List of Contributors xv
Series Preface xvii
Preface xix
1 Introduction to Thermochemical Processing of Biomass into Fuels, Chemicals, and Power 1
Xiaolei Zhang and Robert C. Brown
1.1 Introduction 1
1.2 Thermochemical Conversion Technologies 5
1.2.1 Direct Combustion 5
1.2.2 Gasification 6
1.2.3 Pyrolysis 7
1.2.4 Solvent Liquefaction 8
1.3 Diversity of Products: Electric Power, Transportation Fuels, and Commodity Chemicals 8
1.3.1 Biopower 9
1.3.2 Biofuels 10
1.3.3 Bio-Based Chemicals 11
1.4 Economic Considerations 11
1.5 Environmental Considerations 12
1.6 Organization of This Book 13
References 14
2 Condensed Phase Reactions During Thermal Deconstruction 17
Jake K. Lindstrom, Alexander Shaw, Xiaolei Zhang, and Robert C. Brown
2.1 Introduction to Condensed Phase Reactions During Thermal Deconstruction of Biomass 17
2.2 Thermochemical Processes 19
2.2.1 Processes Yielding Chiefly Solids 20
2.2.2 Processes Yielding Chiefly Liquids 22
2.2.3 Processes Yielding Chiefly Gases 24
2.3 Understanding Condensed Phase Reactions 28
2.3.1 Challenges in Investigating Condensed Phase Reactions 28
2.3.2 The Role of Cell Wall Structure in Thermal Deconstruction 30
2.3.3 Use of Computational Chemistry to Understand Thermal Deconstruction 34
2.4 Conclusions 41
References 42
3 Biomass Combustion 49
Bryan M. Jenkins, Larry L. Baxter, and Jaap Koppejan
3.1 Introduction 50
3.2 Combustion Systems 51
3.2.1 Fuels 51
3.2.2 Types of Combustors 53
3.3 Fundamentals of Biomass Combustion 59
3.3.1 Combustion Properties of Biomass 59
3.3.2 Combustion Stoichiometry 65
3.3.3 Equilibrium 68
3.3.4 Rates of Reaction 68
3.4 Pollutant Emissions and Environmental Impacts 71
3.4.1 Oxides of Nitrogen and Sulfur 72
3.4.2 Products of Incomplete Combustion 74
3.4.3 Particulate Matter 74
3.4.4 Dioxin-Like Compounds 74
3.4.5 Heavy Metals 76
3.4.6 Radioactive Species 76
3.4.7 Greenhouse Gas Emissions 77
References 77
4 Gasification 85
Karl M. Broer and Chad Peterson
4.1 Introduction 85
4.1.1 History of Gasification 85
4.1.2 Gasification Terminology 87
4.2 Fundamentals of Gasification 88
4.2.1 Heating and Drying 89
4.2.2 Pyrolysis 89
4.2.3 Gas–Solid Reactions 90
4.2.4 Gas-Phase Reactions 91
4.3 Feed Properties 91
4.4 Classifying Gasifiers According to Method of Heating 95
4.4.1 Air-Blown Gasifiers 95
4.4.2 Oxygen/Steam-Blown Gasifiers 96
4.4.3 Indirectly Heated Gasifiers 96
4.5 Classifying Gasifiers According to Transport Processes 98
4.5.1 Fixed Bed 99
4.5.2 Bubbling Fluidized Bed (BFB) 101
4.5.3 Circulating Fluidized Bed (CFB) 103
4.5.4 Entrained Flow 104
4.6 Pressurized Gasification 106
4.7 Products of Gasification 106
4.7.1 Gaseous Products 106
4.7.2 Char and Tar 109
4.8 System Applications 110
4.8.1 Process Heat 110
4.8.2 Combined Heat and Power (CHP) 117
4.8.3 Fuel and Chemical Synthesis 117
Acknowledgement 118
References 118
5 Syngas Cleanup, Conditioning, and Utilization 125
David C. Dayton, Brian Turk, and Raghubir Gupta
