Recent Technologies for Waste to Clean Energy and its Utilization 9811937834, 9789811937835

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Clean Energy Production Technologies Series Editors: Neha Srivastava · P. K. Mishra

Dan Bahadur Pal   Editor

Recent Technologies for Waste to Clean Energy and its Utilization

Clean Energy Production Technologies Series Editors Neha Srivastava, Department of Chemical Engineering and Technology, IIT (BHU) Varanasi, Varanasi, Uttar Pradesh, India P. K. Mishra, Department of Chemical Engineering and Technology, IIT (BHU) Varanasi, Varanasi, Uttar Pradesh, India

The consumption of fossil fuels has been continuously increasing around the globe and simultaneously becoming the primary cause of global warming as well as environmental pollution. Due to limited life span of fossil fuels and limited alternate energy options, energy crises is important concern faced by the world. Amidst these complex environmental and economic scenarios, renewable energy alternates such as biodiesel, hydrogen, wind, solar and bioenergy sources, which can produce energy with zero carbon residue are emerging as excellent clean energy source. For maximizing the efficiency and productivity of clean fuels via green & renewable methods, it’s crucial to understand the configuration, sustainability and technoeconomic feasibility of these promising energy alternates. The book series presents a comprehensive coverage combining the domains of exploring clean sources of energy and ensuring its production in an economical as well as ecologically feasible fashion. Series involves renowned experts and academicians as volume-editors and authors, from all the regions of the world. Series brings forth latest research, approaches and perspectives on clean energy production from both developed and developing parts of world under one umbrella. It is curated and developed by authoritative institutions and experts to serves global readership on this theme.

Dan Bahadur Pal Editor

Recent Technologies for Waste to Clean Energy and its Utilization

Editor Dan Bahadur Pal Department of Chemical Engineering Harcourt Butler Technical University Kanpur, Uttar Pradesh, India

ISSN 2662-6861 ISSN 2662-687X (electronic) Clean Energy Production Technologies ISBN 978-981-19-3783-5 ISBN 978-981-19-3784-2 (eBook) https://doi.org/10.1007/978-981-19-3784-2 © The Editor(s) (if applicable) and The Author(s), under exclusive license to Springer Nature Singapore Pte Ltd. 2023 This work is subject to copyright. All rights are solely and exclusively licensed by the Publisher, whether the whole or part of the material is concerned, specifically the rights of translation, reprinting, reuse of illustrations, recitation, broadcasting, reproduction on microfilms or in any other physical way, and transmission or information storage and retrieval, electronic adaptation, computer software, or by similar or dissimilar methodology now known or hereafter developed. The use of general descriptive names, registered names, trademarks, service marks, etc. in this publication does not imply, even in the absence of a specific statement, that such names are exempt from the relevant protective laws and regulations and therefore free for general use. The publisher, the authors, and the editors are safe to assume that the advice and information in this book are believed to be true and accurate at the date of publication. Neither the publisher nor the authors or the editors give a warranty, expressed or implied, with respect to the material contained herein or for any errors or omissions that may have been made. The publisher remains neutral with regard to jurisdictional claims in published maps and institutional affiliations. This Springer imprint is published by the registered company Springer Nature Singapore Pte Ltd. The registered company address is: 152 Beach Road, #21-01/04 Gateway East, Singapore 189721, Singapore

Preface

Clean energy technology refers to any process, product, or service that reduces negative environmental impacts through significant energy efficiency improvements, sustainable use of resources, or environmental protection activities. Clean energy technologies also endure economic growth by enhancing the supply of energy demand and tackling environmental challenges and their impacts due to the use of other conventional sources of energy. The conventional/nonconventional energy production techniques are efficient, but it has adverse effects on the environment and human health. As environmental concerns are not avoidable therefore the necessity of clean energy production comes into the picture. The clean energy can be produced by various wastes which are caused for the environmental pollution, energy, catalyst and wastewater treatment. This book covers all aspects of new and renewable clean energy production technologies. On the basis of recent research and development, step-by-step descriptions are provided for clean energy generation. The advanced technology for production of clean energy from water bodies, air bodies, and solid biomass waste has been discussed. Chapter 1 discusses biomass energy utilization and conversion technologies in various sectors. Chapter 2 discusses biohydrogen production using microbial electrolysis cell. Chapter 3 discusses microbial biomass for sustainable and renewable energy in waste land ecosystem and its assessment. Chapter 4 discusses microbial waste biomass as a resource of renewable energy. Chapter 5 discusses vanadium redox flow batteries for large-scale energy storage. Chapter 6 discusses biomass fast pyrolysis simulation, a thermodynamic equilibrium approach. Chapter 7 discusses the potential of waste cooking oil for emphasizing on biodiesel: put waste to green energy. Chapter 8 discusses low-cost biomass adsorbents for arsenic removal from wastewater. Chapter 9 discusses biodiesel production from algal biomass. Chapter 10 discusses the valorization of agricultural and food waste biomass for the production of bioenergy. Chapter 11 discusses biomass conversion: production of oxygen-

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ated fuel additives. Chapter 12 discusses the application of microbial based adsorbent for removal of heavy metal from aqueous solution. Kanpur, Uttar Pradesh, India

Dan Bahadur Pal

Contents

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Biomass Energy Utilization, Conversion Technologies . . . . . . . . . . . Ravikant R. Gupta and Richa Agarwal

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Bio-hydrogen Production Using Microbial Electrolysis Cell . . . . . . Shravan Kumar, Rahul, Manish Singh Rajpoot, Shambhavi Mishra, Harshit Kumar Jaiswal, and Prateek Mishra

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Microbial Biomass for Sustainable and Renewable Energy in Wasteland Ecosystem and Its Assessment . . . . . . . . . . . . . . . . . . . . Malay Kumar Adak and Arijit Ghosh

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Microbial Waste Biomass as a Resource of Renewable Energy . . . . Shivani Singh, Pooja Saraswat, and Rajiv Ranjan

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Vanadium Redox Flow Batteries for Large-Scale Energy Storage . . Sanjay Kumar, Nandan Nag, Shivani Kumari, Ila Jogesh Ramala Sarkar, and Arvind Singh

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Biomass Fast Pyrolysis Simulation: A Thermodynamic Equilibrium Approach . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 111 Leena Kapoor

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Potential of Waste Cooking Oil for Emphasizing Biodiesel: Put Waste to Green Energy . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 127 D. A. T. Madusanka and M. M. Pathmalal

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Low-Cost Biomass Adsorbents for Arsenic Removal from Wastewater . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 153 Dan Bahadur Pal, Amit Kumar Tiwari, Shraddha Awasthi, Sumit Kumar Jana, and Nirupama Prasad

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Biodiesel Production from Algal Biomass . . . . . . . . . . . . . . . . . . . . 171 Somen Jana and Ravikant R. Gupta

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Valorisation of Agricultural and Food Waste Biomass for Production of Bioenergy . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 197 Soumya Pandey and Neeta Kumari

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Biomass Conversion: Production of Oxygenated Fuel Additives . . . 219 Subhash B. Magar, Amit Kumar Tiwari, Dan Bahadur Pal, and Sumit Kumar Jana

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Application of Microbial-Based Adsorbent for Removal of Heavy Metal from Aqueous Solution . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 245 Shravan Kumar, Rahul, Prateek Mishra, Shubhang Shukla, Shambhavi Mishra, and Shreya Tirkey

About the Editor

Dan Bahadur Pal, B. Tech, M. Tech, PhD is currently working as an Assistant Professor, Department of Chemical Engineering, Harcourt Butler Technical University, Kanpur-208002, Uttar Pradesh India. He has received his M.Tech. and Ph.D. in the field of Chemical Engineering from Indian Institute of Technology (BHU) Varanasi, Uttar Pradesh, India. Before that, he has completed his B.Tech. in Chemical Engineering from UPTU, Lucknow. Dr. Pal’s research interest is nanotechnology, catalysis, energy and environment, and waste management with a special focus on developing processes and materials by using waste as raw materials. He also prefers to work on biowaste processing and value addition. Dr. Pal published more than 75 publications in reputed journals and books along with 25 book chapters and edited 6 books.

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Chapter 1

Biomass Energy Utilization, Conversion Technologies Ravikant R. Gupta and Richa Agarwal

Abstract The world’s energy demands rely heavily on the fossil fuels as a source of thermal energy. Increasing energy demands, depleting sources of fuels, and growing pollution are the major concerns of the world. For sustainable energy, the demand of biomass energy became the reliable trend to replace fossil fuels to meet the world’s energy demand. Biomass resources are found almost everywhere, and the main sources of biomass are from the traditional forest, agricultural waste, animal manure, fuel wood, and aquatic biomass (e.g., algae). All these resources contain abundant amount of energy. The low cost, less sulfur, and minimum greenhouse gas emissions associated with use of biomass respond to better environmental sustainability for power generation processes. This chapter discusses the different biomass utilization technologies and conversion technologies to promote energy development through waste. Biomass utilization is not limited to combustion method, but the modern advanced conversion technologies such as chemical, thermal, and biological processes are efficient to produce the high-grade energy sources to replace fossil fuels. Keywords Biomass utilization · Biodiesel · Conversion technology · Thermochemical conversion · Biochemical conversion

1.1

Introduction

Sustainable and affordable development goals for energy have been shifted to the use of biomass as a fuel source. Biomass is an important energy source for the world considering its advantages for energy generation, fuel, and other valuable products which need to be produced effectively for better utilization of biomass. The common biomass include agricultural waste, woody crops, logging, milling residues, etc. Apart from being used as feedstock for biofuels, biomass waste can be utilized for

R. R. Gupta (*) · R. Agarwal Department of Chemical Engineering, Banasthali Vidyapith, Tonk, Rajasthan, India e-mail: [email protected] © The Author(s), under exclusive license to Springer Nature Singapore Pte Ltd. 2023 D. B. Pal (ed.), Recent Technologies for Waste to Clean Energy and its Utilization, Clean Energy Production Technologies, https://doi.org/10.1007/978-981-19-3784-2_1

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pulp and soil manure. Biomass wastes are carbon-neutral and available in abundance for production of renewable power gas. In recent years, increase of agricultural waste burning and forest fires due to overstocked waste has created strong pollution hazard to the environment. A potential way to utilize these waste to energy or other valuable purposes is increasingly becoming important around the world (Nicholls et al. 2008). Considering India, bioenergy demand will increase by 11% over the projection period to 2040. The biomass-based power plant capacity will reach around 120 TWh in 2040 which is five times higher than the current production. This will not be possible without policy support, modern biomass technologies, and better utilization of available biomass for high-efficiency and low-emission conversion systems.

1.2

Source of Biomass

Biomass power approach from various resources. The potential main sources are classified on the basis of primary, secondary, and tertiary biomass available from the source as shown in Table 1.1. The study shows that in India agricultural residues are mainly used for cattle food. Rice husk and mustard husk are primarily used as industrial fuel and bagasse mostly for power manufacture. For example, China and India are high producer and consumer of rice, and the residues of rice are burned in the field which increases pollution and is also hazardous to environmental health. The rice straw can be utilized as clean energy fuel through thermal or biochemical conversion method. Table 1.1 Classification of available sources of biomass (Glenting and Jakobsen 2017) Type of biomass Primary

Woody Plantation and forest trees, wood trunks

Secondary

Thinning and logging by products, sawdust, black liquor

Tertiary

Used wood or biomass derived after the processing of primary biomass

Herbaceous Agricultural crops, grass, whole cereal, aquatic plants Straw crop processing byproducts

Used fiber products

Biomass from fruit and seeds Energy grain

Shells, kernels husks, food processing industry byproducts Used products of fruits and seeds

Others

Bio-sludge, slaughter byproducts, cattle waste, horticultural byproducts, municipal solid waste

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1.3

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Biomass Utilization

The increasing energy demand and global warming have urged utilization of biomass for energy production in the world with inclusion of updated technologies. One of the best ways to utilize biomass is production of biofuels and biomaterials for the betterment of economic and environmental systems. Many biomass feedstocks, agricultural waste, forest biomass, and milling waste have competing uses; hence, their utilization among different uses must be determined. The biggest biomass producer is the agricultural waste with 58 million tons of biomass yearly. The biggest energy potential in the agriculture was the flammable crop straw from fields. The biggest issue with the utilization of biomass from agriculture is the investments (Čonka et al. 2014). The ecosunnomic principle method along with mathematical model was developed by Gan and Smith (2012), to suggest utilization of biomass among a variety of alternatives. Their model incorporates the costs of harvesting, transport, processing, and conversion and the benefits of CO2 offsets, in addition to energy value for the biomass allocation for utilization. Outcome of work suggested that mill residues should be used for ethanol production instead of power. Forest biomass should be utilized for electricity production instead of ethanol production which also leads to decrease in greenhouse gas emission. The utilization of biomass among different uses depends upon market and nonmarket demand including greenhouse gas emission and national energy security. Biomass can be converted to valuable product in any state like solid, liquid, or gas, through advance thermal and biochemical technology. Some of the valuable products derived from biomass are shown in Fig. 1.1.

Fig. 1.1 Utilization of biomass to biofuel and byproducts (Source: EBRI, UK)

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1.3.1

Utilization for Bio-power

1.3.1.1

Process and Space Heating

Biomass is used for facility heating, combining heat and power generation. Woody biomass is commonly used for facility heating in three forms: logs, chips, and pellets. Heat appliances from small-scale stoves for room heating to industrial boilers use biomass as fuel. Direct and indirect combustions are the most common processes for producing heat from biomass. The hot gas from the combustion chamber which is used directly to provide heat or steam is generated through the boiler. Further, the steam can be used as utility for process or space heating. For wet biomass fermentation process can be opted to produce combustible biogas. The gas can be treated further to get methane which can be used directly by the consumer in boilers or small combined heat and power (CHP) systems. Using biomass for facility and process heating is cost-effective, efficient, and scalable and also has the highest carbon saving in comparison to other uses. The disadvantage of this process is emissions from biomass combustion which must be monitored and controlled. The major markets which use biomass heating solutions are community heating system, commercial and institutional buildings, and process heat applications.

1.3.1.2

Power Generation

The biomass is mostly used for direct combustion for cooking and heating and electricity production from biogas is still relatively rare. Electricity production through a biomass shares some similarities with fossil fuel power plants because both involve the combustion of a feedstock to generate electricity. The combustion, gasification, and digestion processes are used to convert biomass to flue gases. The flue gas is expanded in a turbine or in an engine used to convert mechanical energy to power generation. Currently, electricity from biomass is produced through combustion followed by power generation in steam turbines, especially using co-firing of biomass with coal. The properties of different biomasses provide different biogas compositions after combustion. Traditionally, sewage sludge and cattle manure have been used for biogas production, but nowadays biomass pellets are increasingly being used as feedstock for biogas production in power plants. The nonwoody biomass are cheaper and mainly blend with wood biomass to improve the combustion performance (García et al. 2019). In India biomass power and cogeneration program has been started for efficient utilization of biomass through bagasse-based cogeneration plant in sugar mills. The most common biomass materials used in India for power generation include bagasse, rice husk, straw, cotton stalk, coconut shells, soya husk, de-oiled cake, groundnut shells, sawdust, etc. The Ministry of New and Renewable Energy of India projects the target 18,000 MW of power generation through biomass which includes

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7000 MW through bagasse based and 550 MW through sugar mills (Bio Energy 2020).

1.3.2

Biomass Utilization for Biofuels

The utilization of biomass for biofuels will relieve the dependence on petroleum as source of energy and its import cost. There is a huge variety of fuel that can be produced from biomass by using different processes, e.g., hydrogen, ethanol, methanol, and biodiesel. The liquid fuel derived from biomass has similar property to the current petroleum fuel source; their utilization does not require extensive change in infrastructure. For example, gasoline can be replaced by alcohol biofuels in the spark-ignition engine and blended biodiesel are used in compression ignition engines. The biomass feedstock can be classified into three classes: lignocellulosic, triglyceride, and starchy feedstocks (including sugars). Lignocellulosic biomass is the most utilized class of biomass for biofuels as it is available in most of the energy crop. The three main components of lignocellulosic biomass are lignin, cellulose, and hemicellulose. Lignin is a polymer component which provides structural strength and water transport system to plant. To access the carbohydrate fraction in biomass, lignin must be removed through pretreatment step during processing. The extracted depolymerize lignin can be utilized for heat and power production or to produce valuable chemical like phenolic resins (Alonso et al. 2010). The hemicellulose part of plant generally composed of sugar monomers which is removed during pretreatment process; it is removed from the biomass through physical and chemical method. Subsequent hydrolysis step after pretreatment is performed to recover glucose from cellulose. The extracted glucoses are the main raw materials for ethanol production. The cellulose fraction from lignin and hemicellulose are further processed to extract glucose through enzymatic hydrolysis or by strong acid treatment. The diversity among biomass composition like cellulose, hemicellulose, and lignin mostly affects the conversion processes for production of biofuel. The challenge in biomass to biofuel is the utilization of co-products produced during the process and their market value to reduce the production cost. Lignocellulosic biomass has been utilized as an appropriate feedstock to produce sustainable fuel like ethanol, methanol, biodiesel, etc.

1.3.2.1

Ethanol and Methanol

The higher price of oil has attracted greater attention to biofuels, especially bioethanol and methanol. They are becoming promising alternatives to gasoline around the globe. Bioethanol and methanol are used worldwide as transportation fuels blended with gasoline ranging from 15 to 85% (% is amount of ethanol). In comparison to gasoline, bioethanol has higher flame speed, higher octane number,

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higher compression ratio, and low NOx emissions. The major disadvantages of bioethanol are its high separation cost due to formation of azeotrope with water and its low vapor pressure and low energy density in comparison to gasoline. The potential feedstocks for ethanol include sugarcane, cornstarch, and lignocellulosic materials like crop residues, wood chips, switch grass, and sawdust. Lignocellulosic materials are pretreated and hydrolyzed to release the sugar compounds and further fermented to form ethanol. Currently, sugarcane and grain are mostly used to produce bioethanol (Hasegawa et al. 2010). Industrial wastes are highly encouraged due to the presence of high carbon and cellulose for the production of ethanol and methanol (Karthiga Devi et al. 2019). In India methanol economy will result in minimum 15% of reduction in fuel bill annually for the country by 2030. Additionally, Rs. 6000 Crore can be saved annually by blending of 20% DME (dimethyl ether—a derivative of methanol) in LPG (Data from NITI Aayog, Govt. of India).

1.3.2.2

Biodiesel

Biodiesel mainly composed of methyl ester long-chain fatty acids obtained from a feedstock such as edible and nonedible vegetable oil (peanut, palm, soybean, jatropha, etc.) or animal fat. The quality of biodiesel mainly depends upon the amount of fatty acids present in feedstock. Transesterification is the common technique used for producing biodiesel. It can also be produced from biomass lignin through biorefinery technologies which include fractionation, liquefaction, pyrolysis, hydrolysis, and fermentation processes. Nowadays, algae are becoming attractive and main sources of feedstock for the biodiesel production in the world. They have the advantage of being noncompetitive as no land is required for their cultivation. A better growth rate and less maintenance compared to the terrestrial crops make the algae the most efficient feedstock for biodiesel production. Generally, the method to extract fatty acids from algae consists of several steps: (Alonso et al. 2010) algae production and growth, (Amer and Elwardany 2020) selection and harvesting, (Atnaw et al. 2017) filtration, (Babinszki et al. 2020) drying, (Balat 2006) oil extraction, and (Bankar 2018) biodiesel production. Though biodiesel can be produced from algae, the process needs a technological development to make it more economical (Khan et al. 2017). The methylating reagent (tetramethylammonium hydroxide) TMAH has been tested to convert algae directly to fatty acid required in production of biodiesel (Johnson et al. 2012). Biodiesel is often used as a blend with petroleum diesel in the ratio of 2% (B2), 5% (B5), and 20% (B20). It was found that using blended biodiesel in oil-fired boilers reduces the NOx and SO2 emissions by 20% which also reduces the risk of illness and life-threatening diseases.

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1.3.2.3

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Pyrolysis Liquid/Bio-oil

Pyrolysis liquid was used for caulking boats and certain embalming agents during ancient Egyptian era (Mohan et al. 2006). Pyrolysis oil is a kind of liquid made from condensation of vapor derived from biomass combustion. Thermochemical-based processes are the best ways to convert biomass to bio-oil. The bio-oil produced is generally in dark brown viscous liquid with composition consisting of phenol derivative, alkanes, esters, sugar, alcohol, and aromatic hydrocarbons. It is considered as potential option to replace petroleum-based fuel. The feedstock required for bio-oil has huge diversity which ranges from agricultural waste, forest waste, municipal waste, wood residue, and microalgae. The major components of biomass are cellulose, hemicelluloses, and lignin. The bio-oil is the product of thermal treatment of these three components. It was found that hemicellulose and cellulose are the easiest components used to produce pyrolysis oil. The highest yield of pyrolysis oil obtained through cellulose and hemicellulose is 26% (Yang et al. 2014; Shahbaz et al. 2020), whereas lignin produces a solid residue known as biochar (i.e., 58%). So for high yield of pyrolysis oil, a less lignin content is favored to minimize high molecular weight compounds present in liquid. In addition to the three components, the ratios of volatile matter, moisture, fixed carbon, and ash content are also important parameters to produce high-quality pyrolysis oil.

1.3.3

Biogas

An efficient method for the conversion of biomass to energy is the production of biogas through anaerobic digestion. The different microorganism populations and specific environmental conditions are required for the efficient degradation of feedstock. The compositions of biogas mainly consist 50–65% methane, CO2 (25–50%), H2, H2O, NH3, H2S, and digestate (solid byproduct) which has excellent agricultural application (Karuppiah and Azariah 2019). This makes biogas a valuable source of fuel. The biogas produced required cleaning and upgrading according to intended use, like direct combustion for cooking and heating, production of electricity, as a fuel in gas-operated vehicles, and production of a variety of chemicals. The digestate can be used as a high-quality organic fertilizer which is more advantageous than undigested fertilizer. Biogas contains several undesirable components (CO2, H2S, O2, N2, H2O, siloxanes, and particulate matter) which decrease its calorific value and/or are corrosive to downstream equipment. Depending on the end use, different biogas treatments (cleaning and/or upgrading) are necessary. It has been suggested that the biogas should contain at least 95% CH4 in order to be economically viable (Song et al. 2014). If biogas produced from biomass is cleaned and upgraded to methane concentration of 98%, it will have the same properties as natural gas.

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In 2018, 59.3 billion m3 of biogas was produced globally with an annual growth rate of 9% (2000–2018). Further, 637 TWh of bio-power was generated in 2018 with an annual growth rate of 8% from 2000 to 2018, and the share of biogas was merely 14% (Global Bioenergy Statistics 2020). Biogas can also be converted directly into electricity and heat using fuel cells where electrochemical conversion of biogas with oxygen takes place.

1.3.4

Synthesis Gas

The synthesis gas (syngas) production is an efficient way to utilize biomass for energy and industrial applications. Syngas is formed by a variety of techniques with feedstock ranging from fossil fuels to renewable organic compounds. The compositions of syngas depend upon the feedstock and generally consist of carbon monoxide (30–45%), carbon dioxide (5–15%), hydrogen (25–30%), and methane (5–15%) (Zaichenko et al. 2020). Production method of syngas includes thermal technologies like pyrolysis, gasification, reforming, and combustion. It can also be produced by biochemical routes such as direct biophotolysis, indirect biophotolysis, biological water–gas shift reaction, photo-fermentation, and dark fermentation. Feedstocks like agricultural straw, sugarcane, forestry waste and residues, corn, and wood are being used for the syngas production in which wood plays the major role as feedstock. Research is mainly focused on production of synthesis gas from biomass for transportation fuels and less on chemicals. Hydrogen generation is the most important product of syngas platform. Hydrogen is commonly produced from steam reforming process, but if hydrogen should be produced from renewable resources, biomass gasification is generally opted (Shi et al. 2020). Hydrogen demand could increase by at least fivefold by 2050 in India, and nearly 80% of India’s hydrogen is projected to be “green”—produced by renewable resources. Utilizing of biomass waste in hydrogen production routes could be a cost-effective way of meeting a portion of hydrogen demand.

1.3.5

Charcoal Briquettes

A charcoal fuel briquette can be a block of compacted paper waste, charcoal dust, sawdust, agricultural waste, yard waste, wood chips, or biomass, which can be serve as a fuel for domestic and industrial applications. Briquettes are formed by obtaining small particles of charcoal from biomass mixed with flour, additives, and water, and after that they are compacted at a low pressure (30–50 MPa) into the required shape and size. Later, they are placed in a dryer to remove the moisture from charcoal briquettes. Charcoal briquettes are economical and have high heat value (4.4–8.25 kJ/g) than the traditional charcoal, which is widely used for domestic purposes (Kongprasert et al. 2019). It was found that material possessing low-energy

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content can be used as high-energy fuel after composting, compaction, and combustion. The advantage of charcoal briquettes is that it has longer extinguishing time, higher heating value, lower ash content, and higher compressive strength than tradition coal.

