Aqueous pretreatment of plant biomass for biological and chemical conversion to fuels and chemicals

Aqueous Pretreatment of Plant Biomass for Biological and Chemical Conversion to Fuels and Chemicals 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 & Herman Van Langenhove Introduction to Chemicals from Biomass James H Clark & Fabien E.I Deswarte Biofuels WimSoetaert & Erick Vandamme Handbook of Natural Colorants Thomas Bechtold & Rita Mussak Surfactants from Renewable Resources Mikael Kjellin & Ingeg€ard Johansson Industrial Application of Natural Fibres: Structure, Properties and Technical Applications J€ org M€ ussig 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 Forthcoming Titles Introduction to Wood and Natural Fiber Composites Douglas Stokke, Qinglin Wu & Guangping Han Bio-based Plastics: Materials and Applications Stephan Kabasci Cellulosic Energy Cropping Systems Doug Karlen Biobased Materials in Protective and Decorative Coatings Dean Webster Aqueous Pretreatment of Plant Biomass for Biological and Chemical Conversion to Fuels and Chemicals Editor CHARLES E WYMAN Department of Chemical and Environmental Engineering and Center for Environmental Research and Technology, University of California, Riverside, USA and BioEnergy Science Center, Oak Ridge, USA This edition first published 2013 # 2013 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 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Hardback ISBN: 9780470972021 Set in 10/12pt, Times by Thomson Digital, Noida, India Contents List of Contributors xvii Foreword xxi Series Preface Preface Acknowledgements Introduction Charles E Wyman 1.1 Cellulosic Biomass: What and Why? 1.2 Aqueous Processing of Cellulosic Biomass into Organic Fuels and Chemicals 1.3 Attributes for Successful Pretreatment 1.4 Pretreatment Options 1.5 Possible Blind Spots in the Historic Pretreatment Paradigm 1.6 Other Distinguishing Features of Pretreatment Technologies 1.7 Book Approach 1.8 Overview of Book Chapters Acknowledgements References Cellulosic Biofuels: Importance, Recalcitrance, and Pretreatment Lee Lynd and Mark Laser 2.1 Our Place in History 2.2 The Need for Energy from Biomass 2.3 The Importance of Cellulosic Biomass 2.4 Potential Barriers 2.5 Biological and Thermochemical Approaches to the Recalcitrance Barrier 2.6 Pretreatment Acknowledgements References xxiii xxv xxvii 9 10 10 11 17 17 17 18 18 19 20 21 21 vi Contents Plant Cell Walls: Basics of Structure, Chemistry, Accessibility and the Influence on Conversion Brian H Davison, Jerry Parks, Mark F Davis and Bryon S Donohoe 3.1 3.2 3.3 3.4 3.5 3.6 3.7 3.8 23 Introduction Biomass Diversity Leads to Variability in Cell-wall Structure and Composition Processing Options for Accessing the Energy in the Lignocellulosic Matrix Plant Tissue and Cell Types Respond Differently to Biomass Conversion The Basics of Plant Cell-wall Structure Cell-wall Surfaces and Multilamellar Architecture Cell-wall Ultrastructure and Nanoporosity Computer Simulation in Understanding Biomass Recalcitrance 3.8.1 What Can We Learn from Molecular Simulation? 3.8.2 Simulations of Lignin 3.8.3 Simulations of Cellulose 3.8.4 Simulation of Lignocellulosic Biomass 3.8.5 Outlook for Biomass Simulations 3.9 Summary Acknowledgements References 23 24 26 28 29 30 31 32 32 33 34 35 35 35 36 36 Biological Conversion of Plants to Fuels and Chemicals and the Effects of Inhibitors Eduardo Ximenes, Youngmi Kim and Michael R Ladisch 39 4.1 4.2 4.3 Introduction Overview of Biological Conversion Enzyme and Ethanol Fermentation Inhibitors Released during Pretreatment and/or Enzyme Hydrolysis 4.3.1 Enzyme Inhibitors Derived from Plant Cell-wall Constituents (Lignin, Soluble Phenolics, and Hemicellulose) 4.3.2 Effect of Furfurals and Acetic Acid as Inhibitors of Ethanol Fermentations 4.4 Hydrolysis of Pentose Sugar Oligomers Using Solid-acid Catalysts 4.4.1 Application of Solid-acid Catalysts for Hydrolysis of Sugar Oligomers Derived from Lignocelluloses 4.4.2 Factors Affecting Efficiency of Solid-acid-catalyzed Hydrolysis 4.5 Conclusions Acknowledgements References Catalytic Strategies for Converting Lignocellulosic Carbohydrates to Fuels and Chemicals Jesse Q Bond, David Martin Alonso and James A Dumesic 5.1 5.2 5.3 Introduction Biomass Conversion Strategies Criteria for Fuels and Chemicals 5.3.1 General Considerations in the Production of Fuels and Fuel Additives 5.3.2 Consideration for Specialty Chemicals 39 40 42 43 48 50 50 51 56 57 57 61 61 62 64 64 66 Contents 5.4 vii Primary Feedstocks and Platforms 5.4.1 Cellulose 5.4.2 Hemicellulose 5.5 Sugar Conversion and Key Intermediates 5.5.1 Sugar Oxidation 5.5.2 Sugar Reduction (Polyol Production) 5.5.3 Sugar Dehydration (Furan Production) 5.6 Conclusions Acknowledgements References 66 66 67 68 69 70 77 91 92 92 Fundamentals of Biomass Pretreatment at Low pH Heather L Trajano and Charles E Wyman 103 6.1 6.2 Introduction Effects of Low pH on Biomass Solids 6.2.1 Cellulose 6.2.2 Hemicellulose 6.2.3 Lignin 6.2.4 Ash 6.2.5 Ultrastructure 6.2.6 Summary of Effects of Low pH on Biomass Solids 6.3 Pretreatment in Support of Biological Conversion 6.3.1 Hydrolysis of Cellulose to Fermentable Glucose 6.3.2 Pretreatment for Improved Enzymatic Digestibility 6.3.3 Pretreatment for Improved Enzymatic Digestibility and Hemicellulose Sugar Recovery 6.4 Low-pH Hydrolysis of Cellulose and Hemicellulose 6.4.1 Furfural 6.4.2 Levulinic Acid 6.4.3 Drop-in Hydrocarbons 6.5 Models of Low-pH Biomass Reactions 6.5.1 Cellulose Hydrolysis 6.5.2 Hemicellulose Hydrolysis 6.5.3 Summary of Kinetic Models 6.6 Conclusions Acknowledgements References Fundamentals of Aqueous Pretreatment of Biomass Nathan S Mosier 7.1 7.2 7.3 7.4 Introduction Self-ionization of Water Catalyzes Plant Cell-wall Depolymerization Products from the Hydrolysis of the Plant Cell Wall Contribute to Further Depolymerization Mechanisms of Aqueous Pretreatment 103 104 104 105 106 107 107 108 108 108 109 110 114 114 115 115 116 117 118 120 122 123 123 129 129 130 131 131 viii Contents 7.4.1 Hemicellulose 7.4.2 Lignin 7.4.3 Cellulose 7.5 Impact of Aqueous Pretreatment on Cellulose Digestibility 7.6 Practical Applications of Liquid Hot Water Pretreatment 7.7 Conclusions References Fundamentals of Biomass Pretreatment at High pH Rocıo Sierra Ramirez, Mark Holtzapple and Natalia Piamonte 8.1 8.2 Introduction Chemical Effects of Alkaline Pretreatments on Biomass Composition 8.2.1 Non-oxidative Delignification 8.2.2 Non-oxidative Sugar Degradation 8.2.3 Oxidative Delignification 8.2.4 Oxidative Sugar Degradation 8.3 Ammonia Pretreatments 8.4 Sodium Hydroxide Pretreatments 8.5 Alkaline Wet Oxidation 8.6 Lime Pretreatment 8.7 Pretreatment Severity 8.8 Pretreatment Selectivity 8.9 Concluding Remarks References Primer on Ammonia Fiber Expansion Pretreatment S.P.S Chundawat, B Bals, T Campbell, L Sousa, D Gao, M Jin, P Eranki, R Garlock, F Teymouri, V Balan and B.E Dale 9.1 9.2 9.3 9.4 9.5 9.6 9.7 Historical Perspective of Ammonia-based Pretreatments Overview of AFEX and its Physicochemical Impacts Enzymatic and Microbial Activity on AFEX-treated Biomass 9.3.1 Impact of AFEX Pretreatment on Cellulase Binding to Biomass 9.3.2 Enzymatic Digestibility of AFEX-treated Biomass 9.3.3 Microbial Fermentability of AFEX-treated Biomass Transgenic Plants and AFEX Pretreatment Recent Research Developments on AFEX Strategies and Reactor Configurations 9.5.1 Non-extractive AFEX Systems 9.5.2 Extractive AFEX Systems 9.5.3 Fluidized Gaseous AFEX Systems Perspectives on AFEX Commercialization 9.6.1 AFEX Pretreatment Commercialization in Cellulosic Biorefineries 9.6.2 Novel Value-added Products from AFEX-related Processes 9.6.3 AFEX-centric Regional Biomass Processing Depot Environmental and Life-cycle Analyses for AFEX-centric Processes 131 134 136 137 138 140 140 145 145 146 147 148 150 151 153 155 155 158 161 161 163 163 169 169 170 175 175 176 178 183 185 185 186 186 186 186 190 192 193 Contents 9.8 Conclusions Acknowledgements References 10 Fundamentals of Biomass Pretreatment by Fractionation Poulomi Sannigrahi and Arthur J Ragauskas 10.1 Introduction 10.2 Organosolv Pretreatment 10.2.1 Organosolv Pulping 10.2.2 Overview of Organosolv Pretreatment 10.2.3 Solvents and Catalysts for Organosolv Pretreatment 10.2.4 Fractionation of Biomass during Organosolv Pretreatment 10.3 Nature of Organosolv Lignin and Chemistry of Organosolv Delignification 10.3.1 Composition and Structure of Organosolv Lignin 10.3.2 Mechanisms of Organosolv