Emerging Technologies for Waste Valorization and Environmental Protection [1st ed.] 9789811557354, 9789811557361

Table of contents :
Front Matter ....Pages i-xiv
Bird Diversity in the Mining Area of Bellary-Hospet Region, Karnataka, India (J. P. Kotangale, Arindam Ghosh, Amit Kumar Ghosh)....Pages 1-7
IoT-Based Waste Management System Through Cloud Computing and WSN (M. Humera Khanam, V. Yamini, C. Sucharitha, Samia Anjum, Y. C. Thejaswini)....Pages 9-17
A Study on Selection of the Biofilm for the Hybrid Up-Flow Anaerobic Sludge Blanket (HUASB) Reactor Using the Computational Fluid Dynamics (CFD) Analysis (R. Loganath, J. Senophiyah-Mary, Teema Thomas)....Pages 19-27
Experimental Investigations on the Combined Effect of TiO2 Nanoadditive and EGR on Engine Performance by Using Mimusops Elangi Biodiesel Blend (R. L. Krupakaran, B. Dhinesh, B. Sachuthananthan, N. Manigandan)....Pages 29-47
Production and Application of Chitosanases in Valorization of Crustacean Waste to Wealth—A Review (P. Jeevana Lakshmi, Y. Hepsiba, Ch. M. Kumari Chitturi)....Pages 49-58
Capture of CO2 from Automobile Exhaust by Using Physical Adsorption Technique (S. Mohankumar, B. Dhinesh, Muhammad Usman Kaisan, P. Mohamed Shameer)....Pages 59-68
Chemical Characterization and Environmental Implications of Recycled Sewage Sludge in the Proximity Soil of Treatment Plant (P. Balaganesh, M. Vasudevan, S. M. Suneethkumar, N. Natarajan)....Pages 69-78
Novel Techniques of Synthesis of Nanocellulose from Sugarcane Bagasse and Its Applications in Dye Removal (Shubhalakshmi Sengupta, Megha Srivastava, Uttariya Roy, Papita Das, Siddhartha Datta, Aniruddha Mukhopadhyay)....Pages 79-85
Assessment of Greenhouse Gases and Perception of Communities on Emissions from the Largest Dumpsite in Africa (Michael A. Ahove, Olasunkanmi M. Ojowuro, Chinenye L. Okafor)....Pages 87-99
Performance Analysis of Treatment of Distillery Spent Wash Using EGSB Reactor with Addition of Iron and Manganese (G. M. Hiremath, Veena S. Soraganvi)....Pages 101-111
Recent Trends in Valorization of Non-metallic Ingredients of Waste Printed Circuit Board: A Review (Debnil Bose, Sourav Barman, Rajat Chakraborty)....Pages 113-126
Paper Mill Lime Sludge Valorization as Partial Substitution of Cement in Mortar (Prabhat Vashistha, Vivek Kumar)....Pages 127-134
Wealth from Poultry Waste (V. V. Lakshmi, D. Aruna Devi, K. P. Jhansi Rani)....Pages 135-144

Citation preview

Sadhan Kumar Ghosh Chiranjib Bhattacharya Suggala V. Satyanarayana S. Varadarajan   Editors

Emerging Technologies for Waste Valorization and Environmental Protection

Emerging Technologies for Waste Valorization and Environmental Protection

Sadhan Kumar Ghosh Chiranjib Bhattacharya Suggala V. Satyanarayana S. Varadarajan •

•

•

Editors

Emerging Technologies for Waste Valorization and Environmental Protection

123

Editors Sadhan Kumar Ghosh Department of Mechanical Engineering Jadavpur University Kolkata, West Bengal, India

Chiranjib Bhattacharya Pro-Vice Chancellor Jadavpur University Kolkata, West Bengal, India

Suggala V. Satyanarayana Department of Chemical Engineering Jawaharlal Nehru Technological University Anantapur Anantapuramu, Andhra Pradesh, India

S. Varadarajan Department of Electronics and Communication Engineering S. V. University Guntur, Andhra Pradesh, India

ISBN 978-981-15-5735-4 ISBN 978-981-15-5736-1 https://doi.org/10.1007/978-981-15-5736-1

(eBook)

© Springer Nature Singapore Pte Ltd. 2020 This work is subject to copyright. All rights are reserved by the Publisher, whether the whole or part of the material is concerned, specifically the rights of translation, reprinting, reuse of illustrations, recitation, broadcasting, reproduction on microfilms or in any other physical way, and transmission or information storage and retrieval, electronic adaptation, computer software, or by similar or dissimilar methodology now known or hereafter developed. The use of general descriptive names, registered names, trademarks, service marks, etc. in this publication does not imply, even in the absence of a specific statement, that such names are exempt from the relevant protective laws and regulations and therefore free for general use. The publisher, the authors and the editors are safe to assume that the advice and information in this book are believed to be true and accurate at the date of publication. Neither the publisher nor the authors or the editors give a warranty, expressed or implied, with respect to the material contained herein or for any errors or omissions that may have been made. The publisher remains neutral with regard to jurisdictional claims in published maps and institutional affiliations. This Springer imprint is published by the registered company Springer Nature Singapore Pte Ltd. The registered company address is: 152 Beach Road, #21-01/04 Gateway East, Singapore 189721, Singapore

Preface

Waste valorization aims recycling of waste, favourable disposal, storage, sorting and in some cases synthesis of valuable products. The depletion of raw materials, the demand for eco safe green products and socioeconomic concerns have promoted the technologies for direct recycling of wastes and residues. Waste valorisation also accredits the use of renewable energy, elimination and use of toxic chemicals and development of bio-benign products, to allow return and reuse to the biosphere, and elimination of waste through the superior design of materials, products systems and business models. Various valorization techniques are currently showing promise in meeting industrial demands. Due to resource scarcity, increasing greenhouse emissions energy crisis and awareness of the need for sustainable development in terms of safely reusing waste and biomass, the transformation of waste/biomass to valuable materials and energy is emerging as a promising trend. The search of more sustainable ways to live is emphasized on the cutting of waste production and waste recycling. In our society, widespread feeling of “environment in danger” has nucleated a general realization of minimizing waste production in our daily lives and has boosted many methods to achieve sustainable development, with improved waste management leading to the production of industrially important materials, chemicals and fuels, in essence, valuable end products from the waste. Driven by technological advances or by changes in social–economic circumstances, the technologies showing steady growth in interest and applications, in both research and industry, are called “novel” or “emergent” technologies which hold the potential to change the paradigm and revolutionize the bioprocessing industry. Various valorization techniques are currently showing promise in meeting industrial demands. Scientists and engineers are working on prototype technologies that can begin this job. Waste valorization is one of the current research areas that have attracted a great deal of attention over the past few years as a potential alternative to the disposal of a wide range of residues in landfill sites. In particular, the development of environmentally sound and innovative strategies to process such waste is an area of increasing importance in our current society. There are numerous strategies for waste recycling or processing such as composting, v

vi

Preface

regenerated animal feed and bedding, anaerobic digestion and so on. There are numerous strategies for waste recycling or processing such as composting, regenerated animal feed and bedding, anaerobic digestion and so on. Lignin biomass conversion into fine chemicals using designer photocatalytic nanomaterial has become a promising technology. Some of these techniques have been successful in making their way to commercialization. The agro-food industries generate huge quantities of biodegradable solid or liquid wastes and consist of organic residues of the processed raw materials, and hence, various technological developments are emerging based on food industries to convert biomass into renewable fuels (biomethane, bioalcohol, biohydrogen, bio-oil/biochar). Recovery of value-added components from agro-waste using various emerging techniques like ultrasonication, microwave-based techniques, pulsed electric field, bioreactors, membrane bioreactor, enzyme membrane reactors is gaining importance globally. Synthesis of biopolymers, production of biofertilizers, isolation of single-cell protein, organic acids of speciality application, development of bio-adsorbents are also some innovative approaches emerging from agro-wastes. Technological developments for waste management to control plastic pollution and the synthesis of bio-based plastics are appearing as the most important issues in the circular economy era. The multi-valorization of underused bioresources such as agro-food wastes, forestry surplus, seaweeds or microalgae is a desirable approach to meet the bio-economy challenges, hence using biomass as a sustainable renewable feedstock in bio-refinery systems is crucial for the transition from a non-biodegradable fossil carbon-based economy to a bio-based economy. Since the strategies replying on single conventional treatment technologies do not lead to optimal utilization of the valuable resources in the waste, “cascading approaches”, viz. coupling the generation of product and by-product processing to high value product emerging to address the challenge technological feasibility issue. This editorial volume is covering various aspects of waste management and control with technological developments of novel recycling approaches to provide a comprehensive global perspective of waste recycling, value addition to waste and circular process economy aspects of emerging technologies. The 8th IconSWM 2018 received 380 abstracts and 320 full papers from 30 countries. Three hundred accepted full papers have been presented in November 2018 at Acharya Nagarjuna University, Guntur, Andhra Pradesh, India. After a thorough review by experts and required revisions, the board has finally selected thirteen chapters in this book Emerging Technologies for Waste Valorization and Environmental Protection. The IconSWM movement was initiated focusing better waste management, resource circulation and environmental protection since the year 2009. It helps generating awareness and bringing all the stakeholders together from all over the world under the aegis of the International Society of Waste Management, Air and Water (ISWMAW). It established a few research projects across the world involving the CST at Indian Institute of Science, Jadavpur University, and a few other institutions in India and experts from more than 30 countries in the research project on the circular economy. Consortium of Researchers in International

Preface

vii

Collaboration (CRIC) and many other organizations across the world are helping the IconSWM movement. IconSWM has become one of the biggest platforms in India for knowledge sharing and awareness generation among the Urban Local Bodies (ULBs), government departments, researchers, industries, NGOs, communities and other stakeholders in the area of waste management. The primary agenda of this conference is to reduce the waste generation encouraging the implementation of 5Rs (Reduce, Reuse, Recycle, Remanufacturing and Repair) concept. The conference provided holistic pathways to waste management and resource circulation conforming to urban mining and circular economy. The success of the 8th IconSWM is the result of effective contribution of the government of Andhra Pradesh, several industry associations, chamber of commerce and industries and the AP higher education council, various organizations and individuals in India and abroad. Support of the UNEP, UNIDO, UNCRD, delegation from the European Union and other foreign organizations was significant. The 8th IconSWM 2018 was attended by nearly 823 delegates from 22 countries. The 9th IconSWM 2019 was held at KIIT, Bhubaneswar, Odisha, during 27–30 November 2019, with nearly 900 participants from 30 countries. This book will be helpful for the educational and research institutes, policy makers, government, implementers, ULBs and NGOs. Hope to see you all in 10th IconSWM-CE 2020 in December 2020. Kolkata, India April 2020

Prof. Sadhan Kumar Ghosh Prof. Chiranjib Bhattacharya Prof. S. Varadarajan Prof. Suggala V. Satyanarayana Editors

Acknowledgements

We thank Hon’ble Chief Minister and Hon’ble Minister of MA&UD for taking personal interest in this conference. We are indebted to Shri. R. Valavan Karikal, IAS, Dr. C. L. Venkata Rao, Shri. B. S. S. Prasad, IFS (Retd.), Prof. S. Vijaya Raju and Prof. A. Rajendra Prasad, VC, ANU, for their unconditional support and guidance for preparing the platform for the successful 8th IconSWM at Guntur, Vijayawada, Andhra Pradesh. We must express our gratitude to Mr. Vinod Kumar Jindal, ICoAS, Shri. D. Muralidhar Reddy, IAS, Shri. K. Kanna Babu, IAS, Mr. Vivek Jadav, IAS, Mr. Anjum Parwez, IAS, Mr. Bala Kishore, Prof. S. Varadarajan, Mr. K. Vinayakam, Prof. Shinichi Sakai, Kyoto University, JSMCWM, Prof. Y. C. Seo and Prof. S. W. Rhee of KSWM, Shri. C. R. C. Mohanty of UNCRD, members of Industry Associations in Andhra Pradesh, Prof. P. Agamuthu, WM&R, Prof. M. Nelles, Rostock University, Dr. Rene Van Berkel of UNIDO, Ms. Kakuko Nagatani-Yoshida and Mr. Atul Bagai of UNEP and UN Delegation of India for their active support. IconSWM-ISWMAW committee acknowledges the contribution and interest of all the sponsors, industry partners, industries, co-organizers, organizing partners around the world, the government of Andhra Pradesh, Swachh Andhra Corporation as the principal collaborator, the vice chancellor and all the professors and academic community at Acharaya Nagarjuna University (ANU), the chairman, vice chairman, Secretary and other officers of Andhra Pradesh State Council of Higher Education, for involving all the universities in the state, the chairman, member Secretary and the officers of the Andhra Pradesh Pollution Control Board, the director of factories, the director of boilers, director of mines and officers of different ports in Andhra Pradesh and the delegates and service providers, for making the 8th IconSWM a successful event. We must specially mention the support and guidance by each of the members of the international scientific committee, CRIC members, the core group members and the local organizing committee members of the 8th IconSWM who are the pillars for the success of the programme. The editorial board members including the

ix

x

Acknowledgements

reviewers, authors and speakers and Mr. Aninda Bose and Ms. Kamiya Khatter of M/s. Springer India Pvt. Ltd. deserve thanks who were very enthusiastic in giving me inputs to bring this book. We must mention the active participation of all the team members in IconSWM Secretariat across the country with special mention of Prof. H. N. Chanakya and his team in IISc, Bangalore, Ms. Sheetal Singh and Dr. Sandhya Jaykumar and their her team in CMAK and BBMP, Mr. Saikesh Paruchuri, Mr. Anjaneyulu, Ms. Senophiah Mary, Mr. Rahul Baidya, Ms. Ipsita Saha, Mr. Suresh Mondal, Mr. Bisweswar Ghosh, Mr. Gobinda Debnath, Mr. Soumen Chatterjee, Ms. Ritasree Chatterjee and the research team members in the mechanical engineering dept. and ISWMAW, Kolkata HQ, for various activities for the success of the 8th IconSWM 2018. Special thanks to Sannidhya Kumar Ghosh, for being the governing body member of ISWMAW supported the activities from the USA. I am indebted to Mrs. Pranati Ghosh who gave me guidance and moral support in achieving the success of the event. Once again the IconSWM and ISWMAW express gratitude to all the stakeholders, delegates and speakers who are the part of the success of the 8th IconSWM 2018. Prof. Sadhan Kumar Ghosh

Contents

Bird Diversity in the Mining Area of Bellary-Hospet Region, Karnataka, India . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . J. P. Kotangale, Arindam Ghosh, and Amit Kumar Ghosh IoT-Based Waste Management System Through Cloud Computing and WSN . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . M. Humera Khanam, V. Yamini, C. Sucharitha, Samia Anjum, and Y. C. Thejaswini A Study on Selection of the Biofilm for the Hybrid Up-Flow Anaerobic Sludge Blanket (HUASB) Reactor Using the Computational Fluid Dynamics (CFD) Analysis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . R. Loganath, J. Senophiyah-Mary, and Teema Thomas Experimental Investigations on the Combined Effect of TiO2 Nanoadditive and EGR on Engine Performance by Using Mimusops Elangi Biodiesel Blend . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . R. L. Krupakaran, B. Dhinesh, B. Sachuthananthan, and N. Manigandan Production and Application of Chitosanases in Valorization of Crustacean Waste to Wealth—A Review . . . . . . . . . . . . . . . . . . . . . . P. Jeevana Lakshmi, Y. Hepsiba, and Ch. M. Kumari Chitturi Capture of CO2 from Automobile Exhaust by Using Physical Adsorption Technique . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . S. Mohankumar, B. Dhinesh, Muhammad Usman Kaisan, and P. Mohamed Shameer Chemical Characterization and Environmental Implications of Recycled Sewage Sludge in the Proximity Soil of Treatment Plant . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . P. Balaganesh, M. Vasudevan, S. M. Suneethkumar, and N. Natarajan

1

9

19

29

49

59

69

xi

xii

Contents

Novel Techniques of Synthesis of Nanocellulose from Sugarcane Bagasse and Its Applications in Dye Removal . . . . . . . . . . . . . . . . . . . . Shubhalakshmi Sengupta, Megha Srivastava, Uttariya Roy, Papita Das, Siddhartha Datta, and Aniruddha Mukhopadhyay Assessment of Greenhouse Gases and Perception of Communities on Emissions from the Largest Dumpsite in Africa . . . . . . . . . . . . . . . . Michael A. Ahove, Olasunkanmi M. Ojowuro, and Chinenye L. Okafor

79

87

Performance Analysis of Treatment of Distillery Spent Wash Using EGSB Reactor with Addition of Iron and Manganese . . . . . . . . . 101 G. M. Hiremath and Veena S. Soraganvi Recent Trends in Valorization of Non-metallic Ingredients of Waste Printed Circuit Board: A Review . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 113 Debnil Bose, Sourav Barman, and Rajat Chakraborty Paper Mill Lime Sludge Valorization as Partial Substitution of Cement in Mortar . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 127 Prabhat Vashistha and Vivek Kumar Wealth from Poultry Waste . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 135 V. V. Lakshmi, D. Aruna Devi, and K. P. Jhansi Rani

About the Editors

Prof. Sadhan Kumar Ghosh is a Professor in Mechanical Engineering and Chief Coordinator of Centre for Sustainable Development and Resource Efficiency Management at Jadavpur University. He is the former Dean, Faculty of Engineering and Technology & Ex-Head of the Mechanical Engineering Department at Jadavpur University, India. He is well known international experts in the fields of waste management, circular economy, SME sustainability, green manufacturing, ISO Standards and TQM. He served as the Director, CBWE, Ministry of Labour and Employment, Government of India and L&T Ltd. Prof. Ghosh is the Founder and Chairman of the IconSWM-CE and the President of the International Society of Waste Management, Air and Water (ISWMAW), as well as the chairman of the “Indian Congress on Quality, Environment, Energy and Safety Management Systems (ICQESMS)”. He was awarded a Distinguished Visiting Fellowship by the Royal Academy of Engineering, UK, to work on “Energy Recovery from MSW” and working as PI at JU for Horizon 2020 project, “INDIA H20”. He received several national and international awards. He is involved in collaborative research with experts from more than 30 countries and in a few national committees. He has three patents, more than 200 publications.

xiii

xiv

About the Editors

Prof. Chiranjib Bhattacharya is the Pro ViceChancellor of Jadavpur University. He is a Professor and former Head in Chemical Engineering. He works as the Dean of Faculty of Engineering and Technology & Registrar at Jadavpur University. He completed his M.Tech. from the Indian Institute of Technology, Kanpur (1991), and Ph.D. from Jadavpur University (1998) in Chemical Engineering. His areas of research interests include mass transfer studies in ultrafiltration, simulation of ultrafiltration process; other membrane separation processes like emulsion liquid membrane; wastewater treatment with specific emphasis on the membrane route; bioremediation; bioprocess engineering. He has more than 11 years of research and teaching experience. He has published many papers in international journals and conferences. He has also supervised 15 Ph.D. students and 34 M.Tech. Students. Prof. Suggala V. Satyanarayana is Dean and Professor, Chemical Engineering, JNTU, Andhra Pradesh, India. He was the President of Indian Institute of Chemical Engineering. He completed his B.Tech. from Osmania University, Hyderabad, India; M.Tech. and Ph.D. from the Indian Institute of Technology, Kanpur, India, in Chemical Engineering. He has 20+ years of teaching experience. He has supervised 20 Ph.D. students. He has published more than 100 papers in international/national journals and conferences.

Prof. S. Varadarajan is a professor at S.V. University and former Secretary, AP State Council of Higher Education, Andhra Pradesh, India. He completed his B.Tech. from S.V. University; M.Tech. from National Institute of Technology, Warangal, and Ph.D. from S.V. University in Radar Signal Processing. He has 10 years of teaching experience. He has published 04 books—“Embedded Real-Time Systems” with Narosa Publisher; “Electromagnetic Theory and Transmission Lines” with Alpha Science International Ltd.; “Signals and Systems” with I.K. International Publishing House; “Electronic Devices and Circuits” in press with Lambert Publishers. He has supervised 18 Ph.D. students and 29 M.Tech. students. He is a fellow of IETE, Member of IEEE and Life Member of ISTE.

Bird Diversity in the Mining Area of Bellary-Hospet Region, Karnataka, India J. P. Kotangale, Arindam Ghosh, and Amit Kumar Ghosh

Abstract Bird survey was conducted in Bellary-Hospet region which has intensive iron ore mining activities. A total of 77 species of birds were observed of which 15 were aquatic/semi-aquatic. House crow was the most dominant species with 14.32% followed by laughing dove (11.85%) and house sparrow (10.32%). Species diversity index was calculated as 9.98. The birds were found to avoid core zone of iron ore mines, whereas no such finding occurred away from mining areas. Keywords Bird diversity · Bellary-Hospet region · Iron ore mining

1 Introduction Bellary-Hospet region in India’s southern state of Karnataka lies between 75° 42 to 77° 10 E and 14° 33 to 15° 50 N (longitude and latitude, respectively). Total study area is 3745.48 km2 with Hospet taluk having 904.17 km2 , Bellary taluk with 1688.59 km2 , and Sandur taluk with 1152.42 km2 . Geographically, the landscape comprises parts of Bellary Forest Division which consists of two distinct regions namely eastern region and the western region separated by Sandur Hills. The forests of Bellary Forest Division vary from mixed dry deciduous type to thorny scrub type. The region is rich in biological resources particularly in the terrestrial flora which are mostly confined to the hill ranges. The good forest is present only in part of Sandur taluk viz. Kumaraswamy range, while other hill ranges are covered by poor forest cover with scrub vegetation and rocky barren land. Fabaceae is the most widely represented family with 9 genera and 17 species. Anogeissus latifolia and Hardwickia binata are major species in terms of value and distribution. Common trees include Anogeissus latifolia, Azadirachta indica, and bamboo occurring as understory in Sandur. Common shrubs are Adhatoda zeylanica, J. P. Kotangale (B) · A. Ghosh CSIR-NEERI, Nehru Marg, Nagpur 440020, India e-mail: [email protected] A. K. Ghosh FTBE Department, Jadavpur University, Kolkata 700032, India © Springer Nature Singapore Pte Ltd. 2020 S. K. Ghosh et al. (eds.), Emerging Technologies for Waste Valorization and Environmental Protection, https://doi.org/10.1007/978-981-15-5736-1_1

1

2

J. P. Kotangale et al.

Calotropis procera, and Lantana camara. About 0.5% of total species include Emblica officinalis, Haldina cordifolia, Diospyros montana, Pterocarpus marsupium, Ficus bengalensis, Madhuca indica, Terminalia bellirica, Albizia lebbeck, Terminalia chebula, Bridelia retusa, Limonia elephantum, and Elaeodendron glaucum. About 120 medicinal species are available in the region. The mining activities in Sandur and Bellary regions are among the biggest mining operations in Karnataka. Due to higher percentage of iron content (65%) in the ore, the demand for iron ore from this region is very high. Mining involves various processes such as drilling, blasting, excavation, transportation, dumping, and stocking which lead to the dust pollution. The dense forest in the study region is very less as compared to open forest in the area. The density and diversity of the vegetation in the study region is very less. The forests in the whole region are extremely poor having stunted branching and growth. In this context, it was decided to study the birds in this region and delineate birds’ population and diversity.

2 Materials and Methods Field observations were made during morning and evening when the birds were most active. The study was conducted continuously for a week. The birds were studied by direct observations with a 7 × −15 × 35 “Optima Zenith” binocular and were identified with standard literature (Ali 1996; Ali and Ripley 1983, 1987). A distance of 3–5 km was travelled at each site in which designated areas occurred. The odometer of motor vehicle was used to measure the stretch of each study site. The field data were collected by walking through the study region and listing taxonomic position of each species encountered (Clarke 1986; Richter and Sondgerath 1990; Bibby et al. 2000). The data were subjected to detailed analysis, and different indices like dominance index, species diversity index, and encounter rate were derived from the collected data (Kotangale and Ghosh 2002; Gopi Sundar et al. 2000; Hellawell 1978). The study was conducted at 56 sites given in Table 1.

3 Results and Discussion The study revealed the presence of 77 species of birds (Table 2) during the walk through survey, of which 15 species were aquatic/semi-aquatic. They were found along or near the water bodies. House crow emerged as the most dominant species with dominance index value of 14.32%, followed by laughing dove (11.85%) and house sparrow (10.32%). Other common birds found in the study region were cattle egret, little egret, red-wattled lapwing, rock pigeon, rose-ringed parakeet, little green bee-eater, black drongo, Indian myna, jungle crow, red-vented bulbul, jungle babbler, and Indian robin (Table 2). These birds were found in close association with human beings and cattle. Majority of them were omnivorous preferring insects, worms, etc.,

Bird Diversity in the Mining Area of Bellary-Hospet …

3

Table 1 List of 56 study sites at Bellary-Hospet region Gunda

Gollalingamanahalli

Joga

Kudatini

Collarahalli

Yerradamanahalli

Gundalaodgere

Donimalai

Nuginatti

Tumbraguddi

Bommalgunda

Jaisinghpura

Byalakunda

Bomagatta

Kakubalu

Deogiri

Sandur

Devallamullapura

Hanumapura

Venkatgiri

Sushilanagar

Ankamanahalli

Rajapura

Sultanpur

Allipura

Kammathuru

Jagadahalli

Bhujanganagar

Obalapuram

Kumaraswamy temple

Malapura

Narihalla Dam

Siddhapura

Nandihalli

Antapura

Ankenahatti

Basapura

Swamihalli

Kodalu

Honnahalli

Vittalpura

Vadarahalli

Torangallu

Araginadona

Ganglapura

Tungabhadra Dam

Banahatti

Naganhalli

Hirehal

Hospet

Belagallu-Tanda

Motulkunta

Madiginahalli

Tonasigeri

Krishnanagar

Kalahalli

as their principle food items. The inclusion of the insects and worms in birds’ diet is very essential for their existence as animal food is essential for their breeding and egg-laying, as they cannot obtain from fruits or other vegetable matter (Snow and Snow 1971; Foster 1978). This is especially true during the breeding season when protein becomes crucial to the successful raising of young ones (Levey 1988). Female’s reproductive success depends on her access to protein-rich food, while a male’s reproductive success depends on his access to female (White 1993). However, very few birds were encountered in the active mining zones. Dominance index and encounter rate of each species are presented in Table 2. Species diversity index (Margalef 1958) was calculated as 9.98. Highest value of encounter rate was found for house crow (3.425), and these values for other species were observed accordingly (Table 2). The density of birds was generally more where feeding and nesting sites were more. Accordingly, the diversity of birds was found to be more in and around forests and less in plain areas. In general, wide varieties of birds were observed in the study area and included aquatic, arboreal, and terrestrial birds. The birds were found to avoid the core zones of iron ore mines, whereas no such finding was observed away from the mining areas.

4

J. P. Kotangale et al.

Table 2 Birds available in and around Bellary-Hospet region, Karnataka, India Sr. No.

Common name

Scientific name

1

Dabchick

Tachybaptus ruficollis

Dominance index 0.444

Encounter rate 0.1125

2

Little cormorant

Phalacrocorax niger

1.235

0.3125

3

Grey heron

Ardea cinerea

0.049

0.0125

4

Indian pond heron

Ardeola grayii

1.728

0.4375

5

Cattle egret

Bubulcus ibis

3.210

0.8125

6

Little egret

Egretta garzetta

2.222

0.5625

7

Painted stork

Mycteria leucocephala

0.099

0.0250

8

Black-shouldered kite

Elanus caeruleus

0.543

0.1375

9

Black kite

Milvus migrans govinda

0.148

0.0375

10

Brahminy kite

Haliastur indus

0.296

0.0750

11

Shikra

Accipiter badius

0.099

0.0250

12

Whiterumped vulture

Gyps bengalensis

0.198

0.0500

13

Crested serpent eagle

Spilornis cheela

0.049

0.0125

14

Grey francolin

Francolinus pondicerianus

0.444

0.1125

15

Grey quail

Coturnix coturnix

0.444

0.1125

16

Jungle bush quail

Perdicula asiatica

0.148

0.0375

17

Indian peafowl

Pavo cristatus

0.049

0.0125

18

Whitebreasted waterhen

Amaurornis phoenicurus

0.049

0.0125

19

Redwattled lapwing Vanellus indicus

0.691

0.1750

20

Common sandpiper

Actitis hypoleucos

0.298

0.0500

21

Blackwinged stilt

Himantopus himantopus

0.543

0.1375

22

River tern

Sterna aurantia

0.099

0.0250

23

Common green pigeon

Treron phoenicoptera

0.099

0.0250

24

Rock pigeon

Columba livia

1.531

0.3875

25

Spotted dove

Streptopelia chinensis

0.049

0.0125

26

Eurasian collared dove

Streptopelia decaocto

0.642

0.1625 (continued)

Bird Diversity in the Mining Area of Bellary-Hospet …

5

Table 2 (continued) Sr. No.

Common name

Scientific name

Dominance index

Encounter rate

27

Laughing dove

Streptopelia senegalensis

11.852

3.0000

28

Roseringed parakeet Psittacula krameri

1.926

0.4875

29

Asian koel

Eudynamys scolopacea

0.099

0.0250

30

Greater coucal

Centropus sinensis

0.543

0.1375

31

House swift

Apus affinis

0.444

0.1125

32

Lesser pied kingfisher

Ceryle rudis

0.049

0.0125

33

Whitethroated kingfisher

Halcyon smyrnensis

0.494

0.1250

34

Little green bee-eater

Merops orientalis

3.358

0.8500

35

Indian roller

Coracias benghalensis

1.086

0.2750

36

Eurasian hoopoe

Upupa epops

0.396

0.0750

37

Common grey hornbill

Tockus birostris

0.049

0.0125

38

Coppersmith barbet

Megalaima haemacephala

0.198

0.0500

39

Ashycrowned finch-lark

Eremopterix grisea

2.370

0.6000

40

Blackcrowned finch-lark

Eremopteryx nigriceps

0.395

0.1000

41

Common swallow

Hirundo rustica

1.926

0.4875

42

House martin

Delichon urbica

2.420

0.6125

43

Baybacked shrike

Lanius vittatus

0.049

0.0125

44

Redbacked shrike

Lanius collurio

0.049

0.0125

45

Black drongo

Dicrurus macrocercus

2.815

0.7125

46

Brahminy starling

Sturnus pagodarum

0.198

0.0500

47

Indian myna

Acridotheres tristis

5.778

1.4625

48

Rufous tree pie

Dendrocitta vagabunda

0.247

0.0625

49

House crow

Corvus splendens

14.321

3.6250

50

Jungle crow

Corvus macrorhynchos

4.593

1.1625

51

Large wood shrike

Tephrodornis virgatus

0.346

0.0875 (continued)

6

J. P. Kotangale et al.

Table 2 (continued) Sr. No.

Common name

Scientific name

52

Common wood shrike

Tephrodornis pondicerianus

0.099

0.0250

53

Redwhiskered bulbul

Pycnonotus jocosus

0.049

0.0125

54

Redvented bulbul

Pycnonotus cafer

4.296

1.0875

55

Common babbler

Turdoides caudatus

0.593

0.1500

56

Large grey babbler

Turdoides malcolmi

0.543

0.1375

57

Jungle babbler

Turdoides striatus

3.753

0.9500

58

Black and orange flycatcher

Muscicapa nigrorufa

0.099

0.0250

59

Bluethroated flycatcher

Muscicapa rubeculoides

0.049

0.0125

60

Ashy wren-warbler

Prinia socialis

0.790

0.2000

61

Plain wren-warbler

Prinia subflava

0.049

0.0125

62

Common tailor bird

Orthotomus sutorius

0.099

0.0250

63

Magpie robin

Copsychus saularis

0.049

0.0125

64

Stone chat

Saxicola torquata

0.049

0.0125

65

Pied bush chat

Saxicola caprata

0.099

0.0250

66

Indian robin

Saxicoloides fulicata

2.173

0.5500

67

Paddyfield pipit

Anthus novaeseelandiae

0.346

0.0875

68

Tawny pipit

Anthus campestris

0.593

0.1500

69

Yellow wagtail

Motacilla flava

0.099

0.0250

70

Yellowheaded wagtail

Motacilla citreola

0.790

0.2000

71

White wagtail

Motacilla alba

0.099

0.0250

72

Tickell’s flowerpecker

Dicaeum erythrorhynchos

0.148

0.0375

73

Purple sunbird

Nectarinia asiatica

0.642

0.1625

74

House sparrow

Passer domesticus

10.321

2.6125

75

Whitethroated munia

Lonchura malabaricus

0.247

0.0625

76

Whitebacked munia Lonchura striata

2.72

0.6875

77

Spotted munia

0.247

0.0625

Lonchura punctulata

Dominance index

Encounter rate

Bird Diversity in the Mining Area of Bellary-Hospet …

7

References Ali S (1996) The book of Indian birds, Revised Centenary edn. Oxford University Press, Mumbai Ali S, Ripley DS (1983) A pictorial guide to the birds of the Indian Subcontinent. Oxford University Press, Mumbai Ali S, Ripley DS (1987) Compact handbook of the birds of India and Pakistan, 2nd edn. Oxford University Press, Delhi Bibby CJ, Burgess ND, Hill DA, Mustoe SH (2000) Bird census techniques, 2nd edn. Academic Press, London Clarke R (1986) The handbook of ecological monitoring: a GEMS/UNEP publication. Clarendon Press, Oxford Foster MS (1978) Total frugivory in tropical passerines: a reappraisal. Trop Ecol 19:135–154 Gopi Sundar K, Kaur J, Choudhury BC (2000) Distribution, demography and conservation status of the Indian Sarus Crane (Grus antigone antigone) in India. J Bombay Nat Hist Soc 97:319–339 Hellawell JM (1978) Biological surveillance of rivers. Water Research Center, Stevenage Kotangale JP, Ghosh T (2002) Inventory of avifauna in Jamshedpur area of Jharkhand State, India. In: Tripathi G, Tripathi YC (eds) Biological and biotechnological resources. Campus Books International, New Delhi, pp 313–323 Levey DJ (1988) Spatial and temporal variation in Costa Rican fruit and fruit-eating bird abundance. Ecol Monogaph 58:251–269 Margalef R (1958) Information theory in ecology. Gen Syst 3:36–71 Richter O, Sondgerath D (1990) Parameter estimation in ecology. VCH Verlagsge Seischaft, Weinheim Snow BK, Snow DW (1971) The feeding ecology of tanagers and honeycreepers in Trinidad. Auk 88:291–322 White TCR (1993) The inadequate environment—nitrogen and the abundance of animals. SpringerVerlag, Berlin Heidelberg

IoT-Based Waste Management System Through Cloud Computing and WSN M. Humera Khanam, V. Yamini, C. Sucharitha, Samia Anjum, and Y. C. Thejaswini

Abstract Solid waste management is the primary problem in India. It is seen that most of the garbage across the roadsides are overflowed in advance before the commencement of the next cleaning process, and this may lead to a lot of inconvenience to people. Most of the time wet and dry wastes are not separately collected. The goal of the paper is to overcome all these problems by designing a smart dustbin connected to the cloud to communicate with the waste management officials. The system involves the ultrasonic sensors to sense the level of garbage in the bin, flame sensors to detect the fire, load sensors to measure the load, and moisture sensors to separate out wet and dry garbage. The system also consists of a trash bin attached to the primary trash bin which expands if it reaches its maximum capacity. By using GSM (global system for mobile), the garbage collectors are notified through SMS or through webpage. The whole system is powered by solar panels attached to the lid of the trash bin, thus making it a smart and environmentally friendly system. Keywords IoT · WSN · Arduino Mega 2560 · GSM · Ultrasonic sensors · Moisture sensor · Smoke sensor · Load sensors · Cloud server

1 Introduction Over the past few decades, the world population has been quadrupled and there has been major relocations from rural to urban areas. The significant rise in urban migration leads to change in lifestyle, which in return lead to generation of huge amount of waste. Tackling waste management is a huge challenge faced by the countries across the globe. M. Humera Khanam (B) · V. Yamini · C. Sucharitha · S. Anjum · Y. C. Thejaswini Department of Computer Science and Engineering, SV University, Tirupati, India e-mail: [email protected] V. Yamini e-mail: [email protected] C. Sucharitha e-mail: [email protected] © Springer Nature Singapore Pte Ltd. 2020 S. K. Ghosh et al. (eds.), Emerging Technologies for Waste Valorization and Environmental Protection, https://doi.org/10.1007/978-981-15-5736-1_2

9

10

M. Humera Khanam et al.

From collection to processing and disposal requires abundance of labour and is time-consuming process. Waste management modes which are in current use are not powerful enough, and the smart cities are in the need of labour. The vision for the smart city is to be the global benchmark for a capital city. To achieve this vision, information technology is to be integrated with Internet of Things (IoT) framework, which represents things and their presence on the Internet. IoT consolidates the real and virtual world through cloud by bridging devices and applications. Many number of systems and methods have been reported for smart waste management but most of the works involve incommodious implementation and expensive solutions. In this paper, ultrasonic sensor technology is used to send notification by SMS via GSM network. The proposed system also includes an android application installed on mobile phones of workers for real-time monitoring and action.

