]

28

[K(18-crown-6)]Ser

298/1

0.63

[189]

29

[K(18-crown-6)]Thr

298/1

0.73

[189]

30

[K(18-crown-6)]Val

298/1

0.79

[189]

31

[Li(12-crown-4)]PhO

298.15

0.75

[189] (continued on next page)

370

17. Carbon dioxide capture and utilization in ionic liquids

TABLE 17.3 The capacity of CO2 absorption in metal coordination-based ILs—cont’d Entry

Systems

T(K)/P(bar)

mol CO2 per mol IL

Ref.

32

K[Triz]

283/1

0.96

[190]

33

Li[Triz]

283/1

0.90

[190]

34

Na[Triz]

283/1

0.96

[190]

35

DAIL

303/1

1.05

[191]

36

[Li(DETA)]Ntf2

353.15

0.66

[192]

37

[Li(TEG)]Ntf2

353.15

0.01

[192]

38

[Li(TETA)]Ntf2

353.15

0.7

[192]

39

[Li(TTEG)]Ntf2

353.15

0.02

[192]

40

[Bmim]FeCl4

343.15/1.5

0.5086

[193]

41

[Bmim]Zn(Ac)3

343.15/1.5062

0.7181

[193]

42

[Bmim]ZnCl3

343.15/1.5478

0.2448

[193]

43

[Li(DEA)]Ntf2

313.15

0.52

[194]

44

[Li(DGA)]Ntf2

313.15

0.55

[194]

45

[Li(DOBA)]Ntf2

333.15

0.9

[194]

46

[Li(EA)]Ntf2

313.15

0.54

[194]

47

[Li(HDA)]Ntf2

313.15

0.88

[194]

48

[K(DEA)2 ]Im

333.15

1.11

[195]

49

[K(MDEA)2 ]Im

333.15

0.81

[195]

50

[K(DGA)2 ]Im

333.15

1.37

[195]

51

[Na(DGA)2 ]Im

333.15

1.23

[195]

52

[Li(DGA)2 ]Im

333.15

0.73

[195]

while that of [Emim]Zn(Ntf2 )3 was 1.8953 mol CO2 /mol IL, indicating that the introduction of Zn2+ was conducive to the improvement of CO2 absorption. They noted that [Emim]Zn(Ntf2 )3 can absorb CO2 through chemical interaction, but it has not been confirmed. Peng et al. [193] synthesized three metal anion coordination ILs by reacting [Bmim]Cl, [Bmim]Ac with equimolar ZnCl2 , FeCl3 and ZnAc2 . They found that the density, viscosity and CO2 absorption of new synthesized ILs were measured and compared with pure ILs. It showed that the CO2 absorption and density of [Bmim]ZnCl3, [Bmim]FeCl4 , and [Bmim]ZnAc3 are greater than that of [Bmim]Cl and [Bmim]Ac under the same conditions. The viscosity of [Bmim]ZnCl3 and [Bmim]ZnAc3 is much higher than that of the corresponding [Bmim]Cl and [Bmim]Ac, while the viscosity of [Bmim]FeCl4 is much lower than that of [Bmim]Cl. Metal chelated-ILs used for CO2 absorption are mainly metal cation-chelated ionic liquids. Metal cation-chelated ILs is a new type of functionalized ionic liquid. Its cations are formed

