Ananda S. Amarasekara is a professor in the Department of Chemistry at Prairie View A&M University in Texas. He received his PhD in organic chemistry from the City University of New York in 1985. His research interests include cellulosic ethanol, renewable fuels, catalysis in biomass processing, and renewable polymeric materials. For his current research projects, he has received funding from numerous funding agencies including the NSF, USDA, and ACS PRF. He has published more than eighty research publications in peer-reviewed journals.

• Preface xviiPart 1 Introduction to Cellulosic Ethanol 11 Renewable Fuels 31.1 Introduction 31.2 Renewable Energy 61.3 Biofuels 71.4 Renewable Energy in the United States 141.5 Renewable Fuel Legislature in the United States 20References 252 Bioethanol as a Transportation Fuel 292.1 Introduction — History of Bioethanol as a Transportation Fuel 292.2 Alcohol Fuels 312.3 Fuel Characteristics of Ethanol 312.4 Corn and Sugarcane Ethanol 342.5 Advantages of Cellulosic Ethanol 35References 403 Feedstocks for Cellulosic Ethanol Production 433.1 Introduction 433.2 Cellulosic Ethanol Feedstock Types 463.3 Potential of Agricultural Wastes 463.4 Major Crop Residue Feedstock 503.5 Forestry Residue, Logging and Mill Residue 683.6 Grass Feedstocks 703.7 Purpose-Grown Trees as Feedstock 923.8 Municipal and Other Waste as Feedstock for Cellulosic Ethanol 101References 108Part 2 Aqueous Phase Biomass Hydrolysis Route 1314 Challenges in Aqueous-Phase Biomass Hydrolysis Route: Recalcitrance 1334.1 Introduction – Two Ways to Produce Cellulosic Ethanol 1334.2 Challenges in Aqueous-Phase Biomass Hydrolysis 1344.3 Structure of Plant Cells and Lignocellulosic Biomass 1354.4 Major Components of Lignocellulosic Biomass 1374.5 Cellulose Recalcitrance 140References 1435 Pretreatment of Lignocellulosic Biomass 1475.1 Introduction 1475.2 Different Categories of Pretreatment Methods 1505.3 Physical Pretreatment 1505.4 Physicochemical Pretreatment 1535.5 Chemical Pretreatment 1775.6 Biological Pretreatment 1905.7 Conclusion 191References 1976 Enzymatic Hydrolysis of Cellulose and Hemicellulose 2196.1 Introduction 2196.2 Enzymatic Actions on Lignocellulosic Biomass 2206.3 Enzymatic Hydrolysis of Cellulose 2216.4 Enzymatic Hydrolysis of Hemicellulose 2336.5 Future Directions in Enzymatic Cellulose Hydrolysis Research 237References 2397 Acid Hydrolysis of Cellulose and Hemicellulose 2477.1 Introduction 2477.2 Concentrated Acid Hydrolysis 2487.3 Dilute Acid Hydrolysis 2527.4 Ionic Liquid-Based Direct Acid Hydrolysis 2627.5 Solid Acid Hydrolysis 269References 2758 Fermentation I – Microorganisms 2838.1 Introduction 2838.2 Detoxification of Lignocellulosic Hydrolyzate 2848.3 Separate Hydrolysis and Fermentation (SHF) 2888.4 Microorganisms Used in the Fermentation 2888.5 Fermentation Using Yeasts 2898.6 Fermentation Using Bacteria 2948.7 Simultaneous Saccharification and Fermentation (SSF) 3008.8 Immobilization of Yeast 317References 3229 Fermentation II – Fermenter Configuration and Design 3399.1 Introduction 3399.2 Batch Fermentation 3409.2.1 Examples of Batch Fermentation 3409.3 Fed-Batch Fermentation 3409.4 Continuous Fermentation 3469.5 New Directions in Fermenter Configuration and Design 352References 35310 Separation and Uses of Lignin 35710.1 Introduction 35710.2 Structure of Lignin 35910.3 Separation of Lignin in the Cellulosic Ethanol Process 36010.4 Physical and Chemical Properties of Lignin 36310.5 Applications of Lignin 36510.5.1 