Sustainable Development in Energy and Environment: Select Proceedings of ICSDEE 2019 [1st ed.] 9789811546372, 9789811546389

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Springer Proceedings in Energy

V. Sivasubramanian Arivalagan Pugazhendhi I. Ganesh Moorthy   Editors

Sustainable Development in Energy and Environment Select Proceedings of ICSDEE 2019

Springer Proceedings in Energy

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V. Sivasubramanian Arivalagan Pugazhendhi I. Ganesh Moorthy •

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Editors

Sustainable Development in Energy and Environment Select Proceedings of ICSDEE 2019

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Editors V. Sivasubramanian Department of Chemical Engineering National Institute of Technology Calicut Kozhikode, Kerala, India

Arivalagan Pugazhendhi Faculty of Environment and Labour Safety Ton Duc Thang University Ho Chi Minh City, Vietnam

I. Ganesh Moorthy Department of Biotechnology Kamaraj College of Engineering and Technology Madurai, Tamil Nadu, India

ISSN 2352-2534 ISSN 2352-2542 (electronic) Springer Proceedings in Energy ISBN 978-981-15-4637-2 ISBN 978-981-15-4638-9 (eBook) https://doi.org/10.1007/978-981-15-4638-9 © 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

Foreword

It is with deep satisfaction that we write this foreword to the proceedings of the International Conference on Sustainable Development in Energy and Environment (ICSDEE) held in Kamaraj College of Engineering and Technology, 18–20 July 2019. The Department of Biotechnology continues a tradition of bringing researchers, academicians and professionals together from all over the world and experts in economic and social sciences. This conference intended to bring the scientific community together to discuss various topics related to energy and environment, viz. • • • • • • • • • • • • •

Fuel and solar cells Biofuels and biorefineries Process design and intensification Sustainable synthesis analysis and design Hydrogen production and storage Materials for energy and environment systems Climate change and global warming Air pollution control Solid waste management Water policy and regulation Water and wastewater treatment Life cycle assessment Health care

One hundred fifty-seven abstracts were received under various themes, and 126 participants from multiple countries, including India, Vietnam, Thailand and South Korea, attended the conference. This volume consists of select papers presented at the conference. Sustainable development in energy and environment approaches can be extremely rewarding when the efforts led to important discoveries potentially benefit many and be an essential strategy for the growth and development. Until recently, these sectors have operated independently with little collaboration between researchers. With the rise of demand and the need for alternative sustainable v

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sources, several new trends and perspectives are emerging in these two important domains of research in engineering and technology. We thank all the administrative authorities of our institution for the opportunity provided to organise this year’s international conference. Support extended by the organising committee comprising of staff and students of the Department of Biotechnology right from the planning stage is highly appreciated, and we express our sincere thanks to each one of them. We place on record our sincere thanks to all the delegates who graciously accepted our invitation and their willingness to share their research experience with the young participants. We thank all the authors and participants for their contributions. This proceeding will furnish the researchers all over the world with an excellent reference book, and this will be an impetus to do further study and research in these areas. Madurai, India July 2019

Dr. Anant Achary Coordinator/ICSDEE’19 Dr. I. Ganesh Moorthy Dr. S. Karthikumar Mr. P. N. Karl J. Samuel Organising Secretaries/ICSDEE’19

Contents

A Review on the Production of Biogas from Biological Sources . . . . . . . Yamini Vasudevan, Dhivyadharshini Govindharaj, Gowthama Prabu Udayakumar, Anusiya Ganesan, and N. Sivarajasekar Bioethanol Production from Sweet Potato and Cassava by Simultaneous Saccharification and Fermentation . . . . . . . . . . . . . . . Harikrishnan Hariharan, Elizabeth Nirupa Joshy, Kavya Sajeevan, and Krishnasree Moneyraj Biobutanol: Insight, Production and Challenges . . . . . . . . . . . . . . . . . . . Swetha Juliet Anandharaj, Jeyashree Gunasekaran, Gowthama Prabu Udayakumar, Yogesan Meganathan, and N. Sivarajasekar Numerical Simulation Study on Failure Prediction of FRP Laminate Composite Using COMSOL Multiphysics® . . . . . . . . . . . . . . . . . . . . . . J. Jerold John Britto, A. Vasanthanathan, S. Rajakarunakaran, and R. Prabhakaran Production of Biodiesel from Municipal Primary Sewage Sludge Via Transesterification Process Using Nanocomposite . . . . . . . . . . . . . . P. Bharathi, V. Varsha, and S. Gayathri Numerical Simulation of Self-Expanded NitinolBased Shape Memory Alloy Stent . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . J. Jerold John Britto, A. Vasanthanathan, S. Rajakarunakaran, and K. Vigneshwaran Comparison and Evaluation of Electrospun Nanofiber Membrane for the Clarification of Grape Juice . . . . . . . . . . . . . . . . . . . . . . . . . . . . Gowthama Prabu Udayakumar, G. B. Kirthikaa, Subbulakshmi Muthusamy, Baskar Ramakrishnan, and N. Sivarajasekar

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Finite Element Simulation of Dynamic Behavior of FRP Laminate Composite Under Forced Vibration . . . . . . . . . . . . . . . . . . . . . . . . . . . . J. Jerold John Britto, A. Vasanthanathan, S. Rajakarunakaran, and K. Amudhan

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Properties and Applications of Natural Pigments Produced from Different Biological Sources—A Concise Review . . . . . . . . . . . . . . 105 Subbulakshmi Muthusamy, Sruthilaya Udhayabaskar, Gowthama Prabu Udayakumar, G. B. Kirthikaa, and N. Sivarajasekar Optimization of Nutrient-Rich Herbal Noodles . . . . . . . . . . . . . . . . . . . 121 Soundira Rajan Nithya Priya, A. Sakthipriyadarshni, Joel John Varghese, R. Sanjana, M. Jancy Mary, K. Suvalakshmi, S. Aarthy, and J. Jaynub Rapid Method for Detection of Aflatoxin Presence in Groundnut by Bioanalyser . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 131 S. Janaki alias Priya and Anurag Chathurvedi Validation and Verification of FRP Laminate Composite Material Characterization Under Numerical Simulation Using COMSOL Multiphysics® . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 141 J. Jerold John Britto, A. Vasanthanathan, S. Rajakarunakaran, and R. Venkatesh Heavy Metal Bioaccumilation by Some Common Aquatic Plants—A Study on Their Bioremediation Efficiency . . . . . . . . . . . . . . . . . . . . . . . 163 R. S. A. Sorna Kumar, P. N. Karl J. Samuel, N. Swetha, P. Dhanapriya, and Shaleesha A. Stanley Biomass and Bioenergy Production from Myxosarcina sp.: Molecular Interactions of a-Cyclodextrin with Isocitrate Dehydrogenase for Biodiesel Production . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 169 Kalimuthu Jawaharraj, Prabu Manoharan, Rathinam Navanietha Krishnaraj, Rathinasamy Karpagam, Balasubramaniem Ashokkumar, Perumal Varalakshmi, and I. Ganesh Moorthy Numerical and Experimental Evaluation of Material Characterization on Glass Fiber/Epoxy Composite Material . . . . . . . . . . . . . . . . . . . . . . . 185 J. Jerold John Britto, A. Vasanthanathan, S. Rajakarunakaran, M. Manikandan, and P. Ari Ramalingam Effect of Blended Waste LDPE/LLDPE on Properties of Bitumen for Rural Roads . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 197 Sagarika Panda, Siba Prasad Mishra, and Minati Mohanty

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Application of Metal Nanoparticles for Textile Dye Remediation . . . . . . 217 Suresh Kumar Krishnan, Kavitha Subbiah, Senthilkumar Kandasamy, and Kalidass Subramaniam Continuous Sorption of Chlorpyrifos from Aqueous Solution Using Endoskeleton Powder of Sepia officinalis . . . . . . . . . . . . . . . . . . . . . . . . 225 Karthikumar Sankar, Shyam Kumar Rajaram, I. Ganesh Moorthy, K. Naresh, S. Vaitheeswaran, R. K. Akash Kumar, G. R. Murary Viyas, and P. N. Karl J. Samuel

Editors and Contributors

About the Editors Dr. V. Sivasubramanian is currently Professor in the Department of Chemical Engineering, National Institute of Technology, NIT Calicut. He obtained his B.Tech in Chemical Engineering from Alagappa College of Technology, Anna University, Chennai in 1993. His M.Tech. and PhD was also from Alagappa College of Technology, Anna University, Chennai. He also obtained an MBA in Operations Management from IGNOU in 2002. He worked as a Senior Plant Engineer in M/s. Tamil Nadu Explosives Ltd., Katpadi, Vellore for five years (1995-2000). Later he joined as Teaching Research Associate in Department of Chemical Engineering, Alagappa College of Technology, Anna University, Chennai in 2001. After completing his PhD, he worked as Lecturer in Alagappa College of Technology for two years (2005-2007) and moved to NIT Calicut in 2007. His research interests include fluidization, hydrodynamics, mass transfer, biochemical engineering, environmental engineering, industrial effluent treatment, energy engineering, nanoparticles, biofuels, bio-separation, bio-plastics and dye decolourization. He has conducted various Workshop and Conferences to promote research activities. He has published more than 50 research articles in peer-reviewed journals and presented many papers in conferences on topics related to energy and environment like development and use of magnetic bio-composite for water treatment, energy-efficient alternative to conventional distillation process, electro-coagulation for dye industry wastewater treatment, development of biodegradable plastics, biogas production through anaerobic digestion of food waste, green diesel production, and inulin-based biofuel. Dr. Arivalagan Pugazhendhi is currently working as an Assistant Professor in the Faculty of Environment and Labour Safety, Ton Duc Thang University, Ho Chi Minh City, Vietnam. He is the Head of Innovative Green Product Synthesis and Renewable Environment Research Group. He obtained his PhD in Environmental Biotechnology from Bharathidasan University, Tamil Nadu, India. During PhD period he was

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awarded the ‘Canadian Commonwealth Scholarship (CCSP)’ fellowship by the Canadian Government (Canada). He then worked for the Post-doctoral Researcher, Daegu University, South Korea for 1.5 years and he managed the Biohydrogen research. Thereafter, he joined Ton Duc Thang University as a lecturer and worked there between 2017 and 2019. And he promoted as an Assistant Professor at the same University. He is an Editorial Board Member of Nature Scientific Reports. His research interests include the development of biological processes (Waste to Energy) for Biofuels (Biohydrogen, Biodiesel, Bioethanol, Biobutanol, Bioplastics), wastewater and waste gas treatment, resource recovery of metals, Nanoparticles. He has published over 140 articles in refereed journals and conference proceedings volumes, and also contributed several chapters to books. His university teaching is mainly on Wastewater Treatment and Environmental Pollution. Dr. I. Ganesh Moorthy is currently an Associate Professor in the Department of Biotechnology, Kamaraj College of Engineering and Technology, Madurai. He completed his B. Tech in Chemical Engineering from Erode Sengunthar Engineering College, Erode and his M. Tech in Chemical Engineering from National Institute of Technology, Tiruchirappalli. He received his PhD from Anna University, Chennai. His current areas of research include statistical and stochastical modelling and optimization, bioprocess modelling, enzyme engineering, bioremediation, bioenergy, environmental biotechnology and industrial effluent treatment. He has completed many funded projects and is currently associated with the Department of Biotechnology, Government of India. He has published 30 research articles in peer-reviewed journals and presented more than 100 articles in national and international conferences, on topics related to energy and environment. He has also contributed a few book chapters in the field of energy and environment. He has one patent granted and filed one patent. He organized many workshops, conferences to promote research activities among students. He is also a reviewer in 12 international peer-reviewed journals such as Biomass and Bioenergy, Trends in Food Science and Technology, Food Research International, Carbohydrate Polymers, Process Biochemistry, International Journal of Biological Macromolecules, Alexandria Engineering Journal, Arabian Journal of Chemistry, Polish Journal of Chemical Technology, International Journal of Environment and Sustainable Development, Journal of Molecular liquids and Preparative Biochemistry and Biotechnology. He acted as a session chair in many international and national conferences.

