Biodiesel Production

Samuel Lalthazuala Rokhum, PhD, is a Postdoctoral Fellow in the laboratory of Prof. Andrew EH Wheatley in the Department of Chemistry, Cambridge University, UK and Assistant Professor in the Department of Chemistry, National Institute of Technology in Silchar, India. His research interest includes organic chemistry, material chemistry, renewable energy, and heterogeneous catalysis. He is actively engaged in numerous scientific societies and currently served as an Academic Editor of Journal of Chemistry (Hindawi) and a guest editor in several journals. Gopinath Halder, Ph.D., is Professor in the Department of Chemical Engineering, National Institute of Technology Durgapur, India. As a chemical engineer, Prof. Halder has more than two decades of teaching and research experience in biofuel synthesis from non-edible and microalgal feedstock, preparation of heterogeneous carbonaceous catalyst, process optimization and bioremediation of contaminated waste water containing heavy metals, fluoride ions and pharmaceutical active compounds. Suttichai Assabumrungrat is Full Professor in Chemical Engineering, and the Director of Bio-Circular-Green economy Technology and Engineering Center (BCGeTEC), Faculty of Engineering at Chulalongkorn University, Bangkok, Thailand. His research interest includes applications of multifunctional reactors and process intensification for chemical, petrochemical and biorefinery industries. Particular focuses are on technologies related to production of biofuels, bio-based chemicals and hydrogen as well as CO2 capture and utilization. Kanokwan Ngaosuwan is Associate Professor in Chemical Engineering at the Division of Chemical Engineering, Rajamangala University of Technology Krungthep, Bangkok, Thailand. She earned her Ph.D. degree in chemical engineering from Chulalongkorn University, Thailand. Her research interests include biomass conversion, heterogenous catalysis and catalytic reaction engineering, and process intensification.

• Preface xvList of Contributors xviiAn Overview of Biodiesel Production xxiPart 1 Biodiesel Feedstocks 11 Advances in Production of Biodiesel from Vegetable Oils and Animal Fats 3Umer Rashid and Balkis Hazmi1.1 Introduction 31.2 History of the Use of Vegetable Oil in Biodiesel 61.3 Feedstocks for Biodiesel Production 61.3.1 Generations of Biodiesel 71.3.2 First-Generation Biodiesel 71.3.3 Second-Generation Biodiesel 81.3.4 Third-Generation Biodiesel 81.4 Basics of the Transesterification Reaction 81.5 Variables Affecting Transesterification Reaction 101.6 Alkaline-Catalyzed Transesterification 101.7 Acid-Catalyzed Transesterification 151.8 Enzymatic-Catalyzed Transesterification 161.9 Fuel Properties and Quality Specifications for Biodiesel 191.10 Conclusion 20References 212 Green Technologies in Valorization of Waste Cooking Oil to Biodiesel 33Bisheswar Karmakar and Gopinath Halder2.1 Introduction 332.1.1 The Necessity for Biodiesel 332.1.2 Sourcing the Correct Precursor 332.2 Importance of Valorization 352.3 Purification and Characterization 352.4 Transesterification: A Comprehensive Look 362.5 Conversion Techniques 372.5.1 Traditional Conversion Approaches 382.5.1.1 Acid Catalysis 382.5.1.2 Alkali Catalysis 382.5.1.3 Enzyme Catalysis 402.5.1.4 