2 Related Work Navghane, Killedar, and Rohokale provided the idea of using the smart technologies for waste management. The paper also introduced for the using of Wi-Fi in smart bins. An automatic waste bin and make use of cloud computing paradigm to evolve a more robust and effective smart waste management mechanism.

3 Proposed Work In addition to the above reviews, we will use smoke sensor, moisture sensor and GSM. The purpose of these components is described below: • Smoke sensor: This module is used to detect the different types of gases present around the air. In this project, the smoke sensor is used to detect the harmful gases around the dustbin and shows the % of harmful gases. • Moisture sensor: These sensors are used to calculate the volumetric content in the soil. In this project, this is used to separate the wet and dry content of the garbage. • GSM: It is a module used to establish mobile communication. In this project, this is used to notify the garbage collectors through SMS to perform suitable action.

IoT-Based Waste Management System Through Cloud Computing and WSN

11

By placing the above sensors in the bins, we can access the information about the garbage in and around the bins. This helps to reduce the risk of spreading infectious diseases through the wastes, thus making a clean and green environment.

4 System Architecture Design Implementation of this architecture includes following elements • Wireless sensors: These sensors are placed in each bin in the city. The sensors that are placed in these bins are smoke sensor, humidity and temperature sensor, ultrasonic sensors, LCD display, and microcontroller. These sensors gather the contextual data from the bins, and microcontroller samples the sensed data. These data are transmitted to the central station using a wireless module. • Cloud server: This is a linked web organization that receives, stores, displays and examines the data provided by the various wireless sensing nodes in real time. It also notifies the worker to perform related action. • Software Android App: This is an Application Software system that the workers install this on their smart phones for mobile live monitoring of bins and perform related action.

5 Modules 5.1 Ultrasonic Sensor An ultrasonic sensor HC-SR04 model is used for garbage volume sensing in bins due to its good accuracy and low cost. The ultrasonic sensor is placed in the head of the container. The module works by sending sound waves that on getting reflected after touching the floor of the container is received back. Time taken is calculated to give the distance. Distance Travelled = (time taken ∗ sound velocity)/2

12

M. Humera Khanam et al.

5.2 Microcontroller Arduino Mega 2560 microcontroller based on ATmegal1280 is used in smart bin monitoring system. This is an efficient and inexpensive board. The board is powered by 5 V supply and operates at CPU frequencies of up to 16 MHz. It comprises of I2C bus interfaces, UART’s, 128 KB of flash memory, up to 8 KB of SRAM memory, USB device interface and 16 analog input pins.

IoT-Based Waste Management System Through Cloud Computing and WSN

13

5.3 Smoke Sensor Smoke sensor is used to detect harmful gases. MQ2 gas sensor is a smoke sensor. It is used to identify flammable gases like alcohol, smoke, LPG, CH4 , CO, H2 etc.; when flammable gases are present, the conductivity gets higher. This change in conductivity can be converted in voltage output signals through a simple circuit and the output can be analog signal (A0) that can be read with an analog input of the Arduino (D0).

5.4 LCD Display The LCD is interfaced with Arduino Mega. A 16 * 2 alphanumeric dot matrix LCD display is used.

14

M. Humera Khanam et al.

5.5 Humidity Sensor It provides the information related to the presence of wet and dry waste bin. DHT11 sensor is used to detect water vapour by measuring the electrical resistance.

5.6 Load Sensor It is easy and reliable method of calibrating the dead weight. They consist of four wire load sensors out of which two are excitation wires and the other two are signalling wires (positive and negative). These types of sensors are used to measure the loads either directly or indirectly. Hydraulic load cells, pneumatic load cells and strain gauge load cells are some of the types used in the load detection. Among them, the strain gauge load sensors which are commonly used in industries and researches are transducer and thereby convert force into electrical signals, and the deformation in the electrical signals helps to find out the approx. load.

5.7 Cloud Server Cloud computing provides access to store and access the data over the Internet (cloud) instead of computer’s hard drive. In the cloud, the real-time analysis has to be enabled to generate reports on area generating maximum waste, segregation reports etc. The data of dry and wet segregation level will help in evaluating the current waste management plans and also to refine the plans to increase the inefficiency.

6 Implementation The software architecture for an IoT-based detection requires:

6.1 Arduino IDE The Arduino IDE software includes the text editors, message areas, text console and toolbars. The writing sketches are the programs written using the Arduino software. The toolbar serves many functions such as creation, open, close and save sketches. Other than these, the program can be verified and also updated using the toolbar. The

IoT-Based Waste Management System Through Cloud Computing and WSN

15

message area is used for displaying the errors and also gives feedback. Text console is used as a source of displaying output by the Arduino software.

6.2 WSN A wireless sensor network holds a base station with large number of sensor nodes which are used to pass information from the environment to the base station. The base station analyses and processes the collected data. It acts as an interface for the real and virtual environment.

6.3 Blynk App The Blynk app is specially designed for IoT and therefore making the approach easier. The hardware components connected through IoT can be controlled remotely using this app. The data from the sensors can be displayed and visualized. The data that are displayed can also be stored.

6.4 Arduino Language The Arduino language is a set of functions in C/C++. The functions can be called from the used code with minor changes in it (e.g. generation of function prototypes automatically and then passing it directly to a C/C++ compiler).

Sensor

Sensor

Sensor

LCD CLOUD SERVER

MICROCONTROLLE

GSM

R

module

VEHICLE DISPATCHING

SMS to worker

The system is switched on, and it collects the information from the sensor. The moisture sensor detects the moisture and then separates the waste, load sensor displays the weights, and the ultrasonic sensor measures the distance between the sensor and the waste inside the container and sends its information to the server.

16

M. Humera Khanam et al.

The filling percentage of the container is estimated based on the latest measurements produced by the sensors. It is obtained on the web application. There are three level indicators for waste bin level: 1. GREEN: less than 50% 2. YELLOW: less than 100% and more than 50% 3. RED: more than 100%. If the indicator reaches RED, the trash bin which is attached extends to form space for extra garbage. These are controlled by microcontroller and displays on LCD. The GSM module is used to notify the garbage collectors and a vehicle is dispatched for cleaning.

7 Results The prototypes designed and the ultrasonic sensors are placed nearer to the area of impact. The threshold levels are used to detect the amount of garbage (80–90%). These threshold values are the levels, and based on them, the triggers are initiated. If the levels are high or reaching the optimal values, the signals are sent to the nearby commissioning office for further disposal action to be taken. The open source applications of IoT are used. The HTTP protocols are used for storing and retrieving the data.

8 Conclusion The objective of this paper is for the real-time access of information about the dustbin and also to reduce the possibility of overflowing the trash in a cost-effective and ecofriendly manner. Being wireless, the system is easy to install and maintain. The main goal of this is to make the world a hazard-free zone. This is crucial to the environment as it reduces the risk of spreading infectious diseases. This system not only saves fuel and time but also aids in construction of a greener and cleaner environment for us to live in a well and healthier ecosystem and build better world for future generation.

9 Future Scope of the Work In future, we can look after for a better system that includes of android apps, or small gadgets attached to our street areas to monitor the wastage disposal.

IoT-Based Waste Management System Through Cloud Computing and WSN

17

It can have advancement in the range of the IR sensors and usage of camera or machine learning methods for better classification of recyclable and non-recyclable materials. And IoT to implement hand gestures can also be used for better usage of the dustbin to open/close without touching the lid.

A Study on Selection of the Biofilm for the Hybrid Up-Flow Anaerobic Sludge Blanket (HUASB) Reactor Using the Computational Fluid Dynamics (CFD) Analysis R. Loganath, J. Senophiyah-Mary, and Teema Thomas Abstract At this present scenario, treating the industrial and domestic wastewater in economical and time-consuming manner is the biggest challenge to the scientists. In aerobic treatment, the power consumption rate and land area requirement are very high compared to the anaerobic treatment. Because of these disadvantages, industries are moving to anaerobic treatment plant. In this kind of treatment plants, the efficiency of the treatment is high and recovery of biogas is also possible which is cost-effective too. Due to these advantages, the Hybrid Up-flow Anaerobic Sludge Blanket (HUASB) Reactor plays a significant role among various high rate anaerobic reactor. The main problem in the HUASB Reactor is clogging in the biofilm portion. The reasons behind this problem were addressed as suspended solid attachment in the biofilm and lacks of solid–liquid movement. To resolve this issue, no computational studies have been done till date. To address this issue, various biofilm designs have been developed with respect to the various structures and different surface areas. In this study, the laboratory-scale HUASB Reactor was designed with respect to different biofilm model and it has been operated to visualize the fluid flow interactions inside the reactor with respect to the velocity, pressure, turbulence flow, density and shear stress. Depending on these physical parameters, optimum biofilm was chosen with the help of CFD analysis. This could be implemented to develop the industrial-scale reactor for better performance to avoid the practical difficulties.

R. Loganath (B) Department of Civil Engineering, Indian Institute of Engineering Science and Technology, Shibpur, Shibpur, Howrah 711103, India e-mail: [email protected] J. Senophiyah-Mary Department of Civil Engineering, Government College of Technology, Coimbatore, Tamil Nadu 641013, India e-mail: [email protected] T. Thomas Department of Civil Engineering, National Institute of Technology Karnataka Surathkal, Surathkal, Karnataka 575025, India e-mail: [email protected] © Springer Nature Singapore Pte Ltd. 2020 S. K. Ghosh et al. (eds.), Emerging Technologies for Waste Valorization and Environmental Protection, https://doi.org/10.1007/978-981-15-5736-1_3

19

20

R. Loganath et al.

Keywords Anaerobic digestion · Hybrid up-flow anaerobic sludge blanket (HUASB) reactor · Clogging · Biofilm · CFD modelling · Physical parameters

1 Introduction Nowadays, due to the population growth the urbanization and industrialization are increasing rapidly. Due to the industrialization, the ground water/surface water usage was increased drastically, and the same amount of water has been returned as wastewater. To treat this kind of wastewater is always difficult task for the industry as well as the researchers. Treatment of this kind of wastewater is a mandatory operation to protect the environment (Chatterjee et al. 2018; Granada et al. 2018; Liu et al. 2018; Sokkanathan et al. 2018). There are various kinds of treatment options available to treat the industrial wastewater, but the problem arises from the suitable technology with the optimal and cost-effective manner. In biological treatment of industrial wastewater, aerobic treatment and anaerobic treatment technologies are pioneer in the field. Compared to the aerobic treatment process, anaerobic treatment process has the various advantages such as less electrical energy requirement, low space requirement, able to operate under high organic loading rate and maintenance-free design (Schaider et al. 2017; Worku and Leta 2017; Yan et al. 2017; Zinatizadeh et al. 2017). Even though, still there are few demerits addressed by the industrialist during operating the large-scale reactors such as clogging inside the reactor due to the insignificant biofilm designs, mixing pattern was unknown or it may be in single way pattern. This problem arises because of the improper mixing condition as well as the lack of understanding of the flow interactions in the biofilm, before the reactor fabrication (Rajakumar et al. 2011; Bustillo-Lecompte and Mehrvar 2016; Krithika and Philip 2016). To avoid this kind of issues using the CFD analysis, the flow patterns inside the reactors can be easily visualized for the reactor better performance (Liu and Tay 2002; Ren et al. 2009; Jiang et al. 2014). The understanding of the hydrodynamic phenomena inside the anaerobic reactors are still limited, and to be specific for a hybrid system, it is still in the beginning level of the study. Still from the various studies, the most of the researchers mainly focused on the performance of the reactor with respect to the different industrial wastewater (De Nardi et al. 2008; Ün et al. 2009; Bazrafshan et al. 2012; Grandclement et al. 2017; Massara et al. 2017; Nancharaiah and Reddy 2017). Thereafter, they found the optimal influencing parameter such as pH, temperature, HRT, OLR and biogas recovery rate was discussed (Akkaya et al. 2015; Antwi et al. 2017a; Appels et al. 2011; Badshah et al. 2012; Basu and Asolekar 2012; Loganath and Mazumder 2018). Even though, few studies reported mainly on the sludge granulation, various bacteria causing the reaction, characterization of the mature sludge in terms of the size, structure, rheology and metabolism of the granular sludge (Abbasi and Abbasi 2012; Abbasi et al. 2012; Alphenaar 1994; Antwi et al. 2017b; Gupta and Gupta 2005). In analysis with the experimental results, only few studies were reported with the computational simulation of the anaerobic reactors. From the in-depth literature

A Study on Selection of the Biofilm for the Hybrid Up-Flow … Table 1 Characteristics of sago wastewater

21

S. No.

Parameters

Observed result (mg/l)

1

pH

4.2–4.6

2

Colour

Milky white

3

Total solids

16,300–16,500

4

Total dissolved solids

8060–14,260

5

Total suspended solids

2240–8240

6

Volatile solids

13,570–14,580

7

Chemical oxygen demand

3000–5000

8

VFA (as acetic acid)

440–450

9

Chlorides

990–1010

10

Acidity

900–1000

survey, it is very clear that no studies were carried out to verify the fluid structure over the biofilm of the any anaerobic reactor. To address this issue in this study, in Hybrid Up-flow Anaerobic Sludge Blanket (HUASB) Reactor the hydrodynamic movement over biofilm was analysed to verify the applicability of that biofilm for the anaerobic reactor.

2 Materials and Methods 2.1 Wastewater Collection The sago industry wastewater was collected from the local industry located near the Erode, Tamil Nadu, India. The detailed characteristics were shown in Table 1. The seed sludge used in this study was collected from the anaerobic reactor treating sago mill wastewater for prolonged period; this has been selected due to it had the sufficient amount of the acetogenesis and methanogenesis bacteria. Because of this criterion, the start-up period has been reduced drastically. The detailed characteristics of the sago wastewater used in this study were shown in Table 1.

2.2 Experimental Set-up The laboratory-scale 4.2 L working volume HUASB Reactor was fabricated with the transparent acrylic fibre material. The specification of the reactor was 100 mm dia with the 600 mm height and 30 mm thickness. Four brass sampling port has been provided at equal distance. The inlet was provided at the bottom most of the reactor and the outlet provided at the top most of the reactor and similarly the gas outlet also provided at the top of the reactor. The gas outlet was attached with the brine

22

R. Loganath et al.

Fig. 1 The top view design of biofilm used in this study. All the units mentioned in mm

solution to evaluate the biogas production through the water displacement method. The reactor was operated under the mesophilic temperature (27 ± 5 °C).

2.3 Biofilm Used in This Study The basic consideration while designing the biofilm was maximum surface area with high porosity. The polypropylene material was selected for fabrication of the biofilm due to its density and recyclable property. Four different biofilms were chosen for the comparison study. The comparison was done with the surface area, porosity, and all the other parameters. Depending on the comparison result, the best biofilm was chosen to fabricate the HUASB Reactor to treat the sago wastewater. The specification of the selected biofilm is as follows: height-30 mm, outer diameter-36 mm, inner diameter-24 mm. The biofilm is designed and fabricated in a hexagonal shape to fit within the reactor. Figure 1 shows the biofilm used in this study. The schematic representation of the biofilm used in this study is shown in Fig. 1.

2.4 Computational Fluid Dynamics Simulation The commercial computational fluid dynamics (CFD) package ANSYS FLUENT was used to simulate the three-dimensional fluid flow inside the reactor before construction of the HUASB Reactor. A conceptual model was developed by the software, and this proposed CFD model is composed of the core hydrodynamics model for the liquid and solid phases, and coupled with the sludge. CFD simulation helps to describe flow of the liquid and solid components of the multiphase flow.

A Study on Selection of the Biofilm for the Hybrid Up-Flow …

23

The continuous phase is the wastewater and sludge, and the dispersed phase is air or biogas. The assumptions made for the dispersed phase are as follows: the bubbles are spherical, the bubbles have constant diameter, no collisions, coalescence or break-up of bubbles, and the gas phase physical properties, for example density and viscosity, were air properties. For the liquid phase, the density was considered to be that of water, while in terms of viscosity. The main objective is to plot a relation between the analytical experiment and mathematical deduction. Upon a successful relation, all further projections can be deduced with the linearity constant. The computational fluid dynamics (CFD) predicts the flow of water from one point to another. The basis is that the fluid experiences an induced shear stress; as a result, it travels from one node to another. Along with the same, the fluid properties are also transferred, and hence, it leaves a trail which is deduced by us.

3 Results and Discussion 3.1 Experimental Results The performance efficiency of the HUASB Reactor was operated at the various OLR with constant HRT to evaluate the maximum COD removal efficiency and the biogas production. The reactor was operated with the different OLR concentration ranging from the 0.75 to 10.0 kg COD/m3 /d with the constant HRT of 10 h. The maximum COD removal efficiency and biogas production were achieved at the OLR of 9.0 kg COD/m3 /d at 88% and 28 L/d, respectively.

3.2 Computational Modelling and Simulation The HUASB Reactor was designed in the ANSYS workbench as per the system protocol. The default meshing was chosen as the fine meshing. In the problem set-up conditions, k-epsilon model was selected with the standard equation. Then, in the materials section the water, solid and air were selected with the required values. Later, in the cell zone condition inlet was selected and water velocity and pressure were adjusted as per the requirements. Thereafter, in the solution settings water pressure method was selected followed by gradient, pressure, momentum, and turbulent kinetic energy values have been provided. Once set up all the initial values, the solution initialization process was initiated to find any errors were there. After the solution initialization process, the number of iterations runs started to solve the problem. After completing the 1000 no. of iterations, all the profiles respect to the fluid flow inside the reactor were visualized inside the reactor. Later on, to check the fluid flow inside the reactor the animation 3D water flow inside the reactor was done. From these results, it clearly shows that the three-dimensional view of the water flow inside the

24

R. Loganath et al.

reactor was clearly seen. The main purpose of this study was to visualize the water flow through the biofilm. To fulfil this purpose, the water flow was designed and passes through the biofilm. It is clear that the motion of the fluid flow was passing easily through the biofilm due to its proper porosity and design of the biofilm. Figure 2a shows the reactor idle condition before start of the operation. During this condition, the reactor was just loaded with the sludge and rest of the portion was filled with the wastewater for the beginning of the operation. Initially (at time zero), the movement of fluid inside the reactor is nil. From Fig. 2b, it is clear that during the flow how the influent wastewater was moving inside the reactor. In Fig. 2, inside the biofilm there was one round of triangle clearance and another rectangle shape clearance was provided for the purpose of attachment of sludge particles for the sake of better attach growth process. The flow of fluid was satisfactory through out the biofilm which is an important factor for the attached growth process. The outer biofilm portions have some low-velocity movement, and the inside the biofilm, the fluid movement was faster and it can be inferred from the contours scale. From Fig. 3a, b, fluid movement throughout the reactor can be visualized. Figure 3a shows the initial fluid movement inside the reactor at the beginning of the time. From Fig. 3b, it shows that the fluid movement during the flow over the

a

b

Fig. 2 a Hydrodynamic movement inside the reactor before giving the feed and b hydrodynamic movement inside the reactor after giving the feed

a

b

Fig. 3 a Hydrodynamic movement inside the reactor during the feed and b hydrodynamic movement inside the reactor during the feed

A Study on Selection of the Biofilm for the Hybrid Up-Flow …

25

biofilm. In Fig. 3b, it shows that the hydraulic movement occurs smoothly without barriers, because of the proper design of the biofilm as well as the fluid flow outside the biofilm also has proper flow due to the hexagonal shape design and there was a clearance between the two biofilms.

4 Conclusions In this study, it is demonstrated that the proper description of the fluid flow interactions and its behaviour inside the reactor is necessary for the better performance to run the reactor. Various earlier studies reported that industrial-scale reactors are facing the problem with the selection of proper biofilm design and this was affecting while operating the hybrid anaerobic reactors. Compared to the laboratory-scale reactor, this kind of study is more profitable for industrial-scale or pilot-scale/full-scale reactors. This kind of pre-requisite studies is very useful to design the large-scale reactors for different industries which reduces the operational cost and maintenance cost.

References Abbasi T, Abbasi S (2012) Formation and impact of granules in fostering clean energy production and wastewater treatment in upflow anaerobic sludge blanket (UASB) reactors. Renew Sustain Energy Rev 16:1696–1708 Abbasi T, Sanjeevi R, Makhija M, Abbasi S (2012) Role of vitamins B-3 and C in the fashioning of granules in UASB reactor sludge. Appl Biochem Biotechnol 167:348–357 Akkaya E, Demir A, Varank G (2015) Estimation of biogas generation from a UASB reactor via multiple regression model. Int J Green Energy 12:185–189 Alphenaar PA (1994) Anaerobic granular sludge. Alphenaar Antwi P, Li J, Boadi PO, Meng J, Quashie FK, Wang X, Ren N, Buelna G (2017a) Efficiency of an upflow anaerobic sludge blanket reactor treating potato starch processing wastewater and related process kinetics, functional microbial community and sludge morphology. Bioresour Technol 239:105–116 Antwi P, Li J, Boadi PO, Meng J, Shi E, Xue C, Zhang Y, Ayivi F (2017b) Functional bacterial and archaeal diversity revealed by 16S rRNA gene pyrosequencing during potato starch processing wastewater treatment in an UASB. Bioresour Technol 235:348–357 Appels L, Lauwers J, Degrève J, Helsen L, Lievens B, Willems K, Van Impe J, Dewil R (2011) Anaerobic digestion in global bio-energy production: potential and research challenges. Renew Sustain Energy Rev 15:4295–4301 Badshah M, Parawira W, Mattiasson B (2012) Anaerobic treatment of methanol condensate from pulp mill compared with anaerobic treatment of methanol using mesophilic UASB reactors. Bioresour Technol 125:318–327 Basu D, Asolekar SR (2012) Performance of UASB reactor in the biotreatment of 1,1,2trichloroethane. J Environ Sci Health Part A 47:267–273 Bazrafshan E, Mostafapour FK, Farzadkia M, Ownagh KA, Mahvi AH (2012) Slaughterhouse wastewater treatment by combined chemical coagulation and electrocoagulation process. PLoS ONE 7:e40108

26

R. Loganath et al.

Bustillo-Lecompte CF, Mehrvar M (2016) Treatment of an actual slaughterhouse wastewater by integration of biological and advanced oxidation processes: modeling, optimization, and costeffectiveness analysis. J Environ Manage 182:651–666 Chatterjee P, Ghangrekar M, Rao S (2018) Sludge granulation in an UASB–moving bed biofilm hybrid reactor for efficient organic matter removal and nitrogen removal in biofilm reactor. Environ Technol 39:298–307 De Nardi I, Fuzi T, Del Nery V (2008) Performance evaluation and operating strategies of dissolvedair flotation system treating poultry slaughterhouse wastewater. Resour Conserv Recycl 52:533– 544 Granada CE, Hasan C, Marder M, Konrad O, Vargas LK, Passaglia LM, Giongo A, de Oliveira RR, Pereira LdM, de Jesus Trindade F (2018) Biogas from slaughterhouse wastewater anaerobic digestion is driven by the archaeal family Methanobacteriaceae and bacterial families Porphyromonadaceae and Tissierellaceae. Renew Energy 118:840–846 Grandclement C, Seyssiecq I, Piram A, Wong-Wah-Chung P, Vanot G, Tiliacos N, Roche N, Doumenq P (2017) From the conventional biological wastewater treatment to hybrid processes, the evaluation of organic micropollutant removal: a review. Water Res Gupta SK, Gupta S (2005) Morphological study of the granules in UASB and hybrid reactors. Clean Technol Environ Policy 7:203–212 Jiang J, Wu J, Zhang J, Poncin S, Li HZ (2014) Multiscale hydrodynamic investigation to intensify the biogas production in upflow anaerobic reactors. Bioresour Technol 155:1–7 Krithika D, Philip L (2016) Treatment of wastewater from water based paint industries using submerged attached growth reactor. Int Biodeterior Biodegrad 107:31–41 Liu Y, Tay J-H (2002) The essential role of hydrodynamic shear force in the formation of biofilm and granular sludge. Water Res 36:1653–1665 Liu X, Yang J, Ye T, Han Z (2018) Establishment of analysis method for methane detection by gas chromatography. In: IOP conference series: earth and environmental science. IOP Publishing, p 012023 Loganath R, Mazumder D (2018) Performance study on organic carbon, total nitrogen, suspended solids removal and biogas production in hybrid UASB reactor treating real slaughterhouse wastewater. J Environ Chem Eng 6:3474–3484 Massara TM, Komesli OT, Sozudogru O, Komesli S, Katsou E (2017) A mini review of the technoenvironmental sustainability of biological processes for the treatment of high organic content industrial wastewater streams. Waste Biomass Valorization 8:1665–1678 Nancharaiah Y, Reddy GKK (2017) Aerobic granular sludge technology: mechanisms of granulation and biotechnological applications. Bioresour Technol Rajakumar R, Meenambal T, Banu JR, Yeom I (2011) Treatment of poultry slaughterhouse wastewater in upflow anaerobic filter under low upflow velocity. Int J Environ Sci Technol 8:149–158 Ren TT, Mu Y, Ni BJ, Yu HQ (2009) Hydrodynamics of upflow anaerobic sludge blanket reactors. AIChE J 55:516–528 Schaider LA, Rodgers KM, Rudel RA (2017) Review of organic wastewater compound concentrations and removal in onsite wastewater treatment systems. Environ Sci Technol Sokkanathan G, Sharmila VG, Kaliappan S, Banu JR, Yeom IT, Rani RU (2018) Combinative treatment of phenol-rich retting-pond wastewater by a hybrid upflow anaerobic sludge blanket reactor and solar photofenton process. J Environ Manage 206:999–1006 Ün ÜT, Koparal AS, Ö˘gütveren ÜB (2009) Hybrid processes for the treatment of cattleslaughterhouse wastewater using aluminum and iron electrodes. J Hazard Mater 164:580–586 Worku Z, Leta S (2017) Anaerobic digestion of slaughterhouse wastewater for methane recovery and treatability. Int J Sustain Green Energy 6:84 Yan LK, Fung KY, Ng KM (2017) Aerobic sludge granulation for simultaneous anaerobic decolorization and aerobic aromatic amines mineralization for azo dye wastewater treatment. Environ Technol 1–23

A Study on Selection of the Biofilm for the Hybrid Up-Flow …

27

Zinatizadeh A, Mohammadi P, Mirghorayshi M, Ibrahim S, Younesi H, Mohamed A (2017) An anaerobic hybrid bioreactor of granular and immobilized biomass for anaerobic digestion (AD) and dark fermentation (DF) of palm oil mill effluent: mass transfer evaluation in granular sludge and role of internal packing. Biomass Bioenergy 103:1–10

Experimental Investigations on the Combined Effect of TiO2 Nanoadditive and EGR on Engine Performance by Using Mimusops Elangi Biodiesel Blend R. L. Krupakaran, B. Dhinesh, B. Sachuthananthan, and N. Manigandan Abstract The present study focused on combined effect of titanium oxide nanoparticles dispersed into B20 and EGR (Exhaust Gas Recirculation) on the performance and pollutant of a CI engine has been examined. A 25 ppm of titanium oxide nanoparticles (TON) was blended with B20 sample (20% of Mimusops Elangi biodiesel + 80% of diesel) by using ultrasonication process. Moreover, EGR was implemented to diminish nitrogen oxide (NOx ) of a CI engine. The experimental runs were performed on four-stroke CI engine with various fuels like diesel, B20, B20TO25, B20TO25 + 5% EGR-, B20TO25 + 10% EGR-, B20TO25 + 15% EGR-, B20TO25 + 20% EGR-tested fuel samples at various conditions of load. The outcomes of the experimentations reveals that BTE of B20TO25 + 15% EGR fuel decreased by 6.56% and BSFC increased by 6.46% compared to the B20TO25 but for B20TO25 + 15% EGR fuel samples decrease the maximum amount of emission levels with respect to other tested fuels especially NOx was reduced by 32% compared with B20TO25 at full load condition. Keywords Mimusops Elangi biodiesel blend · Titanium oxide nanoparticles · Performance · Emission · Exhaust gas recirculation

1 Introduction An increasing Urbanizing, Population that increases the demand for the diesel fuel and uncontrolled extraction of petroleum derivative, which actuated to look an alternate fuel for diesel engines. Rising energy requirements are the primary explanation behind developing alternative energy across the world (Sanjid et al. 2014). The R. L. Krupakaran (B) · B. Sachuthananthan · N. Manigandan Department of Mechanical Engineering, Sree Vidyanikethan Engineering College, Tirupati, Andhra Pradesh, India e-mail: [email protected] B. Dhinesh Department of Mechanical Engineering, Mepco Schlenk Engineering College, Sivakasi, Virudhunagar, Tamil Nadu, India © Springer Nature Singapore Pte Ltd. 2020 S. K. Ghosh et al. (eds.), Emerging Technologies for Waste Valorization and Environmental Protection, https://doi.org/10.1007/978-981-15-5736-1_4

29

30

R. L. Krupakaran et al.

biodiesel is the only source for replacement of diesel fuel without any engine modification (Girdhar et al. 2017). The researchers focused on Mimusops Elangi biodiesel at a various blends on performance on diesel engine (Krupakaran et al. 2018a) and perceived that increase in BTE and decreased the BSFC at 20% blend. Also, it has been stated that the emissions like HC, CO, and smoke were decreased drastically and, other side, marginally increased in NOx emissions for B20 blend at full load condition. The second-generation researchers were concentrated on waste cooking oil and third generation focused on Grass oil and the algae-based biofuel as an alternative for diesel fuel (Kumar et al. 2013; Dhinesh et al. 2016). Later the researchers concentrated on nanoparticle as additives, it dispersed into the tested fuel blends which in turn for improving the fuel properties and performance of the engine and minimize the pollutants in CI engine to tested fuel blends to improve the engine performance and decrease the emission levels (Shaafi et al. 2015). Performance of the engine and characteristics of pollutants with the inclusion of CeO2 nanoparticles to the rice brain methyl ester and its mixture were studied. The researchers investigated the engine performance and emissions characteristics of diesel engine powered with modified fuel (B20 with addition of CeO2 nanoparticle). The results reveal that there is improvement in engine performance and reduction in emission magnitude such as HC, CO, and NOx (Karthikeyan et al. 2016). Again the researchers were focused on the impact of boron, iron, and aluminum nanoparticles in addition with diesel fuel on CI engine. They observed the BTE was increased by 9% for alumina, 4% for boron, and 2% for iron 8 and 4% for alumina reduced nanoparticles respectively, and the pollutants like CO and HC and iron nanofuels but marginally increased NOx emissions (Rakhi et al. 2014). The cerium oxide was synthesized by sol-gel method and examined the characteristics of Cerium oxide (CeO2 ) nanoparticles by XRD, SEM, TEM, and EDAX. The influence of CeO2 nanoparticles as an additive for Cymbopogon flexuous biofuel on performance of the engine and pollutants were explored. The outcomes exhibited the superior performance and decreased the emission levels with addition of CeO2 nanoparticle to biofuel (Annamalai et al. 2016). The author conducted the experiment on Mahua oil methyl ester with the addition of copper oxide nanoparticle for diesel engine. They resulted that the BTE was improved by 2.19% for the B20 blend with addition of 50 ppm CuO2 nanoparticles equated to the B20-blended samples (Vijayakumar et al. 2016). The researchers focused on CI engine performance by applying waste cooking oil methyl ester with inclusion of alumina nanoparticles. They reported that both BTE and EGT were raised by 10.36 and 5.8%, respectively; however, the emissions like CO and HC were diminished by 2.94 and 20.56% and the emission NOx was improved by 43.61% with the inclusion of alumina nanoparticle (Hosseini et al. 2017). The palm oil methyl ester with addition of γ-Al2 O3 nanoparticle additive on engine performance, combustion, and emission magnitude was analyzed. It revealed that superior performance and decreased emission levels were achieved (Krupakaran et al. 2016). The author also investigated the different injection timings on engine performance with Mimusops Elangi biodiesel with titanium oxide nanoparticle. The result revealed that at an injection timing 25° bTDC the BTE was improved and decreased the emission

Experimental Investigations on the Combined Effect of TiO2 …

31

levels (Krupakaran et al. 2018b). The performance characteristics on diesel engine using different biodiesels with various nanoparticle additives have been presented by different authors in various papers, and their results proven that the improvement in performance and reduction in emission levels (Dhinesh et al. 2017a; Madhan Raj et al. 2016; Dhinesh and Annamalai 2018; Vigneswaran et al. 2018; Ramalingam et al. 2018). When the combustion temperature increases, this leads to development of NOx emission magnitude in CI engine. The NOx emission increased because nitrogen is reacted with oxygen at higher temperatures (Oberweis and Al-Shemmeri 2010). Many researchers have been described that biodiesel contains excess oxygen buffer that leads to superior combustion and decreased the exhaust pollutants but increased the NOx emissions of diesel engine (Alagu and Sundaram 2010; Belagur and Chitimini 2010; Mohon Roy 2011). The researcher investigated the addition of alumina nanoparticles with Calophyllum Inophyllum biodiesel blend on CI engine performance with 40 ppm at 20% EGR and it has been perceived that the pollutants of NOx were getting reduced by 36.84% for CIB20ANP40 + 20% EGR while comparing with the B20 at peak load (Anchupogu et al. 2017). The author conducted the experiment on CI engine with the amalgamated effect of EGR and DTBP (Di Tertiary Butyl Peroxide) and reported that at 15% EGR exhibits in higher BTE and lower BSFC. It has been established that with the amalgamated influence of EGR and cetane enhancer decreases the NOx pollutants by 25% but remaining pollutants like CO, HC, and smoke opacity were getting increased (Venkateswarlu et al. 2013). The researcher incorporated the EGR technique to minimize the NOx pollutants from the exhaust of diesel engines. They allowed the part of exhaust gas into engine cylinder to reduce the heat release rate in the combustion chamber, which leads to the reduction of NOx emission (Ladommatos et al. 1998). Other researchers conducted the experiments on diesel engine by using Jatropha methyl ester with EGR technique to reduce the NOx emission (Gomaa et al. 2011). However, Jatropha methyl ester amalgamated with EGR in diesel engines, which reduces NOx emissions significantly (Pradeep and Sharma 2007). The NOx emission was reduced by 25% with respect to diesel fuel by providing 15% EGR with sunflower methyl ester biodiesel blend (B20) reported by the author (Rajana and Senthilkumar 2009). The researcher described that higher EGR provides a fruitful way for reducing the NOx pollutant with fulfill the EURO-V norms and emission of NOx from the outlet gas of the CI engine are, the more effect on human health and the environment (Peixoto et al. 2009; Vallero 2014). Few authors examined the significance of EGR on engine behavior and emission magnitude (Mailboom et al. 2007; Yasin et al. 2017). For enhancing the thermal efficiency and minimization of emission levels, few authors concentrated on fuel modification and engine modification. They revealed that better performance was achieved for both the cases (Balasubramanian et al. 2018; Dhinesh et al. 2017b, 2018; Lalvani et al. 2015, 2016). The present study focused on combined effect of titanium oxide nanoparticles dispersed into B20 and EGR on the behavior of the engine and pollutant of a diesel engine was examined. A 25 ppm of titanium oxide nanoparticles (TON) was blended with B20 sample by the process of ultrasonication. Moreover, EGR was implemented to diminish oxides of nitrogen (NOx ) pollutants of a CI engine.