Contributors S. Aarthy Department of Biotechnology, Kumaraguru College of Technology, Coimbatore, India R. K. Akash Kumar Department of Biotechnology, Kamaraj College of Engineering and Technology, Madurai Dist., Tamil Nadu, India

Editors and Contributors

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K. Amudhan Department of Mechanical Engineering, Ramco Institute of Technology, Rajapalayam, India Swetha Juliet Anandharaj Laboratory for Bioremediation Research, Department of Biotechnology, Kumaraguru College of Technology, Coimbatore, Tamil Nadu, India P. Ari Ramalingam Project Development, Rane NSK Steering Systems Private Limited, Chennai, India Balasubramaniem Ashokkumar Department of Genetic Engineering, School of Biotechnology, Madurai Kamaraj University, Madurai, Tamil Nadu, India P. Bharathi Karpaga Vinayaga College of Engineering and Technology, Chinnakolambakkam, Madhuranthagam TK, India Anurag Chathurvedi Department of Foods and Nutrition, Acharya N. G. Ranga Agricultural University, Hyderabad, India P. Dhanapriya Jeppiaar Engineering College, Chennai, India Anusiya Ganesan Laboratory for Bioremediation Research, Department of Biotechnology, Kumaraguru College of Technology, Coimbatore, Tamil Nadu, India I. Ganesh Moorthy Department of Biotechnology, Kamaraj College of Engineering and Technology, Madurai Dist., Tamil Nadu, India S. Gayathri Karpaga Vinayaga College of Engineering and Technology, Chinnakolambakkam, Madhuranthagam TK, India Dhivyadharshini Govindharaj Laboratory for Bioremediation Research, Department of Biotechnology, Kumaraguru College of Technology, Coimbatore, Tamil Nadu, India Jeyashree Gunasekaran Laboratory for Bioremediation Research, Department of Biotechnology, Kumaraguru College of Technology, Coimbatore, Tamil Nadu, India Harikrishnan Hariharan Department of Food Technology, Saintgits College of Engineering, Kottayam, Kerala, India S. Janaki alias Priya Department of Foods and Nutrition, Acharya N. G. Ranga Agricultural University, Hyderabad, India M. Jancy Mary Department of Biotechnology, Kumaraguru College of Technology, Coimbatore, India Kalimuthu Jawaharraj Department of Molecular Microbiology, School of Biotechnology, Madurai Kamaraj University, Madurai, Tamil Nadu, India

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J. Jaynub Department of Biotechnology, Kumaraguru College of Technology, Coimbatore, India J. Jerold John Britto Department of Mechanical Engineering, Ramco Institute of Technology, Rajapalayam, India Elizabeth Nirupa Joshy Department of Biotechnology, MET’S School of Engineering, Thrissur, Kerala, India Senthilkumar Kandasamy Department of Chemical Engineering, Kongu Engineering College, Erode, Tamil Nadu, India Rathinasamy Karpagam Department of Molecular Microbiology, School of Biotechnology, Madurai Kamaraj University, Madurai, Tamil Nadu, India G. B. Kirthikaa Laboratory for Bioremediation Research, Unit Operations Lab, Department of Biotechnology, Kumaraguru College of Technology, Coimbatore, Tamilnadu, India Suresh Kumar Krishnan Department of Biotechnology, Karunya Institute of Technology and Sciences, Coimbatore, Tamil Nadu, India Rathinam Navanietha Krishnaraj Department of Biotechnology, National Institute of Technology, Durgapur, West Bengal, India M. Manikandan Department of Mechanical Engineering, Ramco Institute of Technology, Rajapalayam, India Prabu Manoharan Centre of Excellence in Bioinformatics, School of Biotechnology, Madurai Kamaraj University, Madurai, Tamil Nadu, India Yogesan Meganathan Laboratory for Bioremediation Research, Department of Biotechnology, Kumaraguru College of Technology, Coimbatore, Tamil Nadu, India Siba Prasad Mishra Centurion University of Technology and Management, Jatni, Bhubaneswar, India Minati Mohanty Centurion University of Technology and Management, Jatni, Bhubaneswar, India Krishnasree Moneyraj Department of Biotechnology, MET’S School of Engineering, Thrissur, Kerala, India G. R. Murary Viyas Department of Biotechnology, Kamaraj College of Engineering and Technology, Madurai Dist., Tamil Nadu, India Subbulakshmi Muthusamy Laboratory for Bioremediation Research, Unit Operations Lab, Department of Biotechnology, Kumaraguru College of Technology, Coimbatore, Tamilnadu, India

Editors and Contributors

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K. Naresh Department of Biotechnology, Kamaraj College of Engineering and Technology, Madurai Dist., Tamil Nadu, India Soundira Rajan Nithya Priya Department of Biotechnology, Kumaraguru College of Technology, Coimbatore, India Sagarika Panda Centurion University of Technology and Management, Jatni, Bhubaneswar, India R. Prabhakaran Department of Mechanical Engineering, Ramco Institute of Technology, Rajapalayam, India S. Rajakarunakaran Department of Mechanical Engineering, Ramco Institute of Technology, Rajapalayam, India Shyam Kumar Rajaram Department of Biotechnology, Kamaraj College of Engineering and Technology, Madurai Dist., Tamil Nadu, India Baskar Ramakrishnan Laboratory for Bioremediation Research, Unit Operations Lab, Department of Biotechnology, Kumaraguru College of Technology, Coimbatore, Tamilnadu, India Kavya Sajeevan Department of Biotechnology, MET’S School of Engineering, Thrissur, Kerala, India A. Sakthipriyadarshni Department of Biotechnology, Kumaraguru College of Technology, Coimbatore, India P. N. Karl J. Samuel Department of Biotechnology, Kamaraj College of Engineering and Technology, Madurai Dist., Tamil Nadu, India R. Sanjana Department of Biotechnology, Kumaraguru College of Technology, Coimbatore, India Karthikumar Sankar Department of Biotechnology, Kamaraj College of Engineering and Technology, Madurai Dist., Tamil Nadu, India N. Sivarajasekar Laboratory for Bioremediation Research, Department of Biotechnology, Kumaraguru College of Technology, Coimbatore, Tamil Nadu, India R. S. A. Sorna Kumar Jeppiaar Engineering College, Chennai, India Shaleesha A. Stanley Jeppiaar Engineering College, Chennai, India Kavitha Subbiah Department of Biotechnology, Karunya Institute of Technology and Sciences, Coimbatore, Tamil Nadu, India Kalidass Subramaniam Department of Animal Science, Manonmaniam Sundaranar University, Tirunelveli, Tamil Nadu, India; Institute of Food Security and Sustainable Agriculture (IFSSA), Universiti of Malaysia Kelantan, Jeli, Kelantan, Malaysia

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K. Suvalakshmi Department of Biotechnology, Kumaraguru College of Technology, Coimbatore, India N. Swetha Jeppiaar Engineering College, Chennai, India Gowthama Prabu Udayakumar Laboratory for Bioremediation Research, Unit Operations Lab, Department of Biotechnology, Kumaraguru College of Technology, Coimbatore, Tamilnadu, India Sruthilaya Udhayabaskar Laboratory for Bioremediation Research, Department of Biotechnology, Kumaraguru College of Technology, Coimbatore, Tamil Nadu, India S. Vaitheeswaran Department of Biotechnology, Kamaraj College of Engineering and Technology, Madurai Dist., Tamil Nadu, India Perumal Varalakshmi Department of Molecular Microbiology, School of Biotechnology, Madurai Kamaraj University, Madurai, Tamil Nadu, India Joel John Varghese Department of Biotechnology, Kumaraguru College of Technology, Coimbatore, India V. Varsha Karpaga Vinayaga College of Engineering and Technology, Chinnakolambakkam, Madhuranthagam TK, India A. Vasanthanathan Department of Mechanical Engineering, Mepco Schlenk Engineering College, Sivakasi, India Yamini Vasudevan Laboratory for Bioremediation Research, Department of Biotechnology, Kumaraguru College of Technology, Coimbatore, Tamil Nadu, India R. Venkatesh Department of Mechanical Engineering, Ramco Institute of Technology, Rajapalayam, India K. Vigneshwaran Department of Mechanical Engineering, Ramco Institute of Technology, Rajapalayam, India

A Review on the Production of Biogas from Biological Sources Yamini Vasudevan, Dhivyadharshini Govindharaj, Gowthama Prabu Udayakumar, Anusiya Ganesan, and N. Sivarajasekar

1 Introduction Biogas is a renewable form of energy source obtained as a product of anaerobic digestion. It is a compromising replacement that has the potential to meet the world’s energy demands and helps in the reduction of waste and Green House Gas (GHG) release [1, 2]. Anaerobic digestion, a classical method for the digestion of organic substrates from biological feedstock, is commonly employed for the sludge stabilization and industrial waste treatment [3, 4]. Global interest on anaerobic digestion research and its applications has been a serious concern due to the erupting fuel prices and awareness about global warming and greenhouse gas emissions. Research now focuses on the most abundant form of solid organic waste, cattle dung, due to its intensive waste disposal problems. Optimizing the treatment of cattle dung might enhance the commercial production [5, 6]. Anaerobic digestion of such organic matter produces biogas containing methane (CH4 ) and carbon dioxide (CO2 ) enabling it to be used as a fuel for gaseous vehicles, as an alternative for natural gas, as a source for the manufacture of chemicals and in bioenergy production [7]. Increasing capital investment and reduced revenue growth prospects depletes the part of anaerobic digestion using biological waste treatment. National Biogas and Manure Management Program (NBMMP), Waste To Energy Program (WTE) and Off-Grid Biogas Power Generation Program (OGBPG) are some of the support schemes executed by the Government of India for the production of biogas. Despite several efforts, biogas synthesis is hindered by financial, social and institutional factors. Few researchers concentrate on the obstacle to bioenergy dissemination in rural India while others have focused on the view of the stakeholder and bioenergy potential. The energy content of 1.0m3 of purified biogas equals 0.97m3 of natural gas and 1.1L gasoline, 1.7L bioethanol [8]. For cleaning and improvising Y. Vasudevan · D. Govindharaj · G. P. Udayakumar · A. Ganesan · N. Sivarajasekar (B) Laboratory for Bioremediation Research, Department of Biotechnology, Kumaraguru College of Technology, Coimbatore, Tamil Nadu 641049, India e-mail: [email protected] © Springer Nature Singapore Pte Ltd. 2020 V. Sivasubramanian et al. (eds.), Sustainable Development in Energy and Environment, Springer Proceedings in Energy, https://doi.org/10.1007/978-981-15-4638-9_1

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the biogas, several technologies have been developed and commercialized. Comparatively, methane is a clean fuel that produces minimum carbon dioxide per unit energy. Continuous research on biogas aims to enhance the overall efficiency and to meet the economic needs. Under the International Energy Agency (IEA), IEA bioenergy has executed about 10 tasks based on bioenergy, which focus on improving the information on utilization of biogas [9]. In addition to the production of biogas, the anaerobic mesophilic treatment of industrial wastewater with high primary load is implied to reduce the atmospheric pollution [10, 11]. The significance of the share and circulation rate of biogas in rural areas is negligible. The biogas development program has installed about five million small-sized family biogas plants and 400 biogas-based off-grid power plants with 5.5 MW power generating capacity. At present, there are fifty-six operational biogas plants in India, mainly located in Maharashtra, Kerala and Karnataka. Methane, an essential component of the biogas was produced in large amounts by maize crop digestion carried in a small digester. Energy value model from crude protein, cellulose, crude fat of maize was calculated and the addition of glycerol increased the production and biomass growth [12, 13]. Biomass obtained from grasslands can be effectively utilized as a raw material for biogas production in green bio-refineries industry. Manure from cattle with minimum milk capitulate also plays a major role in production of methane [14–16]. The effective utilization of grassland biomass varies based on their specific properties. Hence, the crop feed stocks supplied during the production of biogas obtained a maximum methane yield per unit area (m3 ha−1 ) [17]. This review focuses on providing a collective knowledge about the various available sources for production of biogas and their corresponding yield from different sources. The process and the influencing parameters for the production considering the future perspectives for the growing need for an alternative fuel has been discussed.