Delignification 10.3.3 Commercial Applications of Organosolv Lignin 10.4 Structural and Compositional Characteristics of Cellulose 10.5 Co-products of Biomass Fractionation by Organosolv Pretreatment 10.5.1 Hemicellulose 10.5.2 Furfural 10.5.3 Hydroxymethylfurfural (HMF) 10.5.4 Levulinic Acid 10.5.5 Acetic Acid 10.6 Conclusions and Recommendations Acknowledgements References ix 194 195 195 201 201 202 202 202 203 209 210 210 213 214 214 216 216 217 218 218 219 219 219 219 11 Ionic Liquid Pretreatment: Mechanism, Performance, and Challenges Seema Singh and Blake A Simmons 223 11.1 Introduction 11.2 Ionic Liquid Pretreatment: Mechanism 11.2.1 IL Polarity and Kamlet–Taft Parameters 11.2.2 Interactions between ILs and Cellulose 11.2.3 Interactions between ILs and Lignin 11.3 Ionic Liquid Biomass Pretreatment: Enzymatic Route 11.3.1 Grasses 11.3.2 Agricultural Residues 11.3.3 Woody Biomass 11.4 Ionic Liquid Pretreatment: Catalytic Route 11.4.1 Acid-catalyzed Hydrolysis 11.4.2 Metal-catalyzed Hydrolysis 11.5 Factors Impacting Scalability and Cost of Ionic Liquid Pretreatment 11.6 Concluding Remarks Acknowledgements References 223 225 226 226 227 228 228 230 230 231 232 232 233 234 234 234 x Contents 12 Comparative Performance of Leading Pretreatment Technologies for Biological Conversion of Corn Stover, Poplar Wood, and Switchgrass to Sugars Charles E Wyman, Bruce E Dale, Venkatesh Balan, Richard T Elander, Mark T Holtzapple, Rocıo Sierra Ramirez, Michael R Ladisch, Nathan Mosier, Y.Y Lee, Rajesh Gupta, Steven R Thomas, Bonnie R Hames, Ryan Warner and Rajeev Kumar 12.1 Introduction 12.2 Materials and Methods 12.2.1 Feedstocks 12.2.2 Enzymes 12.2.3 CAFI Pretreatments 12.2.4 Material Balances 12.2.5 Free Sugars and Extraction 12.3 Yields of Xylose and Glucose from Pretreatment and Enzymatic Hydrolysis 12.3.1 Yields from Corn Stover 12.3.2 Yields from Standard Poplar 12.3.3 Yields from Dacotah Switchgrass 12.4 Impact of Changes in Biomass Sources 12.5 Compositions of Solids Following CAFI Pretreatments 12.5.1 Composition of Pretreated Corn Stover Solids 12.5.2 Composition of Pretreated Switchgrass Solids 12.5.3 Composition of Pretreated Poplar Solids 12.5.4 Overall Trends in Composition of Pretreated Biomass Solids and Impact on Enzymatic Hydrolysis 12.6 Pretreatment Conditions to Maximize Total Glucose Plus Xylose Yields 12.7 Implications of the CAFI Results 12.8 Closing Thoughts Acknowledgements References 13 Effects of Enzyme Formulation and Loadings on Conversion of Biomass Pretreated by Leading Technologies Rajesh Gupta and Y.Y Lee 13.1 13.2 13.3 13.4 13.5 13.6 13.7 13.8 13.9 13.10 13.11 13.12 Introduction Synergism among Cellulolytic Enzymes Hemicellulose Structure and Hemicellulolytic Enzymes Substrate Characteristics and Enzymatic Hydrolysis Xylanase Supplementation for Different Pretreated Biomass and Effect of b-Xylosidase Effect of b-Glucosidase Supplementation Effect of Pectinase Addition Effect of Feruloyl Esterase and Acetyl Xylan Esterase Addition Effect of a-L-arabinofuranosidase and Mannanase Addition Use of Lignin-degrading Enzymes (LDE) Effect of Inactive Components on Biomass Hydrolysis Adsorption and Accessibility of Enzyme with Different Cellulosic Substrates 239 240 242 242 243 243 244 244 245 245 247 248 249 251 252 252 253 253 254 255 256 257 258 261 261 262 263 264 265 269 269 270 270 271 271 271 524 Index alkaline pretreatment (Continued) chemical effects on biomass composition 146–53 economic analysis of pretreatment 315, 317, 321–27 experimental pretreatment systems 420, 429 fractionation 205 high-throughput pretreatment and hydrolysis systems 480–1 laboratory-scale pretreatment systems 489–1, 504, 509, 511 lime pretreatment 158–60 non-oxidative delignification 147–8 non-oxidative sugar degradation 148–50 oxidative delignification 150–2 oxidative sugar degradation 151–3 selectivity of pretreatment 161–3 severity of pretreatment 161 sodium hydroxide pretreatments 155–6 wet oxidation 155–8 see also ammonia pretreatments alkaline wet oxidation pretreatment (AWOP) 158 American Society for Testing and Materials (ASTM) 336–40, 342–4, 348, 355 amino acids 178–9, 191–2 9-aminopyrene-1,4,6-trisulfonate (APTS) 407–8 ammonia fiber expansion (AFEX) 8, 146, 153, 169–200 ammonia recycle 187–8 biological conversion 48, 241, 243, 245–7, 252–7, 265–7, 269, 272, 274 cellulase binding to biomass 175–6 commercialization 186–90 crystallinity of cellulose 383 economic analysis of pretreatment 317, 321, 324–7 environmental and life-cycle analyses 193–4 enzyme catalyzed hydrolysis 175–6, 183–4 enzyme digestibility of AFEXtreated biomass 169–70, 176–8, 190–1 experimental pretreatment systems 425 high-throughput pretreatment and hydrolysis systems 483 historical perspective 169–70 ionic liquid pretreatment 230 laboratory-scale pretreatment systems 491, 496, 504 macro-/micro-accessibility 285 microbial fermentability of AFEX-treated biomass 178–83 physicochemical impacts 170–5 regional biomass processing depots 192–3 research developments 185–6 scale-up designs 188–90 techno-economic analyses 190 transgenic plants 183–4, 192 value-added products 190–2 ammonia pretreatments 146, 153–5, 169–200 ammonia recycle 187–8 biological conversion 48, 241, 243, 245–7, 252–7, 265–7, 269, 272, 274 cellulase binding to biomass 175–6 cellulosic biomass 7–8 commercialization of AFEX processes 186–3 crystallinity of cellulose 383 economic analysis of pretreatment 317, 319, 321–27 environmental and life-cycle analyses 193–4 enzyme catalyzed hydrolysis 175–6, 183–4 enzyme digestibility of AFEX-treated biomass 169–70, 176–8, 190–1 experimental pretreatment systems 420, 425 high-throughput pretreatment and hydrolysis systems 483 historical perspective 169–70 ionic liquid pretreatment 230 laboratory-scale pretreatment systems 489–91, 496, 501–3, 504, 509 macro-/micro-accessibility 285 microbial fermentability of AFEXtreated biomass 178–83 physicochemical impacts 170–5 regional biomass processing depots 192–3 scale-up designs for AFEX processes 188–90 techno-economic analyses 190 transgenic plants 183–4, 192 value-added products 190–2 ammonia recycle percolation (ARP) 153–5 biological conversion 241, 243, 245–7, 252–3, 265–7 crystallinity of cellulose 383 economic analysis of pretreatment 319, 322–27 laboratory-scale pretreatment systems 501–2, 504 amorphous cellulose acid pretreatment 104–5, 117 aqueous pretreatment 208, 214–15 enzyme formulation and loadings 262, 272–3 experimental enzymatic hydrolysis systems 452, 458 macro-/micro-accessibility 284, 289–91 nuclear magnetic resonance spectroscopy 381–5 angelicalactones 86–7 animal feed alkaline pretreatment 159, 163 ammonia pretreatments 169–70, 176–8, 190–1 summative analysis of biomass 339 anion-exchange chromatography 398, 404–7 annualized cost of production 314 AOAC see Association of Official and Analytical Chemists International APR see aqueous-phase reforming APTS see 9-aminopyrene-1,4, 6-trisulfonate aqueous-phase reforming (APR) 72–4, 75–7 aqueous pretreatment 129–43 acid pretreatment 112–13 biological conversion 50, 56, 245–9, 252–3, 265–7, 269 cell walls 27–8, 29, 130–1 cellulose 136–8 chemical pretreatments digestibility of cellulose 137–8 economic analysis of pretreatment 315, 317, 321, 326–8 Index experimental pretreatment systems 419, 422–3 hemicelluloses 131–4, 140 high-throughput pretreatment and hydrolysis systems 471–88 hydrolysis products and cell wall depolymerization 131 kinetic parameters 133–4 laboratory-scale pretreatment systems 489–91, 499–501 lignin 134–6 mechanisms 131–7 practical applications 138–40 self-ionization of water 130 xylooligosaccharides 397–8, 406 arabinan 360 arabinomethylglucuronoxylans 50 arabinose acid pretreatment 105 ammonia pretreatments 176 aqueous pretreatment 132 biological conversion 55, 242 catalytic conversion 63, 65, 70–2 ionic liquid pretreatment 231 macro-/micro-accessibility 287 ARP see ammonia recycle percolation aryl ether linkages, fractionation 212–13 ash acid pretreatment 107 economic analysis of pretreatment 323 summative analysis of biomass 338 Aspergillus niger 44 Association of Official and Analytical Chemists International (AOAC) 336, 339–40 ASTM see American Society for Testing and Materials ATP/ATPase see adenosine-5’triphosphate autocatalysis 208–9, 419 autohydrolysis 394–6, 505 see also aqueous pretreatment Avicel 262–3, 272–3, 294, 383–5 AWOP see alkaline wet oxidation pretreatment AXE see acetyl xylan esterase axial parenchyma cells 28 b-aryl ether bonds 