32

R. L. Krupakaran et al.

2 Materials and Methods 2.1 Preparation of Biodiesel Blends M. Elangi oil seeds were collected from Sree Vidyanikethan Engineering College, Andhra Pradesh, Tirupati, and it was dried for a week in sunlight and decorticated manually. The seed has been separated from the fruit by manually. The pulp and shell were separated by hammering the seed at upright position. The oil was extracted by mechanical extraction. Mimusops Elangi methyl esters is made by transesterification process by using methyl alcohol and KOH as catalyst.

2.2 Preparation of Nanofluid Synthesis of titanium oxide nanoparticles was carried out using sol-gel combustion technique. The 25 ppm of titanium oxide nanoparticles were disseminated into B20 blend with the help of an ultrasonicator. The following fuels were prepared from various methods: 20% of Mimusops Elengi biodiesel and 80% diesel (B20 + 80D), 25 ppm of titanium oxide nanoparticle with 20% of Mimusops Elengi biodiesel and 80% diesel (B20 + 25 ppm), the detailed test fuel properties are represented in Table 1 and preparation of nanofluid are shown in Fig. 1.

2.3 Characterization of TiO2 The typical XRD pattern of TiO2 nanoparticles is depicted in Fig. 2. All the diffraction peaks are in good agreement with the tetragonal structure of TiO2 . Figure 3 shows the SEM micrograph of prepared TiO2 nanoparticles with different magnification. Figure 4 represents the TEM images of prepared titanium oxide nanoparticles calcined at 600 °C. The particle size of the sample ranges between 10 and 20 nm, which are in good agreement with the result evaluated from XRD studies. Table 1 Table 1 The comparison of properties of nanofuel with diesel fuel Properties

ASTM standards

Diesel

B20 + 80D

B20 + 80D 25 ppm

Kinematic viscosity (cSt) @40 °C

ASTM D445

2.14

2.76

3.13

Density (kg/m3 ) @ 15 °C

ASTM D1298

831

843

845.7

Calorific value (MJ/kg)

ASTM D6751

44.5

43.574

43.67

Flash point (°C)

ASTM D92

52

76

82

Cetane number

ASTM D613

55

53

52

Experimental Investigations on the Combined Effect of TiO2 …

33

Fig. 1 Preparation of nanofluid

Fig. 2 XRD pattern of titanium oxide nanoparticles

exhibits the properties of B20 sample and nanofuel, and Table 2 depicts the detailed specification of the engine.

34

R. L. Krupakaran et al.

Fig. 3 SEM analysis

Fig. 4 TEM report

2.4 Experimental Arrangement and Method of Operation The experimental runs were performed on four-stroke diesel engine, single cylinder, with an electrical loading. The CI engine is run at 1500 rpm (invariable speed). The Kistler pressure transducer measured the pressure inside of the cylinder, which is

Experimental Investigations on the Combined Effect of TiO2 … Table 2 Test engine specification

Engine make

35

Kirloskar TAF1

Type

Vertical diesel engine, four stroke

No. of cylinders, fuel

One, diesel

Cooling system

Air cooled

Ignition system

Compression ignition

Rated brake power

4.4 kW @ 1500 rpm

Displacement

661 cm3

Bore and stroke

87.5 and 110 mm

Compression ratio

17.5:1

Injection timing

23° bTDC (rated)

Injection pressure

200 bar

located on head of the cylinder. The engine details of the engine are given in Table 2. The emissions from outlet were assessed using AVL Digas 444N gas analyzer. The opacity of smoke has been assessed by means of AVL 437C smoke meter. The schematic of test setup was depicted in Fig. 5. Initially, the CI engine was running with standard diesel fuel and later remaining fuel was considered at various load conditions like 0, 25, 50, 75, and 100% (McLaughlin et al. 2006; Parthasarathy et al. 2016; Subramani et al. 2018).

Fig. 5 Test engine setup

36

R. L. Krupakaran et al.

Fig. 6 Schematic diagram of EGR system

2.5 The Exhaust Gas Recirculation (EGR) EGR is a standout among the best strategies to control NOx discharges from the exhaust of diesel engine. The principle work of providing EGR is to reduce the oxygen concentration and increase the heat absorption rate. A partial amount of exhaust gas along with fresh air was admitted into cylinder to decrease the NOx emission. The EGR valve has been used for controlling the rate of flow of outlet gas recirculation. The % EGR was evaluated from the concentration of CO2 at the entry to the CO2 concentration in the outlet by using following Eq. (1). %EGR =

Volume of EGR × 100 Total charge intake into the cylinder

Another way to define the EGR ratio is by the use of CO2 concentration (Krupakaran et al. 2018a): EGR ratio =

[CO2 ]intake − [CO2 ]ambient [CO2 ]exhaust − [CO2 ]ambient

(1)

The experimental setup of Exhaust gas recirculation is shown in Fig. 6.

2.6 Uncertainty Analysis The uncertainty analysis in terms of percentage of different parameters such as pressure and speed was analyzed by the square root method. The following equation used to calculate the overall percentage of uncertainty: Percentage of Uncertainty =

√ (Pr)2 + (Speed)2 + (Load)2 + (BP)2 + (BSFC)2

Experimental Investigations on the Combined Effect of TiO2 …

37

+(ETE)2 + (HC)2 + (CO)2 + (NOx)2 + (Smoke)2 √ = (1.1)2 + (1.2)2 + (0.6)2 + (0.5)2 + (0.3)2  +(0.4)2 + (0.2)2 + (0.6)2 + (0.5)2 + (0.83)2 = 2.2%



3 Results and Discussion 3.1 Brake Thermal Efficiency The discrepancy of BTE is illustrated in Fig. 7 with different loads for diesel, B20, B20TONP25, B20TONP25 + 5% EGR-, B20TONP25 + 10% EGR-, B20TONP25 + 15% EGR-, and B20TONP25 + 20% EGR-tested fuel samples. The BTE increases with increment of load for all the fuel tests. It is perceived that the BTE of the B20TONP25-tested fuel is more than the B20 fuel samples due to more oxygen and calorific value in the tested fuel (Krupakaran et al. 2016). However, the BTE reduced when EGR percentage increased. This happens because of lower oxygen present inside the cylinder. In addition, the exhaust gas absorbed the part of heat energy available in the cylinder. The result revealed that the BTE of B20TONP25 + 15% EGR decreased by 6.56% with respect to the B20 fuel. This happens because of the lower oxygen molecules present in the air, which tends to reduction of engine efficiency.

Brake thermal Efficiency (%)

35 diesel

30

B20

25

B20+25ppm

20

B20+25ppm & 5% EGR B20+25ppm & 10% EGR

15

B20+25ppm & 15% EGR

10

B20+25ppm & 20% EGR 5 0 0

25

50

75

100

Load (%)

Fig. 7 Variation of brake thermal efficiency with load

38

R. L. Krupakaran et al.

Brake Specific fuel consump on (Kg/kW.hr)

0.8 0.7

DIESEL

0.6

B20

0.5

B20+25ppm

0.4

B20+25ppm & 5% EGR B20+25ppm & 10% EGR

0.3

B20+25ppm & 15% EGR

0.2

B20+25ppm & 20% EGR

0.1 0 0

25

50

75

100

Load (%)

Fig. 8 Variation of brake-specific fuel consumption with load

3.2 Brake-Specific Fuel Consumption The discrepancy of BSFC with various loads are illustrated in Fig. 8 and for diesel, B20, B20TONP25, B20TONP25 + 5% EGR-, B20TONP25 + 10% EGR-, B20TONP25 + 15% EGR-, and B20TONP25 + 20% EGR-tested fuel samples. The BSFC decreases with an increment in testing load for all tested fuels. The BSFC was increased by 8.6% for B20TONP25 + 15% EGR fuel while comparing with the diesel fuel. This could be due to superior viscosity and lesser calorific value of biodiesel (Anchupogu et al. 2017). With 25 ppm of titanium oxide nanoparticles into B20 fuel (B20TONP25), the BSFC was decreased by 6.46% while comparing with the B20 fuel. This happens because of better air–fuel mixture and more availability of oxygen results in increase of the surface to volume ratio due to presence of nanoparticles. More oxygen buffers present in the fuel and which increases the combustion rate, this could be due to a catalytic effect of nanoparticles (Madhan Raj et al. 2016). The BSFC of B20TONP25 fuel with EGR increases with increasing the load. By providing EGR, the insufficiency of oxygen element present in the air, which tends to incomplete combustion of the tested fuel (Yasin et al. 2017).

3.3 Heat Release Rate (HRR) and Cylinder Pressure (CP) Figures 9 and 10 depict the deviations of HRR and CP with respect to the angle of crank for diesel, B20, B20TONP25, B20TONP25 + 5% EGR-, B20TONP25 + 10% EGR-, B20TONP25 + 15% EGR-, and B20TONP25 + 20% EGR-tested fuel samples. B20TONP25 fuel shows the better HRR while comparing with B20 sample and other fuel samples due to the presence of rich oxygen content in the tested fuel which leads to provide more HRR and CP. The brake thermal efficiency has been

Experimental Investigations on the Combined Effect of TiO2 …

39

140 Heat Release Rate (J/Deg.CA)

120 100

Diesel

80

B20 B20+25ppm

60

B20+25ppm+5%EGR B20+10% EGR

40

B20+15%EGR

20

B20+25ppm+20%EGR

0 -40

-20

-20

0

20

40

60

80

100

Crank angle (deg)

Fig. 9 Variation of heat release rate with crank angle 80 70

Diesel B20 B20+25ppm B20+25ppm +5% EGR B20+25ppm +10% EGR B20+25ppm +15% EGR B20+25ppm +20% EGR

Pressure (bar)

60 50 40 30 20 10 0 -400

-200

0

200

400

Crank Angle (deg)

Fig. 10 Variation of cylinder pressure with crank angle

increased due to higher cylinder pressure (CP) and heat release rate (HRR), whereas CP and HRR decrease while EGR percentage increases, and this could be because of insufficient oxygen available in the cylinder and because CO2 absorbs the heat release in the cylinder (Anchupogu et al. 2017).

3.4 Carbon Monoxide The variant of CO pollutant with the different loads for all considered tested fuels are illustrated in Fig. 11. It is identified that CO pollutants for B20 sample fuel was less while comparing with standard diesel fuel, this is due to the presence of rich oxygen

40

R. L. Krupakaran et al. 0.2 0.18

DIESEL

0.16

B20

0.14

B20+25ppm B20+25ppm+5%EGR

CO (% Vol)

0.12

B20+25ppm+10%EGR

0.1

B20+25ppm+15%EGR 0.08 B20+25ppm+20%EGR 0.06 0.04 0.02 0 25%

50%

75%

100%

LOAD (%)

Fig. 11 Variation of CO with load

content in the tested fuel. The CO emission magnitude was decreased by 9.03% for modified fuel (B20+25ppm TiO2 ) while comparing with B20 fuel. This is due to the enhanced combustion with the addition of titanium oxide nanoparticles in the biodiesel samples (Sanjid et al. 2014). It is also identified that CO pollutants increase by 12.83, 19.62, 24.58, and 32.45%, with the EGR modes 5, 10, 15, and 20% equated with B20 at peak load condition. This could be due to insufficiency of oxygen present in the combustion chamber, which leads to the CO pollutant formation (Dhinesh et al. 2017a).

3.5 Hydrocarbons Figure 12 shows that the pollutants of HC with respect to different loads for all the tested fuel samples. It is noticed that pollutants of HC are lesser for tested blends while comparing with diesel fuel. This could be due to the improved combustion inside the engine cylinder (Anchupogu et al. 2017). The addition of titanium oxide nanoparticle into B20 fuel leads to reduction in the HC emissions by 14.64%, while comparing with the B20 fuel the presence of nanoparticles in the biodiesel blend samples reduces the temperature of carbon activation and endorses the improved combustion (Krupakaran et al. 2016). It is also noticed that the pollutants of HC were increased for all the EGR condition. It is 18.62, 23.24, 29.36, and 33.24% with the EGR modes 5, 10, 15, and 20% compared to B20 at 100% load condition.

Experimental Investigations on the Combined Effect of TiO2 … 30

DIESEL B20 B20+25ppm B20+25ppm+5%EGR B20+25ppm+10%EGR B20+25ppm+15%EGR B20+25ppm+20%EGR

25 20 HC (ppm)

41

15 10 5 0 25%

50% LOAD (%)

75%

100%

Fig. 12 Variation of HC with load

Insufficiency of oxygen present in the combustion chamber tends to the CO pollutant formation (Dhinesh et al. 2017a). With all percentage of EGR increases consequences in deprived combustion and tends to the HC pollutant formation (Mailboom et al. 2007).

3.6 Oxides of Nitrogen Figure 13 shows that variant of NOx pollutant with respect to different loads for all tested fuel samples. The pollutants of NOx were getting increased with an increment in testing load for all tested fuel samples. It is identified that emissions of NOx for the B20 are superior to the standard diesel fuel. This could be due to increased ABT which means adiabatic flame temperature and rich oxygen contents present in the biodiesel-blended samples, that leads to an improvement in the nitrogen oxide pollutants formation (Yasin et al. 2017). The emissions of NOx decreased by 15.56% with the addition of TiO2 nanoparticles to the B20-blended fuel samples while comparing with B20 fuel sample. This could be capable of increasing catalytic activity and thereby makes possibility of nanoparticles to scavenge nitric oxide radical (Dhinesh et al. 2017a). The NOx emissions have been decreased by 35.56% provided the EGR to the engine fueled with B20TON25 while comparing with that of B20 fuel samples which causes reduction in EGR temperature of flames, due to the lesser amount of oxygen present in the combustion chamber. It is also resulted that emissions of NOx were significantly reduced for the B20TON25 + 15% EGR.

0

200

400

600

800

1000

1200

1400

25%

Fig. 13 Variation of NOx with load

NOx(ppm)

1600

50% LOAD (%)

75%

100%

DIESEL B20 B20+25ppm B20+25ppm+5%EGR B20+25ppm+10%EGR B20+25ppm+15%EGR B20+25ppm+20%EGR

42 R. L. Krupakaran et al.

Smoke opacity (FSN)

Experimental Investigations on the Combined Effect of TiO2 …

50 45 40 35 30 25 20 15 10 5 0

43

DIESEL B20 B20+25ppm B20+25ppm+5%EGR B20+25ppm+10%EGR B20+25ppm+15%EGR B20+25ppm+20%EGR 25%

50%

75%

100%

LOAD (%) Fig. 14 Variation of smoke with load

3.7 Smoke Opacity The disparity of smoke opacity with different tested loads for all tested fuels is illustrated in Fig. 14. It is noticed that smoke opacity for B20-blended sample fuel was inferior to the standard diesel fuel. This could be higher a cetane number and inbuilt oxygen presence in the biodiesel that results in improved combustion and getting decreases the smoke opacity (Anchupogu et al. 2017). The smoke opacity was decreased by 4.2% for B20TON25 compared with B20. This could be due to improved mixture of air–fuel with the nanoparticles that tends to improvement in rate of combustion and getting decreased in smoke opacity. It also resulted that smoke opacity was getting increased by 28.72% and 34.62%, respectively, with B20TON25 ppm + 15% EGR and B20TON25 ppm + 20% EGR fuel while comparing with the B20 fuel samples without EGR. The EGR reduces the content of oxygen in the engine cylinder, and it tends to an increase in the smoke opacity. Due to amalgamated effect of titanium oxide, nanoparticles, and EGR to the B20 fuel sample (B20TON25 ppm + 15% EGR), the smoke was getting decreased in an acceptable manner.

4 Conclusions As per the exploration performed, the conclusions are made on combined influence of nanoparticle additive and EGR on diesel engine fueled with diesel, B20, B20ANP25, B20ANP25 + 5% EGR, B20ANP25 + 10% EGR, B20ANP25 + 15% EGR, and B20ANP25 + 20% EGR, at various tested load conditions were focused as following:

44

R. L. Krupakaran et al.

• The BTE for all tested fuel with EGR percentage was getting decreased while comparing with standard diesel fuel and with B20 fuel samples. The BSFC is a reciprocal of BTE. Hence, BSFC getting increased with an increment in EGR percentage for all tested fuel samples. • For combustion phenomena, both HRR and CP were getting increased due to addition of titanium oxide nanoparticle for B20 while comparing with diesel fuel and with B20. This could be due to rich oxygen content present in the fuel which in turn increases the combustion rate and hence increases the both heat HRR and CP. But, when EGR percentage increases to B20TON25 ppm both HRR and cylinder pressure decrease. This could be due to insufficient oxygen present in the fuel. Further, CO2 present in the exhaust which control the combustion rate and hence decrease the HRR and CP. • Pollutants such as CO, HC, and smoke decrease for both B20 fuel sample and B20TON25 ppm fuels while comparing with the diesel fuel. This could be due to more oxygen available in the fuels which in turn increase the combustion efficiency and decrease the emissions like CO, HC, and smoke. Whereas increasing the EGR percentage, the emissions namely CO, HC, and smoke were getting increased because of incomplete combustion in the cylinder due to unavailable oxygen in the cylinder. • The NOx pollutant is mainly, due to the rise the cylinder temperature. When adding titanium oxide for B20 fuel which enhance the combustion rate, hence it increase the cylinder temperature, which leads to increase the NOx emission. Whereas, when EGR percentage increase for B20TON25 ppm fuel the NOx emission drastically decreases due to incomplete combustion and less quantity of oxygen present in the cylinder. • The main motivation to adopt both nanoadditive and EGR technique is to improve the BTE and decrease the NOx emission, which achieved by the fuel at B20TON25 ppm + 15% EGR. The 15% EGR was shown a reasonable level of thermal efficiency and more reduction in NOx emission levels.

Nomenclature 20% of Mimusops Elangi biodiesel + 80% of diesel 20% of Mimusops Elangi biodiesel + 80% of diesel with 25 ppm of TiO2 B20TO25 + 5% EGR 20% of Mimusops Elangi biodiesel + 80% of diesel with 25 ppm of TiO2 with 5% EGR B20TO25 + 10% EGR 20% of Mimusops Elangi biodiesel + 80% of diesel with 25 ppm of TiO2 with 10% EGR B20TO25 + 15% EGR 20% of Mimusops Elangi biodiesel + 80% of diesel with 25 ppm of TiO2 with 15% EGR B20TO25 + 20% EGR 20% of Mimusops Elangi biodiesel + 80% of diesel with 25 ppm of TiO2 with 20% EGR B20 B20TO25

Experimental Investigations on the Combined Effect of TiO2 …

SEM TEM XRD

45

Scanning Electron Microscopy Transmission Electron Microscopy X-ray diffractometer

Acknowledgements The authors acknowledge the Sophisticated Test and Instrumentation Centre, Cochin University of Science and Technology Cochin—682022, Kerala, India, for providing the SEM, XRD, and EDS reports of titanium oxide nanoparticles.

References Alagu RM, Sundaram EG (2010) Nitrogen oxide emission in biodiesel fuelled CI engines—a review. In: Frontiers in automobile and mechanical engineering (FAME), 25–27 Nov 2010 Anchupogu P, Rao LN, Banavathu B (2017) Effect of alumina nano additives into biodiesel-diesel blends on the combustion performance and emission characteristics of a diesel engine with exhaust gas recirculation. Environ Sci Pollut Res. https://doi.org/10.1007/s11356-018-2366-7 Annamalai M, Dhinesh B, Nanthagopal K, Sivarama Krishnan P, Lalvani JIJR, Parthasarathy M, Annamalai K (2016) An assessment on performance, combustion and emission behavior of a diesel engine powered by ceria nanoparticle blended emulsified biofuel. Energy Convers Manage 123:372–380 Balasubramanian D, Arumugam SRS, Subramani L, Chellakumar IJLJS, Mani A (2018) A numerical study on the effect of various combustion bowl parameters on the performance, combustion, and emission behavior on a single cylinder diesel engine. Environ Sci Pollut Res 25(3):2273–2284 Belagur KV, Chitimini VR (2010) Effect of injector opening pressures on the performance, emission and combustion characteristics of diesel engine running on honne oil and diesel fuel blend. Therm Sci 14(4):1051–1061 Dhinesh B, Annamalai M (2018) A study on performance, combustion and emission behaviour of diesel engine powered by novel nano nerium oleander biofuel. J Clean Prod 196:74–83 Dhinesh B, Lalvani JIJR, Parthasarathy M, Annamalai K (2016) An assessment on performance, emission and combustion characteristics of single cylinder diesel engine powered by Cymbopogon flexuosus biofuel. Energy Convers Manage 117:466–474 Dhinesh B, Bharathi RN, Lalvani JIJR, Parthasarathy M, Annamalai K (2017a) An experimental analysis on the influence of fuel borne additives on the single cylinder diesel engine powered by Cymbopogon flexuosus biofuel. J Energy Inst 90(4):634–645 Dhinesh B, Annamalai M, Lalvani JIJR, Annamalai K (2017b) Studies on the influence of combustion bowl modification for the operation of Cymbopogon flexuosus biofuel based diesel blends in a DI diesel engine. Appl Therm Eng 112:627–637 Dhinesh B, Raj YMA, Kalaiselvan C, Krishnamoorthy R (2018) A numerical and experimental assessment of a coated diesel engine powered by high-performance nano biofuel. Energy Convers Manag 171:815–824 Girdhar J, Jitendra KP, Sravendra R, Devendra SR (2017) Challenges and opportunities for the application of biofuel. Renew Sustain Energy Rev 79:850–866 Gomaa M, Alimin AJ, Kamarudin KA (2011) The effect of EGR rates on NOx and smoke emissions of an IDI diesel engine fuelled with Jatropha biodiesel blends. Int J Energy Environ 2(3):477–490 Hosseini SH, Ahmad TA, Barat G, Ahmad AM (2017) Effect of added alumina as nano-catalyst to diesel-biodiesel blends on performance and emission characteristics of CI engine. Energy 124:543–552. https://doi.org/10.1016/j.energy.2017.02.109 Karthikeyan S, Elango A, Prathima A (2016) The effect of cerium oxide additive on the performance and emission characteristics of a CI engine operated with rice bran biodiesel and its blends. Int J Green Energy 13(3):267–273

46

R. L. Krupakaran et al.

Krupakaran RL, Hariprasad T, Gopalakishna A, Pejjai B (2016) The performance and exhaust emissions investigation of a diesel engine using γ-Al2 O3 nanoparticle additives to biodiesel. Carbon Manag 7:233–241. https://doi.org/10.1080/17583004.2016.1218713 Krupakaran RL, Hari Prasad T, Gopalakrishna A (2018a) Impact of various blends of Mimusops elengi methyl esters on performance and emission characteristics of a diesel engine. Int J Green Energy. https://doi.org/10.1080/15435075.2018.1469496 Krupakaran RL, Hariprasad T, Gopalakishna A (2018b) Experimental investigation on the performance and emission characteristics of a diesel engine by varying the injection pressure and injection timing using mixed biodiesel. Int J Ambient Energy. https://doi.org/10.1080/15435075. 2018.1464923 Kumar N et al (2013) Performance and emission characteristics of biodiesel from different origins: a review. Renew Sustain Energy Rev 21:633–658 Ladommatos N, Adelhalim SM, Zhao H, Hu Z (1998) The effects of carbon dioxide in exhaust gas recirculation on diesel engine emissions. Proc Inst Mech Eng Part D J Automob Eng 212(1):25–42 Lalvani JIJR, Parthasarathy M, Dhinesh B, Annamalai K (2015) Experimental investigation of combustion, performance and emission characteristics of a modified piston. J Mech Sci Technol 29(10):4519–4525 Lalvani JIJR, Parthasarathy M, Dhinesh B, Annamalai K (2016) Pooled effect of injection pressure and turbulence inducer piston on combustion, performance and emission characteristics of a D.I diesel engine powered with biodiesel blend. Ecotoxicol Environ Saf 134:336–343 Madhan Raj N, Gajendiran M, Pitchandi K, Nallusamy N (2016) Investigation on aluminum oxide nano particles blended diesel fuel combustion, performance and emission characteristics of a diesel engine. J Chem Pharm Res 8(3):246–257 Mailboom A, Tauzia X, Hetet JF, Cormerais M, Tounsi M, Jaine T, Blanchin S (2007) Various effect of EGR on combustion and emissions on a automotive DI diesel engine: numerical and experimental study. SAE 01:1834. https://doi.org/10.4271/2007-01-1834 McLaughlin YX, Li NB, Patterson BS, Burtt SD (2006) Fuel efficiency and exhaust emissions for biodiesel blends in an agricultural tractor. Can Biosyst Eng 48 Mohon Roy M (2011) Performance and emissions of a diesel engine fueled by diesel-biodiesel blends with special attention to exhaust odor. Can J Mech Sci Eng 2(1) Oberweis S, Al-Shemmeri TT (2010) Effect of biodiesel blending on emissions and efficiency in a stationary diesel engine. In: International conference on renewable energies and power quality (ICREPQ’10), Granada, 23–25 Mar 2010 Parthasarathy M, Lalvani JIJR, Dhinesh B, Annamalai K (2016) Effect of hydrogen on ethanolbiodiesel blend on performance and emission characteristics of a direct injection diesel engine. Ecotoxicol Environ Saf 134:433–439 Peixoto V, Argachoy C, Trindade I, Airoldi M (2009) Combustion optimization of a diesel engine with EGR system using 1D and 3D simulation tools. Department of Engine Design Engineering, MWM International Diesel Engines of South America Ltd., Sao Paulo Pradeep V, Sharma RP (2007) Use of HOT EGR for NOx control in a compression ignition engine fuelled with bio-diesel from Jatropha oil. Renew Energy 32:1136–1154 Rajana K, Senthilkumar KR (2009) Effect of exhaust gas recirculation (EGR) on the performance and emission characteristics of diesel engine with sunflower oil methyl ester. Jordan J Mech Ind Eng (JJMIE) 3(4):306–311 Rakhi NM, Mousumi C, Parikh PA (2014) Nanofuels: combustion, engine performance and emissions. Fuel 120:91–97 Ramalingam K, Kandasamy A, Subramani L, Balasubramanian D, Thadhani JPJ (2018) An assessment of combustion, performance characteristics and emission control strategy by adding anti-oxidant additive in emulsified fuel. Atmos Pollut Res 9(5):959–967 Sanjid A, Masjuki HH, Kalam MA, Rahman SMA, Abedin MJ, Shahir A (2014) An experimental investigation of biodiesel production, characterization, engine performance, emission and noise of Brassica juncea methyl ester and its blends. J Clean Prod 79:74–81

Experimental Investigations on the Combined Effect of TiO2 …

47

Shaafi T, Gopinath A, Sairam K, Kumaresan G, Velraj R (2015) Effect of dispersion of various nano additives on the performance and emission characteristics of a CI engine fuelled with diesel, biodiesel and blends—a review. Renew Sustain Energy Rev 49:563–573 Subramani L, Parthasarathy M, Balasubramanian D, Ramalingam K (2018) Novel Garcinia gummigutta methyl ester (GGME) as a potential alternative feedstock for existing unmodified DI diesel engine. Renew Energy 125:568–577 Vallero D (2014) Fundamentals of air pollution. Academic Press. https://doi.org/10.1016/b978-012-401733-7.01001-x Venkateswarlu K, Murthy BSRC, Subbarao VV (2013) The effect of exhaust gas recirculation and di-tertiary butyl peroxide on diesel-biodiesel blends for performance and emission studies. Int J Adv Sci Technol 54 Vigneswaran R, Annamalai K, Dhinesh B, Krishnamoorthy R (2018) Experimental investigation of unmodified diesel engine performance, combustion and emission with multipurpose additive along with water-in-diesel emulsion fuel. Energy Convers Manag 172:370–380 Vijayakumar C, Murugesan A, Panneerselvam N, Subramaniam D, Bharathiraja M (2016) The role of nano additives for biodiesel and diesel blended transportation fuels. Transp Res Part D Transp Environ 46:145–156 Yasin MHM, Mamat R, Ahmad FY, Daing M, Nafiz DI, Yusaf T, Rasul M, Najafi G (2017) Study of a diesel engine performance with exhaust gas recirculation (EGR) system fuelled with palm biodiesel. Energy Procedia 110:26–31

Production and Application of Chitosanases in Valorization of Crustacean Waste to Wealth—A Review P. Jeevana Lakshmi, Y. Hepsiba, and Ch. M. Kumari Chitturi

Abstract The large amount of waste produced each year by the shellfish processing industry is an appealing opportunity for the State of Andhra Pradesh (AP), India, to produce valuable products from underutilized waste. In order to highlight this important market-opportunity, crustacean waste can be utilized to generate good financial return. However, large investment on capital and effective management remains a significant hurdle in achieving returns on investment. There is no single, simple, cost-effective solution for crustacean waste management. Circular economy and green chemistry have encouraged the reduction of such bio-wastes, and their exploitation as an alternative resource has become a must for a global sustainable future. About 2.5 lakh marine food is being produced annually along the AP coast, including 30,000 tonnes of shrimp and 7000 tonnes of crab. Of this, 70% is wasted and is usually disposed of in landfills or dumped in the sea. The shellfish processing industry is generating about 8.5 million tons of waste every year, with shrimp processing accounting for more than one lakh tonnes of industrial waste. This large amount of waste produced is an appealing opportunity for the A.Ps market to produce valuable products from underutilized waste. Chitin, chitosan, and other derivatives such as glucosamine and chito-oligosaccharides from shrimp and shell waste are in good demand from many types of industries and pharma sector. The study surveys environmentally friendly methods for deriving a sustainable model in conversion of crustacean waste to wealth by adopting two methods—stabilization of waste at the production site and use of microbial technology in production and applicative use of chitosanases. The study finds it promising to use microbial technology to circumvent the chemical processing involved in extraction and valorization of this chitin rich waste. Keywords Crustacean waste · Chitin · Chitosan · Chitosanase · Microbial technology

P. Jeevana Lakshmi · Y. Hepsiba · Ch. M. Kumari Chitturi (B) Department of Applied Microbiology, Sri Padmavati Mahila Visvavidyalayam (Women’s University), Tirupati, Andhra Pradesh, India e-mail: [email protected] © Springer Nature Singapore Pte Ltd. 2020 S. K. Ghosh et al. (eds.), Emerging Technologies for Waste Valorization and Environmental Protection, https://doi.org/10.1007/978-981-15-5736-1_5

49

50

P. Jeevana Lakshmi et al.

1 Introduction Chitin is a natural linear homo-polysaccharide with high molecular weight and is composed of N-acetyl-D-glucosamine residues with beta (1–4) linkage. Chitin and its derivative, chitosan, are biocompatible natural polymers and are biodegradable. They have been widely used in manufacturing of biomedical devices, pulp, paper, cosmetics, etc., and are useful in water treatment, agriculture, and veterinary therapeutics as biotechnological products. 10% of global landfills and aquatic waste products are mostly chitin-based substances from shells of shrimp, crabs, and lobsters. Prevention of dumping of shells of crabs and lobsters at sea has driven for development of an alternate technology wherein utilization of this waste in various fields has come to limelight (Archer 2007; Sastry et al. 2015; Kim and Rajapakse 2005). The problem is further aggravated by the increase in consumption of fish and other seafood leading to piling and dumping of this crustacean waste leading to environmental pollution. The increase in this chitin-rich waste annually has made the chitin, a biodegradable polysaccharide that is second to cellulose in abundance. Chitin is classically processed by chemical treatment to be used in various industries. The chemical processing not only adds to the cost of the product but also produces process waste that pose a threat to environment. The study looks into various sustainable methods building an ideal eco-friendly process for the utilization of this crustacean waste.

2 Chitin and Chitosan Chitin, a structural component of cell wall of yeasts and fungi and also a component of exoskeletons of insects and arthropods, is a linear polysaccharide. Chitin is insoluble in water and exists mainly in two crystalline polymorphic forms, alpha and beta. Alpha-chitin is made up of sheets consisting of both parallel and antiparallel chains, whereas beta-chitin consists of only parallel chains of N-acetyl-D-glucosamine residues. Alpha-chitin occurs more frequently in nature than beta-chitin. Partial deacetylation of chitin results in formation of chitosan, a hetero-polymer, which is made up of N-acetyl glucosamine and D-glucosamine residues. Two deacetylation methods are used for preparation of chitosan: homogeneous deacetylation process (Sannan et al. 1976; Roberts 1992) and heterogeneous deacetylation process. Most commonly used commercial process is heterogenous deacetylation. Increased solubility of chitosan with its unique properties like biodegradability, biocompatibility, and non-toxicity finds numerous applications in agriculture and industry (Dodane and Vilivalam 1998; Harish Prashanth and Tharanathan 2007; Kim and Rajapakse 2005). Chemical or enzymatic treatment of chitosan results in formation of oligomers called chito-oligosaccharides (CHOS). There are different methods for production

Production and Application of Chitosanases in Valorization …

51

of chito-oligomers. They include use of physical methods such as treatment with microwaves, ultrasonic waves, gamma-rays, and hydrothermal method (Sato et al. 2003; Xing et al. 2005; Wu et al. 2008) whereas chemical treatment is with acid, sodium nitrate, and hydrogen peroxide (Domard and Cartier 1992; Einbu and Vårum 2007; Morris et al. 2009). Chemical treatment traditionally used is acid hydrolysis, whereas enzymatic methods include the action of glycosyl hydrolases like chitinases or chitosanases. The type of the CHOS produced depends on the nature of the chitosan substrate and specificity of the enzyme used in the treatment. There are innumerable applications of CHOS; however, very little is known about their biological mechanisms.

2.1 Sources of Chitin Chitin is abundantly available in nature. Though fungal and plant sources are reported in large number, commercial chitosan and chitosanase production utilize crustacean shells as main source of chitin. An approximate 1010–1011 tons of chitin is produced annually (Gooday 1990). Around 30,000 metric tons of chitin and 10,000 metric tons of chitosan were utilized along with their derivatives in 2007 (Sandford 2002). Worldwide crustacean shell production is estimated to be 1000 million metric tons, and India records 1.25 lakh tons of shrimp processing waste annually. Andhra Pradesh state of India has second largest coast line in the country of 794 km and is a source of income owing to large fishing industry accounting to 2.76 million metric tons per annum. AP ranks first in total fish and shrimp production contributing to 70% of shrimp cultivation in the country. The State ranks third in global shrimp production with 0.3 million tons and sixth in aquaculture production with 1.57 million tons. Andhra Pradesh contributes to 1.19% of global and 20.77% of national fish production (Socio Economic Survey 2016–17). The State Government has planned to make Andhra Pradesh a world ‘aqua hub’ by increasing fish production from 25 lakh tons, reported in February 2017, to 42 lakh tons with gross value addition of Rs. 80,000 core by 2019–2020. This scenario portrays a large picture of generation of millions of tons of crustacean waste production in the state.

2.2 Processing of Chitin-Rich Crustacean Waste There are two main management options for processing of Crustacean waste—use or disposal of the waste in its original form or making it available for the development of other products. The second option involves stabilization of crustacean waste at the place of production so that it is available for development of the other products incurring in-house financial costs. There are a variety of alternatives to each of these methods leaving behind wholesome solution to this problem. Adoption of first method of use or disposal by the producer involves investment, which may

52

P. Jeevana Lakshmi et al.

go several thousands of rupees per ton where the waste is composted or disposed off. In the second procedure where the waste is stabilized, pretreatment techniques like decanting and drying are adopted again involving large in-house cost and a major concern is environmental pollution (Mathew and Nair 2006). The cost-benefit analysis may come in the way of pretreatment as there is no specific method available for stabilization and it may vary with the target product. It is necessary that a large-scale waste stabilization facility is available in the local area that can handle a large amount such waste with less income. A wide range of extracts and products are available that can be made from crustacean waste, and lot of research and development work has been devoted for identification of these processes and end-uses of these derivatives. These products exhibit a high market value and a significant global demand. The crustacean waste being a rich source of chitin and its deacetylated product, chitosan, is used as a substrate for production chito-oligosaccharides (Pachapur et al. 2016). Owing to the enormous applications of CHOS in agriculture, medicine, and industry, the demand for chitin and chitosan substrates has increased drastically. This resulted in concentration of research on the variety of methods used for extraction of CHOS (Jung and Park 2014). However, owing to pollution due to physical and chemical processing of these substrates, microbial techniques have gained importance and hence studied elaborately (Fig. 1). The microorganisms degrading crustacean waste produce chitinases and chitosanses that are effective in degradation of crustacean waste. Among these, chitosanases have gained lot of importance due to production of variety of specific oligomers produce with enduses (Somashekar and Joseph 1996). Based on the substrate specificity type of cleavage, chitosanases are classified into subclasses I, II, and III (Fukamizo et al. 1994). The end product of this enzymatic process depends

Fig. 1 Processing of chitin-rich crustacean waste by both chemical and microbial processes

Production and Application of Chitosanases in Valorization …

53

on the choice of the substrate (chitosan), the enzyme selected, and the processing time used. These parameters open up scope for research thus manipulating the end products (Sikorski et al. 2005).

