Table Of Content

Introduction to Chemicals from Biomass Wiley Series in Renewable Resources Series Editor Christian V. Stevens – Faculty of Bioscience Engineering, Ghent University, Ghent, Belgium Titles in the Series Wood Modification – Chemical, Thermal and Other Processes Callum A.S. Hill Renewables-Based Technology – Sustainability Assessment Jo Dewulf and Herman Van Langenhove Introduction to Chemicals from Biomass James Clark and Fabien Deswarte Biofuels Wim Soetaert and Erick Vandamme Handbook of Natural Colorants Thomas Bechtold and Rita Mussak Surfactants from Renewable Resources Mikael Kjellin and Ingegärd Johansson Industrial Application of Natural Fibres – Structure, Properties and Technical Applications Jörg Müssig Thermochemical Processing of Biomass – Conversion into Fuels, Chemicals and Power Robert C. Brown Biorefinery Co-Products: Phytochemicals, Primary Metabolites and Value-Added Biomass Processing Chantal Bergeron, Danielle Julie Carrier and Shri Ramaswamy Aqueous Pretreatment of Plant Biomass for Biological and Chemical Conversion to Fuels and Chemicals Charles E. Wyman Bio-Based Plastics: Materials and Applications Stephan Kabasci Introduction to Wood and Natural Fiber Composites Douglas Stokke, Qinglin Wu and Guangping Han Cellulosic Energy Cropping Systems Douglas L. Karlen Forthcoming Titles Cellulose Nanocrystals: Properties, Production and Applications Wadood Hamad Lignin and Lignans as Renewable Raw Materials: Chemistry, Technology and Applications Francisco García Calvo-Flores, José A. Dobado, Joaquín Isac García and Francisco J. Martin-Martinez Sustainability Assessment of Renewables-Based Products: Methods and Case Studies Jo Dewulf, Steven De Meester and Rodrigo Alvarenga Biorefinery of Inorganics: Recovering Mineral Nutrients from Biomass and Organic Waste Erik Meers and Gerard Velthof Bio-Based Solvents François Jerome and Rafael Luque Introduction to Chemicals from Biomass SECONd EdITION Edited by JAMES CLARK Department of Chemistry, Green Chemistry Centre of Excellence, University of York, UK FABIEn DESWARTE Biorenewables Development Centre, The Biocentre, York Science Park, UK This edition first published 2015 © 2015 John Wiley & Sons, Ltd Registered office John Wiley & Sons, Ltd, The Atrium, Southern Gate, Chichester, West Sussex, PO19 8SQ, United Kingdom For details of our global editorial offices, for customer services and for information about how to apply for permission to reuse the copyright material in this book please see our website at www.wiley.com. 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In view of ongoing research, equipment modifications, changes in governmental regulations, and the constant flow of information relating to the use of experimental reagents, equipment, and devices, the reader is urged to review and evaluate the information provided in the package insert or instructions for each chemical, piece of equipment, reagent, or device for, among other things, any changes in the instructions or indication of usage and for added warnings and precautions. The fact that an organization or Website is referred to in this work as a citation and/or a potential source of further information does not mean that the author or the publisher endorses the information the organization or Website may provide or recommendations it may make. Further, readers should be aware that Internet Websites listed in this work may have changed or disappeared between when this work was written and when it is read. no warranty may be created or extended by any promotional statements for this work. neither the publisher nor the author shall be liable for any damages arising herefrom. Library of Congress Cataloging-in-Publication Data Introduction to chemicals from biomass / edited by James Clark, Fabien Deswarte. – Second edition. pages cm Includes bibliographical references and index. ISBn 978-1-118-71448-5 (cloth) 1. Biomass chemicals. 2. Organic compounds. I. Clark, James H., editor. II. Deswarte, Fabien E. I., editor. III. Title: Chemicals from biomass. TP248.B55I68 2015 662ʹ.88–dc23 2014045943 A catalogue record for this book is available from the British Library. Set in 10/12pt Times by SPi Publisher Services, Pondicherry, India 1 2015 Contents 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 vi Contents 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 Contents vii 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 viii Contents 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