5.1 Introduction 125
5.2 Syngas Cleanup and Conditioning 126
5.2.1 Particulates 128
5.2.2 Sulfur 130
5.2.3 Ammonia Decomposition and HCN Removal 132
5.2.4 Alkalis and Heavy Metals 132
5.2.5 Chlorides 133
5.2.6 Tars and Soot 134
5.3 Syngas Utilization 137
5.3.1 Syngas to Gaseous Fuels 138
5.3.2 Syngas to Liquid Fuels 145
5.4 Summary and Conclusions 159
References 164
6 Fast Pyrolysis 175
Robbie H. Venderbosch
6.1 Introduction 175
6.2 Fundamentals of Pyrolysis 175
6.2.1 Effects of the Chemical and Physical Structure of Biomass and Intermediate Products 176
6.2.2 Effects of Ash 179
6.3 Properties of Pyrolysis Liquids 184
6.4 Fast Pyrolysis Process Technologies 186
6.4.1 Ensyn (CFB) 186
6.4.2 Valmet/UPM (CFB) 188
6.4.3 BTG-BtL (Rotating-cone) 188
6.4.4 Dynamotive Technologies Corp 190
6.5 Applications of Pyrolysis Liquids 192
6.5.1 Combustion 192
6.5.2 Diesel Engines 193
6.5.3 Co-refining Options 194
6.5.4 Gasification 199
6.6 Chemicals 200
6.7 Catalytic Pyrolysis 202
6.8 Concluding Remarks 202
Acknowledgement 203
References 203
7 Upgrading Fast Pyrolysis Liquids 207
Karl O. Albrecht, Mariefel V. Olarte, and Huamin Wang
7.1 Introduction 207
7.2 Bio-oil Characteristics and Quality 208
7.2.1 Feedstock Factors Affecting Bio-oil Characteristics 209
7.2.2 Effect of Pyrolysis Operating Conditions on Bio-oil Composition 210
7.2.3 Need for Upgrading Bio-oil 211
7.3 Norms and Standards 212
7.4 Physical Pre-treatment of Bio-oil 213
7.4.1 Physical Filtration 213
7.4.2 Solvent Addition 213
7.4.3 Fractionation 214
7.5 Catalytic Hydrotreating 214
7.5.1 Stabilization Through Low Temperature Hydrotreating 214
7.5.2 Deep Hydrotreating 217
7.6 Vapor Phase Upgrading via Catalytic Fast Pyrolysis 218
7.6.1 CFP Chemistry 221
7.6.2 Key Factors Impacting Catalytic Fast Pyrolysis 221
7.6.3 Practical Catalytic Fast Pyrolysis of Lignocellulosic Biomass 223
7.7 Other Upgrading Strategies 223
7.7.1 Liquid Bio-oil Zeolite Upgrading and Co-processing in FCC 223
7.7.2 Reactions with Alcohols 227
7.8 Products 228
7.8.1 Liquid Transportation Fuel Properties 228
7.8.2 Chemicals 232
7.8.3 Hydrogen Production 235
7.9 Summary 235
References 238
8 Solvent Liquefaction 257
Arpa Ghosh and Martin R. Haverly
8.1 Introduction 257
8.1.1 Definition of Solvent Liquefaction 257
8.1.2 History of Solvent Liquefaction 257
8.2 Feedstocks for Solvent Liquefaction 259
8.2.1 Feedstock Types 259
8.2.2 Benefits of Liquid Phase Processing 259
8.2.3 Reaction Types 261
8.2.4 Processing Conditions 262
8.3 Target Products 263
8.3.1 Bio-oil 263
8.3.2 Production of Fuels and Chemicals 264
8.3.3 Co-products 265
8.4 Processing Solvents 265
8.4.1 Inorganic Solvents 268
8.4.2 Polar Protic Solvents 271
8.4.3 Polar Aprotic Solvents 274
8.4.4 Ionic Liquids 276
8.4.5 Non-Polar Solvents 277
8.4.6 Influence of Process Conditions 278
8.5 Solvent Effects 283
8.5.1 Physical Effects 283
8.5.2 Solubility Effects 284
8.5.3 Structural Effects 287
8.5.4 Chemical Effects 287