Fig. 1 Waste to energy cycle from solid/liquid effluents to power generation

A Review on the Production of Biogas …

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2 Various Sources for Biogas Production 2.1 Municipal Waste Household digesters are affordable and productive technologies that are available to distribute energy to the economically backward in the rural areas. The decomposition of tons of organic waste from various sources constitutes to the large-scale contamination of the environment (Fig. 1). For instance, anaerobic degradation of shells of Lophira lanceolata revealed a notable rise in the biogas production when added with co-digested pig waste and cassava [18, 19]. Conventional municipal solid waste (MSW) management disposed by land filling causes anthropogenic methane emission which is the main reason for global warming (IPCC 1996). Anaerobic digestion is renewable and environment friendly as a suitable alternative for other methods like incineration and composting. The wastewater containing high levels of microbial load from industries can be treated in-house using anaerobic mesophilic treatment [20]. For instance, the biological treatment methods for potato wastewater produced by a potato processing plant in Harare, Zimbabwe produce high amount of biogas. Anaerobic treatment installed at the potato processing plant was found to enable the plant to treat the potato wastewater with the required effluent quality devoid of the microbium present in it [9].

2.2 Agro-waste The crop feedstock is applied as a source for the production of biogas to obtain maximum methane yield per unit area (m3 ha−1 ) which covers organic biomass dry matter yield (kg ODM ha−1 ) and specific feedstock methane yield (m3 kg ODM−1 ) [21]. The composition of the organic gases in the biogas have been listed in Table 1. For productive anaerobic digestion, degree of disruption is required as its chemical structure is highly resistant against microbes, degradation and oxidative stress [22]. Over the past few years, bioenergy production using grassland has been increasedand put into practice for biogas production. Subsequently afterthe production of biogas, Table 1 Composition of agricultural plant biomass

Components

Amount present

Methane

48–65%

Carbon dioxide

36–41%

Nitrogen

17%

Oxygen

9400MT join the sea down to earth Oct 3, 2019. The consumption of plastic in India is increasing at a very faster rate. In last ten years from 2008 to 2018, it has gone up from 8 million MT to 18 million MT in India.

2 Review of Literature Indian Road Congress (IRC) [4] predicted that half of the surfacing of pavements shall be done by modified bitumen, and search for the modifying material is in quest (IRC: SP: 53-2010). Mohammad et al. [5] indicated that the modified mixture has a higher stability VMA percentage compared to the nonmodified mixtures. They have positive influence on the rutting resistance of these mixtures and can modify asphalt mixture with high-density polyethylene (HDPE)polyethylene enhances its asphaltic properties better than LDPE (low-density polyethylene). Zahra et al. [6] used polyethylene terephthalate waste by way of additives to bitumen at various mix proportions and had observed that the admix has better resistant to deformations (the rutting parameter: G*/sin δ is high) where the rutting occurs during the early stage or midlife of the pavement life and should be 1.00 and 2.2 kPa for the fresh asphalt. Panda et al. [7] and Casey et al. [8] had found 4% substitute of recycled HDPE polymer as modified binder for consumption with mastic asphalt added to chips of stone give better result. Gonzalez et al. [9] has reported that the blending of bitumen with

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y = 1173.7x + 8670.1 R² = 0.9895

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Fig. 2 Growth of plastic consumption from FY 2013–14 to 2017–18

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Fig. 3 The seven categories of plastic and their uses

high density polyethylenes (HDPE’s) and linear low-density polyethylene (LLDPE) increases the stability of the road. Bindu et al. [10], Swami et al. [11] have reported that 10% shredded waste plastic perform as a stabilizing additive to mastic asphalt when added to chips of stone satisfying Marshall characteristics with advantages of bleeding during hot days and acoustics problems can be reduced. Pareek et al. [12], inferred that modified bitumen with polymer upshots elastic recovery up to 79% has longevity and high resistance characteristics. Viscoelastic properties rise when G* (the complex shear modulus) rises and the δ (phase angle) drops [13]. Gawande et al. [14] and Al-Humeidawi [15] said that use of modified bitumen with the addition of processed waste polyethylene of about 5–9% of bitumen by weight adds to improve the longevity and pavement performances and some saving is made on bitumen usage. The properties like penetration and ductility test results show bitumen modified with polythene is decreased when plastic proportion is ≥12% by weight of bitumen. Khan et al. [16] reported about the modified process of bitumen with polythene discarded boosts resistance to cracking, formation of pothole, develops rutting as softening point increases and develops hardness and reduce stripping. The developed properties enhance the live performance of pavements for long period as the mix add impervious coating over the aggregates which lessens porosity, trapping of moisture and binding characteristics. Prusty [17] stated that bitumen concrete blended with waste polythene satisfies the Marshall properties such as stability, flow value, unit weight, air voids and is more stable. Rajsekharan et al. [18], reported that softening of waste plastics varies between 110 and 140 °C without any toxic gases. Li et al. [19] has reported that low-density polyethylene (LDPE/LLDPE) is used in shopping/garbage bags, plastic covers and cups are rarely recycled and after recycling used as packaging, nursery sheets and film industry. So, when the hot plastic at 160 °C is sprayed over coarse aggregates of road, bed bituminous concrete gets a coating making the concrete water proof and impart better longevity to bitumen road. CIPS [20] reported that about 9–10% out of ≈25940 MT/day (CPCB report) of garbages generated in India are toxic, geo-bio-environmental degrading plastics which can be

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Plastic waste 13 Indian states (2018)

7000 6000 5000 4000 3000 2000 1000 0

MSW TMT/year (2018)

Plasc waste in TMT(@8%)

Fig. 4 Major plastic wastes in 13 states in India. Source CPCB 2018 and MOEFCC 2019

pioneered for use in rural flexible pavement construction [21]. Prachi [3] has reported 80% of six Billion MT of plastics generated since 1950 has been deposited as landfill and alternate use of poly-propylene to liquid fuel in Swachha Bharat Mission claims to free India from single use of plastics in any form [22]. The state UP is having the maximum plastic waste generation (Fig. 4) out of total MSW plastic waste is considered as 8%. The growth rate of Plastics Processing Industry at (CAGR) of 10% (likely to grow @10.5% by FY 2020) and in volume terms from 8.3 MMTPA in FY2010 to FY 2013 in India Mohanty Smita (CIPET- 2018). The globe is worried about plastic waste invasion, ill-impacts on deteriorated geobio environment, mineral mediation and demands the utility of peoples participation, outreach and media vents to elucidate various forms of presentation of plastic trash and through an interdisciplinary model [23].

3 Study Area The polyethylene/polystyrene wastes pollute geo-hydro-bio-novo environment, including water system. The plastics create unaesthetic and unpleasant scenery both on land and ocean. The recent discover of the anthropogenic-mediated agglutinated rock/mineral with composition of raw/burnt plastics (first discovered at Kamilo Beach, Hawai’I, 2012) named as plastiglomerate which shall be left over for our ancestors. It is formed due to agglutination of beach sand/sediments with highdensity melted plastic and buried under beach sands and lake beds [24, 25]. So, the disposal of these polystyrene wastes is major problem for us. An attempt has been

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made in this research to reuse the waste polystyrene as an ingredient of the bituminous pavement materials. Rural roads should be of low cost. The required stipulations for pavement ingredients in different stratums should be most economical, compatible, adhering to the traffic flow and resistant to the climatic disorders. The local materials are of prime importance as they are less expensive and comprise less haulage. Safe disposal of non-biodegradable waste polyethylene is preferred additives for bitumen as they cause environmental pollutions and cause diseases in livings on earth. The major states of India are recycling these deadly Anthropocene polymers for polymerized bituminous road construction. As per notified in Rule 8 (b) Gazette of India, publication Part-II, Section-3, Sub-section (i) of MOEFCC for the plastic waste (Management and Handling) (Amendment) Rules, 2011, uses and recyclability of seven categories of plastics are in Fig. 3 (MOEFCC: Ministry of Environ, forest and climate change).

4 Category of Plastic Waste Abandoned plastic wastes can congest the drains, pollute the environment containing other wastes and even on burning, issues during landfall and recycled areas creating health hazards and mineral mediation for the upcoming generation in form of plastiglomerate. In finished state, plastics are large polymers of high molecular weight and flow under different state of temperature [26]. The monster and apocalyptic plastic cannot be banned as it has become a part to our life but if possible recycled Fig. 5. India spawns 5.6 MMT/year of plastic waste and targets to ban mono-use plastic objects by 2022. The plastic industries must register Plastic Waste Management Rules, 2016 provisions.

Plastics Thermoplastics Recyclable PVC (Poly Vinyl Chloride), PET (Polyethylene Terephthalate), LDPE (Low Density Poly Ethylene), (PP) Polypropylene, HDPE (High Density Poly Ethylene), (PS) Polystyrene and many others

Thermosetting Plastics Non-recyclable

Epoxy, alkyd, ester, (melamine or phenolic or urea or silicon formaldehyde, multilayer plastics polyurethane etc

Fig. 5 Classification of plastic wastes and their recyclability

Effect of Blended Waste LDPE/LLDPE …

Bitumen Mix

Asphalt Processes i. Hot mix ii. Warm mix iii. Cold mix

Plastic as modifier

203

Plastic mixed when aggregate is hot (Dry mix)

Plastic as binder

Plastic mixed when Bitumen is hot

Others

Recycled plastic, new additives or modified

Hot Mix

Bituminous concrete (BC), Mastic Asphalt concrete (MAC), cut back asphalt concrete,Modified bitumen mix, Dense graded Bitumen mix, Semidense Bituminus concrete (SDBC), Open graded Bitumen mix, Gap graded Bitumen mix

Fig. 6 Road construction processes flowchart for bitumen mix with plastics at different states

5 Bitumen Mix Bituminous binders are widely used in road paving, and their viscoelastic properties are dependent on their chemical composition. At present, there is continuous enhancement of intensity to traffic as profit-making and comfort adding automobiles, to adapt the climatic changes in daily and seasonally. To combat the climatic anomalies, alternative means for the upgrading of the road surface characteristics are to be modified to cope and confront the strength and the economic criterion Fig. 6. As an alternative, modification and blending of bitumen have become inevitable by using additives, and the best possible solution to the problem is waste plastics or polyethylene. The bitumen grade 80/100 was followed properties such as ductility (cm) 45 °C, respectively (IS 73: 2013). The requirement for paving bitumen of grade VG-30 is in Table 3.