1.3.6

Byproducts

1.3.6.1

Citric Acid

Citric acid is a naturally available organic acid, found in all citrus fruits, and an extensively used acid in many industries. Over the years, production of citric acid is carried through natural sources (lemon, orange, etc.) and by microbial fermentation (sugar fermentation). Nowadays, citric acid commercial production is mainly done by microbial fermentation process which involves complex biochemical reaction and controlled operating parameters. The market of citric acid demand is growing extensively due its huge application in many industries like beverage, food, metal finishing, animal feed, lubricants, etc. (Show et al. 2015). So with this huge demand, there is also a high demand for alternative, environmental-friendly, and economical substrate for the production of citric acid. The biomass wastes generated from food industry and agricultural are rich in nutrients and can be utilized as an ideal substrates for citric acid production (Bankar 2018). However, the biomass substrates need pretreatments prior to the fermentation process. The feedstock should be low in moisture content as higher water content leads to contamination of microorganisms, resulting in uncontrolled microbial growth during the process. Apart from moisture content, the quality and yield of citric acid also depend on the type of biomass and sugar content (Munshi et al. 2013). The utilization of waste will help the fruit-processing industry to reduce their processing cost involved in treatment and transportation of wastes in landfill sites. Citric acid can be produced through pyrolysis liquid through fermentation. The main component is levoglucosan which is present in pyrolysis liquid about 17.5%. Yang et al. (2014) proposed a sequential two-step process in which fermentation of corn stover pyrolysis liquid to citric acid was done. The first step involves removal of other compounds by Phanerochaete chrysosporium (P. chrysosporium) except levoglucosan. Then the remaining levoglucosan is further fermented into citric acid by Aspergillus niger. The solid biomass obtained during the process can be used for biogas production or for fertilizer preparation.

1.3.6.2

Composite Material and Fibers

Composite materials have many benefits over conventional materials like high specific strength, stiffness, and fatigue characteristics. Natural fibers are bio-based fibers which can be obtained either from the plant (cellulosic) or from animal

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(protein). Nowadays, agricultural wastes are utilized in making fiber-reinforced composite for commercial use. Natural fibers obtained from agricultural wastes such as jute, hemp, kenaf, cotton, and coir fibers are found as promising alternatives to synthetic fibers. All natural fibers majorly consist of lignin, cellulose, and hemicelluloses along with lower amounts of extractives, pectin, and pigments. Cellulose is the strongest and the stiffest and provides mechanical structural stability to the fibers. Lignin provides thermal stability and has least water sorption property. Hemicelluloses are amorphous components which make them hygroscopic in nature. Lignocellulosic-based composite materials are used in manufacturing of automotive hardware parts and construction industries and as a feed in the energy sector. The natural fiber–polymer composite is strongly dependent on various aspects such as fiber content, fiber aspect ratio, fiber/matrix interfacial adhesion, fiber orientation, etc. The hydrophilic nature of natural fibers makes them unsuited with the hydrophobic polymeric matrix and leads to provide poor interfacial bonding. Researchers have now developed hybrid composites made up of synthetic and natural fibers through chemical modification that show excellent increase in strength and performance of the natural fiber. For example, composite made up of glass fiber and cellulose possesses improved mechanical strength and is cheaper and healthier than glass fiber. The application of bio-composite will increase in the near future in various applications. But bio-composites also have poor long-term application, and can be used only for low strength application. Better technology can be used to overcome these limitations, as it shows good prospects like nanotechnology-based coatings. This coating helps to improve water resistance, reduce biodegradation and volatile organic compounds, and improve flame resistance.

1.4

Conversion Technologies

In general, conversion of biomass to valuable product depends upon the feedstock which can be highly uneven in mass, power density, and intermittent supply. So with such a variety of feedstock, it is required to choose specified conversion technology based on feedstock property to achieve the desired product. In most of the cases, the end product type determines the appropriate process selection. The conversion technology of biomass to valuable product is mostly classifiedinto two categories as shown in Fig. 1.2: thermochemical and biochemical conversion routes. Thermochemical conversion technologies include processes like direct combustion, pyrolysis, gasification, etc. They mainly use lignocellulosic biomass as feedstock to produce second-generation biofuel production. Biochemical conversion includes two main processes: anaerobic digestion and fermentation. In this process, organic nonwoody material decomposes with the help of microorganisms and in the absence of oxygen with controlled conditions. The most important products of biochemical routes are methane and carbon dioxide. Biochemical conversion process is a time-consuming process and only uses feedstock of cellulose and hemicellulose portions of biomass, for conversion (Zhang and Zhang 2019).

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Fig. 1.2 Biomass conversion processes

Research found that thermochemical conversion technologies are more efficient and flexible.

1.4.1

Thermochemical Processes

Thermochemical processes are the simplest and earliest examples of technologies use to convert biomass feedstock to energy products and chemicals. Thermochemical routes are classified by their heating rate, particle size, and associated and oxidation environment, ranging from endothermic (oxygen-free) to full exothermic oxidation of biomass (Tanger et al. 2013). The four main thermochemical processes are shown in Fig. 1.2 which are carbonization, pyrolysis, gasification, and liquefaction.

1.4.1.1

Pyrolysis

Pyrolysis has open many possibilities for efficient utilization of biomass to obtain high-quality product especially bio-oil and biochar. In pyrolysis process, organic material decomposed under high temperature and inert atmosphere to produce bio-oil, non-condensable gases, and biochar. It is also considered as the initial step of combustion and gasification process and significantly increases the performance of these processes. The pyrolysis of wood-based biomass mainly depends upon the decomposition of cellulose, hemicellulose, and lignin and their interaction among them. Depending on the biomass (structure, particle size, composition) and process conditions (residence time, heating rate, and temperature), the quality and yield of pyrolysis product change (Ronsse et al. 2015). For liquid products, a short gas residence time, high heating rate, and low temperature are required. For a maximum solid (char) production, the process should be on low temperature and low heating

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Fig. 1.3 Flow diagram of pyrolysis process (Kundu et al. 2018)

rate. If the required product is fuel gas, a high temperature, low heating rate, and long gas residence time should be followed (Demirbas 2009). The typical pyrolysis process consists of three main stages which include feedstock preparation, pyrolysis, and upgradation to final product (as show in Fig. 1.3). Feedstock preparation includes handling and pretreatment such as shredding, drying, and storage. The second step is the pyrolysis of the prepared biomass in a suitable reactor to get a main product, i.e., bio-oil, with some traces of gas and char. Finally, the last step is the upgradation of bio-oil into a marketable end product by processes like hydrotreating, hydrocracking, and stream reforming (Varma et al. 2018). Pyrolysis can be classified into three types: slow, fast, and flash pyrolysis. The slow pyrolysis process is also known as carbonization; it is a traditional way of producing smokeless charcoal. Fast pyrolysis is a process that treats feedstock with high temperature in the absence of oxygen. The vapor evolved during this process is condensed into dark brown liquid (bio-oil). The advanced technology of fast pyrolysis with a promising amount of bio-oil yield is known as flash pyrolysis. It is performed between the temperature range of 400 and 1000 ∘ C and with less residence time (0.2–0.3 s). Due to short residence time and low secondary degradation, the high yield of bio-oil is obtained. The comparison between all three pyrolysis processes based on operating conditions and percentage yield of product is shown in Table 1.2. The continued research and development in pyrolysis technology led to various reactor designs which have been proposed to produce high-quality bio-oil. Different types of pyrolytic reactors for bio-oil production include fixed bed, bubbling fluidized bed, circulating fluidized bed, ablative (vortex and rotating blade), and rotating disk reactor and rotating cone reactor (Bridgwater 2019). Apart from these, vacuum pyrolysis, microwave-driven pyrolysis, and screw reactors are also used for pyrolysis, but they are not successful due to low bio-oil yield and low heat transfer rate.

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Table 1.2 Difference between operating conditions and percentage yield of product for pyrolysis process (Jahirul et al. 2012) Type of pyrolysis Slow Fast Flash

1.4.1.2

Residence time (s) 449–549 0.5–10 999

Particle size (mm) 5–49 20% w/w) as a dry weight are called as oleaginous microorganisms which can be utilised for biofuel production. The microbes like bacteria, microalgae and yeasts are highly used in biodiesel production. On the other hand, some thraustochytrids, microalgae and fungi are able to produce polyunsaturated fatty acids (PUFA), for example, omega-3 fatty acids (Patel et al. 2020). Under nitrogen-limiting conditions, the bacterial species of Rhodococcus and Nocardia are capable of accumulating neutral

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lipids (triacylglycerols) and low concentrations of diacylglycerols (Alvarez et al. 1997). The bacterial biomass processing is considered as one the efficient ways to produce biofuels because they are enriched with fatty acids and triacylglycerol (TAG). Biofuels like diesel have high-chain monoalkyl esters and TAG as their components of the cell which are produced by the transesterification of alcohols with the help of catalyst. Hydrocarbons are often produced from fatty acids and TAGs by the metabolic activity of various bacterial species. Also, the TAG and lipids present in bacteria are preliminary materials required for the production of biofuel (Kumar et al. 2020). Hwangbo and Chu (2020) have reported that biofuels based on lipids can be formed by different forms of biolipids present in bacteria such as TAGs, wax esters (WEs) and polyhydroxybutyrate (PHB). In addition, the biolipids from prokaryotes have been found easier to synthesis due to their straightforward and not so complicated cultivation strategies, and their tendency to accumulate high content of biolipids. However, they have a limitation due to the high cost for extraction process. Hwangbo and Chu (2020) also reported the various production methods for extraction of biolipids from prokaryotes. It’s worth noting that oleaginous bacteria can be used to make lipid-based biofuels. The capacity of oleaginous bacteria to use a diverse range of renewable feedstock as a carbon source bodes well for commercial deployment. However, more efforts are needed to improve the productivity and yield of microbial lipid-based biofuels (Adrio 2017).

4.4.2

Yeast

Yeasts are unicellular eukaryotic organisms that belong to the fungus family, which also includes moulds and mushrooms. They are facultative organisms, meaning they can grow in the absence or presence of oxygen. Yeasts are well-known for their ability to ferment, yet contrary to common perception, only around half of the species can do so. However, several of these yeasts have evolved into useful biotechnological tools (Rawat 2015; Türker 2014). For thousands of years, humans have employed yeast to make fermented foods like bread, beer and wine. Yeasts were first used instinctively, but as science and technology progressed, these microorganisms became the focus of various researches for novel purposes (Żymańczyk-Duda et al. 2017). Antonie van Leeuwenhoek recorded the first microscopic view of a yeast cell in 1680. Many years later, Louis Pasteur’s contributions on yeast metabolism in 1857 were crucial in understanding the fermentation process (Türker 2014). Because yeast cells have the potential to convert basic materials into valuable molecules that can be utilised as food additives. Considerable progress in genetic engineering have been made in the last century to convert yeast cells into miniature factories. As a result, the demand for yeast biomass expanded, favouring the manufacturing of a wide range of items, not just food and beverages. Nowadays, yeasts are primarily employed in the food

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sector, but they are increasingly being used in other industries. In terms of the environment, yeasts can be utilised for bioremediation and heavy metal removal from waste waters; in agriculture, they may be utilised as biocontrol agents; and in medicinal applications, they can be utilised to make a variety of chemicals and biofuels, among other things. The creation of films and coatings in the materials sector, mostly for food packaging, is a very recent and novel use (Türker 2014; Peris et al. 2018). Yeast and fungal biomass are close to zero and plentiful sources of biopolymers, as they may be a by-product of industrial processes such as brewing or other biotechnological processes that discard the biomass (cells or mycelia) when the ultimate product is obtained (Peltzer et al. 2018; Kadimaliev et al. 2015; Guimarães et al. 2006). It is seen that the lipid-producing microbes (oleaginous microorganisms) are utilised for different requirements such as a means of nutrition, value-based products and biofuels. However, after taking out all the possible value-added products from the microbial cultures, the waste is often discarded. In a study, a new bio-based acid catalyst, i.e. yeast residue-based solid acid (YSA), has been synthesised from the waste yeast cultures by sulphonation process and resulted in biodiesel production. The study also reported that the obtained catalyst YSA showed high yield of fatty acid methyl ester (FAME) and yeast oil as 96.2 and 94.8 wt %, respectively, and all the properties required for a biodiesel were followed as per the international fuel standards (Deeba et al. 2020). Several other similar researches have been reported where yeast biomass is used as a source for biofuel production (Spagnuolo et al. 2019; Liu et al. 2021).

4.4.3

Fungi

The use of liquid biofuels is found as an alternative to conventional energy resources (fossil fuels) whose increased uses have already caused a lot of harm to the environment and humans. The first-generation biofuels have been highly condemned for their harmful effects on sustainable management of food supply. Keeping this in mind, the bio-based fuels have gained attention in the past years. More precisely, biofuels based on lignocellulose (bioethanol) and oil (biodiesel) have been extensively considered. But with their tedious method of production, pretreatments and hydrolysis are often not economically efficient. Therefore, there is a need to make research more advanced in this field and direct it towards beneficial techniques and methods to beat the upcoming challenges. Fungi as a source of biomass are a relatively recent concept. Enzymes, organic acids and antibiotics are some of the more common products made from them. Their production times are significantly longer than those of yeasts and bacteria (5–12 h). As they grow through extension of mycelium, this is an apparent generation period; growth is not truly exponential. They have lower protein content (50%) than yeasts and bacteria, and they are poor in sulphur-containing amino acids. There are also issues with wall digestion. The nucleic acid content, on the other hand, is modest

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(3–5%). Fungi’s main advantages include their ability to use a wide range of complex growth ingredients such as cellulose and starch, as well as their ease of recovery via simple filtration, which lowers manufacturing costs. Fungi can be employed in the production of biofuels mainly in three ways: used as cellulose, lipids, and lipase in the bioethanol production and biodiesel production, respectively. Trichoderma reesei is a fungus that may be found in soil all around the world. It feeds by secreting a large amount of cellulase. This fungus was first found during World War II, and it was responsible for ‘jungle rot’, which caused the cellulose in US soldiers’ tents and clothes to break down. The fungus has been genetically engineered by a Canadian business to create more cellulase and convert straw into glucose, which may subsequently be converted into ethanol. They were successful in converting 75% of the straw to glucose (Liao et al. 2016). Filamentous fungi (Mortierella, Aspergillus, Penicillium, Cunninghamella, Mucor and Rhizopus) (Subramaniam and Dufreche 2010) are another type of oleaginous microbes that are a good source of feedstock for biodiesel synthesis (Kot et al. 2016). Most of the oleaginous fungi are able to deposit a reasonable amount of lipid content (20–25%) of their dry weight; few of such fungi have high oil contents up to 25% or more. Mortierella isabellina is a fungus that stores oil biomass up to 86% (Huang et al. 2016). Oleaginous fungi have also been used to produce high-value nutraceuticals such as polyunsaturated fatty acids including eicosapentaenoic acid, gamma-linolenic acid by Mucor circinelloides and Mucor rouxii and arachidonic acid by Mortierella alpina (Du Preez et al. 1995; Koike et al. 2001).

4.4.4

Algae

The photosynthetic organisms like bacteria and algae attract researchers for the production of renewable energy. Algae belong to the group of microbes with similar morphology and physiology in terms of food synthesis (similar metabolic pathways) and exist in water and thallus body organisation (no clear division of organs) (Surriya et al. 2015). The metabolism varies from one alga to the other. And some of them enable changes in their metabolic pathways under changed conditions. Also, they differ in the protein, carbohydrate and fat contents in different cell types. Say, for example, a Spirulina maximum is rich in proteins (60–71%w/w), Porphyridium cruentum is rich in carbohydrates (40–57%w/w) and Scenedesmus dimorphus has lipid content nearly 40%w/w (Nigam and Singh 2011). Also, certain species like Botryococcus and Chlorella exhibit higher concentrations of terpenoids and glycerol lipids that are supposed to get converted into short hydrocarbons (major crude oil) (Tran et al. 2010). The biomass composition often depends on the available growth conditions. Also, composition of biomass depends on the growth conditions. Algae’s potential benefits are based on their ability to reproduce on carbon dioxide as the sole carbon source. Because of its rapid growth rate and ability to grow in water bodies

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Table 4.2 Algae that produce biofuels or algal biofuel precursors are listed below S. no. 1.

2.

3. 4.

Name of algae Chlamydomonas sp., Nannochloropsis sp., Scenedesmus sp., Acutodesmus, Scenedesmus obliquus, Oocystis sp., Microspora sp., Scenedesmus and Chlorella vulgaris Botryococcus braunii, Botryococcus sp., Chlorella vulgaris, Scenedesmus sp. and Synechocystis Scenedesmus obliquus and Rhodosporidium toruloides Scenedesmus biomass After lipid extraction and Nannochloropsis sp.

Synthesised biofuel Biogas

Biodiesel

Bioethanol Biohydrogen

Reference Alzate et al. (2012), Keymer et al. (2013), Mendez et al. (2014)

Sheng et al. (2012) Clarens et al. (2010), Lee et al. (2010) Miranda et al. (2012) Yang et al. (2010), Efremenko et al. (2012)

(waste water or waste land), algae are thought to be a good source of renewable energy. The use of microalgae has attained a lot attention worldwide, due to their wider applications in various fields including renewable energy (Table 4.2). They are perfect replacement to fossil fuels in terms of cost and environment-related concerns. They have great ability for conversion of atmospheric CO2 to beneficial products like organic compounds and bioactive metabolites. Microalgae are single-celled microorganisms with lipids, carbohydrates and proteins as their main components. Generally, microalgae have a tough cell wall, which makes the biofuel conversion technology difficult to use. In this approach, the composition and structure of the microalgae cell wall limit the lipid extraction for biodiesel synthesis and hydrolysis for biogas production. The production of algal mass requires special type of system known as bioreactors (Nigam and Singh 2011). The biofuel production using algae follows various steps as shown in Fig. 4.2 which include (1) cultivation of microalgae to increase the algal biomass under specific conditions (bioreactors or under natural conditions, (2) collection of biomass using different filtration techniques, (3) required pretreatments for biomass, (4) microbial conversions (biomassbiofuel) and (5) purification (Voloshin et al. 2016). Microalgae can be cultured by different methods and under different conditions (light, temperature, nutrients, mixing, salinity, etc.) (Khan et al. 2018). Also, there is a need to optimise all the necessary conditions for efficient fuel production, for example, selection of efficient strain with maximum yield, tolerance to stress factors and optimum culture conditions. There are several advantages of microalgae over others for biofuel production (Nigam and Singh 2011) which include high amount of fats in dry mass (20–50%), products that can be obtained annually in comparison to the plants, less water requirement, absorption of huge amount of CO2 (Voloshin et al. 2016). Many organic substrates, such as sewage sludge and lignocellulosic biomass, have been successfully disintegrated using pretreatment procedures (Carrère et al. 2010;

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Fig. 4.2 Stages in the conversion of algal biomass to biofuel

Hendriks and Zeeman 2009) and were emphasised as a critical step in the disruption of microalgae cells and the creation of biofuel (Chen and Oswald 1998). Meier in 1955 presented the idea of creating biofuels from microalgae in the 1950s in the United States (Meier 1955). Biofuels, which primarily include biodiesel, bioethanol and biogas, are likely to be one of the most important sources of renewable energy for the future (Anastasi et al. 1990; Demirbas 2008). The synthesis of different biofuels has to undergo different procedures. For example, biodiesel production is done via transetherification of triglyceride, and bioalcohol production is done by fermentation of algal biomass. Other than that, biohydrogen is synthesised by direct and indirect biophotolysis, and fermentation (Voloshin et al. 2016). The future acceptancy of biofuels is largely dependent on its economic value. The low carbohydrate content is one of the limitations in biofuel acceptance, though the content of algal biomass could be increased by regulating environmental conditions or by doing changes at genetic level. The cells can be grown under various stress conditions (Ho et al. 2012; Siaut et al. 2011), and genetic modifications can be performed to bring changes in the metabolic pathways of the algal cells. These changes result in the higher production of organic compounds of interest (Gimpel et al. 2013). Hence, such efforts are helping in development of carbohydrate-rich microalgae using bioengineering.

4.4.4.1

Bioethanol

Bioethanol, biomethanol, biopropanol and biobutanol are the main types of bio-based alcohols produced by using microbes. Among them, bioethanol is the most common one which is a clean fuel used in transportation. It has several advantages over conventional renewable resources which include the following: (1) it has high octane number, thereby protecting vehicle engines from knocking,

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(2) high oxygen content is present which produces lesser greenhouse gases, (3) it can be directly utilised in vehicles without any changes and (4) it is able to mix with oils (Balat et al. 2008; Walker 2011). The feedstocks rich in sugars are suitable for fermentation reaction. Earlier, there have been different feedstocks for bioethanol production like sucrose, starch and lignocellulose (Shah and Sen 2011). However, algae are found as a good source for fermentation and synthesis of biohydrogen and bioethanol. Various other microbes (yeast, bacteria and fungi) have been known with potential to synthesise bioethanol (Maruthai et al. 2012). But the algal sugars are considered as a perfect biomass for the bioethanol production. Microalgae contain higher concentrations of glycogen, cellulose, etc. that can be changed to sugars for further production of bioethanol (Ueda et al. 1996). Some common examples of microalgae that produce a good amount of starch are Chlorella, Chlamydomonas, Dunaliella, Scenedesmus and Spirulina which have high potential for ethanol production (Hirano et al. 1997; Harun et al. 2010). Microalgae are able to accumulate cellulose which is converted to bioethanol by fermentation (Hu et al. 2012). Also, microalgae are seen performing self-fermentation to synthesise bioethanol. There are several advantages related to the synthesis of bioethanol by fermentation which include the following: (1) all the biomass and waste (after oil extraction) can be utilised and (2) it requires liquid as medium and does not need additional steps like drying (Hu et al. 2012).

4.4.4.2

Biodiesel

When oils/fats and alcohol are reacted together in the presence of a catalyst, methyl or ethyl esters are formed which are the components of a biodiesel (Karthikeyan et al. 2014; Karthikeyan and Prathima 2017). Biodiesel is often less polluting in comparison to diesel. The algae is grown in liquid medium or cultures to obtain commercially valuable products, used in bioremediation and also for biofuel synthesis (Karthikeyan and Prathima 2016; Karthikeyan et al. 2018). The methane production from microalgae, bio-oil (pyrolysis) and bio-hydrogen (photobiological processes) are some of the examples of the biofuels. Conversion of microalgae oil to biodiesel requires various stages such as extraction of lipids from biomass, removal of unnecessary or not required solvents and transesterification process. The lipids from the algal biomass may be isolated and refined into fatty acids, which could then be transesterified to make biodiesel. Biodiesel, green jet fuel and green gasoline could all benefit from algal lipids as a feedstock because they do not include food and agricultural costs and do not have the ability to trap substantial amounts of carbon dioxide (Bomgardner 2012). Biogas is made up of methane, CO2, nitrogen, hydrogen sulphide (H2S) and small traces of other gases. Most of the organic wastes are capable of transforming into biogas and other useful compounds by anaerobic digestion. Thus helping in sustainable management of waste effectively. According to Heeg et al. (2014), production of biogas through anaerobic digestion of biomass is a combination of various microbes all together. Biogas can be produced via anaerobic digestion or thermal

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cracking of algal biomass (Montingelli et al. 2015). Direct fermentation can be utilised to produce bioethanol from the carbohydrate component. Methane gas is produced through anaerobic fermentation of biomass. Biomass is burned directly to generate electricity or syngas.

4.5

Conclusion

With fossil fuels, there is a grave existential dilemma. Reserves will run out at some time in the not-too-distant future since they are a limited resource that cannot be recreated. Moving away from fossil fuels and more towards alternate sources of energy will play a vital role in finding solutions to these problems. Mitigation of challenges like these is achievable with new ways like the use of microbes to produce better biofuels. Therefore, microbes are considered as a viable option to these problems. Researches are going on with an aim to develop biofuels from microbes at reasonable cost. The performance and economic aspects are very well considered for the development of new ideas related to the synthesis of biofuels from waste microbial biomass. The researchers are trying to develop these biofuels at reasonable expenses and expand the lipid production in the coming years. Researchers are utilising lipids to make biodiesel and algae carbohydrates to make bioethanol in small-scale laboratory bioreactors but their is a need to scale it up to industrial levels, so that the biomass-based biofuels might become a significant source of energy. For long-term sustainability and environmental advantages, all phases of microbial biofuel manufacturing should be streamlined without using a large amount of energy. Much more research will be required to give these answers on a large scale, but they are becoming more accessible as time goes on.