8.6 Engineering Challenges 292
8.6.1 High Pressure Feed Systems 292
8.6.2 Separation of Solid Residue 293
8.6.3 Solvent Recovery and Recycle 293
8.7 Conclusions 294
References 294
9 Hybrid Processing 307
Zhiyou Wen and Laura R. Jarboe
9.1 Introduction 307
9.2 Thermochemical Conversion of Lignocellulosic Biomass for Fermentative Substrates 308
9.2.1 Fast Pyrolysis for Production of Pyrolytic Substrates 308
9.2.2 Gasification of Biomass for Syngas Production 309
9.3 Biological Conversion of Fermentative Substrates into Fuels and Chemicals 310
9.3.1 Fermentation of Pyrolytic Substrates 310
9.3.2 Fermentation of Syngas 313
9.4 Challenges of Hybrid Processing and Mitigation Strategies 318
9.4.1 Pyrolysis–Fermentation Process 318
9.4.2 Gasification–Syngas Fermentation Process 320
9.5 Efforts in Commercialization of Hybrid Processing 322
9.6 Conclusion and Perspectives 323
References 323
10 Costs of Thermochemical Conversion of Biomass to Power and Liquid Fuels 337
Mark M. Wright and Tristan Brown
10.1 Introduction 337
10.2 Electric Power Generation 338
10.2.1 Direct Combustion to Power 338
10.2.2 Gasification to Power 339
10.2.3 Fast Pyrolysis to Power 339
10.3 Liquid Fuels via Gasification 340
10.3.1 Gasification to Fischer-Tropsch Liquids 340
10.3.2 Gasification to Mixed Alcohols 341
10.3.3 Gasification to Gasoline 342
10.3.4 Gasification and Syngas Fermentation to Ethanol 343
10.3.5 Gasification and Syngas Fermentation to PHA and Co-product Hydrogen 343
10.4 Liquid Fuels via Fast Pyrolysis 344
10.4.1 Fast Pyrolysis and Hydroprocessing 344
10.4.2 Catalytic Fast Pyrolysis and Hydroprocessing 345
10.4.3 Fast Pyrolysis and Gasification to Fuels 346
10.4.4 Fast Pyrolysis and Bio-oil Fermentation to Ethanol 346
10.5 Liquid Fuels via Direct Liquefaction 348
10.6 Liquid Fuels via Esterification 349
10.7 Summary and Conclusions 349
References 350
11 Life Cycle Assessment of the Environmental Performance of Thermochemical Processing of Biomass 355
Eskinder Demisse Gemechu, Adetoyese Olajire Oyedun, Edson Norgueira Jr., and Amit Kumar
11.1 Introduction 355
11.2 Life Cycle Assessment 356
11.2.1 Introduction to LCA and Life Cycle Thinking 356
11.2.2 Goal and Scope Definition 357
11.2.3 Life Cycle Inventory 357
11.2.4 Life Cycle Impact Assessment 358
11.2.5 Life Cycle Interpretation 359
11.2.6 Sensitivity and Uncertainty Analyses 359
11.3 LCA of Thermochemical Processing of Biomass 360
11.3.1 Overview of the Thermochemical Processing of Biomass 360
11.3.2 The Use of LCA to Promote Low Carbon Technologies 360
11.3.3 Review of LCA Studies on Thermochemical Processing of Biomass 360
11.4 Discussion on the Application of LCA for Thermochemical Processing of Biomass 369
11.4.1 Establishing Goal and Scope 369
11.4.2 Life Cycle Inventory Analysis 370
11.4.3 Life Cycle Impact Assessment 371
11.5 Conclusions 372
Acknowledgements 373
References 373
Index 379
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