Lignin-Based Phenol Formaldehyde Resins 365References 373Part 3 Biomass Gasification Route 38111 Biomass Pyrolysis and Gasifier Designs 38311.1 Introduction 38311.2 Chemistry of the Conversion of Biomass to Syngas 38411.3 Classifications of Biomass Gasifiers 38711.4 Fixed-Bed Gasifier 38811.5 Fluidized-Bed Gasifier 38911.6 Bubbling Fluidized-Bed (BFB) Gasifier 39011.7 Circulating Fluidized-Bed (CFB) Gasifier 39211.8 Allothermal Dual Fluidized-Bed (DFB) Gasifier 39211.9 Entrained-Flow Gasifier 39511.10 Syngas Cleaning 39611.11 Tar Control and Treatment Methods 403References 40312 Conversion of Syngas to Ethanol Using Microorganisms 40712.1 Introduction 40712.2 Metabolic Pathways 41012.3 Microorganisms Used in Syngas Fermentation 41412.4 Biochemical Reactions in Syngas Fermentation 41412.5 The Effects of Operation Parameters on Ethanol Yield 41612.6 Syngas Fermentation Reactors 42412.7 Industrial-Scale Syngas Fermentation and Commercialization 426References 42713 Conversion of Syngas to Ethanol Using Chemical Catalysts 43313.1 Introduction 43313.2 Homogeneous Catalysts 43413.3 Introduction to Heterogeneous Catalysts 43713.4 Heterogeneous Catalyst Types 43713.5 Rhodium-Based Catalysts 43813.6 Copper-Based Modified Methanol Synthesis Catalysts 44913.7 Modified Fischer-Tropsch-Type Catalysts 45513.8 Molybdenum-Based Catalysts 45613.9 Catalyst Selection 459References 461Part 4 Processing of Cellulosic Ethanol 46714 Distillation of Ethanol 46914.1 Introduction 46914.2 Distillation of the Beer 47014.3 How Distillation Works 47014.4 Conventional Ethanol Distillation System 47214.5 Steam Generation for Distillation Process 47514.6 Studies on Development of Hybrid Systems for Ethanol Distillation 476References 47915 Dehydration to Fuel Grade Ethanol 48115.1 Introduction 48115.2 Dehydration Methods 48215.3 Adsorption Method 48215.4 Azeotropic Distillation Method 48815.5 Extractive Distillation Methods 49115.6 Membrane-Based Pervaporation Methods 49415.7 Other Dehydration Methods 49815.8 Comparisons of Common Dehydration Methods 498References 500Part 5 Fuel Ethanol Standards and Process Evaluation 50716 Fuel Ethanol Standards, Testing and Blending 50916.1 Introduction 50916.2 Fuel Grade Ethanol Standards in the United States 51016.3 Quality Assurance and Test Methods 51416.4 European Fuel Ethanol Standards 51716.5 Material Safety Data Sheet (MSDS) for Denatured Fuel Ethanol 51816.6 Gasoline Ethanol Blends 52016.7 Engine Performance Using Gasoline Ethanol Blends 524References 52817 Techno-Economic Analysis and Future of Cellulosic Ethanol 53117.1 Introduction 53117.2 Techno-Economic Aspects of Biomass Hydrolysis Process 53217.3 Techno-Economic Aspects of Biomass Gasification Process 53317.4 Comparison of Biomass Hydrolysis and Gasification Processes 53917.5 Some Cellulosic Plants around the World 54017.6 Challenges in Cellulosic Ethanol 55017.7 Future Prospects of Cellulosic Ethanol 553References 554Appendix 1 557Index

Ananda S. Amarasekara is a professor in the Department of Chemistry at Prairie View A&M University in Texas. He received his PhD in organic chemistry from the City University of New York in 1985. His research interests include cellulosic ethanol, renewable fuels, catalysis in biomass processing, and renewable polymeric materials. For his current research projects, he has received funding from numerous funding agencies including the NSF, USDA, and ACS PRF. He has published more than eighty research publications in peer-reviewed journals.