147–8 b-glucosidases acid pretreatment 112 biological conversion 44–5, 47–8, 56, 241, 243, 261–4, 269, 272–3 economic analysis of pretreatment 328 experimental enzymatic hydrolysis systems 453 macro-/micro-accessibility 282, 285 b-xylosidase 265–8, 272–3, 282, 396–7 ball-milled lignins 378–81 batch reactors acid pretreatment 112 alkaline pretreatment 154–5 ammonia pretreatments 170–1 economic analysis of pretreatment 330–1 experimental pretreatment systems 420, 424–7 high-throughput pretreatment and hydrolysis systems 473 laboratory-scale pretreatment systems 491–501 Bauer Rapid Cycle Digester 425–6 benzene-toluene-xylene (BTX) 64 BESC see BioEnergy Science Center BHMF see 2,5-bishydroxymethylfuran biocrudes 28 biodiesel 86, 207 biodiversity 18 BioEnergy Science Center (BESC) 475–6, 479–82, 485 biofuels ammonia pretreatments 192–3 aqueous processing of cellulosic biomass 3–5 biological conversion 240 biological and thermochemical conversion 19–20 catalytic conversion 61, 64–6, 75–7, 82 cellulosic biomass 17–21 energy density 17–18 experimental pretreatment systems 417 fractionation 201, 207 high-throughput pretreatment and hydrolysis systems 471 historical fuel dependence 17 importance of cellulosic biomass 18 ionic liquid pretreatment 225 laboratory-scale pretreatment systems 489 525 land-use 18–19 lignocellulosic biomass 61, 64–6, 75–7, 82, 86 need for energy from biomass 17–18 pretreatment of cellulosic biomass 20–1 recalcitrance barrier 18–20 summative analysis of biomass 335–54 biological conversion 39–60 alpha-L-arabinofuranosidase and mannanase supplementation 270–1 adsorption and accessibility of enzymes 271–2 b-glucosidase supplementation 269 biofuels 19–20 CAFI pretreatments 243–4 cell wall constituents 43–8 comparative performance of leading technologies 239–59 compositions of solids 251–4 corn stover 242–3, 245–7, 252–4 economic analysis of pretreatment 311–33 enzyme catalyzed hydrolysis 39–48, 240, 245–9, 251, 253–4, 257, 264–5 enzyme effectiveness 283–4, 285–6, 288–9, 291, 293–296 enzyme formulation and loadings 243, 261–79 ethanol fermentations 40–1, 48–9 feedstocks 242–54 fermentation inhibitors 42–9 feruloyl esterase and acetyl xylan esterase supplementation 270 free sugars and extraction 244 hemicellulose structure and hemicellulolytic enzymes 263–4 implications of CAFI results 255–6 inactive components and biomass hydrolysis 271 ionic liquid pretreatment 228–31 lignin-degrading enzyme supplementation 271 lignocellulosic biomass 40–2, 43–4, 50–1, 53 macro-/micro-accessibility 281–309 material balances 244 materials and methods 242–4 526 Index biological conversion (Continued) overview 40–2 pectinase supplementation 269 pentose sugar oligomer hydrolysis 50–6 poplar wood 242–3, 248–9, 253–4 pretreatment requirements 39–40, 41, 56, 254–5 solid-acid catalysts 50–6 substrate characteristics 264–5 switchgrass 242–3, 247–54 synergism among cellulolytic enzymes 262–3 tuning enzyme formulations to feedstocks 272–3 xylanase supplementation 265–8 yields of xylose and glucose 245–51, 254–6 biological pretreatment biomass loading/concentration 233, 328 bio-oils 62, 214 biphasic reactors 79–80 2,5-bishydroxymethylfuran (BHMF) 82–4 blow-down vessels 438–9, 444 BLUE Map scenario 18 BTX see benzene-toluene-xylene butanol 205 butene 13 C NMR spectroscopy 372–5, 381–3, 385–7 CAFI see Consortium for Applied Fundamentals and Innovation calibration of high-throughput analysis 355–7, 358–9, 364–5 cane leaf 180 capillary electrophoresis (CE) 407–8 carbohydrate-binding domain (CBD) 175, 282, 452–3 carbohydrates alkaline pretreatment 148–9, 155–6, 159, 162–3 biological conversion 261 catalytic conversion 61–103 experimental enzymatic hydrolysis systems 451 macro-/micro-accessibility 281–2 carbon dioxide 5, 41 carboxymethyl cellulose (CMC) 263, 273 cash-flow economic analyses 314 catalytic conversion acid pretreatment 114–16 aqueous-phase reforming 72–4, 75–7 biomass conversion strategies 62–4 chemical products 61, 66, 68–91 combined reforming and hydrogenolysis 75–7 dehydration of sugars 77–91 fuels and fuel additives 61, 64–6, 75–7, 82, 89 hydrogenolysis 74–7 ionic liquid pretreatment 231–3 lignocellulosic biomass 61–103 oxidation of sugars 69–70 primary feedstocks and platforms 66–8 reduction of sugars 70–7 sugar conversion and key intermediates 68–91 upgrading strategies 81–5 catalytic domain (CD) 175, 282 CBD see carbohydrate-binding domain; cellulose-binding domain CBEMR see cyclic batch enzyme membrane reactor CBH see cellobiohydrolases CBP see consolidated bioprocessing CBU see cellobiose unit CD see catalytic domain CE see capillary electrophoresis CEL see cellulolytic enzyme lignin cell walls 23–38 ammonia pretreatments 172–4, 183–4 aqueous pretreatment 130–1, 135–6, 140 biological conversion 39, 41, 43–8 biomass diversity 24–6 computer simulations of recalcitrance 32–5 depolymerization assisted by hydrolysis products 131 depolymerization catalyzed by selfionization of water 130 differential responses to biomass conversion 28–9 fermentation inhibitors 43–8 processing options 26–8 recalcitrance barrier 23, 30, 32–5 structural and compositional variability 24–6 structure 29 summative analysis of biomass 336, 342–3 surfaces and multilamellar architecture 30–1 transgenic plants 183–4 ultrastructure and nanoporosity 31–2 xylooligosaccharides 392–3 cellobiohydrolases (CBH) ammonia pretreatments 175–7 economic analysis of pretreatment 328 enzyme formulation and loadings 261–3, 272–3 experimental enzymatic hydrolysis systems 453 macro-/micro-accessibility 282, 287, 289, 291–294 cellobiose hydroxyls 226 cellobiose unit (CBU) 461 cellulases ammonia pretreatments 175–6 biological conversion 42, 44–6, 243, 261–2, 264–74 economic analysis of pretreatment 312–13, 318–20, 328 experimental enzymatic hydrolysis systems 452–3, 455–65 experimental pretreatment systems 418 ionic liquid pretreatment 231 macro-/micro-accessibility 285, 289 cellulolytic enzyme lignin (CEL) 372 cellulose acid pretreatment 104–5, 108–10, 117–18, 122–3 alkaline pretreatment 146, 148, 152, 157 ammonia pretreatments 172, 175, 187–90 aqueous pretreatment 136–8 biological conversion 39–41, 50–1, 240, 244, 261–5, 272–3 catalytic conversion 62–3, 66–8 cell walls 24–6, 29, 34–5 chain length/reducing ends 291–3 composition and structure of cellulose 216–17, 219 computer simulations of recalcitrance 34–5 digestibility after aqueous pretreatment 137–8 Index economic analysis of pretreatment 312–13, 316, 318–19 enzyme effectiveness 285–6, 288, 291, 293–296 experimental enzymatic hydrolysis systems 451–3, 455–65 experimental pretreatment systems 417–20 fractionation 201, 205–9, 215–16, 219 high-throughput analysis 356 ionic liquid pretreatment 223–27, 229, 233 kinetics of enzymatic hydrolysis 455–7 laboratory-scale pretreatment systems 501, 506, 513 macro-/micro-accessibility 282–296 nuclear magnetic resonance spectroscopy 369–70, 381–87 summative analysis of biomass 335, 342–3 xylooligosaccharides 392 cellulose-binding domain (CBD) 175, 282, 452–3 cellulosic biomass acid catalyzed hydrolysis 1–2, 4–5 ammonia pretreatments 187–90 aqueous processing 3–5 attributes for successful pretreatment 5–6 biofuels 17–21 biological conversion 240 blind spots in historic pretreatment paradigm definition and characteristics 2–3 enzyme catalyzed hydrolysis 4–5 ionic liquid pretreatment 223–5 laboratory-scale pretreatment systems 489 pretreatment options 7–8 pretreatment technologies centrifugal partition chromatography (CPC) 401–2 cerium zirconate catalysts 75–7, 84 charcoal chromatography 399 chemical loadings 329–30 chemical pretreatments autohydrolysis cell walls 27–8, 31 economic analysis of pretreatment 313 oxidizing agents solvation see also acid pretreatment; alkaline pretreatment; ammonia pretreatments chemical products ammonia pretreatments 190–2 aqueous processing of cellulosic biomass 3–5 catalytic conversion 61, 66, 68–91 fractionation 214 lignocellulosic biomass 61, 66, 68–91 xylooligosaccharides 394 chloromethylfurfural (CMF) 80, 87 CHP see combined heat and power chromatographic separation 398–9 CHW see controlled-pH hot water CI see crystallinity index Clostridium spp 8, 183, 207, 452–3 CMC see carboxymethyl cellulose CMF see chloromethylfurfural co-hydrolysis 473–5, 485–6 colorimetric analysis 345, 402, 481–2 combined heat and power (CHP) 317 combined severity (CS) factor acid pretreatment 104, 118 aqueous pretreatment 140 economic analysis of pretreatment 330 experimental pretreatment systems 429 