17.2 Capture of CO2 in ILs

371

by multi-point coordination between metal ions and ligands (such as amine, alcohol amine, crown ether, etc.). Its cation not only retains the reactivity of alcohol or amine with CO2 , but also effectively improves the thermal stability of alcohol or amine in the system [196,197]. In 2012, Wang et al. [194] first reported the work of capturing CO2 with metal cation-chelated ionic liquids. These ionic liquids are prepared by the equimolar reaction of LiNtf2 with different alcohol amines. It can be seen from Table 17.3 that with the increase of the number of coordination atoms in alcohol amine, the absorption of CO2 by metal chelating cation ILs also increases, in which [DOBA] has the largest number of coordination atoms. [Li(DOBA)]Ntf2 still maintains good absorption performance at higher absorption temperature, and its absorption capacity is significantly better than that of other metal cation chelated ionic liquids. By comparing IR and 13 C NMR before and after CO2 absorption by metal cation chelated ionic liquids, they found that alcohol amines in chelated cationic ions can contact CO2 to form carbamic acid, which indicates that CO2 absorption by ionic liquids is a chemical action [194]. The adsorbed CO2 can be decomposed in nitrogen atmosphere, and the metal chelated cationic ionic liquid can repeatedly absorb CO2 . Li et al. [198] calculated and optimized the configurations of [Li(DOBA)]Ntf2 , [Li(HDA)]Ntf2 , [Li(DEA)]Ntf2 and [Li(EA)]Ntf2 by density functional theory (DFT). The interaction energy of anions and cations was calculated. It showed that lithium ion in metal cation-chelated ILs has multi-points coordination with alcohol amine, and the coordination intensity increases with the increase of the number of coordination atoms. The interaction energy order of anions and cations is [Li(EA)]Ntf2 > [Li(DEA)]Ntf2 > [Li(HDA)]Ntf2 > [Li(DOBA)]Ntf2 , which is opposite to the coordination intensity of CO2 absorption and chelating cation. The above results prove theoretically that the coordination strength of chelated cation and the interaction energy of cation and anion are directly related to the carbon capture performance of ionic liquids. The greater the coordination strength of cation, the weaker the interaction energy between cation and anion is, which is conducive to the interaction between coordination cation and CO2 , so as to improve the absorption rate. The chemical interaction between chelating cation and CO2 are an important reason to improve the trapping ability [194], but the anion Ntf2 - in the above metal cation-chelating ionic liquid does not participate in CO2 capture. Therefore, in subsequent studies, functional anions such as amino acids [200], oxazolyl [108–169] and hydroxypyridine [201,202] were introduced to further enhance the CO2 capture performance of metal cation-chelated ionic liquids. Da et al. [189] synthesized a series of metal cation chelated ionic liquids from alkali metal amino acid salts, phenol salts and crown ethers, and studied their performance of CO2 capture at room temperature and pressure. It showed that [K(18-crown-6)]Pro-has the best absorption performance. Due to the interaction between Pro- and CO2 , equimolar absorption is achieved within 10 min. In addition, it can be seen from Table 17.3 that anion type is the key factor affecting CO2 absorption performance, and the absorption amount of Pro- is better than that of PhO- .The absorption capacity of [Li(12-crown-4)]PhO, [Na(15-crown-5)]PhO and [K(18crown-6)]PhO are basically the same as those of [P66614 ]PhO ILs, indicating that capturing CO2 in crown-ether metal cation-chelated ILs is mainly through the chemical interaction between anions and CO2 , while crown ethers in chelated cation ions lack the ability to react with CO2 . Quan et al. [177] developed a metal cation-chelated ionic liquid with anion and cation bifunctionalization by introducing azo anion with CO2 reaction activity on the basis of retaining chelated cation to react with CO2 . It is found that the ionic liquid still has good absorption performance at high temperature. For example, [Na(MDEA)2 ]Pyr is prepared by the reaction