2.3 Applications of Chitosanases The chitosanase treated crustacean waste from treatment process, acknowledge versatile applications of partially digested chitosan and chito-oligosaccharides in several fields including cosmetics, medicine, paper manufacturing, and textile industry as listed in Table 1. Partially digested crustacean waste with chitosanases has drastic influence in enhancing production and productivity levels in agricultural systems and hence is an area open to research. Chitosan and materials based on chitosan polymer have demonstrated an enormous potential to efficiently remove hydrocarbons, heavy metals, and pollutants from contaminated water (Sieber et al. 2018; Escudero-Oñate and Martínez-Francés 2018). Shrimp waste is used in the production of soluble chitosan by chemical and microbial treatment, and it is a crystalline powder which is colorless, odorless, and nonharmful in nature. The composition of powder was calculated. Atomic absorption spectrophotometry has revealed that the powder contains 63.8% and contains Ca, Fe, Cu, and Mn in concentration of 168, 35.58, 38.28, and 6.72 mg/L. This makes the powder rich in nutrients. Partially digested crustacean waste is rich in CHOS and has rich resource of these nutrients and hence has innumerable applications in agriculture. The action of chitosanase treated waste was found to have control over plant pathogens—fungal, bacterial, insect pests, and nematodes (Sharp 2013). It was found to enhance the beneficial microorganisms and plays an important role in signaling growth promoting microbes (Staehelin et al. 2000; Hamid et al. 2013). It also enhanced the plant defenses (Lizama-Uc et al. 2007). It also helps in effective and slow release of nutrients in the soil (Jamnongkan and Kaewpirom 2010). Figure 2 explains various steps involved in the processing of the crustacean waste to be utilized as bio-fertilizer. The small fish farmers or shrimp processors underutilized the crustacean waste due to lack of awareness of the value of this waste or due to the cost incurred in the pretreatment processes. There is an urgent necessity for the govt. to support them by providing them with a large in-house facility where the waste is stabilized at the place of production before it is put to use with generation of end products. Hence, a comprehensive model needs to be worked out wherein small decanting and drying units are provided for the farmers for stabilization of the waste as per the requirements of the end process bringing in the value addition to the waste.

54

P. Jeevana Lakshmi et al.

Table 1 Applications of chito-oligosaccharides produced by chitosanase treatment Area of application

End-use

References

Medicine

Immune enhancer

Xu et al. (2012)

Food industry

Antimicrobial packing

Asthma treatment

Zhu et al. (2004)

Antioxidant activity

Park and Kim (2010)

Antibacterial agents

Rhoades et al. (2006)

Increased bone strength

Klokkevold et al. (1996), Ratanavaraporn et al. (2009)

Gene therapy

Köping-Höggård et al. (2003, 2004)

Reduction of metastasis in cancer

Muzarelli (1997), Nam et al. (2007), Shen et al. (2009)

Wound dressings

Ribeiro et al. (2009), You et al. (2004)

Lowering of serum glucose in diabetics

Lee et al. (2003)

Inhibition of malaria parasite

Shahabuddin et al. (1993)

Antifungal activities

Oliveira et al. (2008), Seyfarth et al. (2008)

Neuro-protective

Gong et al. (2009)

Preservatives

Sethulekshmi (2014), Barikani et al. (2014)

Antimicrobial agent

Khoushab and Yamabhai (2010)

Improvement of mycological quality

El-Diasty et al. (2012)

Edible packaging

Muzzarelli and Muzzarelli (2005)

Improvement in nutritional quality

Sinha et al. (2014)

Enhanced shelf life

Dutta et al. (2012)

Dietary fiber

Xia et al. (2010)

Probiotics

Morganti et al. (2011), Harish and Prashanth (2007), Tharanathan and Kittur (2003)

Stabilizing agent

Rinaudo (2006), Arvanitoyannis (2008)

Paper manufacturing

Strengthening additives

Ashford et al. (1977)

Agriculture

Antiviral agent

Struszczyk et al. (1989)

Metal recovery

Onsoyen and Skaugrud (1990)

Dietary supplements

Antifungal

Seo et al. (1992)

Cosmetics

Film forming agent

Lang and Clausen (1989)

Textiles

Dye binding agent

Ashford et al. (1977)

Production and Application of Chitosanases in Valorization …

55

Fig. 2 Steps involved in the development bio-fertilizer—an application of chitosanase technology

3 Conclusion Millions of tons of chitin-rich crustacean waste needs to be addressed immediately so that it is put to use with value addition. In this scenario, chitosanase technology provides ample opportunities for the fish and shrimp farmers to utilize this waste generated in the state of Andhra Pradesh, India. The state being a future hub for the aquaculture industry with a long coastline is a potential source of chitin-rich waste substrate for chitosanases. Valorization of this waste is the need of the hour, and hence, there is requirement for the development of a comprehensive model involving indigenous chitosanase technology wherein the producer of crustacean waste works hand in hand with the farmer as well as with the industry. Acknowledgements Authors would like to acknowledge DST SERB, Govt. of India for funding Major Research Project.

References Archer M (2007) Crustacea processing waste management. Res Dev 2008(1) Arvanitoyannis IS (2008) The use of chitin and chitosan for food packaging applications. In: Chiellini E (ed) Environmentally compatible food packaging. Woodhead Publishing, Cambridge, pp 137–157 Ashford NA, Hattis DB, Murray AE (1977) MIT Sea Grant program. Massachusetts Institute of Technology Barikani M, Oliaei E, Seddiqi H, Honarkar H (2014) Preparation and application of chitin and its derivatives: a review. Iran Polym J 23:307–326 Dodane V, Vilivalam VD (1998) Pharmaceutical applications of chitosan. Pharm Sci Technol Today 1:246–253 Domard A, Cartier N (1992) Glucosamine oligomers: 4. Solid state-crystallization and sustained dissolution. Int J Biol Macromol 14:100–106

56

P. Jeevana Lakshmi et al.

Dutta J, Tripathi S, Dutta PK (2012) Progress in antimicrobial activities of chitin, chitosan and its oligosaccharides: a systematic study needs for food applications. Food Sci Technol Int 18(1):3–34 Einbu A, Vårum KM (2007) Depolymerization and de-N-acetylation of chitin oligomers in hydrochloric acid. Biomacromolecules 8:309–314 El-Diasty EM, Nesreen Z, Hoda AM (2012) Using of chitosan as antifungal agent in kariesh cheese. N Y Sci J 5:5–10 Escudero-Oñate C, Martínez-Francés E (2018) Review of chitosan-based materials for the removal of organic pollution from water and bioaugmentation. In: Chitin-chitosan—myriad functionalities in science and technology. Intech Open Fukamizo T, Ohkawa T, Ikeda Y, Goto S (1994) Specificity of chitosanase from Bacillus pumilus. Biochim Biophys Acta Prot Struct Mol Enzym 1205:183–188 Gong Y, Gong L, Gu X, Ding F (2009) Chitooligosaccharides promote peripheral nerve regeneration in a rabbit common peroneal nerve crush injury model. Microsurgery 29(8):650–656 Gooday GW (1990) The ecology of chitin degradation. Adv Microb Ecol 11:387–430 Hamid R, Khan MA, Ahmad M, Ahmad MM, Abdin MZ, Musarrat J, Javed S (2013) Chitinases: an update. J Pharm Bioallied Sci 5:21–29 Harish Prashanth KV, Tharanathan RN (2007) Chitin/chitosan: modifications and their unlimited application potential—an overview. Trends Food Sci Technol 18:117–131 Jamnongkan T, Kaewpirom S (2010) Potassium release kinetics and water retention of controlledrelease fertilizers based on chitosan hydrogels. J Polym Environ 18:413–442 Jung WJ, Park RD (2014) Bioproduction of chitooligosaccharides: present and perspectives. Mar Drugs 12(11):5328–5356 Khoushab F, Yamabhai M (2010) Chitin research revisited. Mar Drugs 8:1988–2012 Kim SK, Rajapakse N (2005) Enzymatic production and biological activities of chitosan oligosaccharides (COS): a review. Carbohydr Polym 62:357–368 Klokkevold PR, Vandemark L, Kenney EB, Bernard GW (1996) Osteogenesis enhanced by chitosan (poly-N-acetyl glucosaminoglycan) in vitro. J Periodontol 67:1170–1175 Köping-Höggård M, Mel’nikova YS, Vårum KM, Lindman B, Artursson P (2003) Relationship between the physical shape and the efficiency of oligomeric chitosan as a gene delivery system in vitro and in vivo. J Gene Med 5:130–141 Köping-Höggård M, Vårum KM, Issa M, Danielsen S, Christensen BE, Stokke BT, Artursson P (2004) Improved chitosan-mediated gene delivery based on easily dissociated chitosan polyplexes of highly defined chitosan oligomers. Gene Ther 11:1441–1452 Lang G, Clausen T (1989) The use of chitosan in cosmetics. In: Skjoak-Brok G, Anthonsen T, Sandford P (eds) Chitin and chitosan. Elsevier Science, London, pp 139–147 Lee HW, Park YS, Choi JW, Yi SY, Shin WS (2003) Antidiabetic effects of chitosan oligosaccharides in neonatal streptozotocin-induced noninsulin-dependent diabetes mellitus in rats. Biol Pharm Bull 26:1100–1103 Lizama-Uc G, Estrada-Mota IA, Caamal-Chan MG, Souza-Perera R, Oropeza-Salín C, Islas-Flores I, Zúñiga-Aguilar JJ (2007) Chitosan activates a MAP-kinase pathway and modifies abundance of defense-related transcripts in calli of Cocos nucifera L. Physiol Mol Plant Pathol 70:130–141 Mathew P, Nair KGR (2006) Ensilation of shrimp waste Lactobacillus fermentum. Fish Technol 43:59–64 Morganti P, Morganti G, Morganti A (2011) Transforming nanostructured chitin from crustacean waste into beneficial health products: a must for our society. Nanotechnol Sci Appl 4:123–129 Morris VB, Neethu S, Abraham TE, Pillai CKS, Sharma CP (2009) Studies on the condensation of depolymerized chitosans with DNA for preparing chitosan-DNA nanoparticles for gene delivery applications. J Biomed Mater Res 89(B):282–292 Muzarelli RAA (1997) Chitin. Pergamon Press, Oxford, London, pp 262–270 Muzzarelli RAA, Muzzarelli C (2005) Chitosan chemistry: relevance to the biomedical sciences. Adv Polym Sci 186:151–209 Nam KS, Kim MK, Shon YH (2007) Inhibition of proinflammatory cytokine-induced invasiveness of HT-29 cells by chitosan oligosaccharide. J Microbiol Biotechnol 17:2042–2045

Production and Application of Chitosanases in Valorization …

57

Oliveira EN Jr, Gueddari NE, Moerschbacher BM, Peter MG, Franco TT (2008) Growth of phytopathogenic fungi in the presence of partially acetylated chitooligosaccharides. Mycopathologia 166:163–174 Onsoyen E, Skaugrud O (1990) Metal recovery using chitosan. J Chem Technol Biotechnol 49(4):395–404 Pachapur VL, Guemiza K, Rouissi T et al (2016) Novel biological and chemical methods of chitin extraction from crustacean waste using saline water. J Chem Technol Biotechnol 91(8) Park BK, Kim MM (2010) Applications of chitin and its derivatives in biological medicine. Int J Mol Sci 11:5152–5164 Ratanavaraporn J, Kanokpanont S, Tabata Y, Damrongsakkul S (2009) Growth and osteogenic differentiation of adipose-derived and bone marrow-derived stem cells on chitosan and chitooligosaccharide films. Carbohydr Polym 78:873–878 Rhoades J, Gibson G, Formentin K, Beer M, Rastall R (2006) Inhibition of the adhesion of enteropathogenic Escherichia coli strains to HT-29 cells in culture by chito-oligosaccharides. Carbohydr Polym 64:57–59 Ribeiro MP, Espiga A, Silva D, Baptista P, Henriques J, Ferreira C, Silva JC, Borges JP, Pires E, Chaves P, Correia IJ (2009) Development of a new chitosan hydrogel for wound dressing. Wound Repair Regen 17:817–824 Rinaudo M (2006) Chitin and chitosan: properties and applications. Prog Polym Sci 31:603–632 Roberts GAF (1992) Chitin chemistry. The Macmillan Press Ltd., Hong Kong Sandford PA (2002) Commercial sources of chitin & chitosan and their utilization. In: Vårum KM, Domard A, Smidsrød O (eds) Advances in chitin science, vol VI. Tapir, Trondheim Sannan T, Kurita K, Iwakura Y (1976) Studies on chitin. 2. Effect of deacetylation on solubility. Macromol Chem 177:3589–3600 Sastry KR et al (2015) Assessment of current trends in R&D of chitin-based technologies in agricultural production-consumption systems using patent analytics. J Intellect Prop Rights 20:19–38 Sato K, Saimoto H, Morimoto M, Shigemasa Y (2003) Depolymerization of chitin and chitosan under hydrothermal conditions. Sen-I Gakkaishi 59:104–109 Seo H, Mitsuhashi K, Tanibe H (1992) Advances in chitin and chitosan. Elsevier Science Sethulekshmi C (2014) Chitin and its benefits. Int J Adv Res Biol Sci 1:171–175 Seyfarth F, Schliemann S, Elsner P, Hipler UC (2008) Antifungal effect of high- and low-molecularweight chitosan hydrochloride, carboxymethyl chitosan, chitosan oligosaccharide and N-acetylD-glucosamine against Candida albicans, Candida krusei and Candida glabrata. Int J Pharm 353:139–148 Shahabuddin M, Toyoshima T, Aikawa M, Kaslow DC (1993) Transmission-blocking activity of a chitinase inhibitor and activation of malarial parasite chitinase by mosquito protease. Proc Natl Acad Sci USA 90:4266–4270 Sharp RG (2013) A review of the applications of chitin and its derivatives in agriculture to modify plant-microbial interactions and improve crop yields. Agronomy 3:757–793 Shen KT, Chen MH, Chan HY, Jeng JH, Wang YJ (2009) Inhibitory effects of chitooligosaccharides on tumor growth and metastasis. Food Chem Toxicol 47:1864–1871 Sieber V, Hofer M, Brück WM, Garbe D, Brück T, Lynch CA (2018) ChiBio: an integrated biorefinery for processing chitin-rich bio-waste to specialty chemicals. In: Grand challenges in marine biotechnology. Springer, pp 555–578 Sikorski P, Stokke BT, Sørbotten A, Vårum KM, Horn SJ, Eijsink VG (2005) Development and application of a model for chitosan hydrolysis by a family 18 chitinase. Biopolymers 77:273–285 Sinha S, Chand S, Tripathi P (2014) Microbial degradation of chitin waste for production of chitosanase and food related bioactive compounds. Appl Biochem Microbiol 50:125–133 Somashekar D, Joseph R (1996) Chitosanases—properties and applications: a review. Biosour Technol 55:35–45

58

P. Jeevana Lakshmi et al.

Staehelin C, Schultze M, Tokuyasu K, Poinsot V, Promé JC, Kondorosi E, Kondorosi A (2000) N-deacetylation of Sinorhizobium meliloti Nod factors increases their stability in the Medicago sativa rhizosphere and decreases their biological activity. Mol Plant Microbe Interact 13:72–79 Struszczyk H, Pospieszny H, Kotlinski S (1989) Some new application of chitosan. In: Skjoak-Brok G, Anthonsen T, Sandford P (eds) Chitin and chitosan. Elsevier Science, London, pp 733–742 Tharanathan RN, Kittur FS (2003) Chitin-the undisputed biomolecule of great potential. Crit Rev Food Sci Nutr 43:61–87 Wu T, Zivanovic S, Hayes DG, Weiss J (2008) Efficient reduction of chitosan molecular weight by high-intensity ultrasound: underlying mechanism and effect of process parameters. J Agric Food Chem 56:5112–5119 Xia W, Liu P, Zhang J, Chen J (2010) Biological activities of chitosan and chitooligosaccharides. Food Hydrocolloids 25:170–179 Xing RE, Liu S, Yu HH, Guo ZY, Wang PB, Li CP, Li Z, Li PC (2005) Salt-assisted acid hydrolysis of chitosan to oligomers under microwave irradiation. Carbohydr Res 340:2150–2153 Xu C, Lei C, Meng L, Wang C, Song Y (2012) Chitosan as a barrier membrane material in periodontal tissue regeneration. J Biomed Mater Res Part B Appl Biomater 100:1435–1443 You Y, Park WH, Ko BM, Min BM (2004) Effects of PVA sponge containing chitooligosaccharide in the early stage of wound healing. J Mater Sci Mater Med 15:297–301 Zhu Z, Zheng T, Homer RJ, Kim YK, Chen NY, Cohn L, Hamid Q, Elias JA (2004) Acidic mammalian chitinase in asthmatic Th2 inflammation and IL-13 pathway activation. Science 304:1678–1682

Capture of CO2 from Automobile Exhaust by Using Physical Adsorption Technique S. Mohankumar, B. Dhinesh, Muhammad Usman Kaisan, and P. Mohamed Shameer

Abstract Carbon dioxide is considered as a major contributor toward global warming. The amount of carbon dioxide from automobiles is approximately 65%, which is more than any other sources of emissions. On considering the upcoming stringent emission norms, this problem needs to be addressed properly. In this work, an attempt was made to capture CO2 emission from automobile exhaust using activated carbon. The concept of physical adsorption by van der Waals forces of attraction, CO2 found to be adsorbed on the surface of activated carbon. Experiments were conducted on a three-cylinder, carbureted, variable-speed, water-cooled diesel engine at various load conditions (0, 25, 50, 75, and 100%). Test results were obtained by conducting experiments at various exhaust temperatures. Final results obtained shows that considerable amount of HC, CO, and CO2 gets reduced while operating engine with idle and part load conditions at reduced exhaust gas temperature. Activated carbon found to be a suitable one for CO2 capture from engine exhaust, and it has great scope to be implemented in a vehicle exhaust system. Keywords Carbon dioxide · Greenhouse gases · Activated carbon · van der Waals forces

1 Introduction Internal combustion engines seem to be promising power source found to be used for both commercial and industrial applications for several decades (Subramaniam S. Mohankumar (B) Kumaraguru College of Technology, Coimbatore, India e-mail: [email protected] B. Dhinesh Mepco Schlenk Engineering College, Sivakasi, India M. U. Kaisan Ahmadu Bello University, Zaria, Nigeria P. Mohamed Shameer V V College of Engineering, Tirunelveli, India © Springer Nature Singapore Pte Ltd. 2020 S. K. Ghosh et al. (eds.), Emerging Technologies for Waste Valorization and Environmental Protection, https://doi.org/10.1007/978-981-15-5736-1_6

59

60

S. Mohankumar et al.

et al. 2016). Although it has several advantages in terms of power and efficiency, it has got many drawbacks. The release of harmful emissions like HC, CO, NOx , and particulate matter into atmosphere effects both human begins and atmosphere (Mohankumar and Senthilkumar 2017). There are several pre-combustion and postcombustion techniques available to control these emissions effectively (Mohankumar and Senthilkumar 2017). Nowadays, although CO2 considered as a desired products of combustion, it is considered as a leading contributor toward greenhouse gas emissions (Rashidi et al. 2016; Sivakumar et al. 2017). The International Panel on Climate Change (IPCC) calculated that CO2 average concentration will rise to about 570 ppm by the year 2010. This scenario increases the mean sea level of about 38 cm with a rise in mean global average temperature of about 1.9 °C further (IPCC 2001; Stewart and Hessami 2005). Automobiles are considered as a second major source for CO2 emission, and it contributes around 14% (Liaquat et al. 2010). Several methodologies like absorption, membrane separation, and cryogenic separation are adapted to capture CO2 emission in industries (Singh and Kumar 2016a). There are only a few works carried out to capture CO2 emission from the vehicular exhaust. In this work, an attempt was made to capture CO2 emission from vehicle exhaust using activated carbon as an adsorbent. Adsorption is considered as a predominant technique to capture CO2 emission while compared with the above-mentioned techniques (Singh and Kumar 2016a). The various advantages are higher CO2 trap efficiency, less backpressure, and lower regeneration energy requirements (Yong et al. 2002; Choi et al. 2009). The concept of physical adsorption on its surface by van der Waals forces is the basic scenario for CO2 adsorption in activated carbon. Also other physical adsorbents like zeolites are available, but activated carbon has an extremely developed porous material (Zhao et al. 2007). They are also having other advantages like low acid/base reactivity, large porous specific surface area, thermodynamically stable structure, and larger microporous volume (El Qada et al. 2008; Maring and Webley 2013). Activated carbon used in this work was made from coconut shell, which is in granular form. The activated carbon obtained from coconut shell has high adsorption capacity while compared with other adsorbents (Mohankumar and Senthilkumar 2015). Initially, part of this work, the trap, is designed based upon the displacement volume of the engine to be tested. Then, the trap is filled with activated carbon and is tested under various load and speed conditions. The complete experimental setup, procedure, and design of the trap will be explained in the upcoming sections.

2 Experimental Setup and Design Experiments were carried out in a three-cylinder, four-stroke, water-cooled, variablespeed petrol engine, and it was a naturally aspirated one. The overall specification of a test engine is shown in Table 1. K-type thermocouple was used to measure exhaust gas temperature, and velocity of exhaust gases was measured using hot wire anemometer. Load to the engine was given by using eddy current dynamometer which operates under the principle of faradays law and Lenz laws. Regarding emission

Capture of CO2 from Automobile Exhaust by Using Physical …

61

Table 1 Engine specifications Cubic capacity

796 cc

No. of cylinders

3

Engine type

Inline SOHC water Cooled

Max. power

37 bhp @ 5000 rpm

Max. torque

59 Nm @ 2500 rpm

Bore × stroke

68.5 × 72 mm

Compression ratio

8.8:1

Fuel supply system

Multi-point fuel injection

1.Engine 2.Dyanamometer 3.Fuel Tank 4.Carburater 5.Fuel Measuring unit 6. CO2 Trap 7 Krypton exhaust gas analyzer 8.Nox analyser

Fig. 1 The layout of engine test setup

measurement, the HC, CO, CO2 , and O2 measurement was carried out using krypton gas analyzer. NOx emission was measured out using a separate analyzer. Exhaust gas analyzers and dynamometer were calibrated before doing the experiments in order to get accurate results (Balasubramanian et al. 2018). The overall engine experimental setup is shown in Fig. 1.

3 Experimental Procedure Before starting the engine, it was made to run with petrol at ideal conditions for 10 min at a constant speed to attain its steady state conditions (Parthasarathy et al. 2016; Lalvani et al. 2015, 2016; Dhinesh et al. 2016, 2017a, b). Then, the calibration

62

S. Mohankumar et al.

of eddy current dynamometer with known weights was done in order to avoid loading error. The recirculation of cooling water and lubrication oil level were ensured before starting the experiments (Annamalai et al. 2016; Subramani et al. 2018; Dhinesh and Annamalai 2018; Dhinesh et al. 2018). Once the engine attains its steady-state condition, the various emission measurement devices were connected to take the readings (Vigneswaran et al. 2018; Ramalingam et al. 2018). Initially, the experiments were conducted without connecting the trap, and then, readings were taken after connecting the trap. The difference between these two readings gives the trapping efficiency of an activated carbon. Finally, the readings were taken at various load conditions (0, 3, 6, 9, and 12 kg) and the corresponding results were plotted. Since the temperature is a main dependent parameter which influences activated carbon trapping efficiency, the readings were taken at different exhaust temperatures and the results were plotted. To ensure the accuracy of the results, two to three readings were taken under similar conditions and the average of those readings was plotted.

4 Trap Design The main important parameter needs to be considered is while designing, the trap is a back pressure developed after connecting the trap (Mohankumar and Senthilkumar 2015). In this work, trap is designed based upon CFD analysis results made from the several previous works. According to the previous works analysis results, the overall trap designed is shown in Fig. 2. Next important parameter needs to be considered is trap volume to be filled by activated carbon. The amount of activated carbon required for the adsorption of CO2 is with respect to the stroke volume of the engine considered (Muthiya et al. 2015). In general, 1/3rd stoke, the volume is considered as required volume for filling activated carbon Hence, the total volume (Vc) of activated carbon required is calculated as 146,989 mm3 . The complete specification of an activated

Fig. 2 Trap designed

Capture of CO2 from Automobile Exhaust by Using Physical … Table 2 Specification of an activated carbon

Iodine adsorption

63 400–1200 mg/g ± 25

PH

7.5–10

Total surface area

800–1400 m2 /g

Bulk density

0.46–0.58 g/cc

Moisture

1.5% max

Ball-pan hardness no.

90–98%

Ash content

2.5–10%

carbon used in this work is given in Table 2. The three-dimensional view of the trap designed is shown in Fig. 2.

5 Results and Discussion Experiments were conducted at various load conditions (0, 3, 6, 9, and 12 kg) by running the engine at constant rpm. The corresponding test results obtained were summarized as follows and are shown in Figs. 3, 4, 5 and 6. Figure 3 shows the variation of HC emission at various load conditions with and without a trap. The obtained trend clearly shows that HC emission linearly increases with the increase in load. This scenario occurs since as applied load increases the amount of fuel injected also increases. So the injected fuel contains more amounts of carbon particles in its composition, this paves the way for the increase in the amount of hydrocarbon since the formation of hydrocarbon emission is directly depends upon the mass of unburned fuel vapor.

Fig. 3 Load versus HC

64

S. Mohankumar et al.

Fig. 4 Load versus CO2

Fig. 5 Load versus CO

Regarding trapping efficiency of UHBC, the maximum of about 45% is obtained while running the engine at idle load conditions after connecting the AC trap. This shows clearly that activated carbon has a great potential to reduce UHBC emissions also. Similarly, at the part load condition, the trapping efficiency of around 33% is achieved and for higher load conditions, it goes up to 29%. This main reason behind this scenario is that UHBC got adsorbed on the surface of AC is due to van der Waals forces of attraction developed between UHBC and AC (Choi et al. 2009). This forces developed will attract the UHBC on the surface of the AC which acts as an adsorbent. The maximum trap efficiency of around 45% achieved while running

Capture of CO2 from Automobile Exhaust by Using Physical …

65

Fig. 6 Load versus NOx

the engine at idle load conditions. This scenario occurs since idle load conditions the temperature of exhaust gases is lower. Activated carbon adsorption rate increases as operating temperature get reduced (Singh and Kumar 2016b). Similarly, the trapping efficiency reduces as applied load increases due to increase in exhaust gases operating temperature. The core reason for this trend is that as operating temperature increases leads to a reduction of van der Waals forces between adsorbent and adsorbate (Choi et al. 2009). So finally reduces the trapping efficiency of UHBC by AC with the increase in applied load. Figure 4 shows the variation of CO2 emission under various load conditions with and without a converter. The obtained trend shows that CO2 emission linearly increases with the applied load. The main reason behind this scenario is that as applied load increases the in-cylinder temperature also rises. This paves the way for the complete combustion of fuel, and it leads to a rise in CO2 percentage. Regarding the trapping efficiency of CO2 on activated carbon, it shows the maximum of around 17% at higher load conditions. The CO2 adsorption efficiency linearly increases with the applied load. This main reason behind this scenario is that as applied load increases the exhaust gases contains more amount of CO2 in its composition. The van der Waals forces of adsorption between the AC and CO2 molecules get enhanced, and it increases the adsorption efficiency. At higher load condition the operating temperature is optimum which paves the way for more amount of CO2 molecules get adsorbed on the surface of AC. Another reason is that activated carbon obtained from coconut shell has very good adsorption capacity while operating at a higher temperature while compared with other types. Figure 5 shows the variation of CO emission at various load conditions with and without a trap. The obtained trend clearly shows that CO emission linearly increases with the increase in load. This scenario occurs since as applied load increases the amount of fuel injected also increases. So the injected fuel contains more amounts of

66

S. Mohankumar et al.

carbon particles in its composition; this paves the way for the increase in the amount of CO emission. Another reason is that as applied load increases, the amount of oxygen availability also reduces in the air–fuel mixture. Since the oxygen content is displaced by the carbon particles in the mixture, it increases CO emissions. Regarding the trapping efficiency, the maximum of around 30% is achieved at idle load conditions. As already discussed at idle load conditions, exhaust gas temperature is low; the adsorption efficiency increases. The main reason is that the van der Waals forces of attraction are higher at low operating temperatures. Then, at medium and higher load conditions, the reduction efficiency of around 16 and 23% was observed. This clearly indicates AC also had the ability to trap CO emissions, and the pores present in the surface of AC have a greater affinity toward CO emissions. The trap developed is effectively reduced HC, CO, and CO2 emissions simultaneously. Figure 6 shows that NO2 emission trend with respect to the applied load with and without a trap. The obtained trend clearly indicates that NOx emission increases linearly with the applied load. The core reason is that as load increases, the in-cylinder temperature also raises; this leads to an increase in NOx emissions. Regarding trapping efficiency, the slight amount of adsorption is noted while operating engine at idle load conditions. Then, the adsorption efficiency reduces as applied load increases further. This clearly shows that AC carbon effectively removes NOx emissions while operating the engine at a lower temperature.

6 Conclusions In this work, an attempt is made to capture CO2 emission from petrol engine using activated carbon made from coconut shell as an adsorbent. Experiments were conducted on a three-cylinder, four-stroke, water-cooled, variable-speed petrol engine, and it was a naturally aspirated one. The following observations were made from the test obtained are as follows: • Maximum reduction of around 45% is achieved for HC emissions while operating the engine at idle load conditions. At part load and higher load conditions, a reduction percentage of around 33 and 30% is observed. • Regarding CO2 emission, the maximum reduction percentage of around 17% is achieved while operating the engine at higher load conditions. A slight amount of NOx reduction is also observed while operating the engine at the idle load condition. • Finally, the CO emission trend shows that the maximum reduction percentage of around 30% is achieved at idle and part load conditions. The final conclusion shows that activated carbon not only reduces CO2 emission but also has a tendency to reduce HC and CO emissions. So the designed trap effectively reduces the HC, CO, and CO2 emission altogether while operating engine at part load and idle load conditions.

Capture of CO2 from Automobile Exhaust by Using Physical …

67

References Annamalai M, Dhinesh B, Nanthagopal K, Sivaramakrishnan P, Lalvani JIJR, Parthasarathy M, Annamalai K (2016) An assessment on performance, combustion and emission behavior of a diesel engine powered by ceria nanoparticle blended emulsified biofuel. Energy Convers Manag 123:372–380 Balasubramanian D, Arumugam SRS, Subramani L, Chellakumar IJLJS, Mani A (2018) A numerical study on the effect of various combustion bowl parameters on the performance, combustion, and emission behavior on a single cylinder diesel engine. Environ Sci Pollut Res 25(3):2273–2284 Choi S, Drese JH, Jones CW (2009) Adsorbent materials for carbon dioxide capture from large anthropogenic point sources. ChemSusChem 2:796–854 Dhinesh B, Annamalai M (2018) A study on performance, combustion and emission behaviour of diesel engine powered by novel nano nerium oleander biofuel. J Clean Prod 196:74–83 Dhinesh B, Lalvani JIJR, Parthasarathy M, Annamalai K (2016) An assessment on performance, emission and combustion characteristics of single cylinder diesel engine powered by Cymbopogon flexuosus biofuel. Energy Convers Manag 117:466–474 Dhinesh B, Annamalai M, Lalvani JIJR, Annamalai K (2017a) Studies on the influence of combustion bowl modification for the operation of Cymbopogon flexuosus biofuel based diesel blends in a DI diesel engine. Appl Therm Eng 112:627–637 Dhinesh B, Lalvani JIJR, Parthasarathy M, Annamalai K (2017b) An experimental analysis on the influence of fuel borne additives on the single cylinder diesel engine powered by Cymbopogon flexuosus biofuel. J Energy Inst 90(4):634–645 Dhinesh B, Raj YMA, Kalaiselvan C, Krishnamoorthy R (2018) A numerical and experimental assessment of a coated diesel engine powered by high-performance nano biofuel. Energy Convers Manag 171:815–824 El Qada EN, Allen SJ, Walker GM (2008) Influence of preparation conditions on the characteristics of activated carbons produced in laboratory and pilot scale systems. Chem Eng J 142:1–13 IPCC (2001) Climate change, impacts, adsorption and vulnerability Lalvani JIJR, Parthasarathy M, Dhinesh B, Annamalai K (2015) Experimental investigation of combustion, performance and emission characteristics of a modified piston. J Mech Sci Technol 29(10):4519–4525 Lalvani JIJR, Parthasarathy M, Dhinesh B, Annamalai K (2016) Pooled effect of injection pressure and turbulence inducer piston on combustion, performance and emission characteristics of a D.I diesel engine powered with biodiesel blend. Ecotoxicol Environ Saf 134(Part 2):336–343 Liaquat AM, Kalam MA, Masjuki HH, Jayed MH (2010) Potential emissions reduction in road transport sector using biofuel in developing countries. Atmos Environ 44:3869–3877 Maring BJ, Webley PA (2013) A new simplified pressure/vacuum swing adsorption model for rapid adsorbent screening for CO2 capture applications. Int J Greenhouse Gas Control 15:16–31 Mohankumar S, Senthilkumar P (2015) Numerical and experimental investigation of back pressure in various models of catalytic converter. Int J Appl Eng Res 10(61). ISSN 0973-4562 Mohankumar S, Senthilkumar P (2017) Particulate matter formation and its control methodologies for diesel engine: a comprehensive review. J Renew Sustain Energy Rev 80:1227–1238 Muthiya SJ, Amarnath V, Senthilkumar P, Mohankumar S (2015) Experimental investigation and controlling of CO2 emission from automobile exhaust by CCS technique. Int J Appl Eng Res 10(61). ISSN 0973-4562 Parthasarathy M, Lalvani JIJR, Dhinesh B, Annamalai K (2016) Effect of hydrogen on ethanolbiodiesel blend on performance and emission characteristics of a direct injection diesel engine. Ecotoxicol Environ Saf 134(2):433–439 Ramalingam K, Kandasamy A, Subramani L, Balasubramanian D, Thadhani JPJ (2018) An assessment of combustion, performance characteristics and emission control strategy by adding anti-oxidant additive in emulsified fuel. Atmos Pollut Res 9(5):959–967 Rashidi NA, Yusup S, Borhan A (2016) Isotherm and thermodynamic analysis of carbon dioxide on activated carbon. Procedia Eng 148:630–637

68

S. Mohankumar et al.

Singh VK, Kumar EA (2016a) Measurement, and analysis of adsorption isotherms of CO2 on activated carbon. Appl Therm Eng 97:77–86 Singh VK, Kumar EA (2016b) Comparative studies on CO2 adsorption kinetics by solid adsorbents. Energy Procedia 90:316–325 Sivakumar AS, Satish S, Karmugil V (2017) Development of eco-friendly emission control unit using TiO2 coated catalytic converter. J Adv Res Dyn Control Syst 9(14) Stewart C, Hessami M (2005) A study of methods of carbon dioxide capture and sequestration. The sustainability of a photosynthetic bioreactor approach. Energy Convers Manag 46:403–420 Subramani L, Parthasarathy M, Balasubramanian D, Ramalingam K (2018) Novel Garcinia gummigutta methyl ester (GGME) as a potential alternative feedstock for existing unmodified DI diesel engine. Renew Energy 125:568–577 Subramaniam MK, Pachamuthu S, Arulanandan J, Muthiya J (2016) Simultaneous reduction of HC, NOx , and PM by using active regeneration technique. SAE technical paper. Dio 4271/201601-0912 Vigneswaran R, Annamalai K, Dhinesh B, Krishnamoorthy R (2018) Experimental investigation of unmodified diesel engine performance, combustion and emission with multipurpose additive along with water-in-diesel emulsion fuel. Energy Convers Manag 172:370–380 Yong Z, Meta V, Rodrigues AE (2002) Adsorption of carbon dioxide at the high temperature—a review. Sep Purif Technol 26:195–203 Zhao Z, Cui X, Ma J, Li R (2007) Adsorption of carbon dioxide on alkali-modified zeolite 13X adsorbents. Int J Greenhouse Gas Control 1:355–359