laboratory-scale pretreatment systems 511–12 competitive inhibition 457 condensation reactions alkaline pretreatment 148, 150 catalytic conversion 85–6 fractionation 210, 213 Conductor-like Screening Model–Real Solvents (COSMO-RS) 229 consolidated bioprocessing (CBP) 8, 41, 140 Consortium for Applied Fundamentals and Innovation (CAFI) 8, 240–57, 265, 316–34, 490, 503 continuous reactors economic analysis of pretreatment 330–1 experimental pretreatment systems 420, 427–46 laboratory-scale pretreatment systems 491, 501–6, 513 pretreatment operations 527 controlled-pH hot water (CHW) 265–7, 269 copper catalysts 74–5, 90–1, 232–3 corn silage 181 corn stover acid pretreatment 105–6, 110, 114 alkaline pretreatment 158 ammonia pretreatments 172–80, 182 aqueous pretreatment 137–40 biofuels 18 biological conversion 242–3, 245–6, 252–6, 265–6 cell walls 32 cellulosic biomass laboratory-scale pretreatment systems 503–4 macro-/micro-accessibility 285, 287–8 xylooligosaccharides 406 COSMO-RS see Conductor-like Screening Model–Real Solvents CP/MAS see cross-polarization/magic angle spinning CPC see centrifugal partition chromatography cross-polarization/magic angle spinning (CP/MAS) NMR 381–3, 385–7 cross-validation 364–5 crystallinity index (CI) acid pretreatment 105 aqueous pretreatment 136 biological conversion 262–5 enzyme effectiveness 289–1 experimental enzymatic hydrolysis systems 451, 459 fractionation 201, 215–16 ionic liquid pretreatment 223–4, 233 macro-/micro-accessibility 289–91 nuclear magnetic resonance spectroscopy 381–4 summative analysis of biomass 335 CS see combined severity cyclic batch enzyme membrane reactor (CBEMR) 464 DALA see delta-aminolevulinic acid DATCS see dilute acid pretreatment of corn stover DCFROR see discounted cash-flow rate of return 528 Index DDGS see dried distiller’s grains with solubles decarbonylation 64 decarboxylation 64, 90 degree of polymerization (DP) acid pretreatment 104–5 aqueous pretreatment 136 biological conversion 262–4 fractionation 208, 215–16 macro-/micro-accessibility 286, 290–3 nuclear magnetic resonance spectroscopy 369, 383 xylooligosaccharides 391, 396–7, 399–2, 403–8 dehydration strategies 64, 77–91 delignification alkaline pretreatment 146–8, 150–5, 157, 161–3 ammonia pretreatments 153–4, 185 biological conversion 267, 271–2 fractionation 201–4, 207–10, 212–16 ionic liquid pretreatment 232, 234 macro-/micro-accessibility 285 mechanisms of organosolv delignification 212–16 non-oxidative delignification 147–8 oxidative delignification 150–2 sodium hydroxide pretreatments 155 wet oxidation 157 delta-aminolevulinic acid (DALA) 86 density functional theory (DFT) 33–5 dewatering systems 430–2 DFF see 2,5-diformylfuran DFT see density functional theory diferulate ester links 172 2,5-diformylfuran (DFF) 81–2 dilute acid pretreatment of corn stover (DATCS) 174 dinitrosalicylic acid (DNS) assay 345, 402, 481–2 discharge devices 438 discounted cash-flow rate of return (DCFROR) 314, 318–19, 327 DNS see dinitrosalicylic acid downregulated lignins 376–7, 380–1 dried distiller’s grains with solubles (DDGS) 176, 185, 187, 191–2, 287, 376–7, 380–1 drop-in hydrocarbons 115–16, 122 economic analysis of pretreatment 311–33 acid pretreatment 312, 315, 317, 321, 324–7, 329–30 alkaline pretreatment 315, 317, 321–27 balance between enzymes and pretreatment 328, 331 batch versus continuous processing 330–1 biomass loading/concentration 328 capital costs of pretreatment 325–6 chemical loading/recovery/ metallurgy 329–30 comparative pretreatment economics 316–26 conversion to oligomers/ monomers 328 future needs 331 historical perspective 313 impact of key variables 327–31 importance of pretreatment 311–13 laboratory-scale pretreatment systems 512 methodologies 314 minimum ethanol selling price 314, 318–19, 324–6, 331 modeling basis and assumptions 317–20 overview of pretreatment technologies 315–16 reaction conditions 330 reactor design and costing data 320–3 reactor orientation 330 solvent-based pretreatments 316, 331 sugar and ethanol yields 324–5, 327–8 xylooligosaccharides 393 effectiveness see enzyme effectiveness EG see endoglucanases electrospray ionization (ESI) 408 ELSD see evaporative light scattering detectors EMF see ethylmethylfurfural empirical kinetic models 455 endo-acting hemicellulases 454 endoglucanases (EG) economic analysis of pretreatment 328 enzyme formulation and loadings 261–3, 272–3 experimental enzymatic hydrolysis systems 452–3 macro-/micro-accessibility 282, 292–3 energy density 17–18, 64–6, 84 environmental analyses 193–4 enzyme catalyzed hydrolysis acid pretreatment 109–14 ammonia pretreatments 175–6, 183–4, 186 aqueous pretreatment 136, 137–2, 140 biological conversion 39–48, 240, 245–9, 251, 253–4, 257, 264–5 blind spots in historic pretreatment paradigm cell walls 28 cellulase binding to biomass 175–6 cellulose and cellulases 109–10, 452–3, 455–65 cellulosic biomass 4–5, economic analysis of pretreatment 311–12, 317, 320, 327–8 experimental pretreatment systems 418, 439 experimental systems 451–69 fermentation inhibitors 42–8 fractionation 205, 207, 209 hemicellulose and hemicellulases 110–14, 451–2, 453–4 high-throughput pretreatment and hydrolysis systems 471–88 ionic liquid pretreatment 223–5, 228–31 kinetics of enzymatic hydrolysis 454–9 laboratory-scale pretreatment systems 498, 501, 503–5, 507–9, 512–13 macro-/micro-accessibility 288, 293 nuclear magnetic resonance spectroscopy 369–82, 383, 386–7 rate limitations and rate–conversion relation 457–9 transgenic plants 183–4 xylooligosaccharides 396–7 enzyme deactivation 458 enzyme digestibility alkaline pretreatment 159–60, 163 ammonia pretreatments 169–70, 176–8, 190–1 crystallinity of cellulose 385 Index laboratory-scale pretreatment systems 496, 506 macro-/micro-accessibility 284–90, 293, 296 enzyme effectiveness cellulose chain length/reducing ends 291–3 cellulose crystallinity 289–91 definitions 283–4 hemicelluloses 288–9 lignin 285–6, 288–9 enzyme inhibition 457–8 EOL see ethanol organosolv lignin epithelial parenchyma cells 28 epoxy resins 214 Escherichia coli 4, 178–9, 182 ESI see electrospray ionization ethanol ammonia pretreatments 178 aqueous processing of cellulosic biomass 4–5 biofuels 19–20 biological conversion 40–1, 48–9, 261 economic analysis of pretreatment 314, 318–19, 324–5, 331 experimental enzymatic hydrolysis systems 463–4 fermentation inhibitors 48–9 fractionation 203–6, 210, 216–18 ethanol organosolv lignin (EOL) 210–12, 380 ethylene glycol 207 ethylmethylfurfural (EMF) 80 1-ethyl-3-methylimidazolium acetate 225, 227–31, 233 eucalyptus evaporative light scattering detectors (ELSD) 403 exo-acting hemicellulases 454 experimental enzymatic hydrolysis systems 451–69 adsorption in cellulose hydrolysis models 456–7 b-glucosidase 453 cellobiohydrolase 453 cellulases 452–3, 455–65 empirical kinetic models 455 endoglucanases 452–3 enzymatic saccharification of lignocellulosic biomass 461–2 hemicellulases 453–4 kinetics of enzymatic hydrolysis 454–9 laboratory protocols 460–3 measurement of enzyme activity 460–1 Michaelis–Menten-based models 455–6, 459 rate limitations and rate–conversion relation 457–9 scale-up designs 463–5 simultaneous saccharification and fermentation 458–9, 462–3 experimental pretreatment systems 417–50 blow-down vessel and flash vapor recovery 438–9 contacting with water/pretreatment chemicals 421–2, 429–32 feedstock handling and size reduction 427–9 gravity-flow reactor systems 441–6, 446 heating and cooling capability 421 historical perspective 417–21, 439–41 instrumentation and control systems 424 laboratory-scale pretreatment equipment 421–4, 445 mass and heat transfer 422–3 materials of construction 423 pilot-scale batch pretreatment equipment 424–7 pilot-scale continuous pretreatment equipment 427–39 pilot-scale continuous pretreatment reactor systems 439–46 pressurized continuous pretreatment feeder equipment 432–6 pretreatment reaction conditions 419–20 reactor discharge devices 438 reactor throughput and residence time control 436–8, 444, 446 translating laboratory-scale to pilot-scale systems 424 extractive AFEX (E-AFEX) 172, 175, 186 extractives cell walls 25 high-throughput pretreatment and hydrolysis systems 483 529 summative analysis of biomass 339–40 FDCA see 2,5-furandicarboxylic acid FE see feruloyl esterase fermentation biological conversion 39, 42–9 inhibitors 42–9, 103 see also separate hydrolysis and fermentation; simultaneous saccharification and fermentation ferulate ester links 172 