Introduction to Chemicals from Biomass

Introduction to Chemicals from Biomass, Second Edition presents an overview of the use of biorenewable resources in thetwentyfirst century for the manufacture of chemical products,materials and energy. The book demonstrates that biomass isessentially a rich mixture of chemicals and materials and, as such,has tremendous potential as feedstock for producing a wide range ofchemicals and materials with applications in industries frompharmaceuticals to furniture. Completely revised and updated to reflect recent developments,this new edition begins with an introduction to the biorefineryconcept. This is followed by chapters addressing the various typesof available biomass feedstocks, including waste, and the differentpretreatment and processing technologies being developed to turnthese feedstocks into platform chemicals, polymers, materials andenergy. The book concludes with a discussion on the policies andstrategies being put in place for delivering the so–calledbioeconomy. Introduction to Chemicals from Biomass, Second Edition isa valuable resource for academics, industrial scientists and policy–makers working in the fields of industrialbiotechnology, biorenewables, chemical engineering, fine and bulkchemical production, agriculture technologies, plant science andenergy and power generation. We need to reduce our dependence on fossil resources andincreasingly derive all the chemicals we take for granted and usein our daily life from biomass. We must also ensure that we do thisusing green chemistry and sustainable technologies. For more information on the Wiley Series in Renewable Resources,visit www.wiley.com/go/rrs Praise for the 1st edition Drawing on the expertise of the authors the book involves adegree of plant biology and chemical engineering, which illustratesthe multidisciplinary nature of the topic beautifully

List of Contributors xi

Series Preface xiii

Preface xv

1 The Biorefinery Concept: An Integrated Approach 1
James Clark and Fabien Deswarte

1.1 Sustainability for the Twenty–First Century 1

1.2 Renewable Resources: Nature and Availability 2

1.3 The Challenge of Waste 4

1.3.1 Waste Policy and Waste Valorisation 6

1.3.2 The Food Supply Chain Waste Opportunity 7

1.3.3 Case Study: Citrus Waste 8

1.4 Green Chemistry 9

1.5 The Biorefinery Concept 11

1.5.1 Definition 11

1.5.2 Different Types of Biorefinery 12

1.5.3 Challenges and Opportunities 20

1.5.4 Biorefinery Size 24

1.6 Conclusions 24

1.7 Acknowledgement 25

References 25

2 Biomass as a Feedstock 31
Thomas M. Attard, Andrew J. Hunt, Avtar S. Matharu, Joseph A. Houghton and Igor Polikarpov

2.1 Introduction 31

2.2 Lignocellulosic Biomass 32

2.3 Food Supply Chain Waste 40

2.4 Mango Waste: A Case Study 44

2.5 Concluding Remarks 46

References 47

3 Pretreatment and Thermochemical and Biological Processing of Biomass 53
Wan Chi Lam, Tsz Him Kwan, Vitaliy L. Budarin, Egid B. Mubofu, Jiajun Fan and Carol Sze Ki Lin