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Chapter 5

Vanadium Redox Flow Batteries for Large-Scale Energy Storage Sanjay Kumar, Nandan Nag, Shivani Kumari, Ila Jogesh Ramala Sarkar, and Arvind Singh

Abstract In the past few decades, there has been a rapid increase in global warming effects because of burning of fossil fuels in the industrial sector. Fossil fuels are limited on earth, so there is a need to decrease the generation of greenhouse gases and increase access to alternative sources or power generation to protect our environment. Vanadium redox flow battery (VRFB) is one of the most promising battery technologies in the current time to store energy at MW level. VRFB technology has been successfully integrated with solar and wind energy in recent years for peak shaving, load leveling, and backup system up to MW power rating. The life cycle of this system goes up to more than 200,000 cycles. It has several advantages as compared to other battery technologies such as lower cost, more safety, fully dischargeable, energy stored in electrolyte tank, more than 15-year life cycle, and scalable energy capacity. This book chapter aims to critically discuss the vanadium redox flow battery emerging technology up to MW level and compare it other battery technologies. It also provided valuable information for recent VRFB installation up to MW power rating and recent experimental and modeling studies by the researcher.

S. Kumar (*) Department of Chemical Engineering, Faculty of Technology, Marwadi University, Rajkot, India Department of Chemical Engineering, B.I.T. Sindri, Jharkhand, India N. Nag Department of Metallurgical Engineering, B.I.T. Sindri, Jharkhand, India S. Kumari Department of Chemical Engineering, B.I.T. Sindri, Jharkhand, India I. J. R. Sarkar Department of Chemical Engineering, Faculty of Technology, Marwadi University, Rajkot, India A. Singh Department of Chemical Engineering & Biochemical Engineering, Rajiv Gandhi Institute of Petroleum Technology, Jais, Amethi, India © The Author(s), under exclusive license to Springer Nature Singapore Pte Ltd. 2023 D. B. Pal (ed.), Recent Technologies for Waste to Clean Energy and its Utilization, Clean Energy Production Technologies, https://doi.org/10.1007/978-981-19-3784-2_5

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Keywords Redox flow battery · Energy storage · Vanadium redox flow battery · Vanadium redox flow battery coupled · Energy efficiency

5.1

Introduction

Prior to the development of electrochemical energy storage systems, fossil fuels like coal, petroleum, and natural gas were used for electricity generation. The main drawbacks of such technologies were the absence of a rechargeable feature. However, with modernization where connectivity, either through mobilization or through the network, is playing a significant role, such fossil fuel technologies cannot stand up to satisfaction. Apart from being non-rechargeable, such systems cause certain environmental concerns; this is primarily due to the emission of carbon dioxide which accumulates into the atmosphere in the form of acid rain clouds. Acid rain causes major issues like degradation of materials in the form of corrosion and land erosion, which affect the aquatic lives and reduce the productivity of the land. The Millennium Ecosystem Assessment had shown that the loss of ecosystem causes a lot of problems in the arid, semiarid, and subhumid region such as the following: • Lack of water supply: the byproduct of such fossil fuels depletes the ozone layer, thereby increasing the permeability of ultraviolet radiations from space. • Degradation of land: due to the erosion of the topmost layer which contains all the necessary nutrients for plant growth, hence affecting the productivity of the land. • Climatic conditions: this causes severe issues such as extremes of temperature as well as drought conditions (Biggs et al. 2005). In order to prevent such environmental degradations, the government has planned to put a limit on the carbon emissions; therefore, frequent pollution check is carried out over the fossil fuel-based systems. Furthermore, carbon emission can be controlled by the enhancement of energy efficiency through an alternative clean and environmentally friendly energy storage system, utilizing the scrap material, and collection as well as deposition of carbon dioxide (Sinha and Chaturvedi 2019). Different types of rechargeable batteries are available nowadays to reduce the consumption of fossil fuels such as lead-acid batteries, lithium-ion batteries, several redox flow batteries, sodium-ion batteries, nickel-cadmium batteries as well as supercapacitors. Electrochemical energy storage systems have motivated the researchers to use the minerals abundant in the earth’s crust such as lead, iron, and zinc. Moreover, recycling technologies aid to leach the consumed materials, which are harmful to human health, and make them available for use to prevent their disposal. In an electrochemical energy storage system, chemical energy is directly converted to electrical energy through electrochemical reactions. During the reactions, electron travels through the load which is powered by the battery and the ions travel through the electrolyte. Such systems have a charge storing capability and they can be rechargeable. The two electrodes attached on either side of the battery either stores charge or stores electrons, i.e., upon charging the cathode dissolves into the

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Fig. 5.1 Schematic of a vanadium redox flow battery (VRFB) in a full discharge condition

solution and the equilibrium is maintained by subsequent removal of electrons from the anode and cathode; in discharge condition, reverse reaction, occurs. Diverse mechanisms operate for different kinds of batteries, such as in redox flow batteries, charge-discharge cycles take place by subsequent reduction and oxidation reactions occurring in the electrolytes used in anodic and cathodic side, respectively; in lithium- or sodium-ion batteries, Li+ or Na+ ions are dissolved into the electrolyte, respectively, for the operation of the battery; and in supercapacitors, the charge is stored both electrostatically and electrochemically; hence, the term double-layered capacitor is coined for supercapacitors. In redox flow batteries, apart from redox reactions carried out, the electrolytic flow also plays a significant role; these electrolytes are used to drain the heat generated while cycling, therefore preventing the system from heating (Wang et al. 2013). Vanadium redox flow batteries (VRFBs) are the most recent battery technology developed by Maria Skyllas-Kazacos at the University of New South Wales in the 1980s (Rychcik and Skyllas-Kazacos 1988) to store the energy up to MW power range as shown in Fig. 5.1. In this system, electrolyte flow through flow field design is made up in the graphite plate for uniform circulation in electrode regions such as serpentine, interdigitated, parallel, and conventional flow field (Kumar and Jayanti 2016). Usually, serpentine and interdigitated flow fields show high workability because of their ability to homogenously distribute the electrolyte, improving the structural uniformity and enhancing the mass transfer coefficient. VRFBs can be integrated into the photovoltaic system as well as in wind turbines for a continuous supply of power. Apart from VRFB, the conventional liquid electrolyte is used in other batteries such as zinc-chloride, zinc-bromine, and zinc-air.

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Recent Technology in Energy Storage Device Lead-Acid Battery

The manufacture of fuel cell technology on commercial scale requires the development of grid connected systems without integrated thermal and electric buffer storage systems. Moreover, these systems are economical as the cost of buffer device is avoided. Lead acid is one kind of fuel cell technology which is used to store and deliver current within the voltage range of 5–24 V. Moreover, it has distinct advantages such as low price, high availability, and ease of manufacture. Leadacid batteries are of two types: sealed lead-acid batteries and valve-regulated leadacid batteries, and these batteries can also be used as a redox flow battery. The electrolyte used in lead-acid battery is sulfuric acid and the PbSO4 in the form of paste is applied over the electrodes. The redox reaction is carried out within the battery and accordingly, PbO2 is deposited over the cathode. Apart from sulfuric acid, perchloric acid, fluorosilicic acid, tetra fluoroboric acid, and methane sulphonic acid can be used. Lead(II) have shown high solubility toward methane fluorosulfonic acid (Pletcher and Wills 2005). On performing a series of charge-discharge cycles at current densities of 20, 40, and 60 mA/cm2, Pletcher et al. found that the first charge is constant at a high value of current density, whereas the subsequent cycle is lower but shows a significant rise over a period to reach the constant achieved during the first charge. Similar connotation was found by Hazza et al. (2004) while they were carrying out a cyclic voltammogram experiment and found that current associated with oxidation and reduction is much larger on the fifth cycle as compared to first one. It could be because the high surface energy of PbO2 at the fifth cycle remains on the surface even after 700 mV. Moreover, when battery design does not include separator, it requires some additive addition to the electrolyte. Hazza et al. worked on developing a lead-acid battery using sodium lignosulfonate as an additive to the electrolyte (1.5 M Pb (CH3SO3)2 + 0.9 M CH3SO3H). Sodium lignosulfonate addition increases the deposition and dissolution of lead, but they are relatively much smaller when compared with other voltage losses in the battery (Hazza et al. 2004). Moreover, this additive is required when a high current density is allowed to pass through the cell; furthermore, it has been found that smoothening of deposits changes from an uneven angular and dendritic structure to uniform cauliflower form. Therefore, sodium lignosulfonate improves the quality and uniformity of the lead deposited during change without any detrimental effect on the cathode. Several lead-acid battery companies such as CSIRO in Australia and Japan’s Furukawa Battery have been the eminent lead-acid battery developers. Ultra-battery demonstrated by All Lead-Acid Battery Consortium, funded by US Department of Energy, is made available in the market in the form of 12 V hybrid LC battery by Civic HONDA HEV (Prengaman and Mirza 2017).

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Lithium-Ion Battery

Lithium-ion battery had been the promising energy storage device since its first availability in commercial scale by SONY Corporation in 1991. There has been a continual development in the properties of lithium-ion battery such as energy density, power density, conductivity, and charge-discharge capacities for its versatility in application. Before its commercial viability, metallic dichalcogenides such as TiS2 and TaS2 were used for charge storage, for example, in 1972, Exxon first developed lithium-ion battery using TaS2 as cathode, lithium as anode, and lithium perchlorate as electrolyte. However, there were safety concerns with lithium perchlorate electrolyte because of its shock sensitiveness; therefore, the lithium-ion battery designed could not be commercialized. Lithium-ion batteries with conventional liquid electrolytes were the first to be on economic scales, with conventional liquid electrolytes being LiMnO4 and LiCoO2. Although with soaring energy densities, such batteries had significantly low-power capacitance. Therefore, lithiumbased electrolytes such as LLTO (Li7La3Zr2O12) and LLZT (Li6.5La3Zr1.5Ta0.5O12) elevated the power density and charge-discharge cycling time along with the energy density. Such lithium alloys have high diffusion coefficients and ionic fluxes which soared up the Li-ion transportation, however lacks maintenance of safer energy storage facilities. This is because of the growth of dendrites perpendicular to the electrodes, due to accumulation of Li-ions in the cracked surface of solid electrolyte layer. These cracks are a result of continuous expansion and contraction of electrodes during the charge-discharge cycles (Tarascon and Armand 2001; Li et al. 2018). In order to overcome such safety issues and to develop high-energy and highpower capacity lithium-ion battery, several organic electrolytes such as ethyl carbonate, dimethyl carbonate, propylene carbonate, and organic polymers such as LiTFSI, LiPF6, and VTES-LiPF6 had been developed. Researchers have also worked on the separator as well as covering materials such that on integration with electrolytes, it will aid in developing battery models with thin shape and that are lightweight apart from being safe, biodegradable, and versatile in application. Such electrolyte and separator symmetries were PAN/PMMA membrane incorporated with N-methyl-N-butyl pyrrolidinium bis(trifluoromethanesulfonyl) imide (Rao et al. 2012) and cellulose nanofibrils with liquid electrolytes (Willgert et al. 2014). Graphite has been the prominent anode material for lithium-ion battery; however silicon, lithium, or intermetallic compounds such as LiNi0.5Mn1.5O4 have been used in order to stabilize the oxidation product over the anode. Nanomaterial such as single-walled carbon nanotube, graphene, has been a better alternative to graphite in terms of charge storing capacities and non-scattering charge mobility (Zheng et al. 2019). The advancement in the materials for electrolytes, anodes, and separators has encouraged the use of lithium-ion batteries in several large-scale as well as smallscale industries, e.g., large-scale industries such as Japan’s Sendai substation with 40 MW/20 MWh of lithium-ion storage and Japan’s Tohuku Minami-Soma substation with 40 MW/40 MWh lithium-ion storage (Abdin and Khalilpour 2018).

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Redox Flow Battery

A redox flow battery is a kind of energy storage system in which electrical energy is converted into electrical energy through redox reaction carrying out at the cathodic as well as anodic side. Unlike lithium-ion batteries, lead-acid battery, or any other battery, redox flow battery does not allow the charge storage at the electrodes; rather, they store the incoming fuels in the form of two dissolved redox pairs which converts into electricity at the electrodes (Wang et al. 2013). The interesting part of this battery is that the electrode material is not taken into consideration, but only in the electrode, the reduction reaction carrying out on the cathode side, as well as the oxidation reaction on the anode side, the electrolytes on their corresponding side are named as catholyte and anolyte, respectively. There several advantages of using redox flow battery over other battery: • Unlike other batteries like lithium-ion battery, lead acid, and sodium-based battery, where electrolyte deposition takes place over the respective electrodes upon cycling, in redox flow batteries, the charge-discharge cycle depends on the reduction and oxidation reaction taking place at the corresponding cathodic and anodic side. • In all batteries, on every charge-discharge cycles, the efficiency of discharge with respect to their corresponding charging is always less than 100%, as some part of efficiency is used up in the form of irreversible capacities, heat loss forms a significant part in the irreversible capacity, and in redox batteries the heat loss is drained out through the electrolytes rather than causing a serious heat dissipation issue as in solid electrolyte batteries. • To improve the current density and energy density of the cell, researchers have come up with various flow field models, where the potential drop created at the flow field pipe increases the flow rate of the electrolytes, therefore affecting the properties abovementioned. These flow field designs are made by molding the pipes into specific directions, as Kumar and Jayanti (2016)) have designed them into serpentine model, parallel model, interdigitated model, and split serpentine model. Moreover, to our knowledge, the cross section as well as the thickness of the fluid flow channel also affects the flow rate of the battery. The different types of redox flow batteries such as zinc-chloride battery, zinc-air battery, zinc-bromide battery, and vanadium redox flow battery are discussed below.

5.2.3.1

Zinc-Chloride Battery

Zinc-chloride battery is one of the various redox flow batteries; similar to all other redox flow batteries, the charge-discharge cycles takes place through the redox reactions carried out at the cathode and anode side. Zinc chloride employs the oxidation of chlorine to chloride ion near the anode and the reduction in the form of zinc plating over the cathode.

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Zinc chloride is of significant importance because of the commercial viability of zinc as compared to other metals like Li and Ni, which is abundant in the earth’s crust. Moreover, it is highly soluble in its electrolyte, which further increases its energy density aiding to rapid diffusion of charges across the battery. The chargedischarge cycles in a zinc chloride take place with electroplating of cathode, in the form of solid electrolyte layer. Although the thickening of solid electrolyte layer supports the rapid diffusion of charges by decreasing the overpotential, it leads to the formation of dendrites over the cathode. These dendrites grow horizontally perpendicular to the direction of electrode, leading to problems like short circuit of cell (Oren and Landau 1982). These issues can be overcome by using solid electrolyte liquid-based lithium-brass/zinc-chloride battery, where brass powder is used as the cathode, lithium as anode, and Li6.4La3Zr1.4Ta0.6O12 as electrolyte. Brass-based cathode leads to continuous alloying and dealloying of zinc-copper, suppressing the continuous zinc electroplating (Liu et al. 2020). However, the polymer electrolytes, like mixture of ethylene carbonate, dimethyl carbonate, and diethyl carbonate in a ratio of 1:1:1, used with some polymers or cellulose fibers would help in strictly constricting with no replacement in the materials for anode and cathode (Winsberg et al. 2016). Some examples is a hybrid-flow battery via zinc foil anode (0.75 M Zn (ClO4)2.6H2O) ethylene carbonate-dimethyl, carbonate-diethyl carbonate (in 1:1:1 ratio) as both anolyte and catholyte and separated by a dialysis membrane (regenerated cellulose, molecular weight cutoff (MWCO) of 1000 g/mol) (Winsberg et al. 2016). A zinc-chloride battery with 6.875 PVDF (polyvinylidene fluoride): ZnCl2:12.5EC (ethylene carbonate):12.5PC (propylene carbonate) as an electrolyte (Udawatte et al. 2018) is an example of other battery.

5.2.3.2

Zinc-Air Battery

Zinc-air batteries were developed for stationary applications, because the materials used in the preparation of zinc-air batteries are abundant in the earth’s crust and such materials have no harmful effect on the environment. These batteries give highenergy density and are expensive to produce. In zinc-air batteries, charge-discharge cycle is carried out by the dissolution of zincate ions into the anolyte (negative electrolyte) while discharging and decomposition of zincate ion as zinc over the anode, while charging, followed by hydrogen evolution at the negative electrode. The properties such as energy density, conductivity, and charge-discharge cycle are decided by zinc electroplating over the air electrodes. Although energy density and conductivity increase on subsequent charge-discharge cycling, the buildup of nonuniform thick zinc layers as dendrites over air electrodes is the main reason for short battery life and circumstances such as short circuiting of the cell (Amunátegui et al. 2018; Zelger et al. 2019). In order to reduce zinc electroplating, researchers worked on developing several surfactants, which would act as corrosion inhibitors in zinc-air batteries. Various types of surfactants such as poly(oxyethylene) nonyl phenyl ether (cationic surfactants), sodium dodecyl sulfate (anionic surfactants) acting as zinc corrosion

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inhibitor, and cetyltriethylammonium bromide (CTAB) and sodium dodecyl benzene sulfonate (SDBS) affected the zinc oxide crystal growth. With this motivation Hosseini et al. (2018) worked on discussing the effects of SDS (anionic surfactant) using KOH electrolyte on the electrochemical behavior of zinc granules and observed that on adding SDS to KOH solution, the intensity of the peak of zinc dissolution shifted to positive potential. Moreover, SDS suppresses the zinc dissolution as well as prevents the transfer of discharged product from the surface to the electrolyte. SDS promotes the formation of zinc oxide directly on the active surface, by migrating the zincate ion toward the electrolyte and transferring hydroxide ion from the electrolyte to the anode surface. Therefore, the passive zinc oxide layer formed over the zinc inhibits the zinc dissolution process (Hosseini et al. 2018).

5.2.3.3

Zinc-Bromide Battery

Similar to zinc-chloride and zinc-air batteries, zinc-bromide battery also shows highenergy density (70 Wh/g) at a less cost rate; the difference remains with the electrolyte used, i.e., in zinc-bromide battery. Zinc bromide is used as an electrolyte rather than metallic zincate (in case of zinc-air battery) and zinc chloride (in case of zinc-chloride battery). The ionic flux created within the battery for charge transportation is because of the electrochemical reaction being carried out in the form of zinc electroplating over the cathode and polybromide phase formation on the anode. However, such systems required two storage tanks as well as two pumps which significantly increased the weight of the system. The experimental energy density shows lower than theoretical energy density. This problem can be overcome by using a single solution for the electrolyte and designing a battery model without any ion exchange membrane. As discussed that there is an electroplating of Zn taking place over the cathode during charge-discharge cycles, this increased the energy density, however affecting the life of the battery as well as causing safety risks (as on repeated buildup of electroplated Zn over the cathode upon continuous cycling led to short circuiting of the cell). However, using single-walled carbon nanotube/multi-walled carbon nanotube as the anode worked onto decreasing the overpotential at the zinc electrode, therefore increasing charge-discharge efficiencies. Munaiah et al. (2014) designed a zinc-bromide battery using cathode made of zinc electrode dipped in a solution containing 1:1 volume ratio of carbon nanotube (CNT) and dimethylformamide (DMF), a catholyte containing a solution of 3 M of zinc bromide solution and N-methyl-N-ethylmorpholinium bromide (MEP) and N-methyl-Nethylpyrrolidinium (MEM) in a 1:1 volume ratio and an anolyte prepared by taking 3 M zinc bromide solution, 1 M zinc chloride, and quaternary ammonium salt (mixture of MEP and MEM (Munaiah et al. 2014)). Moreover to their findings, they also found that the exchange current density of 2Br-/Br2 redox couple using CNT electrode was significantly higher than graphite electrode and boron-doped diamond electrode.

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Vanadium Redox Flow Battery

Increasing in demand of renewable energy sources has led to the subsequent development in the field of redox flow batteries. Among all redox flow batteries, vanadium redox flow battery is promising with the virtues of high-power capacities, tolerances to deep discharge, long life span, and high-energy efficiencies. Vanadium redox flow batteries (VRFBs) employ VO2+/VO2+ on the positive side and V2+/V3+ redox couple for the anolyte. The electrolyte used is VOSO4.xH2O and on using additives the energy density of the cell is increased. Since all the properties such as current density, energy density, and power capacity are dependent on the flow rate of the electrolytes within the VRFB, various flow fields are attached to both sides of the VRFB cell in order to increase uniform flow in the reaction zone. And various flow fields are used in experimentation as well as simulation of VRFB such as serpentine, interdigitated, split serpentine, and parallel flow field (Kumar and Jayanti 2016; Sun et al. 2019; Zhang et al. 2019). Serpentine flow field gives high-power density as compared to other flow field designs, so this can be used for stack design of VRFB also (Kumar and Jayanti 2016). The catholyte and anolyte reaction in VRFB is shown below.

The VRFB technology has reached the commercial stage level. Many companies are supplying up to commercial level of VRFB system such as Sumitomo, UET, Cellstrom, Rongke Power, etc. In Japan, larger VRFB cells with the power capacities such as 4MWh/6MWh has been installed in Subaru wind farm by Sumitomo industries, Japan (Ulaganathan et al. 2015), and 5 MW/20 MWh system in 2017, Ontario IESO, Canada, for smooth power flow for wind and solar energy.

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Sodium-Sulfur Battery

Alkali metals have been found to be the noble materials for energy storage, and this can be attributed to their reactivities. Among all the alkali metals, Na and Li are the promising materials because of their lower densities as compared to other alkali metals. Similar to Li+-ion batteries, Na+-ion batteries show high-energy storage, low cost, and versatility in application. Moreover, the redox potential of Na+-ion is only 0.3 V positive than Li+-ion (i.e., Na+/Na ¼ 2.71 V against Li+/Li ¼ 3.04 V); however, one thing that sets apart the Na+-ion batteries from Li+-ion batteries is their natural abundance. In sodium-sulfur batteries, sodium is used as an anode and sulfur as a cathode. Solid electrolyte, ceramic electrolyte, and polymer electrolyte batteries have been seen to be replacing the conventional liquid electrolytes. This is attributed to the density of the electrolytes which helps in increasing the ionic flux created throughout the battery as well as high diffusion coefficient which aids in faster transport of charges. In addition to that, in ceramic electrolytes, the charge transport takes place through the mobility of ionic point defects. Therefore, Na-S batteries have been found to be the one using ceramic electrolytes and replacing Na+-ion batteries (Hueso et al. 2013). Earlier in the 1970s and 1980s, β-aluminum was found to be the electrolyte for Na-S batteries; nowadays these have been replaced by NASSICON-type, glass, and glass ceramic-type electrolytes. The main problem with ceramic/solid electrolytes is the crack in the electrolyte layer under fatigue stress, generated as a result of repeated expansion and contraction of the electrodes during the charge-discharge cycles. A similar case is in β-aluminum electrolyte wherein the crack of sodium β-aluminum causes the penetration of molten aluminum leading to short circuit of the cell. Therefore, polymer electrolytes have been the better alternative to solid electrolytes as they are safer and maintain higher energy density. Organic liquids such as ethylene carbonate and dimethyl carbonate or polymers like polyethylene oxide and polyvinylidene have been apparently used as polymer electrolytes (Wang et al. 2007). Key companies such as NGK Insulators, Ltd., BASF SE, Tokyo Electric Power Company Holdings, Inc., and FIAMM Group have been using Na-S batteries on a large scale.