Chemical Characterization and Environmental Implications of Recycled Sewage Sludge in the Proximity Soil of Treatment Plant P. Balaganesh, M. Vasudevan, S. M. Suneethkumar, and N. Natarajan

Abstract Recycling of organic waste materials as soil amendment is a proven sustainable practice, addressing waste management, soil fertility and crop productivity issues. However, inefficient utilization of biodegradable components as well as inappropriate application methods limits the expected benefits of conventional soilwaste mixing strategy. Moreover, accidental or prolong release of organic wastes in soil can result in chronic disorder in soil nutrients distribution. Hence, it is important to understand the environmental implications of such activities in order to optimize the soil-waste mixing strategy. Present study aims to investigate chemical characteristics of soil in the proximity of an overloaded sewage treatment plant (STP) operating in the mode of activated sludge process at Bannari Amman Institute of Technology, Sathyamangalam, Tamil Nadu, India and the implications of its operational and maintenance activities on soil organic matter (SOM). Samples were collected near the treatment units and were assessed periodically for crucial parameters like pH, electrical conductivity (EC), total nitrogen (TN), nitrate nitrogen (NO3 –N), total organic carbon (TOC) and chlorides. The experiment findings clearly infer that soil in the proximity of aerators, clarifiers and sludge drying bed have high TOC, TN and NO3 –N values due to the direct release of washing water and wasting of excess sludge. This has resulted in significant accumulation of organic carbon (52%) and nitrogen (79%) in the soil to the extent that partial replacement of compost with STP soil up to 60% could replenish the soil organic matter in a sugarcane mono-cultured soil. It is suggested that the interchanging of top soils in mono-cultured low fertile soil with STP soil may enhance the soil fertility and promotes nutrient uptakes by the plants. Keywords Agriculture · Sewage treatment plant · Soil nutrients · Sewage sludge · Co-composting P. Balaganesh (B) · M. Vasudevan · S. M. Suneethkumar Department of Civil Engineering, Bannari Amman Institute of Technology, Sathyamangalam, Tamil Nadu 638401, India e-mail: [email protected] N. Natarajan Department of Civil Engineering, Dr. Mahalingam College of Engineering and Technology, Pollachi, Tamil Nadu 642003, India © Springer Nature Singapore Pte Ltd. 2020 S. K. Ghosh et al. (eds.), Emerging Technologies for Waste Valorization and Environmental Protection, https://doi.org/10.1007/978-981-15-5736-1_7

69

70

P. Balaganesh et al.

1 Introduction Soil is a multitude of all living creatures, decayed organic matter and dilapidated composite mineral materials of rock (Ahmad Wani et al. 2014). Different soil types, habitats, crops and climatic conditions represent the farming system with different soil fertility (Tola et al. 2016). Microbes play vital role in material cycling of soil and in turn soil quality (Luo et al. 2018). Soil investigations are the essential key in two major fields such as construction field to assess load bearing and agricultural field to examine nutrient uptake by the plants. It is the best approach to identify potential fertilizer application to the specific soil (Ganorkar et al. 2013). In Indian agricultural practices due to high productivity, numerous chemical fertilizers are rapidly replacing the traditional manures but chemical fertilizers rigorously deteriorating the quality of soil (Borkar 2015). Physico-chemical parameter analysis is the essential step to all farming creations and woodland development. The quality of soil include it is water holding capacity, carbon confiscation, plant yield, squander remediation and other functions or even more keenly defined. Soil pH is the first and foremost soil parameter relates most of other parameters. Acidic soil has pH less than 6, normal soils have 6–8.5 pH and alkaline soil has pH above 8.5. High soil organic matter (SOM) reveals low pH conditions which denote that pH is inversely proportional to SOM content (Kekane et al. 2015; Kemal Fauzie and Ahmad 2015). In soil solution, the soil pH inversely proportional to cationic form of metals (Van Herk 2012). The pH influences several microorganism behaviours and nutrient values of soil (Borkar 2015; Sharma and Chaudhary 2017). The other significant parameters are carbon and nitrogen. Nitrates, nitrites, ammonia nitrogen and total nitrogen are the various forms of nitrogen. Proteins are synthesized by amino acids and amino acids have the vital element nitrogen (Sharma and Chaudhary 2017). Similarly, electrical conductivity (EC) is another simple, economic and rapid health indicator of soil (Kekane et al. 2015). Soil EC shows a relationship with soil texture, cation exchange capacity (CEC), crop productivity and organic matter (Sharma and Chaudhary 2017). It also indicates cationic and anionic nutrients availability (Gümüs and Seker 2017). Soil organic matter is very important soil property, rich in SOM content minimizes soil erosion. Best agricultural practices need sufficient SOM and it can be added by crop residue, green manure, manures of animal, organic fertilizer, compost, etc. Organic carbon is also soil nitrogen indicator (Borkar 2015; Kekane et al. 2015). Soil organic matter influences the binding of metal (Van Herk 2012). SOM persuade the exchange reactions, water relation and soil porosity and also responsible for carbon cycle, availability of nutrients, biological and chemical processes, crop productivity and yield (Middha et al. 2015). Deprived energy sources reduce the soil organic carbon and nutrient mineralization. Due to this, the activity of microbial biomass is minimized (Geetha and Reddy 2017). Plant cells acquire nitrate nitrogen either in organic or living form (Sharma and Chaudhary 2017). Blue green algae fix the atmospheric nitrogen into ammonia. Nitrogen is the essential plant growth stimulators of soil (Kekane et al. 2015; Kemal Fauzie and Ahmad 2015; Chaudhari 2013). Soil degradation along with nitrogen

Chemical Characterization and Environmental Implications …

71

loss leads to environmental issues and reduced soil fertility (Gümüs and Seker 2017). Effects of agricultural systems growth, increases leaching of nitrous oxide (N2 O), ammonia (NH3 ) and nitrate (NO3− ) from human induced global nitrogen flow. Microorganisms availed carbon and nitrogen depends upon the soil mineralization and immobilization rates. Typically nitrogen immobilization occurring as a result of increased carbon nitrogen ratio (Clough et al. 2013). It is tedious to understand apparent global carbon cycle of soil (Chapin et al. 2009). Sewage sludge contains good nitrogen, phosphorus sources and micronutrients, and it is also superior soil conditioner. Application of sewage sludge to agricultural practices makes ease the waste disposal for the water treatment plants and economical. Mostly raw sewage sludge contains the form of nitrogen as organic nitrogen and may be further vulnerable to microbial decay on soil application. It may contain little ammonia nitrogen but it differs based on the quantity and quality of it. Whereas in dissimilarity digested sludge in liquid phase has a very high proportion of ammonia nitrogen due to anaerobic digestion of sewage sludge which mineralizes the readily degradable organic matter. Through this, it is clear that nitrogen dynamics of sludge amended soil is based on types of sludge (Smith and Tibbett 2004). Environmental conditions and nitrogen deposition together may influence the soil carbon and nutrient cycling (Choi et al. 2017). Objective of the study is to compare the soil nutrient replenishing capacity of contaminated soil and partially digested sludge obtained from sewage treatment facility for low fertile native soil in mono-cultured field. The study also emphasizes the significance of co-compost using sewage sludge for the mono-cultured sugarcane field.

2 Materials and Methods 2.1 Study Area and Sampling The study area comprises of STP located (Fig. 1) in Bannari Amman Institute of Technology, Sathyamangalam (Lat 11.4952°N and Long 77.2764°E), Tamil Nadu, India with 7.5 MLD installed capacity, spread around 2654 m2 area. The STP is highly loaded with potential contaminants. In addition to this, occasionally excess sewage sludge (overflow) after pumping into sludge drying bed is dumping into the empty land around 4 m distance from the plant area. This leads to massive availability of nutrients in the site area. So sampling sites were randomly chosen and listed in ellipsis (Table 1). From the each site (0–15) cm depth, soil samples were taken for analysis. Recycled sludge from STP periodically assessed for physico-chemical characteristics.

72

P. Balaganesh et al.

Fig. 1 Sampling location and site map of the sewage treatment plant, Bannari Amman Institute of Technology Sathyamangalam Table 1 List of ellipsis and its expansion

S. No.

Expansion

Ellipsis

1

Sewage treatment plant

STP

2

STP front

SF

3

STP right corner

SRC

4

Near collection tank of STP

NCT

5

Near I filter of STP

NIF

6

Near I clarifier of STP

NIC

7

Near II clarifier of STP

NIIC

8

Near I aerator of STP

NIA

9

Near II aerator of STP

NIIA

10

Near sludge drying bed of STP

NSD

11

Electrical conductivity

EC

12

Total organic carbon

TOC

13

Total nitrogen

TN

14

Nitrate nitrogen

NO3 –N

15

Chloride

Cl

16

Soil replaced compost

SRC

17

Soil organic matter

SOM

Chemical Characterization and Environmental Implications …

73

2.2 Co-compost Preparation Composting performed in three HDPE bins with 50% ratio of STP sludge and other domestic wastes. The mixture was moistened with water to about 70% moisture content. Bins were turned manually every 3 days and then once a week for the rest of the 3 weeks. Water was sprayed every 2 days for maintaining the moisture content of the bins throughout the experiment. Temperature readings were monitored daily by inserting a thermometer probe into the bins of approximately equal length in each bin. Moisture content also monitored daily and it was assessed by gravimetric method. The prepared co-compost from STP sludge partially replaced with low fertile soil in proportions 20, 40 and 60% also taken for analysis.

2.3 Chemical Analysis Five-gram soil sample is taken for the chemical analysis. To assess pH, nitrate nitrogen the measured soil is extracted with 50 ml 2M KCl solution (Shahandeh et al. 2010; Amponsah et al. 2014) in orbital shaker. Further, 10-g sample is extracted with 20 ml distilled water (1:2) to find EC, total organic carbon, total nitrogen and chloride (Van Herk 2012; Pawan et al. 2017). Nitrate nitrogen estimated using Systronics PC based double beam spectrophotometer 2202. The reagents used were nitrate stock solution, nitrate standard solution, Brucine-sulphanilic acid solution and sulphuric acid solution. The absorbance values of blank, standard and sample were measured at 410 nm. Elico LI120 Digital pH meter was calibrated using buffer capsules of pH 4.0 and 9.0 then pH of samples measured. Total organic carbon and total nitrogen measured at 680 °C using Shimadzu TOC-L and TNM-L analyzer. The reagents used were double distilled water, 25% phosphoric acid and 1M HCl. Electrical conductivity measured using Elico CM 180 digital conductivity meter. It was calibrated by standard reference solution (0.01N KCl solution, 0.0014118 mhos/cm). Amount of chlorides estimated using titrimetric method. Potassium chromate solution and silver nitrate solution were the reagents used. Silver nitrate solution standardized using sodium chloride solution.

3 Results and Discussion 3.1 Relative Abundance of PH Range and Other Conductive Ions Existence in Sample Soil pH is the most crucial parameter which relates all the major physico-chemical parameters. The best pH range of soil for the effective plant growth is 6.8–8.0 (Middha et al. 2015). The pH values of experiment (Fig. 2) showed that mostly the soil samples

74

P. Balaganesh et al.

Fig. 2 Variation of pH and EC in STP proximity soil

were slightly alkaline and the ranges from 7.4 to 8.2. It reveals that the soil promotes plant growth by increasing the accumulation of soil organic carbon. Since acidic soils cannot hold the soil organic carbon to the maximum. The minimum pH 7.4 observed from NIIC soil and maximum pH 8.2 observed from NIA soil. Concentration of ion in solution is reported as conductance or EC and it is the good indicator for plant nutrient absorption (Middha et al. 2015; Wu et al. 2017). EC values observed from 0.209 to 1 mS/cm. NIF soil showed the minimum conductive ions and NIIA soil showed maximum value of conductive ions. NIA and NIIA both showed augmented EC values when compared to other.

3.2 Nitrate Nitrogen and Total Nitrogen Distribution The variation of TN and NO3 –N in STP proximity soil showed in Fig. 3. The minimum value 3.9 mg/L of NO3 –N observed from SF soil and maximum 14.297 mg/L by NIA soil. TN is minimum 11.28 mg/L in NIC soil and maximum 167.6 mg/L in NIIC soil. From the graph, it is clear that NIIC and NIA soils showed peak NO3 –N and TN values. So the proximity of aerators and clarifiers along with sludge drying bed is rich in plant growth stimulator nitrogen nutrients. Observed elevated nutrient values of soil were through different mass transfer processes like diffusion, absorption, adsorption, stripping and leaching in the proximity of STP encumbered with nutrient rich contaminants. Nitrogen is the important nutrient which induces plant growth. Excess nitrogen values leads to serious issues in our environment, so to protect environmental issues by runoff in STP proximity and to utilize the nutrient for deficient areas, soil from clarifiers, aerators, sludge drying bed and collection tank will be the best loom for interchanging.

Chemical Characterization and Environmental Implications …

75

Fig. 3 Variation of total nitrogen (TN) and nitrate-nitrogen (NO3 –N) in the STP proximity soil

3.3 Spatial Variation of Total Organic Carbon and Chloride The variation of TOC and Cl in STP proximity soil showed in Fig. 4. TOC of NIC soil showed minimum 34.77 mg/L and maximum 134.9 mg/L TOC observed from SF soil. Soil organic carbon reduces soil erosion, so the high TOC values of SF soil infer its suitability. This significant result expose reduced nitrogen values are essential to get good C/N values. Nowadays generally anthropogenic CO2 rise induces carbon level in our ecosystem by photosynthetic carbon fixation (Choi et al. 2017). NIF soil showed minimum 7.09 mg/L chloride value and SF soil showed maximum chloride level 35.45 mg/L. Fig. 4 Variation of total organic carbon (TOC) and chloride (Cl) in the STP proximity soil

76

P. Balaganesh et al.

3.4 Recycled Sewage Sludge as Organic Amendment Generally, sewage sludge has the potential to replenish soil with fertility due to its physico-chemical characteristics along with effective microbial consortium in it. The experiment findings of recycled sewage sludge are tabulated (Table 2) and it reveals that contaminated sewage showed rich in nutrient level (TOC 156.11 mg/L and TN 33.01 mg/L). Similarly, EC values 1.007 mS/cm expose that sufficient ions presence to promote nutrients. Higher chloride values will be the risk to growth of microorganisms and in turn it affects the nutrient levels. To remove the risk of waste and to increase productivity using it, the sludge processed with suitable bulking materials as high return co-compost. The low fertile NIC soil, which has similar nutrient profile of nearby sugarcane monocultured soil, partially replaced with cocompost prepared from sludge, and it was resulted in linear increase by 20, 40 and 60% replacement of soil (Fig. 5). Table 2 Chemical characteristics of the sewage sludge Sample

NO3 –N (mg/L)

Chloride (mg/L)

TOC (mg/L)

TN (mg/L)

EC (mg/L)

pH (mS/cm)

Recycled sludge

10.36

738.54

156.11

33.01

1.007

7.69

Fig. 5 Partial replacement of low-nutrient soil (NIC sample) with the prepared compost

Chemical Characterization and Environmental Implications …

77

4 Conclusions Present study dealt with chemical characteristics investigation of soil in the proximity of an overloaded STP and the implications of its operational and maintenance activities on SOM. The experiment findings clearly infer that the proximity of aerators, clarifiers and sludge drying bed has high TOC, TN and NO3 –N values and also all the samples evenly showed optimum pH ranges for the plant growth. This consequence increase significant accumulation of organic carbon (52%) and nitrogen (79%) in the soil to the extent that partial replacement of compost with low fertile STP soil NIC up to 60% could replenish the soil organic matter in a sugarcane monocultured soil. It has shown advantage on direct recycling of sewage sludge through co-composting for enhancing soil nutrients in sugarcane field. In addition to this, based on the experiment it is suggested that the low fertile monoculture top soil from agricultural field may be interchanged with STP proximity soil to induce crop yield, fertility and to effectively manage the contaminants in STP proximity. To satisfy the organic nutrient requirements in agricultural field and to deal the waste effectively, it is supposed to utilize the waste resources as useful returns. This will support for the economical and sustainable approach. Acknowledgements This research was funded by Science and Engineering Research Board, Department of Science and Technology, Government of India under Swachh Bharat Mission (ECR/2016/001114/ES). The authors would like to acknowledge the support rendered by the management, staff and students of Bannari Amman Institute of Technology, Sathyamangalam.

References Ahmad Wani K, Yadav R, Singh S, Kant Upadhyay K (2014) Comparative study of physicochemical properties and fertility of soils in Gwalior, Madhya Pradesh. World J Agric Sci 10(2):48–56 Amponsah D, Godfred E, Sebiawu DO (2014) Determination of the amount of the exchangeable Ammonium-Nitrogen in soil samples from the University of Cape Coast School Farm. Int J Sci Eng Res 5(6):731–736 Barot Pawan STV, KS (2017) Assessment of macro and micronutrients in soils from region. Newest Int Multidiscip J 3(4):25–29 Borkar AD (2015) Studies on some physicochemical parameters of soil samples in Katol Taluka District Nagpur (MS), India. Res J Agric Fores Sci 3(1):16–18 Chapin FS, McFarland J, David McGuire A, Euskirchen ES, Ruess RW, K ielland K (2009) The changing global carbon cycle: linking plant-soil carbon dynamics to global consequences. J Ecol 97:840–850 Chaudhari KG (2013) Studies of physicochemical parameters of different soil samples. Arch Appl Sci Res 5(6):72–73 Choi I-Y, Hang V-M, Nguyen JHC (2017) Effects of controlled environmental changes on the mineralization of soil organic matter. Environ Eng Res 22(4):347–355 Clough T, Condron L, Kammann C, Müller C (2013) A review of biochar and soil nitrogen dynamics. Agronomy 3:275–293

78

P. Balaganesh et al.

Ganorkar RP, Chinchmalatpure PG, Ganorkar RP (2013) Physicochemical assessment of soil in Rajura Bazar in Amravati District of Maharashtra (India). Int J Chem Environ Pharm Res 4(2&3):46–49 Geetha S, Reddy B (2017) Physico-chemical analysis of selected agricultural soil samples in Kommangi Panchythi, Chintapalli Madal. Int J Inf Res Rev 4(1):3530–3532 Gümü¸s I, Seker ¸ C (2017) Effects of spent mushroom compost application on the physicochemical properties of a degraded soil. Solid Earth 8:1153–1160 Kekane RP Chavan, Shinde DN, Patil CL, Sagar SS (2015) A review on physico-chemical properties of soil. Int J Chem Stud 3(4):29–32 Kemal Fauzie A, Ahmad Khudsar F (2015) Analysis of soil physico-chemical properties in various sites at Yamuna Biodiversity Park, Delhi, India. Int J Innov Res Sci Eng Technol 4(8):7220–7228 Luo C, Deng Y, Inubushi K et al (2018) Sludge biochar amendment and alfalfa revegetation improve soil physicochemical properties and increase diversity of soil microbes in soils from a rare earth element mining wasteland. Int J Environ Res Public Health 15:1–22 Middha R, Jain S, Juneja SK (2015) A comparative study of physico-chemical parameters of restored and unrestored soils of two villages of Chaksu Block, Jaipur, Rajasthan. Int J Eng Technol Sci Res 2:9–13 Shahandeh H, Wright AL, Hons FM (2010) Use of soil nitrogen parameters and texture for spatiallyvariable nitrogen fertilization. Precis Agric 12:146–163 Sharma KM, Chaudhary HS (2017) Physico chemical analysis of soil of Digod Tehsil, Kota and their statistical interpretation. Int J Sci Res 6:1681–1683 Smith MTE, Tibbett M (2004) Nitrogen dynamics under Loliumperenne after a single application of three different sewage sludge types from the same treatment stream. Bioresour Technol 91:233– 241 Tola E, Al-Gaadi KA, Madugundu R, Zeyada AM, Kayad AG, Biradar CM (2016) Characterization of spatial variability of soil physicochemical properties and its impact on Rhodes grass productivity. Saudi J Biol Sci 24(2):421–429 Van Herk A (2012) Physicochemical parameters in soil and vegetable samples from Gongulon Agricultural Site, Maiduguri, Borno State, Nigeria. Int J Chem 1:21–36 Wu X, Wei Y, Wang J et al (2017) Effects of soil physicochemical properties on aggregate stability along a weathering gradient. Catena 156:205–215

Novel Techniques of Synthesis of Nanocellulose from Sugarcane Bagasse and Its Applications in Dye Removal Shubhalakshmi Sengupta, Megha Srivastava, Uttariya Roy, Papita Das, Siddhartha Datta, and Aniruddha Mukhopadhyay

Abstract Agricultural wastes requires it’s utilization by the use of novel techniques. Lignocellulosic materials present in them could be utilized for various purposes. Nanocellulose could be synthesized from it. In this study, nanocellulose fibres from sugarcane bagasse were synthesized using sustainable methods and were ascertained by using microscopic techniques (scanning electron microscopy and transmission electron microscopy). The nanocellulose thus obtained was used in removing azo dye blue from water. Batch adsorption studies were conducted obtaining a removal efficiency of 75% dye removal in 2 h. Adsorption of dye molecules on the nanocellulose fibres were further visualized under scanning electron microscopy. Thus, agricultural wastes are renewable resources which could be utilized in removal of hazardous dyes from waste waters. Keywords Agricultural wastes · Nanocellulose · Dye removal S. Sengupta (B) · M. Srivastava · U. Roy · P. Das · S. Datta Department of Chemical Engineering, Jadavpur University, 188, Raja S C Mullick Road, Kolkata 700032, India e-mail: [email protected] M. Srivastava e-mail: [email protected] U. Roy e-mail: [email protected] P. Das e-mail: [email protected] S. Datta e-mail: [email protected] S. Sengupta Department of Sciences and Humanities, Vignan’s Foundation for Science Technology and Research (VFSTR), Vadlamudi, Guntur 522213, Andhra Pradesh, India A. Mukhopadhyay Department of Environmental Science, University of Calcutta, 32, Ballygunge Circular Road, Kolkata 700019, India e-mail: [email protected] © Springer Nature Singapore Pte Ltd. 2020 S. K. Ghosh et al. (eds.), Emerging Technologies for Waste Valorization and Environmental Protection, https://doi.org/10.1007/978-981-15-5736-1_8

79

80

S. Sengupta et al.

1 Introduction Environmental problems of today’s world pose various challenges towards mankind. One of the major challenges faced by our planet is to find innovative ways to reduce the carbon footprint. In the quest of such an objective, use of renewable resources is a viable option. Agricultural wastes are one such type of renewable resources whose usage results in sustainable product development. In countries like India, lignocellulosic materials generated from agricultural wastes have abundant usages. In India, a large amount of waste is generated due to agricultural production of crops like mustard, sorgum, oilseeds, cotton and sugarcane. They often do not find any alternative use and are left in fields or buried. Use of agricultural wastes reduces which are a renewable resource can lead to the development of materials which could have various usages (Srivastava et al. 2017). Among these agricultural wastes, sugarcane bagasse is rich in lignocellulosic materials which can lead to production of wide range of products starting from alternative fuels, cellulose based materials and adsorbents. Cellulose, hemicellulose and lignin are the polymers which comprises lignocellulosic materials. These are linked with one another in a hetero-matrix in different degrees and whose varying composition varies based on type, source of biomass and species (Srivastava et al. 2017). It is well known that cellulose is the most abundant polymer in nature with wide range of application potential. Structurally, cellulose is organized as microfibrils being linked together to form cellulose fibres and exhibits many application possibilities. One of them is adsorption of dyes from waste water specially in its nano form (Xie et al. 2011). Thus, in this study, a novel technique has been used for production of nanocellulose from sugarcane bagasse, an agricultural waste and has been deployed in removal of azodye from waste water.

2 Literature Survey It is well known that cellulose exhibits interesting properties like high modulus, strength, low density, high aspect ratio and low production cost. Recently, cellulose nanofibres have received great deal of attention due to its great properties, abundance in nature and applicable properties. Thus, synthesizing nanocellulose from agricultural lignocellulosic wastes like sugarcane bagasse is a novel approach for production sustainable materials (Sain et al. 2014). Again, dyes are organic compounds which are a by-product of various industries like textile, pulp, paper, paint, food and cosmetics. These are often discharged into the environment posing great threat to the aquatic ecosystem as well as to human water consumption (Roy et al. 2018a). They cause diseases like dermatitis, allergy, cancer, skin irritation, mutations and even cancer in humans. So, their removal from the waste waters is an area of grave concern. Among the dyes used, azo dyes which are often defined as derivatives of diazene are used widely in leather and textile industries. These dyes are often mutagenic and toxic to human beings. However, they are often

Novel Techniques of Synthesis of Nanocellulose from Sugarcane …

81

not removed properly from the waste waters properly. There are various methods like ion exchange, chemical precipitation, flocculation, osmosis, coagulation, reverse osmosis and adsorption for dye removal. Among the various methods, adsorption is an effective method for dye removal (Roy et al. 2018b). There are various reports lignocellulosic materials have been used for effectively removing dyes from waste waters (Annadurai et al. 2002; Crini 2006; Manna et al. 2017).

3 Materials and Methods 3.1 Materials Sugarcane bagasse was collected from local fields and was repeatedly washed and then crushed and grounded to pieces for synthesis of nanocellulose. The chemicals sodium chlorite, sodium hydroxide, sodium bisulphite and sulphuric acid were procured from Loba chemie, India. Azo blue (C34 H24 N 4 N a 2 O 8 S2, CAS. No: 6059-34-3) dye was procured from Himedia, India, for making simulated azo blue waste water.

3.2 Extraction of Nanocellulose from Sugarcane Bagasse At first, raw sugarcane bagasse was treated with 0.7% NaClO3 solution at pH 4 and kept for 2 h at near boiling temperature with continuous stirring to remove the lignin fraction. This step was repeated twice for complete lignin removal. The mass was then filtered and washed in 2% sodium bisulphate solution for 15 min. This was then vacuum dried and then treated with 17.5% NaOH for about 20 min and then macerated. After alkali treatment, it was subjected to acid hydrolysis (50% H2 SO4 ) for 4 h at 50 °C following the standard procedure. The prepared nanocellulose was washed further, centrifuged, filtered and dried. It was then subjected to ultrasonication to further get the desired nanocellulose.

3.3 Characterizations The nanocellulose was further characterized in order to ascertain its proper extraction.

82

3.3.1

S. Sengupta et al.

Scanning Electron Microscopy (SEM)

Surface morphologies of raw sugarcane bagasse, nanocellulose before ultrasonication, were analysed by scanning electron microscope (SEM) Zeiss EVO 18, Carl Zeiss, Germany, after gold coating and then operated at 5 kV.

3.3.2

Transmission Electron Microscopy (TEM)

The ultrasonicated nanocellulse was viewed under transmission electron microscope (HRTEM: JEOL JEM 2010, Japan) operating at an accelerating voltage of 200 kV.

3.4 Batch Adsorption Studies In order to determine the applicability of the nanocellulose in dye removal, preliminary batch adsorption study was conducted on 25, 50, 75 and 100 mg/L of azo blue dye waters at intervals of 15 min, 30 min, 45 min, 1 h and 2 h at 35 °C temperature under agitation of 120 rpm, respectively. 100 mg of nanocellulose was used after optimization with various amount. The initial dye concentration and the dye concentration after adsorption studies were analysed spectrophotometrically (Perkin elmer, USA) at 574 nm. The percentage of dye removal was calculated from the final and initial dye concentrations (Roy et al. 2018a)

4 Results and Discussion 4.1 Characterizations 4.1.1

Scanning Electron Microscopy (SEM)

The SEM image of raw sugarcane bagasse and the extracted nanocellulose is given in Fig. 1. From the image, it is evident that considerable reduction in size and smoothening of surface due to removal of lignin and hemicellulose fractions were observed. However, from this technique of nanocellulose synthesis, a mixture of nano and microcellulose is produced. Thus, further treatments are required on this produced mass.

Novel Techniques of Synthesis of Nanocellulose from Sugarcane …

83

Fig. 1 SEM micrographs of raw sugarcane bagasse (a) and nanocellulose (b)

4.1.2

Transmission Electron Microscopy (TEM)

The ultrasonicated nanocellulose was viewed under TEM for better observations (Fig. 2). This image revealed further reduction in size and ascertained a homogenization of the micro and nano fractions. Thus, this process ensured synthesis of nanocellulose which could be further used for application in dye removal. Fig. 2 TEM image of ultrasonicated nanocellulose

84

S. Sengupta et al. 80 70

25 mg/L 50 mg/L 75 mg/L 100 mg/L

% Removal of dye

60 50 40 30 20 10 0 0

15

30

45

60

75

Time (mins) Fig. 3 Percentage of azo blue dye removal by nanocellulose at different time intervals

4.2 Batch Adsorption Studies This preliminary adsorption study mainly focused on the effect of time for maximum dye adsorption before reaching equilibrium. From Fig. 3, it is evident the dye adsorption is rapid initially and slows down on reaching equilibrium. Initially, the surface of the nanocellulose with its free bonds adsorbs the dye particles rapidly and as it gets filled the process slows down. However, lower the initial dye concentration, higher is the removal with 75% dye adsorption at 25 mg/L dye concentration. But at higher dye concentration levels (100 mg/L), removal was achieved up to 67% of the initial dye concentration. Thus, dye efficient dye removal was achieved using a low cost adsorbent required at very low amount.

5 Conclusion Thus, in this study, a novel technique was employed to synthesize nanocellulose from an agricultural waste, i.e. sugarcane bagasse. Utrasonication of the extracted nanocellulose gave better yield of it. This nanocellulose was used effectively in removal of a azo blue dye from waste water. Thus, this agricultural waste product could be used in synthesis of nanocellulose which have great applications, with one of them being adsorption of dyes from industrial waste waters.

Novel Techniques of Synthesis of Nanocellulose from Sugarcane …

85

Acknowledgements SS would like to acknowledge UGC DS Kothari Postdoctoral Fellowship (Sanction No. CH/15-16/0163) Scheme for financial assistance during the tenure of this work.

References Annadurai G, Juang RS, Lee DJ (2002) Use of cellulose-based wastes for adsorption of dyes from aqueous solutions. J Hazard Mater 92(3):263–274 Crini G (2006) Non-conventional low-cost adsorbents for dye removal: a review. Bioresource Technol 97(9):1061–1085 Manna S, Roy D, Saha P, Gopakumar D, Thomas S (2017) Rapid methylene blue adsorption using modified lignocellulosic materials. Proc SAF Environ 107:346–356 Roy U, Sengupta S, Banerjee P, Das P, Bhowal A, Datta S (2018a) Assessment on the decolourization of textile dye (reactive yellow) using pseudomonas sp. immobilized on fly ash: response surface methodology optimization and toxicity evaluation. J Environ Manage 223:185–195 Roy S, Sengupta S, Manna S, Das P (2018b) Chemically reduced tea waste biochar and its application in treatment of fluoride containing wastewater: batch and optimization using response surface methodology. Proc SAF Environ 116:553–563 Sain S, Sengupta S, Kar A, Mukhopadhyay A, Sengupta S, Kar T, Ray D (2014) Effect of modified cellulose fibres on the biodegradation behaviour of in-situ formed PMMA/cellulose composites in soil environment: Isolation and identification of the composite degrading fungus. Polym Degrad Stab 99:156–165 Srivastava M, Sengupta S, Das P, Datta S (2017) Novel pre treatment techniques for extraction of fermentable sugars from natural waste materials for bio ethanol production. Int J Env Sci Nat Res 7:1–7 Xie K, Zhao W, He X (2011) Adsorption properties of nano-cellulose hybrid containing polyhedral oligomeric silsesquioxane and removal of reactive dyes from aqueous solution. Carbohydr Polym 83(4):1516–1520

Assessment of Greenhouse Gases and Perception of Communities on Emissions from the Largest Dumpsite in Africa Michael A. Ahove, Olasunkanmi M. Ojowuro, and Chinenye L. Okafor

Abstract Human quest for survival and improved quality of life has led to uncontrolled consumption patterns with numerous unfavourable environmental behaviours. We are generating more waste than we can handle especially in developing economies with low citizenry’s level of awareness, poor waste management and technological skills. Africa is one of such regions having numerous municipal solid waste landfills and open dumpsites which generate major greenhouse gases (GHGs) during anaerobic decomposition within many communities. The largest of such in Africa is the 103 acres landfill located on the outskirts of Lagos with surrounding communities. This is a major contributor to climate change with methane having global warming potential 25–30 times more effectiveness than carbon dioxide. This study is an attempt to assess major GHGs emissions, detectable within 12 selected locations from communities bordering Olushosun waste dumpsite. In addition to this, the perception of 348 respondents (213 male and 135 female), living or working within the adjourning communities of the dumpsite, was assessed on GHGs and odour emitting from the site. Gamma Air Quality device was employed for the detection of GHGs, and methane and carbon dioxide were the only GHGs detectable as well as carbon monoxide. The demographic data of respondents were found to be heterogeneous, about 90% says they are aware of the existence of the dumpsite, 85% claimed to significantly perceive the bad odour, 27% have previous knowledge of the existence of methane within the site but only 41% of the samples are willing to use it for cooking while 71% are willing to tap methane from the site for other domestic uses such as electricity generation. Other relevant analyses are reported, implications for climate change impact, climate change education and risk assessment are drawn, and conclusions and recommendations were made. M. A. Ahove (B) · O. M. Ojowuro · C. L. Okafor Centre for Environmental Studies and Sustainable Development, Lagos State University, Lagos State Waste Water Management Office, Ministry of the Environment, Lagos, Nigeria e-mail: [email protected]; [email protected] O. M. Ojowuro e-mail: [email protected] C. L. Okafor e-mail: [email protected] © Springer Nature Singapore Pte Ltd. 2020 S. K. Ghosh et al. (eds.), Emerging Technologies for Waste Valorization and Environmental Protection, https://doi.org/10.1007/978-981-15-5736-1_9

87

88

M. A. Ahove et al.

Keywords Dumpsite · Greenhouse gases · Community odour perception · Climate change · Nigeria

1 Introduction The quest for human survival and improved quality of life led to the emergence of the industrial, scientific and technological revolutions and has made modern human the culprit of the earth’s degradation. This is traceable to our uncontrolled consumption patterns including numerous unfavourable environmental behaviours (Ahove and Bankole 2018) such as excessive use of polyvinyl chloride (PVC) especially as shopping bags and sometimes its indiscriminate disposal. Municipal solid waste (MSW) appears to be a bone in the neck to humanity worldwide becoming increasingly complicated day after day mostly due to the rise in population, industrialisation and the consequent changes introduced in the lifestyle of people (Singh et al. 2018). Solid waste generation bears the characteristics of the nation’s economic growth, demographic pattern, nature of the city, community and the seasons. The characteristics of MSW may be generally classified into degradable (such as food waste, paper, textiles, yard waste, disposable napkins and many others) and nondegradable waste (includes but not limited to plastics, metals, glass and electronic waste). Increase in greenhouse gases (GHGs) emissions has contributed immensely to climate change, which is a current threat to human existence on earth. GHGs generated from anaerobic decomposition in landfills and open dumping sites around the world are adding to the global warming issue, and the three major greenhouse gases emitted from this decomposition are methane (CH4 ), carbon dioxide (CO2 ) and nitrous oxide (N2 O). Poor management of MSW in terms of treatment and disposal processes form a major reason for its contribution to climate change. Studies have shown that methane (CH4 ) generated from the decomposition of MSW is the second largest global contributor to GHGs (see Rafiq et al. 2018) (Fig. 1). When the anaerobic condition prevails, owing to methanogen activities, the MSW emits CH4 for years, even if the landfill is closed. Gas production normally starts 2–6 months after internment of the wastes and continues as much as 100 years. The constituents of gas in a landfill typically include 45–60% methane (CH4 ) and 40–60% carbon dioxide (CO2 ). It also include small amounts of nitrogen (N2 ), oxygen (O2 ), ammonia (NH3 ), hydrogen sulphide (H2 S), hydrogen (H2 ), carbon monoxide (CO), and non-methane organic compounds (NMOCs) such as trichloroethylene, benzene and vinyl chloride (Rafiq et al. 2018). The global warming potential of CH4 is 25–30

Complex Organics Waste

First stage (Acid Forming Bacteria)

Organic Acids

CH4 and CO2

Second Stage (Methane Forming Bacteria)

Fig. 1 Two stages of the anaerobic decomposition of complex organic wastes Source: McKendry et al. (2002)

Assessment of Greenhouse Gases and Perception …

89

times more effective than carbon dioxide making it a very important GHG and over the last centuries and its concentration in the atmosphere has gradually increased. It is also estimated to rank second (18%) among the GHGs. GHG is the nomenclature for a cluster of gases basically consisting of methane (CH4 ), carbon dioxide (CO2 ), nitrous oxide (N2 O) and chlorofluorocarbons. These gases form a blanket in addition to the natural quantity of carbon dioxide in the atmosphere thereby forming a thicker layer of blanket that traps the sun’s radiation within the troposphere causing gradual increase in average global temperature referred to global warming. Thus, gradual increase in global temperature for decades led us into a climatic condition now referred to as climate change (Ahove and Bankole 2018). Municipal solid waste disposal and management in Africa has continued to grow into a complex challenge for individuals and families whose wastes are disposed, communities where dumpsites are sited and waste disposal agencies as well as government institutions in charge of waste management. These challenges may be laid at the feet of poor leadership, population explosion, low level of literacy, poverty of most citizenry, urbanisation and industrialisation. These have consequently resulted to a large quantity of waste generation and spread of illegal dumpsite. The weaknesses within the political, legal, educational and economic institutions of most developing countries have not helped matters significantly.