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Table 1 Chemical properties of the shredded LDPE used in OMFED polythene #

Characteristic

LDPE/LLDPE

Properties

Results

Chemical behavior

1

Melting point

less than VG-30

105–115 °C

2

Chemical resistance

Better resistance

Resistance to dilute alkalis, alcohols and acids

Sensible resistance

Hydrocarbons (both aliphatic and aromatic), mineral oils, oxidizers and halogenated hydrocarbons

3

Temperature

Resistance

Up to 80 °C continuously and occasional 95 °C

4

Economics

Cost and process ability

Low cost and good processability

5

Electrical properties

Insulating

Very good insulator and poor resistance to UV ray

6

Absorption

Water

Very low

7

Susceptibility

To stress

Crack occur

8

Flammability

To fire

Highly flammable

9

Thermal properties

Strength, stiffness and temperature

Low strength and stiff at high temp. limiting use in extreme temperatures

Source https://omnexus.specialchem.com/selection-guide/polyethylene-plastic, Jordan et al. [27], https://omnexus.specialchem.com/selection-guide/polyethylene-plastic/hdpe-ldpe-lldpecomparison

The properties need to be studied for bitumen binder in construction of flexible pavement arestability, durability, flexibility, skid resistance and workability. Different tests to be conducted are specific gravity test, penetration test, ductility test, softening point test, flash and fire. The properties of 80/100 bitumen penetration grade (VG-30) are found appropriate for hot mix bituminous flexible pavements for BC and wearing course.

11 The Present Work In present work on polyethylene envisages the stabilization of bitumen for pavements as an additive. The waste polyethylene was added in different ratio of 5–15% by weight to study the fallowing properties: The steered tests are to assess the suitability of blending bitumen with LDPE/LLDPE. The tests conducted are (a) Specific Gravity Test, (b) Penetration Test, (c) Ductility Test, (d) Softening Point Test, (e) Flash and Fire Test and (f) Marshal Test.

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Table 2 Physical and mechanical properties of LDPE and LLDPE (OMFED pouche) #

Characteristic

Properties

Results

LDPE/LLDPE

Physical/mechanical properties

10

Specific gravity

LDPE LLDPE

0.910–0.925 0.915–0.925

Thermal expansion coefficient (linear)

Both LDPE and LLDPE

10–20 × 10–5/°C

Shrinkage

LDPE LLDPE

2–4% 2–2.5%

Water absorption 24 h

LDPE LLDPE

0.005–0.015% 0.005–0.01%

Flexibility (flexural modulus)

LDPE LLDPE

0.245–0.335 GPa 0.28–0.735 GPa

Strength at break (tensile)

LDPE LLDPE

10–20 MPa 25–45 MPa

Young modulus

LDPE LLDPE

0.13–0.3 GPa 0.266–0.525 GPa

Density

LDPE LLDPE

0.917–0.94 g/cm3 0.915–0.95 g/cm3

Ductile/Brittle transition temp.

LDPE LLDPE

70 °C 70 °C

Thermal insulation (thermal conductivity)

LDPE LLDPE

0.32–0.35 W/m K 0.35–0.45 W/m K

12 Experimental Works Specific gravity (sp. gr.): The relative proportion of the mass of the bitumen to the mass of water of an equal volume at temperature of the both at 27 °C is based upon the provisions given in IS: 1203-1978 and the range of values allowed. The recommended specific gravity value for VG 30 bitumen is 1.01–1.05. It was observed that the sp. gr. of the blended bitumen is 1.05–1.057 between 5 and 10% mixing of OMFED pouches. The addition of 10% of polyethylene with bitumen gave decreased sp. gr. from 1.05 to 1.015 (Fig. 9).

13 Penetration Test The test examines the consistency of a bitumen sample finding the distance in mm and further fractions that a standard needle vertically penetrates the bitumen specimen under known conditions of loading, time and temperature. This is the old ASTM method and was widely used to measure the consistency of bitumen. It classifies rather than assessing the quality.

Sp. gr. = [(c − a)/[(b − a) − (d − c)] = 1.01–1.05

Specific gravity (Sp. Gr.) = weight of bituminous material/weight of same volume of water

Absolute viscosity at 60 °C, Poises

Kinematic viscosity at 135 °C, cSt, Min

Flash point (FP) (Cleveland open cup), °C, Min

Softening point (R&B), in °C,

Ductility at 25 °C, cm, after Rotating thin film oven test

2

3

4

5

6

7

Source http://www.bitumina.co.uk/pdf/BITUMEN_80-100_PEN_EC.pdf

Range 40–100 cm

Minimum 42–52 °C

220 °C minimum to 225 °C

350

Viscosity (= K * t ) (2400–3600 poise)

Standard 45 mm

Minimum penetration at 25 °C, 100 g, 5 s, 0.1 mm, Min

1

Formulae used/range of results

Properties IS 73: 2013

#

The property to elongation of bitumen under traffic load without getting cracked

IS 1208-1978

IS 1205-1978

IS 1448-1998 [P: 69]

Correction to the observed FP = C + 0.25 (101.3-P), where, C = observed FP, °C; P = pressure, kPa. The temperature when the bitumen achieves the degree of softening under specified conditions of test

IS 1206 (Part 3): 1996, 4th rev.

IS 1206 (Part 2)

K = Calibration factor in poise per second and t = time of in Sec. flow Specification: 250, Min(IS73-2006)

IS: 1203-1978; Rev 1990

IS 1203-1978; Rev 1990

Reference IS code

a = wt of sp. Gr. bottle, b = “a” + filled water, c = a + 1/2 filled water bitumen, d = c + the rest with distilled water(all in gms)

80/100 asphalt is the penetration extent ranging 80–100 mm

Paving grade VG 30

Table 3 Specification requirement for VG 30 grade bitumen as per IS; 73-2013 and lab results

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1.1 1.05 Sp. Gr. Value

1.047 1.05 1.015 1 y = -0.0011x2 + 0.0067x + 1.0476 R² = 0.9914 0.95 Specific gravity…

0.9

0.905

0.85

.

0

5

10

% of Polythene addition

15

20

Fig. 9 Specific gravity value at 0%, 5%, 10%, 15% LDPE hot mix with VG 30 bitumen

Penetration test is done to find the consistency of the tar in use and was means for classifying standard grading of the asphalt or the tar. Higher the penetration, softer is the consistency. Bitumen with lower penetration value is opted in tropics/hot climates and vice versa. The penetration values indicate hard or soft bitumen in use. Generally, the penetration values largely influence the inaccuracy toward the size of the needle, weight positioned on the needle and the temperature at which the test is conducted. For example, 40/50grade of bitumen exhibits the penetration value lies within 40–50 at normal test settings. The standard values of bitumen blending as per IS 1203-1998(revised) and IS 732013, the viscosity grade lies between 50–70mm. After hosting the LDPE/LLDPE at 5%, 10% and 15%, the penetration values are gradually falling and are within a range between 64 to 68 mm. So, addition of LDPE/LLDPE can be putative from penetration point of view Fig. 10.

14 Ductility Test on Blended Bitumen The ductility test of asphalt or modified bitumen is done to know the amount of elongation occurs to the pavement under load imposed by traffic without cracking. It measures the distance in cm to which it stretches before breaking. According to IS 1208-1978 (rev 1996), the allowable ductility value ranges from 40 to 100 cm. The ductility test is a measure of adhesiveness of bitumen and its ability to expand. The flexible pavement desires the binder should form a thin ductile film around aggregates so that physical interlocking of the aggregates can be improved. The poor ductility of a binder deforms the bitumen film, and cracks develop on road surface.

Effect of Blended Waste LDPE/LLDPE …

211

71 70 69

PenetraƟon value (mm)

70

In mm

68 68

67 66

67

y = -0.01x2 - 0.23x + 69.85 R² = 0.976

65 64

64

63 0

2

4

6 8 10 %of mix of polyethylene

12

14

16

Fig. 10 Penetration value at 0%, 5%, 10%, 15% LDPE hot mix with bitumen

The recommended ductility value according to IS 1208-1978 for VG 30 bitumen should range from 75 to 100 cm. The present test results are approaching and lying within the range 71 and 92 cm, so it is acceptable up to 10% moderation with LDPE/LLDPE where the ductility also decreases from 92 to 79 cm within permissible values. The modified bitumen (bitumen + polyethylene) with 10% polyethylene addition can be safely used in pavement and to dispose the waste polyethylene Fig. 11.

100 92

DucƟlity in Cm

80

87 71

79

60 y = -0.03x2 - 0.97x + 92.15 R² = 0.9982

40 20

DucƟlity value in…

0 0

2

4

6

8

10

12

% of addiƟon LDPE?LLDPE

Fig. 11 Ductility value at 0%, 5%, 10%, 15% LDPE hot mix with bitumen in cm

14

16

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15 Softening Point Test The softening point of the tar to be used signifies the temperature when the bitumen reaches specific mark of softening. The temperature (in deg C), at which a standard ball permits a sample of asphalt in the mold when dropped from 2.5 cm high, during heating in water or glycerene under specific setting of the test. The fluidity of the binder should be as per norms sufficiently before construction of pavement (IS: 334-1982; ASTM E28-67; ASTM D36; or ASTM D6493-11). The softening point value indicates the optimum temperature which should be attained by the bituminous binder before use in the pavements. Softening point can also be found by ring and ball device. Softening point designates the high temperature when binders achieve the identical viscosity. Bituminous ingredients have no specific melting point but somewhat indicate the state change from solid to liquid. It is steady over a varied range of temperature. Knowing softening point is significant when bituminous materials are used as filling joints and cracks. During the work, bitumen of the high-valued softening point does not flow easily. The higher values of softening point indicates the lesser values of temperature susceptibility. The asphalt having greater value of softening point is chosen in hot and dry workplace (Fig. 12). Suggested values of bitumen softening point of VG 30 grade asphalt (IS 1205: 1978) is 35–70 °C.