• Preface xviiPart 1 Introduction to Cellulosic Ethanol 11 Renewable Fuels 31.1 Introduction 31.2 Renewable Energy 61.3 Biofuels 71.4 Renewable Energy in the United States 141.5 Renewable Fuel Legislature in the United States 20References 252 Bioethanol as a Transportation Fuel 292.1 Introduction — History of Bioethanol as a Transportation Fuel 292.2 Alcohol Fuels 312.3 Fuel Characteristics of Ethanol 312.4 Corn and Sugarcane Ethanol 342.5 Advantages of Cellulosic Ethanol 35References 403 Feedstocks for Cellulosic Ethanol Production 433.1 Introduction 433.2 Cellulosic Ethanol Feedstock Types 463.3 Potential of Agricultural Wastes 463.4 Major Crop Residue Feedstock 503.5 Forestry Residue, Logging and Mill Residue 683.6 Grass Feedstocks 703.7 Purpose-Grown Trees as Feedstock 923.8 Municipal and Other Waste as Feedstock for Cellulosic Ethanol 101References 108Part 2 Aqueous Phase Biomass Hydrolysis Route 1314 Challenges in Aqueous-Phase Biomass Hydrolysis Route: Recalcitrance 1334.1 Introduction – Two Ways to Produce Cellulosic Ethanol 1334.2 Challenges in Aqueous-Phase Biomass Hydrolysis 1344.3 Structure of Plant Cells and Lignocellulosic Biomass 1354.4 Major Components of Lignocellulosic Biomass 1374.5 Cellulose Recalcitrance 140References 1435 Pretreatment of Lignocellulosic Biomass 1475.1 Introduction 1475.2 Different Categories of Pretreatment Methods 1505.3 Physical Pretreatment 1505.4 Physicochemical Pretreatment 1535.5 Chemical Pretreatment 1775.6 Biological Pretreatment 1905.7 Conclusion 191References 1976 Enzymatic Hydrolysis of Cellulose and Hemicellulose 2196.1 Introduction 2196.2 Enzymatic Actions on Lignocellulosic Biomass 2206.3 Enzymatic Hydrolysis of Cellulose 2216.4 Enzymatic Hydrolysis of Hemicellulose 2336.5 Future Directions in Enzymatic Cellulose Hydrolysis Research 237References 2397 Acid Hydrolysis of Cellulose and Hemicellulose 2477.1 Introduction 2477.2 Concentrated Acid Hydrolysis 2487.3 Dilute Acid Hydrolysis 2527.4 Ionic Liquid-Based Direct Acid Hydrolysis 2627.5 Solid Acid Hydrolysis 269References 2758 Fermentation I – Microorganisms 2838.1 Introduction 2838.2 Detoxification of Lignocellulosic Hydrolyzate 2848.3 Separate Hydrolysis and Fermentation (SHF) 2888.4 Microorganisms Used in the Fermentation 2888.5 Fermentation Using Yeasts 2898.6 Fermentation Using Bacteria 2948.7 Simultaneous Saccharification and Fermentation (SSF) 3008.8 Immobilization of Yeast 317References 3229 Fermentation II – Fermenter Configuration and Design 3399.1 Introduction 3399.2 Batch Fermentation 3409.2.1 Examples of Batch Fermentation 3409.3 Fed-Batch Fermentation 3409.4 Continuous Fermentation 3469.5 New Directions in Fermenter Configuration and Design 352References 35310 Separation and Uses of Lignin 35710.1 Introduction 35710.2 Structure of Lignin 35910.3 Separation of Lignin in the Cellulosic Ethanol Process 36010.4 Physical and Chemical Properties of Lignin 36310.5 Applications of Lignin 36510.5.1 Lignin-Based Phenol Formaldehyde Resins 365References 373Part 3 Biomass Gasification Route 38111 Biomass Pyrolysis and Gasifier Designs 38311.1 Introduction 38311.2 Chemistry of the Conversion of Biomass to Syngas 38411.3 Classifications of Biomass Gasifiers 38711.4 Fixed-Bed Gasifier 38811.5 Fluidized-Bed Gasifier 38911.6 Bubbling Fluidized-Bed (BFB) Gasifier 39011.7 Circulating Fluidized-Bed (CFB) Gasifier 39211.8 Allothermal Dual Fluidized-Bed (DFB) Gasifier 39211.9 Entrained-Flow Gasifier 39511.10 Syngas Cleaning 39611.11 Tar Control and Treatment Methods 403References 40312 Conversion of Syngas to Ethanol Using Microorganisms 40712.1 Introduction 40712.2 Metabolic Pathways 41012.3 Microorganisms Used in Syngas Fermentation 41412.4 Biochemical Reactions in Syngas Fermentation 41412.5 The Effects of Operation Parameters on Ethanol Yield 41612.6 Syngas Fermentation Reactors 42412.7 Industrial-Scale Syngas Fermentation and Commercialization 426References 42713 Conversion of Syngas to Ethanol Using Chemical Catalysts 43313.1 Introduction 43313.2 Homogeneous Catalysts 43413.3 Introduction to Heterogeneous Catalysts 43713.4 Heterogeneous Catalyst Types 