Perface ......................................................... v
Chapter 1. What is Biomass ...................................... 1
Fang Huang
1 Introduction ................................................. 1
2 Drivers for Biomass .......................................... 3
3 Biomass Types ................................................ 5
4 Understanding Lignocellulosic Biomass ........................ 6
4.1 Composition of lignocellulosic biomass .................. 6
4.2 Physical and chemical characteristics of
lignocellulosic biomass ................................. 7
4.2.1 Cellulose ........................................ 8
4.2.2 Hemicellulose ................................... 12
4.2.3 Lignin .......................................... 13
4.2.4 Ash content and inorganic element profiles ...... 19
4.2.5 Extractive content .............................. 19
4.2.6 Elemental composition ........................... 20
4.2.7 Heating values .................................. 22
Acknowledgments ............................................. 22
References .................................................. 22
Chapter 2. Biomass Recalcitrance and the Contributing Cell
Wall Factors ................................................... 27
Marcus Foston
1 Introduction ................................................ 27
2 Structural Features ......................................... 30
3 Molecular Features .......................................... 32
3.1 Cellulose crystallinity ................................ 32
3.2 Cellulose degree of polymerization ..................... 35
3.3 Cellulose accessibility ................................ 37
4 Chemical Features ........................................... 39
4.1 Lignin ................................................. 39
4.2 Hemicellulose .......................................... 41
4.3 Pectin ................................................. 41
4.4 Acetyl groups .......................................... 42
References .................................................. 43
Chapter 3. Reduction of Biomass Recalcitrance via Water/Acid
Pretreatments .................................................. 45
Fan Нu
1 Introduction ................................................ 45
2 Technical Process of DAP and HTP ............................ 47
2.1 Dilute acid pretreatment ............................... 47
2.2 Hydrothermal pretreatment .............................. 49
3 Hemicelluloses Hydrolysis and Porosity during DAP and HTP ... 50
4 Cellulose Crystallinity and Degree of Polymerization
during DAP and HTP .......................................... 56
5 Lignin Behavior during DAP and HTP .......................... 60
6 Pseudo-lignin Formation ..................................... 64
7 Conclusions and Outlook ..................................... 67
Acknowledgments ............................................. 67
References .................................................. 67
Chapter 4. Reduction of Biomass Recalcitrance via Organosolv
Pretreatments .................................................. 75
Xianzhi Meng
1 Introduction ................................................ 75
2 Overview of Organosolv Pretreatment ......................... 77
3 Mechanism of Organosolv Pretreatment for Reduction
of Recalcitrance ............................................ 78
4 Cellulose Behavior during Organosolv Pretreatment ........... 81
5 Lignin Behavior during Organosolv Pretreatment .............. 84
6 Conclusions and Outlook ..................................... 90
Acknowledgments ............................................. 91
References .................................................. 91
Chapter 5. Reduction of Biomass Recalcitrance via Ionic
Liquid Pretreatments ........................................... 95
Alistair W.T. King, Haibo Xie, Juha Fiskari, Ilkka
Kilpeläinen
1 Introduction ................................................ 96
1.1 What are ionic liquids? ................................ 96
1.2 What biofuels are possible from IL pretreatments ....... 98
2 Biomass Solubility ......................................... 100
2.1 Solubility and stability of wood and wood biopolymers
in ILs ................................................ 100
2.2 Solubility of wood in IL-based organic electrolytes ... 105
3 IL-Aided Fractionation as a Pretreatment for
Saccharification ........................................... 108
4 Tolerance of Enzymes/Microorganisms to IL Systems .......... 112
5 Ionic Liquid Recyclability and Recycling Strategies ........ 115
6 Challenges and Future Outlook .............................. 118
References ................................................. 120
Chapter 6. Enzymatic Deconstruction of Lignocellulose
to Fermentable Sugars ......................................... 127
Qining Sun
1 Introduction ............................................... 127
2 Enzymatic System ........................................... 129
