Editors James Clark, Green Chemistry Centre of Excellence, University of York, UK Fabien Deswarte, Biorenewables Development Centre, York Science Park, UK Series Editor Christian Stevens, Faculty of Bioscience Engineering, Ghent University, Ghent, Belgium

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• List of Contributors xiSeries Preface xiiiPreface xv1 The Biorefinery Concept: An Integrated Approach 1James Clark and Fabien Deswarte1.1 Sustainability for the Twenty-First Century 11.2 Renewable Resources: Nature and Availability 21.3 The Challenge of Waste 41.3.1 Waste Policy and Waste Valorisation 61.3.2 The Food Supply Chain Waste Opportunity 71.3.3 Case Study: Citrus Waste 81.4 Green Chemistry 91.5 The Biorefinery Concept 111.5.1 Definition 111.5.2 Different Types of Biorefinery 121.5.3 Challenges and Opportunities 201.5.4 Biorefinery Size 241.6 Conclusions 241.7 Acknowledgement 25References 252 Biomass as a Feedstock 31Thomas M. Attard, Andrew J. Hunt, Avtar S. Matharu, Joseph A. Houghton and Igor Polikarpov2.1 Introduction 312.2 Lignocellulosic Biomass 322.3 Food Supply Chain Waste 402.4 Mango Waste: A Case Study 442.5 Concluding Remarks 46References 473 Pretreatment and Thermochemical and Biological Processing of Biomass 53Wan Chi Lam, Tsz Him Kwan, Vitaliy L. Budarin, Egid B. Mubofu, Jiajun Fan and Carol Sze Ki Lin3.1 Introduction 533.2 Biomass Pretreatments 543.2.1 Mechanical Pretreatment of Biomass 543.2.2 Physical Pretreatment of Biomass 573.2.3 Chemical Pretreatment of Biomass 603.2.4 Microwave-Assisted Hydrothermal Biomass Treatment 633.2.5 Biological Pretreatment 653.2.6 Summary 663.3 Thermochemical Processing of Biomass 663.3.1 Direct Liquefaction 663.3.2 Direct Combustion 703.3.3 Gasification 723.3.4 Pyrolysis 733.3.5 Torrefaction 743.4 Biological Processing 783.4.1 Fermentation 783.4.2 Anaerobic Digestion 793.5 Summary 83References 834 Platform Molecules 89Thomas J. Farmer and Mark Mascal4.1 Introduction 894.2 Fossil-Derived Base Chemicals 914.3 Definition of a Platform Molecule 934.4 Where Platform Molecules Come From 964.4.1 Saccharides 974.4.2 Lignin 1034.4.3 Protein 1054.4.4 Extracts 1094.5 Process Technologies: Biomass to Platform Molecules 1144.6 Bio-Derived v. Fossil-Derived: Changing Downstream Chemistry 1174.7 List of Platform Molecules 1194.8 Example Platform Molecules 1304.8.1 Synthesis Gas Platform: Thermal Treatment 1304.8.2 5-(Chloromethyl)furfural: Chemical-Catalytic Treatment 1334.8.3 n-Butanol (Biobutanol): Biological Treatment 1354.8.4 Triglyceride Platform: Extraction 1374.9 Conclusion 142References 1435 Monomers and Resulting Polymers from Biomass 157James A. Bergman and Michael R. Kessler5.1 Introduction 1575.2 Polymers from Vegetable Oils 1595.2.1 Isolation of Vegetable Oil 1635.2.2 Thermosets of Vegetable Oils and Comonomers 1635.2.3 Epoxidized and Acrylated Epoxidized Vegetable Oil 1645.2.4 Polyurethanes from Vegetable Oil 1655.2.5 Polyesters 1675.2.6 Polyamides 1685.2.7 Vegetable Oil Conclusion 1685.3 Furan Chemistry 1695.3.1 Production of Furfural and HMF 1695.3.2 Second-Generation Derivatives 1715.3.3 Addition Polymerizations 