Other Novel Heterogeneous Catalysts 402.5.1.5 Two-Step Catalyzed Process 412.5.2 Modern Conversion Approaches 412.5.2.1 Supercritical Fluids 412.5.2.2 Microwave Irradiation 432.5.2.3 Ultrasonication 432.6 Economics and Environmental Impact 442.7 Conclusion and Perspectives 45References 453 Non-edible Oils for Biodiesel Production: State of the Art and FuturePerspectives 49Valeria D’Ambrosio, Enrico Scelsi, and Carlo Pastore3.1 Introduction 493.2 Vegetable Non-edible Oils 503.2.1 General Cultivation Data 503.2.2 Composition and Chemical–Physical Properties of Biodiesel Obtained from Non-edible Vegetable Oils 503.2.3 Biodiesel Production from Non-edible Vegetable Oil 543.2.3.1 Extraction Methods 543.2.3.2 Biodiesel Production 573.2.4 Criticisms Related to Non-edible Oils 573.3 Future Perspectives of Non-edible Oils: Oils from Waste 583.4 Conclusion 60Acknowledgments 61References 614 Algal Oil as a Low-Cost Feedstock for Biodiesel Production 67Michael Van Lal Chhandama, Kumudini Belur Satyan, and Samuel Lalthazuala Rokhum4.1 Introduction 674.1.1 Microalgae for Biodiesel Production 684.2 Lipid and Biosynthesis of Lipid in Microalgae 704.2.1 Lipid Biosynthesis 714.2.2 Lipid Extraction 724.3 Optimization of Lipid Production in Microalgae 734.3.1 Nitrogen Stress 734.3.2 Phosphorous Stress 734.3.3 pH Stress 744.3.4 Temperature Stress 744.3.5 Light 754.4 Conclusion 75References 76Part 2 Different Catalysts Used in Biodiesel Production 835 Homogeneous Catalysts Used in Biodiesel Production 85Bidangshri Basumatary, Biswajit Nath, and Sanjay Basumatary5.1 Introduction 855.2 Transesterification in Biodiesel Synthesis 865.3 Homogeneous Catalyst in Biodiesel Synthesis 885.3.1 Homogeneous Acid Catalyst 885.3.2 Homogeneous Base Catalyst 905.4 Properties of Biodiesel Produced by Homogeneous Acid and Base-Catalyzed Reactions 935.5 Relevance of Homogeneous Acid and Base Catalysts in Biodiesel Synthesis 965.6 Conclusion 96References 976 Application of Metal Oxides Catalyst in Production of Biodiesel 103Hui li6.1 Basic Metal Oxide 1036.1.1 Monobasic Metal Oxide 1036.1.1.1 Alkaline Earth Metal Oxide 1036.1.1.2 Transition Metal Oxide 1056.1.2 Multibasic Metal Oxide 1056.1.2.1 Supported on Metal Oxide 1066.1.2.2 Supported on Activated Carbon 1066.1.2.3 Supported on Metal Organic Framework 1076.1.3 Active Site-Doped Basic Metal Oxide 1076.1.3.1 Alkali Metal Doped 1076.1.3.2 Active Metal Oxide Doped 1076.1.4 Mechanism of Transesterification Catalyzed by Basic Metal Oxide 1086.2 Acid Metal Oxide 1086.2.1 Monoacid Metal Oxide 1096.2.2 Multiacid Metal Oxide 1096.2.3 Supported on Metal Organic Framework 1126.2.4 Mechanism of Transesterification/Esterification Catalyzed by Acid Metal Oxide 1126.3 Deactivation of Metal Oxide 113References 1147 Supported Metal/Metal Oxide Catalysts in Biodiesel Production 119Pratibha Agrawal and Samuel Lalthazuala Rokhum7.1 Introduction 1197.2 Supported Catalyst 1207.3 Metals and Metal Oxide Supported on Alumina 1207.4 Metals and Metal Oxide Supported on Zeolite 1237.5 Metals and Metal Oxide Supported on ZnO 1257.6 Metals and Metal Oxide Supported on Silica 1277.7 Metals and Metal Oxide Supported on Biochar 1287.7.1 Solid Acid Catalysts 1297.7.2 Solid Alkali Catalysts 1297.8 Metals and Metal Oxide Supported