3.1 Introduction 53

3.2 Biomass Pretreatments 54

3.2.1 Mechanical Pretreatment of Biomass 54

3.2.2 Physical Pretreatment of Biomass 57

3.2.3 Chemical Pretreatment of Biomass 60

3.2.4 Microwave–Assisted Hydrothermal Biomass Treatment 63

3.2.5 Biological Pretreatment 65

3.2.6 Summary 66

3.3 Thermochemical Processing of Biomass 66

3.3.1 Direct Liquefaction 66

3.3.2 Direct Combustion 70

3.3.3 Gasification 72

3.3.4 Pyrolysis 73

3.3.5 Torrefaction 74

3.4 Biological Processing 78

3.4.1 Fermentation 78

3.4.2 Anaerobic Digestion 79

3.5 Summary 83

References 83

4 Platform Molecules 89
Thomas J. Farmer and Mark Mascal

4.1 Introduction 89

4.2 Fossil–Derived Base Chemicals 91

4.3 Definition of a Platform Molecule 93

4.4 Where Platform Molecules Come From 96

4.4.1 Saccharides 97

4.4.2 Lignin 103

4.4.3 Protein 105

4.4.4 Extracts 109

4.5 Process Technologies: Biomass to Platform Molecules 114

4.6 Bio–Derived v. Fossil–Derived: Changing Downstream Chemistry 117

4.7 List of Platform Molecules 119

4.8 Example Platform Molecules 130

4.8.1 Synthesis Gas Platform: Thermal Treatment 130

4.8.2 5–(Chloromethyl)furfural: Chemical–Catalytic Treatment 133

4.8.3 n–Butanol (Biobutanol): Biological Treatment 135

4.8.4 Triglyceride Platform: Extraction 137

4.9 Conclusion 142

References 143

5 Monomers and Resulting Polymers from Biomass 157
James A. Bergman and Michael R. Kessler

5.1 Introduction 157

5.2 Polymers from Vegetable Oils 159

5.2.1 Isolation of Vegetable Oil 163

5.2.2 Thermosets of Vegetable Oils and Comonomers 163

5.2.3 Epoxidized and Acrylated Epoxidized Vegetable Oil 164

5.2.4 Polyurethanes from Vegetable Oil 165

5.2.5 Polyesters 167

5.2.6 Polyamides 168

5.2.7 Vegetable Oil Conclusion 168

5.3 Furan Chemistry 169

5.3.1 Production of Furfural and HMF 169

5.3.2 Second–Generation Derivatives 171

5.3.3 Addition Polymerizations 171

5.3.4 Furfuryl Alcohol 172

5.3.5 Polyesters 172

5.3.6 Polyamides 173

5.3.7 Other Polymers 175

5.3.8 Furan Conclusion 176

5.4 Terpenes 176

5.4.1 Production of Turpentine 177

5.4.2 Cationic Polymerization of Pinenes 178

5.4.3 Copolymerization of Pinenes 178

5.4.4 Polymerization of Non–Pinene Terpenes 179

5.4.5 Terpenoids 180

5.4.6 Terpene Conclusion 181

5.5 Rosin 181

5.5.1 Production and Chemistry of Rosin 181

5.5.2 Epoxy Resins from Rosin 183

5.5.3 Polyesters and Polyurethanes from Rosin 184

5.5.4 Thermoplastic Polymers from Rosin: Controlled Radical Techniques 184

5.5.5 Rosin Conclusion 185

5.6 The Potential of Tannins 186

5.6.1 Recent Work with Tannin Polycondensation 187

5.6.2 Tannins Conclusion 189

5.7 Alpha–Hydroxy Acids 189

5.7.1 Production of PLA 190

5.7.2 Properties of PLA 192

5.7.3 Applications of PLA 193

5.8 Conclusion 193

References 193

6 Bio–based Materials 205
Antoine Rouilly and Carlos Vaca–Garcia

6.1 Introduction 205

6.2 Wood and Natural Fibres 206

6.2.1 Molecular Constitution 206

6.2.2 Hierarchical Structure of Wood and Timber 208

6.2.3 Plant Fibres 214

6.3 Isolated and Modified Biopolymers as Biomaterials 219

6.3.1 Cellulose 220

6.3.2 Cellulose Derivatives 224

6.3.3 Starch 228

6.3.4 Starch Derivatives 230

6.3.5 Chitin and Chitosan 230

6.3.6 Proteins 231

6.4 Agromaterials, Blends and Composites 236

6.4.1 Agromaterials 236

6.4.2 Blends of Synthetic Polymers and Starch 239

6.4.3 Composites with Natural Fibres 240

6.4.4 Wood–Based Boards 243

6.4.5 Materials for Construction 244

6.5 Conclusion 245

References 245

7 Biomass–Based Energy Production 249
Mehrdad Arshadi and Anita Sellstedt

7.1 Introduction 249

7.2 Physical Upgrading Processes 250

7.2.1 Refinement of Biomass into Solid Fuels 250

7.2.2 Wood Powder 250

7.2.3 Briquette Production 251

7.2.4 Pellet Production 252

7.2.5 Storage of Solid Biomass 255

7.2.6 Torrefaction Technology 256

7.3 Microbiological Processes 257

7.3.1 Organisms and Processes 257

7.3.2 Hydrogen Production 257

7.3.3 Classification of Hydrogen–Forming Processes 258

7.3.4 Butanol Production Using Bacteria as Biocatalysts 259

7.3.5 Microbiological Ethanol Production 260

7.3.6 Production of Biodiesel from Plants and Algae 262

7.3.7 Biogas Production 263

7.4 Thermochemical Processes 265

7.4.1 Thermal Processing Equipment 266

7.4.2 Gasification 269

7.4.3 Pyrolysis 271

7.4.4 Liquefaction 272

7.4.5 Combustion 273

7.5 Chemical Processes 274

7.5.1 Dimethyl Ether (DME) 274

7.5.2 Biodiesel 274

7.6 Primary Alcohols 276

7.6.1 Methanol 276

7.6.2 Ethanol 277

7.6.3 Butanol 280

7.7 Conclusions 280

References 281

8 Policies and Strategies for Delivering a Sustainable Bioeconomy: A European Perspective 285
David Turley

8.1 Introduction 285

8.2 Drivers for Change 287

8.3 The Starting Point: Strategies for Change 288

8.4 Direct Measures 289

8.4.1 Integrated Development 290

8.4.2 Policy Mechanisms 291

8.4.3 Preferential Purchasing Policies 293

8.5 Supporting Measures 294

8.5.1 Supply–Side Drivers 294

8.5.2 Demand–Side Drivers 297

8.6 Bioeconomy Definitions 298

8.6.1 Biobased Content 298

8.6.2 Biodegradability 301

8.6.3 Composting Standards 302

8.6.4 Material Recycling 303

8.7 Life–Cycle Analysis 303

8.8 Ecolabels 304

8.9 Concluding Remarks 307

References 308

Index 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