372

17. Carbon dioxide capture and utilization in ionic liquids

of pyrazole sodium (NaPyr) and N-methyldiethanolamine (MDEA) in a molar ratio of 1:2. This ILs can reach absorption equilibrium within 6 min at 0.1 MPa and 353.15 K with an absorption capacity of 0.75 mol CO2 /mol ILs. The viscosity of the system (323.2 K) decreased from 1310 MPa.s before absorption to 713.9 MPa.s [177–192]. IR and 13 C NMR studies showed that both chelate-cation and pyrazole anion reacted with CO2 . In order to further study the effects of alcohol amine ligands and central metal ions on absorption properties and clarify the reaction sequence between anions and cations and CO2 . Su et al. [195] designed and synthesized 9 kinds of metal catio-chelated ionic liquids. These metal cation-chelated ILs come from alkali metal (Li+ , Na+ and K+ ) imidazoliums and alkanolamines of primary amine (DGA), secondary amine (DEA) and tertiary amine(MDEA). Combined with CO2 absorption experiment, DFT calculation and spectrum, a detailed study was carried out for these ILs. It showed that the CO2 capture performance of metal cationchelated ILs is related to the central metal ions when the alcohol amine ligands are the same. The order of CO2 absorption is K+ > Na+ > Li+ . When the central alkali metal ions remain unchanged, the carbon capture performance of ionic liquids is related to the alcohol amine level, and the absorptioncapacity follows DGA > DEA > MDEA. Among them, [K(DGA)2 ]Im has the best CO2 absorption performance, reaching 1.37 mol CO2 /mol ILs in 15 min at 333.15 K and 0.1 MPa, and has good circulation performance. IR and 13 C NMR results showed that Im- reacted with CO2 preferentially over [K(DGA)2 ]+ . DFT calculation results showed that the binding energy of chelating cation depends on the polydentate coordination ability of central metal ions and alcohol amines, which is consistent with the results of Li et al. [198]. The binding energy of chelated cation is consistent with the CO2 absorption of ionic liquids, but opposite to the viscosity of ionic liquids. The binding energy of different ionic liquids has a linear relationship with absorption or viscosity, because with the increase of chelating cation coordination strength, the interaction between cations and anions weakens, and the viscosity of the system decreases. It is conducive to the chemical interaction between ionic liquids and CO2 and chelating cation, and improves the absorption performance. Wang’s group [192] developed a strategy to reduce the viscosity of the system by mixing ILs, realizing the capture of CO2 in high-temperature flue gas. They mixed the metal cation chelating ILs ([Li(DETA)]Ntf2 , [Li(TETA)]Ntf2 , [Li(TEPA)]Ntf2 ) with three polyamines (DETA, TETA, TEPA) as ligands with the metal cation chelating ILs ([Li(TEG)]Ntf2 , [Li(TTEG)]Ntf2 ) with two Polyols (TEG, TTEG) as ligands at the molar ratios of 1:1, 1:2 and 1:3. The CO2 absorption capacity of above 6 mixed ILs were measured at different molar ratios. It was shown that all of absorption capacities for these 6 ILs were large than 1.0 mol CO2 /mol IL. [Li(TEPA)]Ntf2 /[Li(TEG)]Ntf2 mixed system has the best absorption performance. When the molar ratio of the two is 1:1, 1:2 and 1:3, the capacity of CO2 absorption in the mixed system is 1.61, 1.95 and 2.01 mol CO2 /mol IL respectively. The capacity of CO2 absorption in the mixed system increases with increasing the molar ratio of [Li(TEG)]Ntf2 or [Li (TTEG)]Ntf2 . Because both polyamine ligand metal cation chelating ILs and polyol ligand metal cation chelating ILs have good thermal stability, the above mixed system shows good cyclic absorption performance at higher absorption temperature. After 8 absorption desorption cycles, the absorption capacity remains basically unchanged. Therefore, the above efficient and reversible method has the potential application value of capturing CO2 from flue gas in industry. Metal cation-chelated ILs is a kind of excellent CO2 capture solvent which can be used at higher temperature. Compared with metal anion-coordinated ILs, metal cation-chelated ILs

17.2 Capture of CO2 in ILs

373

can capture carbon through the chemical interaction of anion, cation and CO2 , so it has more excellent carbon capture ability. In addition, changing the types of alcohol amines, central metal ions, and anions can effectively regulate the absorption performance of metal cation chelated ILs, so as to ensure that it can still maintain good carbon capture capacity at higher absorption temperature. It is similar to metal anion coordination ILs, and the viscosity of metal anion coordination ILs is relatively large. It can effectively reduce the viscosity of the system by coordinating with other ILs with similar structure to form a mixed system, So as to improve the carbon capture capacity of the system.