2.1 Cellulase enzyme system ............................... 130
2.2 Hemicellulase enzyme system ........................... 132
2.3 Lignin modifying enzymes .............................. 133
2.4 Pectin degrading enzymes .............................. 133
3 Cellulose Enzymatic Saccharification ....................... 134
3.1 Enzyme behavior in hydrolysis ......................... 134
3.2 Cellulase adsorption and desorption ................... 135
3.3 Carbohydrate-bonding modules .......................... 139
3.4 Trichoderma reesei system ............................. 140
4 Factors Influencing Lignocelluloses Enzymatic Hydrolysis ... 141
4.1 Experimental conditions involved factors .............. 141
4.2 Substrate features involved factors ................... 142
4.3 Enzyme related factors ................................ 143
5 Strategies to Enhance Enzymatic Hydrolysis ................. 144
5.1 Synergistic effects on enzymatic hydrolysis ........... 144
5.2 Additives and surfactants ............................. 145
6 Conclusions and Outlook .................................... 146
Acknowledgments ............................................ 146
References ................................................. 146
Chapter 7. Fermentation to Bioethanol/Biobutanol .............. 155
Tao Ma, Matyas Kosa, Qining Sun
1 Introduction ............................................... 155
2 Biochemical Fermenting Microorganisms and Developments ..... 158
2.1 Yeast-Saccharomyces cerevisiae ........................ 159
2.2 Bacteria-Zymomonas mobilis ............................ 160
2.3 Genetically engineered microorganisms ................. 162
2.3.1 Pentose metabolism in yeast, bacteria and
fungi .......................................... 164
2.3.2 Metabolic engineering of yeast strains ......... 165
2.3.3 Engineering of Z. mobilis for xylose and
arabinose metabolism ........................... 166
2.3.4 Engineering of Escherichia coli for ethanol/
butanol production ............................. 168
2.3.5 Engineering K. oxytoca for ethanol production .. 169
3 Direct Ethanol Fermentation Processing Strategies .......... 171
3.1 Separate hydrolysis and fermentation (SHF) ............ 172
3.2 Simultaneous saccharification and fermentation (SSF) .. 172
3.3 Simultaneous saccharification and co-fermentation
(SSCF) ................................................ 173
3.4 Consolidated bioprocessing (СВР) ...................... 173
4 Biomass-derived Syngas Fermentation to Biofuels ............ 174
4.1 Biomass gasification .................................. 175
4.2 Metabolic pathways and biochemical reactions .......... 175
4.3 Reactor design for syngas fermentation ................ 177
4.4 Important factors affecting syngas fermentation ....... 178
4.4.1 Inhibitory compounds ........................... 178
4.4.2 Mass transfer .................................. 179
4.4.3 pH and temperature ............................. 180
4.4.4 Types of microorganism and growth media ........ 180
4.4.5 Industrial-scale syngas fermentation and
economics ...................................... 181
5 Biobutanol Fermentation .................................... 181
6 Summary and Outlook ........................................ 184
Acknowledgments ............................................ 184
References ................................................. 185
Chapter 8. Pyrolysis of Biomass to Bio-oils ................... 191
Haoxi Ben
1 Introduction ............................................... 191
2 Lignocellulose ............................................. 193
2.1 Cellulose ............................................. 193
2.2 Hemicelluloses ........................................ 195
2.3 Lignin ................................................ 197
3 Pyrolysis of Biomass Components ............................ 198
3.1 Pyrolysis of lignin .................................... 198
3.1.1 Gas products of pyrolysis of lignin ............ 198
3.1.2 Liquid products of pyrolysis of lignin ......... 200
3.2 Pyrolysis of cellulose ................................ 205
3.3 Pyrolysis of hemicellulose ............................ 208
3.4 Pyrolysis of tannin ................................... 213
4 Characterization Methods of Pyrolysis Oil .................. 215
4.1 FT-IR analysis of lignin pyrolysis oil ................ 215
4.2 NMR analysis of pyrolysis oil ......................... 216
4.3 Elemental analysis, viscosity, acidity, heating
value and solid residue of pyrolysis oil .............. 219
Acknowledgments ............................................ 223
References ................................................. 223
Chapter 9. Upgrade of Bio-Oil to Bio-Fuel and Bio-Chemical .... 229
Haoxi Ben
1 Introduction ............................................... 229
2 Aging Process of Pyrolysis Oils ............................ 233
3 Upgrade Pyrolysis Oil with Zeolites ........................ 240