70 62

In deg cen grade

60 50

60 y = 49.547e0.0158x R² = 0.931

52

50

40 30 20 10

0 0

2

4

6

So ening point 8 10

12

% mix of LDPE/LLDPE Fig. 12 Softening point at 0%, 5%, 10%, 15% LDPE hot mix with bitumen

14

16

Effect of Blended Waste LDPE/LLDPE …

213

16 Discussion Bitumen is the appropriate element for paver’s construction due to its viscoelastic properties and a good binder (both cohesive and adhesive) with coarse aggregates of bituminous concrete. Under settings of traffic load when the stability becomes lower than the traffic demand, surficial shoving and flow occur. Cracking occurs in cold and rutting occurs in hot climate. The properties of asphalt are possible to improve by air blowing to impart hardness, and diluent oils are fluxed to make it soft. But addition of polymers helps in improving the quality of asphalt. The advantages (waste to wealth) of inserting waste OMFED polyethylene in bitumen as a binder material in roads construction are eco-friendly, saving ≈8–10% of bitumen, reducing lassitude health of roads, and develop longevity, strength and better performances. Simultaneously, the dark side is spreading piling of polythene in atmosphere, increases concentration of CO2 , other noxious fumes such as Furans, Dioxins and Polychlorinated Biphenyls in the atmosphere which degrades the health of plants, vegetation, animals and also human. The other advantages are: Shedding and Pothole Formation: Bitumen films on the pavement are at times made uncovered off the masses due to percolation and absorption of water that create pothole on the road. The potholes are enlarged and aggravated during the vehicle and traffic movement. When polymers are coated over aggregate, the cover makes the material impervious which does not allow water to penetrate through it. Consequently, the blended aggregates restrict stripping and reduce pothole formation over roads. Leaching: Polymer stick over the aggregates shall not be wiped out from the bitumen layer, even after construction of the road using blended plasticsbitumen-aggregate concrete. Effect of Bleeding: The polymer-asphalt and chips made concrete exhibit high softening temperature which prevent the bleeding of bitumen during summer in hot and temperate areas..However, the drawbacks of the plastic blended roads are evolution of toxic gases. Toxic compounds: Roads made from plastic–bitumen mix inhibit leaching of toxic compounds into soil.

17 Conclusion The blending of polyethylene wastes with asphalt in road construction increases the cementing properties of aggregate and bitumen. Use of waste polyethylene in flexible pavements particularly in rural roads shows good outcome in comparison with conventional orthodox flexible village road formations. This can minimize the harmful/eco-hazardous disposal of polyethylene wastes. It will certainly add to an eco-friendly technique that can add to sustainability. Veneering polymer to the pavement aggregate has ample advantages, which ultimately helps to improve the quality of flexible pavement.

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The experimental study is inferred to the modified bitumen (bitumen + polyethylene) in pavement, and it is better way to dispose the waste polyethylene in useful way. Addition of 10% of polyethylene with bitumen gives satisfactory results.

References 1. Geyer R, Jambeck JR, Law KL (2017) Research article plastics; production, use, and fate of all plastics ever made. Sci Adv 3(7):1–5. https://doi.org/10.1126/sciadv.1700782 2. Prachi P (2019) New technique converts plastic waste to fuel. The Anthropocene, Daily Science. https://www.anthropocenemagazine.org/2019/02/new-techniqueconverts-plastic-waste-to-fuel/ (source: Wan-Ting Chen, Kai Jin and Nien-Hwa Linda Wang. Use of Supercritical Water for the Liquefaction of Polypropylene into Oil. ACS Sustainable Chem. Eng. 2019) 3. Mishra SP (2017) Emerging construction technology. In: Anthropocene epoch, India: The EPSC Panel. Int J Eng Sci Math 6(8):269–279, ISSN: 2320-0294, www.ijesm.co 4. IRC 090 (2010) Guidelines of selection, operation and maintenance of bituminous hot mix plant (first revision). Public Safety Standards of the Republic of India, Bureau of Indian Standards 5. Mohammad T, Shbeeb A (2007) The use of polyethylene in hot asphalt mixtures. Am J Appl Sci 4(6):390–396. https://doi.org/10.3844/ajassp.2007.390.396 6. Zahra NK, Aziz MA, Mohammad RK (2011) Effect of the waste plastic bottles on properties of asphalt. In: Proceedings of the Eastern Asia society for transportation studies, vol 8, 2011 7. Panda M, Mazumdar M (2002) Utilization of reclaimed polyethylene in bituminous paving mixes. Mater Civil Eng 14(6):527–553. https://pdfs.semanticscholar.org/5337/ 3921b334fd9639aedf0b4751069a13b922ee.pdf 8. Casey D, McNally C, Gibney A, Gilchrist MD (2008) Development of a recycled polymer modified binder for use in stone mastic asphalt. J Resour Conserv Recycl 52:1167–1174 9. Gonzalez O, Muz ME, Santamaria A (2006) Bitumen/polyethylene blends: using mLLDPE to improve stability and viscoelastic properties. Rheol Acta J 45(5):603–610 10. Bindu CS, Beena KS (2010) Waste plastic as a stabilizing additive in SMA. Int J Eng Technol 2:379–387 11. Swami V, Jirge A, Patil K, Patil S, Salokhe K (2012) Use of waste plastic in construction of bituminous road. Int J Eng Sci Technol 4(5):2351–2355 12. Pareek A, Gupta T, Sharma RK (2012) Performance of polymer modified bitumen for flexible pavement. Int J Struct Civil Eng Res 1(1):77–86 13. Zahra K (2012) Properties of bituminous mix and binder modified with waste poly-ethylene terephthalate. M. Tech. Dissertation, University of Malaya, pp 1–104 14. Gawande A, Zamare G, Renge VC, Tayde S, Bharsakale G (2012) An overview on waste plastic utilization in asphalting of roads. J Eng Res Stud 3(2):147–157 15. Al-Humeidawi Basim H (2014) Utilization of waste plastic and recycle concrete aggregate in production of Hot Mix Asphalt. Al-Qadisiya J Eng Sci 7(4):323–327 16. Khan I, Gundaliya PJ (2012) Utilization of waste polyethylene materials in bituminous concrete mix for improved performance of flexible pavements. J Appl Res 1(12):85–86 17. Prusty B (2012) Use of waste polyethylene in bituminous concrete mixes. Unpublished B Tech project, NIT RKL 18. Rajasekaran S, Vasudevan R, Paulraj S (2013) Reuse of waste plastics coated aggregatesbitumen mix composite for road application—green method. Am J Eng Res (AJER) 02(11):1– 13 19. Li Dawei, Zhou Liwei, Wang Xuan, He Lijuan, and Yang Xiong, (2019) Effect of crystallinity of polyethylene with different densities on breakdown strength and conductance property. Materials, MDPI, pp 1–13. https://doi.org/10.3390/ma12111746

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Application of Metal Nanoparticles for Textile Dye Remediation Suresh Kumar Krishnan, Kavitha Subbiah, Senthilkumar Kandasamy, and Kalidass Subramaniam

1 Introduction Water happens to be an indispensable sustenance for life [1]. Pollution of water happens predominantly by industrial wastes, composed of various kinds of dyes and other pollutants [2]. Dyes have been extensively used in a number of industries viz., textile, leather tanning, cosmetics, and pigment [3–5]. Intrusion of these effluents into the water bodies poses a significant threat to animal, plant, and human life because of their sustainability and their recalcitrant nature. Persisting dyes and other related substances in water can lead to a number of discomforts to the fauna and flora. These compounds are responsible for color changes in fresh water. These pollutant molecules prevent sunlight reach the aquatic plant and animal species and quenches the photo-synthetically active radiation (PSA) in the ecosystem [6]. They tend to increase chemical and biological oxygen demands. Dye substances and their metabolites can be toxic and are capable of having mutagenic, carcinogenic, and teratogenic properties [7]. Hence, there occurs a need to treat the dye effluents and render them nontoxic before they enter into the fresh water. S. K. Krishnan · K. Subbiah (B) Department of Biotechnology, Karunya Institute of Technology and Sciences, Coimbatore 641114, Tamil Nadu, India e-mail: [email protected] S. Kandasamy Department of Chemical Engineering, Kongu Engineering College, Erode 638060, Tamil Nadu, India K. Subramaniam (B) Department of Animal Science, Manonmaniam Sundaranar University, Tirunelveli 627012, Tamil Nadu, India e-mail: [email protected] Institute of Food Security and Sustainable Agriculture (IFSSA), Universiti of Malaysia Kelantan, Jeli, Kelantan, Malaysia © Springer Nature Singapore Pte Ltd. 2020 V. Sivasubramanian et al. (eds.), Sustainable Development in Energy and Environment, Springer Proceedings in Energy, https://doi.org/10.1007/978-981-15-4638-9_17

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An array of physical and chemical methods was employed for water treatment in the past. These methods suffered a major disadvantage with respect to their high operational costs, lower degradation efficiency, and production of sludge in larger quantities. In the recent times, biological treatment is extensively being used to remove the biological oxygen demand and chemical oxygen demand of polluted waters. Conventional aerobic, anaerobic, and combined processes are employed for color removal. That being said, the lack of complete color and toxicity removal is a hindrance to this approach [8]. More recently, works carried out with nanosized metal particles show that they play a significant role in dye effluent treatment [9–11]. Nanosized particles are preferred over bulk-sized materials because of their enhanced degradation efficiency confined to its quantum confinement effect [12]. The size and shape of the nanoparticles play a crucial role in the decolourization process. Particle aggregation tends to lower the catalytic activity of metal nanoparticles. Therefore, particles are coated with low molecular weight polymeric compounds to prevent the aggregation irreversibly [13].

2 Iron Nanoparticles Iron has long been employed in permeable barriers to ameliorate contaminated surface sites which was eventually stopped because of the corrosive nature of the metal [14]. Subsequently, microsized and nanosized iron particles were used for water remediation [15]. Zero-valent iron particles are highly preferred because of their surface volume and significant reaction ability [16]. The zero-valent iron particles donate electrons and the reacting contaminants accept electrons [17]. The nZVI particles reduce to ferrous and ferricions and the released protons react with textile dye particle to bring about azo-bond reduction [18]. The auxochrome bond (–N=N) also needs to be cleaved to decolorize the dyes. The organic intermediates formed are further mineralized into carbon dioxide, water, and other inorganic ions [19] (Fig. 1). Chen [21] put forth the initial application of iron nanoparticles for dye remediation. A number of physiological factors are responsible for the degradation efficiency. These factors include the process pH, particle size, particle load, concentration, and volume of the pollutant. Treatments have been carried out either using bare or supported iron nanoparticles and/or in combination with other degradation techniques. A number of carriers are used as support agents. An ideal support is the one which does not show any cross reactivity with the nanoparticles. The carriers used include zinc, nickel, nickel-montmorillonite, kaolin, bentonite, biochar, cellulose, and clinoptilolite. Adding a secondary metal like nickel or zinc enhances the reactivity and stability toward dye degradation [22, 23].

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Fig. 1 ZVI in dye degradation [20]

In recent times, green technology for nanoparticle preparation is highly preferred. ‘Green synthesis’ prevents the production of toxic metabolites through an environment friendly approach. Abbassi et al. [24] and Luo et al. [25] have carried out green synthesis of iron nanoparticles using the leaf extracts of Camellia sinensis and grapes and assessed their role in textile dye removal.

3 Titanium Nanoparticles Titanium dioxide-based nanoparticles have also been studied as one of the most promising photocatalysts as a means of environmental remediation [26, 27]. The advantages of using titanium particles are they are nontoxic, cost effective, widely available, have longer stability, and are highly stable. TiO2 particles show a well-pronounced activity when applied as nanomaterials rather than in the bulk form [28]. The activity of titania particles is further enhanced by doping them with other materials viz., transition metal cations, noble metals, anions, and metalloids. Co-doping of titanium nanoparticles helps in the charge segregation of the metals (Fig. 2).