on Metal Organic Frameworks 1317.9 Metal/Metal Oxide Supported on Magnetic Nanoparticles 1347.10 Summary 135References 1368 Mixed Metal Oxide Catalysts in Biodiesel Production 143Brandon Lowe, Jabbar Gardy, Kejun Wu, and Ali Hassanpour8.1 Introduction 1438.2 Previous Research 1448.3 State of the Art 1508.3.1 Solid Acid MMO Catalysts 1508.3.2 Solid Base MMO Catalysts 1508.3.3 Solid Bifunctional MMO Catalysts 1568.4 Discussion 1578.5 Conclusion 1618.6 Symbols and Nomenclature 162References 1629 Nanocatalysts in Biodiesel Production 167Avinash P. Ingle, Rahul Bhagat, Mangesh P. Moharil, Samuel Lalthazuala Rokhum, Shreshtha Saxena, and S. R. Kalbande9.1 Introduction 1679.2 Transesterification of Vegetable Oils 1699.3 Conventional Catalysts Used in Biodiesel Production: Advantages and Limitations 1719.3.1 Homogeneous Catalysts 1719.3.2 Heterogeneous Catalysts 1729.3.3 Biocatalysts 1739.4 Role of Nanotechnology in Biodiesel Production 1739.5 Different Nanocatalysts in Biodiesel Production 1739.5.1 Metal-Based Nanocatalysts 1749.5.2 Carbon-Based Nanocatalysts 1759.5.3 Zeolites/Nanozeolites 1809.5.4 Magnetic Nanocatalysts 1829.5.5 Nanoclays 1849.5.6 Other Nanocatalysts 1849.6 Conclusion 185Acknowledgment 185References 18510 Sustainable Production of Biodiesel Using Ion-Exchange Resin Catalysts 193Naomi Shibasaki-Kitakawa and Kousuke Hiromori10.1 Introduction 19310.2 Features of Ion-Exchange Resin Catalysts 19410.3 Cation-Exchange Resin Catalyst 19410.3.1 Notes of Caution When Comparing the Activity of Resins with Different Properties 19410.3.2 Reversible Reduction of Resin Catalytic Activity by Water 19610.3.3 Search for Operating Conditions for Maximum Productivity Rather than Maximum Catalytic Activity 19810.3.4 Challenges Regarding One-Step Reaction with Simultaneous Esterification and Transesterification Catalyzed by Cation-Exchange Resin 19810.4 Anion-Exchange Resin Catalysts 19910.4.1 Requirements for High Catalytic Activity in the Transesterification of Triglycerides 19910.4.2 Analysis of Previous Studies 20110.4.3 Decreased Catalytic Activity and Regeneration Method 20310.4.4 Additional Functions Unique to Anion-Exchange Resins 20410.5 Summary 204References 20511 Advances in Bifunctional Solid Catalysts for Biodiesel Production 209Bishwajit Changmai, Michael Van Lal Chhandama, Chhangte Vanlalveni, Andrew E.H. Wheatley, and Samuel Lalthazuala Rokhum11.1 Introduction 20911.2 Application of Solid Bifunctional Catalyst in Biodiesel Production 21011.2.1 Acid–Base Bifunctional Catalysts 21011.2.1.1 Oxides of Acid–Base 21111.2.1.2 Acid–Base Hydrides 21311.2.2 Bifunctional Acid Catalyst 21711.2.2.1 Bifunctional Brønsted–Lewis Acid Oxides 21711.2.2.2 Heteropolyacid-Based Bifunctional Catalyst 22011.2.3 Biowaste-Derived Bifunctional Catalyst 22211.3 Summary and Concluding Remarks 224Acknowledgment 225References 22512 Application of Catalysts Derived from Renewable Resources in Production of Biodiesel 229Kanokwan Ngaosuwan, Apiluck Eiad-ua, Atthapon Srifa, Worapon Kiatkittipong, Weerinda Appamana, Doonyapong Wongsawaeng, Armando T. Quitain, and Suttichai Assabumrungrat12.1 Introduction 22912.2 Potential Renewable Resources for Production of Biodiesel Catalysts 23012.2.1 Animal Resources 23012.2.1.1 Eggshells (Chicken and