5.2.5

Nickel-Cadmium Battery

Apart from storing electrical charges and releasing it in the form of electrical energy, batteries depend on other specific applications such as peak load saving and power density storage. Cadmium is used as the negative electrode and nickel as the cathode in the nickel-cadmium battery. Nickel-cadmium battery is a kind of battery in which carbon dioxide is used for carrying out the diffusion of charges. Carbon dioxide is either absorbed by the electrolyte or used as an additive to the aqueous electrolyte,

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where hydroxide ion is converted into carbonate ion upon CO2 addition. The electrolyte used in nickel-cadmium is mostly alkaline in nature, KOH electrolyte with LiOH as an additive is one kind of alkaline electrolyte that is used in nickelcadmium battery, and 2.2 wt% of LiOH and 1.3 wt% of LiOH are the electrolytes advised by manufacturers for battery installation and regeneration (Pourabdollah 2017). However, carbonate and hydroxide ions are deposited as nonporous layers over the anode, thereby hindering the charge transport leading to reduced battery efficiency. Pourabdollah (2017) worked on developing several additives to KOH electrolyte in the form of κ-formate, κ-acetate, and κ-propionate of which the one with higher conductivity with respect to time is used in order to neutralize the rate of hydroxide formation, and this would lead to better life cycles. To his observation, he found that κ-acetate is the most effective one. Apart from lower cyclability, nickel-cadmium battery is not as energy efficient as lithium-ion and Ni-MH batteries. Cadmium used as an anode in nickel-cadmium battery is a toxic material; therefore, disposing it after complete usage has been found to be an environmentally friendly method rather than recycling it. Several leaching methods have been found to recycle the decomposed cadmium. One of them is VMS method which retraces 99.9% of cadmium in the pure state, and then there is Ausmelt Catalytic Waste Converter which is developed in the USA and the cadmium retraced satisfies the US toxicity leach criteria (Abdul Bashid et al. 2017). During leaching different factors have been found to be having different concentrations of Ni and Cd recovery. One of these factors is adding 10–20% sulfuric acid; on 5 h of leaching, the spent Ni-Cd battery powder recovers 98% Cd and 26% Ni, and on increasing the temperature from 308 K to 318 K, the recovery of Ni increases significantly from 76% to 90% and at higher temperatures such as 363–373 K, the recovery of Ni is 94–99%. Ni-Cd batteries can be commercially recycled at IMNETCO (USA), ACCUREC (Germany), SABNIFE (Sweden), and SNAM-SVAM (France) (Randhawa et al. 2016).

5.2.6

Supercapacitors

With the government’s plan to limit carbon emission, it paved the path for electrical vehicles. Although the alkali-ion batteries such as Li-ion, Li-S, Na-S, or redox flow batteries like Zn-Cl and Zn-Br have been the reliable energy source till now, their time for charging as well as their power density remains quite lower than the fuelbased vehicles. Therefore, electrochemical supercapacitors are used when properties such as high-power density is required. Electrochemical supercapacitors are different from normal capacitors, as in supercapacitor charge storage takes place both electrochemically and electrostatically. Similar to electrochemical batteries, supercapacitors also use two electrodes dipped in an electrolyte; the only difference is that in supercapacitors, these electrodes are highly porous and act as two capacitors. Moreover, there is a buildup of double layer of charge over the electrodes after

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each charge or discharge cycle, and this is attributed to the separate charge layers by electrochemical and electrostatic methods; therefore, these supercapacitors can also be termed as double-layer capacitor. Nanomaterials such as single-walled carbon nanotubes, multi-walled carbon nanotubes, and graphene have been the promising materials for the electrodes of supercapacitors. Ionic liquids such as N-methyl-Nethyl methoxypyrrolidinium bis(trifluoromethanesulfonic) imide and lithium bis (trifluoromethanesulfonic) imide and their combination with ethylene carbonate, dimethyl carbonate and diethyl carbonate, polyvinyl difluoride, and poly-tetrafluoroethylene have been used as the noble electrolytes for the supercapacitors (Frackowiak 2007; Vivekchand et al. 2008). Table 5.1 shows the anode, cathode, and electrolyte used in different types of battery.

5.3 5.3.1

Vanadium Redox Flow Battery System Recent VRFB Installation kW to MW Level

The most effective battery as compared to other batteries is the vanadium redox flow batteries which have been commercialized since the 1980s. It has been found out that there are 26 companies manufacturing VRFBs worldwide, and there are several plants which have installed VRFBs. Some of installed companies like Minami Hayakita in Japan, Fraunhofer ICT in Germany, as well as UniEnergy Technologies, US-WA, are the largest manufacturers of VRFB cells producing 15 MW and 60MWh energy storage systems respectively. Moreover, Rongke Power of China has been a major project till now with 200 MW power and 800MWh energy storage system. On completion of this project, it will stand as the largest electrochemical energy storage plant around the globe (Sánchez-Díez et al. 2021). Some of the major installed plants are listed in Table 5.2. Redox flow batteries are one of the most efficient and promising energy storage technologies. According to their field of application, VRFBs can be divided into various generations. • Application of VRFBs in test plants is considered to be first generation; however, research is conducted for commercialization. • Development in VRB cells for higher power as well as energy density is the second-generation systems. • Advancement in materials and their chemistries for their appeal in smart gridoriented systems is the third-generation systems. With an erratic renewable energy source, VRFBs allow a diversity of progressive operations on an extensive range of timescale, such as power leveling, sag compensation, load leveling, load following, and UPS with main technical and economic benefits. Upcoming high-density systems are even predicted as appropriate for operating electric vehicles (Alotto et al. 2014).

2.75–4.2 V

6V

1V

-1.8 V– 0.8 V

Lithium-ion battery

Lithium-ion battery

Zinc-chloride battery

Zinc-air battery

Polyvinylidene fluoride + zinc chloride + ethylene carbonate + propylene carbonate Sodium dodecyl sulfate

PAN/PMMA incorporated with N-methyl-N-butylpyrrolidinium bis (trimethanesulfonyl) imide 5% methoxy polyethylene glycol (methyl) methacrylate +95% LiPF6

1 M methane sulfonic acid

1.5 M Pb(CH3SO3)2 + 0.9 M (CH3SO3) H

1.9 V

1.7 V

VOSO4.xH2O

1.2 V

VRFB (interdigitated flow field) Lead-acid battery

Lead-acid battery

Electrolyte VOSO4.xH2O

Cell voltage 1.3575 V

Types of battery VRFB (SFF)

Table 5.1 Properties of different types of batteries

Zinc-anode, nickel zincatecathode

Zinc-cathode, graphite-anode

100

15

0.04

0.06

Lithium-cathode, stainless steel-anode Stainless steel electrodes

50

50

100

Lead- cathode, graphiteanode

Lead- cathode, graphiteanode

Vanadium

Anode/cathode material Vanadium

Current density mA/ cm2 60

298 K

298 K

315 K

298 K

333 K

298 K

298 K

Operating temperature 300 K

96%

96%

91%

92%

90%

91%

96%

Efficiency 97.16%

(continued)

Willgert et al. (2014) Udawatte et al. (2018) Hosseini et al. (2018)

References Ali et al. (2020a) Zhang et al. (2019) Pletcher and Wills (2005) Hazza et al. (2004) Rao et al. (2012)

5 Vanadium Redox Flow Batteries for Large-Scale Energy Storage 91

Cell voltage 1.58 V

3.05 V

Types of battery Zinc-bromide battery

Sodium-sulfur batteries

Table 5.1 (continued)

Electrolyte 3 M zinc bromide + mixture of N-methyl-N-ethyl morpholinium bromide and N-methyl-N-ethyl pyrrolidinium bromide (1:1 molar ratio) β-Al2O3 Sodium-cathode, nickel chloride-anode

Anode/cathode material Glassy carbon electrodecathode, single-walled carbon nanotube 0.01

Current density mA/ cm2 10

473 K

Operating temperature 298 K

92%

Efficiency 82%

Hueso et al. (2013)

References Munaiah et al. (2013)

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200 kW 170 kW 1.5 MW 250 kW 500 kW 45 kW 500 kW 250 kW

2000 2001 2001 2001 2001 2001 2003 2003 2004 2005 2010 2015 2016 2017 2017 2021

PacifiCorp by VRB Power

SEI for Electric Power Development Co., Ltd.

Vierakker, the Netherlands, by Cellstrom GmbH Pullman Washington Zhangbei Project San Miguel Substation Ontario IESO Dalian Battery

18 kW 1 MW 2 MW 2 MW 2 MW 200 MW

4 MW

250 kW

Power 200 kW 450 kW

Year 1996 1996

Location Mitsubishi Chemicals at Kashima-Kita Electric Power Sumitomo Electric Industries (SEI) at Tasumi Sub-Station, Kansai electric SEI at Kansai Electric SEI at Hokkaido Electric Power Wind farm SEI in a semiconductor fabrication plant at Tottori Sanyo Electric VRB Power at Stellenbosch University for ESKOM Power Corporation SEI at GwanseiGakuin University SEI at CESI, for R & D about distributed power systems SEI in a High Tech Factory Pinnacle VRB for Hydro Tasmania at Huxley Hill Wind Farm

Table 5.2 Major VRFB plant installed worldwide (Alotto et al. 2014)

100 kWh 4 MWh 8 MWh 8MWh 8MWh 800 MWh

6 MWh

2 MWh

5 MWh 90 kWh 2 MWh 1 MWh

500 kWh

1.6 MWh 1 MW 1.5 MWh

Energy 800 kWh 900 kWh

Load shifting, frequency regulation Smooth power flow from wind and solar Smooth power flow from wind and solar Smooth power flow from wind and solar Peak shaving, grid stabilization

Peak shaving Peak shaving UPS/peak shaving Wind energy storage and diesel fuel replacement Voltage support and rural feeder augmentation Wind energy storage and wind power stabilization

Peak shaving Wind turbine output power stabilization Peak shaving and emergency backup power Peak shaving and UPS backup power

Application Load leveling Peak shaving

Austria USA China USA USA China

Moab, US-UT Japan

Japan Italy Japan King Island

South Africa

Japan Japan Japan

Country Japan Japan

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Comparison of VRFB with Other Battery

The electroplating of electrode has been found to be the main drawback in the field of batteries using conventional electrolytes, solid electrolytes, or ceramic electrolytes. Therefore, organic carbonates such as diethyl carbonate, dimethyl carbonate, and ethylene carbonate and organic polymers such as LiPF6, LiTFSI, etc. are used either as an additive to conventional electrolytes or individually in order to improve the battery chemistries. These drawbacks were a result of high overpotentials created and hence led to the nonporous solid electrolyte layer, characterized by molecular dynamics. However, due to the homogenous distribution of electrolytes, as a result of various flow fields being attached to the cells, the overpotential decreases, thereby preventing the electroplating of electrodes. Therefore, VRFB cells do not require any additive to the electrolyte; hence, they are found to be cheaper than other redox flow batteries discussed in Sect. 5.2.3. Apart from cost, the dendritic growth over electrodes due to electrode electroplating decreases the number of charge-discharge cycles of a battery. After batteries like nickel-cadmium and lithium-ion batteries are being completely used up, several leaching techniques are applied for recycling, because of their toxicity, whereas vanadium redox flow batteries are environmentally friendly energy storage systems. The versatility of VRFB, as its electrical energy can be varied from kWh to multi-MWh and power from kW to multi-MW in a simple model, aids it to be used in renewable integration as well as grid applications, in comparison with other battery technologies. VRFB can be modulated down to 5 kW/10 kW h, with an efficiency of 75–80%, can be left entirely discharged for lengthy times without any side effect, has small maintenance requirement, and has a life cycle as high as 10,000 at 100% depth of charge (Dassisti et al. 2016). Comparison of VRFB with other batteries like Li-ion and lead-acid batteries is tabulated below. Lithium batteries give higher energy or power savings in comparison to VRFBs for every measured system. However, VRFBs have higher efficiency than lithiumion batteries. According to this review, an improvement in efficiency supports economic viability. Moreover, importance rests on the efficiency of partial loading particularly on the discharge of the battery. VRFB is cheaper than other electrochemical energy storage systems. Upon comparing the range of energy and power savings with the slope of the cost curve, it has been found out that costs pertaining to energy savings do not decline. However, without a substantial drop in power-related costs (i.e., a factor of 4 for 2 kW and a factor of 8 for 5 kW), the market for home storage will not be breached significantly. Since the cost of a lithium-ion battery is higher, extra efforts are required to lessen energy- and power-associated costs. However, no energy storage system has been found out which will be economically viable for home storage. Moreover, decreasing system costs are going to improve it further (Uhrig et al. 2016). In other batteries, power as well as energy storage is considered to be a single unit; therefore, they are considered to be inadequate upon dealing with huge volumes of energy. VRFB shows the highest flexibility among the existing technologies.

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Table 5.3 Contrast of VRFB features and other conventional technologies Properties Life span (years) Capacity and power Technology readiness level Depth of discharge Cost (€ kWh-1) Operational risks Life cycle assessment

VRFB 15–20

Lithium-ion 3–5

Lead-acid 4

Unlinked

Linked

Linked

Advanced and optimization

Phase consolidated

Consolidated (economic but obsolete)

100%

80% in 2500 cycles

200–400

120–300

50% in 700 cycles at DOD¼ 80% 600–1000

Fundamentally safe in aqueous electrolyte Eco-friendly, vanadium electrolyte is fully recyclable

Upon crushing, it needs protective circuitry, venting and possible for thermal runaway Little environmental effect

Explosion hazard while in hydrogen evolution Hazardous to the environment, due to the presence of toxic material like lead

Although showing single long-term storing capability, it performs short-term functions that soar up the quality of the power that runs across the battery. VRFB enfolds the power and discharge time therefore leading to a very eloquent area of the so-called discharge time against rated power chart, creating this method available to a more number of electrical system applications. Table 5.3 shows the properties of VRFB in contrast with another two energy storage batteries existing in the market (Dassisti et al. 2016).

5.3.3

Advantage of VRFB with Other Batteries

Vanadium redox flow battery (VRFB) is the most auspicious, commonly researched, and followed redox flow battery technology. The electrolyte storage technique differentiates the redox flow batteries from other electrochemical energy storage technologies. The flow batteries store electrolytes in cathodic and anodic storage tanks added on either side of the battery. Vanadium ions’ different oxidation states (V2+, V3+, VO2+, or V4+and VO2+ or V5+) are present in the storage tank in such a way that there’s a distinct redox couple in each tank. There are several advantages with VRFB technology precisely. Some advantages of VRFB technology include the following: • There is no contamination of vanadium ions present in different storage tanks, as the diffusion is prevented by the membrane present in between.

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• The battery is operated through the reduction and oxidation reactions occurring in the respective storage tanks. • Depending on the operating conditions, the efficiencies are calculated to be quite moderate (i.e., 70–90%). • During quick charge-discharge cycles, lower amounts of gases are evolved. • The electrolyte can be easily recycled. • Membranes are nonporous to the vanadium ions. • Independent generation of variable and energy ratings. • Immediate recharge by swapping of electrolyte. • Efficiencies up to 90% can be achieved. • Longer life cycle (>11,000 and 20 years) without any additive to the electrolyte (i.e., VOSO4.xH2O). • The constant voltage at all charges, equal charge/discharge rates, maintenance cost very low, can be fully discharged, and operates at room temperature (Taylor et al. 2011; Lourenssen et al. 2019). However, this review is successful in showing that the efficiency of VRFB varies widely depending on the battery’s load point. This is perilous to any valuation of the hands-on use of an energy storage system and significantly affects the financial estimation of such a system. Researchers are working on examining the true technical and economic cost of the installation of wind farms powered by all vanadium redox battery systems (Taylor et al. 2011). The all-vanadium redox flow batteries (VRFBs) have taken countless awareness because of benefit correlated to operate the same active electrochemical metal mutually in electrolytes, mainly reduction of competent losses due to contamination of membrane, electrolytes, and electrodes, which are formed by the crossover of species between electrolyte partitions of an electrochemical cell. VOSO4.xH2O is the electrolyte used in VRFB cells with vanadium at different oxidation states at different electrolyte storage tanks, i.e., in V2+/V3+ into negative electrolyte tank and V4+/V5+ (VO2+/VO2+) in the positive one. The subjective ratio between storage capacity and power capacity permits for exceptional flexibility of a flow battery to the proposed use case. The life of a battery can be changed by subsequent addition of more cells or more electrolytes. Moreover, the cost pertaining to the energy density is low. For a large discharge capacity, the expenditure behind the energy storage medium accounts for the marginal cost of vanadium redox flow batteries. The cost of a VRFB cell is influenced by significant cost of preparation for the electrolyte. The specific operational energy density of a VRFB cell is such that there is rational power density; hence, it is lower than the theoretical energy density. Therefore, the cost for the vanadium electrolyte lies in the range of 270 €(kWh)-1 mentioned to the useable capacity (König 2017).

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Table 5.4 Experimental comparison of VRFB cell parameters reported in recent literature

Flow field SFF

Active area (cm2) 25

Flow rate (ml min-1) 180

Current density (mA/cm2) 60

Energy-/ power-based efficiency (%) 97.16

Cell voltage (V) 1.3575

Detached SFF SFF

9

20

100

66.5

25

40

60

95.45

1.35

Rotary SFF

40.96

120

40

86

–

SFF

100

0.3

40

83

1.55

SFF

25

50

990

85

1.7

SFF

420

151

60

84.13

1.8

Hierarchical IFF IFF

40

3

240

83.2

1.75

9

30

50

96

1.4

IFF

410

1000

100

90

1.004

IFF

900

1680

300

–

IFF

400

20

60

83

1.25

IFF

900

806

60

98.31

1.8

References Ali et al. (2020b) Sun et al. (2019) Lee et al. (2019) Lu et al. (2020) Xu et al. (2013) Pichugov et al. (2020) Gundlapalli and Jayanti (2019) Zeng et al. (2019) Sun et al. (2019) Zhang et al. (2019) You et al. (2016) Knudsen et al. (2015) Gundlapalli and Jayanti (2020)

SFF serpentine flow field, IFF interdigitated flow field

5.3.4

Experimental and Modeling Studies

Vanadium redox flow battery (VRFB) is an electrochemical energy storage system that depends on a reversible chemical reaction within an impenetrable electrolyte. Numerous models have been established which now offer a moral understanding of the VRB functioning principles; this knowledge is significant to evaluate its performance when applied in power systems (Ontiveros and Mercado 2014). Some experimental performances on vanadium redox flow batteries are summarized in Table 5.4. Experimental studies can hardly measure maximum component limits which oversee the operation of flow battery. Scientists have designed VRFB of 10 kW and 100 kWh capacities in energy (FB10/100 battery) along with smart controller.

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Fig. 5.2 (a) VRFB with 31 cells and (b) stack performance at 60 mA cm-2 and 90 mA cm-2 (adopted from Park D. J., et al. (2017) with permission)

Wu et al. mentioned a multistage operation method leads to the whole battery performance in contrast to all loads in operation (Wu et al. 2017). Many systems have been advanced as a model VRFB structure with a mixed acid-associated electrolyte shown in Fig. 5.2 for diverse current density load conditions (Park et al. 2017. The 1 kW/1 kWh VRFB system stayed estimated statistically and analytically, carried beyond 1.1 kW at 15–85% SoC with an energy efficacy of 82%. A lesser principal cost and a basic system proposal had conveyed with mixed acid electrolytes (Kim et al. 2013). The work reported by Bryans, the 200 kW/400 kWh VRFB setup located at Martigny (Switzerland), had been investigated to check its optimal data. The overall efficiency was obtained 48–60% and they concluded that this battery would be suitable for the charging of electric vehicles (Bryans et al. 2018). Guarnieri et al. (2018) have accomplished an overall experimental performance of a VRFB test capacity of industrial scale, which involves a 40-cell stack of 600 cm2 space to supply 4 kW and two tanks with 550 L of vanadium solution. The obtained results were of an ultimate power of 8.9 kW along with a stack specific power of 77 W/kg and a high current density of 665 mA/cm2 (Guarnieri et al. 2018). Recent report by Trovò has utilized a facility to improve battery management system (BMS) as a valued device for regulation and evaluation of VRFB (Trovò 2020). A VRFB stack comprising 31 cells with an electrode area of 2714 cm2 was developed

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by Park et al. (2017). The setup had been subjected to different current densities of 60 and 90 mA/cm2 to meet for electric storing with higher efficiency (Park et al. 2017). Hence, developing an extensive relation of pressure losses and electrochemical reaction rate with the help of proper studying the flow field distribution will definitely lead a timely commercialization of VRFBs. The two important parameters to obtain lower overpotential and maximum efficiency are electrolyte equal distribution and pressure drop which establish a proper stack configuration. Differentiating various patterns for identical flow rate needs to be observed, as performance of matching outline has significant alterations when studying it at dissimilar flow rates. The common electrode like graphite felt (GF) has meager wettability effects with electrolyte solution, and developing new and improved electrode material is underway. Hence, a surface pre-treatment is usually applied to reach sufficient hydrophilic surface. Nowadays, computational fluid dynamics (CFD) technique is a proven convenient technology to generate possible mathematical models for optimization of energy schemes related to redox flow batteries, which collective with demanding experiments convey valuable information regarding the performance of intended flow field arrangement. CFD allow to go through several important constraints (such as flow rate, flow circulation through channels and electrodes, pressure drop, and charge-discharge states) to advance the performance and generation of VRFBs. An optimal expenditure price for redox flow battery systems means that in coming years VRFBs have the capability to be one of the best cost-efficient energy storage system technologies (Aramendla et al. 2020). In this article, a software model of a VRFB system capable of showing a wide range of applications is offered. MATLAB™ Simulink environment was used to establish the battery model depending on the outcomes which were attained through experiments with a profitable 10 kW VRFB unit. The model enhances a unit of VRFB to signify numerous system sizes through a modular battery method. Using this model, the optimum quantity of modules for specific power levels with charging and discharging operations was evaluated. In addition, the reliance on the system efficiency as well as on the state of charge of battery was explained in parallel to a common bus, connecting the power electronics components such as the rectifier and inverter that are essential for converting AC to DC and vice versa. Two tanks are situated at the bottom of the stack container for the catholyte and an anolyte of VRFB, and 2500 L of electrolytic fluid is present in the tank. Because battery functioning is dependent on the temperature, smart temperature controllers are attached to the battery in order to maintain the temperature of the battery between 20 to 30 ∘ C for maintaining smooth battery operation. In order to create more accurate conditions, most of the implemented measurements were not based on total charge-discharge cycles, but somewhat on short cycles at diverse SOCs. Charge-discharge cycles for 1 hour were performed state of charges of 75%, 60%, 40%, and 20% in several fixed power values typically ranging from 2 to 10 kW.

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Furthermore, some wide-ranging discharge runs within the operating range (15–90% SOC) with constant power values were evaluated (Turker et al. 2013). On the basis of experimental data, a megawatt-scale VRFB software model was designed in MATLAB™ Simulink environment. Custom MATLAB™ script is used to import the matrix form of Simulink model. It calculates the energy efficiency and ranges in which theoretical MW scale of VRFB operates for an optimal design, and it does not consider further aspects such as component deprivation, ease of structure, and ease of maintenance of a large-scale system. For computing an optimized battery model, the following steps were undertaken: • Step 1: Parameters like highest discharging power as well as number of modules are defined by users. • Step 2: Model sets the charging power to the same value as the demanded discharging power in step 1. • Step 3: Operation ranges and string efficiency table that are attained through VRFB characterization are considered to be input parameters. • Step 4: The number of strings/modules can be determined by dividing the extreme discharging power by the number of modules and the trivial power of a Cell-Cube string (2 kW). • Step 5: The battery operates at well-defined range, i.e., the product of the no. of strings along with operational range of strings. Operational ranges of precise SOC are taken as in Cell-Cube. • Step 6: State of charge and precise power alignment are certain from a formerly distinct grid covering the entire operating range of the battery. • Step 7: Power requirement as well as equivalent effectiveness on each of the online string is determined for each probable numbers of virtual modules. • Step 8: The best quantity of modules for any specific power alignment and SOC selected in step 6 is decided because the least quantity of online modules that could provide a performance lies inside 5% of the height feasible performance value. • Step 9: Repetition of steps 6–8 covers the complete working variety of the battery. Using this set of rules which is programmed in MATLAB™, battery structures with diverse nominal strength ranges have been modeled and evaluated. Numerous charging/discharging cycles were carried out at diverse operating conditions of VRFB unit developed by Cellstrom GmbH. Values attained for the round-experience efficiencies are in right phrases with the values suggested inside the literature. Experimental results tell us about the solid correlation between power, SOC, and total efficiency. Driving losses look difficult at very low-power levels (Produktionstechnik 2014).