17.2.4 CO2 capture by ILs based mixtures The CO2 adsorption in conventional ILs is mainly physical adsorption process, which is much weaker than the chemical adsorption in alcohol amine systems [203–239]. The main disadvantages of ILs is that they have higher cost and larger viscosity than other solvents. Therefore, one of the most direct methods is to mix the ILs with organic solvents or water to form a mixture solution to reduce the viscosity and the cost for CO2 absorption [203–239]. Table 17.4 shows the CO2 absorption in ILs/solvents mixture. It showed that the nonvolatile ionic liquid can overcome the volatility of alcohol amine aqueous solution. At the same time, compared with a single absorbent, the mixture absorbent can provide more unique physical properties [209,218–220]. Camper et al. [209] used mixture formed with equimolar alkyl ethanolamine and imidazole ILs for CO2 capture. It is shown that the mixture of [Hmim]Ntf2 and monoethanolamine (MEA) can absorb 0.5 mol CO2 with per mole of MEA, and the product of the reaction of CO2 and MEA was insoluble in the compound solvent and separated from the system, which accelerated the capture process. Zhang et al. [218] pointed out that imidazole ILs are expensive and difficult to be economically accepted for large-scale application. The ILs/solvents with a equi-mass fraction of Nmethyldiethanolamine (MDEA), [MDEA]BF4 , H2 O and a little piperazine (PZ) was used to capture CO2 . At the optimal conditions (303.15K and 1.5MPa), the capture capacity of CO2 in mixture is 0.15 g CO2 /1 g solvent. They also used other complex solvents containing ILs prepared by neutralizing alkyl alcohol amines with inorganic acids, such as [MDEA]BF4 , [MEA]BF4 , [MDEA]HSO4 , [MDEA]Cl and [MDEA]H2 PO4 for CO2 capture. They pointed out that the ILs/solvents is easy to prepare and has lower corrosion to the equipment than the traditional amine solution, so it has the prospect of industrial application. Zhang et al. [220] added tetramethylammonium glycine, tetraethylammonium glycine, tetramethylammonium lysine and tetraethylammonium lysine as activators into MDEA aqueous solution to form a new CO2 absorbent. They studied the effects of ILs types and dosage on the absorption performance of the mixed absorbers, analyzed the mechanism, absorption capacity and regeneration efficiency. It is showed that TSILs addition can significantly improve the CO2 absorption rate in MDEA aqueous solution. The more TSILs is added, the faster absorption rate is. The glycine/MDEA aqueous solution has the maximum absorption capacity and regeneration efficiency. Lei et al. [221] used acetone and [Emim]BF4 to form a ILs/solvent to capture the CO2 . It is showed that the ILs/solvent has a good solubilty of CO2, which combines the respective

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17. Carbon dioxide capture and utilization in ionic liquids

TABLE 17.4 CO2 capture in ILs/solvents mixture (Rma : mass ratio, Rmo : mole ratio, xA : molar fraction of A,wA: mass fraction of A). Entry

Systems

P (bar) /(K)

mol CO2 per mol IL

Ref.

1

H2 O + [P66614 ]2-CNPyr (Rma = 4.5:95.5)

0.01/295

0.9

[130]

2

[Emim]TFA + [Emim]Ac (Rmo = 50.02:49.98)

0.01/323

0.124

[137]

3

[Emim]Ac + [Emim]EtSO4 (Rmo = 1:1)

0.393/298

0.19

[137]

4

[Eeim]Ac+H2 O (xH2 O = 0.208)

2/300

0.27

[137]

5

[Eeim]Ac+H2 O (xH2 O = 0.208)

0.75/300

0.21

[137]

6

[Eeim]Ac+H2 O (xH2 O = 0.208)

0.07/300

0.10

[137]

7

[Eeim]Ac+H2 O (xH2 O = 0.35)

0.10/300

0.08

[137]

8

[Eeim]Ac+H2 O (xH2 O = 0.533)

0.16/300

0.06

[137]

9

[Emim]TFA + [Emim]Ac (Rmo = 50.02 :49.98)

1.0/323

0.124

[137]

10

[Hmim]Ntf2 + MEA (Rmo = 1 : 1)

1.01/313

0.5

[137]

11

[N1111 ]Gly+H2 O (wH2 O = 0.2)

0.63/298

0.25

[139]

12

[N1111 ]Gly+H2 O (wH2 O = 0.35)

0.63/298

0.31

[139]

13

H2 O + [N1111 ]Gly (wH2 O = 0.5)

0.63/298

0.40

[139]

14

H2 O + [N1111 ]Gly (wH2 O = 0.7)

0.64/298

0.60

[139]

15

H2 O + [C1 C4 Pyrro]Ac (xH2 O = 0.35)

0.09/303

0.12

[142]

16

H2 O + [C1 C4 Pyrro]Ac (xH2 O = 0.6)

0.15/303

0.06

[142]

17

H2 O + [C1 C4 Pyrro]Ac (xH2 O = 0.85)

0.64/303

0.01

[142]

18

[BHEA]Ac + H2 O (Rma = 8 : 2)

3.7/298

0.1078

[203]

19

MEA +[BHEA]Ac + H2 O (Rma = 1 : 1 : 3)

3.92/298

0.6628

[203]

20

H2 O+[Bmim]BF4 (Rma = 8 : 2)

3.6/298

0.1155

[203]

21

[Bmim]BF4 + MEA + H2 O (Rma = 1 : 1 : 3)