1715.3.4 Furfuryl Alcohol 1725.3.5 Polyesters 1725.3.6 Polyamides 1735.3.7 Other Polymers 1755.3.8 Furan Conclusion 1765.4 Terpenes 1765.4.1 Production of Turpentine 1775.4.2 Cationic Polymerization of Pinenes 1785.4.3 Copolymerization of Pinenes 1785.4.4 Polymerization of Non-Pinene Terpenes 1795.4.5 Terpenoids 1805.4.6 Terpene Conclusion 1815.5 Rosin 1815.5.1 Production and Chemistry of Rosin 1815.5.2 Epoxy Resins from Rosin 1835.5.3 Polyesters and Polyurethanes from Rosin 1845.5.4 Thermoplastic Polymers from Rosin: Controlled Radical Techniques 1845.5.5 Rosin Conclusion 1855.6 The Potential of Tannins 1865.6.1 Recent Work with Tannin Polycondensation 1875.6.2 Tannins Conclusion 1895.7 Alpha-Hydroxy Acids 1895.7.1 Production of PLA 1905.7.2 Properties of PLA 1925.7.3 Applications of PLA 1935.8 Conclusion 193References 1936 Bio-based Materials 205Antoine Rouilly and Carlos Vaca-Garcia6.1 Introduction 2056.2 Wood and Natural Fibres 2066.2.1 Molecular Constitution 2066.2.2 Hierarchical Structure of Wood and Timber 2086.2.3 Plant Fibres 2146.3 Isolated and Modified Biopolymers as Biomaterials 2196.3.1 Cellulose 2206.3.2 Cellulose Derivatives 2246.3.3 Starch 2286.3.4 Starch Derivatives 2306.3.5 Chitin and Chitosan 2306.3.6 Proteins 2316.4 Agromaterials, Blends and Composites 2366.4.1 Agromaterials 2366.4.2 Blends of Synthetic Polymers and Starch 2396.4.3 Composites with Natural Fibres 2406.4.4 Wood-Based Boards 2436.4.5 Materials for Construction 2446.5 Conclusion 245References 2457 Biomass-Based Energy Production 249Mehrdad Arshadi and Anita Sellstedt7.1 Introduction 2497.2 Physical Upgrading Processes 2507.2.1 Refinement of Biomass into Solid Fuels 2507.2.2 Wood Powder 2507.2.3 Briquette Production 2517.2.4 Pellet Production 2527.2.5 Storage of Solid Biomass 2557.2.6 Torrefaction Technology 2567.3 Microbiological Processes 2577.3.1 Organisms and Processes 2577.3.2 Hydrogen Production 2577.3.3 Classification of Hydrogen-Forming Processes 2587.3.4 Butanol Production Using Bacteria as Biocatalysts 2597.3.5 Microbiological Ethanol Production 2607.3.6 Production of Biodiesel from Plants and Algae 2627.3.7 Biogas Production 2637.4 Thermochemical Processes 2657.4.1 Thermal Processing Equipment 2667.4.2 Gasification 2697.4.3 Pyrolysis 2717.4.4 Liquefaction 2727.4.5 Combustion 2737.5 Chemical Processes 2747.5.1 Dimethyl Ether (DME) 2747.5.2 Biodiesel 2747.6 Primary Alcohols 2767.6.1 Methanol 2767.6.2 Ethanol 2777.6.3 Butanol 2807.7 Conclusions 280References 2818 Policies and Strategies for Delivering a Sustainable Bioeconomy: A European Perspective 285David Turley8.1 Introduction 2858.2 Drivers for Change 2878.3 The Starting Point: Strategies for Change 2888.4 Direct Measures 2898.4.1 Integrated Development 2908.4.2 Policy Mechanisms 2918.4.3 Preferential Purchasing Policies 2938.5 Supporting Measures 2948.5.1 Supply-Side Drivers 2948.5.2 Demand-Side Drivers 2978.6 Bioeconomy Definitions 2988.6.1 Biobased Content 2988.6.2 Biodegradability 3018.6.3 Composting Standards 3028.6.4 Material Recycling 3038.7 Life-Cycle Analysis 3038.8 Ecolabels 3048.9 Concluding Remarks 307References 308Index 311