43713.5 Rhodium-Based Catalysts 43813.6 Copper-Based Modified Methanol Synthesis Catalysts 44913.7 Modified Fischer-Tropsch-Type Catalysts 45513.8 Molybdenum-Based Catalysts 45613.9 Catalyst Selection 459References 461Part 4 Processing of Cellulosic Ethanol 46714 Distillation of Ethanol 46914.1 Introduction 46914.2 Distillation of the Beer 47014.3 How Distillation Works 47014.4 Conventional Ethanol Distillation System 47214.5 Steam Generation for Distillation Process 47514.6 Studies on Development of Hybrid Systems for Ethanol Distillation 476References 47915 Dehydration to Fuel Grade Ethanol 48115.1 Introduction 48115.2 Dehydration Methods 48215.3 Adsorption Method 48215.4 Azeotropic Distillation Method 48815.5 Extractive Distillation Methods 49115.6 Membrane-Based Pervaporation Methods 49415.7 Other Dehydration Methods 49815.8 Comparisons of Common Dehydration Methods 498References 500Part 5 Fuel Ethanol Standards and Process Evaluation 50716 Fuel Ethanol Standards, Testing and Blending 50916.1 Introduction 50916.2 Fuel Grade Ethanol Standards in the United States 51016.3 Quality Assurance and Test Methods 51416.4 European Fuel Ethanol Standards 51716.5 Material Safety Data Sheet (MSDS) for Denatured Fuel Ethanol 51816.6 Gasoline Ethanol Blends 52016.7 Engine Performance Using Gasoline Ethanol Blends 524References 52817 Techno-Economic Analysis and Future of Cellulosic Ethanol 53117.1 Introduction 53117.2 Techno-Economic Aspects of Biomass Hydrolysis Process 53217.3 Techno-Economic Aspects of Biomass Gasification Process 53317.4 Comparison of Biomass Hydrolysis and Gasification Processes 53917.5 Some Cellulosic Plants around the World 54017.6 Challenges in Cellulosic Ethanol 55017.7 Future Prospects of Cellulosic Ethanol 553References 554Appendix 1 557Index

Ananda S. Amarasekara is a professor in the Department of Chemistry at Prairie View A&M University in Texas. He received his PhD in organic chemistry from the City University of New York in 1985. His research interests include cellulosic ethanol, renewable fuels, catalysis in biomass processing, and renewable polymeric materials. For his current research projects, he has received funding from numerous funding agencies including the NSF, USDA, and ACS PRF. He has published more than eighty research publications in peer-reviewed journals.

• Preface xviiPart 1 Introduction to Cellulosic Ethanol 11 Renewable Fuels 31.1 Introduction 31.2 Renewable Energy 61.3 Biofuels 71.4 Renewable Energy in the United States 141.5 Renewable Fuel Legislature in the United States 20References 252 Bioethanol as a Transportation Fuel 292.1 Introduction — History of Bioethanol as a Transportation Fuel 292.2 Alcohol Fuels 312.3 Fuel Characteristics of Ethanol 312.4 Corn and Sugarcane Ethanol 342.5 Advantages of Cellulosic Ethanol 35References 403 Feedstocks for Cellulosic Ethanol Production 433.1 Introduction 433.2 Cellulosic Ethanol Feedstock Types 463.3 Potential of Agricultural Wastes 463.4 Major Crop Residue Feedstock 503.5 Forestry Residue, Logging and Mill Residue 683.6 Grass Feedstocks 703.7 Purpose-Grown Trees as Feedstock 923.8 Municipal and Other Waste as Feedstock for Cellulosic Ethanol 101References 108Part 2 Aqueous Phase Biomass Hydrolysis Route 1314 Challenges in Aqueous-Phase Biomass Hydrolysis Route: Recalcitrance 1334.1 Introduction – Two Ways to Produce Cellulosic Ethanol 1334.2 Challenges in Aqueous-Phase Biomass Hydrolysis 1344.3 Structure of Plant Cells and Lignocellulosic Biomass 1354.4 Major Components of Lignocellulosic Biomass 1374.5 Cellulose Recalcitrance 140References 1435 Pretreatment of Lignocellulosic Biomass 1475.1 Introduction 1475.2 Different Categories of Pretreatment Methods 1505.3 Physical Pretreatment 1505.4 Physicochemical Pretreatment 1535.5 Chemical Pretreatment 1775.6 Biological Pretreatment 1905.7 Conclusion 191References 1976 Enzymatic Hydrolysis of Cellulose and Hemicellulose 2196.1 Introduction 2196.2 Enzymatic Actions on Lignocellulosic Biomass 2206.3 Enzymatic Hydrolysis of Cellulose 2216.4 Enzymatic Hydrolysis of Hemicellulose 2336.5 Future Directions in Enzymatic