2 Background on Olushosun: Lagos, Nigeria Nigeria is the most populous country in Africa possessing a land area of about 910,000sq km lying between 4° and 14° N latitudes and 3° and 13° E longitudes. It is bordered by Benin Republic in the west, Niger Republic in the north, Cameroon in the east and the Atlantic Ocean in the south. Lagos, the former capital of Nigeria, is approximately 3,345 km2 in size and lies between latitudes 6°23’N and 6°4’N and stretches between longitudes 2°42’E and 3°42’E. It is now Africa’s newest biggest city, a state located in south-western part of Nigeria along the west coast of Africa. This coastal city state with a population of over 195 Million (UN 2017) has the highest concentration of residential, industrial, commercial, educational and military facilities in West Africa (Adelekan 2010) and hosts 90% of Nigeria’s foreign trade as well as about 80% of the overall value import. It is a fast growing urban (with a growth rate of 3.5%) city state, with the emergence of several slums and shanties, where diverse opportunities abound as well as socio-economic and environmental concerns. The dumpsite, Olushosun and not Olusosun, is the official spelling as adopted by the Lagos State Ministry of the Environment. It has been in existence since 1992, with a closure plan of 2022. Olushosun as a location was founded by the Nigerian Military around the last 1960s and 70s as a shooting range for criminals. When it was closed down at the end of the civil war, the site was used as a soil mining site for road construction especially the neighbouring Lagos-Ibadan Express way. The site in 1992 was selected by Lagos State Waste Management Authority (LAWMA) as a dumpsite

90

M. A. Ahove et al.

located within Longitude 6° 35’ 50”E to 6° 36’ 30”E and Latitude 3° 22’ 45”N to 3° 23’ 30”N (LAWMA 2009). The dumpsite is topographically characterised by hills, valleys and gorges, located on the outskirts of Lagos city, initially avoiding the dense populace of the city, but today the story is different. The dumpsite is transverse by five major roads but three authorised entrances; first is the Motorways, Off LagosIbadan Expressway, Ikosi; secondly is Olushosun Street, Off Kudirat Abiola Way, Oregun; and finally Ojota Motor Garage, Off Ikorodu Road, Ojota. The Olushosun Dumpsite is owned and operated by the Lagos State Government and is being patronised by LAWMA Trucks, Private Sector Participation (PSP) Trucks, Highway Managers, Cart Pushers and Waste Pickers. Its catchment area extends to all parts of Lagos Metropolis and receives the greatest proportion of solid waste, more so with the high number of PSP Operators. Olushosun is the biggest repository of waste in the most populous city in sub-Saharan Africa (Alani et al. 2017). It is reported to be the largest in Africa and one of the fifteen largest in the world (Mills 2018), and it receives more than 50% of the 16,000 tons of waste generated daily in the state (CLI 2018). The purpose of this paper is to assess the perception of people living in selected neighbouring communities along Olushosun dumpsite on the peculiar stench emanating from the dumpsite and the amount of greenhouse gases (methane and carbon dioxide) detectable within the communities.

3 The Problem One of the ‘shame of Lagos’ is experienced along the Lagos-Ibadan express way as you drive into the city from the inter-land in Ogun state as well as along Ikorodu or Kudiratu Abiola way, you are greeted with this very strong offensive stench emitting from the Olushosun dumpsite. This is the bitter but daily nightmare reality of the people living and working within this neighbourhood, whose years of numerous complain has yielded no significant result. Thus, it is a case of learn to live with it else move out of the location, which is apparently a part of the business district of Lagos. Methane emissions are peculiar to dumpsite especially this massive site in focus, whose amount of methane released into the neighbouring communities, can only be imagined than experienced. The 103 acres dumpsite will obviously be a significant contributor to global warming. One of the fears of the inhabitants of these communities is on the fire outbreaks and its attendant consequences of irritating, chocking and poisonous fumes emanating during fire outbreaks. Many individuals, families, businesses and organisations go through this ordeal.

Assessment of Greenhouse Gases and Perception …

91

4 Research Questions 1. What is the level of methane and carbon dioxide obtained in the ambient air neighbouring the communities? 2. What is the perception of people living in the neighbouring communities on the stench from the landfill? 3. What is the previous knowledge of the residents on the major landfill gases (GHGs) and their alternative uses?

5 Methodology The method adopted for this study was twofold. First was the collection of air quality data, and secondly was the assessment of residential, store occupiers, factory and office workers’ (along Olushosun neighbourhood) perception on odour and methane emanating from the dumpsite. The first phase deployed the use of Gamma air quality analyser in detecting the air quality and the amount of GHGs present within the selected locations in the communities. The gases detected by the device at every point of the 12 locations were noted as well as the percentage quantity. The selection of the sampling points was influenced by the number of people that complain about the odour (minimum of 20) to the team of researchers on arrival at their axis, the group so selected by this method must be at least within 100 m distance from one sampling point to another, availability of respondents and their willingness to be part of the study (Fig. 2). The study was conducted at the end of the dry season (earlier March) just before the commencement of the south-west monsoon rain (April-October) when about 80% eighty of the annual rainfall (1160 mm) will take place relative to the remaining 20% (250 mm) of the northeast monsoon (November–March) in line with the suggestion of Aderemi and Otitoloju (2012). The research design for the second phase of the data gathering was a survey involving the administration of a self-developed questionnaire. The first section of the questionnaire has six demographic items such as gender, educational status, occupier status and others. The second section had 15 items that sought information from the respondents on issues bothering on respondents’ experiences with odour and methane gas emanating from the dumpsite and other related views were sought. A total of 348 participants (213 male and 135 female) were found to have properly responded to the questionnaire and therefore appropriate for analysis. Individuals aged eighteen (18) and above available at the moment and willing to respond to the questionnaire were administered the questionnaire. This is in addition to the criteria earlier spelt out for the selection of sampling point for the air quality assessment. The 348 questionnaires were scored and subjected to descriptive analysis to provide answers to the research questions articulated in this paper.

92

M. A. Ahove et al.

Fig. 2 Google map data showing olushosun dumpsite and 12 sample points (2018)

6 Result and Discussions Three research questions were articulated to provide guide and illumination to the variables for investigation in this study. These questions will be attended to sequentially in the light of participants’ responses. Before addressing these questions, it is essential to discuss on the demographics of the respondents. A greater percentage of the respondents (52%) were within the age range of 26–40 years, 22.7% within 41–50 years, 18.4% within 18–25 yrs and while the remaining few (6.9%) were above 50 years. They were mostly single (62.4%) with 34.5% being married and 3.2% divorced. Their educational background ranked from primary to secondary (50.4%) while the rest had higher education. The respondents are an active part of the work force with majority (53.2%) involved in business and finance related work; about 23% in science and technology, 15.5% in administrative positions, 1.7% in the legal sectors while the remaining 6.6% are in military or paramilitary. Most of the

Assessment of Greenhouse Gases and Perception …

93

respondents (49.4%) have lived in the neighbourhood within 5 years, 21.6% within 6–10 years while the rest 29% have being around for over 10 years. This shows that majority of the respondents have not lived in the neighbourhood for too long. This could be traceable to the hazardous propensity of the dumpsite producing light white fumes and offensive stench (Aderemi and Otitoloju 2012) which we found in this study to extend to the residents in the adjourning communities around Olushosun. Aderemi and Otitoloju (2012) also reported the presence of dioxin in the fumes at Olushosun when dumpsite fires occur either naturally (methane induced within high temperature and combustible material or intentionally (by the acts of the landfill waste pickers as a technique of sorting out steel from tyres). This experience is quite common in the entire major landfills sites in Lagos state. However, the Lagos State Waste Management Authority officials are often up to the task of controlling these challenges.

7 GHGs Assessment Within the Communities The first research question states that what is the level of methane and carbon dioxide obtained in the neighbouring communities? The Gamma air quality device detected the presence of methane (CH4 ) and carbon dioxide (CO2 ), (being the GHGs) including carbon monoxide (CO) and oxygen (O2 ). However hydrogen sulphide (H2 S) was not detectable at any of the 12 sampling points contrary to expectation and is traceable to instrument detection limitation. The popular local names of the sampling points and their coordinates, distance by road from the sampling point to the dumpsite and the percentage of detectable gas at each sampling point, are well spelt out in Table 1. Result indicates that methane concentration was 5% ppm in four locations but 4% ppm in the other eight locations. Methane concentration as low as 5% ppm is dangerous enough to cause explosion especially in closed facility because of the asphyxiate propensity in displacing oxygen. The danger behind this result is that any closed facility within the range of this dumpsite at 5% ppm of methane may be considered at risk to fire incident. However, these results were obtained in open air with oxygen concentration of between 20.7 and 21.1 ppm but three of the four locations with higher methane (5% ppm) concentration showed lower oxygen concentration (20.7–20.9) relative to locations with lower methane (4% ppm) concentration with oxygen concentration of 21.0 ppm–21.1 ppm.

8 Community Perception of Odour The second research question states that what is the perception of people living in the neighboring communities on the stench from the landfill? Four items in the questionnaire were designed to provide answers to this research question. The first item requires a Yes or No response from the participants if they

94

M. A. Ahove et al.

Table 1 Showing sampling locations, distance, coordinates and gases detected within olushosun neighbourhood communities S.No.

Location

Distance (km) from the dumpsite

Coordinates

Gases (% ppm) CO

H2 S

CH4

CO2

O2

1

Ola Adeshega 2.6 street

6.59869, 3.36452

ND

ND

5

0.03

20.7

2

Daystar Church

4.5

6.60023, 3.37248

6

ND

4

0.06

21.1

3

GLO office

4.8

6.57867, 3.37869

5

ND

4

0.06

21.1

4

LAGBUS garage

0.6

6.59799, 3.37826

5

ND

4

0.06

21.0

5

Opebi link road

3.4

6.59472, 3.36324

4

ND

5.5

0.04

20.9

6

Ikosi Oregun junction

1.7

6.59987, 3.37008

6

ND

5

0.03

21.1

7

Ibijoke street

2.6

6.59947, 3.36293

28

ND

5

0.02

20.7

8

Dangote

2.1

6.60038, 3.36695

7

ND

4

0.05

21.1

9

Lifemate office

1.9

6.60029, 3.36856

22

ND

4

0.04

21.1

10

Mechanic village

4.3

6.58243, 3.38306

5

ND

4

0.09

21.1

11

Motorways

0.85

6.59989, 3.37706

2

ND

4

0.04

21.1

12

Tantaliser

4.3

6.58754, 3.39754

13

ND

4

0.09

21.0

ND: Not detectable

perceive the odour emanating for the dumpsite. Among the 348 participants, 85.6% says Yes and 14.4% says No to perceiving the stench emanating from the dumpsite (see Fig. 3). This shows that the vast majority of the respondents perceived the stench. The outcome of this result is similar with the findings of Sakawi et al. (2011) where 94.7% of the total participants (190) from the neighbouring community confirmed that they could perceive the odour emanating from the Pajam and Ampar Tenang landfill sites in Malaysia. Fig. 3 Odour perception of the respondents

Percieved Odour NO YES 0.00%

50.00%

100.00%

Assessment of Greenhouse Gases and Perception …

Odour Frequency

Once a month

Twice a month

Once a week

Thrice a week

60.00% 40.00% 20.00% 0.00% Daily

Fig. 4 Respondents’ odour perception frequency

95

How frequently the respondents perceive the odour was the next item. Results indicate that 40.5% claim to perceive the odour daily, 19.3% mentioned thrice weekly, 18.4% once a week, 4.6% twice a month and 17.2% once a month as shown in Fig. 4. On the contrary to the method adopted on frequency of odour perception, Sakawi et al. (2011) reported on the basis of ‘once a day’, ‘once a week’ and ‘once a month’ being the frequency of perception as indicated in their study. Another item which assessed the respondents’ perception on the intensity of the odour was placed on a five point scale of response. Very strong was the view of 52.9% of the respondents, 21.3% rated it as strong, mild had 12.9%, very mild was 11.8% and nothing (meaning no odour was perceived) had 1.1% (see Fig. 5). The study of Sakawi et al. (2011) showed four levels of responses on odour intensity and result indicates: strong (74.2%), medium (16.3%), weak (8.4%) and No smell (1.1%). In this study, the summation of the responses of very strong (52.9%) and strong (21.3%) gives a score of 74.2%, if we assume both figures are on ‘strong’ in terms of intensity. Therefore, a juxtaposition of this outcome (74.2%), with Sakawi et al. (2011) study with focus on ‘strong’, coincidentally gives exactly the same percentage score of 74.2%. Also the score of the respondents in the two independent studies also shows that ‘No smell’ in the study of Sakawi et al. (2011) and ‘Nothing’ in this study were the same scores 1.1%. These are interesting similarities in these studies and an emerging prove of consistency, on perception on odour intensity among people who Fig. 5 Odour intensity by the respondents

Odour Intensity NOTHING VERY MILD MILD STRONG VERY STRONG 60.00%

40.00%

20.00%

0.00%

96 Fig. 6 Weather factors on odour by the respondents

M. A. Ahove et al.

Weather Factors DRY SEASON/DAY

RAINY SEASON/DAY 90.00%

80.00%

70.00%

60.00%

50.00%

40.00%

30.00%

20.00%

10.00%

0.00%

live and work in communities neighbouring open dumpsites. It may not be out of tune to argue that the nasal cavity and especially the olfactory nerve of the respondents in both studies displayed proportionate smell reception. The perception of the respondents on the influence of weather and season on the odour from the dumpsite was also assessed. Result shows that 78.4% of the respondents claim that during rainy season or rainy day, the odour is stronger but 21.6% had a contrary view as shown in Fig. 6. This peculiar stench has strong impact on the environment and people living in the neighbouring communities creating a comfortable environment harbouring disease causing vectors such as rodents and flies (Aderemi and Otitoloju 2012) a common finger print of the African dumpsites. An interesting result obtained from the respondents was that 190 of 348 say they can still tolerate the stench irrespective of the intensity but 158 share a contrary perception.

9 Knowledge and Perception on GHG and Alternative Uses The third research question says what is the previous knowledge of the residents on the major landfill gases (GHGs) and their alternative uses? The analysis of this question indicates that most of the respondents were ignorant and had no previous knowledge of the names of the GHGs that could be found or emanating from Olushosun dumpsite. 65.2% of the respondents claim they have no idea of the GHGs at the dumpsite, 27.3% says methane can be found or emanates from the dumpsite while 7.5% claim that carbon monoxide (CO) or carbon dioxide (CO2 ) emanates or can be found at the dumpsite. Figure 7 gives a pictorial analysis of this result. It is surprising that this sampled population with over 87% respondents that have acquired at least a secondary education displayed this high level of ignorance. This level of education should have provided the respondents with the knowledge of the presence of carbon monoxide (CO), carbon dioxide (CO2 ) and methane as dominate gases in waste dumpsite, usually in a secondary school biology or health science class

Assessment of Greenhouse Gases and Perception … Fig. 7 Previous knowledge of dumpsite gases by respondents

97

Previous Knowledge Of Dumpsite Gases METHANE CO & CO2 NO IDEA

70.00%

60.00%

50.00%

40.00%

30.00%

20.00%

10.00%

0.00%

(being a mandatory subject students are exposed in class up till 2017). The low level of ignorance may be traceable to forgetfulness, and it may be that the respondents have lost intellectual contact with the subject in question and are now given to business or some other activities that is of interest to them. Therefore, recalling the right answers may be a challenge. Another dimension that was investigated relates to the respondents’ perception on alternative uses of methane from the dumpsite. This perception was conducted from three perspectives as shown in Table 2. The first was on using methane from the dumpsite for cooking, with 58.9% decline while 41.1% support the idea and are willing to use methane from the dumpsite for cooking their meals. Result from qualitative response from all respondents who decline in the use of methane for cooking did so because of the stench. Some are of the opinion that the stench will affect their meals while cooking others cannot because of the uncomfortable feelings they experience when they imagine that the gas from the stench is used for cooking the meal which may be contaminated; also the memory of the stench will be recalled if they are consuming the meal. These experiences and feeling is unbearable to them. The second item focused on preference for methane gas if cheaper than methane from liquefied natural gas (methane obtained from fossil fuel). Result as shown in Table 2 indicates that 60.1% of the respondents, relative to 39.9%, confessed that they prefer methane gas from dumpsite if the cost is found to be cheaper than methane from liquefied natural gas. On the perception of ‘methane from dumpsite if not tapped will increase global warming’, 71.3% supports the idea but 28.7% are of contrary opinion. This outcome indicates that when people within this community are aware of the potential benefit of methane, they will be glad that it is tapped for use rather than spew into the environment and result in disaster. Table 2 Showing preference and readiness to use dumpsite methane gas S.No. Items

Yes (%) No (%)

1

I will use dumpsite methane gas for cooking

41.1

58.9

2

Preference for methane gas from dumpsite if cheaper

60.1

39.9

3

Methane from dumpsite if not tapped will increase global warming 71.3

28.7

98

M. A. Ahove et al.

10 Implications for Climate Change Impact and Climate Change Education The implication that may be drawn from the outcome of this study is that significant percentage of methane are being released from the Olushosun dumpsite in view of the significant concentration of methane found in the air within a vast area of the dumpsite. This clearly implies that large quantities of methane are being emitted thus increasing the tropospheric quantity of GHGs which contributes to the challenge of climate change. Olushosun dumpsite by implication is contributing to the negative impact of climate change. Nigeria must reduce her own share of the expected significant increase in GHGs from developing nations to 64% by 2030 and 76% by the year 2050; and climate change education will provide different options, especially behavioural change, that the stake holders required to reduce significantly methane emission from Olushosun dumpsite.

11 Conclusions and Recommendations This study found a relatively high occurrence of methane, carbon dioxide and carbon monoxide within the neighbouring communities of Olushosun dumpsite. The concentration in air appears high enough in some locations to cause explosion in closed facilities. The dumpsite appears to be a major contributor of GHGs as a result of the high concentration of the methane gas even from a far distance. Very offensive stench were observed by the researchers and also reported by the respondents who live and work in the communities. In view of the outcome of this study, it may not be out of place to mention that contemporary solid waste management is a challenge to the human society especially in the developing economies. The reality is that GHGs will continue to emanate from our dumpsites unless and until we develop first and foremost appropriate behaviour through environmental education and systematic waste disposal techniques by sorting from source to reduce waste and encourage recycling. It is essential to start extracting with immediate effect the methane locked within the dumpsite for use. We should begin to embrace circular economy, waste to compost as tools to effective waste management. Sanitary land fill should be the last option as we strive towards zero landfilling as we embrace total consumption of our municipal solid waste. Further studies are encouraged to analyse the GHGs in the dumpsite rather than from the air quality in the neighbourhood as conducted in this study. For a beautiful blue planet with less climate change challenges, developing nations must put their acts together for effective SWM.

Assessment of Greenhouse Gases and Perception …

99

References Adelekan IO (2010) Vulnerability of poor urban coastal communities to flooding in Lagos. Niger Environ Urbanization 22(2):433–450 Aderemi AO, Otitoloju AA (2012) An assessment of landfill fires and their potential health effectsa case study of a municipal solid waste landfill in Lagos. Niger Int J Environ Prot 2(2):22–26 Ahove MAN, Bankole SI (2018) Petroleum industry activities and climate change: global to national perspective. In: Ndimele PE (ed) The political ecology of oil and gas activities in Nigerian aquatic ecosystem. Elsevier, United States of America, pp 277–292 Alani R, Abdulfatai M, Ogbe R, Akinade B (2017) Health hazards safety risks and security threats posed by Olusosun dumpsite on Olusosun community at Ojota Lagos Nigeria. Am J Life Sci 5(3):43–51 Cleaner Lagos Initiative (CLI) (2018) Evolving innovative tools for waste management: wealth not wastes. Paper presented at the Lagos climathon hackaton at the Lagos state environmental protection agency Ikeja, Lagos on the 26th October Lagos State Waste Management Authority (LAWMA) (2009) Report of the resettlement action plan for the waste pickers of Olushosun dumpsite. The resettlement action committee. LAWMA, Lagos, Nigeria McKendry P, Looney J, McKenzie A (2002) Managing odour risk at landfill sites: main report. Millennium science & engineering Ltd (MSE). Retrieved from www.viridis.co.uk Mills C (2018) 15 of the World’s largest landfills with photos and statistics. Retrieved from www. owlcation.com Rafiq A, Rasheed A, Arslan C, Tallat U, Siddique M (2018) Estimation of greenhouse gas emissions from Muhammad Wala open dumping site of Faisalabad, Pakistan. Geol Ecol Landscapes 2(1):45– 50. https://doi.org/10.1080/24749508.2018.1452463 Sakawi Z, Mastura S, Jaafar O, Mamud M (2011) Community perception of odour from landfills. Malays J Soc Space 7(3):18–23 Singh KC, Kumar A, Roy SS (2018) Quantitative analysis of the methane gas emissions from municipal solid waste in India. Scientific reports 8:2913 https://doi.org/10.1038/s41598-018-213 26-9 United Nations (2017) The World’s cities in 2016. Retrieved from: https://www.un.org/en/develo pment/desa/population/publications/pdf/urbanization/the_worlds_cities_in_2016_data_booklet. pdf

Performance Analysis of Treatment of Distillery Spent Wash Using EGSB Reactor with Addition of Iron and Manganese G. M. Hiremath and Veena S. Soraganvi

Abstract This paper addresses treatment of distillery spent wash using expanded granular sludge blanket (EGSB) with the addition of elemental metals. In batch reactors, accelerated granulation was carried out with non-granulated sludge from UASB (up-flow anaerobic sludge blanket), septic tank sludge and cow dung along with the macro, micro-nutrients, methanol, chitosan and aluminium sulphate. Granulation was achieved on 21st day. Specific methanogenic activity (SMA) test was conducted to check the activity of granular sludge. To start with, the reactors R1 (control) and R2 (with elemental metals) were first loaded with 9 L of active granular sludge, and the spent wash was fed at an organic loading rate (OLR) of 2.3 kg COD/m3 /day with 24 h hydraulic retention time (HRT). Observations were made on pH, COD (chemical oxygen demand) removal efficiency, effluent volatile fatty acids (VFA), effluent alkalinity and methane generation. The pH of effluent varied from 6.5 to 8.10 in R1 and 6.5 to 7.95 in R2. VFA/Alkalinity ratio varied from 0.39 to 0.15 in R1 and 0.36 to 0.10 in R2. At an OLR of 38.40 kg COD/m3 /day in R1 and R2, COD removal efficiencies achieved were 81.40% and 85.20% and methane production was 2.61 L/LR /day and 3.78 L/LR /day respectively. Addition of iron powder (10 g/L) and manganese (4 g/L) resulted in enhancing hydrolysis, methanogenesis and VFA reduction. Production of methane was higher in reactor R2 (1.45 times) than reactor R1, which is a clear indication that the addition of manganese and iron metal powder enhanced the methane production. Keywords Granulation · Anaerobic digestion · Elemental metals · Methane production

G. M. Hiremath · V. S. Soraganvi (B) Department of Civil Engineering, Basaveshwar Engineering College, Bagalkot, India e-mail: [email protected] G. M. Hiremath e-mail: [email protected] © Springer Nature Singapore Pte Ltd. 2020 S. K. Ghosh et al. (eds.), Emerging Technologies for Waste Valorization and Environmental Protection, https://doi.org/10.1007/978-981-15-5736-1_10

101

102

G. M. Hiremath and V. S. Soraganvi

1 Introduction Effluent from distillery industries is highly acidic (pH 4–4.3) and concentrated. Biological treatment method is found to be the best compared to physical and chemical treatment methods, as it can handle high COD (chemical oxygen demand) and BOD (biochemical oxygen demand). Generation of wastewater is increasing day by day, and its proper treatment is necessary before releasing into the environment. Through anaerobic digestion (AD), treatment can be achieved along with energy production (Nandy et al. 2002). Nowadays, industries are opting to incineration, but during the incineration process, nutrients are lost; therefore, AD had gained importance throughout the world. This study focuses on the overview for the optimization of the AD process by addition of elemental metals to increase methane generation, along with the removal of organic material ensuring high efficiency. Several studies have illustrated the aggregation of bacterial biomass called as granulation which enhances the process of treatment and production of biogas. Hiremath and Soraganvi (2015) performed a study on accelerated granulation in the EGSB reactor. In this study, chitosan and aluminium sulphate were used to accelerate the granulation, at an OLR of 4 kg COD/m3 /d. Spherical granules of an average diameter of 2 mm were observed on 21st day. Tay et al. (2006) studied on bio-granulation methods to treat different types of wastewater. To form granules in an anaerobic reactor, more number of conditions has to be satisfied. As yet, no model is connecting the entire anaerobic granulation process correctly. Physical, chemical and biological factors which stimulate granulation should be integrated and optimized. Distillery spent wash is highly concentrated and toxic; therefore, its treatment is challenging due to its very high COD and low pH. Lekshmi (2013) conducted a study on treating and recycling of distillery spent wash. A hybrid anaerobic baffled reactor (HABR) was designed to treat spent wash and succeeded to decrease the concentration, with a COD removal efficiency of 92%. Carlos and Marcos (2005) studied the factors affecting and described nutrients required for anaerobic digestion. The amount of nitrogen content for high-yield coefficient was as follows: COD:N:P = 350:5:1 or C:N:P = 130:5:1 the required quantity of phosphorus established was around 1/5 to 1/7 of that of nitrogen. Most of the bacteria use sulphide as a source of sulphur, since sulphur is essential for digestion of proteins. In general, sulphur and phosphorous appear to be requisite in the same amount. Chou et al. (2011) conducted a study on EGSB reactor for treating wastewater which involved sulphate. The reactor was having a high h/d ratio of 17.5 and higher up-flow recirculation velocity (4–6 m/h), which helped in better contact between liquid and sludge bed. Several researchers have worked towards enhancement of methane generation during the treatment of wastewater (Tartakovsky et al. 2011; Liu et al. 2012, 2015; Sen et al. 2015). Liu et al. (2015) used different forms of iron metals such as iron powder, clean and rusty scrap for methane generation from sludge in batch reactor. By experimental study, both clean and rusty iron enhanced the methane generation compared to iron powder. In Liu et al. (2012), the addition of iron to UASB was resulted in enhancing the hydrolysis and fermentation, resulting in COD removal

Performance Analysis of Treatment of Distillery Spent …

103

(45–56%) and VFA production (1170–1340 mg/L) with HRT varying from 6 to 2 h. Addition of iron metal (10 g/L) showed a positive sign for acetogenesis and methanogenesis while propionate generation was reduced and also improved the acidogenesis phase by obtaining higher efficiency. Sen et al. (2015) studied about enhancement of methanogenic activity by addition of manganese metal to the wastewater in batch reactors. Adding up of elemental manganese (4 g/L) helped to increase in methane production by 3–5 times, and also it results in more acetate utilization and reduction in the propionate generation. In the methanogenesis stage, manganese metal acted as an electron donor to carbon dioxide. The addition of manganese resulted in 96.9% methane generation which was 2 times more than the control (46.6%). Several studies are illustrating the capability of the EGSB reactors in treating wastewater and also enhancing the biogas production. But the mineral addition to EGSB reactors to enhance biogas generation was not found in the literature and is addressed in this work. In this study, an EGSB reactor was used for the treatment of spent wash with the addition of optimum dosage (10 g/L) of iron and manganese powder (4 g/L) to enhance the hydrolysis and the biogas production. The performance was compared with a control reactor, and the results are promising.

2 Materials Two EGSB reactors were setup to study the performance analysis of treatment of spent wash and biogas generation. One is control EGSB reactor R1 and another one is EGSB with metal additions known as R2. In this work, the two laboratory scale EGSB reactors were fabricated using acrylic and PVC pipe of 100 mm diameter and overall height of 1900 mm. Openings of 18 mm at inlet, outlet, recirculation, gas outlet and sludge outlet arrangements were provided to avoid clogging action in the reactors. For the separation of gas, liquid and solids, a separator (GLSS) was provided. The sludge outlet was provided at the bottom so as to remove excess sludge in the reactor. Gas collection outlet was provided at the top of the reactor, and methane is measured by gas flow meter after passing through a 5% NaOH solution.

2.1 Inoculum Inoculum was prepared in the batch reactors after 21 days of achieving accelerated granulation by mixing active sludge, which was obtained from UASB reactor treating sugar mill wastewater (from EID Parry India Ltd, at Nainegali, Hungund taluk Bagalkot, India, septic tank sludge and cow dung in the proportion of 1:1:1.

104 Table 1 Characteristics of distillery spent wash

G. M. Hiremath and V. S. Soraganvi Parameter

Values

Colour

Dark brown

pH

4.2–4.5

COD (mg/l)

96,400–105,200

BOD (mg/l)

46,000–55,000

Total solids (mg/l)

86,400–93,600

Chlorides (mg/l)

3850–4200

Sulphates (mg/l)

3940–4350

Total Nitrogen (mg/l)

3940–4350

Phosphorous as P2 O5 (mg/l)

780–1040

Potassium (mg/l)

7900–8710

2.2 Substrate Distillery spent wash was collected from Kartik Agro Industry, Bagalkot, and several tests have been conducted and various parameters thus obtained are listed in Table 1.

2.3 Chitosan For accelerated granulation, chitosan was used as a polymer and added at the rate of 2 mg/g of total solids Hiremath and Soraganvi (2015).

2.4 Glucose Glucose was added as a carbon source for bacteria.

2.5 Methanol Methanol was added at start up for the enhancement of the growth of methanogenic bacteria. The addition of methanol is dependent upon the composition of the spent wash (Nandy et al. 2002).

Performance Analysis of Treatment of Distillery Spent …

105

2.6 Chemicals The various chemicals required for the reactor operation and the micro and macronutrients were added as per the study carried out by Tartakovsky et al. (2011).

2.7 Metals Zero valent iron is a reducing metal. It was evaluated that essential iron enhances the hydrolysis and fermentation stage in the anaerobic procedure. Iron acts as an electron donor for changing over CO2 to CH4 through hydrogenotrophic methanogenesis Liu et al. (2015). The reaction is shown in Eq. (1) CO2 + 4Fe0 + 8H+ = CH4 + 4Fe2+ + 2H2 O

(1)

Manganese is a reducing metal, it works as an electron donor for methane production from CO2 , due to its better reducing nature, it is more competent than iron. Manganese was consumed by methanogens to generate CH4 . The reaction in Eq. (2) will indicate methanogenesis process with expansion of manganese (Sen et al. 2015). CO2 + 4Mn0 + 8H+ = CH4 + 4Mn2+ + 2H2 O

(2)

Iron (10 g/L) and manganese (4 g/L) metals were being used in the study. Iron powder helps in hydrolysis and acidification, producing acetic acid and reducing the propionate acid, whereas manganese metal works in the range of hydrogenotrophic methanogens for the production of methane from CO2 .

3 Methodology 3.1 Batch Reactors In the first stage, the granulation was carried out by the batch process. To achieve accelerated granulation sludge from active UASB, septic tank and cow dung were collected and sieved so that waste floating particles/matter were removed. These were mixed in the proportion of 1:1:1. The non-granulated sludge was fed the with macro and micro nutrients, methanol, chitosan and glucose. Glucose added was about 1000 mg/l, chitosan 2 mg/g of TS, ethanol and micronutrients, aluminium sulphate (200 mg/L) were also added. The granulation was achieved on 21st day. In the reactors, initially the pH of the sludge was varying and later was maintained at around 7. The pH and COD values were measured at a regular intervals.

106

G. M. Hiremath and V. S. Soraganvi

3.2 Evaluation of Microbial Activity of Granulated Sludge The analysis of specific methanogenic activity (SMA) of the sludge has been conducted in the four flasks with different substrate (sodium acetate) concentrations of 2, 4, 6 and 10 mg/L. The flask containing 4 mg/L (i.e. Flask 2) substrate showed the maximum methane gas production of 228 mL in 48 hours. Figure 1 shows the variations in biogas production in each of the flasks with respect to the time.

3.2.1

Procedure for (SMA) Test (Carlos and Marcos 2015)

1. Initially, the volatile solids present in the sludge had to be analysed (g VS/L). 2. Four reaction flasks of each 500 mL were taken, and the pre-determined amounts of sludge were placed into the reaction flasks. Before starting the test, the sludge was placed 12–24 hours before starting the test at 30 °C. 3. The total concentration of the mix (substrate, sludge and solution) must be equal to 2.5 g VS/L after the addition of nutrient and buffer solutions to the flasks. 4. Add the elemental metals iron (10 mg/L of sludge) and manganese (4 mg/L of sludge). 5. The total volume must not cross the 70–90% of the flask volume. 6. For the proper mixing, a magnetic stirrer was used. 7. During the test, the volume of biogas liberated at every time interval (mL/h) was observed. 8. The methane present in the biogas was determined by passing the biogas through the alkaline solution (e.g. 5% NaOH) to arrest the carbon dioxide. The activity of sludge was nearing to 0.75 g COD-CH4 /gVS.d as observed in the flask-2.

Fig. 1 Methane production analysis by SMA test

Performance Analysis of Treatment of Distillery Spent …

107

3.3 Continuous Reactors In this work, the two laboratory scale EGSB reactors were fabricated and elemental metal of 10 g/L of Iron and 4g/L of Manganese are added to the reactor R2. Indeed, the addition of iron can lower oxidation–reduction potential and serve as an acid buffer, thus helping maintain a stable and favourable condition for methanogens and could promote hydrolysis/acidification and optimize volatile fatty acid (VFA) compositions. Wherein, with the addition of elemental manganese, it was assumed that the manganese metal could also serve as an electron donor for methane formation from CO2 and is more effective than iron element due to its stronger reducibility. Therefore, the addition of elemental metals like iron and manganese to the anaerobic digester could be a potentially cost-effective approach to improve methane production from distillery spent wash (Sen et al. 2015; Balakrishnan and Batra 2005). Parameters like pH, alkalinity, VFA and COD were analysed as per standard methods (APHA/AWWA/WEF 1998). The biogas generated was made to pass through a 5% concentrated NaOH solution, which dissolves CO2 .