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Fig. 2 Mechanism of photocatalytic dye degradation [29]

4 Zinc Oxide Nanoparticles Zinc oxide (ZnO) is one of the other metal nanoparticles employed as a photocatalytic agent for pollutant remediation. Being an n-type semiconductor, ZnO possesses a higher binding energy which accounts for significant stability and compatibility. High electron mobility and high quantum yield make them an effective tool for water remediation [30]. The major setbacks associated with zinc oxide particles are charge recombination and corrosion. To avoid this, they are altered to be stable under the visible light range. Zinc oxide particles in suspension are used for pollutant remediation degradation of organic pollutants. Like other nanoparticles studied, ZnO nanoparticles also show maximum potential under immobilized conditions. This facilitates easy recovery of the nanoparticles after the process is complete, which will aid in the process being cost effective.

5 Magnesium Oxide Nanoparticles Magnesium oxide (MgO), a semiconductor by nature, plays a significant role in contaminants remediation. Magnesium oxide particles are employed owing to their nontoxicity, stable nature, and lesser costs. Magnesium oxide particles stay noncompatible with other conductors, because it requires high energy utilization. Hence, magnesium oxide-based photocatalytic processes require additional technology for textile dye remediation [31].

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6 Bismuth Oxide Nanoparticles The e-type BiFeO3 (BFO) particles have gained significant attention due to their high chemical stability, narrowing band-gap energy, and exhibiting simultaneous co-existence of ferroelectric and magnetic order parameters. Soltani and Entezari [32] degraded reactive black 5 by ultrasound-synthesized bismuth-iron particles irradiated under light. They demonstrated that the bismuthiron particles showed greater catalytic activity under sunlight.

7 Cobalt Nanoparticles Application of cobalt nanoparticles in pollutant degradation has been documented in a fewer number of reports. The application of cobalt nanoparticles is limited owing to their elaborated synthesis protocol and lack of stability. Mondal et al. [33] demonstrated that cobalt nanoparticles facilitated dye degradation when used along with an electron donor (sodium borohydride). They observed that the borohydride produced a remarkable enhancement in the reaction rate.

8 Other Nanoparticles Apart from the above-mentioned nanomaterials, a considerable number of studies have been made employing the use of oxides of copper (CuO), nickel (NiO), tin (SnO2 ), manganese (Mn3 O4 ), and cerium (CeO2 ) for dye remediation with varied results. Alternatively, eco-friendly nanoparticles, i.e., nanoparticles preparation in the presence of plant materials are also gaining momentum in the field of dye remediation [34, 35].

9 Conclusion Industrial discharge into waters is causing an alarming threat to the environment and human health. A number of standard techniques have been put to use for the past two decades, each having a pronounced drawback. Hence, alternative technologies are being looked upon, one such technology is the use of metal nanoparticles for dye remediation. This technology has been emerging since last decade. A number of reports have demonstrated successful degradation of many stable and recalcitrant industrial dyes.

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The future of nanotechnology aims at the following: • Development of industrial-scale models for water treatment employing greensynthesized and native nanomaterials. • Optimization of combination treatments methods for a complete degradation of any pollutant. • Assessment of the replenishing ability of nanoparticles after repeated treatment cycles.

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Continuous Sorption of Chlorpyrifos from Aqueous Solution Using Endoskeleton Powder of Sepia officinalis Karthikumar Sankar, Shyam Kumar Rajaram, I. Ganesh Moorthy, K. Naresh, S. Vaitheeswaran, R. K. Akash Kumar, G. R. Murary Viyas, and P. N. Karl J. Samuel

1 Introduction Pesticides play a vital role in agriculture where the global rise in food demand is tackled. According to the record of India central statistics, 15–25% of the potential crop production is lost due to various pests and diseases. Use of pesticide can increase crop productivity by 25–50%. Hence, pesticides are very essential to ensure food security [1]. Although, pesticides cause various deleterious effects to the animals and humans; total restriction to usage of pesticides momentarily is impractical. In global pesticide production, India is ranked fourth place after the USA, Japan and China [1]. Chlorpyrifos ((O,O-Diethyl O-3,5,6-trichloropyridin-2-yl phosphorothioate) is one of the organophosphate pesticides, which is commonly used for variety of crops. Chlorpyrifos controls wide range of pests including mosquitos, cockroach, cutworms, termites, flies, lice, beetles and corn rootworms [2]. In humans, chlorpyrifos poisoning involves competitive inhibition of carboxylic ester hydrolases mainly acetylcholinesterase (Ache) which results neuronal disorders. It also causes oxidative stress and endocrine disruption [3]. The lipid solubility and half-life of the chlorpyrifos in the human body is increased by chlorine moiety in the structure [3]. The active site of the neuropathy target esterase is also blocked by chlorpyrifos which results in loss of function of myelin and axon fibers of peripheral and central nerves system [4]. The human health risk of chlorpyrifos calls for creative and effective novel solutions to tackle the problem. Bio-sorption using nanoparticles [5–7], electrochemically assisted remediation and advanced oxidation processes [8, 9] are considered as excellent process of pesticide elimination from water bodies [10]. However, the K. Sankar (B) · S. K. Rajaram · I. Ganesh Moorthy · K. Naresh · S. Vaitheeswaran · R. K. Akash Kumar · G. R. Murary Viyas · P. N. K. J. Samuel Department of Biotechnology, Kamaraj College of Engineering and Technology, S.P.G.C.Nagar, Near Virudhunagar, Madurai Dist., Tamil Nadu, India e-mail: [email protected] © Springer Nature Singapore Pte Ltd. 2020 V. Sivasubramanian et al. (eds.), Sustainable Development in Energy and Environment, Springer Proceedings in Energy, https://doi.org/10.1007/978-981-15-4638-9_18

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technical complexity and high cost involved in electrocoagulation and advanced oxidation process have limited its applications. Among various methods, adsorption technique is very common in removing pollutants from water due to its simplicity and availability of cost-effective natural adsorbent materials. Further, bio-sorption processes come out as a better alternative since it is an economical technique and attributed with advantages such as scope of product recovery, ability to treat large amounts of pollutants and no active sludge production. Eco-friendly, low-cost adsorbent materials such as silkworm feces [11], eucalyptus bark, corn cob, bamboo chips, rice husk, rice straw [12, 13] and lingo cellulosic sorbents [14] are used for various applications. Endoskeleton is an inner shell mass of cuttle fish Sepia officinalis. Endoskeleton has excellent adsorptive properties arise from its high surface area and porous nature along with the presence of various functional groups [15, 16]. Several papers reported the applications of endoskeleton powder as filler in natural rubber production [17], solid matrix for enzyme immobilization [16], material for preparing bone grafts [18], removal of Pb (II) (Pathompong [19], phenol derivatives [20] and chromium [21]. Report on the removal of pollutants from aqueous environment using endoskeleton powder is very limited. Hence, the present work aims to explore the usage of endoskeleton powder for the adsorption of chlorpyrifos from water in continuous column. The effect of influent chlorpyrifos concentration, flow rate and column bed height on chlorpyrifos adsorption was investigated. Various dynamic adsorption isotherm models such as Yoon–Nelson, Thomas and Adams–Bohart models were used to predict the column performance.

2 Materials and Methods 2.1 Chemicals All chemicals used in this study were analytical grade. Chlorpyrifos 50% EC was procured from local pesticide selling shop, Madurai. Desired concentration of chlorpyrifos was prepared by diluting required volume in distilled water. pH of the chlorpyrifos solution used for various experiments was 7.3 ± 0.2.

2.2 Adsorbent Preparation Cuttlefish bone (cuttlebone) was collected from Bay of Bengal coastline, Tuticorin, Tamilnadu. The cuttlebone was thoroughly washed with distilled water several times to remove any sand, debris or dirt particles and dried at 343 K for 1 h. Inner mass of endoskeleton was scrubbed out from the shell, then ground and sieved through a set of sieve mesh (600–25 μM).

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2.3 Adsorbent Characterization The physical-chemical properties of the prepared cuttlebone powder were investigated. The scanning electron microscope, EVO 18, Carl Zeiss, Germany was used to examine surface morphological features of cuttlebone. Nitrogen adsorption study was performed in automated gas sorption analyzer, ASiQwin™, Quantachrome® Instruments, Florida, to determine the surface area and pore size distribution. The system inbuilt Brunauer Emmett Teller (BET) isotherm tools in the software were used to calculate the surface area and pore volume. Fluorescence emission properties of the chlorpyrifos were determined in fluorescence spectrophotometer FL-2700, Shimatzu, Japan.

2.4 Determination of Chlorpyrifos Concentration Fluorescence spectrophotometric method was used to determine the chlorpyrifos concentration in the influent and effluent solution. Emission spectra of the chlorpyrifos concentration in the range of 2–50 ppm (Fig. 1a) were obtained from 290 to 700 nm with the bandwidth of 5 nm. Excitation wavelength was kept at 290 nm (Fig. 1). A calibration curve to the distinct emission peak at 585 nm was constructed and used to measure the chlorpyrifos concentration in influent and effluent solution.

Fig. 1 Scanning electron micrograph of cuttlebone powder

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2.5 Batch Adsorption In order to understand the interaction between chlorpyrifos and cuttlebone powder, a batch adsorption study was performed in 250 mL glass vial. A measured quantity of cuttlebone powder was taken in glass beaker containing different concentration of chlorpyrifos solution. The glass bottles were kept under agitation (100 rpm) at 310 K for 30 min. Chlorpyrifos concentration in the bulk solution was measured in fluorescence spectrophotometer before and after adsorption process. Common adsorption isotherm models such as Langmuir, Freundlich and Dubinin-Radushkevich isotherms were used to fit the experimental data.

2.6 Continuous Column Adsorption A glass column with 30 cm height and 2 cm inner diameter was used for continuous adsorption studies. Endoskeleton powder with average particle size of 90 μm was packed as an adsorbent. Known concentration of chlorpyrifos solution was pumped to the packed bed from top of the column through a peristaltic pump. Samples were collected at regular interval, and the concentration of chlorpyrifos in effluent was analyzed by monitoring the emission profile of chlorpyrifos (λex 270 nm, λem 585 nm). The effect of influent chlorpyrifos concentration (0.2, 0.4, 0.6 mg L−1 ), flow rate (2.5, 5.0, 7.5 mL min−1 ) and column bed height (5 cm (50 g), 10 cm (100 g), 15 cm (150 g)) on breakthrough curve was studied. All the experiments were carried out at 310 K.

2.7 Mathematical Description The adsorption of chlorpyrifos in continuous column is evaluated from breakthrough curve. The breakthrough time and shape of the curve determine the operation and dynamic adsorption of chlorpyrifos [22]. The breakthrough curve shows the loading behavior of chlorpyrifos to be removed from solutions in a fixed bed and is expressed in terms of adsorbed chlorpyrifos concentration (C ad = inlet chlorpyrifos concentration (C 0 ). The chlorpyrifos concentration (C) or normalized concentration defined as the ratio of effluent chlorpyrifos concentration to influent chlorpyrifos concentration (C/C 0 ). Breakthrough curves were constructed by plotting the normalized chlorpyrifos concentration (mg L−1 ) (C/C 0 ) against service time (min). Time at which the concentration of chlorpyrifos is detected in the effluent is called as breakthrough time (t b ), and the time at which the concentration of chlorpyrifos in the effluent is closer to the influent concentration is called exhaustion time (t e ). The performance of endoskeleton powder packed column was determined over relative concentration (C/C 0 ) from 0.01 to 0.95, 1% and 95% of breakthrough, respectively.