feruloyl esterase (FE) 264, 269–70 fiber cells 28–30 fiber swelling 146 see also ammonia fiber expansion filter paper units (FPU) 460–1 flash vapor recovery 438–9 flowthrough pretreatment systems 134, 501–4, 513 fluidized gaseous AFEX (FG-AFEX) 171–2, 186 fluidized sand baths 493–494, 507, 513 food additives 69–70, 79 food and feed industry 336, 339 see also animal feed forage sorghum 181 forestry residues cellulosic biomass fractionation 201 summative analysis of biomass 337 formic acid acid pretreatment 112 alkaline pretreatment 150 catalytic conversion 87–8 fractionation 204, 207–8, 216 ionic liquid pretreatment 233 fouling of solid-acid catalysts 55 Fourier transform infrared attenuated total reflectance (FTIRATR) 105 Fourier transform infrared (FTIR) spectroscopy 107 FPU see filter paper units fractionation 201–23 co-products 216–19 commercial applications of organosolv lignin 214 composition and structure of cellulose 214–15, 219 composition and structure of organosolv lignin 210–12, 219 530 Index fractionation (Continued) fractionation of biomass during organosolv pretreatment 209–10 mechanisms of organosolv delignification 212–14 method overview 202–3 organosolv pretreatment 202–19 pretreatment severity 212 pulping systems 202, 207–8 solvents and catalysts 203–9 fructose 78–9 FTIR see Fourier transform infrared FTIR-ATR see Fourier transform infrared attenuated total reflectance fuel additives 64–6, 89, 207 fuels see biofuels 2,5-furandicarboxylic acid (FDCA) 81–2 furans biological conversion 49 catalytic conversion 77–91 cell walls 27 furfural acid pretreatment 103, 105–6, 112, 114–15, 120, 123 aqueous pretreatment 132–4 aqueous processing of cellulosic biomass biological conversion 48–9 catalytic conversion 64, 80–5 fractionation 201, 204, 208, 216–18 high-throughput analysis 356 high-throughput pretreatment and hydrolysis systems 485 laboratory-scale pretreatment systems 501 furfuryl alcohol 90–1 G/S see guaiacyl/syringyl galactoglucomannans 50 galactose acid pretreatment 105 biological conversion 55, 242 catalytic conversion 71–2 ionic liquid pretreatment 231 gamma-valerolactone (GVL) 5, 65, 87–91 gas chromatography (GC) 345, 402–3, 408 gas chromatography-mass spectrometry (GC/MS) 347, 408 gasification 3, 62 GC see gas chromatography GC/MS see gas chromatography-mass spectrometry gel permeation chromatography (GPC) 399 gel-type ion exchange resins 52–3 GH see glycosyl hydrolases GHG see greenhouse gases GLBRC see Great Lakes Bioenergy Research Center Global Sustainable Bioenergy Project 18 glucan alkaline pretreatment 150, 159, 162–3 ammonia pretreatments 175, 177 biological conversion 40, 242–4, 252–4, 266 experimental enzymatic hydrolysis systems 453 macro-/micro-accessibility 285–9, 296 glucaric acid 69–70 glucomannans 263–4 gluconic acids 69–71 glucose acid catalyzed hydrolysis 1, 4–5 acid pretreatment 105, 108–9, 112, 117 alkaline pretreatment 148–9, 155–6 ammonia pretreatments 176–9, 182–3 aqueous pretreatment 131–2, 137, 139–40 biological conversion 55–6, 241, 245–51, 254–6 catalytic conversion 63, 65, 67, 70–1 economic analysis of pretreatment 320–1 fractionation 205, 208, 219 high-throughput pretreatment and hydrolysis systems 481–2 ionic liquid pretreatment 230–1, 233 laboratory-scale pretreatment systems 504 glucose oxidase/peroxidase (GOPOD) assay 481–3 glucuronic acid 69–70 glucuronoxylan (GX) structures 392 glycerol 207 glycolic acid 150 glycosyl hydrolases (GH) 40–1, 176 GOPOD see glucose oxidase/ peroxidase GPC see gel permeation chromatography gravity-flow reactor systems 441–4, 446 Great Lakes Bioenergy Research Center (GLBRC) 477, 480–2 greenhouse gases (GHG) 193–4 GREET model 193–4 guaiacyl/syringyl (G/S) ratio 375, 377, 484 GVL see gamma-valerolactone H NMR spectroscopy 372 hammer-milling processes 428–9 hardwood biomass acid pretreatment 106, 110, 113–14 alkaline pretreatment 146–7 aqueous pretreatment 137–8 biological conversion 50, 242–3, 248–9, 253–4, 263–5, 267, 273 cell walls 24 experimental pretreatment systems 428 high-throughput analysis 360–2 high-throughput pretreatment and hydrolysis systems 484 ionic liquid pretreatment 230–1 laboratory-scale pretreatment systems 508 macro-/micro-accessibility 284–5, 287, 294 nuclear magnetic resonance spectroscopy 370, 372–5, 379–81, 385–7 summative analysis of biomass 336–3, 340–8 hemicellulases 453–4 hemicelluloses acid catalyzed hydrolysis 1–2, 4–5 acid pretreatment 103, 105–6, 110–14, 118–20, 122–3 alkaline pretreatment 146–7 153, 157 ammonia pretreatments 172, 174–5, 177, 187 aqueous pretreatment 131–4, 140 aqueous processing of cellulosic biomass 4–5 Index attributes for successful pretreatment biological conversion 39, 48, 50, 53, 240, 244, 261, 263–4, 270–1 catalytic conversion 62–3, 67–8 cell walls 25, 27–8, 29 economic analysis of pretreatment 312, 316, 320 enzyme effectiveness 288–9 experimental enzymatic hydrolysis systems 451–2, 453–4 experimental pretreatment systems 417–20 fermentation inhibitors 48 fractionation 204, 206–9, 216–17, 219 high-throughput analysis 356, 360 ionic liquid pretreatment 223, 225–6, 229 laboratory-scale pretreatment systems 490, 501, 504, 506, 513 macro-/micro-accessibility 283–4, 286–9, 295–6 nuclear magnetic resonance spectroscopy 369–70 pentose sugar oligomer hydrolysis 50, 53 pretreatment technologies structure and hydrolysis 68 sugar conversion and key intermediates 68 summative analysis of biomass 335, 340 xylooligosaccharides 392, 396 herbaceous biomass acid pretreatment 107 alkaline pretreatment 146–7 aqueous pretreatment 136–8 cell walls 24–5 experimental pretreatment systems 428–9 high-throughput analysis 360–2 high-throughput pretreatment and hydrolysis systems 483–4 ionic liquid pretreatment 228–30 nuclear magnetic resonance spectroscopy 370, 383–4 summative analysis of biomass 336–7, 341–2 heteronuclear single quantum coherence (HSQC) correlation spectroscopy 375–7 high-fructose corn syrup (HFCS) 79 high-intensity mixing 465 high-performance anion-exchange chromatography (HPAEC) 404–7, 407 high-performance liquid chromatography (HPLC) high-throughput analysis 356, 360 summative analysis of biomass 347–9 xylooligosaccharides 402–4, 408 high-pH anion-exchange chromatography with pulsed amperometric detection (HPAE/ PAD) 347–9 high-solids enzymatic hydrolysis 463 high-throughput (HTP) analysis 355–68 calibration and validation 355–7, 358–9, 364–5 multivariate analysis 355, 362–6 quality assurance/quality control 364–6 quality calibration data 359–62 rapid spectroscopic techniques 357–8 standard reference materials 364–6 validation of new methods 364–5 high-throughput pretreatment and hydrolysis (HTPH) systems 471–88 co-hydrolysis 473–5, 485–6 current systems 473–8 future applications 485 historical perspective 472–3 key steps 478–82 material distribution 479–80 material preparation 478–9 need for high-throughput technologies 471–2 philosophy, difficulties and limitations 482–3 pretreatment and enzymatic hydrolyis step 480–1 research enabled by HTPH systems 484–5 sample analysis 481–2 transferable technologies 472–3 HMF see 5-hydroxymethyl furfural holocellulose method 342 horizontal reactors economic analysis of pretreatment 330 531 experimental enzymatic hydrolysis systems 463–4 experimental pretreatment systems 441–3, 446 hot water treatment see aqueous pretreatment HPAEC see high-performance anion-exchange chromatography HPE/PAD see high-pH anion-exchange chromatography with pulsed amperometric detection HPLC see high-performance liquid chromatography HSQC see heteronuclear single quantum coherence HTO see hydrothermal oxidation HTP see high-throughput hydrofluoric acid 109 hydrogenation 82–4, 90–1 hydrogenolysis 64, 74–7, 84 hydrothermal oxidation (HTO) 155 hydrothermal pretreatment see aqueous pretreatment 5-hydroxymethyl furfural (HMF) acid catalyzed hydrolysis 1–2, acid pretreatment 112, 117–18 aqueous pretreatment 132, 140 attributes for successful pretreatment biological conversion 48–9 catalytic conversion 77–80, 81–5 fractionation 201, 204, 208, 216, 218 high-throughput analysis 356 high-throughput pretreatment and hydrolysis systems 485 ionic liquid pretreatment 232 laboratory-scale pretreatment systems 501 IFAFS see Initiative for Future Agricultural and Food Systems IMP see ion-moderated partition impregnation laboratory-scale pretreatment systems 421–2, 496, 499, 510–11 pilot-scale pretreatment systems 428, 429–32, 442–3 inhibitors 42–9 acetic acid 48–9 acid pretreatment 103 cell wall constituents 43–8 532 