Cellulose Hydrolysis Research 237References 2397 Acid Hydrolysis of Cellulose and Hemicellulose 2477.1 Introduction 2477.2 Concentrated Acid Hydrolysis 2487.3 Dilute Acid Hydrolysis 2527.4 Ionic Liquid-Based Direct Acid Hydrolysis 2627.5 Solid Acid Hydrolysis 269References 2758 Fermentation I – Microorganisms 2838.1 Introduction 2838.2 Detoxification of Lignocellulosic Hydrolyzate 2848.3 Separate Hydrolysis and Fermentation (SHF) 2888.4 Microorganisms Used in the Fermentation 2888.5 Fermentation Using Yeasts 2898.6 Fermentation Using Bacteria 2948.7 Simultaneous Saccharification and Fermentation (SSF) 3008.8 Immobilization of Yeast 317References 3229 Fermentation II – Fermenter Configuration and Design 3399.1 Introduction 3399.2 Batch Fermentation 3409.2.1 Examples of Batch Fermentation 3409.3 Fed-Batch Fermentation 3409.4 Continuous Fermentation 3469.5 New Directions in Fermenter Configuration and Design 352References 35310 Separation and Uses of Lignin 35710.1 Introduction 35710.2 Structure of Lignin 35910.3 Separation of Lignin in the Cellulosic Ethanol Process 36010.4 Physical and Chemical Properties of Lignin 36310.5 Applications of Lignin 36510.5.1 Lignin-Based Phenol Formaldehyde Resins 365References 373Part 3 Biomass Gasification Route 38111 Biomass Pyrolysis and Gasifier Designs 38311.1 Introduction 38311.2 Chemistry of the Conversion of Biomass to Syngas 38411.3 Classifications of Biomass Gasifiers 38711.4 Fixed-Bed Gasifier 38811.5 Fluidized-Bed Gasifier 38911.6 Bubbling Fluidized-Bed (BFB) Gasifier 39011.7 Circulating Fluidized-Bed (CFB) Gasifier 39211.8 Allothermal Dual Fluidized-Bed (DFB) Gasifier 39211.9 Entrained-Flow Gasifier 39511.10 Syngas Cleaning 39611.11 Tar Control and Treatment Methods 403References 40312 Conversion of Syngas to Ethanol Using Microorganisms 40712.1 Introduction 40712.2 Metabolic Pathways 41012.3 Microorganisms Used in Syngas Fermentation 41412.4 Biochemical Reactions in Syngas Fermentation 41412.5 The Effects of Operation Parameters on Ethanol Yield 41612.6 Syngas Fermentation Reactors 42412.7 Industrial-Scale Syngas Fermentation and Commercialization 426References 42713 Conversion of Syngas to Ethanol Using Chemical Catalysts 43313.1 Introduction 43313.2 Homogeneous Catalysts 43413.3 Introduction to Heterogeneous Catalysts 43713.4 Heterogeneous Catalyst Types 43713.5 Rhodium-Based Catalysts 43813.6 Copper-Based Modified Methanol Synthesis Catalysts 44913.7 Modified Fischer-Tropsch-Type Catalysts 45513.8 Molybdenum-Based Catalysts 45613.9 Catalyst Selection 459References 461Part 4 Processing of Cellulosic Ethanol 46714 Distillation of Ethanol 46914.1 Introduction 46914.2 Distillation of the Beer 47014.3 How Distillation Works 47014.4 Conventional Ethanol Distillation System 47214.5 Steam Generation for Distillation Process 47514.6 Studies on Development of Hybrid Systems for Ethanol Distillation 476References 47915 Dehydration to Fuel Grade Ethanol 48115.1 Introduction 48115.2 Dehydration Methods 48215.3 Adsorption Method 48215.4 Azeotropic Distillation Method 48815.5 Extractive Distillation Methods 49115.6 Membrane-Based Pervaporation Methods 49415.7 Other Dehydration Methods 49815.8 Comparisons of Common Dehydration Methods 498References 500Part 5 Fuel Ethanol Standards and Process Evaluation 50716 Fuel Ethanol Standards, Testing and Blending 50916.1 Introduction 50916.2 Fuel Grade Ethanol Standards in the United States 51016.3 Quality Assurance and Test Methods 51416.4 European Fuel Ethanol Standards 51716.5 Material Safety Data Sheet (MSDS) for Denatured Fuel Ethanol 51816.6 Gasoline Ethanol Blends 52016.7 Engine Performance Using Gasoline Ethanol Blends 524References 52817 Techno-Economic Analysis and Future of Cellulosic Ethanol 53117.1 Introduction 53117.2 Techno-Economic Aspects of Biomass Hydrolysis Process 53217.3 Techno-Economic Aspects of Biomass Gasification Process 53317.4 Comparison of Biomass Hydrolysis and Gasification Processes 53917.5 Some Cellulosic Plants around the World 54017.6 Challenges in Cellulosic Ethanol 55017.7 Future Prospects of Cellulosic Ethanol 553References 554Appendix 1 557Index