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Processed volume of the chlorpyrifos solution was determined from V = Q × ttotal

(1)

where Q and t total are volumetric flow rate (mL min−1 ) and total flow time (min), respectively. Total amount of chlorpyrifos delivered to the packed column was estimated from Chlorpyrifostotal =

C0 Qttotal 1000

(2)

Total chlorpyrifos adsorbed in CBP was determined from the following equation qtotal (mg) =

Q t=ttotal ∫ Cad dt 1000 t=0

(3)

C ad adsorbed concentration of chlorpyrifos. Chlorpyrifos adsorption percentage (%) was determined from the ratio of chlorpyrifos adsorbed on the column and total amount of chlorpyrifos sent to the column Adsorption(%) =

qtotal × 100 Chlorpyrifostotal

(4)

The equilibrium adsorption of chlorpyrifos was determined from qe =

qtotal X

(5)

where X is the unit mass of CBP packed in the column The residual chlorpyrifos concentration in the effluent at equilibrium in the column (C eq ; mg L−1 ) is determined by the following equation Ceq =

Chlorpyrifostotal − qtotal × 1000 Veff

(6)

2.8 Adsorption Isotherms and Kinetic Models The following common adsorption isotherm models were used to determine the adsorption behavior of chlorpyrifos on the surface of cuttlebone powder Langmuir isotherm:

1 1 1 1 = × + qe qmax K L C qmax

(7)

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Dimensionless separation factor: RL = Freundlich isotherm: ln qe =

1 1 + K L C0

1 lnC × ln K F n

Dubinin-Radushkevich isotherm: lnqe = lnqs − K ad ε2  K1 Pseudo-first-order kinetic equation: log(qe − qt ) = logqe − ×t 2.303   t 1 1 + Pseudo-second-order kinetic equation: =  ×t qt qe K 2 × qe2

(8) (9) (10)



(11) (12)

where qe is the adsorption capacity of the cuttlebone powder at equilibrium condition (mg g−1 of adsorbent), C is chlorpyrifos concentration in bulk (mg mL−1 ), qmax is maximum loading capacity of cuttlebone powder (mg g−1 of adsorbent), K L (ml mg−1 of chlorpyrifos) and K F (ml mg−1 of cuttlebone powder) are the adsorption coefficient constant of Langmuir and Freundlich adsorption isotherm models, respectively. n is the Freundlich dimensionless exponent. K 1 is the pseudo-first-order rate constant (min−1 ), and K 2 is the pseudo-second-order adsorption rate constant (g mg−1 min−1 ).

2.9 Thomas Model Thomas model is frequently used to predict the breakthrough curve and absorptive capacity of an adsorbent in fixed bed adsorption column. This model assumes the adsorption process is second-order reversible kinetics and obey Langmuir isotherm. Further, this model is widely considered where external and internal diffusion resistance are negligible [23].  ln

 kTH qe m C0 −1 = − kTH C0 t C Q

(13)

where kTH is Thomas rate constant, m is the mass of adsorbent (endoskeleton powder) packed inthe column, Q is feed flow rate. The kTH and qe were determined from the  plot of ln CC0 − 1 versus t (time).

2.10 Adams–Bohart Model Initially, Adams–Bohart model is developed for the adsorption of chlorine gas on charcoal. However, it is widely used to describe the relationship between the

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normalized concentration and time in various continuous adsorption system. 

C ln C0

 = kAB C0 t − kAB qAB

q=

H v

qAB qAB BVs = m ρ

(14) (15)

2.11 Yoon–Nelson Model Yoon–Nelson model is relatively simple and addresses the breakthrough curve of single component system. This model assumes that the rate of decrease in probability of adsorption is proportional to the adsorbate adsorption and breakthrough. Yoon– Nelson model is expressed by the following equation 

C ln C0 − C

 = kYN (t − τ )0

(16)

where, kYN and τ are the rate constant and time required to achieve 50% breakthrough, respectively.

3 Results and Discussion 3.1 Physiochemical Characterization of CBP The scanning electron micrograph of cuttlebone powder showed an irregular flake with rough surface (Fig. 1). It seems that the unique characteristics of the lamellar structures in cuttlebone are fragmented and created more surface area for adsorbate binding. It also shows that a uniformed grit on the surface. The SEM morphological features and elemental analysis of the cuttlebone powder (Table 1) are in accordance with the reports by Cadman et al. [24], Ivankovic et al. [25], Periasamy et al. [26]. Cuttlebone powder showed very high thermal stability. In our earlier studies on thermogravimetric, cuttlebone powder was found to retain half of its properties at 700 °C [27]. All the surface bound proteins and debris were denatured at around 300 °C, the cuttlebone powder retained its maximum thermal stability up to 580 °C, and further increase in temperatures caused prompt denaturation.

232 Table 1 Physical properties and elemental composition of cuttlebone powder

K. Sankar Property

Value

Average particle size

89.95 μm

Pore volume

0.005 cc g−1

Pore diameter

Dv (d) 3.634 nm

Surface area

1.631 m2 g−1

Ca

42.7 (%)

C

12.0 (%)

O

45.3 (%)

3.2 Fluorescence Spectroscopic Analysis of Chlorpyrifos A series of diluted chlorpyrifos (2 ppm to 50 ppm) in water samples were tested for emission peak profile in portable fluorescence spectrophotometer at excitation wavelength of 290 nm. Figure 2 depicts the emission spectra of chlorpyrifos. A distinct emission peak at 585 nm increased with increasing concentration of chlorpyrifos. Fluorescence spectroscopic analysis has been considered as very sensitive techniques to measure the differences in the fluorescence emission intensity. Regression plot was constructed by plotting the fluorescence intensity values against the concentration of chlorpyrifos, and coefficient of determination was found to be 0.964.

Fig. 2 Fluorescence emission spectra and calibration curve of chlorpyrifos in water (λex 290 nm)

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3.3 Batch Adsorption Studies The distribution of adsorbate in liquid and solid phase can be elucidated by fitting the experimental data with several adsorption isotherms. Linearized Langmuir, Freundlich and Dubinin-Radushkevich adsorption isotherms of chlorpyrifos obtained in batch studies at 310 K are shown in Fig. 3a–c, respectively. Various adsorption kinetic

Fig. 3 Various adsorption isotherms and kinetic models of chlorpyrifos, Langmuir (a), Freundlich (b), Dubinin-Radushkevich (c), Intra-particle diffusion (d), Pseudo-first order (e) and Pseudo-second order (f)

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Table 2 Comparison of various isotherm constants for the removal of chlorpyrifos on endoskeleton powder Langmuir qm (mg g−1 ) K L (L R2

mg−1 )

Freundlich 131.5

n

Dubinin-Radushkevich 1.009

qm (mg g−1 )

2.72

mol−1 )

2.23

0.002

KF

3.974

E (kJ

0.999

R2

0.999

R2

0.955

parameters are depicted in Table 2. According to the linear regression coefficients of the adsorption data in the studied concentration, both Langmuir and Freundlich isotherms fitted very well than that of Dubinin-Radushkevich isotherm. Al-Qodah et al. [28] reported similar trend in adsorption of pesticides Deltamethrin and lambdacyhalothrin on oil shale ash. According to Langmuir isotherm model, the chlorpyrifos binds on the surface of the cuttlebone powder as saturated monolayer, and all the surface of cuttlebone powder has same activation energy. Further, there is no interaction among bound chlorpyrifos molecules. Overall, the Langmuir isotherm explains the homogeneous nature of binding. Langmuir constant (K L ) and maximum adsorbed chlorpyrifos on endoskeleton powder (qm ) were determined from 1/C e versus 1/qe plot as 0.002 L mg−1 and 131.5 mg g−1 , respectively. The separation factor (RL ) determined for the studied chlorpyrifos concentrations was found to be in the range of 0.92–0.98. Generally, the RL parameter indicates whether the adsorption process is unfavorable (RL > 1), linear (RL = 1), favorable (0 < RL < 1) or irreversible (RL = 0) [29]. Hence, the adsorption of chlorpyrifos on endoskeleton powder was favorable. The parameters K F and n, the Freundlich constant and intensity of the adsorption were determined from lnC e versus lnqe plot. Freundlich isotherm assumes that the adsorbate binds on adsorbent with heterogeneous nature, and the binding is a multilayer formation and a favorable adsorption process tends to have an n value between 1 and 10. Larger value of n indicates a strong interaction between adsorbent and adsorbate, whereas n closer to 1 implies the adsorption is a linear with identical adsorption energy at all binding sites [30]. In the present study, K F and n were found to be 3.974 and 1.00, and hence, chlorpyrifos adsorb linearly on endoskeleton powder at studied concentration. The assumption of Dubinin-Radushkevich adsorption isotherm model is not based on the homogenous surface or constant adsorption potential, whereas it considers the porosity and adsorption energy of an adsorbent. The adsorption energy (E, kJ mol−1 ) provides insight to distinguish whether adsorption process is physisorption or chemisorption. When the value of E is between 1 and 8 kJ mol−1 indicates physisorption, between 8 and 16 kJ mol−1 indicates the adsorption process is by ion-exchange and E value between 20 and 40 kJ mol−1 chemisorption [11, 31]. In the present study, the linear regression coefficient of 0.955 revealed that the experimental data fitted well with Dubinin-Radushkevich model. Further, the determined E value of 2.23 kJ mol−1 suggesting the binding of chlorpyrifos on endoskeleton powder was by physisorption (Table 2).

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In order to understand the mechanism of chlorpyrifos adsorption from aqueous solution to surface of endoskeleton powder, intra-particle diffusion, pseudo-first and second-order rate models were analyzed, and the plots are shown in Fig. 3d, e and f, respectively. The kinetic model of chlorpyrifos adsorption on endoskeleton powder fitted very well to pseudo-second order with the correlation coefficient of 0.991, whereas pseudo-first order model showed R2 of 0.864. The similar kinetic results were reported by Mohammad and Ahmed [11] in removal of oxamyl pesticide from aqueous solution using silkworm feces activated carbon. In practice, diffusion mechanism of any adsorbate into a porous adsorbent is well explained by intra-particle diffusion model. The kinetic constant (C) of intra-particle diffusion model provides insight on the thickness of the boundary layer, i.e., higher the C value, greater the boundary effect. Further, the intra-particle diffusion is considered as rate controlling step, where the plot of qt versus t 1/2 is linear and pass through the origin [11]. In the present study, the regression plot was not linear suggesting that intra-particle diffusion is not a rate limiting step in adsorption of chlorpyrifos on endoskeleton powder (Fig. 3d).

3.4 Fixed Bed Column Adsorption Studies Fixed bed column adsorption experiments were carried out for removal of chlorpyrifos using endoskeleton powder as adsorbent. The effect of change in influent chlorpyrifos concentration, column bed height and feed flow rate on breakthrough and exhaustion time of chlorpyrifos was investigated. As shown in Table 3, maximum chlorpyrifos removal was recorded where inlet concentration, bed height and feed flow rate at 0.4 mg L−1 , 10 cm and 1 mL min−1 , respectively.