Ostrich) 23112.2.1.2 Seashells (Snail, Mussel, Oyster, and Capiz) 23112.2.1.3 Bones 23312.2.2 Plant Resources 23312.2.2.1 Carbon-Supported Catalysts 23312.2.2.2 Silica-Supported Catalysts 23612.2.2.3 Other Potential Elements from Plant Residues 23612.2.3 Natural Resources 23612.2.3.1 Dolomitic Rock (Calcined Dolomite and Modified Dolomite) 23612.2.3.2 Lime 23712.2.3.3 Natural Clays 23712.2.3.4 Zeolites 23812.2.4 Industrial Waste Resources 24012.2.4.1 Food Industry Wastes 24012.2.4.2 Mining Industry Wastes 24012.3 Advantages, Disadvantages, and Challenges of These Types of Catalyst for Biodiesel Production 242Acknowledgment 243References 24313 Biodiesel Production Using Ionic Liquid-Based Catalysts 249B. Sangeetha and G. Baskar13.1 Introduction 24913.2 Mechanism of IL-Catalyzed Biodiesel Production 25013.3 Acidic and Basic Ionic Liquids (AILs/BILs) as Catalyst in Biodiesel Production 25013.4 Supported Ionic Liquids in Biodiesel Production 25113.5 IL Lipase Cocatalysts 25513.6 Optimization and Novel Biodiesel Production Technologies Using ILs 25713.7 Recyclability of the Ionic Liquids on Biodiesel Production 25913.7.1 Recovery of ILs 25913.7.2 Reuse of Ionic Liquids 26013.8 Kinetics of IL-Catalyzed Biodiesel Production 26013.9 Techno-Economic Analysis and Environmental Impact Analysisof Biodiesel Production Using Ionic Liquid as Catalyst 26113.10 Conclusion 262References 26314 Metal–Organic Frameworks (MOFs) as Versatile Catalysts for Biodiesel Synthesis 269Vasudeva Rao Bakuru, Marilyn Esclance DMello, and Suresh Babu Kalidindi14.1 Introduction 26914.1.1 Metal-Containing Secondary Building Units 27114.1.2 Organic Linker 27214.1.3 Pore Volume 27214.2 Biodiesel Synthesis Over MOF Catalysts 27314.2.1 Transesterification Reaction 27414.2.1.1 Transesterification at SBUs of MOFs 27414.2.1.2 Transesterification at Linker Active Sites 27614.2.2 Esterification of Carboxylic Acids 27714.2.2.1 Esterification of Carboxylic Acids at SBUs of MOFs 27714.2.2.2 Esterification of Carboxylic Acids at Linker Active Sites 27914.2.2.3 Esterification at Pore Volume (Guest Incorporation) 28014.3 Conclusion 281References 281Part 3 Technologies, By-product Valorization and Prospects of Biodiesel Production 28515 Upstream Strategies (Waste Oil Feedstocks, Nonedible Oils, and Unicellular Oil Feedstocks like Microalgae) 287Aleksandra Sander and Ana Petračić15.1 Introduction 28715.1.1 Classification of Biodiesel 28715.1.2 Commercial Production of Biodiesel 28815.2 Biodiesel Feedstocks 29015.2.1 Edible Oils as Feedstock for Biodiesel Production 29115.2.2 Nonedible Oils as Feedstocks for Biodiesel Production 29215.2.3 Waste Feedstocks (Waste Cooking Oils, Waste Animal Fats, Waste Coffee Ground Oil, Olive Pomace) 29215.2.4 Unicellular Oil Feedstocks (Microalgae, Yeasts, Cyanobacteria) 29315.3 Composition of Oils and Fats 29315.4 Methods for Oil Extraction 29415.4.1 Mechanical Extraction 29415.4.2 Solvent Extraction 29515.4.3 Enzymatic Extraction 29615.5 Purification of Oils and Fats 29715.5.1 Deacidification 29715.5.2 Winterization 29815.5.3 Demetallization 29815.5.4 Degumming 29815.6 Production of Biodiesel 29915.6.1 Catalysts for Biodiesel Production 30015.6.2 Homogeneous Catalysts 30015.6.3 Heterogeneous Catalysts 30115.7 Future Prospects 302References 