Index inhibitors (Continued) enzyme catalyzed hydrolysis 42–8 ethanol fermentations 48–9 furfurals 48–9 hemicelluloses 48 lignin and soluble phenolics 43–7 mechanisms of inhibition 46–7 removal of phenols 47 Initiative for Future Agricultural and Food Systems (IFAFS) 8, 240, 257 intercellular spaces 30 internal rate of return (IRR) 314, 327 International Energy Agency 18 International Standards Organization (ISO) 355 ion exchange resins 51–3, 79 ion-moderated partition (IMP) 403–4 ionic liquid pretreatment 223–38 acid catalyzed hydrolysis 232 agricultural residues 230 biological conversion 228–31 biomass loading 233 catalytic conversion 67, 231–3 economic analysis of pretreatment 316, 331 grasses 228–30 high-throughput pretreatment and hydrolysis systems 477 interactions between ILs and cellulose 226–7 interactions between ILs and lignin 227–8 macro-/micro-accessibility 295–6 mechanisms 225–8 metal catalyzed hydrolysis 232–3 polarity and Kamlet–Taft parameters 226, 231 recovery and recycle 233 scalability and costs 233 woody biomass 230–1 IRR see internal rate of return ISO see International Standards Organization isocyanate resins 214 Kamlet–Taft parameters 226, 231 Kamyr-type reactors 185 Karl–Fischer method 338 2-keto-gluconic acid 69–70 Klason lignin 252–4, 340–2, 485 knife-milling processes 337, 428–9 Kraft pulping 202 LA see levulinic acid Laboratory Analytical Procedures (LAP) 336–40, 342–4, 348 laboratory-scale enzymatic hydrolysis systems 463–4 laboratory-scale pretreatment systems 489–521 batch reactors 491–501 biomass handling and comminuting 508 construction materials 508–9 continuous reactors 491, 501–4, 513 cost minimization 512 deconstruction of biomass 503–5 direct and indirect heating 506–8, 513 equipment 421–4, 445 heat and mass transfer 505–8, 514 heat-up and cool-down rates 510, 513–14 high/low solids concentration 510 microwave reactors 491–2, 497–9, 507 mixed reactors 491–2, 495–6, 507, 513 mixing and catalyst impregnation 421–2, 496, 499, 510–11 pretreatment severity 511–12 reactor selection criteria and applications 510–12 sealed glass reactors 491–2 steam reactors 491–2, 499–501 temperatures, residence times and yields 511 tubular reactors 491–495, 507 Zipperclave reactors 491–2, 496–7, 513 lactic acid 150 land-use 18–19 Langmuir adsorption isotherm 456, 459 LAP see Laboratory Analytical Procedures Laser model 190, 193–4 LCA see life-cycle analysis LCC see lignin-carbohydrate complex LDE see lignin-degrading enzyme leaf protein concentrate (LPC) 191 level-off degree of polymerization (LODP) 104–5 levulinic acid (LA) acid catalyzed hydrolysis 1–2, acid pretreatment 103, 112, 115, 117–18, 123 catalytic conversion 80, 85–7, 91 fractionation 204, 216, 218–19 life-cycle analysis (LCA) 193–4 lignin acid catalyzed hydrolysis 1–2, 4–5 acid pretreatment 106–7, 111–12 alkaline pretreatment 145–8, 150–5, 157, 161–3 ammonia pretreatments 153–4, 172, 174–5, 184–5, 186, 192 aqueous pretreatment 134–6 aqueous processing of cellulosic biomass biofuels 19–20 biological conversion 39, 43–7, 50, 242–4, 251–4, 261, 267, 271–2 biological pretreatments catalytic conversion 62–4, 68 cell walls 25–6, 29, 33–4 chemical pretreatments 7–8 commercial applications of organosolv lignin 214 composition and structure of organosolv lignin 210–12, 219 computer simulations of recalcitrance 33–4 economic analysis of pretreatment 312, 316, 320, 325 enzyme effectiveness 285–6, 288–9 experimental enzymatic hydrolysis systems 453, 459, 465 experimental pretreatment systems 417–20 fermentation inhibitors 43–7 fractionation 201–4, 206–14, 216–17, 219 high-throughput analysis 356 high-throughput pretreatment and hydrolysis systems 484–5 ionic liquid pretreatment 223–4, 226, 227–8, 231–4 laboratory-scale pretreatment systems 489, 501, 513 macro-/micro-accessibility 281, 283–9, 295–6 mechanisms of organosolv delignification 212–14 non-oxidative delignification 147–8 Index nuclear magnetic resonance spectroscopy 369–81 oxidative delignification 150–2 pretreatment technologies sodium hydroxide pretreatments 155 summative analysis of biomass 335–6, 339–42 transgenic plants 184, 192 wet oxidation 157 see also delignification lignin-carbohydrate complex (LCC) ammonia pretreatments 172 macro-/micro-accessibility 287 nuclear magnetic resonance spectroscopy 369 xylooligosaccharides 392 lignin-degrading enzyme (LDE) 271 lignocellulosic biomass acid pretreatment 103–8 alkaline pretreatment 145–56 ammonia pretreatments 172–85, 187 aqueous pretreatment 129–37 biofuels 18–19 biological conversion 40–2, 43–4, 50–1, 53, 261 biomass conversion strategies 62–4 catalytic conversion 61–103 cell walls 24–8, 31–2, 35 chemical products 61, 66, 68–91 computer simulations of recalcitrance 35 dehydration of sugars 77–91 economic analysis of pretreatment 311–13, 316, 318–20 experimental enzymatic hydrolysis systems 451, 459, 461–2, 465 fermentation inhibitors 43–4 fractionation 201–19 fuels and fuel additives 61, 64–6, 75–7, 82, 89 high-throughput analysis 356 high-throughput pretreatment and hydrolysis systems 471–2 ionic liquid pretreatment 223–34 laboratory-scale pretreatment systems 489 macro-/micro-accessibility 281–296 oxidation of sugars 69–70 pentose sugar oligomer hydrolysis 50–1, 53 primary feedstocks and platforms 66–8 reduction of sugars 70–7 sugar conversion and key intermediates 68–91 summative analysis of biomass 335–6, 342–3 xylooligosaccharides 391–415 lime pretreatment 158–60 biological conversion 247, 255, 257 economic analysis of pretreatment 317, 323, 326 experimental pretreatment systems 420 laboratory-scale pretreatment systems 504 linear solvation energy relationship (LSER) 226 liquefaction of lignocellulosic biomass 62 liquid alkanes 64 liquid hot water see aqueous pretreatment lock-hopper feeders 432–3 LODP see level-off degree of polymerization long-term lime pretreatment 158 LPC see leaf protein concentrate LSER see linear solvation energy relationship MAC see maximum adsorption capacity macro-/micro-accessibility 281–309 cellulose chain length/reducing ends 291–3 cellulose crystallinity 289–1 definitions 283–4 enzyme effectiveness 283–4, 285–6, 288–9, 291, 293–296 hemicelluloses 283–4, 286–9, 295–6 lignin 281, 283–9, 295–6 macroreticular resins 52–3 Mahalanobis distance 366 Maillard end-products 172–4 MALDI-TOF see matrix-assisted laser desorption time-of-flight mannanases 270–1 mannose acid pretreatment 105, 111–12 biological conversion 55 533 catalytic conversion 63, 65, 70–1 ionic liquid pretreatment 231 mass spectrometry (MS) 408–9 matrix-assisted laser desorption time-of-flight (MALDI-TOF) 408–9 maximum adsorption capacity (MAC) 284 MCC see microcrystalline cellulose MD see molecular dynamics mechanical decrystallization membrane separation 399–401 mesoporous resins 52–3 MESP see minimum ethanol selling price metal catalyzed hydrolysis 232–3 metallurgy 329–30 methanol 203–6 methanolysis 344–5, 346 3-methyl-2benzothiazolinonehydrozone (MTBH) assay 482 methylglucuronoxylans 50 methylisobutyl ketone (MIBK) 79–80, 208–9 Michaelis–Menten-based models 455–6, 459 micro-accessibility see macro-/microaccessibility microbial fermentability 178–83 microbial nutrients 192 microcrystalline cellulose (MCC) 224, 226 microfiltration 401 micronutrients 178–9 microwave reactors 491–2, 497–9, 507 milled wood lignin (MWL) 210–12, 372–5 milling processes 337, 428–9 Milox pulping 207–8 mineral acids 103 minimum ethanol selling price (MESP) 314, 318–19, 324–7, 331 Miscanthus 3, 228–30 mixed inhibition 457–8 mixed reactors 491–2, 495–6, 507, 513 moisture content 338 molecular dynamics (MD) 33–5, 226–7 534 Index monoethanolamine method 343 monosaccharides alkaline pretreatment 161 aqueous pretreatment 137, 140 biological conversion 39 fractionation 204 summative analysis of biomass 345–6 MS see mass spectrometry MTBH see 3-methyl-2benzothiazolinonehydrozone muconic acids 152 multilamellar architecture of cell walls 30–1 multivariate analysis (MVA) 355, 362–6 municipal solid wastes MVA see multivariate analysis MWL see milled wood lignin nanoporosity of cell walls 31–2 National Renewable Energy Laboratory (NREL) ammonia pretreatments 188, 190, 194 biofuels 20 biological conversion 261 economic analysis of pretreatment 312–14, 317–18 enzyme effectiveness 285 experimental enzymatic hydrolysis systems 460, 462 experimental pretreatment systems 425, 430–2, 441–4 high-throughput analysis 355, 360 high-throughput pretreatment and hydrolysis systems 476, 479–83, 485 laboratory-scale pretreatment