Fig. 2 Expanded granular sludge bed (EGSB) reactor (with metal addition)

108

G. M. Hiremath and V. S. Soraganvi

4 Results and Discussions The study was carried out to observe the performance of EGSB reactors to treat distillery spent wash for varying COD concentrations at different HRTs. During this study, observations were recorded for various parameters such as pH, VFA, Alkalinity, COD removal efficiency and methane production at regular intervals. Figure 3 illustrates pH variation during the operational period in both the reactors. The influent pH was maintained at 7 by adding a suitable amount of NaHCO3 . The methanogenic bacteria are sensitive to the pH change. Thus, the methane production is primarily dependent on pH. The optimal range of pH for the growth of methanogenic bacteria lies in between 6.6 and 7.6 pH values; less than 6.0 and more than 8.3 pH are avoided as pH below 6 results in increase of acids and also slows up hydrolysis and acidogenesis activity (Carlos and Marcos 2005). Hence, pH was maintained in between 6.6 and 7.6 in the effluent. The systematic verification of alkalinity is more significant than the assessment of pH. Conversion of intermediate volatile fatty acids, conversion of proteins and amino acids render some alkalinity to the system. The optimum ratio of VFA/Alkalinity should be less than 0.3 (Carlos and Marcos 2005). Higher the VFA/Alkalinity more will be the disturbance in the anaerobic digestion process. High levels of alkalinity are necessary because of the high concentration of volatile acids. NaHCO3 was added to the reactor to boost the alkalinity, if necessary. During the operational period, the VFA/Alkalinity ratio was observed to be in between 0.1 and 0.32. Figure 4 shows the VFA/Alkalinity ratio with respect to OLR.

Fig. 3 Effluent pH comparison

Performance Analysis of Treatment of Distillery Spent …

109

Fig. 4 Variation of VFA/Alkalinity ratio with OLR

The COD removal achieved was almost the same in both reactors. Hydrolysis and acidification were boosted by the metals in R2. The reactor R2 showed slightly higher COD removal efficiency as metal addition resulted in hydrolysis, in the formation of acetic acid and finally to the methane conversion. COD removal efficiency for both the reactors was compared with OLR. In Fig. 5, R1 and R2 showed peak COD removal efficiencies of 81.40% and 85.20% respectively at 38.4 kg COD/m3 /day. Elemental iron improved hydrolysis and acidification in the anaerobic process where proteins and cellulose were degraded (Nandy et al. 2002). Apart from this, it

Fig. 5 COD removal efficiency (%) with OLR

110

G. M. Hiremath and V. S. Soraganvi

Methane production (L/L/Day)

4 3.5 3 2.5 Methane producƟon

2 1.5

Methane producƟon in EGSB with metals

1 0.5 0 2.3

4.6

6.9 9.6 18.2 25.6 38.4 OLR (kg COD/m3/Day)

57.6

Fig. 6 Methane production (L/LR /d) with OLR

acted as an electron donor for converting CO2 to CH4 through hydrogenotrophic methanogenesis. Similarly manganese metal also behaved as that of iron metal. The contribution of metals added towards COD removal is not significant. Figure 6 shows methane production of both the reactors. R2 showed methane production of 3.78 L/LR /d and R1 showed 2.61 L/LR /d at an OLR of 38.4 kg COD/m3 /d. There was an increase of 45% in the methane production in R2 compared to that obtained in R1.

5 Conclusions Two laboratory scale EGSB rectors were run to understand the possibility for treating distillery spent wash along with biogas production. Addition of chitosan had shown a positive effect on sludge granulation. Granulation was accomplished within a short period of 21 days in batch reactors. The organic loading rate was optimized to 38.4 kg COD/m3 /day at 6 hours HRT in continuous reactors. Addition of iron (10 g/L) and manganese (4 g/L) had shown a positive effect on hydrolysis and methanogesis. COD removal efficiency in EGSB with metal (85.20%) is at slightly at higher side compared with the control EGSB reactor (81.40%). It showed that iron and manganese have significantly enhanced methane production rather than hydrolysis. The Methane production rate in EGSB with metals (R2) is 1.45 times higher than that of control EGSB reactor (R1). Addition of manganese and iron metal powders have resulted in an increase in biogas production significantly, whereas the effect on COD removal efficiency is not much significant.

Performance Analysis of Treatment of Distillery Spent …

111

References Balakrishnan NK, Batra VS (2005) Improving industrial water use: case study for an Indian distillery. Resour Conserv Recycl 43:163–174 Carlos AL, Marcos VS (2005) Biological wastewater treatment in warm climate region. Department of Sanitary and Environmental Engineering, vol 1, pp 664–835 Chou H, Huang J, Chen S, Lee M (2011) Process kinetics of an expanded granular sludge bed reactor treating sulphate containing wastewater. Chem Eng J 170:233–240 Hiremath GM, Soraganvi V (2015) Accelerated granulation in EGSB reactor using distillery spent wash with chitosan and aluminium sulfate. In: Proceedings of the third international conference on advances in civil, structural and environmental engineering. ACSEE, Switzerland, pp 91–95 Lekshmi SR (2015) Treatment and reuse of distillery wastewater. Int J Environ Eng Manage 4(4):339–344 Liu Y, Wang Q, Zhang Y, Ni B (2015) Zero valent iron significantly enhances methane production from waste activated sludge by improving biochemical methane potential rather than hydrolysis rate. Sci Rep 5:01–06 Liu Y, Zhang Y, Quan X, Li Y, Zhao Z, Meng X, Chen S (2012) Optimization of anaerobic acidogenesis by adding Fe0 powder to enhance anaerobic wastewater treatment. Chem Eng J 192:179–185 Nandy T, Shastry S, Kaul SN (2002) Wastewater management in cane molasses distillery involving bioresource recovery. J Environ Manage 65:25–38 Sen Q, Tian T, Benyu Q, Zhou J (2015) Methanogenesis from wastewater stimulated by addition of elemental manganese. Sci Rep 5:1–10 Standard Methods for the Examination of Water and Wastewater (APHA/AWWA/WEF), 20th edn. 1998 Tay J, Tay ST, Liu Y, Show K, Volodymyr I (2006) Biogranulation for wastewater treatment. Waste management series. Elsevier Publisher, pp 5–8 Tartakovsky B, Mehta P, Bourque JS, Guiot SR (2011) Electrolysis-enhanced anaerobic digestion of wastewater. Biores Technol 102:5685–5691

Recent Trends in Valorization of Non-metallic Ingredients of Waste Printed Circuit Board: A Review Debnil Bose, Sourav Barman, and Rajat Chakraborty

Abstract Extraction and subsequent valorization of several non-metallic ingredients present in waste printed circuit boards (WPCBs) is a challenging area of research and development nowadays. Various technologies are being explored to procreate an environmentally viable as well as cost-effective recycling protocol concerning WPCB. From literature review, it can be deduced that several simple recycling techniques comprising of thermal, chemical, and hydrometallurgical methods can be employed to produce various value-added and precious materials from WPCB, which in turn reduces the generation of unusable solid wastes; thus mitigating waste management problems. This article provides an insight on various conventional and emerging technologies as well as challenges incurred in valorization of WPCB. Keywords Waste printed circuit board · Pyrolysis · Non-metallic ingredients · Recycling · Sustainable methodologies

1 Introduction In recent times, technological advances have rendered creation of several useful products; nevertheless, the life cycles of these products are quite limited, thus leaving no option for disposition. Unworkable printed circuit boards (PCBs) are generally waste materials which if normally disposed can have harmful effects on the environment due to the presence of various toxic materials (Guo et al. 2009). In developing countries, because of lack of infrastructure, the e-waste is usually dismantled manually, thereby releasing non-degradable plastics and persistent hazardous chemicals to the environment which contribute to deterioration of air, water, and soil quality (Muniyandi et al. 2013; Myavagh and Mckay et al. 2016). Hence, recycling of WPCB for production of valuable materials through green technologies is of utmost importance in order to reduce obnoxious effects on environment.

D. Bose · S. Barman · R. Chakraborty (B) Department of Chemical Engineering, Jadavpur University, Kolkata 700032, India e-mail: [email protected]; [email protected] © Springer Nature Singapore Pte Ltd. 2020 S. K. Ghosh et al. (eds.), Emerging Technologies for Waste Valorization and Environmental Protection, https://doi.org/10.1007/978-981-15-5736-1_11

113

114

D. Bose et al.

Over recent past, researchers have reported several advanced methodologies for metal recovery from WPCB. However, recycling of non-metallic ingredients (NMI) has not been developed yet to a reasonable extent considering its lower economic value (Guo et al. 2009; Huang et al. 2009). In previous practices, these NMI were either incinerated or land-filled (Guo et al. 2010). Recently, several recycling methodologies viz. ‘physical treatment’ (crushing, grinding, sedimentation); ‘thermal treatment’ (pyrolysis, gasification); and ‘chemical treatment’ (viz. hydrometallurgical treatment, solvent extraction) have been investigated (Kan et al. 2015). These reports implied that combined physicothermal treatment (PTT) and physicochemical treatment (PCT) were much more efficient for NMI recycling than corresponding individual treatments (Huang et al. 2009). Chemical treatment is much more useful than thermal treatment since in chemical treatment, the metallic as well as non-metallic ingredients of PCB can be separated for subsequent conversion to several valuable materials by following different pathways, whereas in thermal treatment, WPCB can only be converted to fuels leaving behind untreated solid residues (Williams 2010; Marques et al. 2013). Thus, whether PCT should be followed for extracting the NMI or whether direct PTT should be used without recovering the NMI is debatable concerning the economic and environmental aspects. This article encompasses a meticulous review on usual and emerging technologies to valorize WPCB through production of several useful NMIs.

2 Thermochemical Routes for WPCB Valorization 2.1 Pyrolysis Over recent times, researchers have demonstrated pyrolysis as a promising thermal technique for conversion of e-wastes into valuable products. Before pyrolysis, the WPCBs consisting of large and vain components such as capacitors, solder joints, insulators, and resistors are generally separated through a pre-treatment procedure, wherein separation of the dispensable components can be accomplished via manually disassembling or treating these components at higher temperatures. The resultant WPCBs obtained after pre-treatment or directly collected and isolated in its nascent stage are then pyrolyzed at higher temperatures. The pyrolysis temperatures usually range from 200 °C to several thousand degrees. However, the optimal temperature at which pyrolysis occurs generally range from approximately 500 to 700 °C (Jie et al. 2008; Long et al. 2010; Quan et al. 2010; Chiang et al. 2007). Through pyrolysis technique, several non-metallic fractions of PCBs are cracked to obtain various valuable products, e.g., pyro-oils viz. phenol, furans, bisphenol A and pyro-gases such as CO2 , H2 O and solid residues viz. char and tar from which various materials can be retrieved (Li et al. 2010). In addition, most WPCBs contain valuable amount

Recent Trends in Valorization of Non-metallic Ingredients …

115

of glass fibers and other solid components which can be separated and recycled for re-use. Table 1 illustrates that Jie et al. (2008) pyrolyzed WPCB in a non-catalytic quartz tubular reactor with nitrogen as carrier gas at pyrolysis temperatures ranging from 300 to 700 °C. It was reported that a temperature of at least 500 °C was required to ensure complete pyrolysis of PCB resulting in 78% yield of carbonaceous solid residue, 10% liquid/pyro-oil (Fig. 1), and 13% gaseous products. The gases mainly comprised of C1 –C4 hydrocarbons, CO, and CO2 . Noticeably, Vasile et al. (2008) (Table 1) obtained various products from pyrolysis of WPCBs in a non-catalytic semibatch operation at an optimum temperature of 540 °C. They reportedly obtained a significantly high liquid yield of 23%, the liquid obtained comprised of approximately 5 wt% of aqueous fraction, in addition to pyro-oil. Moreover, due to the presence of commercially available DHC-8 and metal loaded activated carbon as catalyst, the rate of subsequent catalytic hydrogenation of pyrolysis-oils vehemently increased, thus implying beneficial role of catalyst. Conversely, Ng et al. (2014) (Table 2) obtained specifically higher amount of pyrooils with a requirement of lower temperature and time, signifying low energy requirement and operating cost through the application of catalyst. This evidently highlights the advantages of catalytic pyrolysis over conventional/non-catalytic pyrolysis. Besides, this process also generated lower amount of toxic compounds. However, catalytic pyrolysis also possesses some major pitfalls. Significantly, it has been reported by several researchers that pyro-oils derived from pyrolysis of WPCB produces several toxic compounds consisting of benzofuran, cresol, thymol, etc., which can have severe harmful impacts on the environment. Hence, certain supplementary stages are required in addition to pyrolysis to further separate or discard these toxic compounds from pyro-oils. A 2-stage decay of WPCB comprising of pyrolysis and catalytic treatment was therefore adopted by several researchers. This proves to be an effective and precious methodology for separation of toxic compounds from resultant pyro-oils obtained by pyrolysis (Vasile et al. 2008).

2.2 Gasification Route Although retrieval of metals and production of valuable solid, liquid, and gaseous products from WPCB through pyrolysis route is routinely common nowadays, in recent years, production of valuable products through steam and atmospheric gasification of WPCB has become a promising technology and can be used as an effective replacement of pyrolysis methodology. As evident from Table 3, it can be observed that Salbidegoitia et al. (2015) investigated catalytic steam gasification of waste phenolic boards (WPBs) in the presence of eutectic ternary carbonates at temperatures of 823–948 K for efficient hydrogen production. It was reported that unsupported nickel metal powder or small nickel pieces in molten carbonate could be used as an effective catalyst for hydrogen production from steam gasification of WPB. Moreover, it was also observed that a significant decrease in char (from nearly 49

Type of pyrolysis

Atmospheric (N2 ) pyrolysis

Vacuum pyrolysis (20 kPa)

Atmospheric pyrolysis

Atmospheric (N2 ) pyrolysis

S. No.

1

2

3

4

Continuous non-catalytic electrical furnace quartz tube; length, 0.7 m, dia., 0.03 m; time, 30 min; temperature, 500 °C

Semi-batch non-catalytic cylindrical stainless steel fixed-bed reactor; length, 0.375 m, internal dia., 0.057 m; time, 120 min; temperature, 700 °C

Batch non-catalytic pilot-scale fixed bed reactor; length, 0.35 m, internal dia., 0.16 m; time, 120 min; temperature, 500 °C

Continuous non-catalytic quartz tubular reactor; length, 1.2 m, internal dia., 0.06 m; time, 30 min; temperature, 500 °C

Reactor type/reaction conditions Solid-78 Liquid-10 Gas-12

Products yield (%)

Solid (glass fiber, carbon) Solid-39 Liquid (n-octane, acetone, Liquid-30 benzene, Gas-31 methyl-ethyl-ketone, etc.) Gas (HBr, CO and CO2 , O2 )

Solid (glass fiber, carbon) Solid-76.8 Liquid (phenol, Liquid-17.8 4-(1-ethylethyl)-phenol, Gas-5.4 phenolic resin, cresol) Gas (hydrocarbons, O2 )

Solid (glass fiber, carbon) Solid-74.7 Liquid (acetone, toluene, Liquid-15 benzofuran, phenol) Gas-10.3 Gas (H2 , HBr, hydrocarbons, CO2 , CO, O2 )

Solid (glass fiber) Liquid (phenol) Gas (hydrocarbons, CO2 , CO, O2 )

Valuable product

Table 1 Different products and their yields obtained from non-catalytic pyrolysis of WPCB

Jie et al. (2008)

References.

Quan et al. (2010)

(continued)

High reaction Chiang et al. (2007) temperature, production of toxic compounds

High reaction time and temperature

High reaction time and Long et al. (2010) temperature, generation of toxic compounds

Separation problem, contains harmful pollutants viz. bromine

Comments

116 D. Bose et al.

Type of pyrolysis

Atmospheric pyrolysis

Atmospheric (N2 ) pyrolysis

Atmospheric pyrolysis

S. No.

5

6

7

Table 1 (continued)

Semi-batch non-catalytic thermal reactor; residence time, 1.0-2.5 s; temperature, 540 °C; catalyst, DHC-8 and metal loaded activated carbon

Continuous non-catalytic fixed-bed reactor; space velocity, 1000 h−1 ; time, 30 min; temperature, 549.85 °C

Continuous non-catalytic fixed bed reactor; length, 0.26 m; internal dia., 0.0445 m; time, 135 min; temperature, 800 °C

Reactor type/reaction conditions

Solid (glass fiber) Liquid (phenol, furan, acetone, bromophenol, styrene etc.) Gas (O2 , CO2 )

Solid (glass fiber) Liquid (light naphtha and heavy gas oil) Gas (HBr, bromine)

Solid (glass fiber) Liquid (bisphenol-A, phenol, cresol etc.) Gas (hydrocarbons, CO, CO2 , O2 )

Valuable product

Solid-70 Liquid-23 Gas-7

Solid-34.5 Liquid-40.6 Gas-24.9

Solid-68.9 Liquid-22.7 Gas-4.7

Products yield (%)

Hall and Williams (2007)

References.

High reaction temperature

Vasile et al. (2008)

High reaction Chien et al. (2000) temperature, production of toxic compounds

High reaction temperature and time, production of toxic compounds

Comments

Recent Trends in Valorization of Non-metallic Ingredients … 117

118

D. Bose et al.

Fig. 1 Typical pyro-oil yield (%) in non-catalytic pyrolysis of NMI at 500 °C

to 23%) formation occurred in the presence of unsupported nickel as catalyst and a subsequent increase in the carbon yield of gases. As a result, modern generation researchers are trying to shift toward combined pyrolysis gasification technology to reduce severe process conditions as well as generation of toxic compounds. Zhang et al. (2012) investigated steam gasification of epoxy board samples (EBS) in the presence of eutectic carbonate products having activation energy of 122 kJ/mol. It was reported that subsequent higher yields (60.8%) of gaseous products consisting mainly of H2 and CO2 could be obtained at a rapid rate due to the presence of carbonates. A two-step degradation process was reportedly followed for gasification of EBS comprising of an initial rapid pyrolysis followed by catalytic steam gasification of resultant char obtained from pyrolysis for obtaining better yield of hydrogen-rich synthetic gas. On the other hand, Yamakawi et al. (2003) reported significant decrease in the production of toxic compounds like brominated dioxins from atmospheric gasification of waste electrical and electronic equipment under proper operating conditions. In addition, it could also be reported that the gasification process was done at significantly higher temperatures of over 1200 °C. Although this process could significantly reduce the production of toxic compounds, but higher reaction temperature resulted in significant energy consumption (Table 4; Fig. 2).

3 Chemical Methods for WPCB Valorization Extraction and recycling of non-metallic fractions of WPCB using non-aqueous solvents have been gaining importance in recent years. Various cost-effective nonaqueous solvents have been used for treatment of the non-metallic ingredients comprising mainly of epoxy resins to valorize WPCB at temperatures above glass transition temperature (T g ). Zhu et al. (2012) investigated usage of a solvent 1-ethyl3-methylimizadolium tetrafluoroborate for effective treatment of brominated epoxy resins (BER) at optimum temperatures of 260 °C and maintaining a processing time

Type of pyrolysis

Vacuum pyrolysis (10 kPa)

Atmospheric (N2 ) pyrolysis

Atmospheric (N2 ) pyrolysis

S.No.

1

2

3

Semi-batch catalytic reactor (3.5 dm3 ); catalyst, ZSM-5; temperature, 440 °C; residence time, 30 min

Continuous catalytic fluidized bed reactor; length, 0.61 m; diameter, 0.038 m; catalyst, fluid catalytic cracking (FCC) catalyst; WPCB-to-catalyst ratio, 10:90; temperature, 275 °C; residence time, 90 min

Continuous catalytic tubular furnace with a condensation separation system; catalyst, activated Al2 O3 ; WPCB-to-catalyst ratio (w/w), 1:2.0; temperature, 600 °C, residence time, 60 min

Reactor type/reaction conditions

Products yield (%)

Solid (Char, glass fiber) Liquid (styrene, toluene, ethyl-benzene, gasoline, etc.) Gas (H2 , hydrocarbons)

Solid- 2.1 Liquid- 54.3 Gas- 43.6

Solid (Char, glass fiber) Solid- 58.03 Liquid (phenol, Liquid- 22.43 pentadecanenitrile, Gas-19.54 p-methylphenol, triphenyl phosphate, etc.)

Solid (glass fiber) Solid-24.6 Liquid (phenol, Liquid-19.3 p-hydroxybiphenyl, Gas-56.0 2-bromophenol, 4-methylphenol, 2-methylbenzofuran, etc.) Gas (HBr, CO, CO2 , O2 )

Valuable product

Table 2 Different products and their yields obtained from catalytic pyrolysis of WPCB

High reaction temperature, production of toxic compounds

High residence time, unused solid residue

High reaction temperature, lower oil content in pyro-liquids in presence of Al2 O3

Comments

López et al. (2011)

Ali et al. (2014)

Wang et al. (2015)

References

Recent Trends in Valorization of Non-metallic Ingredients … 119

Type of gasification

Steam gasification (mixture of N2 and steam) (atmospheric pressure)

Rapid pyrolysis followed by steam gasification

Rapid pyrolysis followed by steam gasification

S. No.

1

2

3

Continuous catalytic thermal reactor; length, 0.125 m; internal dia., 0.032 m; temperature, 700 °C; catalyst, lithium carbonate, sodium carbonate, and potassium carbonate

Continuous catalytic thermal reactor; inner dia., 0.032 m, height, 0.125 m; time, 10 min; temperature, 675 °C; catalyst, mixture of three eutectic carbonates

Continuous catalytic thermal reactor; length, 0.125 m; internal dia., 0.032 m; time, 240 min; temperature, 674.85 °C; catalyst, unsupported nickel metal powder in molten carbonate

Reactor type/reaction conditions

Solid (tar) Liquid (phenol) Gas (CO2 , H2 , CO, CH4 )

Solid (char, tar) Gas (CO2 , H2 , CO, CH4 )

Solid(tar, char) Gas (hydrogen generation, CO2 )

Valuable product

Table 3 Different products and their yields from catalytic gasification of WPCB

Solid-19.2 Liquid-12.2 Gas-60.8

Solid-31.4 Gas-68.6

Solid-29.4 Gas-70.6

Products yield (%)

Salbidegoitia et al. (2015)

References

High reaction temperature

(continued)

Zhang et al. (2012)

Production of toxic Zhang et al. (2013) compounds, unused solid residue

High reaction temperature, high reaction time

Comments

120 D. Bose et al.

Type of gasification

Rapid pyrolysis followed by steam gasification

S. No.

4

Table 3 (continued)

Waste plastics; continuous catalytic furnace tube (for both pyrolysis and gasification); time, 30 min; temperature, 500 °C; catalyst, Ni–Mg–Al

Reactor type/reaction conditions Solid (coke, plastics) Gas (CO2 , H2 , CO, hydrocarbons)

Valuable product Solid-30.9 Gas-69.1

Products yield (%) High reaction temperature, production of toxic compounds

Comments Wu et al. (2010)

References

Recent Trends in Valorization of Non-metallic Ingredients … 121

122

D. Bose et al.

Table 4 Different products and their yields from non-catalytic gasification of WPCB S. No.

Type of gasification

Reactor Valuable type/reaction product conditions

1

Atmospheric Continuous gasification non-catalytic pilot-scale fixed bed reactor; (0.05 * 0.05) m2 ; time, 2.5 s; temperature, 1200 °C

2

Steam gasification (0.1 MPa)

Products yield (%)

Comments

References

Liquid Liquid-80 High Yamawaki (dioxins, Gas-20 reaction et al. dibenzofurans) temperature, (2003) Gas (CO2 ) unused solid residue

Semi-batch Solid (carbon) non-catalytic Gas (CO2 , H2 , gold inner CO, CH4 ) reactor; thickness, 0.0005 m; time, 120 min; temperature, 700 °C

Solid-30 Gas-70

High reaction time, high reaction temperature

Kamo et al. (2011)

Fig. 2 Typical yields (%) of liquids obtained from catalytic gasification at temperature of 700 °C

of 20 min, respectively. However, it is to be noted that the regeneration of the aforementioned solvent was done at 300 °C which leads to degradation of epoxy resin. As a result, this drawback made the procedure highly energy-consuming and that eventually resulted in higher production costs. Moreover, complete and effective separation of products was also not accomplished.

Recent Trends in Valorization of Non-metallic Ingredients …

123

These drawbacks led the aforementioned researchers to shift toward utilization of cheaper solvents. Zhu et al. (2013) reportedly utilized polar solvent dimethyl sulfoxide (DMSO) as organic solvent, respectively. This resulted in complete separation of the NMI at an optimum temperature of 170 °C. This process also resulted in lower yields of toxic compounds because lower temperature (below 300 °C) did not promote the degradation of epoxy resins present in WPCB. In addition, several researchers have also reported the use of N, N-dimethyl formamide (DMF) to degrade the brominated epoxy resins. Verma et al. (2016) reported significant advantages of using DMF because of its low specific heat, low hygrospicity, and low viscosity as compared  to other solvents. In addition, utilization of an ionic liquid such as [EMIM+ ] BF− 4 has also been significantly utilized by many researchers across the globe (Zhu et al. 2012). Several reports have cited that ionic liquids resulted in higher degradation of epoxy resins with subsequent increase in temperature. Subsequently, from these literature reviews, it can be concluded that utilization of non-aqueous solvents is highly effective in WPCB valorization, and hence, this field is required to be explored for development of cheaper, less toxic non-aqueous solvents.

4 Mechanical Operations for WPCB Valorization Mechanical treatment for WPCB valorization indicates the recycling techniques for valorization and recovery of non-metallic ingredients without bringing any changes in its physical state. In this process, the WPCB are finely grinded and are subsequently passed through several physical separation systems (Biswal et al. 2015). In recent times, physical processes involving magnetic separation, corona electrostatic separation, eddy current separation, floatation, etc., have emerged as significant methods (Li et al. 2008; Lu et al. 2008; Cui and Forssberg 2003). These recycled non-metallic ingredients (NMIs) obtained from mechanical treatment of WPCB are either added to new materials or converted to several new valuable materials for their effective, efficient, and varied commercial usage. Wang et al. (2012) utilized NMI as an admixture in cement mortar at varied NMI-to-cement ratios. They signified that the addition of NMI to the fresh mortar could enhance water-retention characteristics, air content while reducing bulk density, and water capillary adsorption capacity at optimal conditions but it also conveyed gradual decrease in compressive strength, flexural strength, and tensile bond strength. However, despite the drawbacks, it proved to be environment-friendly material for construction as well as other applications. Although, mechanical treatment significantly reduces generation of solid wastes; however, significant changes or improvements are necessary. This is because the non-metallic fractions of WPCB contain several toxic compounds that are not really discarded by means of physical treatment like flotation, magnetic separation, electrostatic separation, etc. In addition, the presence of various components in these non-metallic fractions may drastically reduce the efficiency of physical treatment

124

D. Bose et al.

which is generally not observed in newer and trending technologies like thermal, chemical (using organic solvents), etc.

5 Conclusions This article emphasizes on recovery and valorization of NMI of WPCB through various feasible and trending technologies. It can therefore be inferred from this review that utilization of these viable technologies viz. thermal, chemical, and hydrometallurgical can more or less result in significant decrease of production cost of valuable materials. At the same time, this also increases the sustainability of the environment by reducing the generation of unused wastes. However, WPCB contains significant proportions of bromine as flame retardants, thus reducing the efficiency and potential usage of oils and other products due to the inevitable production of toxic compounds. Hence, separation of bromine from WPCB is an area of major concern that needs to be investigated further. In addition, problems related to separation of products derived from WPCB are also encountered. Nevertheless, the benefits of these methodologies far outweigh the drawbacks. Hence, substantial future research works should be conducted for development of economically competitive and environmentally sustainable methods for utilization of WPCB.

References Ali S, Ng CH, Hashim H (2014) Catalytic pyrolysis and a pyrolysis kinetic study of shredded printed circuit board for fuel recovery. Bull Chem React Eng Catal 9(3):224–240 Biswal M, Jada N, Mohanty S, Nayak SK (2015) Recovery and utilisation of non-metallic fraction from waste printed circuit boards in polypropylene composites. Plast Rubber Compos 44(8):314– 321 Chiang HL, Lin KH, Lai MH, Chen TC, Ma SY (2007) Pyrolysis characteristics of integrated circuit boards at various particle sizes and temperatures. J Hazard Mater 149(1):151–159 Chien YC, Wang HP, Lin KS, Huang YJ, Yang YW (2000) Fate of bromine in pyrolysis of printed circuit board wastes. Chemosphere 40(4):383–387 Cui J, Forssberg E (2003) Mechanical recycling of waste electric and electronic equipment: a review. J Hazard Mater 99(3):243–263 Guo J, Guo J, Xu Z (2009) Recycling of non-metallic fractions from waste printed circuit boards: a review. J Hazard Mater 168(2–3):567–590 Guo Q, Yue X, Wang M, Liu Y (2010) Pyrolysis of scrap printed circuit board plastic particles in a fluidized bed. Powder Technol 198(3):422–428 Hall WJ, Williams PT (2007) Separation and recovery of materials from scrap printed circuit boards. Resour Conserv Recycl 51(3):691–709 Huang K, Guo J, Xu Z (2009) Recycling of waste printed circuit boards: a review of current technologies and treatment status in China. J Hazard Mater 164(2–3):399–408 Jie G, Ying-Shun L, Mai-Xi L (2008) Product characterization of waste printed circuit board by pyrolysis. J Anal Appl Pyrol 83(2):185–189

Recent Trends in Valorization of Non-metallic Ingredients …

125

Kamo T, Wu B, Egami Y, Yasuda H, Nakagome H (2011) Influence of mixed molten carbonate composition on hydrogen formation by steam gasification. J Mater Cycles Waste Manage 13(1):50–55 Kan Y, Yue Q, Kong J, Gao B, Li Q (2015) The application of activated carbon produced from waste printed circuit boards (PCBs) by H3 PO4 and steam activation for the removal of malachite green. Chem Eng J 260:541–549 Li J, Lu H, Liu S, Xu Z (2008) Optimizing the operating parameters of corona electrostatic separation for recycling waste scraped printed circuit boards by computer simulation of electric field. J Hazard Mater 153(1–2):269–275 Li J, Duan H, Yu K, Liu L, Wang S (2010) Characteristic of low-temperature pyrolysis of printed circuit boards subjected to various atmosphere. Resour Conserv Recycl 54(11):810–815 Long L, Sun S, Zhong S, Dai W, Liu J, Song W (2010) Using vacuum pyrolysis and mechanical processing for recycling waste printed circuit boards. J Hazard Mater 177(1–3):626–632 López A, De Marco I, Caballero BM, Laresgoiti MF, Adrados A, Aranzabal A (2011) Catalytic pyrolysis of plastic wastes with two different types of catalysts: ZSM-5 zeolite and Red Mud. Appl Catal B 104(3–4):211–219 Lu H, Li J, Guo J, Xu Z (2008) Movement behavior in electrostatic separation: recycling of metal materials from waste printed circuit board. J Mater Process Technol 197(1–3):101–108 Marques AC, Marrero JMC, de Fraga Malfatti C (2013) A review of the recycling of non-metallic fractions of printed circuit boards. Springer Plus 2(1):521 Muniyandi SK, Sohaili J, Hassan A, Mohamad SS (2013) Converting non-metallic printed circuit boards waste into a value added product. J Environ Health Sci Eng 11(1):2 Myavagh PH, McKay G (2016) Development of high-efficiency adsorbent from e-waste and aluminosilicate-based materials for removal of toxic heavy metal ions from wastewater. U.S. Patent Application No. 14/771,810 Quan C, Li A, Gao N (2010) Characterization of products recycling from PCB waste pyrolysis. J Anal Appl Pyrol 89(1):102–106 Salbidegoitia JA, Fuentes-Ordóñez EG, González-Marcos MP, González-Velasco JR, Bhaskar T, Kamo T (2015) Steam gasification of printed circuit board from e-waste: effect of coexisting nickel to hydrogen production. Fuel Process Technol 133:69–74 Vasile C, Brebu MA, Totolin M, Yanik J, Karayildirim T, Darie H (2008) Feedstock recycling from the printed circuit boards of used computers. Energy Fuels 22(3):1658–1665 Verma HR, Singh KK, Mankhand TR (2016) Dissolution and separation of brominated epoxy resin of waste printed circuit boards by using di-methyl formamide. J Clean Prod 139:586–596 Wang R, Zhang T, Wang P (2012) Waste printed circuit boards nonmetallic powder as admixture in cement mortar. Mater Struct 45(10):1439–1445 Wang Y, Sun S, Yang F, Li S, Wu J, Liu J, Zhong S, Zeng J (2015) The effects of activated Al2O3 on the recycling of light oil from the catalytic pyrolysis of waste printed circuit boards. Process Saf Environ Protect 98:276–284 Williams PT (2010) Valorization of printed circuit boards from waste electrical and electronic equipment by pyrolysis. Waste Biomass Valorization 1(1):107–120 Wu C, Williams PT (2010) Pyrolysis–gasification of post-consumer municipal solid plastic waste for hydrogen production. Int J Hydrogen Energy 35(3):949–957 Yamawaki T (2003) The gasification recycling technology of plastics WEEE containing brominated flame retardants. Fire Mater 27(6):315–319 Zhang S, Yoshikawa K, Nakagome H, Kamo T (2012) Steam gasification of epoxy circuit board in the presence of carbonates. J Mater Cycles Waste Manage 14(4):294–300 Zhang S, Yoshikawa K, Nakagome H, Kamo T (2013) Kinetics of the steam gasification of a phenolic circuit board in the presence of carbonates. Appl Energy 101:815–821 Zhu P, Chen Y, Wang LY, Zhou M (2012a) Treatment of waste printed circuit board by green solvent using ionic liquid. Waste Manag 32(10):1914–1918

126

D. Bose et al.

Zhu P, Chen Y, Wang LY, Qian GY, Zhou M, Zhou J (2012b) A new technology for separation and recovery of materials from waste printed circuit boards by dissolving bromine epoxy resins using ionic liquid. J Hazard Mater 239:270–278 Zhu P, Chen Y, Wang LY, Qian GR, Zhou M, Zhou J (2013) A novel approach to separation of waste printed circuit boards using dimethyl sulfoxide. Int J Environ Sci Technol 10(1):175–180

Paper Mill Lime Sludge Valorization as Partial Substitution of Cement in Mortar Prabhat Vashistha and Vivek Kumar

Abstract The solid waste accumulation from industries is becoming the cause of environmental concerns. Millions of tons of lime sludge are generated by the Pulp and paper and other industries all over the world. For the reduction of the solid waste threat to the environment, its application as a raw material in other industries could be the suitable option. In this study, lime sludge from recovery section of the paper mill is used in mortar in its as-received condition and in calcined condition to partially substitute cement. Calcination of lime sludge is performed at the relatively lower temperature of 650–750 °C, which takes less energy input than the industrial process of calcination. The M25 grade of mortar is prepared, with the substitution of cement by as received lime sludge in the range of 10, 20, 30 and 40% by weight. These blends of mortars are also prepared with calcined lime sludge. Produced mortar mixtures are tested for compressive strength and also compared with conventional mortar. Compressive strength is evaluated with 7, 28 days of curing. As a result, the compressive strength of mortar with as received lime sludge, match with the M25 grade of mortar up to 10% addition of lime sludge, after that compressive strength of mortar decreased with the further addition of lime sludge. Mortar blends with calcined lime sludge achieved the M25 grade compressive strength till 30% replacement of cement in mortar blends. Lime sludge after calcination produced more compressive strength in mortar than as received lime sludge due to the presence of reactive lime and pozzolanic materials. This study helps in developing the sustainable utilization of large amount of lime sludge, produced from paper industries ended up in landfills. Keywords Paper mill · Solid waste · Lime sludge · Cement · Mortar · Compressive strength · Calcination

P. Vashistha (B) Indian Institute of Technology Roorkee, Roorkee, India e-mail: [email protected] V. Kumar Indian Institute of Technology Delhi, Delhi, India e-mail: [email protected] © Springer Nature Singapore Pte Ltd. 2020 S. K. Ghosh et al. (eds.), Emerging Technologies for Waste Valorization and Environmental Protection, https://doi.org/10.1007/978-981-15-5736-1_12

127

128

P. Vashistha and V. Kumar

1 Introduction The industrial waste becomes a hassle for industries under severe management guidelines and the eye on environment. It is making the industries to find inventive ways of their generated waste to be consumed in various other industries as their raw materials. Lime sludge is produced from pulp and paper industries, and it is one of their kind of waste seeks such utilization. Figure 1 represents the lime sludge generation process in pulp industry (Suriyanarayanan et al. 2010). Lime sludge utilization in mortar can give an option for its utilization as supplementary cementitious materials as building products. Utilization of waste can also provide an approach for reduction of solid waste, which is very much inclined towards maintaining the ecosystem (Suriyanarayanan et al. 2010; Sahu and Gayathri 2014; Maheswaran 2011). Generally, mortar is used to keep building materials for example brick or stone unitedly. Mortar is composed of thick miscellany of OPC (ordinary Portland cement) or lime, water, mixture of sand (Archaneswar Kumar 2016). The cement is hydrated by using water and keeps the mix together. Alternatively, pozzolanic materials such as calcined clay are added to the mortar mix for good strength properties (Singh and Garg 2006). By the process of calcination, for example heating to the raw lime sludge in the furnace at various temperatures can transmute it into pozzolanic material (Villa and Frías 2010; Frías et al. 2008; Garcı et al. 2008). Calcination of raw paper lime sludge produced metakaolin that is highly reactive and can be used as additive material in cement. MK (metakaolinite-Al2 O3 .2SiO2 ) which is formed after calcination of kaolinite and other supplementary cementitious material (Pera and Amrouz 2007; FrõÂas and Cabrera 2001). The reuse of lime sludge shows its potential as raw material for yielding a product with pozzolanic activity for manufacture of cement like material. It is also promising for reducing the environmental wallop of cement industry (Cabrera and Rojas 2001; Fernández et al. 2010; Hong and Glasser 2004; Luke 2004). Mahasewaran et al. (2011) used lime sludge with cement in various ratio in cube specimens with increasing age of curing. Kumar et al. (2016) investigated the use of

Fig. 1 Flow diagram for lime sludge generation in paper mill

Paper Mill Lime Sludge Valorization as Partial Substitution …

129

paper mill lime sludge by replacing cement via 5, 10 and 20%, by weight to achieved M20 and M30 type of concrete, and it was observed that up to 10% addition of lime sludge in concrete mixture is suitable for the replacement of cement via lime sludge. Soni et al. (2015) used lime sludge in the concrete mix. The lime sludge as received from the mill was used for replacing cement and fine aggregate, respectively, in various proportions to achieve M20 type concrete. They concluded that the strength of concrete mix was reduced with the replacement of lime sludge. However, the strength reduction is acceptable up to 10% replacement of cement and 25% replacement of fine aggregate by lime sludge. The current research on application of lime sludge in mortar, targets 30% of lime sludge application in M25 grade of mortars.