30216 Mainstream Strategies for Biodiesel Production 311Narita Chanthon, Nattawat Petchsoongsakul, Kanokwan Ngaosuwan, Worapon Kiatkittipong, Doonyapong Wongsawaeng, Weerinda Appamana, and Suttichai Assabumrungrat16.1 Introduction 31116.2 Mainstream Strategies and Technology for Biodiesel Production 31216.2.1 Current Mainstream Operation 31216.2.1.1 Batch Mode 31216.2.1.2 Continuous Mode 31216.2.2 Process Mainstream for Biodiesel Production Based on the Reactor Types 31316.2.2.1 Rotating Reactor 31316.2.2.2 Tubular Flow Reactor 31516.2.2.3 Cavitational Reactor 31716.2.2.4 Microwave Reactor 31816.2.2.5 Multifunctional Reactor (Reactive Distillation, Membrane, Centrifugal Reactors) 31916.2.2.6 Other Process Intensification 32216.3 Future Prospects and Challenges 323Acknowledgment 327References 32717 Downstream Strategies for Separation, Washing, Purification, and Alcohol Recovery in Biodiesel Production 331Ramón Piloto-Rodríguez and Yosvany Díaz-Domínguez17.1 Introduction 33117.1.1 Factors Affecting Biodiesel Yield 33217.1.2 Transesterification Reaction Conditions 33217.1.3 Separation After FAME Conversion 33217.1.4 Washing 33417.2 Glycerol Separation and Refining 33617.3 Membrane Reactors 33717.4 Methanol Recovery 33917.5 Additization 33917.6 Conclusion 342References 34318 Heterogeneous Catalytic Routes for Bio-glycerol-Based Acrylic Acid Synthesis 345Nittan Singh, Pavan Narayan Kalbande, and Putla Sudarsanam18.1 Introduction 34518.2 Acrylic Acid Synthesis from Propylene 34618.3 Acrylic Acid Synthesis from Glycerol 34618.3.1 Glycerol Dehydration to Acrolein 34718.3.2 Acrylic Acid Synthesis from Glycerol 34918.4 Conclusion 351Acknowledgments 353References 35319 Sustainability, Commercialization, and Future Prospects of Biodiesel Production 355Pothiappan Vairaprakash, and Arumugam Arumugam19.1 Introduction 35519.2 Biodiesel as a Promising Renewable Energy Carrier 35619.3 Overview of the Biodiesel Production Process 35819.4 Evolution in the Feedstocks Used for the Sustainable Production of Biodiesel 35919.5 First-Generation Biodiesel and the Challenges in Its Sustainability 35919.6 Development of Second-Generation Biodiesel to Address the Sustainability 36119.7 Algae-Based Biodiesel 36219.8 Waste Oils, Grease, and Animal Fats in Biodiesel Production 36319.9 Technical Impact by the Biodiesel Usage 36319.10 Socioeconomic Impacts 36419.11 Toxicological Impact 36419.12 Sustainability Challenges in the Biodiesel Production and Use 36519.13 Concluding Remarks 366References 36620 Advanced Practices in Biodiesel Production 377Trinath Biswal, Krushna Prasad Shadangi, and Rupam Kataki20.1 Introduction 37720.2 Mechanism of Transesterification 37820.3 Advanced Biodiesel Production Technologies 37920.3.1 Production of Biodiesel Using Membrane Reactor 37920.3.1.1 Principle 37920.3.2 Microwave-Assisted Transesterification Technology 38120.3.2.1 Principle 38120.3.3 Ultrasonic-Assisted Transesterification Techniques 38220.3.4 Production of Biodiesel Using Cosolvent Method 38520.3.4.1 Principle 38520.3.5 In Situ Biodiesel Production Technology 38520.3.5.1 Principle 38520.3.6 Production of Biodiesel Through Reactive Distillation Process 38720.3.6.1 Principle 38720.4 Conclusion 38920.5 Future Perspectives 390References 390Index 397