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101

Challenges in the Integration of VRFB System with Energy Generation System

Vanadium-based battery technology has driven great interest worldwide, but it has not accomplished a genuine breakthrough; thus, research and development programs are required to achieve profitable potential (Alotto et al. 2014). The primary challenge in the integration of VRFB is to enhance its commercialization rate which typically includes capital expenses related to electrolyte tracing as well as galvanic battery production. Some institutional-level challenges comprise efficacy acceptance, development, scrutiny skills, as well as the prenotion of risk associated with the nonappearance of reliability estimates of universally accepted batteries along with enhanced maintenance expense. Renewable energy system has come into utilization leaving behind the conversion based on fossil fuels, which signifies the existence and enhancement of potential marketplace for ESS (Kear et al. 2012). Considering vanadium-based battery systems, it is very evident that advancement is in progress in PRoC in order to decrease the cost of electrolyte, and electrode procedures of redox flow batteries have been amended to the fact in which system competencies of 70–80% would be predicted from kW to MW scales (Shigematsu 2019). Aiming at the improvement of electrode activity, compacted systems having greater energy and power densities would go with the alternative of nonaqueous electrolyte solutions which tends to the possibility of expanding the range of temperature and nanocomposite electrodes tend to attain increased operative electroactive superficial area along with enhanced exchange current density jo (Alotto et al. 2014). In the current scenario, VRFB is proved as the most prominent energy storage system, but there are still a lot of challenges ahead which precisely include high technology expense, thermal precipitation in the electrolyte, inadequate energy/ power densities, and the degradation that will befall inside the cell from the severe atmosphere formed by the vanadium species and sulfuric acid. Enhancement in the system came from enhanced electrolyte structures as well as more operative materials for the electrode, membrane, and bipolar plate. Dropping parasitic as well as resistive losses is vital for preserving high efficacies and confirming the usage of VRFBs in commercial applications (Lourenssen et al. 2019). Many recent research plans are working which aim to lower the cost and size of vanadium-based battery systems to let them compete commercially (Kear et al. 2012).

5.5

Energy Storage Coupled to Energy Generation

Awareness about the improvement of approaches related to energy deposits has tremendously increased worldwide as energy creation inclination toward renewable sources of energy. An inclusive topic like renewable energy has been a significant

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part of ecological and management science. Nowadays, the photovoltaic system has drawn major attention and has undergone great evolution (Cucchiella et al. 2018). Sustainable energy sources infrequently generate steady and instant power output in accordance with the continually mutable power grid requirement. The utmost demanding method to address this problem is altering the current energy source into a long-term storage system to achieve successful distribution along the grid in a precise manner. Low costs and reliable energy storage systems are required for the consumption of intermittent renewable energy sources. Out of diverse electrochemical storage systems in terms of energy, the most profound and auspicious battery system is redox flow batteries having the capability of self-regulating storage capacity and power production competency with localization suppleness, rich productivity, low rescale expense, and exceptionally extended charging/discharging period with metal ions which are commonly used as reacting entities (Alotto et al. 2014). In order to serve the motive of developing the most effective sustainable energysaving system, vanadium redox flow batteries play a significant role and have been seen as one of the most effective practices. Photovoltaic systems tend to erratic energy generation in the presence of favorable climate conditions which further results in a decrement in production level in comparison with existing renewable resources. Current analysis briefly confers the present necessity of renewable energy creation coupled with energy storage (Lourenssen et al. 2019). Significant energy demands are prevailing over the generation along with the need for less fossil fuel utilization. In the past era, natural and industrial activities have grown to a great extent by maintaining a co-relation and balance simultaneously. The electrical energy mandate surpasses 20 × 103 TWh/year and is budding at a percentage of approximately 3% per year. During this interval, fossil fuels have been a foremost energy basis, attaining 66% of the entire electrical energy generation. These statistics has given free rein to a powerful energy dependency of the civilization to such sort of resources, and as a result, many significant environmental effluent-related complications are prevailing in the society. To come out with a solution to this problem, prodigious alternatives are found to generate clean sources of energy independent of all kinds of contaminants. The most promising alternatives to establish a prodigious agreement of applications related to the use of photovoltaic panels and wind turbines are solar and wind energy (López-Vizcaíno et al. 2017).

5.5.1

Solar PV System

Renewable electrical energy is generated by solar PV energy utilizing conversion through the sun. A noteworthy evolution has been noticed in recent years which shows PV systems achieve greater than 402 GW of the current installed systems in 2017. Approximately 77% of power/energy installation worldwide is covered by countries like China (131.1 GW), the USA (51 GW), Japan (49 GW), Germany (42.4 GW), Italy (19.7 GW), and India (18.3 GW). VRFB including solar PV systems is

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one of the promising substitutes to comprehensive and competent power storage and alteration (Alotto et al. 2014). The economic viability of photovoltaic system is conveniently related to individual utilization in an industrialized market along with the subsequent ESS which proves to be as a resolution of this part. However, because of stringent powering voltage necessities of vanadium-based batteries (1.4 to 1.7 V), common photo-batteries, inducing ordinary PV with retrograde photovoltage, are not supposed to be fully charged bias-free, i.e., they should emphasize on utilization of reasonable sun energy or at less current concentrations. On comparison with lithium-ion batteries, vanadium redox flow batteries are more advantageous as they are an eminent source of power storage and conversion: • Structure flexibility: Generally, vanadium redox flow batteries give the advantage of power output decoupling, although it is calculated by the number of cells and electrochemical cell dimensions. Electrolyte characteristics like volume and vanadium content are very useful in the alteration of batteries’ energy storage capacity. In contrast to other batteries, VRBF becomes more convenient for largescale applications. • Robust action: Due to the presence of alike elements in anolyte and catholyte, VRFB resolves the problem of cross-contamination, while lengthy operations tend to infer instant retort-time with less self-discharge and a long life span. • Higher energy density: VRFB operates at high cell potential (>1.4 V) along with the ability to achieve higher power densities in comparison to aq. ROS. Among the vanadium-based batteries driven by solar system as stated, no comprehensive system of charging is being accomplished because of inadequate photovoltage given by the applied solar system like in CdS-driven systems and specifically at unusable lower vanadium concentrations (0.01 M) and less current densities ( 100 ∘ C), resulting in ascending low-density lipoprotein (LDL) and free fatty acid (FFA) levels in oil (Mansir et al. 2017; Awogbemi et al. 2019). Jain and Sharma (2010) reported that heating and other food processing activities alter the percentage of SFAs in cooking oil, significantly increasing the amount of cis-unsaturated fatty acids (Jain and Sharma 2010). WCO with a higher FFA content has low oxidation stability (Jain and Sharma 2010). Unlike SFA, USFA contains at least one double bond in its carbon backbone, which affects the physiochemical properties of the FA when compared to its SFA counterpart. USFA can be monounsaturated fatty acids (MUFA) (where the fatty acid molecule consists of only single double bond in the carbon chain) or polyunsaturated fatty acids (PUFA) (where the fatty acid molecule consists of multiple (two or more) double bonds in the carbon chain). The number of double bonds in USFA affects its chemical reactivity, which increases with the number of double bonds (Awogbemi et al. 2019). Hellier et al. (2015) investigated the fatty acid makeup of seven oils, including palm and sunflower oil. They observed that whereas palm oil consists of between 40% and 47% of palmitic acid and between 36% and 44% of oleic acid, sunflower oil contains between 49 and 57% of linoleic acid and 14–40% of oleic acids. Both Vingering et al. (2010) and Hellier et al. (2015) stated that palm oil has a density of 910 kg/m3 and dynamic viscosity of 19.4 mPas at 20 ∘ C, respectively, and sunflower oil has a density of 916.9 kg/m3 and dynamic viscosity of 17.2 mPas at 59.7 ∘ C. While food is cooked (e.g., fried), heated oil is absorbed by the food, and the food’s compounds dissolve in the heated oil. Because of the numerous physical and

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chemical changes during food processing, used cooking oil contains a higher concentration of FFA. Pikula et al. (2019) classified used cooking oils into two clusters based on their FFA content: yellow fat and brown fat where the brown fat contains more than 15% FFA and water, while yellow fat consists of a lower amount. The literature indicates that the chemical composition of WCO is nearly identical to that of its parent oil but may vary slightly due to derivatives formed during the decomposition and leaching of the oil product (Awogbemi et al. 2019; Mannu et al. 2019a). During frying, vegetable oil undergoes numerous physiochemical transformations that alter its properties, mainly the FA profile. The denaturing process may depend on the cooking duration, cooking or frying temperature, type of food that is fried or cooked, type of oil or fat that is used to cook or fry foods, and other ingredients that are added to food or oil (Panadare and Rathod 2016; Chebet et al. 2016; Mannu et al. 2020). Additionally, many volatile compounds are generated during deep-frying by oxidation and other transformations. Higher frying temperatures and atmospheric air promote a greater oxidation ability (Saguy and Dana 2003; Ziaiifar et al. 2008; Mannu et al. 2019a). Furthermore, exposure to food and tools during frying promotes oil degradation, leaching, and enrichment with metals, spices that are used for food seasoning, and other organic and inorganic compounds used in food preparation (Saguy and Dana 2003; Mannu et al. 2020). According to Mannu et al. (2019c), alkane chemicals like heptane (C7H16), octane (C8H18), and butylcyclopentane (C9H18) can be generated as by-products of the vegetable oil pyrolysis process,. Also, it has been recorded that WCO is derived from peanut oil, consisting of terpenes such as camphene and limonene. Terpenes are a class of organic compounds that consists of natural compounds with the chemical formulation of (C5H8)n. The availability of terpenes may derive from spices or flavoring agents that are used for food seasoning. Furan is another common compound recorded in WCO. Furan derivatives, such as 5-hydroxylmethylfurfural (5-HMF), pyrazines, and 2-pentyl-pyridine-ethenyl are the consequence of chemical interaction between amino acids and reducing sugars that gives browned food its characteristic flavor, commonly known as the Maillard reaction (Wang et al. 2021). WCO contains a variety of volatile chemicals, such as aldehydes, ketones, heterocycles, dienes, alcohols, etc. Mannu et al. (2019a) investigated the composition of oil before and following several frying cycles. It is found that the composition of numerous chemical compounds derived from furan, terpenes, etc. get varied with the frying cycle. Kumar and Negi (2015) have compared the fatty acid composition of vegetable oil before and after repeated use. They concluded that repeated use of cooking oil alters the composition and results in the formation of a number of chemical derivatives, including hydrocarbons, glycerides, etc. Therefore, the use of cooking oil repeatedly, especially for frying, is unfit for human consumption and environmental disposal. According to the literature, changes in the physiochemical properties of the oil (such as pH, density, viscosity, and molecular weight) during the frying process can attribute to contamination and decomposition of food and tools (Table 7.1).

– – 5.96

– 5.34

– – 6.34

– 7.38

8.63

Mastered oil Olive oil Palm oil

Soybean Sunflower oil

Sunfoil

6.14

–

–

919.6

917.8 919.21

916.2 910.2 919.98

910.2

919.8

922 920.4

886.9 – 910.74

–

Density Before Aftera 919.72 913.4

Value may be different from the frying food type Before means oil before use and after means WCO

a

Aftera 5.13

pH Before 6.39

Oil type Depot margarine Groundnut oil

28.224

– 28.74

38.78 55.7 27.962

55.7

43.521

– 31.381

85.68 103.8 42.5905

103.8

Viscosity Before Aftera 29.334 38.407

Table 7.1 Properties of oil before and after processing foods

98.9 121.8 –

–

– – 44.1

81.8

129.4 126.9

92 – 50.8

99.1

Iodine Value Before Aftera – –

119.91

– 690.82

– 887.5 535.08

–

55.18

– 51.94

– – 464.645

–

Molecular weight Before Aftera 562.87 586.05

Das et al. (2013); Sahasrabudhe et al. (2017) Prakash and Yadav (2020) Sahasrabudhe et al. (2017) Chebet et al. (2016); Awogbemi et al. (2019) Sahasrabudhe et al. (2017) Chebet et al. (2016); Awogbemi et al. (2019) Awogbemi et al. (2019)

Referece Awogbemi et al. (2019)

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According to Awogbemi et al. (2019), the oil content changes according to the meal types: fish, chips, and sausages. The obtained results showed that the initial fatty acid composition was completely get altered after the frying process. In the beginning, palm oil contains 12.2% of SFA, 11.45% of MUFA, and 76.25% of PUFA, respectively. After frying fish and chips, the composition was changed to 93% SFA and 7% MUFA. In contrast, after frying chips and sausages, the composition changed to 80% SFA and 20% MUFA, with no PUFA being identified. Moreover, Knothe and Steidley (2009) investigated the fatty acid profiles, viscosity, and acidity of the cooking oil before and after the cooking process where oil was collected from 16 restaurants. They discovered that high-temperature frying modifies the frying oil’s fingerprints via hydrogenation and oxidative degradation processes and results in the changes in the oil’s fatty acid profile and changing the SFA and MUFA to PUFA ratio. Therefore, finally, biodiesel prepared from feedstock which are having different compositions result in biodiesel products with different properties and different FAME compositions. Banani et al. (2015) determined the fatty acid composition of edible vegetable oil after repeated heating at high temperatures using GCMS. The obtained results included 29.83% of oleic acid, 28.85% of linoleic acid, 15.86% of palmitic acid, 4.87% of stearic acid, and 2.49% of linolenic acid, and the density was determined to be 910 kg/m3 at 15 ∘ C, and the kinematic viscosity to be 23.12 cSt. Exposure to the higher temperatures results in higher levels of hydrocarbon and glyceride derivatives, and the composition would be unpredictable due to the many interactions that result in compounds with weak C–H bonds such as unstable intermediate hydrocarbons (Awogbemi et al. 2019; Cherif et al. 2019; Tsoutsos et al. 2019). Additionally, a prolonged increase in the peroxide value enabled water to act as a weak nucleophile for ester linkage. In contrast, thermal oxidation is exacerbated by heat mass transfer and resulted in the generation of oxygen (Awogbemi et al. 2019).

7.1.5.1

Pollution of the Environment, Groundwater, and Surface Water as a Result of Discarded Cooking Oil

Once disposed of in the sewage system or at a landfill, the copious frying oil waste will wreak havoc on the ecosystem (Jain and Sharma 2010; Putra et al. 2018). Inadequate WCO disposal results in many biological, environmental, and municipal problems, including blockage of drainage systems and water treatment facilities (Singh-Ackbarali et al. 2017). According to the literature, even 1 l of waste cooking oil can pollute up to one million gallons of water (Nata et al. 2017). Due to the liquid form of WCO, it is easily absorbed by groundwater from dumping sites and surface water after rain. However, being the final destination of wastewater, restaurant disposals, and residential drainage affect aquatic ecosystems directly or indirectly. Eutrophication can develop as a result of microbes, phytoplankton, and algae utilizing the WCO as a food source, according to Singh-Ackbarali et al. (2017).

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The development of rancid odors is one of the most significant problems connected with WCOs. The pungent odor associated with WCOs is due to their chemical makeup, specifically the volatile component (Singh-Ackbarali et al. 2017; Mannu et al. 2019a). WCO is made of ketones, aldehydes, and fatty acids that are soluble in water influencing both flora and fauna, including people. It is toxic to wildlife when it covers them and damages aquatic life and ecosystems when oxygen levels in polluted water bodies such as rivers and lakes are depleted (Nata et al. 2017; Singh-Ackbarali et al. 2017). Apart from that, the fall in dissolved oxygen levels and subsequent mortality of aquatic plants and animals are caused by the oil coating that develops on bodies of water, blocking sunlight from reaching aquatic plants and so stifling photosynthesis (Singh-Ackbarali et al. 2017).

7.1.5.2

Toxicity of Waste Oil on the Environment

According to the EPA (2015), petroleum oil, vegetable oils, and animal fats share similar physical properties and have comparable environmental effects, as documented in the literature. Specific chemical components of WCO, such as 1-heptane, cis-9-hexadecenal, and i-propyl-14-methyl-pentadecanoate, are highly toxic and poisonous to aquatic life, resulting in reproductive and respiratory impairments (Putra et al. 2018). According to Singh-Ackbarali et al. (2017), when WCO contaminates the upper soil surface, it forms a thin layer that isolates the soil from air and water, resulting in the death of soil inhabitants such as earthworms and bacteria necessary for plant regeneration. Numerous scientists argue that coating animal skins or fur with oil impair animals’ thermal regulation. It has been recorded that WCO is used in animal feed preparation, but much of the literature provides evidence for the unacceptability of the WCO due to the alterations and other reactions that occurred during the frying processes. Although the pre-treatments could be applied prior to utilizing WCO for animal feed, the harmful chemical components such as dioxins and poly-aromatic hydrocarbons (PAHs) are quite stable and cannot be removed via filtering, resulting in adverse health effects on animals (Wee et al. 2016; Tsai 2019).

7.2

Use of Used Cooking Oil for Biodiesel Production

The economic viability of biodiesel can be enhanced by substituting low-cost, low-quality alternatives for conventional biodiesel feedstock such as plant oil and animal fat (Mansir et al. 2017). Efforts to create new sustainable techniques for recycling and managing waste cooking oil (WCO) have accelerated dramatically in recent decades (Degfie et al. 2019; Mannu et al. 2019b). The manufacture of biodiesel by WCO is ecologically beneficial since it recycles wasted cooking oil and creates renewable energy with little pollution. It removes the need to import

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certain types of petrochemical oil and also lowers waste management expenses. Biodiesel manufacturing from used cooking oil has three advantages: economical, environmental, and waste management (Mansir et al. 2017; Degfie et al. 2019). Cooking oil leftovers, food waste, cleaning residues, and animal fat waste all contribute to the comparatively low cost of biodiesel and are frequently employed on an industrial scale. Yellow fats (FFA 15%) are a common source of biodiesel after filtering and purification (Pikula et al. 2019). While WCO looks to be good fuel for the synthesis of biodiesel, its composition remains unknown. Numerous researches on different elements of biodiesel production for direct injection into diesel engines have been done. The majority of present problems relate to increased production costs, which remain more remarkable than those of petrodiesel due to the significant cost of the feedstock. Used cooking oil collected from large-scale or medium-scale food industries such as restaurants, food processing plants, and small-scale fast-food or street food preparing places has been recognized as possible feedstock that functions as a successful alternative for conventional plant oil and other animal fat by lowering the total cost of biodiesel manufacturing while also successfully managing waste cooking oil disposal concerns (Jain and Sharma 2010; Borah et al. 2019). Additionally, the utilization of WCO for biodiesel production reduces improper WCO disposal, produces an additional income, reduces drainage blocking, and reduces oil-based land and water pollution (Prafulla et al. 2012; Awogbemi et al. 2019). Not all WCOs are feasible to be employed in the manufacture of biodiesel or other fuels. According to available statistics, in 2015 the WCO-based biodiesel production was 11.92 million tons and 26.62 million tons for the European Union and the rest of the world, respectively (UFOP 2017). Typically, the treatment of collected waste cooking oils begins with coarse filtering to remove suspended particles. Following that, crude material is directly introduced into production as raw material without extra processing stages. Depending on the use, the WCO raw material may undergo several, including transesterification, processes. Though WCO seems like an ideal feedstock for biodiesel, the oil deterioration occurred due to the higher temperature and other transformations that occurred during the frying process, WCO possesses higher oxidative stability and higher saturation point. Those factors directly affect the final biodiesel product that increases the fuel properties such as kinematic viscosity, cloud point, and cetane number compared to conventional feedstock-based biodiesel.

7.2.1

Transesterification of Waste Cooking Oil

Due to the esterification of WCO, glycerol can be utilized in place of methanol and ethanol. In this scenario, the process is referred to as glycerolysis (Mansir et al. 2017). By turning the waste’s free fatty acids (FFAs) into added-value compounds, glycerolysis may be utilized to improve the added value of starting materials (WCO).

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Other than biodiesel, monoglycerides and diglycerides can be utilized as surfactants or emulsifiers in various sectors such as pharmaceutical, food, and cosmetics (Zhang et al. 2003; Kombe 2015; Madusanka and Manage 2018b; Liu et al. 2020). Biodiesel is categorized under the bio-based fuel that is composed of ester formations of fatty acids that are derived from oil or fat, or fatty acid methyl esters (FAMEs) (Fregolente et al. 2012). Catalysts are defined broadly as any material or substance that accelerates a chemical process by lowering its activation energy (Mansir et al. 2017). The two most often utilized catalyst types in the transesterification process are chemical catalysts and biocatalysts. Apart from that, several articles abstract physical techniques, but their commercial applicability remains disputed.

7.2.1.1

Chemical Catalysts

Chemical catalysts are classified as homogeneous or heterogeneous, with homogeneous materials and mixtures having the same uniform composition and properties throughout the system, while heterogeneous materials and mixtures are having neither the uniform composition nor uniform properties.

Homogeneous Catalysts The most often utilized homogeneous catalysts for biodiesel synthesis are alkali metal hydroxides and alkoxides such as KOH, NaOH, sodium methoxide (CH3ONa), and potassium methoxide (CH3OK) (Mansir et al. 2017; Putra et al. 2018). However, it is difficult to recover a homogeneous strong acid following the reaction. Purification prior to employing the catalyst is expensive since the catalyst separation procedure from the biodiesel is complicated (Wang et al. 2021). Catalysts are not recyclable and are frequently disposed of in the sewage system. This, without a doubt, contributes to the environmental crisis (Putra et al. 2018; Chen and Wang 2019). If the oil has a high concentration of FFAs, it can be converted to biodiesel using an acid catalyst-based esterification; that common acid catalysts include sulfuric acid (H2SO4), hydrochloric acid (HCl), or phosphoric acid (HPO3). However, the acid esterification of FFA takes a prolonged reaction time and creates a significant acidic wastewater amount during the process (Muanruksa et al. 2020). However, homogeneous catalysts are incompatible with manufacturing biodiesel from WCO since they are developed with food-grade oils (palm oil, soybean oil, etc.), making biodiesel production prohibitively costly. Additionally, homogeneous catalysts cause separation problems following the reaction, necessitating regular water washing, which wastes a considerable quantity of water and pollutes the environment by generating acid water (Mansir et al. 2017).

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Heterogeneous Catalysts The attention on the development of heterogeneous catalysts for WCO-based biodiesel production has increased due to their superior properties, including environmental friendliness, ease of catalyst separation, and reusability (Borah et al. 2019). Solid acid catalysis is a significant economic and ecological field of study in catalysis. There are numerous advantages to solid acid catalysts over liquid acid catalysts. As a result, the substitution of heterogeneous catalysts takes additional attention, since heterogeneous acid catalysts seem a sufficient alternative over the traditional homogeneous catalyst in biodiesel production (Mansir et al. 2017; Nata et al. 2017). Solid acid catalysts can be used as a stable and efficient alternative to traditional catalysts in biodiesel production. Solid catalysts exist in a phase distinct from the reaction medium and thus facilitate their separation from the post-reaction mixture (Mansir et al. 2017; Nata et al. 2017). Physical separation of heterogeneous catalysts from the reaction mixture was successful using either filtration or centrifugation. Numerous solid catalysts in nanoscale form have been reported, including Sr3Al2O6 (Rashtizadeh et al. 2014), CaO/Au nanoparticles (Bet-Moushoul et al. 2016), hydrotalcite particles (Deng et al. 2011), amorphous nano-alumina powders (Amini et al. 2013), and sodium titanate nanotubes doped with potassium (Hernández-Hipólito et al. 2015). Calcium oxide (CaO) is a common solid catalyst used to transesterify a variety of feedstocks into biodiesel (Asikin-Mijan et al. 2017; Putra et al. 2018; Degfie et al. 2019). Additionally, natural sources such as eggshells (Viriya-empikul et al. 2009; Mansir et al. 2017), oyster exoskeletons (Nakatani et al. 2009), and shrimp exoskeletons (Yang et al. 2009) have been used to prepare catalysts. Additionally, animal bones can be a significant source. The primary component of bone is calcium phosphate, which can be converted to hydroxyapatite, which has a relatively high catalytic activity, is chemically and thermally stable, and thus can be used effectively in the production of biodiesel (Quina et al. 2017; Borah et al. 2019; Khan et al. 2020). In this regard, waste eggshells may be a viable candidate for use as a low-cost catalyst for biodiesel production. Eggshell waste contains a high concentration of calcium as CaCO3 that can be easily converted into calcium oxide (CaO) through high-temperature calcination. Ninety-four percent of CaCO3 is found in eggshell waste. Additionally, CaO is a low-cost, noncorrosive, and environmentally friendly material that can be recycled and repurposed for additional transesterification. These benefits have prompted numerous researchers to conduct further research on CaO to enhance its overall properties. The catalytic efficiency of heterogeneous catalysts directly depends on the effective surface area of the solid particulates (Jacobson et al. 2008). Both Kouzu et al. (2008) and Niju et al. (2014) reported that CaO has a lower surface area (3–13 m2/g) and chemical integration of silica with CaO overcomes the problem. Some recent studies used CaO/SiO2 as the catalyst, but commercial raw materials and edible oil that they used have increased the cost of production (Samart et al. 2010; Putra et al. 2018; Chen and Wang 2019; Farid et al. 2020). Khan et al. (2020) obtained the CaO source from animal bones obtained from a restaurant and

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stated that similar catalytic efficiency was obtained compared to eggshells. Sukasem and Manophan (2017) reported that an 84.1% yield of biodiesel was obtained by using lime (Ca(OH)2) catalyst. Li et al. (2015) worked on interesting research in producing biodiesel by using carbide slag waste as the catalysts for transesterification and could obtain yields of 91% and 76.4% from soybeans and WCO, respectively. However, compared to homogeneous catalysts, the major disadvantage of heterogeneous catalysts is their lack of or limited catalytic activity. The lack of active sites required to catalyze the transformations can be overcome through mechanical support such as stirring. Apart from that, heterogeneous catalysts require some preparatory steps during their synthesis, which are typically lengthy. Biodiesel would be more expensive due to the high cost of the raw materials required to synthesize these catalysts. Additionally, when exposed to the surrounding atmospheric medium, poisoning of the catalysts’ catalytic active sites may impair their stability and activity (Mansir et al. 2017).