2 Materials Lime sludge was procured from typical pulp and paper industry. Lime sludge used in it was received condition and in calcined form as well. The OPC-43 grade (Ultratech Brand) cement was used in the study and was kept appropriately to minimize environmental and moisture effects. In this work, OPC-43 grade of Ultra Tech cement was utilized. Cement was tested physically and chemically as per IS: 4031 & IS: 4032 respectively. The fine aggregates used in the study were locally available and procured from Local River. Fine aggregates were dark grey in appearance and were dried in natural sunlight. The coarser material such as pebble was also removed from fine aggregates through 5 mm size sieve.

3 Characterization of Lime Sludge Lime sludge has been characterized using XRF (X-ray fluorescence), XRD (X-ray diffraction) and EDX. The lime sludge is the product of recovery circuit in which calcium carbonate is generated via conversion of calcium carbonate, and this is the reason XRF (Table 1) imputes high calcium contents. Figure 2 represents the XRD of lime sludge. It indicates the presence of calcite, talc and kaolinite. Calcination of lime sludge from 650 to 750 °C, for 2 h have converted the inorganic materials like kaolinite to its highest reactive form as metakaolinite that can be used as subsidiary cementitious material. It can be inferred that lime sludge contain significant amount of calcium carbonate and the same has been observed from the results of XRF. Table 1 Chemical composition of the dried lime sludge obtained by XRF Raw materials Oxide content (% weight) Lime sludge

Al2 O3

SiO2

CaO Fe2 O3

MgO

SO3

MnO

NiO

Na2 O LOI (%)

0.25

2.74

52.1

0.02

0.23

0.02

0.02

0.88

0.27

43.18

130

P. Vashistha and V. Kumar

Fig. 2 XRD patterns of raw lime sludge

400000

T -Talc A -Calcite CH -Calcium hydroxide K -Kaolinite M -Metakaolinite

350000 300000

T -Talc

750/3

Intensity(au)

250000

750/2

A

200000 150000

M

CH

100000

CH

CH T

50000

K AM

K

700/3 650/3

A

M

650/2 Raw lime sludge

0 10

20

30

40

50

60

70

2 θ (degree)

Table 2 EDAX of raw lime sludge

Element

Weight (%)

Ca

40.72

Si

25.00

Al

3.33

K

5.60

P

1.10

Na

1.85

Fe

3.30

Mg

1.83

MN

0.61

Ti

0.50

Table 2 represents the EDAX of lime sludge. It determines the elemental composition of lime sludge EDAX of raw lime sludge found different type of inorganic elements, which are present due to impurities like wood ash, grits and some amount of dregs in lime sludge during the process of its generation. Constituent of wood ash, dregs and grits are the elements found in EDAX and XRF as well.

4 Proportioning and Casting Mortar Specimens In accordance with the Indian standard IS: 10262-2009, M 25 grade of mortar has been proportioned. Mortar specimens were prepared with partial substitution of cement with raw and calcined lime sludge. The different mixtures of raw and calcined

Paper Mill Lime Sludge Valorization as Partial Substitution …

131

lime sludge with fine aggregate, ordinary Portland cement and water were used for casting of specimens. Different mixes of mortars were prepared with 0.48–0.8 w/ (c + lime sludge) water to binder (cement + lime sludge) ratio. Table 3 indicates the proportioning of ingredients for the casting of specimens. Cube of standard size 100 × 100 × 100 mm were cast according to the IS: 10086:1982. Figure 3 represents the flow diagram of specimen casting. The mould oil was used to prevent the adhesion of the mortar in the interior surface of the assembled moulds. The casting of test specimens was done as soon as mixture is Table 3 Proportions of mortars with raw and calcined lime sludge (Substitution of cement with lime sludge) S. No.

Substitution of cement with lime sludge (%)

Proportioning of ingredients by weight C

Lime sludge

F.A

W

W/(C + LS) ratio

1

0

1

0

2.25

0.48

0.48

2

10

0.9

0.10

2.25

0.55

0.55

3

25

0.75

0.25

2.25

0.60

0.60

4

30

0.70

0.30

2.25

0.62

0.62

5

35

0.65

0.35

2.25

0.64

0.64

6

40

0.60

0.40

2.25

0.66

0.66

7

50

0.50

0.50

2.25

0.70

0.70

Fig. 3 The schematic diagram of casting of specimens

132

P. Vashistha and V. Kumar

taken out from the mixer. Then, the fresh mortar mixture was poured into the moulds after checking its workability, after that vibrating table was used to give compaction to the mixture. Mortar was poured in three layers, and each layer was vibrated at about 8–10 s for the better compaction of mortar mixture in the moulds. The lime sludge usually takes much time for compaction if used with higher dosage in mortar. The cast specimens were de moulded after 24 h of the casting and marked systematically before immersing them in curing tank.

5 Compressive Strength of Mortar with Substitution of Cement by Raw Lime Sludge The effect on compressive strength of mortar with substitution of cement by raw lime sludge is illustrated in Fig. 3. A decrease in the compressive strength of cement mortars was observed with the replacement of lime sludge over the cement cube mortar without lime sludge. This trend in compressive strength of mortars shows the inactive nature of as received (raw) lime sludge (Maheswaran 2011). According to the results, only 10% substitution of cement by lime sludge is feasible in its raw form (Fig. 4). 25

Compressive strength N/mm2

20

19.45

20

17.25 15.89

15

14

12.74

12.56 10.78 8.2

10

6.32 5

0

0

10

20

30

%Lime sludge (by weight ) 7 days compressive strength

28 days compressive strength

Fig. 4 Compressive strength of mortar with raw lime sludge at 7 & 28 day

40

Paper Mill Lime Sludge Valorization as Partial Substitution …

Compressive strength N/mm2

35

133

32.12

30

27.26

25.35

25.12

25 21.14

20.12

21.09

20

17.43

18.93 16.23 13.46

15

12.86

10 5 0 0

10

20

30

40

% Calcined lime sludge by weight 7 days Compressive strength

28 days compressive strength

Fig. 5 Compressive strength of mortar with calcined lime sludge at 7 & 28 day

6 Compressive Strength of Mortar with Substitution of Cement by Calcined Lime Sludge The increment in compressive strength of mortars might be allocated to pozzolanic activity of calcined lime sludge. The calcination process makes lime sludge reactive and it reacts with the elements like silica and alumina, which make two types of products after reaction, for example hydrates of calcium silicate (CSH) and hydrates of tetra calcium aluminates (TAH) (reaction 1) (FrõÂas and Cabrera 2001; Cabrera and Rojas 2001). These both of products precipitated as soon as reaction reaches to saturation. This reaction is the reason for increased compressive strength of mortars up to 30% replacement of cement (Fig. 5). Al2 O3 + 2SiO2 + 5Ca(OH)2 + 19H2 O → CaAl2 O3 + 2CaO + 19H2 O + 2CaO.SiO2

7 Conclusion On the basis of results, lime sludge has a significant potential for replacing cement mortar. This work has concluded that compressive strength of mortars remains intact until 10% replacement of cement by raw lime sludge. While the use of calcined lime sludge allows replacement of cement up to 30% with compressive strength remains intact as reference. So, lime sludge is suitable as utilization in the formation

134

P. Vashistha and V. Kumar

of reactive pozzalanic material. The metakaolin that is produced after calcination shows high lime reactivity and due to this increase in strength of mortar cubes of OPC-lime sludge is obtained. The increase in strength is caused due to accumulation of increase amount hydrates of calcium silicate (CSH) and hydrates of tetra calcium aluminates (TAH). The utilization of lime sludge of paper industry is recommended as replacement material for cement in mortars, and this will also beneficial for reducing environmental wallop. Acknowledgements This work is completed under Uchchatar avishkar yojana (UAY) project, financially supported by the Ministry of Human Resource Development (MHRD), Indian Institute of Technology (IIT) Roorkee and Ruchira papers pvt. ltd. India.

References Archaneswar Kumar K et al (2016) Experimental investigation on fly ash and lime sludge in cement mortar. IJLTEMAS 5:2278–2540 Cabrera J, Rojas MF (2001) Mechanism of hydration of the metakaolin-lime-water system civil engineering materials unit (CEMU). Cem Concr Res 3:177–182 Fernández R et al (2010) Mineralogical and chemical evolution of hydrated phases in the pozzolanic reaction of calcined paper sludge. Cem Concr Compos 32:775–782 Frías M et al (2008) Calcination of art paper sludge waste for the use as a supplementary cementing material. Appl Clay Sci 42:189–193 FrõÂas M, Cabrera J (2001) Influence of MK on the reaction kinetics in MK/lime and MK-blended cement systems at 20 °C. Cem Concr Res 31:519–527 Garcı R et al (2008) The pozzolanic properties of paper sludge waste. Constr Build Mater 22:1484– 1490 Hong SY, Glasser FP (2004) Phase relations in the CaO–SiO2 –H2 O system to 200 °C at saturated steam pressure. Cem Concr Res 34:1529–1534 Kumar K et al (2016) Experimental investigation on fly ash and lime sludge in cement mortar. IJLTEMAS 5(2):2278–2540 Luke K (2004) Phase studies of pozzolanic stabilized calcium silicate hydrates at 180 °C. Cem Concr Res 34:1725–1732 Maheswaran S et al (2011) Studies on lime sludge for partial replacement of cement. Appl Mech Mater, 71–78 Pera J, Amrouz A (2007) Mineralogical and morphological changes of calcined paper sludge at different temperatures and retention in furnace. Appl Clay Sci 36:279–286 Sahu V, Gayathri V (2014) The use of fly ash and lime sludge as partial replacement of cement in mortar. Int J Eng Technol Innov 4(1):30–37 Singh M, Garg M (2006) Reactive pozzolana from Indian clays-their use in cement mortars. Cem Concr Res 36:1903–1907 Soni Y et al (2015) Lime Sludge: an emerging alternate construction building material for the partial replacement of fine aggregate. In: Presented at AIChE annual meeting 8–13 Nov. Salt Lake City, U.S.A Suriyanarayanan S et al (2010) Studies on the characterization and possibilities of reutilization of solid wastes from a waste paper based paper industry. Global J Environ Res 4(1):18–22 Villa RV, Frías M (2010) New construction materials: calcined paper sludges as active additions. Mater Sci Forum, 636–637

Wealth from Poultry Waste V. V. Lakshmi, D. Aruna Devi, and K. P. Jhansi Rani

Abstract Poultry farming is practiced intensively throughout the world which generates huge quantities of nitrogen-rich waste in the form of poultry litter and feather waste. Feather which is made of almost pure keratin protein is generated in bulk quantities as a by-product of poultry industry all over the world. It is estimated that 400 million chickens are processed every week with huge amount of feather produced as waste globally. Though the by-product is made of pure keratin protein, it is neither profitable nor environment-friendly. Keratin is highly recalcitrant to all common proteases being slowly digested/degraded in the environment leading to dumps, thereby contributing to global environmental pollution problem. Keratin waste has not been considered as source of dietary protein or organic manure (OM) till recently, as value of FM produced traditionally is very poor with locked nutrients thus not serving as good products. Organic farming has gained popularity due to high health risks associated with use of chemical fertilizers. Organic produce are sold in the market at almost double price compared to those produced by using chemical fertilizers. Technology has been developed in SPMVV for efficient degradation of poultry waste in five days by developing native bacteria. Feather meal produced by keratinase treatment was found to be significantly superior in nutritive value compared to ones produced by traditional means, thus increasing their economic value. KTF had higher value as compared to farmyard manure and vermicompost, the commonly used OM in terms of water retention capacity and production of KTF in shorter time at a lower cost. KTF can also be utilized as feed supplement in poultry and aquaculture industry. Digestion of keratin waste has high potential to serve as cheap source for production value-added products having high commercial value. Keywords Chain · International society of waste management · Air and water

V. V. Lakshmi (B) · D. Aruna Devi · K. P. Jhansi Rani Department of Microbiology, Sri Padmavati Mahila Visvavidyalayam, Tirupati, India e-mail: [email protected] © Springer Nature Singapore Pte Ltd. 2020 S. K. Ghosh et al. (eds.), Emerging Technologies for Waste Valorization and Environmental Protection, https://doi.org/10.1007/978-981-15-5736-1_13

135

136

V. V. Lakshmi et al.

1 Introduction Keratin represents a major class of cellular derived, fibrous, insoluble structural protein of animal origin. It is found in biological derivatives of ectoderm such as hair, wool, scales, feathers, quills, nails, hoofs, horns, and silk found in all vertebrates. Hair and feather are examples of almost pure keratin which is highly recalcitrant to all common proteases like trypsin, pepsin, and papain, which is due to its strong cross-linked rigid polypeptide chains leading to a very slowly digestion/degradation in the environment (Brandelli et al. 2015; Bach et al. 2015). Elementally feather is composed of 45% carbon, 14% nitrogen, 2.9 g/kg phosphorus, 1.5 g/kg potassium, and 0.8 g/kg magnesium. Feather keratin has an elevated content of glycine, alanine, serine, cysteine, and valine, but has lower amounts of the amino acids like lysine, methionine, and tryptophan (Govern 2000). Significant amount of keratin waste is generated as by-products of agro-industrial processing. Poultry farming is practiced intensively throughout the world which generates huge quantities of nitrogen-rich waste in the form of poultry litter and feather waste (Onifade et al. 1998; Brandelli et al. 2015). It is estimated that 400 million chickens are processed every week and globally, approximately 8.5 million metric tonnes of poultry waste is generated annually. India ranks fifth in poultry industry, contributes about 3.5 million tons of this waste alone. In addition to the feather waste, poultry industry produces huge quantities of farm litter and animal waste from slaughter houses which is rich in keratin. These emit strong fouling smell and attract flies and ultimately find way into water bodies, thereby significantly contributing to the environmental pollution (Jayathilakan et al. 2012). Keratin waste has not been considered seriously as source of dietary protein, rich source of amino acids or organic manure (OM) till recently, as value of feather meal produced traditionally is very poor and at best barely covered its cost of production. Being slowly degraded in nature, the nutrients are locked, hence not serving as good manure also (Moritz and Latshaw 2001; Grazziotin et al. 2006). Various strategies are adopted to handle the volume of this waste produced continuously. Traditionally, feather waste generated by the member firms is disposed off to waste disposal sites, land-fills, incinerated. The traditional methods of feed production yield poor quality of feed with low commercial value due to destruction of heat labile amino acids to formation of non-nutritive amino acids, thereby limiting the product value as feed supplements. Slow mineralization of feather in nature does not make it an effective fertilizer. Thus, almost pure keratin protein produced in huge quantities is neither profitable nor environmentally friendly, forming a produce of high volume with low-profit margin. Hence, bulk of the waste produced piles up as dumps, thus making the disposal of this waste a global environmental problem contributing to pollution (Papadopoulos 1984; Grazziotin et al. 2006; Brandelli et al. 2010). Though, bioconversion has long been thought to be an attractive and viable option to utilize the keratin-rich waste as some of the microorganisms could degrade keratin by producing keratinase enzyme. Till 1990s, the production of keratinase was reported mainly from mesophilic fungi and actinomycetes. Strains of Doratomyces

Wealth from Poultry Waste

137

microsporum, Aspergillus fumigatus, and Aspergillus flavus producing keratinases are also identified (Santos et al. 1996; Gradisar et al. 2000; Gupta and Ramnani 2006). These findings were mainly of academic interest as it required fairly long time (ranging up to 40 days) to bring ≥50% digestion of keratin and organisms being pathogens further limited their application potential. The growing prominence of keratinases in the last decades is due to isolation of several non-pathogenic microorganisms, which degraded keratin by secreting a specific proteases keratinase. In 1990, Williams et al. isolated and characterized Bacillus licheniformis isolate, which was able to degrade native feathers and subsequently several other strains of B. licheniformis, Bacillus subtilis have been identified which could hydrolyze both native and denatured keratin (Gupta and Ramnani 2006; Suneetha and Lakshmi 2004; Jeevana Lakshmi 2008; Jeevana Lakshmi et al. 2013). Thus, the focus of studies in last two decades has shifted to isolating non-pathogenic microorganisms with good keratinolytic potential. Most of the keratinases reported have been identified to be serine proteases (Lin et al. 1992; Bockle et al. 1995; Friedrich and Antranikian 1996; Suh and Lee 2001), though a few metalloproteases and acidic keratinases are also reported (Allpress et al. 2002; Farag and Hassan 2004). Keratinases also have wide applications in a number of sectors like feed, fertilizer, detergent, leather, textile cosmetic, and pharmaceutical industries and biomedical applications. In leather industry to improve the quality of leather produced as well as for tannery effluents treatment to significantly reduce toxicity of effluents before the release (Gupta and Ramnani 2006; Kumari et al. 2015). The vast application potential for keratinase has resulted in a drive for production of keratinase by fermentation at industrial scale. Though highly promising, the full commercial potential of keratinases is yet to be realized. The biodegradation of agro-industrial waste like feather and its efficient recycling increases energy conservation and reduce environmental pollution load (Brandelli et al. 2010). The major limiting factor in the wide scale usage of keratinases is mainly the availability of efficient and cost effective method for production of keratinases in large scale. In view of the economic importance, microorganisms with keratinase activity were isolated from Tirupati and developed to produce high amounts of enzymes. The application potential of the keratin treated feather (KTF) as organic manure was evaluated which exhibited high nutritive value and enhanced water retention capacity of soil.

2 Materials and Methods Screening for keratinolytic organisms from soil samples (collected from poultry farms and poultry litter from Tirupati) led to isolation of Bacillus subtilis sp. Strain improvement and optimization of parameters of fermentation resulted in designing a cost-effective fermentation media with starch as a carbon source and soya bean meal as nitrogen source with a yield of >500 KU/ml. Semi-solid state fermentation was developed using feather and agricultural waste like black gram husk (BG) and groundnut husk for biodegradation of feather using keratinase producing organisms

138

V. V. Lakshmi et al.

(Kumari 2011; Kumari and Lakshmi 2015). For each batch 20 g ball milled feather, 20 g black gram husk and 20 g of groundnut husk was taken in 2 l conical flask and 250 ml of mineral media (NaCl-0.5 g, KH2 PO4 -0.3 g, K2 HPO4 -0.4 g, MgCl2 -0.1 g/l) was added. The media was sterilized at 10 lb/inch2 for 15 min and inoculated with overnight culture 10 ml of Bacillus sp. BF 20 culture (~109 CFU/ml) producing keratinase enzyme. The flasks were incubated at 37 °C on shaker at 180 rpm for 5 days so as to achieve complete degradation of feather by the keratinase produced, and the product was dried to produce KTF. Six soil amendments made in study included T 1 [soil sample (1 kg)], T 2: soil sample (900 g) + 100 g of farm yard manure (FYM), T 3: soil sample (900 g) + 100 g of vermicompost (VC), T 4: soil sample (900 g) + 100 g of KTF, T 5: soil sample (800 g) + 200 g of KTF, and T 6: soil sample (700 g) +300 g of KTF adopting method of Hadas and Portnoy (1994). Soil parameters analyzed included using methods are soil moisture retention 930.15 (AOAC 2000), electrical conductivity (Jackson 1973), soil organic matter (Nelson and Sommers 1982), CO2 evolution (Anderson 1982), available nitrogen (988.05 of AOAC 2000), phosphorous, potassium, and microelements (Clement et al. 1995), and microbial counts—bacterial, fungal, and actinomycetes by spread plate method.

3 Results and Discussion The KTF was produced by semi-solid state fermentation where complete degradation of feather was achieved in 5 days. After completion of the period, KTF was pooled and subjected to autoclaving at 10 lb/inch2 for 15 min. The product was then cooled to room temperature and dried at 40 °C and powdered. This KTF was blended in size by passing through 200 μm mesh sieve. Subsequently homogenized KTF was stored in airtight containers Fig. 1. Soil amendments were made in order to test the effect of addition of KTF to soil in terms of improvement in soil texture and available nutrients. The KTF amendments

(a) Fig. 1 KTF powder preparation: a SSF product, b dried powder

(b)

Wealth from Poultry Waste

139

in the range of 10–30% were compared with farm yard manure (FYM) and vermicompost (VC) in addition to unamended soil control. The amended samples were maintained in triplicate and incubated at room temperature up to 75 days. Samples drawn at six periodic intervals between 0 and 75 days were analyzed to determine the various soil parameters. Soil amended with 30%KTF showed higher moisture content of 59% up to 75 days which was similar to that of vermicompost amendment, whereas other controls had lower water retention activity in the range of 50–52% (Fig. 2). A 1% increase of soil organic matter is estimated to increase approximately 3.7% water holding capacity of soil. Increase in water retention positively influences the crop yield of a soil by increasing nutrients availability for plant growth (Glaser et al. 2002). Soil EC gradually increased with incubation time, and the magnitude of increase was higher in 20 and 30% KTF amended soils when compared to the controls followed by FYM and VC indicating good stabilization of soil (Table 1). All the KTF amendments showed increased nitrogen content from 0th day to 45th day after which it showed a decreasing trend. T 6 amendment recorded maximum nitrogen content of 126 kg/ac. followed by T 5 (106 kg/ac.), T 4 (92 kg/ac.), T 3 (88 kg/ac.), and T 2 (86 kg/ac.), respectively. All the KTF and organic amendments showed rapid increase in phosphorous content up to 15th day which continued gradually up to 45 days after which it showed a decreasing trend. 30% KTF amendment recorded maximum phosphorous content

Fig. 2 Comparison of moisture retention capacity in soil amendments

Table 1 Change in E.C among various soil amendments Amendment

Soil incubation (days) 0

15

30

45

60

75

Soil electrical conductivity (MS/cm) T 1 (control)

0.64

0.62

0.14

0.18

0.13

0.05

T 2 (FYM)

0.68

0.18

0.15

0.12

0.12

0.05

T 3 (VC)

0.66

0.13

0.18

0.12

0.11

0.09

T 4-10%KTF

0.68

0.11

0.26

0.28

0.23

0.04

T 5-20%KTF

0.71

0.12

0.28

0.22

0.25

0.05

T 6-30%KTF

0.71

0.10

0.28

0.30

0.30

0.08

140

V. V. Lakshmi et al.

(98 kilo/acre) followed by 20% KTF (96 kilo/acre) and 10% KTF (93 kilo/acre). FYM and VC showed 83 kilo/acre and 88 kilo/acre by 45th day. Soil amendment with organic manures showed gradual increase of potassium content up to 45th day after which it shows a gradual decrease up to 75 days. KTF amendments showed increase of zinc content from 0th hour to 45 days and then showed decreased trend up to 75 days. 30% KTF amended soil was observed to have highest amount of Zinc content in soil. Soil amended with organic manures showed 6.2 and 6.48 ppm of manganese contents. KTF amended soil showed much higher amount of manganese content. All the organic amendments including KTF amendments showed increase of manganese content up to 45th day and later showed decline. Highest level of Iron content was noticed in T 6 followed T 5 and T 4, respectively, where maximum of 46.80, 41.26, and 36.04 ppm was observed (Fig. 3). Organic matter content is greater especially in the topsoil where most of the bioactivity takes place (Choi and Nelson 1996). Soil organic matter slowly increased in various organic amendments during the experimental period up to 45 days (Fig. 4). On an average, T 5, T 6, and FYM were found to have higher soil organic matter followed by T 4 and T 3. Control showed least soil organic matter content. Organic matter content in the soil increased up to 45th day, after which there was a slight decrease. Bacteria count was observed to increase significantly on the addition of amendments as compared to control up to 60 days (Table 2). The 0th day count of bacteria in CFU/g for T 1 was 5 × 107 for control, and for FYM and VC, it was in the range

Fig. 3 Available NPK and micronutrient contents in various soil amendments

Fig. 4 Organic matter content of various amendments

5 × 108

9×

11 ×

T3

T4

T5

T6

6×

T2

9 × 108

14 × 108

19 × 108

19 × 108

20 ×

19 ×

108

16 ×

108

108

15 × 108

108

11 × 108

8 × 107

60

12 × 108

12 ×

108

9 × 107

30

108

108

5 × 107

CFU/g of soil

Bacteria

0

T1

Amendment

Soil incubation (days)

Table 2 Viable counts with various amendments

103

16 × 103

20 ×

14 × 103

6 × 103

9× 103

8 × 103

Fungi

0

103

41 × 103

42 ×

39 × 103

24 × 103

31 × 103

30 × 103

30

103 39 × 103

41 ×

35 ×

103

20 × 103

33 × 103

26 × 103

60

102 4 × 102

5×

3×

102

1 × 102

2×

102

1 × 102

103 11 × 103

12 ×

9×

103

7 × 103

4×

103

3 × 103

30

Actinomycetes

0

10 × 103

9 × 103

7 × 103

6 × 103

5 × 103

5 × 103

60

Wealth from Poultry Waste 141

142

V. V. Lakshmi et al.

of 5 × 108 to 6 × 108 , respectively. KTF amendments showed significant increase in bacterial count up to 45th day after which it showed slight decrease up to 75th day. The counts were still significantly higher than control and FYM. Thus, KTF amendments were found to support significantly higher bacterial growth indicating sustained release of nutrients. The fungal populations enumerated in different amendments are given in Table 2. The counts also showed gradual increasing trend from the day of amendment till 45th day, after which there was a marginal decrease up to 75th day. KTF amendments showed similar pattern of higher fungal population up to 45th day as compared to other organic amendments and control indicating good support for fungal growth. Actinomycetes number also increased up to 45th day in control as well as in amendments after which a gradual decrease was observed up to 75th day (Table 2). 20 and 30% KTF amendment showed maximum number of actinomycetes count followed FYM and VC. The microbial count which is an indicator of microbial metabolic activity showed an increasing trend with KTF amendment. Keratinase-treated feather (KTF) had been reported to have better nutritive value in terms of total amino acid content and concentrations of cysteine, serine, and methionine (Suneetha and Lakshmi 2004; Jeevana Lakshmi 2008). There was considerable increase in the availability of free nitrogen (3.82–4.02 g/kg) in the keratinase-treated feather, as compared to heat/acid treated (0.15 g/kg) or trypsin digested feather (1.5 g/kg) (Jeevana Lakshmi and Lakshmi 2015a). Both the digestibility and amino acid balance of feather meal were found to be improved by keratinases. Comparison of in vitro digestibility also showed that keratinase treatment resulted in ~2- to 2.5fold increase in digestibility as compared to commercial feather meal. A significant ~2.5-fold increase in the percentage of proline and glycine content, a ~2-fold increase in cystine, and ~1-fold increase of lysine and methionine was observed in KTF as compared to ones produced by other traditional treatments (Jeevana Lakshmi and Lakshmi 2015b).

4 Conclusion Some of the commonly used organic fertilizers used are bovine dung and urine, sheep manure, poultry waste, chicken manure, night soil, composted agricultural wastes, bat guano, vermicompost, etc. Among these, FYM, VC, and bat guano are widely used as organic manure to improve soil fertility (Edwards and Arancon 2004; Lenin et al. 2010). However, it is still observed that the vegetables and fruits grown using organic means are sold in market at almost double the price compared to those produced by using chemical fertilizers making them unaffordable to common public (Nagavellamma et al. 2004). Active organic matter provides habitat and nutrients for beneficial soil organisms that in turn help in building soil structure and its health. Organic amendments are emerging as an environmentally friendly alternative to the use of chemical fertilizer. KTF amendment of soil was observed to significantly improve the soil parameters and nutrient availability and had significantly higher soil organic matter (SOM) followed

Wealth from Poultry Waste

143

by other organic amendments. Thus, present study highlights the application potential of this indigenously developed nutrient-rich keratinase-treated feather which is an odorless, free running, eco-friendly, low-cost organic fertilizer leading to generation of wealth from poultry waste.

References Allpress JD, Mountain G, Gowland PC (2002) Production, purification and characterization of an extracellular keratinase from Lysobacter NCIMB 9497. Lett Appl Microbiol 34:337–342 Anderson JPE (1982) Soil respiration In: Methods of soil analysis. Part 2. Chemical and microbiological properties. Agronomical Monograph, ASA. Madison, pp 831–866 AOAC (2000) Official methods of analysis of AOAC international, 17th edn. Gaithersburg, USA, pp 240–296 Bach E, Lopes FC, Brandelli A (2015) Biodegradation of α and β-keratins by Gram-negative bacteria. Int Biodeterior Biodegradation 104:136–141 Bockle B, Galunsky B, Mueller R (1995) Characterization of a keratinolytic serine proteinase from Streptomyces pactum DSM 40530. Appl Environ Microbiol 61(10):3705–3710 Brandelli A, Daroit DJ, Riffel A (2010) Biochemical features of microbial keratinases and their production and applications. Appl Microbiol Biotechnol 85(6):1735–1750 Brandelli A, Sala L, Kalil SJ (2015) Microbial enzymes for bioconversion of poultry waste into added-value products. Food Res Int 73:3–12 Choi JM, Nelson PV (1996) Developing a slow-release nitrogen fertilizer from organic sources: II. Using poultry feathers. J Am Soc Hortic Sci 121(4):634–638 Clement RE, Eiceman GA, Koester CJ (1995) Environ Anal Anal Chem 67(12):221–255 Edwards CA, Arancon NQ (2004) 18 the use of earthworms in the breakdown of organic wastes to produce vermicomposts and animal feed protein. Earthworm Ecol, 345–355 Farag AM, Hassan MA (2004) Purification, characterization and Immobilization of a keratinase from Aspergillus oryzae. Enzyme Microbial Technol 34:85–93 Friedrich AB, Antranikian G (1996) Keratin degradation by Fervidobacterium pennivorans, a novel thermophilic anaerobic species of the order Thermotogales. Appl Environ Microbiol 62:2875– 2882 Glaser B, Lehmann J, Zech W (2002) Ameliorating physical and chemical properties of highly weathered soils in the tropics with charcoal–a review. Biol Fertil Soils 35(4):219–230 Govern Mc (2000) Recycling poultry feathers: more bang for the cluck. Environ Health Prospect 108(8):366–369 Gradisar H, Kern S, Friedrich J (2000) Keratinase of Doratomyces microsporus. J Appl Microbiol Biotechnol 53:196–200 Grazziotin A, Pimental FA, de Jong EV, Brandelli A (2006) Nutritional improvement of feather protein by treatment with microbial keratinase. Anim Feed Sci Technol 126:135–144 Gupta R, Ramnani P (2006) Microbial keratinases and their prospective applications: an overview. Appl Microbiol Biotechnol 70(1):21–33 Hadas A, Portnoy R (1994) Nitrogen and carbon mineralization rates of composted manures incubated in soil. J Environ Qual 23(6):1184–1189 Jackson ML (1973) Soil chemical analysis, II edn. Prentice Hall of India Private Limited, New Delhi, pp 59–67 Jayathilakan K, Sultana K, Radhakrishna K, Bawa AS (2012) Utilization of byproducts and waste materials from meat, poultry and fish processing industries: a review. Food Sci Technol 49(3):278– 293

144

V. V. Lakshmi et al.

Jeevana Lakshmi P (2008). Fermentative production of keratinase by Bacillus sp. and its relevance to recycling of poultry feather waste. Ph.D thesis submitted to Sri Padmavati Mahila Visvavidyalayam, Tirupati Jeevana Lakshmi P, Lakshmi VV (2015a) Enhancement in nutritive value and invitro digestability of keratinse treated feather meal. J Sci Eng Res 6(2):36–40 Jeevana Lakshmi P, Lakshmi VV (2015b) Evaluation of degradative products of feather degradation by Bacillus sp. Int J Sci Eng Res 6(2):330–333 Jeevana Lakshmi P, Kumari Ch. M, Lakshmi VV (2013) Efficient degradation of feather by keratinase producing Bacillus sp. Int J Microbiol, Article ID 608321, 7 p. http://dx.doi.org/10.1155/ 2013/608321 Kumari CCM (2011) Production of microbial keratinases and its application in bioremediation of feather. Ph.D. thesis submitted to Sri Padmavathi Mahila Visvavidyalayam, Tirupati Kumari CCM, Lakshmi VV (2015) Fermentative production of keratinase using solid agricultural wastes. Int J Sci Eng Res 6(2):56–57 Kumari CCM, Jeevana Lakshmi P, Lakshmi VV (2015) Microbial Keratinases and their applications. Int J Sci Eng Res 6(2):50–54 Lenin M, Selvakumar G, Thangadurai R (2010) Growth and nutrient content variation of groundnut Arachis hypogaea L. under vermicompost application. J Exp Sci 1(8):210–215 Lin X, Lee CG, Casale ES, Shih JC (1992) Purification and characterization of a keratinase from a feather-degrading Bacillus licheniformis strain. Appl Environ Microbiol 58(10):3271–3275 Moritz JS, Latshaw JD (2001) Indicators of nutritional value of hydrolyzed feather meal. Poult Sci 80:79–86 Nagavellamma KP, Wani SP, Stephane L, Padmaja VV, Vineela C, Babu Rao M, Sahrawat KL (2004) Vermicomposting: recycling wastes into valuable organic fertilizer. Global theme on agroecosystems report no. 8: 20–28 Nelson DW, Sommers L (1982) Total carbon, organic carbon, and organic matter. Methods of soil analysis. Part 2. Chemical and microbiological properties, (methodsofsoilan2), 539–579 Onifade A, Al-Sane N, Al-Musallam A, Al-Zarban S (1998) Potentials for biotechnological applications of keratin degrading microorganisms and their enzymes for nutritional improvement and others keratins as livestock feed resources. Biores Technol 66:1–11 Papadopoulos MC (1984) Feather meal: evaluation of the effect of processing conditions by chemical and chick assays. PhD. thesis, Agricultural University, Wageningen Santos RMDB, Firmino AA, de Sai CM, Felix CR (1996) Keratinolytic activity of Aspergillus fumigatus fresenius. Curr Microbiol 33:364–370 Suh HJ, Lee HK (2001) Characterization of a keratinolytic serine protease from Bacillus subtilis KS-1. J Protein Chem 20:165–169 Suneetha V, Lakshmi VV (2004) Optimization of fermentation parameters for hair degrading microorganisms isolated from Tirumala Hills. Asian J Microbiol Biotechnol Environ Exp Sci 6:231–233