3.1 Influences of Si/Al ratios of zeolites on the
properties of upgraded pyrolysis oils ................. 241
3.2 Influences of frameworks of zeolites on the
properties of upgraded pyrolysis oils ................. 245
4 Hydrodeoxygenation of Pyrolysis Oils ....................... 250
4.1 Catalysts used in hydrodeoxygenation process .......... 251
4.2 Sulfided catalyst ..................................... 252
4.3 Noble metal catalyst .................................. 252
4.3.1 Platinum ....................................... 252
4.3.2 Palladium ...................................... 254
4.3.3 Rhodium ........................................ 254
4.3.4 Ruthenium ...................................... 255
Acknowledgments ............................................ 259
References ................................................. 259
Chapter 10. Corrosion Issues in Biofuels ...................... 267
Lindsey R. Goodman, Preet M. Singh
1 Introduction ............................................... 268
2 Corrosion .................................................. 269
3 Constituents of Biofuels and Their Potential
Relationships to Corrosiveness to Steels ................... 271
3.1 Corrosion issues in ethanol and methanol biofuels ...... 272
3.1.1 Chloride contamination of FGE .................. 272
3.1.2 Effects of water concentration on corrosion
and SCC of steels in methanol and ethanol
biofuels ....................................... 274
3.1.3 Understanding the mechanisms of effects of
water on corrosion and stress corrosion
cracking in methanol and ethanol biofuels ...... 275
3.1.4 Role of dissolved oxygen in corrosion and
stress corrosion cracking of carbon steels in
ethanol biofuels ............................... 277
3.1.5 Corrosive effects of organic impurities in
fuel grade ethanol ............................. 279
3.1.6 Corrosion of materials in ethanol/gasoline
blended fuels .................................. 280
3.2 Corrosion issues in biodiesel ......................... 281
3.2.1 Microbial corrosion in biodiesel ............... 282
3.2.2 Stress corrosion cracking in biodiesel ......... 283
3.3 Corrosion issues in bio-oils or pyrolysis oils ........ 283
3.3.1 Effect of water content and temperature on
pyrolysis oil corrosivity ...................... 286
4 Conclusions ................................................ 288
References ................................................. 289
Chapter 11. Incorporation of Biofuels Technology into
a Pulp Mill ................................................... 295
Marko Hakovirta
1 Introduction ............................................... 295
2 Biofuels Landscape in the United States .................... 297
3 Biorefinery Concepts ....................................... 299
3.1 The conversion pathways ............................... 300
3.1.1 Solid biomass gasification ..................... 302
3.1.2 Gasification-based biorefineries integrated
with pulp mills ................................ 303
3.1.3 Fast pyrolysis ................................. 303
3.1.4 Acid hydrolysis and fermentation ............... 304
3.1.5 Enzymatic hydrolysis and fermentation .......... 307
4 Lignin and Its Opportunities in Biorefineries .............. 308
4.1 Lignin sources in biorefinery concepts ................ 309
4.1.1 Lignin from Kraft pulping process .............. 309
4.1.2 Lignin from sulfite pulping process ............ 310
4.1.3 Other lignin production technologies ........... 310
5 Future of Biorefining in Pulp Mills ........................ 311
Acknowledgments ............................................ 313
References ................................................. 313
Chapter 12. Integrated Possibilities of Producing Biofuels
in Chemical Pulping ........................................... 317
Raimo Alén
1 Introduction ............................................... 317
1.1 Pulping processes ..................................... 317
1.2 Possibilities of pulping-based biofuel production ..... 319
2 Autohydrolysis of Wood Chips ............................... 321
2.1 Basic considerations .................................. 321
2.2 Autohydrolysate-based products ........................ 322
3 By-Products of Kraft Pulping ............................... 324
3.1 Extractives ........................................... 324
3.2 Lignin ................................................ 326
4 Thermochemical Treatment of Black Liquor ................... 328
4.1 General aspects ....................................... 328
4.2 Gasification .......................................... 329
4.3 Liquefaction .......................................... 330
5 By-Products of Acid Sulfite Pulping ........................ 331
6 Conclusions ................................................ 332
References ................................................. 333
Index ......................................................... 339
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