Editors James Clark, Green Chemistry Centre of Excellence, University of York, UK Fabien Deswarte, Biorenewables Development Centre, York Science Park, UK Series Editor Christian Stevens, Faculty of Bioscience Engineering, Ghent University, Ghent, Belgium

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• List of Contributors xiSeries Preface xiiiPreface xv1 The Biorefinery Concept: An Integrated Approach 1James Clark and Fabien Deswarte1.1 Sustainability for the Twenty-First Century 11.2 Renewable Resources: Nature and Availability 21.3 The Challenge of Waste 41.3.1 Waste Policy and Waste Valorisation 61.3.2 The Food Supply Chain Waste Opportunity 71.3.3 Case Study: Citrus Waste 81.4 Green Chemistry 91.5 The Biorefinery Concept 111.5.1 Definition 111.5.2 Different Types of Biorefinery 121.5.3 Challenges and Opportunities 201.5.4 Biorefinery Size 241.6 Conclusions 241.7 Acknowledgement 25References 252 Biomass as a Feedstock 31Thomas M. Attard, Andrew J. Hunt, Avtar S. Matharu, Joseph A. Houghton and Igor Polikarpov2.1 Introduction 312.2 Lignocellulosic Biomass 322.3 Food Supply Chain Waste 402.4 Mango Waste: A Case Study 442.5 Concluding Remarks 46References 473 Pretreatment and Thermochemical and Biological Processing of Biomass 53Wan Chi Lam, Tsz Him Kwan, Vitaliy L. Budarin, Egid B. Mubofu, Jiajun Fan and Carol Sze Ki Lin3.1 Introduction 533.2 Biomass Pretreatments 543.2.1 Mechanical Pretreatment of Biomass 543.2.2 Physical Pretreatment of Biomass 573.2.3 Chemical Pretreatment of Biomass 603.2.4 Microwave-Assisted Hydrothermal Biomass Treatment 633.2.5 Biological Pretreatment 653.2.6 Summary 663.3 Thermochemical Processing of Biomass 663.3.1 Direct Liquefaction 663.3.2 Direct Combustion 703.3.3 Gasification 723.3.4 Pyrolysis 733.3.5 Torrefaction 743.4 Biological Processing 783.4.1 Fermentation 783.4.2 Anaerobic Digestion 793.5 Summary 83References 834 Platform Molecules 89Thomas J. Farmer and Mark Mascal4.1 Introduction 894.2 Fossil-Derived Base Chemicals 914.3 Definition of a Platform Molecule 934.4 Where Platform Molecules Come From 964.4.1 Saccharides 974.4.2 Lignin 1034.4.3 Protein 1054.4.4 Extracts 1094.5 Process Technologies: Biomass to Platform Molecules 1144.6 Bio-Derived v. Fossil-Derived: Changing Downstream Chemistry 1174.7 List of Platform Molecules 1194.8 Example Platform Molecules 1304.8.1 Synthesis Gas Platform: Thermal Treatment 1304.8.2 5-(Chloromethyl)furfural: Chemical-Catalytic Treatment 1334.8.3 n-Butanol (Biobutanol): Biological Treatment 1354.8.4 Triglyceride Platform: Extraction 1374.9 Conclusion 142References 1435 Monomers and Resulting Polymers from Biomass 157James A. Bergman and Michael R. Kessler5.1 Introduction 1575.2 Polymers from Vegetable Oils 1595.2.1 Isolation of Vegetable Oil 1635.2.2 Thermosets of Vegetable Oils and Comonomers 1635.2.3 Epoxidized and Acrylated Epoxidized Vegetable Oil 1645.2.4 Polyurethanes from Vegetable Oil 1655.2.5 Polyesters 1675.2.6 Polyamides 1685.2.7 Vegetable Oil Conclusion 1685.3 Furan Chemistry 1695.3.1 Production of Furfural and HMF 1695.3.2 Second-Generation Derivatives 1715.3.3 Addition