Mixed Catalysts Patil et al. (2010) used a combination of homogeneous and heterogeneous catalysts to perform transesterification and esterification reactions. However, Patil et al. (2010) reported that the difficulty of the separation process could not be overcome and it is not feasible for commercial biodiesel production as well.

7.2.1.2

Biocatalysts

Lipases are considered biocatalysts because they can catalyze both transesterification and esterification of fatty acids in an acidic medium (Badoei-dalfard et al. 2019; Muanruksa et al. 2020). However, there are drawbacks to enzymatic biodiesel production, including high costs, poor stability, and a longer reaction time. Thus, lipase immobilization on a hydrophilic substrate is critical for increasing lipase stability, and immobilization has a variety of advantages since it protects lipase from the reaction with media, changes pH, and fluctuates temperature and shear stress; it also aids in the preservation of the enzyme’s catalytic activity by providing substrates’ easy access to the active region (Urrutia et al. 2018; Oliveira et al. 2019). Alginate, a type of biomacropolymer, is widely used for enzyme immobilization through entrapment due to its biocompatibility, biodegradability, and nontoxic properties (İnal et al. 2017). Muanruksa et al. (2020) reported that gelatine and pectin are associated with alginate that has a great ability to immobile lipase and converts WCO into biodiesel in more than 75%. Generally, four types of immobilization are employed: (1) entrapment, (2) physical adsorption, (3) covalent bonding to the support material, and (4) intermolecular cross-linkage with enzyme molecules (Fernandez-Arrojo et al. 2013; Zhao et al. 2015).

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D. A. T. Madusanka and M. M. Pathmalal

Challenges in Biodiesel Production Using WCO

While producing biodiesel from WCO appears technically feasible, numerous practical obstacles may arise, necessitating biodiesel production from alternative feedstocks.

7.2.2.1

The Amount of Water in Feedstock

Most oils are hydrophobic and insoluble in water (miscibility may vary with the temperature). Free, emulsified, and soluble water is found in biodiesel and diesel fuels. Water solubility depends on temperature and composition (Fregolente et al. 2015; Liu et al. 2020). After using oil, its properties change. The polar and nonpolar chemical composition of WCO varies, allowing for a more significant percentage of water to dissolve than in virgin oil (Jain and Sharma 2010). Thus, water can be incorporated during the manufacturing, transportation, and storage of biodiesel or feedstock. As a result of the hygroscopic nature, biodiesel is able to absorb moisture than fossil fuel and making it significantly more hydrophilic than conventional diesel by having ester bonds. According to the specifications given by ASTM D D6751, the maximum allowed moisture in biodiesel is 500 ppm (Fregolente et al. 2012). Water is used to wash away catalysts, soap, and traces of glycerol during the biodiesel manufacturing process (Fregolente et al. 2015). Following biodiesel production, the water content is reduced to less than 500 ppm by heating the moisture contained biodiesel at 50 ∘ C for a few hours, which consumes energy and increases the production cost (Fregolente et al. 2012). However, even though biodiesel meets limitations for the specified moisture content after the production, water absorption may occur during storage causing microbial growth in storage tanks (Fregolente et al. 2015). This may result in several problems during storage and operation phases: corrosion of metals (notably iron and steel), formation of sludge and slime blocking fuel lines, and clogging of vehicle fuel filters, resulting in fuel injection system damage (Fregolente et al. 2012; Goncalves et al. 2021). Other than heating to remove moisture from biodiesel products, water-absorbing chemicals are also used as alternatives (Fregolente et al. 2012; Muanruksa et al. 2020; Goncalves et al. 2021). Common water-absorbing compounds include hydrogel and anhydrous chemicals.

Hydrogels Hydrogels are three-dimensional networks of hydrophilic polymer chains that have a high capacity for absorbing and retaining water. The extent to which microgel particles swell is a unique property. Their properties make them advantageous in various fields, including oil recovery, molecular separation, environmentally

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sensitive display devices, and biomedical and pharmaceutical applications (Fregolente et al. 2012; Fregolente et al. 2015).

Anhydrous Chemical Compounds It is chemically feasible and self-evident that anhydrous chemical compounds can be used to remove water from the feedstock or finished products. For example, Khan et al. (2020) and Atadashi et al. (2012) used anhydrous Na2SO4 to remove water from the final product. In contrast, Vijay Kumar et al. (2019) and Rial et al. (2020) used anhydrous calcium chloride (CaCl2) and anhydrous magnesium sulfate (MgSO4), respectively. While anhydrous chemical compounds may improve the quality of the feedstock or final product, they may increase production costs. However, anhydrous chemicals can be reused by removing the water content through heating; this will incur additional costs.

7.2.2.2

Waste Catalyst Generation

Biodiesel is produced using homogeneous base catalysts such as sodium hydroxide and potassium hydroxide (Putra et al. 2018). Purification before using the catalyst is costly due to the complexity of the catalyst separation process from the biodiesel (Wang et al. 2021; Putra et al. 2018). Catalysts cannot be recycled and are typically disposed of in the sewage system. This undoubtedly causes an environmental issue (Chen and Wang 2019), which can be solved by using a heterogeneous catalyst in the transesterification reaction of biodiesel production, as has been extensively developed in recent years by a large number of researchers (Nata et al. 2017; Chen and Wang 2019; Wang et al. 2021).

7.2.2.3

Soap Production Occurs During the Transesterification Process

Soap production occurs during the transesterification process. The acidity index of WCO, as described by Mannu et al. (2020), is also chemically significant because it influences the rate of collateral hydrolysis of triacylglycerols during basic esterification (saponification) (Maddikeri et al. 2012). The presence of water in WCOs also aids in the formation of soap. As a result, WCOs are frequently subjected to water removal procedures before being sold to biodiesel producers (Mannu et al. 2020). This factor significantly restricts the process of converting WCO to biodiesel via base-catalyzed transesterification. Commercially available crude oils and fats and waste cooking oil contain a significant amount of free fatty acids (FFA), which react with the alkaline catalyst to form saponified products during base-catalyzed transesterification, which also requires extensive product purification. Not only does saponification consume the alkali catalyst, but the resulting soaps may form emulsions, posing difficulties in the downstream recovery and purification of the

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biodiesel. Given that the FFA content of WCO exceeds 2.0% (w/w), it is prudent to reduce the FFA content via esterification using methanol and an acid catalyst. Saponification is a significant issue for industries because emulsion formation is difficult to concentrate commercially (i.e., biodiesel plants) (Banerjee and Chakraborty 2009). Thus, only oil phases with a low FFA content (less than 0.5% w/w) can be subject to base alkali-catalyzed transesterification to produce biodiesel (Jain and Sharma 2010).

7.3

Additional Uses of WCO

Apart from biodiesel production, recycled WCO is most frequently used to make biolubricants (Hamze et al. 2015; Mannu et al. 2019b), animal feed (Salemdeeb et al. 2017), and direct combustion energy production (Mannu et al. 2019a) or as a fuel additive (Namoco Jr et al. 2017). Mono- and diglycerides, FFA, sterols, and fat-soluble vitamins are common in trace amounts in WCO. Thus, oils and fats are considered as essential components of an animal’s diet since they provide both energy and some vital ingredients that animals cannot synthesize. It appeared as though WCO was repurposed as animal feed additives in this manner (Van Ruth et al. 2010). Apart from that increment of the thermo-oxidative stability of WCO by lowering unsaturated and hydroxyl groups and treating for viscosity, WCO also accounts for biolubricant synthesis (Paul et al. 2018; Sarno et al. 2019; Orjuela and Clark 2020). WCO derivatives, specifically the methyl ester sulfonates, are utilized to manufacture liquid detergents because the sulfonate adds polar moieties to the fatty acid methyl esters, transforming them into surfactants (Orjuela and Clark 2020; Pradhan et al. 2020). Additionally, recent applications of recycled WCO (Mannu et al. 2019a) include the manufacture of environmentally friendly and biodegradable solvents (Mannu et al. 2019c), the application of recycled WCO as an additive in bio-asphalts and bio-concrete (Sun et al. 2017; Asli et al. 2012), and the use of recycled WCO as a nonacid (Lhuissier et al. 2018). Apart from the abovementioned applications, WCO is used as mercury sorbent devices as well (Mannu et al. 2019b, c). WCO also can be used directly for heating purposes, as a source of energy for boilers or heaters (heating value for WCO—approx. 9000 kcal/kg) comparable to fuel oils (Wang 2002). Tsai (2019) stated that WCO can be used for municipal solid waste (MSW) incinerators as fuel. Making soap is one of the simplest ways to utilize WCO. It is composed of fatty acids generated from oil or fat and a hydroxide base (Na or K) (Sanaguano-Salguero et al. 2018). Additionally, the WCO-based soap can be used to degrease and clean a range of surfaces. The saponification reaction in the presence of alkali hydroxide is the basis for this method of soap manufacture (i.e., sodium or potassium hydroxide). WCO must be filtered before production to remove harmful and unpleasant odorous compounds (Sanaguano-Salguero et al. 2018). Recently, WCO was identified as a

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raw material for the manufacture of plasticizers. Plasticizers are essential polymer additives used in the production of plastics, rubber, and adhesives. Syngas can be burned directly or be further processed using the Fischer–Tropsch method to produce additional compounds (Jia et al. 2018; Greco et al. 2017). It may be turned into liquid hydrocarbons such as diesel and kerosene and dimethyl ether (DME). Thermal cracking was used to cleave the long-chain fatty acids in the WCO at the C–C link, yielding short-chain fatty acids that were reformatted to create H2, CO, and CO2. These conditions favor the water–gas shift reaction between CO and H2O, which results in the formation of CO2 and H2 and the dehydrogenation of saturated molecules to yield H2 (Nanda et al. 2016) (Youssef et al. 2011).

7.4

Conclusion

Food-grade vegetable oils used in food are significantly expensive, and feedstock accounts for more than 60% of the overall cost of producing biodiesel. WCO is being investigated as a sustainable, nonedible feedstock for the production of biodiesel due to its abundance and cost-effectiveness. However, WCO is a valuable raw material for various uses, including bioenergy, lubricants, and soap. While it appears that WCO is a direct source for the synthesis of biodiesel, numerous factors should be considered when scaling up a commercial biodiesel plant. Biodiesel production has water issues, mainly when low-quality raw materials such as WCO are used, which contain a higher concentration of water and FFAs. Because the composition of WCO is unpredictable, it is necessary to model proper refinement and transesterification before production to overcome the challenges. To be sustainable, WCO transformation technologies must be updated. Nevertheless, technological advancements, both in terms of processes and materials, aimed to recycle WCOs efficiently and sustainably, are gaining significant attention especially with the energy crisis and emerging green concepts.

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Sun D, Sun G, Du Y, Zhu X, Lu T, Pang Q, Shi S, Dai Z (2017) Evaluation of optimized bio-asphalt containing high content waste cooking oil residues. Fuel 202:529–540. https://doi.org/10.1016/ j.fuel.2017.04.069 Tsai WT (2019) Mandatory recycling of waste cooking oil from residential and commercial sectors in Taiwan. Resources 8(1):38. https://doi.org/10.3390/resources8010038 Tsoutsos T, Tournaki S, Gkouskos Z, Paraíba O, Giglio F, García PQ, Braga J, Adrianos H, Filice M (2019) Quality characteristics of biodiesel produced from used cooking oil in southern Europe. ChemEngineering 3(1):19. https://doi.org/10.3390/chemengineering3010019 Tye CT (2020) Recent advances in waste cooking oil management and applications for sustainable environment. In: Handbook of research on resource management for pollution and waste treatment, pp 47–63. https://doi.org/10.4018/978-1-7998-0369-0.ch003 Union zur Förderung von Oel- und Proteinpflanzen (UFOP) (2017) UFOP supply report 2016/ 2017. https://www.ufop.de/ Urrutia P, Arrieta R, Alvarez L, Cardenas C, Mesa M, Wilson L (2018) Immobilization of lipases in hydrophobic chitosan for selective hydrolysis of fish oil: the impact of support functionalization on lipase activity, selectivity and stability. Int J Biol Macromol 108:674–686. https://doi.org/10. 1016/j.ijbiomac.2017.12.062 Van Ruth SM, Rozijn M, Koot A, Garcia RP, Van der Kamp H, Codony R (2010) Authentication of feeding fats: classification of animal fats, fish oils and recycled cooking oils. Anim Feed Sci Technol 155(1):65–73. https://doi.org/10.1016/j.anifeedsci.2009.09.016 Vijay Kumar M, Veeresh Babu A, Ravi Kumar P (2019) Producing biodiesel from crude Mahua oil by two steps of transesterification process. Aust J Mech Eng 17(1):2–7. https://doi.org/10.1080/ 14484846.2017.1412243 Vingering N, Oseredczuk M, du Chaffaut L, Ireland J, Ledoux M (2010) Fatty acid composition of commercial vegetable oils from the French market analysed using a long highly polar column. Oléagineux Corps Gras Lipides 17(3):185–192. https://doi.org/10.1051/ocl.2010.0309 Viriya-empikul N, Charinpanitkul T, Sano N, Soottitantawat A, Kikuchi T, Faungnawakij K, Tanthapanichakoon W (2009) Effect of preparation variables on morphology and anatase– brookite phase transition in sonication assisted hydrothermal reaction for synthesis of titanate nanostructures. Mater Chem Phys 118(1):254–258. https://doi.org/10.1016/j.biortech.2009.12. 079 Wang T (2002) Soybean oil. In: Gunstone FD (ed) Vegetable oils in food technology: composition, properties, and uses. CRC Press, Boca Raton, FL, pp 18–58 Wang Z, Cai R, Yang X, Gao Z, Yuan Y, Yue T (2021) Changes in aroma components and potential Maillard reaction products during the stir-frying of pork slices. Food Control 123:107855. https://doi.org/10.1016/j.foodcont.2020.107855 Wee HM, Budiman SD, Su LC, Chang M, Chen R (2016) Responsible supply chain management— an analysis of Taiwanese gutter oil scandal using the theory of constraint. Int J Log Res Appl 19 (5):380–394. https://doi.org/10.1080/13675567.2015.1090964 Weerasinghe WMLI, Madusanka DAT, Manage PM (2021) Isolation and identification of cellulase producing and sugar fermenting bacteria for second-generation bioethanol production. Int J Renew Energy Dev 10(4):699–711. https://doi.org/10.14710/ijred.2021.35527 Yang L, Zhang A, Zheng X (2009) Shrimp shell catalyst for biodiesel production. Energy Fuel 23 (8):3859–3865. https://doi.org/10.1021/ef900273y Youssef EA, Nakhla G, Charpentier PA (2011) Oleic acid gasification over supported metal catalysts in supercritical water: hydrogen production and product distribution. Int J Hydrog Energy 36(8):4830–4842. https://doi.org/10.1016/j.ijhydene.2011.01.116

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Chapter 8

Low-Cost Biomass Adsorbents for Arsenic Removal from Wastewater Dan Bahadur Pal, Amit Kumar Tiwari, Shraddha Awasthi, Sumit Kumar Jana, and Nirupama Prasad

Abstract Arsenic (As) contamination in groundwater has become a global problem, as it is highly toxic and poses serious risk to human health and wildlife. To cope up with this, extensive studies have been carried out for the removal of As from the contaminated water. This chapter presents an overview on different technologies developed for the removal of As from wastewater. Common technologies usually used to remove As include oxidation, coagulation-filtration, membrane separation, adsorption (activated alumina, bioadsorbents, iron-based sorbents, iron, indigenous filters, metal organic frameworks, and miscellaneous sorbents), and biological tools (such as plants for phytoremediation and to some extent microorganisms). Among all the methods, application of low-cost adsorbent (biomass) is gaining special interest and replaced expensive methods of removing arsenic from the wastewater. Biomass especially agricultural waste is a highly efficient and renewable source in the removal of arsenic. In addition, these biomasses can be modified for better efficiency and improving its application. Keywords Arsenic · Biomass · Bioadsorbent · Heavy metal · Adsorption

D. B. Pal Department of Chemical Engineering, Birla Institute of Technology, Mesra, Ranchi, Jharkhand, India Department of Chemical Engineering, Harcourt Butler Technical University, Kanpur, Uttar Pradesh, India A. K. Tiwari · S. K. Jana Department of Chemical Engineering, Birla Institute of Technology, Mesra, Ranchi, Jharkhand, India S. Awasthi Department of Environmental science, Motilal Nehru College(E), University of Delhi, Delhi, India N. Prasad (*) Department of Chemical Engineering, Birsa Institute of Technology Sindri, Dhanbad, Jharkhand, India © The Author(s), under exclusive license to Springer Nature Singapore Pte Ltd. 2023 D. B. Pal (ed.), Recent Technologies for Waste to Clean Energy and its Utilization, Clean Energy Production Technologies, https://doi.org/10.1007/978-981-19-3784-2_8

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8.1

D. B. Pal et al.

Introduction

Depletion of safe and potable water is the one of the major global challenges. The contamination of groundwater by arsenic (As) is a severe problem in many countries, like Bangladesh, India, China, Argentina, Pakistan, Germany, Mexico, Nepal, etc. As is recognized as one of the environmental pollutants which has adverse effect on human and marine lives. Highly contaminated groundwater is having adverse effect on the users who rely on it as a primary source. If As-contaminated water is utilized for irrigation, then it will also pollute the soil. Thus, supply of arsenic-free water is a global problem (Yadav et al. 2021). As is a naturally occurring ubiquitous element present abundantly in the earth’s crust in the form of oxides or sulfides or salts of metals (such as iron, copper, sodium, calcium, etc.). As has 33 atomic number, 74.9 g/mol atomic weight, 5.73 g/cm3 specific gravity, 614 ∘ C boiling point, and 817 ∘ C melting point. It is a crystalline solid of silver-gray color which is hard and breakable (Yin et al. 2017; Zakhar et al. 2018). As has metalloid properties and is a highly mobilized element. As also is mainly mobilized in the environment through water. As is utilized in various fields such as agriculture, medicine, electronics, and process industries, and these anthropogenic sources release large amount of As to the environment. Mobility of As is mainly dependent on the parent mineral form, its oxidation state, and its mobilizing mechanism. In the environment, arsenic is found in arsenite (As(III)), arsenate (As(V)), arsenic (As(0)), and arsine (As(III)) forms. Among these forms, inorganic arsenite (As(III)) and arsenate (As(V)) are the most common which are found in groundwater. As(V) is stable and predominates in oxidizing environment, whereas As(III) predominates in reducing conditions. As (III) is considered as more toxic and mobile than As(V) (Basha et al. 2008; Prasad et al. 2013). Although arsenic and compounds containing arsenic have various implementations, majority of the arsenic compounds are prohibited because of their detrimental impacts. Humans get exposed to these poisonous components largely by the consumption of arsenic pollutant liquids (Chung et al. 2014). According to WHO, arsenic is a Group 1 human carcinogen and has the most complicated metabolism; thus, it is the copious and efficient carcinogen for human race (Van Halem et al. 2009). This is because most of the arsenic compounds get readily dissolved in water (Wang and Mulligan 2006). In aqueous medium, arsenic pollutant occurs from natural as well as from anthropogenic resources. The human generating sources comprise of the sewage discharges through various process industries such as wool and cotton industries, glass industries, ceramics industries, semiconductor industries, pesticide industries, chemical manufacturing industries, etc. (Song and Gallegos-Garcia 2014). Arsenic has adversely affected the groundwater in Indian countries like Bangladesh and West Bengal, India (Chakraborti et al. 2010). Population relies on groundwater for water supply in both countries. Approximately 79.9 and 42.7 million people are exposed to arsenic-contaminated groundwater in Bangladesh and India, respectively, with the contamination concentration of about 50 μg/L (Chen et al. 2009). Many researchers have reported that the

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155

concentration of arsenic in some of the tube wells in Bangladesh is as high as 4730 μg/L (Chakraborti et al. 2010). In many developing countries, many peoples are drinking highly As-contaminated (up to 3500 μg/l) groundwater. Given the toxic and carcinogenic effect of As, the World Health Organization (WHO) and Environmental Protection Agency (EPA) have recommended the maximum contaminant limit (MCL) of As in drinking water to be 10 μg/l (de Souza et al. 2019). Various different methods have been developed for the As removal from the wastewater. All the technologies are dependent on the chemical and physical characteristics of the As compound in wastewater. As is most effectively removed or stabilized if it is present in an arsenate (As(V) form. Thus, As removal techniques are considered to be more efficient they follows the two-step approach. In first step, arsenite is oxidized to arsenate followed by the technique for the arsenate removal (Sullivan et al. 2010; Mosaferi et al. 2014; Babaee et al. 2018). Common technologies usually used to remove As include oxidation (oxidation and filtration, photochemical oxidation, photocatalytic oxidation, biological oxidation, and in situ oxidation), coagulation-filtration, ion exchange, membrane separation (microfiltration, ultrafiltration, nanofiltration, and reverse osmosis), adsorption (activated alumina, iron-based sorbents, zerovalent iron, indigenous filters, metal organic frameworks, and miscellaneous sorbents) (Giri et al. 2022; Tiwari et al. 2022; Pal et al. 2017; Ruidas and Pal 2022), and biological tools (such as plants for phytoremediation and to some extent microorganisms) (Ahmad et al. 2017). For the general population, the cost of As removal treatment should be reasonable. As removal techniques should be properly understood and implemented so that contamination from one area should not migrate to another area (Alka et al. 2021). Thus, it is important to understand more about arsenic properties like its chemical form, types, reaction mechanism, solubility, and toxicity. The aim of the present chapter is to provide general overview on the different As removal techniques.

8.2

Conventional Methods

In the recent years, there has been tremendous research that happens in the field of As removal from the environment. Most of the research has been done in the laboratory and the field. The approaches that are presently used are oxidation, coagulation-filtration, ion exchange, membrane separation, adsorption, and phytoremediation. These methods are useful in the removal of As in both soil and water. Each method has some advantages and disadvantages which are discussed in this chapter. Tables 8.1 and 8.2 showed the various oxidants for arsenic removal with different parameters and various coagulants utilized for the removal of arsenic from wastewater and groundwater and its different parameters.

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Table 8.1 Summary of various oxidants for arsenic removal with different parameters Arsenic concentration (μg/L) Greater than 300 μg/L

Source of pollutants Deionized water

Oxidants Cl2

pH 8.3

ClO2

8.12

50 μg/L

Groundwater

NH2Cl

8.12

50 μg/L

Groundwater

KMnO4

8.12

50 μg/L

Groundwater

Photocatalytic oxidation (UV/H2O2)

8

100 μg/L

Groundwater

Biological oxidation

–

–

–

In situ oxidation

–

–

Groundwater

8.2.1

Outcomes and conditions Cl2 completely oxidized As(III) to As (V) at the stoichiometric rate of 0.99 mg Cl2/mg As(III) ClO2 oxidized 86% of As(III) to As(V) in 1 hr. This result was attributed to the occurrence of a few metals in the wastewater that might activate the catalysis of As(III) NH2Cl oxidized 60% of As(III) to As(V) in 18 h KMnO4 completely oxidized As(III) to As (V) in 1 min Combination of H2O2 and UV radiation showed good As(III) oxidation and oxidation further improved with the increase in UV dose. With the UV dose of 2000 mJ/cm2, 85% of As(III) oxidation was observed Chemoautotrophic arsenite (CAOs) a oxidizing bacteria oxidized As(III) to As (V) with the O2 Oxygenated water helps to decrease arsenic composition to 70 μm) microalgae such as Spirulina. The sedimentation of algae depends upon size, density temperature, time, and type of microalgae. To speed up the settling process, a centrifugation process is usually applied. The advantage of centrifugation process is that it doesn’t require any additive agent to separate microalgae. Though the centrifuge process is very effective, it includes high energy and maintenance cost. The high shear and gravitational forces can damage microalgal structure. The most common centrifuge employed in algal harvesting are scroll centrifuge, decanter, and specially designed hydro cyclones with consideration that microalgae are sticky in nature and hard to move from one point to another.