systems 500, 503 summative analysis of biomass 336–40, 342–4, 348 xylooligosaccharides 403 natural enzyme inducers 192 NDF see neutral detergent fiber near-infrared (NIR) spectroscopy calibration and validation 355–7, 358–9, 364–5 high-throughput analysis 355–68 multivariate analysis 355, 362–66 quality assurance/quality control 364–6 quality calibration data 359–63 rapid spectroscopic techniques 357–8 standard reference materials 364–6 validation of new methods 364–5 net energy yield (NEY) 194 net present value (NPV) 314 neutral detergent fiber (NDF) method 339 NEY see net energy yield nickel catalysts 70–1, 73 NIR see near-infrared NIS see non-ionic surfactants nitric acid 419–20 NMR see nuclear magnetic resonance non-competitive inhibition 458 non-ionic surfactants (NIS) 45 non-oxidative delignification 147–8 non-oxidative sugar degradation 148–50 NPV see net present value NREL see National Renewable Energy Laboratory nuclear magnetic resonance (NMR) spectroscopy 369–90 acid pretreatment 106–7 13 C NMR spectroscopy 372–7, 381–3, 385–7 CP/MAS analysis of cellulose 381–3, 385–7 crystallinity of cellulose 381–5 H NMR spectroscopy 372 HSQC correlation spectroscopy 375–7 31 P NMR spectroscopy 377–81 plant biomass constituents 370–2 sample preparation 372 solid-state characterization of cellulose 381–7 solution-state characterization of lignin 371–81 summative analysis of biomass 349 ultrastructure of cellulose 369, 383, 385–7 xylooligosaccharides 408 ODS see oxidatively delignified spruce oligosaccharides aqueous pretreatment 137, 139–40 biological conversion 42, 48, 50–6 cell walls 27 definition 391 high-throughput pretreatment and hydrolysis systems 483 laboratory-scale pretreatment systems 506 linkage types 53–4 sugar degradation 54–5 see also xylooligosaccharides one-tube process 473–5, 485–6 organosolv pretreatment 202–19 co-products 216–19 commercial applications of organosolv lignin 214 composition and structure of cellulose 215–16, 219 composition and structure of organosolv lignin 210–12, 219 economic analysis of pretreatment 316 experimental pretreatment systems 419 fractionation of biomass during organosolv pretreatment 209–10 mechanisms of organosolv delignification 212–14 method overview 202–3 pretreatment severity 212 pulping systems 202, 207–8 solid-state NMR characterization of cellulose 383–4, 386 solution-state NMR characterization of lignin 380 solvents and catalysts 203–9 overliming 329 oxalic acid 115–16 oxidative catalytic conversion 69–70, 81–2 oxidative delignification 150–2 oxidative sugar degradation 69–70, 151–3 oxidatively delignified spruce (ODS) 272 oxidizing agents oxygenates 64–6, 75–6 31 P NMR spectroscopy 377–81 P&ID see piping and instrument diagrams packed-bed AFEX (PB-AFEX) 171, 185–6, 190, 192–3 Pandia-type reactors 185, 188 paper see pulp and paper industry para-crystalline cellulose 385–6 parenchyma cells 28 Parr reactors 491–2, 495–6, 507, 513 Index partial least-squares (PLS) techniques 364–5 particle pump feeders 433, 436 PCA see principal component analysis pectinases 269 pectins 29 pentanoic acid 89–90 pentose sugar oligomers see oligosaccharides peracids 207–8 perennial crops, biofuels 18 petroleum-derived fuels 61–2 PFD see process flow diagrams phenethyl phenyl ether (PPE) 33 phenolic inhibitors 42–7 phenolic resins 64, 214 phenylpropane units 147–8 phosphitylation 211 phosphoric acid acid pretreatment 108, 116 experimental pretreatment systems 419–20 fractionation 208 macro-/micro-accessibility 295–6 photochemical degradation 292 physical pretreatments cell walls 27–8, 29 economic analysis of pretreatment 313 experimental pretreatment systems 427–9 mechanical decrystallization thermal pretreatment 7, 27–8, 29 Pichia stipitis 178, 181–2 pilot-scale pretreatment equipment batch reactors 424–7 continuous reactors 427–39 pilot-scale pretreatment reactor systems 439–46 piping and instrument diagrams (P&ID) 314 piston-compression feeders 433, 435–6 pits in cell walls 31–2 plant cell walls see cell walls platinum/alumina catalysts 72–3 platinum/zirconium phosphate (Pt/ZrP) catalysts platinum–tin (PtSn) catalysts PLS see partial least-squares plug flow AFEX (PF-AFEX) 171 plug-screw feeders 435, 441–4 polarity 226, 231 polydispersity index 211–12, 214 polyols aqueous-phase reforming 72–4, 75–7 catalytic conversion 70–7, 84 combined reforming and hydrogenolysis 75–7 fractionation 207 hydrogenolysis 74–5 polyphenols 214, 370–1 polysaccharides alkaline pretreatment 148–50 aqueous pretreatment 130, 139–40 biological conversion 40–1, 47, 52, 261 cell walls 26–7, 29 ionic liquid pretreatment 224–5, 231 nuclear magnetic resonance spectroscopy 370 summative analysis of biomass 336, 340, 343–5 xylooligosaccharides 391–3 poplar wood acid pretreatment 107–11, 121 alkaline pretreatment 159–62 ammonia pretreatments 181 aqueous pretreatment 205–8, 212–13 biological conversion 242–3, 248–9, 253–4, 265, 267 fermentation inhibitors 49–50 high-throughput pretreatment and hydrolysis systems 484 macro-/micro-accessibility 285, 294 nuclear magnetic resonance spectroscopy 373, 380–1, 385 porosity 293–294 PPE see phenethyl phenyl ether pre-impregnation laboratory-scale pretreatment systems 421–2, 496, 499, 510–11 pilot-scale pretreatment systems 428, 429–32, 442–3 pressure swing adsorption (PSA) 323 pressurized continuous pretreatment feeder equipment 432–6 principal component analysis (PCA) 359, 363 process flow diagrams (PFD) 314 productivity 535 promoters 73–5 proteins ammonia pretreatments 191–2 biological conversion 251, 261, 271 enzyme effectiveness 286 high-throughput analysis 356 summative analysis of biomass 338–9 PSA see pressure swing adsorption pulp and paper industry acid pretreatment 114 alkaline pretreatment 145–7 downstream processing summative analysis of biomass 336, 339–40 pulping systems 202, 207–8 pyrolysis cell walls 28 cellulosic biomass fractionation 214 lignocellulosic biomass 62 quality assurance/quality control (QA/ QC) 364–6 quality calibration data 359–62 quinone methide 147–8 radiation pretreatment 313 Raney-nickel catalysts 70–1, 73 ray parenchyma cells 28 RBPD see regional biomass processing depots reactive intermediates (RI) 4–5, reactive oxygen species (ROS) 150–3 reactor discharge devices 438 recalcitrance barrier biofuels 18–20 biological and thermochemical conversion 19–20 cell walls 23, 30, 32–5 computer simulations 32–5 high-throughput pretreatment and hydrolysis systems 471–2, 486 solid-state NMR characterization of cellulose 383 solution-state NMR characterization of lignin 371 xylooligosaccharides 392–3 recovery and recycle systems ammonia pretreatments 188–9 economic analysis of pretreatment 315–7, 321, 323, 326, 329–30 536 Index recovery and recycle systems (Continued) experimental enzymatic hydrolysis systems 463–5 experimental pretreatment systems 418, 438–9 ionic liquid pretreatment 233 reductive catalytic conversion 70–7, 82–4 regional biomass processing depots (RBPD) 192–3 residence times economic analysis of pretreatment 330 experimental pretreatment systems 436–8, 444, 446 laboratory-scale pretreatment systems 511 return on investment (ROI) 314, 327 RI see reactive intermediates rice straw 180–1 ROI see return on investment ROS see reactive oxygen species rotary valve feeders 433–4 rotating horizontal reactors 463–4 ruthenium catalysts 70–1 ruthenium/alumina catalysts 74 ruthenium/carbon (Ru/C) catalysts acid pretreatment 116 aqueous processing of cellulosic biomass lignocellulosic biomass 74, 87, 90 S/G see syringyl/guaiacyl SAA see soaking in aqueous ammonia saccharification cell walls 28, 30–1 experimental enzymatic hydrolysis systems 461–2 see also simultaneous saccharification and fermentation Saccharomyces cerevisiae 4, 178–83, 205, 230, 462–3 Saeman model 113, 117 sclerenchyma 28 screw-compression feeders 433, 434–5, 441–4 SCWO see supercritical water oxidation sealed glass reactors 491–2 SEC see size-exclusion chromatography self-ionization of water 130 separate hydrolysis and fermentation (SHF) 205, 317 shaking vertical reactors 463–4 SHF see separate hydrolysis and fermentation short-term lime pretreatment 159 signal-to-noise ratio (SNR) 372–3 silica/alumina catalysts silylation of monosaccharides 345–6 simultaneous saccharification and fermentation (SSF) acid pretreatment 113 biological conversion 42 experimental enzymatic hydrolysis systems 458–9, 462–3 experimental pretreatment systems 439 fractionation 205, 216 size-exclusion chromatography (SEC) 398 SNR see signal-to-noise