Polymerizations 1715.3.4 Furfuryl Alcohol 1725.3.5 Polyesters 1725.3.6 Polyamides 1735.3.7 Other Polymers 1755.3.8 Furan Conclusion 1765.4 Terpenes 1765.4.1 Production of Turpentine 1775.4.2 Cationic Polymerization of Pinenes 1785.4.3 Copolymerization of Pinenes 1785.4.4 Polymerization of Non-Pinene Terpenes 1795.4.5 Terpenoids 1805.4.6 Terpene Conclusion 1815.5 Rosin 1815.5.1 Production and Chemistry of Rosin 1815.5.2 Epoxy Resins from Rosin 1835.5.3 Polyesters and Polyurethanes from Rosin 1845.5.4 Thermoplastic Polymers from Rosin: Controlled Radical Techniques 1845.5.5 Rosin Conclusion 1855.6 The Potential of Tannins 1865.6.1 Recent Work with Tannin Polycondensation 1875.6.2 Tannins Conclusion 1895.7 Alpha-Hydroxy Acids 1895.7.1 Production of PLA 1905.7.2 Properties of PLA 1925.7.3 Applications of PLA 1935.8 Conclusion 193References 1936 Bio-based Materials 205Antoine Rouilly and Carlos Vaca-Garcia6.1 Introduction 2056.2 Wood and Natural Fibres 2066.2.1 Molecular Constitution 2066.2.2 Hierarchical Structure of Wood and Timber 2086.2.3 Plant Fibres 2146.3 Isolated and Modified Biopolymers as Biomaterials 2196.3.1 Cellulose 2206.3.2 Cellulose Derivatives 2246.3.3 Starch 2286.3.4 Starch Derivatives 2306.3.5 Chitin and Chitosan 2306.3.6 Proteins 2316.4 Agromaterials, Blends and Composites 2366.4.1 Agromaterials 2366.4.2 Blends of Synthetic Polymers and Starch 2396.4.3 Composites with Natural Fibres 2406.4.4 Wood-Based Boards 2436.4.5 Materials for Construction 2446.5 Conclusion 245References 2457 Biomass-Based Energy Production 249Mehrdad Arshadi and Anita Sellstedt7.1 Introduction 2497.2 Physical Upgrading Processes 2507.2.1 Refinement of Biomass into Solid Fuels 2507.2.2 Wood Powder 2507.2.3 Briquette Production 2517.2.4 Pellet Production 2527.2.5 Storage of Solid Biomass 2557.2.6 Torrefaction Technology 2567.3 Microbiological Processes 2577.3.1 Organisms and Processes 2577.3.2 Hydrogen Production 2577.3.3 Classification of Hydrogen-Forming Processes 2587.3.4 Butanol Production Using Bacteria as Biocatalysts 2597.3.5 Microbiological Ethanol Production 2607.3.6 Production of Biodiesel from Plants and Algae 2627.3.7 Biogas Production 2637.4 Thermochemical Processes 2657.4.1 Thermal Processing Equipment 2667.4.2 Gasification 2697.4.3 Pyrolysis 2717.4.4 Liquefaction 2727.4.5 Combustion 2737.5 Chemical Processes 2747.5.1 Dimethyl Ether (DME) 2747.5.2 Biodiesel 2747.6 Primary Alcohols 2767.6.1 Methanol 2767.6.2 Ethanol 2777.6.3 Butanol 2807.7 Conclusions 280References 2818 Policies and Strategies for Delivering a Sustainable Bioeconomy: A European Perspective 285David Turley8.1 Introduction 2858.2 Drivers for Change 2878.3 The Starting Point: Strategies for Change 2888.4 Direct Measures 2898.4.1 Integrated Development 2908.4.2 Policy Mechanisms 2918.4.3 Preferential Purchasing Policies 2938.5 Supporting Measures 2948.5.1 Supply-Side Drivers 2948.5.2 Demand-Side Drivers 2978.6 Bioeconomy Definitions 2988.6.1 Biobased Content 2988.6.2 Biodegradability 3018.6.3 Composting Standards 3028.6.4 Material Recycling 3038.7 Life-Cycle Analysis 3038.8 Ecolabels 3048.9 Concluding Remarks 307References 308Index 311