3.5 Effect of Influent Chlorpyrifos Concentration The effect of chlorpyrifos concentration in the influent solution on the column performance was studied by varying the chlorpyrifos concentration (0.2, 0.4 and 0.6 mg L−1 ) for while the adsorbent bed height and feed flow rate were constantly maintained at 10 cm and 1.0 mL min−1 . As illustrated in Fig. 4, at higher chlorpyrifos concentration in the influent solution, the break point was appeared quickly. Faster exhaustion of the column was observed at higher initial concentration of adsorbate. The breakthrough time and exhaustion time were increased from 28 to 56 min and from 96 to 204 min, respectively, as the initial chlorpyrifos concentration decreased from 0.6 mg L−1 to 0.2 mg L−1 . Breakthrough time of 36 min and exhaustion time of 168 min were recorded at 0.4 mg L−1 of initial concentration. As the initial concentration of adsorbate increases, the surface of adsorbent became more quickly occupied indicating shorter break point, whereas low initial adsorbate concentration extends

5

10

10

0.4

0.4

10

0.6

15

10

0.4

0.4

10

0.2

0.4

Bed height (cm)

C 0 (mg L−1 )

100.8

100.8

151.2

50.4

100.8

100.8

100.8

CBP mass (g)

0.5

2

1

1

1

1

1

Feed flow rate (mL min−1 )

72

16

44

16

28

36

56

t b (min)}

248

100

204

112

92

144

192

t e (min)

Table 3 Breakthrough parameters for chlorpyrifos adsorption on endoskeleton powder

225

350

240

200

200

300

400

V ef (mL)

0.09

0.14

0.096

0.08

0.12

0.12

0.08

CPtotal (mg)

0.075

0.124

0.091

0.073

0.113

0.118

0.070

qtotal (mg)

83.8

88.6

94.5

91.3

93.9

98.3

87.6

Removal (%)

0.749

1.230

0.600

1.448

1.118

1.156

0.695

qe (mg g−1 ) × 10−3

236 K. Sankar

Continuous Sorption of Chlorpyrifos from Aqueous …

237

Fig. 4 Effect of influent chlorpyrifos concentration on breakthrough curve

the breakthrough point and exhaustion time due to decreased diffusion coefficient or mass transfer coefficient.

3.6 Effect of Column Bed Height The effect of adsorbent (endoskeleton powder) dosage as different column bed height (5, 10. 15 cm) on the dynamic uptake of adsorbate (chlorpyrifos) was systematically studied by varying the column bed height at a constant feed flow (1.0 mL min−1 ) and fixed initial chlorpyrifos concentration (0.4 mg L−1 ). Increase in the bed height identically increased the amount of adsorbent. The longest bed height column was 15 cm, which is equivalent to 150 g of endoskeleton powder. As shown in Fig. 5, increase in the bed height accomplished less sharp breakthrough curve, representing greater extent of exhaustion time. Increased bed height increases the mass transfer zone results longer time to reach break point. The break point for columns with the height of 5, 10 and 15 cm was 10, 36 and 44 min, respectively. Similarly, decrease in the bed height would create a shorter distance for mass transfer zone, which results quick release of chlorpyrifos from the column. In the present study, shorter exhaustion time (112 min) was seen for the bed height of 5 cm. The column with smaller bed heights is saturated with adsorbent in a shorter period of time results

238

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Fig. 5 Effect of column bed height on breakthrough curve

shorter exhaustion time. The exhaustion time was twofold extended when the column was packed up to the height of 15 cm. The column with 10 cm bed height showed 95% exhaustion at 172 min of service period.

3.7 Effect of Feed Flow Rate The breakthrough curve in 10 cm bed height at various influent flow rate (0.5, 1.0 and 2.0 mL min−1 ) and constant influent chlorpyrifos concentration (0.4 mg L−1 ) was studied. As shown in Fig. 6, the breakthrough point occurred faster with a higher flow rate of chlorpyrifos into the column. Similarly, the exhaustion time also reached faster at higher flow rate. At low feed flow rate, chlorpyrifos had more time at mass transfer zone to adsorb onto the adsorbent which resulted longer time for breakthrough point and exhaustion time. At higher feed flow rate (2.0 mL min−1 ), both the breakthrough time and exhaustion time appeared quickly, 24 min and 104 min, respectively. Increase in the feed flow rate resulted the breakthrough curve very steeper. The breakthrough time and exhaustion time for feed flow rate (1.0 mL min−1 ) were observed at 36 min and 180 min, respectively. At low feed flow rate (0.5 mL min−1 ), both the breakthrough time and exhaustion time were extended to 72 min and 280 min, respectively, which can be explained by considering the longer contact time between

Continuous Sorption of Chlorpyrifos from Aqueous …

239

Fig. 6 Effect of chlorpyrifos feed flow rate on breakthrough curve

chlorpyrifos and endoskeleton powder bed and lack of diffusion limitation from liquid phase to solid phase.

3.8 Breakthrough Curve Modeling 3.8.1

Adams–Bohart Model

The experimental adsorption data obtained for 200 min, i.e., initial part of the breakthrough curve were fitted with Adams–Bohart adsorption model to describe the breakthrough curve. The characteristic parameters such as maximum adsorption capacity (N 0 ) and kinetic constant (K AB ) are listed in Table 3, and the breakthrough curve at different initial chlorpyrifos concentration, column bed height and feed flow rate is shown in Fig. 7a, b and c, respectively. The R2 values were in the range of 0.697–0.972. The average regression value was 0.887. R2 value increased with increasing column bed height. Conversely, R2 value was reduced when the flow rate and initial chlorpyrifos were low and higher level. According to regression value, Adams–Bohart model is not fitting to the data point well. There was a decrease in the kinetic constant (K AB ) with increasing flow rate and initial chlorpyrifos concentration in the inlet solution, it suggests that the adsorption rate is not influenced by both

240 Fig. 7 Adam–Bohart model fitting of the experimental data for chlorpyrifos adsorption on endoskeleton powder using different a initial feed concentration, b column bed height, c feed flow rate

K. Sankar

Continuous Sorption of Chlorpyrifos from Aqueous …

241

flow rate and initial concentration. Therefore, external mass transfer is not inclined in adsorption of chlorpyrifos on endoskeleton powder at studied concentration and flow rate. Similar trend was observed by Adhikari et al. [32], López-Cervantes et al. [33].

3.8.2

Yoon–Nelson Model

A simple dynamic adsorption model described by Yoon–Nelson was applied to investigate the breakthrough behavior of chlorpyrifos on endoskeleton powder. The parameters, KYN (rate constant) and τ (time required for 50% chlorpyrifos breakthrough) at various inlet adsorbate concentration, column bed height and feed flow rate were determined from linear plot of ln[C/C 0 − C] versus t. As shown in Fig. 8, the experimental data fitted very well with the Yoon–Nelson model for all the experimental conditions studied. The average R2 value of all the experimental setup was found to be 0.981. Therefore, the experimental data obtained from adsorption of chlorpyrifos on endoskeleton powder fitted very well with Yoon–Nelson adsorption model. The rate constant (K YN ) was higher and comparable when the feed flow rate was 0.2 and 0.6 mL min−1 . Conversely, the rate constant (K YN ) was lower and comparable when column bed height was 5 and 15 cm. However, there was an increasing trend in the value of rate constant (K YN ) was observed while increasing feed flow rate (Table 4). Similar trend was observed by Aksu and Gönen [34] in the removal of phenol using immobilized activated sludge.

3.8.3

Thomas Model

Thomas model was applied to the experimental data with respect to different column bed height and feed flow rate. The average R2 value of 0.972 from all the experimental setup indicated that the experimental values were in agreement with predicted values. Hence, the experimental data obtained from adsorption of chlorpyrifos on endoskeleton powder fitted very well with Thomas model (Fig. 9). Thomas model parameter K TH (rate constant) and qe were determined. As shown in Table 5, while increasing the bed height, the values of qe increased and K TH decreased. Increase in the qe can be explained as increasing bed height provided more surface area for adsorbate to bind. However, higher bed height reduced the reaction rate by extending the contact time between adsorbate and adsorbent. Hence, the value of K TH decreased. Conversely, there was a drop in qe value and raise in K TH value at higher flow rate. This can be attributed as the efficiency of chlorpyrifos adsorption is decreased due to short contact time at higher flow rate. Similarly, higher K TH is attributed by faster mass transfer at higher flow rate. The results are in agreement with the works reported previously on various adsorption systems [32, 33].

242 Fig. 8 Yoon–Nelson model fitting of the experimental data for chlorpyrifos adsorption on endoskeleton powder using different a initial feed concentration, b column bed height, c feed flow rate

K. Sankar

H (cm)

10

10

10

5

15

10

10

C 0 (mg L−1 )

0.2

0.4

0.6

0.4

0.4

0.4

0.4

0.5

2.0

1.0

1.0

1.0

1.0

1.0

Q (mL min−1 )

0.118

0.061

0.071

0.049

0.038

0.051

0.254

K AB

3.761

7.977

5.124

8.114

5.419

5.280

3.391

qAB

Adams–Bohart Model

1.171

2.485

1.596

2.527

1.688

1.644

1.056

q

0.886

0.913

0.957

0.856

0.697

0.972

0.931

R2

0.036

0.058

0.046

0.049

0.063

0.039

0.066

K YN

182.52

60.19

150.26

54.47

49.45

87.50

149.81

τ

Yoon–Nelson model

0.362

0.478

0.398

0.432

0.294

0.347

0.297

q

0.988

0.972

0.985

0.976

0.976

0.979

0.978

R2

Table 4 Correlation parameters of Adams–Bohart and Yoon–Nelson models for adsorption of chlorpyrifos on endoskeleton powder at varying column bed height, influent chlorpyrifos concentration and feed flow rate

Continuous Sorption of Chlorpyrifos from Aqueous … 243

244

K. Sankar

Fig. 9 Thomas model fitting of the experimental data for chlorpyrifos adsorption on endoskeleton powder using different a column bed height, b feed flow rate

Table 5 Correlation parameters of Thomas dynamic adsorption models for adsorption of chlorpyrifos on endoskeleton powder at varying column bed height and feed flow rate H (cm)

Q (mL/min)

K TH

qe

R2

5

1

0.163

0.334

0.987

10

1

0.111

0.351

0.978

10

0.5

0.138

0.387

0.981

10

2

0.143

0.319

0.968

15

1

0.105

0.413

0.952

4 Conclusions The present study focused on the removal of chlorpyrifos pesticide from aqueous solution using low cost, eco-friendly endoskeleton powder. The adsorption process has been studied in both batch and continuous column with the variations in the parameters of adsorbent dose, initial chlorpyrifos concentration and feed flow rate. The adsorption capacity of the column is highly augmented by increase in column bed height and decrease in feed flow rate. The experimental data were analyzed using various adsorption isotherms and kinetic models. The adsorption system obeys the pseudo-second-order kinetic model, and Yoon–Nelson model provides the best correlation of experimental data. The results indicate that the endoskeleton powder could be a promising eco-friendly, low cost adsorbent for the removal of chlorpyrifos from contaminated water. Acknowledgements The authors gratefully acknowledge the management Kamaraj College of Engineering and Technology, S.P.G.C. Nagar, K. Vellakular-625701, Near Virudhunagar-626001, for the facilities provided to carry out this work.

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