9.5.1.4

Biomass Filtration

The conventional filtration process is the most appropriate and traditional method that has high recovery efficiency for harvesting relatively large (>70 μm) microalgae such as Coelastrum and Spirulina. It suitable to use small-size algae such as Scenedesmus, Dunaliella, and Chlorella as they result in a gelatinous layer on the filter medium, also causing plugging of the filters. Conventional filtration operates under pressure or suction, and filtration aids such as diatomaceous earth or cellulose can be used to improve efficiency. The most common convention filters are screening, micro-strainers, vacuum operated, and pressure-based type. For harvest of smaller algal cells ( Mont-K-10 > Mont-Al) gives highest selectivity of 33% toward diand 4% toward tri-tert-butyl glycerol ethers with complete glycerol conversion. It is active for DTBGE and TTBGE production despite its reduced surface area. With a t-butanol/glycerol molar ratio of 20 and a catalyst loading of 0.250 g, the effect of reaction temperature on glycerol conversion and product selectivity was examined over the range of 60 ∘ C–150 ∘ C (27.17 wt percent). At the lowest temperature of 60 ∘ C, the etherification was substantially slower, resulting in a moderate glycerol conversion (34%). Before reaching equilibrium, the conversion of glycerol and the selectivity of products increased as the temperature rose. At 110 ∘ C, the greatest glycerol conversion was attained. The selectivity of TTBG increased from 0% to 7%, and the selectivity of DTBG increased from 0% to 22% when the reaction temperature was increased from 60 to 150 ∘ C.

11.13.2

Catalyst Screening for Esterification Reaction Catalysts

The catalyst’s efficiency was assessed in terms of glycerol conversion and triacetin selectivity. With complete glycerol conversion, the PVP-DTP catalyst demonstrated the maximum selectivity of 54% and 34% toward di- and triacetin, respectively. This could be due to DTP’s good acidic properties and its assimilation into PVP. The different solid acid catalysts used for etherification of glycerol are shown in Table 11.1, and esterification of glycerol is shown in Table 11.2.

11.14

Experimental Procedure: Glycerol Etherification with Tert-Butyl Alcohol

0.92 g glycerol and 14.82 g tert-butyl alcohol were added in a round bottom flask (100 mL capacity) which was attached with reflux condenser and then heated to the preferred temperature for 10 mins to extract initial sample. After this, 0.250 g of required catalyst was added with it and then kept at 110 ∘ C for 6 h to complete the reaction. Thereafter, sample was cooled to room temperature (25 ∘ C). The amount of the reaction was calculated by separating the liquid sample and analyzed by gas chromatography at specific intervals of time by gas chromatogram (Model: Varian 3600) having a stationary phase of polyethylene glycol and FID detector by using HP-FFAP (capillary column).

Catalyst OC OC (0.5)100 OC (0.5)100Mw OC (2)100 OC (2)100 OC (2)100 OC (2)100Mw OC (2)100Mw OC (2)100Mw OC (2)150Mw OC (2)100-Mw OC (5)100 OC (5)100Mw SiO2 PrSO3H Ti SiO2 PrSO3H Ti SiO2 PrSO3H TiO2-SiPr-SO3H TiO2-SO3H SiO2-SO3H (AC) 0 0 0 (AC)-S (AC)RH-S A-15 Graphite (GO) (GO)-S (GO)RH-S 1:4

5

7.5

130

90

0.25

G/TBA ratio 4

Reaction circumstances Catalyst loading Temperature (wt%) [OC] 75 5

600

30

Reaction time [min] 15

Table 11.1 Different solid acid catalysts used for etherification of glycerol

XG 0 31 77 55 82 84 84 45 82 71 66 70 74 93 16 78 19 24 93 0 35 31 64 0 19 50 73

Selectivity (%) (DTBGE +TTBGE) 0 18 28 10 27 20 26 20 26 25 24 23 27 52 9 30 10 20 53 0 20 14 25 0 0 22 29 Miranda et al. (2019)

Aguado-Deblas et al. (2020)

References Estevez et al. (2020)

234 S. B. Magar et al.

[H-NMP] [HSO4] [H-NEP] [HSO4] [Et3NH] [HSO4] [Pr3NH] [HSO4] [Oct3NH] [HSO4] Sulfuric acid Bentonite Amberlyst-15 Blank HY HZSM- 5 Beta h-Beta A-15 A-36 A-15 A-35 A-15 (dry) A-35(dry) A-15 A-119 p-toluenesulphonic Acid 10% DTP/SiO2 20% DTP/SiO2 30% DTP/SiO2 50% DTP/SiO2 BNT DTP 10%DTPBNT

2

5

5

5

4 7.5 7.5

7.5

1

3

100

75

75

82

90 60 90

60

90

110

6 8 8

– – 1:4

1:20

1:2 360

5

8

8

–

4

24

15

30

0.25

4

0.16

15 15 13 10 22 34 12

96 86 50.2 68.6 100 5.9 89

99 99 97.3 98.1 97.9 99.4 50.9 90.4 47.4 9 4 27 77 63

16 68 40 39 48 11 0

60.3 55.2 55.4 52.9 60.1 63.3 21.3 43.0 0.0 13 1 18 35 8 7 22 20 28.5 24.2 81 2.2 47

Biomass Conversion: Production of Oxygenated Fuel Additives (continued)

Magar et al. (2017) and Subhash et al. (2021)

Behr and Obendorf (2002)

Klepacova et al. (2005)

Klepacova et al. (2006)

Chang et al. (2014)

Roze et al. (2013)

Gonzalez et al. (2014)

Estevez et al. (2017)

Keogh et al. (2019)

11 235

20% DTPBNT 30%DTPBNT 40% DTPBNT 60%DTPBNT Mont-Al-pillared Mont-K-10 Mont KSF/O

Catalyst

Reaction circumstances Catalyst loading Temperature (wt%) [OC]

Table 11.1 (continued) G/TBA ratio

Reaction time [min] 32 14 60 21 86 93 96

XG 0 2 12 17 0 9 16

Selectivity (%) (DTBGE +TTBGE) References

236 S. B. Magar et al.

Catalyst Amberlyst-15 K-10 Niobic acid HZSM-5 HUSY HPW Ag1PW Ag2PW Ag3PW Blank ZSM-5 Amberlyst-15 Amberlyst-30 MoO3/ZrO2 WO3/ZrO2 Nb2O5/ZrO2 SO42-/ZrO2 Cs2.5PW Amberlyst-15 HZSM-5 HUSY Blank Amberlyst-35 SO42- -WZr (1:3)-500 Zr (3:1)500 Zr (1:1)500

Gly/AA ratio 1:3

1:10

1:9 1:9 1:9 1:9 1:6 2.3:1

Reaction circumstances Catalyst Temp. loading (∘ C) 150 0.25 g

1

– – – – – 0.023 g

120

110 110 110 110 105 100 120 120 120 270 270 270 270 240 240

15

Reaction time (min) 30

Table 11.2 Different solid acid catalysts used for esterification of glycerol XG (%) 97 96 30 30 14 70.3 96.8 82.5 75.7 21.3 22.9 33.8 39.8 25.6 23.1 24.7 25.5 32.4 97 86 78 73 99 66 100 100 100

Selectivity (%) Monoacetin Diacetin 31 54 44 49 83 – 83 10 79 14 37.7 59.3 46.4 48.4 43.4 52.7 37.1 59.7 16.3 83.5 14.8 83.8 32.0 65.8 37.7 60.3 28.3 70.7 35.5 63.6 15.5 83.1 15.3 83.3 27.7 72.2 – 48 – 26 – 21 – 14 – – 14 46 58 35 53 36 60 36 Triacetin 13 5 – – – 3.0 5.2 3.9 3.2 0.2 1.4 2.2 2.0 1.0 0.9 1.4 1.4 0.1 46 8 6 2 26 0.6 4 5 3

Biomass Conversion: Production of Oxygenated Fuel Additives (continued)

Lei et al. (2019)

Zhou et al. (2013)

Zhu et al. (2013)

References Goncalves et al. (2008)

11 237

Zr (1:1)600 Zr (1:1)700 Zr (1:1)800 SO42- -WBlank 1% Y/SBA-3 2%Y/SBA-3 2.5%Y/SBA-3 3%Y/SBA-3 3.5%Y/SBA-3 1%Y/SBA-3(Im) 3%Y/SBA-3 (Im) γ- Al2O3 Cu/ γ- Al2O3 Ni/γ- Al2O3 2 M SO42-/ γ- Al2O3 4.8 M SO42-/ γAl2O3 [H-NMP] [HSO4] [H-NEP] [HSO4] [Et3NH] [HSO4] [Pr3NH] [HSO4] [Oct3NH] [HSO4] Sulfuric acid Bentonite Amberlyst-15 Blank

Catalyst

Table 11.2 (continued)

1:8

–

0.250 g

2%

120 120 120 100 110

110

100

0.16

1:9

Gly/AA ratio

Reaction circumstances Catalyst Temp. loading (∘ C)

30

300

180

Reaction time (min)

99 99 97.3 98.1 97.9 99.4 50.9 90.4 47.4

100 100 100 63 31 76 79 87 97 86 91 96 82 84 97 97 97

XG (%)

18.9 21.3 5.1 6.4 11.5 24.7 2.4 8.1 0.0 60.3 55.2 55.4 52.9 60.1 63.3 21.3 43.0 0.0 20.8 23.4 39.5 40.7 28.4 12 76.3 48.8 100

Triacetin 3 3 4 0.5 5 5 17 30 56 51 38 41 2 2 3 23 18

56 49 41 12 52 8 12 28 25 29 51 47 27 27 28 50 49

36 36 33 45 43 75 71 42 19 20 21 12 – – – – –

Selectivity (%) Monoacetin Diacetin

Keogh et al. (2019)

Rane et al. (2016)

Khayoon et al. (2014)

References

238 S. B. Magar et al.

PVP-DTP PVP-STA PVP-PMA Mont.KSF 10% BNT 20%DTP/BNT 30%DTP/BNT 60%DTP/BNT KP10 Blank 10% DTP/MCM-41 20% DTP/MCM41 30% DTP/MCM-41 50% DTP/MCM41 100 100 100 99 100 100 100 100 100 85 100 100 100 63

13 20 11 15 8 17 10 4 5 49 14 16 16 65

54 47 43 49 56 63 60 41 45 47 55 54 52 33

34 17 28 28 35 19 30 54 50 5 31 30 33 2

Magar et al. (2020)

11 Biomass Conversion: Production of Oxygenated Fuel Additives 239

240

11.15

S. B. Magar et al.

Experimental Procedure: Glycerol Esterification with Acetic Acid

Esterification of glycerol was conducted with acetic acid in a 100 ml flask (round bottom) fitted with the reflux condenser. In the esterification process, the substrate ratio was 1:20 in which 0.92 g glycerol and 12 g acetic acid were added, then the mixture was heated up to preferred temperature (10 min) to extract the initial sample. After that, 0.250 g of catalyst was added and kept at 110 ∘ C for 6 h to perform the reaction. Then sample was cooled up to ambient temperature (25 ∘ C). This setup consists of magnetic stirrer, rotary evaporator, three-necked round bottom flask, reflux condenser, oil bath, and digital thermostat to carry the various runs. The reaction procedure with specific reaction conditions described in past literature (Rode et al. 2009) is used for production of glycerol ethers and esters. The amount of reaction process was estimated by extraction and filtration of liquid samples at precise time intervals, and then obtained samples were examined by gas chromatography using GC.

11.16

Summary

On the basis of review of available literature and our own finding, it is found that etherification with tert-butanol and esterification with acetic acid may successfully occur if process is conducted with the solid acid catalyst. The catalyst required for the reaction could be prepared after impregnation of heteropoly acids on a porous support system, for the reason that heteropoly acids are highly acidic in nature; therefore, the presence of heteropoly acids can enhance the number and strength of acidic sites in the support system. Mont.KSF/O, PVP-DTP, and 20% DTP/SiO2 were chosen as an excellent catalyst, which were prepared using impregnation method. The catalyst samples were characterized, and better dispersion of heteropoly acid on support material was observed after impregnation. Mont-KSF/O actively catalyzed the etherification reaction among the screened catalysts due to its greatest acidity as determined by NH3-TPD (Mont-KSF/O > Mont-K10 > Mont-Al). It was active for DTBGE and TTBGE production despite its reduced surface area (MontKSF/O Mont-K10 Mont-Al). Temperature, molar ratio (glycerol/TBA), catalyst loading, and reaction duration were all studied to optimize the process. It was discovered that increasing the temperature had a substantial impact on glycerol conversion and the generation of DTBGE. With a 1:20 molar ratio of glycerol/ TBA and 0.250 g (27.17 wt percent) of catalyst loading, almost full glycerol conversion was obtained in 6 h at 110 OC. A 24-hour reaction time resulted in a maximum selectivity of 33% for DTBGE. With regular activity and selectivity, the catalyst could be regenerated efficiently. PVP-DTP, PVP-STA, PVP-PMA, and DTP loaded on MCM-41 at 10 to 60% DTP loading were tested by glycerol esterification. Among all studied catalysts, PVP-DTP catalyst due to its higher acidity showed

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highest selectivity of 54% toward diacetin and 34% toward triacetin with complete conversion of glycerol. PVP-DTP catalyst exhibited minimum weight loss. Selectivity and glycerol conversion of heteropoly acid supported with silica at different concentrations rising from 10% to 50% were compared. Among all these catalysts, 20% DTP/SiO2 found excellent catalyst with selectivity increased from 6% to 45% toward DTBGE and 6% to 23% toward TTBGE by increasing DTP loading from 10% to 20% concentration. Conversion of glycerol was increased from 69% to 96% with varying concentrations of DTP on silica.

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Chapter 12

Application of Microbial-Based Adsorbent for Removal of Heavy Metal from Aqueous Solution Shravan Kumar, Rahul, Prateek Mishra, Shubhang Shukla, Shambhavi Mishra, and Shreya Tirkey

Abstract Changes in the environment due to discharge of heavy metals have become a major environmental concern in today’s nature. Heavy metals in industrial effluent discharge are of great threat to the environment due to their high toxicity and carcinogenic nature. The remedial treatment of this heavy metal is of great concern due to a great threat to the flora and fauna. In addition to being toxic, these metals are also required by living organisms in order to maintain their basic metabolic activities, some of which include cadmium, chromium, cobalt, copper, iron, lead, nickel, selenium, zinc, etc. The rapid industrialization has improved one’s living; along with this, the direct or indirect discharge of these heavy metals into the nature has also expanded enormously, specifically in developing countries. Now, numerous technologies have been studied and implemented for the elimination of such wastes from our water bodies and land surfaces. This paper studies the recent technologies which are implemented in order to treat the heavy metal effluent discharge, some of which comprise flocculation process, electrochemical methods, flotation process, adsorption process, membrane filtration method, ion-exchange method, coagulation process, and chemical precipitation method. This paper also focuses on the current applications and future prospects of this technique. Keywords Heavy metals · Adsorption · Kinetics · Biochar · Isotherm model

S. Kumar Chemical Engineering Department, Indian Institute of Technology, Guwahati, Assam, India Rahul (*) Paint Technology Department, Government Polytechnic Bindki, Fatehpur, Uttar Pradesh, India P. Mishra · S. Shukla · S. Mishra Department of Biotechnology, Dr. Ambedkar Institute of Technology for Handicapped, Kanpur, Uttar Pradesh, India S. Tirkey Department of Biotechnology, Karunya Institute of Technology and Sciences, Coimbatore, Tamil Nadu, India © The Author(s), under exclusive license to Springer Nature Singapore Pte Ltd. 2023 D. B. Pal (ed.), Recent Technologies for Waste to Clean Energy and its Utilization, Clean Energy Production Technologies, https://doi.org/10.1007/978-981-19-3784-2_12

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Introduction

Nowadays, the worldwide attention is toward the threat of heavy metal pollution. It mainly enters the environment from natural sources like volcanic activity, weathering, and deterioration of mineral, rock, etc. as well as anthropique (industrial operation) (Gupta et al. 2001). Mechanization enhanced the living situation; nevertheless, it too influenced the flora and fauna because of discharging large quantity of adulterants into it. Ecologists are bothered with heavy metal availability because their effects are highly toxic, carcinogenic, or mutagenic. Bioaccumulation and consequent biomagnifications of nature at different levels of food chain, making them unavoidable even at very low concentration. Several pandemics are observed in past history like Minamata because of the presence of methyl mercury poising and contamination of Cadmium found in Injects River in Japan which cause “itai-itai” disease. These are common examples of contamination of heavy metals in aquatic habitat. Heavy metal toxicity realized by it. As claimed by the physiological viewpoint, metals are divided into three main categories: nontoxic and essential metals (Ca and Mg), toxic metals (Hg and Cd), and essential but harmful metals above threshold limit. These essential but harmful type of metals such as cadmium (Cd), chromium (Cr), cobalt (Co), copper (Cu), iron (Fe), lead (Pb), nickel (Ni), selenium (Se), zinc (Zn), etc. are essential for typical metabolic functions in life forms. All these elements have their tolerance limit for human consumption. Low levels of these metals can cause deficiency issues and sometimes death in utmost case. Also exceeding its critical level can be detrimental to the organism (Zouboulis et al. 2004; Gupta et al. 2001). Health problems, such as vomiting, skin irritations, stomach cramps, nausea, and anemia, can be caused by the presence of more zinc. In animal metabolism, copper (Cu) played an essential role but brought some significant toxicological concerns, such as cramps, vomiting, convulsions, or even death by immoderate intake of copper (Paulino et al. 2006). Severe problems related to the lung and kidney apart from gastrointestinal distress, pulmonary fibrosis, and skin dermatitis can be caused by exceeding the optimal range of nickel (Borba et al. 2006). Nickel is also known as human carcinogen. Mercury can damage the central nervous system and cause impairment of functions of the lung and kidney, cardiac arrest, and dyspnea because mercury is a neurotoxin. Some researchers proved that cadmium poses severe threat to human health because it is a carcinogen. Kidney dysfunction led by continual exposure of cadmium and extreme range of disclosure will result to death. Lead can cause damage in the central nervous system; it can also harm the human body like the reproductive system, brain functions, kidney, basic cellular processes, and liver (Naseem and Tahir 2001). Cr metal exists in freshwater habitat, where it is found mainly in two forms: chromium (III) and chromium (VI). As a whole, chromium (III) is less poisonous than chromium (VI). Cr (VI) causes severe problem such as expanding the food chain and causing serious health issues varying from lung malignancy to simple skin irritation (Fu and Wang 2011).

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Heavy Metals

The term heavy metal indicates the metal or metalloid has relative density varying from 3.5 to 7 g/cm3. Generally, these elements are considered toxic around lower concentrations. These metals are also required by living organisms in order to maintain their basic metabolic activities. Some of the metals include cadmium (Cd), chromium (Cr), cobalt (Co), copper (Cu), iron (Fe), lead (Pb), nickel (Ni), selenium (Se), zinc (Zn), etc. (Fu and Wang 2011). Rapid industrialization has improved one’s standard of living; along with this, direct or indirect discharge of these heavy metals into the atmosphere has also expanded enormously, especially in the developing countries. Every essential element follows a varying optimal range of secure and sufficient human intake concentration. Decrease in this concentration is reported to cause deficiency symptoms and, in exorbitant condition, death. Immoderate level of required elements present in trace quantity can be deleterious to the organism.

12.2.1

Copper (cu)

Copper is an extensively used metal and generally used in electroplating and electrical industries. It plays an important role in biological reaction in the life of human beings (Volesky & Holan 1995). Copper, being the basic element of many enzymes, plays an important role for the process of transferring electrons. Carrier proteins like plastocyanin, azurin, and stellacyanin consist of copper as the core metal (Bashir et al. 2019). Extreme assimilation of copper causes symptoms like vomiting, diarrhea, nausea, and abnormalities of the brain and/or may even lead to death (Bashir et al. 2019). Researches indicate that 30 gm of CuSO4 is potentially lethal in the human liver and can result in Wilson’s disease leading to liver cirrhosis and ultimate demise of the being.

12.2.2

Chromium (Cr)

Depending upon the contrasting toxicity, mobility, and availability of chromium, chromium exhibits two consecutive oxidation states present in nature, namely, Cr (III) and Cr (VI) (Volesky & Holan 1995). Occurring in trace amounts in the biochemical system, chromium is suggested to have been involved as a factor of glucose tolerance in the human body for the action of insulin (Bashir et al. 2019). This chromium is more noxious when its valency is six and moderately noxious when its valency is three, because its oxidation property is strong (Rowbotham et al. 2000).

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Lead (Pb)

Studies confirm that on subjection to even small amount of lead may affect several crucial organ parts like nervous system, hematopoietic organs, renal, reproductive, and cardiovascular systems (Bashir et al. 2019). It forms complexes with oxo-groups in enzymes, which affect the procedure in the method of hemoglobin synthesis and porphyrin metabolism. Lead can also induce and imbalance the ratio of pro-oxidant and antioxidant which leads to oxidation of protein, peroxidation of lipid, and nucleic acid thereby, causing the cell liable to apoptosis (Flora et al. 2007). Some of the toxicity symptoms are associated with lead such as encephalopathy, seizures, and mental retardation.

12.2.4

Cadmium (Cd)

As per the US Environmental Protection Agency, cadmium has been regarded as a probable human carcinogen (Fu and Wang 2011). A well-known example of toxicity of cadmium is “Itai-Itai”; it is a disease which took place in Japan (Horiguchi et al. 1996); it was characterized by excruciating pain in bones (Volesky & Holan 1995 ). Its exposure leads to severe risks such as renal dysfunction. Increased levels of exposures may even cause death. Studies show that when excessive amount of Cd is assimilated, it exchanges zinc on some key sites of the enzyme leading to renal damage, anemia, bone marrow problems, and destructive to water biome (Bashir et al. 2019). Various guidelines and protocols have been implemented in order to initialize the endurable 29 restrictions for the parts and level of heavy metal that might be available in the effluent wastewater. For the heavy metal, USEPA (Alhendawi 2013) established the Maximum Contaminant Level (MCL) standards, which are enlisted in (Table 12.1).

Table 12.1 Maximum contaminant level (MCL) of hazardous heavy metals Heavy metal Mercury Lead Chromium Copper Nickel Zinc Cadmium Arsenic

Toxicity symptoms Rheumatoid arthritis, brain, kidney, and heart damage Damage excretory, circulatory, and nervous systems Headache, diarrhea, nausea, carcinogen Liver damage, Wilson disease, insomnia Dermatitis, chronic asthma, carcinogen Depression, lethargy, neurological disorder Kidney damage, human carcinogen, renal disorder Visceral cancer, vascular disease, skin diseases

MCL (mg L-1) 0.000030 0.006 0.050 0.250 0.200 0.800 0.010 0.050

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Biosorption

Biosorption is an anabolically static process accountable for the selective isolation of heavy metal by dead/inactive biomaterials (Hansda et al. 2016). It is a physicochemical process, which involves mechanisms, surface complexation, ion exchange, and precipitation. The “bio” prefix indicates toward the collaboration of a biotic entity, viz., life forms or its components or products carried out from it, as used in the spell like biotechnology and bioprocessing. On integrating the term “bio” to a physicochemical expression like “sorption”, it also indicates toward the participation of a process belonging to the abiotic system (Gadd and Griffiths 1977). The only difference between biosorption and conventional absorption is the quality of absorbent though in the case of biosorption, it is a matter of biotic origin (Hansda et al. 2016). These materials are special biological matters. Biosorption is the easy and economical operation process for heavy metal removal. Studies indicate toward the modification of the biosorbents in order to enhance their biosorption properties (Wang & Chen 2009). These materials can be physically modified with the help of heat treatments, which may result in better biosorption accommodation of the biomass due to the removing surface impurities and generating more active site via denaturing all walls of protein (Cabuk et al. 2005). Chemical and genetic modifications are also seen. Origin, availability, and cost-effectiveness of biomass affect the selection process of an appropriate biosorbent. It is the most crucial step (Hansda et al. 2016).