Editors James Clark, Green Chemistry Centre of Excellence, University of York, UK Fabien Deswarte, Biorenewables Development Centre, York Science Park, UK Series Editor Christian Stevens, Faculty of Bioscience Engineering, Ghent University, Ghent, Belgium

Select Guide Rating

• List of Contributors xiSeries Preface xiiiPreface xv1 The Biorefinery Concept: An Integrated Approach 1James Clark and Fabien Deswarte1.1 Sustainability for the Twenty-First Century 11.2 Renewable Resources: Nature and Availability 21.3 The Challenge of Waste 41.3.1 Waste Policy and Waste Valorisation 61.3.2 The Food Supply Chain Waste Opportunity 71.3.3 Case Study: Citrus Waste 81.4 Green Chemistry 91.5 The Biorefinery Concept 111.5.1 Definition 111.5.2 Different Types of Biorefinery 121.5.3 Challenges and Opportunities 201.5.4 Biorefinery Size 241.6 Conclusions 241.7 Acknowledgement 25References 252 Biomass as a Feedstock 31Thomas M. Attard, Andrew J. Hunt, Avtar S. Matharu, Joseph A. Houghton and Igor Polikarpov2.1 Introduction 312.2 Lignocellulosic Biomass 322.3 Food Supply Chain Waste 402.4 Mango Waste: A Case Study 442.5 Concluding Remarks 46References 473 Pretreatment and Thermochemical and Biological Processing of Biomass 53Wan Chi Lam, Tsz Him Kwan, Vitaliy L. Budarin, Egid B. Mubofu, Jiajun Fan and Carol Sze Ki Lin3.1 Introduction 533.2 Biomass Pretreatments 543.2.1 Mechanical Pretreatment of Biomass 543.2.2 Physical Pretreatment of Biomass 573.2.3 Chemical Pretreatment of Biomass 603.2.4 Microwave-Assisted Hydrothermal Biomass Treatment 633.2.5 Biological Pretreatment 653.2.6 Summary 663.3 Thermochemical Processing of Biomass 663.3.1 Direct Liquefaction 663.3.2 Direct Combustion 703.3.3 Gasification 723.3.4 Pyrolysis 733.3.5 Torrefaction 743.4 Biological Processing 783.4.1 Fermentation 783.4.2 Anaerobic Digestion 793.5 Summary 83References 834 Platform Molecules 89Thomas J. Farmer and Mark Mascal4.1 Introduction 894.2 Fossil-Derived Base Chemicals 914.3 Definition of a Platform Molecule 934.4 Where Platform Molecules Come From 964.4.1 Saccharides 974.4.2 Lignin 1034.4.3 Protein 1054.4.4 Extracts 1094.5 Process Technologies: Biomass to Platform Molecules 1144.6 Bio-Derived v. Fossil-Derived: Changing Downstream Chemistry 1174.7 List of Platform Molecules 1194.8 Example Platform Molecules 1304.8.1 Synthesis Gas Platform: Thermal Treatment 1304.8.2 5-(Chloromethyl)furfural: Chemical-Catalytic Treatment 1334.8.3 n-Butanol (Biobutanol): Biological Treatment 1354.8.4 Triglyceride Platform: Extraction 1374.9 Conclusion 142References 1435 Monomers and Resulting Polymers from Biomass 157James A. Bergman and Michael R. Kessler5.1 Introduction 1575.2 Polymers from Vegetable Oils 1595.2.1 Isolation of Vegetable Oil 1635.2.2 Thermosets of Vegetable Oils and Comonomers 1635.2.3 Epoxidized and Acrylated Epoxidized Vegetable Oil 1645.2.4 Polyurethanes from Vegetable Oil 1655.2.5 Polyesters 1675.2.6 Polyamides 1685.2.7 Vegetable Oil Conclusion 1685.3 Furan Chemistry 1695.3.1 Production of Furfural and HMF 1695.3.2 Second-Generation Derivatives 1715.3.3 Addition Polymerizations 1715.3.4 