ratio soaking in aqueous ammonia (SAA) 153–5 biological conversion 241, 243 economic analysis of pretreatment 317, 319, 322–7 sodium hydroxide pretreatments 155–6, 420 softwood biomass acid pretreatment 105–6, 110–14 alkaline pretreatment 146–7 ammonia pretreatments 181 aqueous pretreatment 138, 140 biological conversion 50, 263–4, 272 cell walls 24 experimental pretreatment systems 428 fractionation 205–8, 210–13, 215–17 high-throughput analysis 360–2 ionic liquid pretreatment 230–2 laboratory-scale pretreatment systems 508 macro-/micro-accessibility 284–5, 287 nuclear magnetic resonance spectroscopy 370, 372–4, 383–6, 386 summative analysis of biomass 336–7, 340–2 solid-acid catalysts catalyst stability 55 costs 55 diffusion characteristics 52 efficiency 51–6 fouling 55 lignocellulosic biomass 50–1, 53 linkage types in oligosaccharides 53–4 mesoporous, gel and macroreticular resins 52–3 pentose sugar oligomer hydrolysis 50–6 pore size 51–2 sugar degradation 54–5 solid catalyst poisons 103 solid-state NMR 381–7 Solka-Floc 44–5 solution-state NMR 371–81 solvation solvent extraction 397–8 sorbitol 70–1, 74–5 SPS see steam-pretreated spruce SRM see standard reference materials SSF see simultaneous saccharification and fermentation standard reference materials (SRM) 364–6 steam explosion reactors 491–2, 499–501, 504–6, 508 see also aqueous pretreatment steam-pretreated spruce (SPS) 272 substrate accessibility 459 substrate reactivity 458–9 sucrose 74–5 sugarcane bagasse acid pretreatment 105–6, 110 alkaline pretreatment 158 ammonia pretreatments 180 fractionation 208 macro-/micro-accessibility 285 sugars acid pretreatment 104–6, 108–9, 111–12 alkaline pretreatment 148–50, 155–6, 158, 161–3 ammonia pretreatments 176–9, 182–3 aqueous pretreatment 129, 131–2, 137 biological conversion 54–5, 240–2, 244–51, 254–6 catalytic conversion 63–5, 67–91 dehydration 77–91 economic analysis of pretreatment 320–1, 324–5, 327–8 Index experimental enzymatic hydrolysis systems 451, 461–3 fractionation 204–5, 216–17 high-throughput analysis 356 high-throughput pretreatment and hydrolysis systems 471, 475, 481–91 ionic liquid pretreatment 224–5, 230–1, 233 laboratory-scale pretreatment systems 503–6 lime pretreatment 159 macro-/micro-accessibility 281–2, 296 non-oxidative sugar degradation 148–50 oxidative sugar degradation 69–70, 151–3 reduction 70–7 sodium hydroxide pretreatments 155–6 summative analysis of biomass 340, 342–55 wet oxidation 158 see also monosaccharides; oligosaccharides; polysaccharides sulfite pulping 202 sulfur dioxide acid pretreatment 108, 110–12 biological conversion 248, 252, 255 economic analysis of pretreatment 321 experimental pretreatment systems 419–20 fractionation 204–5 laboratory-scale pretreatment systems 504 sulfuric acid acid pretreatment 108–10, 112–16, 122–3 biological conversion 247–8, 252, 255 experimental pretreatment systems 419–20 fractionation 204–5, 215 summative analysis of biomass 335–54 analysis of monosaccharides 345–6 ash 338 chemical hydrolysis of biomass polysaccharides 343–5 extractives 339–40 moisture content 338 non-structural components of biomass feedstocks 338–40 preparation of biomass feedstocks for analysis 337 protein 338–9 quantitative determination of lignin content 340–6 quantitative determination of sugars 342–9 supercritical water oxidation (SCWO) 155 surfactants 45, 271 switchgrass acid pretreatment 106 ammonia pretreatments 180, 194 aqueous pretreatment 137–8 biological conversion 242–3, 247–54, 265, 267–8 cell walls 28, 31 fractionation 215–16 ionic liquid pretreatment 228–30 nuclear magnetic resonance spectroscopy 381–2, 386 syngas syringyl/guaiacyl (S/G) ratio 375, 377, 484 tannic acid 45, 47 Technical Association of Pulp and Paper Institute (TAPPI) 336–8, 343 technoeconomic analysis (TEA) 316–17, 324–5, 328 TFA see trifluoroacetic acid thermal pretreatment 7, 27–8, 29 Thermobacillus xylanilyticus 47 thermochemical pretreatment biofuels 19–20 experimental pretreatment systems 417–18 laboratory-scale pretreatment systems 489–90 xylooligosaccharides 394–6 tin-nickel catalysts 73 TMS see trimethylsilylation total project investment (TPI) 314, 327 TPI see total project investment trace micronutrients 178–9 transgenic plants 183–4, 192 transportation fuels 64–6, 75–7 Trichoderma reesei 537 ammonia pretreatments 175, 177, 192 biofuels 20 biological conversion 44, 261–2, 266, 270, 274 cell walls 32 experimental enzymatic hydrolysis systems 452–3 trifluoroacetic acid (TFA) 344 trimethylsilylation (TMS) 345–6 tubular reactors 185, 491–495, 507 two-phase substrate 458 two-stage pretreatment systems 111, 153–4 UCR see University of California Riverside ultrafiltration 401, 465 ultrastructure acid pretreatment 107 ammonia pretreatments 172–4 nanoporosity 31–2 nuclear magnetic resonance spectroscopy 369, 383, 385–7 uncompetitive inhibition 457 University of California Riverside (UCR) 475–6, 479–82, 485 University of Dundee 477–82 University of York 477–82 validation of high-throughput analysis 355–7, 358–9, 364–5 vertical reactors economic analysis of pretreatment 330 experimental enzymatic hydrolysis systems 463–4 experimental pretreatment systems 437, 443–4, 446 viscosity 263 WAO see wet air oxidation wastepaper 337 waste water treatment (WWT) 323 water-gas shift (WGS) 72–3 WDG see wet distiller’s grains without solubles wet air oxidation (WAO) 155 wet distiller’s grains without solubles (WDG) 191–2 wet oxidation pretreatment (WOP) 157–8 wet oxidation (WO) 155–8 538 Index WGS see water-gas shift wheat straw 157–8 WO see wet oxidation woody biomass see hardwood biomass; softwood biomass WOP see wet oxidation pretreatment WWT see waste water treatment X-ray diffraction (XRD) 105, 381–3 XOS see xylooligosaccharides XRD see X-ray diffraction xylan acid pretreatment 119 alkaline pretreatment 145, 148–50, 159, 162–3 aqueous pretreatment 131–4 biological conversion 43, 242–4, 251–4, 263–4, 266–9, 272 economic analysis of pretreatment 312–13 fractionation 207, 217 high-throughput analysis 360 ionic liquid pretreatment 231 laboratory-scale pretreatment systems 501, 504–11, 511 macro-/micro-accessibility 285–5 xylooligosaccharide production 394–2, 400–8 xylanases economic analysis of pretreatment 328 enzyme formulation and loadings 263–4, 265–74 macro-/micro-accessibility 287–8 xylooligosaccharides 396–7 xylem cells 28–30 xylooligosaccharides (XOS) 391–415 acid pretreatment 112, 119 adsorption by surface active materials 397–8 aqueous pretreatment 139–40 autohydrolysis 394–6 biological conversion 42, 48, 53–4, 264, 267–70, 273–4 cell wall structure 392–3 centrifugal partition chromatography 401–2 characterization and quantification 402–8 chromatographic separation 398–9 composition characterization 402–3 definition 391 detailed structural determination 408 direct characterization 403–8 economic analysis of pretreatment 393 engineering reaction pathways 393 enzyme catalyzed hydrolysis 396–7 macro-/micro-accessibility 288 membrane separation 399–401 quantification of reducing ends 402 recalcitrance barrier 392–3 separation and purification 397–2 solvent extraction 397–8 thermochemical production 394–6 types released during lignocellulosic biomass pretreatment 391–2 value-added products 394 xylopyranose 120 xylose acid catalyzed hydrolysis 1, acid pretreatment 105–6, 111–16, 118–20 ammonia pretreatments 176–9, 182–3 aqueous pretreatment 132–4, 139–40 biological conversion 48, 55, 241–2, 245–51, 254–6, 263, 268 catalytic conversion 63–5, 70–1 economic analysis of pretreatment 320–1 experimental pretreatment systems 430, 444 fractionation 217–18 high-throughput pretreatment and hydrolysis systems 481–2 ionic liquid pretreatment 231 laboratory-scale pretreatment systems 504–5, 511–12 xylooligosaccharide production 396, 402 xylose dehydrogenase assay 481–2 zeolites 51–2, 79 Zipperclave reactors 491–2, 496–7, 513 Zymomonas mobilis 178–9, 182 ... Aqueous Pretreatment of Plant Biomass for Biological and Chemical Conversion to Fuels and Chemicals precursors for catalytic conversion into hydrocarbon fuels and chemicals In a sense, technology for. .. Webster Aqueous Pretreatment of Plant Biomass for Biological and Chemical Conversion to Fuels and Chemicals Editor CHARLES E WYMAN Department of Chemical and Environmental Engineering and Center for. .. Welcome to Aqueous Pretreatment of Plant Biomass for Biological and Chemical Conversion to Fuels and Chemicals. ” This book provides insights into thermochemical preparation of cellulosic biomass