12.3.1

Biosorption Mechanism

Biosorption is the concept of removing the certain ions or other biomolecule from liquid solution by using certain biomolecule or biomass (Bashir et al. 2019). This can be exhibited through several mechanisms, i.e., complexion, chemisorptions, adsorption chelation, ion exchange, and physisorption (Sud et al. 2008). The extent of affinity of a biosorbent for diffused categories explains its dissemination among the two phases (Kaur et al. 2012). The untreated and chemically treated biosorbents consist of various functional groups like acetamide, phenolic, carbonyl, alcohols, amino, esters, and thiols which seem to operate simultaneously for the removal of metal ions (Bashir et al. 2019). Recent studies report that the basic principle for adsorption of metal ions is surface binding; it takes place because of the biomass mechanism of ion exchange (Matheickal et al. 1997). It has been reported that the ruling mechanism for the biosorption of Cu (II) is ion exchange, by the help of Ecklonia radiata, which involves the swapping of calcium ion (Ca2+) and magnesium ion (Mg2+) present in their cell wall. Heavy metal ions’ removal is result of interaction between the metal cations and active groups present on the cell surface and it causes to the

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development of a complex chelation group on the surface of the cell (Hansda et al. 2016). Certain researchers reported that uptake of Copper (II) by Zooglearamigera and Chlorella vulgar is which takes place by both adsorption and formation of coordinate bonds between metals and amino (- RNH2) and carboxyl (-RCOOH) groups of the cell wall polysaccharides reported by Aksu et al. (1992).

12.3.2

Factors Affecting Biosorption

Several factors can affect biosorption. The physical and enzymatic treatments like boiling, autoclaving, drying, and mechanical disturbance affect the binding properties of the biosorbent. The chemical treatments like alkali treatment often improves the biosorptive capacity, especially seen in some fungi due to the acetylation of chitin to form chitosan-glucan complexes which according to studies have shown higher metal affinities (Gadd and Griffiths 1977). The investigational frameworks such as pH of the solution, initial adsorbate concentration, biosorbent dose, contact time, agitation speed, temperature and pressure of competing ions, and the nature of the biosorbent affect the process of biosorption (Bashir et al. 2019).

12.3.2.1

Effect of pH

pH plays a vital role in the biosorption from aqueous medium of heavy metal ions (Gueu et al. 2007). The pH of the solution can affect the charge of the surface of the biosorbent and the degree of ionization of the functional group associated with it (Dissanayake et al. 2016). Researches state that the competition between cations and protons for binding site occurs which means the biosorption of metals like Cu, Cd, Ni, Co, and Zn is often reduced at low pH value. Metal ion binding can be effected by the absorbent state of charge. Point of Zero Charge (PZC) of absorbent matter provides details about the charge state of the matter (Ou et al. 2015). This PZC is the pH where surface of absorbent is all over neutral. Surface is neutrally charged or negatively charged and it depends on PZC Value (Below the value- neutral and beyond the value- negative) (Bashir et al. 2019).

12.3.2.2

Effect of Temperature

Over usual ranges, temperature marks a tiny effect on biosorption. High temperature like 50 ∘ C, may increase the rate of biosorption in some cases (Tsezos 1999). However, low temperature will affect the living cell systems and any auxiliary metabolism-dependent process that supports biosorption (Gadd and Griffiths 1977).

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12.3.2.3

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Characteristics of Biomass

The key factor for the biosorption process is to determine the nature of the biomass. It is evident in some fungal system that chemical treatments like alkali treatment often improves biosorption capacity whereas, physical treatments like autoclaving and drying disrupt its binding properties (Volesky & Holan 1995 ).

12.3.2.4

Biomass Concentration

Concentration of the biomass is considered as one of the most important factors. It is observed that at provided concentration of equilibrium, biomass absorbs more metal ions at lower cell densities. Restriction to metal ion-binding site is seen when there is a higher concentration of biomass.

12.4

Biosorbents

Heavy metals biosorption of aqueous solution is a relatively new operation affirmed an auspicious measure in the expulsion of heavy metal pollutants. The considerable benefits are their high impact in decreasing the heavy metal particles/ions and utilizing modest/inexpensive biosorbents. Biosorption measures especially appropriate to treat adulterated heavy metal sewerage. There are basically three sources of achieving normal biosorption (Apiratikul & Pavasant 2008): (a) from nonliving biomass such as bark, lignin, shrimp, krill, squid, crab shell, and so forth; (b) from algal biomass; and (c) from microbial biomass, for example bacteria, fungi, and yeast. By some researcher, algal biomass is also considered as microbial biomass. Algae, a viable natural biomass multiply universally furthermore, bounteously in the intertidal zones of world have pulled in consideration of numerous examiners as organism to be tried and utilized as new adsorbents. A few assets of choosing algae as biosorbent incorporate the extensive accessibility, minimal expense, more metal sorption limit, and quality standard (Apiratikul & Pavasant 2008). An enormous number of analysis deals with the biosorption utilizing algal biomass. Instances of ongoing reports incorporate that utilizing dried marine green microalgae Chaetomorpha linum for biosorption of copper ion (Cu2+) and zinc ion (Zn2+) (Ajjabi & Chouba 2009), utilizing green algae Ulvalactuca for the biosorption of chromium from wastewater (El-Sikaily et al. 2007). Ajjabi and Chouba (2009) examined the biosorption of copper ion (Cu2+) and zinc ion (Zn2+) by dried marine green macroalgae (C. linum). At the ideal, molecule size should be 100–315 mm, biosorbent measurements/dosages (20 g/L), and introductory solution pH 5, the dried algae delivered greatest copper ion (Cu2+) and zinc ion (Zn2+).

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12.4.1

Surface Modification and Development of Bioabsorbents

Treating the sewerage sullied with heavy metals in a powerful manner, it is needed to utilize adsorbents having high limit of metal adsorption. In majority of the cases, the successfulness of adsorbents is not just about as high as needed because of their low to medium adsorption limits. Lately, accentuation is provided based on adsorbent surface modification by different procedures to increment adsorption limit. From few decades, many surface modification procedures that have been broadly utilized by investigators include chemical and physical methods. Physical and chemical modifications include acid/base treatment, heat treatment, microwave, and so on (Srivastava et al. 2015).

12.5

Heavy Metal Adsorption Using Microbial Biomass

Adsorption is widely used technique for the removal of heavy metals. Microbes have high efficiency of removing heavy metal and huge surface area-volume ratio. A large number of microbes have been tested for the removal of heavy metal. A large variety of biological materials exploited for their metal desorption capacity. Absorbents are characterized in following categories(a) (b) (c) (d) (e) (f) (g) (h) (i) (j) (k)

SEM (Scanning electron microscope) TEM (Transmission electron microscope) ESR (Electron spin resonance spectroscopy) NMR (Nuclear magnetic resonance) FTIS (Fourier-transformed infrared spectroscopy) EDS (Energy dispersive x-ray spectroscopy) X-ray diffraction (XRD) analysis X-ray photo-electron spectroscopy (XPS) X-ray adsorption spectroscopy (XAS) Thermogravimetric analysis (TGA) Differential scanning calorimetric (DSC)

All above absorbents have their specific outcomes based on their characteristics. Microbial biomass binds heavy metal either by active process or by passive process or by the combination of both. The active process known as bioaccumulation “Bioaccumulation is accumulation of substances such as pesticides, or other chemicals in an organism. It occurs when the rate of absorbance of substance is faster than the substance lost by catabolism and excretion”. Passive process is known as biosorption. “Biosorption is a physiochemical phenomenon that naturally occurs in several biomasses that allows concentrating passively and binding the contaminant to its cellular structure”. Another major advantage of bioaccumulation is that the recovery of accumulated metals accomplishes by simple physical method without any damage to the

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biosorbent’s structural integrity. While, bioaccumulation recovered the accumulated metals by destructive means and damaged the structural integrity (Kuyuca & Volesky). Biosorption is easy and cost-effective achievement of a large-scale fermentation process or bulk gain from natural water bodies (Volesky B). Being a surface phenomenon, most of biosorption generally completed within few minutes of contact with biomass.

12.5.1

Adsorption by Bacterial Biomass

The most abundant and adaptive microorganisms are bacteria. In the living world, bacteria play a crucial role. Approximately 108 g of whole biomass of living world constitute of bacteria. Bacteria are unicellular, are capable of growing under wide range of environment, due to their small size, and are in controlled condition as they are widely used as biosorbent for wastewater treatment. Mostly, all industries belong to food processing and fermentation process releases their by-product in form of bacterial biomass. The bacterial by-products produced by them are employed in bioremediation process and few bacterial species such as Bacillus cherichia, Micrococcus, Pseudomonas, and Streptomyces mainly used for heavy metal remediation. Bacteria that produce enzyme urease have been biomineralized and characterized by Li et al. 2012. This enzyme is produced by hydrolyzing the bacterial strains, urea resulting in the increased pH of the soil, and production of carbonate, leading to mineralization of heavy metal ion and ultimately conversion to carbonate. After incubating the bacterial strain for 48 hours, the removal efficiency ranged from 88 to 99%. The biosorption ability varied with metals and depends on pH and metal concentration. Biosorption of each metal was rapid and could benefit for treatment of contaminated sites in large scale (Table 12.2).

12.5.2

Adsorption with the Help of Algal Biomass

Algae are found abundantly in freshwater bodies such as seas and oceans. It is large and diverse group of eukaryotic organisms that range from unicellular genera like chlorella to other multicellular genera. Among all types of algae, brown algae gain more attention because it has better sorption capacity and grow up to 50 m in length. Algae have excellent photosynthetic efficiency, fast reproduction cycles, and limited requirement of nutrition. The rate at which the algal cells use up the specified nutrition depends on difference between the concentration inside and outside the cell and the diffusion rate through the cell wall. Gupta and Rastogi (2008), utilized spirogyra sp. for biosorption of Pb2+. It was observed that Pb2+ was maximum absorbed 140 mg/g at pH 5.0 with the contact time of 100 minute and with 200 mg/l of metal ion concentration, which is initial. Biosorption is endothermic in nature as temperature increased from 20 ∘ C to 40 ∘ C.

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Table 12.2 Bacterial strains used for removal of heavy metals Sample no. 1

Bacterial species

Heavy metal ion

%Removal

Reference

Pb2+, Cu2+, Cd2+, Ni2+, Zn2+, Co2+, Ge, Y Cd2+, Cr6+

High removal efficiency Up to 83

3

Alcaligenes eutrophusCH34 Bacillus laterosporus/ B. licheniformis Citrobacter freudii

U6+

NA

4

Enterobacter cloacae

Cu2+, Cd2+, Co2+

1.43–65.95

5

Iron-oxidizing bacteria Micrococcus sp.

Cr6+, Cu2+, Zn2+, Ni2+, Pb2+ Cr6+, Ni2+

16.2–91.5

Pseudomonas aeruginosa Sulfate-reducing bacteria Sulfate-reducing bacteria Sulfate-reducing bacteria Sulfate-reducing bacteria

Cd2+

99

Cd2+, Cr6+, Cu2+, Zn2+, As5+ Cr6+, Cu2+, Zn2+, Ni2+

99

Cu2+, Zn2+, As5+, Ni2+, Fe3+, Al3+, Mg2+ U6+, Mn2+, Fe2+, Pb2+, Zn2+

77.5–97.5

Diels et al. (1995) Zouboulis et al. (2004) Xie et al. (2008) Iyer et al. (2005) Xiang et al. (2000) Congeevaram et al. (2007) Wang et al. (1997) Cruz Viggi et al. (2010) Kieu et al. (2011) Jong and Parry (2003) Wang et al. (2008a, 2008b)

2

6 7 8 9 10 11

12.5.3

55–92

94–100

High removal efficiency

Adsorption by Fungal Biomass

The discharged wastewater from chemical industries may contain heavy metal ions that have a toxic effect influence in the living world. Disposing them to the environment is hazardous to both human and ecosystem. New technologies are necessary to being developed to treat wastewater as an alternative to physiochemical process. Fermentation industries are used to produce metabolites like steroids, antibiotics, enzymes, and chemicals. Fungi have been recognized and trusted as cheap adsorbents for wastewater for removal of heavy metal ion. Fungi’s cell walls are made up of chitin and chitosan, in various reactor systems for heavy metal ion elimination and describe the biosorption process of fungus. To investigate the biosorption mechanism, in order to understand the biosorption process, it is vital to identify the functional groups involved. Heavy metal may be absorbed from aqueous solutions by common filamentous fungus; the heavy metal sorption, Copper, Zinc, Cadmium, Lead, Iron, Nickel, Silver, Thorium, Radium, and Uranium, by fungal biomass. It has been observed to varying extent. The concentration of biomass and metal ions, the presence of ligands in a solution, temperature, and pH are all important factors in fungal biosorption.

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The biosorption of metal ions is caused by the development of complexes and ionic interactions between heavy metal ions and the presence of functional groups on the surface of fungal cells (Kapoor & Viraraghavan 1997). In fungal biosorption, the main functional groups involve amine, amide, carboxyl, and phosphate (Akthar et al., 1996). By using Phanerochaete chrysosporium (white rot fungus) from wastewater, Singh et al. (2006) researched on Copper ion (Cu2+), Cadmium ion (Cd2+), and Lead ion (Pb2+). Biosorption equilibrium and biosorption capacity were achieved that are 45.25, 13.24, and 10.72 mg/g for Lead ion (Pb2+), Cadmium ion (Cd2+), and Copper ion (Cu2+), respectively with the contact time of 6 hours at pH 6. Loofah sponge immobilized the P. Chrysosporium, and was utilized for the removal of Copper ion (Cu2+), Zinc ion (Zn2+), and Lead ion (Pb2+) from wastewater (Iqbal & Edyvean 2004). Maximal biosorption of Lead ion (Pb2+), Copper ion (Cu2+), and Zinc ion (Zn2+) was found to be 135.3 mg/g, 102.8 mg/g, and 50.9 mg/g, respectively. For maximum biosorption, optimal pH was 6 and contact time of 60 minutes, respectively. Langmuir isotherm was best fitted isotherm for all the three metal ions (Sing & Yu 1998).

12.5.4

Adsorption by Endophytes

The endophytes are those microorganisms, which live in the living plant tissue. It acts as a biocontrol agent by protecting plant from herbivore (consumption of plant by animals as herbivores adapted to eat plants) by producing compounds which prevent animals from overgrazing on the same plant. Due to peculiar growing environment of endophytes, it experiences high concentration of thrash metals and might have a distinct type of cell wall, which contains special functional group and is required to be an optimistic biosorbents (Xiao et al. 2010; Guo et al. 2010). El-Gendy (2008) carried out the investigation using ten endophytic fungi isolated from plants grown in industrial regions and these exhibited the potential in treatment of heavy metal from aqueous solution. Those endophytic fungi belong to the eight different genera. Degradation and accumulation of heavy metal were performed by these fungal strains. Among all endophytic fungi (P. declauxi, V.fungicola, A. luchuensis, A. tubingensis, C. lunata, P. lilacinum, D. hawaiiensis, M. elegans, R. oryzae, and P. clavispora), the highest removal of Cu2+ (85.4%) was shown by P. lilacinum with smart removal for Cd2+ (31.43%) (Table 12.3).

12.6

Biosorption Selection Biosorbents

The most effective method to choose the biosorbent, which is appropriate among a huge amount of biomaterial, tried. The choice of an appropriate sorbent for guaranteed partition/portion is an intricate issue. The dominating logical/scientific premise for sorbent choice is the equilibrium isotherm. Dispersion rate is optional in significance. From the perspective of useful application, accessibility and

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Table 12.3 Heavy metals are removed with the help of endophytes / 1

Heavy metal ion Cd 2+

%Removal 64–135

2

Bacterial species Actinobacteria, Proteobacteria, Bacteroidetes, Firmicutes Bacillus sp. L14

Cd2+, Cu2+, Pb2+

21.25–80.48

3

Bacillus thuringiensis GDB-1

8–77

4

Microsphaeropsis sp. LSE10

Cd2+, Co2+, Pb2+, Cu2+, Zn2+, As5+ Cd2+

5

Cu2+, Cd2+

31.43–85.4

6

Rhizopus oryzae, Aspergillus luchuensis, Aspergillus tubingensis, Monacrosporium elegans, Penicillium duclauxi, Penicillium lilacinum, Curvularia lunata, Drechslera hawaiiensis, Verticilium fungicola, Pestalotiopsis clavispora Pseudomonas sp. LK9-2P

Cd2+, Cu2+, Pb2+

71.67–99.22

7

Bacillus sp. L14

Cd2+

93.7

NA

Reference Luo et al. (2011a) Guo et al. (2010) Babu et al. (2013) Xiao et al. (2010) El-Gendy (2008)

Luo et al. (2014) Luo et al. (2011b)

cost-effective are main considerations to be taken into represent choosing the biomaterial for removal purposes (Vieira & Volesky 2000). Right evaluation of the metal-binding limit of a few kinds of biomass is likewise vital. Step by step instructions to assess the sorption execution for a certain biosorbent? Systematically instructions to assess the experimental outcomes announced/researchers reported it from various foundations/background? Volesky and his partners/colleague discuss the connected/related queries (Kratochvil & Volesky 1998; Volesky & Holan 1995). For solid-liquid sorption system, two kinds of examinations could help to examine: (a) dynamic persistent stream sorption contemplates and (b) equilibrium batch sorption tests (Chen & Wang 2008). For single solute system, two most acknowledged equilibrium adsorption isotherm models are Langmuir model and the Freundlich model. Qmax, Ce, and b are respectively the most extreme sorption limits concerning complete monolayer coverage (in mmol g - 1), the equilibrium solute concentration (in mmol L-1), and the constant identified with the energy of sorption (or “proclivity”) (in L mmol-1), the Freundlich constants identified with the adsorption limit and intensity of the biosorbent are KF and n, respectively. Biosorbents’ performances might be compared, by utilizing these boundaries from the models (Chen & Wang 2008). Traditional sorption isotherm found from equilibrium batch contact tests under similar ecological conditions (for example temperature, ionic strength, pH) helps in assessment of sorption system. Identical equilibrium (last, lingering/remaining) concentration must be made at a quantifiable comparison of two unique sorption system. Comparisons at high Cf (e.g., 200 mg L- 1) and low Cf (e.g., 10 mg L-1) are

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made in some biosorption screens during this way, as an example, appeared in Kratochvil and Volesky (1998). Equilibrium (last) metal concentration something similar (chose: for instance, 10 or 200 mg L-1) decided biosorption performance as far as metal take-up limit. Correlation of qmax is likewise helpful. qmax and b are two effectively or easily interpretable constants of Langmuir isotherm model. Small values of b are reflected within the lofty starting slant/sloop of a sorption isotherm, indicating a beautiful high fondness. In order to find out the efficient adsorbent for adsorption of heavy metals ions it is required to find out high qmax and a steep beginning sorption isotherm slope (for example, low b) (Kratochvil & Volesky 1998).

12.7 12.7.1

Biosorption Models: Kinetics and Isotherms Biosorption Isotherms

The isotherms of biosorption explain the relation between the concentration of biosorbent and the quantity of it absorbed by the unit mass of the biosorbent by taking constant temperature at equilibrium. This is essential for designing the biosorption systems. The isotherm models give data and facts about the removal capacity of biosorbents. These isotherm models are essential for determining the biosorption parameters and to compare the different biosorbents using different operating conditions.

12.7.1.1

Single Component Isotherm Models

These models give short expression and monocomponent adsorption of ionic metals. These are simple mathematical relationships used to describe different experimental behavior over a large number of experiments under various circumstances. The models are used for substantiating the outcomes that are able to predict metal binding at low as well as high concentrations (Rangabhashiyam et al. 2014). Some important models are as follows:

Langmuir Model In 1918, Irving Langmuir gave the Langmuir model. It assumes that under isothermal condition, an adsorbate shows the property of ideal gas. This model is valid for single layer adsorption. The basis of this model is a continuous monolayer of adsorbate molecules occupying a solid homogeneous surface (Langmuir 1918). In this model, adsorption energy is constant. The Langmuir isotherm model works on certain assumptions. These are:

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1. The surface of adsorbent is uniform, i.e., uniformity of the surface. 2. No interactions between the adsorbed molecules. 3. Molecules get adsorbed at defined sorption sites. The Langmuir isotherm equation is given as: qe ¼

Qm bC e 1 þ bC e

ð12:1Þ

This equation is expressed in linear form as: Ce 1 C ¼ þ e qe bQm Qm

ð12:2Þ

Here, qe is the sorbate amount that adsorbs the sorbent per unit mass at equilibrium, Qm is the maximum consumption of sorbent per unit mass of sorbent, Ce is sorbate concentration in solution, and b is Langmuir constant.

Freundlich Model Freundlich gave this model and this model describes the process of adsorption by the following equation (Freundlich 1906; Freundlich & Heller 1939). 1

qe ¼ KC ne

ð12:3Þ

Here, K and n are Freundlich constants, K is related to capacity of adsorption. Equation of linear form is given as: ln qe ¼ ln K þ

1 ln C e n

ð12:4Þ

Temkin Model The adsorption process is examined by Said et al. (2018). It is given by the equation: qe ¼

RT ln ðK T Ce Þ b

ð12:5Þ

Here, qe is the amount of sorbate adsorbed per unit mass of sorbent at equilibrium, b is Temkin constant, KT is Temkin constant related to binding, and Ce is the concentration of sorbate in solution.

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The linear form of equation is given as: qe ¼ B1 ln K t þ B1 ln C e

ð12:6Þ

Here, B1 ¼ RT b R is the universal gas constant (8.314 KJ/mol.K), T is the absolute temperature in (K).

Toth Model This model is used in a heterogeneous system. It is given by the equation (Said et al. 2018) qe ¼ (

Qm bC e 1 þ ðbC e ÞtÞ

1 t

ð12:7Þ

Redlich –Peterson Model Heterogeneous systems are well described by Toth model. This model proves to be effective when pollutants are present at high concentration (Benzaoui et al. 2018). This model is given by the equation: qe ¼

AR C e R 1 þ BR C m e

ð12:8Þ

Here, AR, BR,and mR are the model parameters, qe is the sorbate amount adsorbed per unit mass of sorbent at equilibrium, Qm is the maximum sorbate uptake per unit mass of sorbent, and Ceis the sorbate concentration in solution.

12.7.2

Kinetic Models

Adsorption kinetics in wastewater treatment is of great significance. It helps us to know about the reaction pathways and mechanisms of adsorption. The kinetic models describe the uptake of solute which in turn controls the time of residence adsorbate at the interface. The residence time is the total time a particular amount of material spends in the reservoir. Information about the kinetics of metal uptake helps us provide the best-suited condition for batch metal removal process

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(Rangabhashiyam et al. 2014). Some of the models given to outline the adsorption kinetic process are as follows:

12.7.2.1

Pseudo First-Order Kinetic Model

The equation of Lagergren rate is one of the most popular rate sorption equations used to describe the process of adsorption (Lagergren 1898; Langmuir 1918). It is expressed as dqt ¼ K 1 ð qe - qt Þ dt

ð12:9Þ

Its linear form is expressed as ln ðqe - qt Þ ¼ ln qe - K 1 t

12.7.2.2

ð12:10Þ

Pseudo Second-Order Kinetic Model

It is based on certain assumptions (Ho & McKay 1999): 1. 2. 3. 4.

Adsorption monolayer is considered. The energy of adsorption is same for each adsorbent. Adsorption occurs on defined sites. There is no interaction between adsorbed pollutants. This model is expressed as: ( ) dqt ¼ K s qeq - qt dt

ð12:11Þ

Here, Ks is the adsorption rate constant. qeq is the pollutant amount adsorbed on the surface of adsorbent. The equation of linear form is given as 1 t t ¼ þ qt K s q2eq qeq

12.7.2.3

Weber and Morris Intra Particle Diffusion Model

It is given by the equation (Weber & Morris 1963):

ð12:12Þ

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Application of Microbial-Based Adsorbent for Removal of Heavy Metal. . . 1

qt ¼ kid t 2 þ C

261

ð12:13Þ

Here, qt is the adsorbed amount at time t, kid is the rate constant, C is the intercept value. This brings idea of the thickness of boundary layer, i.e., the greater the boundary, the larger the effect.

12.8

Conclusion and Future Perspective

Biosorption is facing a major challenge; the failure advertisement is mainly because of the nonspecific peril; it involves the technical alterations, proposed by several investigators. For innovation, solid capitalization is required. The application of biosorbent has not been exploited well at industrial scale; this constitutes the weaknesses that must be faced by biosorbent. All the studies about biosorption until now are enough to provide a base that allows it to be extended. However, this is not widely used process in industry. It is difficult to determine the fact, because at present, few studies are there in which biosorbent is compared with commercial sorbent under similar condition. The use of culturing microbes is a beneficial alternative for removal of metal contaminant as pure biosorptive from commercial effluent. Bacterial, fungal, and algal strains are main types of microorganism that is able to remove organic matter from wastewater. The survey data reveal the biosorption investigations that are quite limited, with only a few types of bacterial, fungal, and algal biomass. Several aspects that affect the biosorption capacity of wastewater are pH, temperature, biomass concentration, ionic strength biological waste, and more components like metal ions, etc. Other parameters that have yet to be examined, like stirring rate and particle size, will require more research.

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