Furfuryl Alcohol 1725.3.5 Polyesters 1725.3.6 Polyamides 1735.3.7 Other Polymers 1755.3.8 Furan Conclusion 1765.4 Terpenes 1765.4.1 Production of Turpentine 1775.4.2 Cationic Polymerization of Pinenes 1785.4.3 Copolymerization of Pinenes 1785.4.4 Polymerization of Non-Pinene Terpenes 1795.4.5 Terpenoids 1805.4.6 Terpene Conclusion 1815.5 Rosin 1815.5.1 Production and Chemistry of Rosin 1815.5.2 Epoxy Resins from Rosin 1835.5.3 Polyesters and Polyurethanes from Rosin 1845.5.4 Thermoplastic Polymers from Rosin: Controlled Radical Techniques 1845.5.5 Rosin Conclusion 1855.6 The Potential of Tannins 1865.6.1 Recent Work with Tannin Polycondensation 1875.6.2 Tannins Conclusion 1895.7 Alpha-Hydroxy Acids 1895.7.1 Production of PLA 1905.7.2 Properties of PLA 1925.7.3 Applications of PLA 1935.8 Conclusion 193References 1936 Bio-based Materials 205Antoine Rouilly and Carlos Vaca-Garcia6.1 Introduction 2056.2 Wood and Natural Fibres 2066.2.1 Molecular Constitution 2066.2.2 Hierarchical Structure of Wood and Timber 2086.2.3 Plant Fibres 2146.3 Isolated and Modified Biopolymers as Biomaterials 2196.3.1 Cellulose 2206.3.2 Cellulose Derivatives 2246.3.3 Starch 2286.3.4 Starch Derivatives 2306.3.5 Chitin and Chitosan 2306.3.6 Proteins 2316.4 Agromaterials, Blends and Composites 2366.4.1 Agromaterials 2366.4.2 Blends of Synthetic Polymers and Starch 2396.4.3 Composites with Natural Fibres 2406.4.4 Wood-Based Boards 2436.4.5 Materials for Construction 2446.5 Conclusion 245References 2457 Biomass-Based Energy Production 249Mehrdad Arshadi and Anita Sellstedt7.1 Introduction 2497.2 Physical Upgrading Processes 2507.2.1 Refinement of Biomass into Solid Fuels 2507.2.2 Wood Powder 2507.2.3 Briquette Production 2517.2.4 Pellet Production 2527.2.5 Storage of Solid Biomass 2557.2.6 Torrefaction Technology 2567.3 Microbiological Processes 2577.3.1 Organisms and Processes 2577.3.2 Hydrogen Production 2577.3.3 Classification of Hydrogen-Forming Processes 2587.3.4 Butanol Production Using Bacteria as Biocatalysts 2597.3.5 Microbiological Ethanol Production 2607.3.6 Production of Biodiesel from Plants and Algae 2627.3.7 Biogas Production 2637.4 Thermochemical Processes 2657.4.1 Thermal Processing Equipment 2667.4.2 Gasification 2697.4.3 Pyrolysis 2717.4.4 Liquefaction 2727.4.5 Combustion 2737.5 Chemical Processes 2747.5.1 Dimethyl Ether (DME) 2747.5.2 Biodiesel 2747.6 Primary Alcohols 2767.6.1 Methanol 2767.6.2 Ethanol 2777.6.3 Butanol 2807.7 Conclusions 280References 2818 Policies and Strategies for Delivering a Sustainable Bioeconomy: A European Perspective 285David Turley8.1 Introduction 2858.2 Drivers for Change 2878.3 The Starting Point: Strategies for Change 2888.4 Direct Measures 2898.4.1 Integrated Development 2908.4.2 Policy Mechanisms 2918.4.3 Preferential Purchasing Policies 2938.5 Supporting Measures 2948.5.1 Supply-Side Drivers 2948.5.2 Demand-Side Drivers 2978.6 Bioeconomy Definitions 2988.6.1 Biobased Content 2988.6.2 Biodegradability 3018.6.3 Composting Standards 3028.6.4 Material Recycling 3038.7 Life-Cycle Analysis 3038.8 Ecolabels 3048.9 Concluding Remarks 307References 308Index 311