Hydrothermal Processing in Biorefineries (eBook)

Dr. Héctor A. Ruiz obtained his Ph.D in Chemical and Biological Engineering from Centre of Biological Engineering at the University of Minho, Portugal in 2011. He then spent 1 year as a postdoctoral researcher at University of Minho (Portugal) and University of Vigo (Spain) under the supervision of Prof. José A. Teixeira and Prof. Juan C. Parajó (2012). He is currently Full Professor in the School of Chemistry at the Autonomous University of Coahuila and founder of the Biorefinery Group in the Food Research Department, Saltillo, Coahuila, Mexico and leader of the pretreatment step in the Cluster of Bioalcohols in the Mexican Centre for Innovation in Bioenergy (Cemie-Bio), Mexico. His research has targeted hydrothermal processing (autohydrolysis) and biorefinery strategies for the production high added-value compounds and bioethanol from lignocellulosic, micro - and macroalgal biomass. Dr. Ruiz has conducted several research stays and technical visits: at the Federal University of Sergipe (Brazil), Brazilian Bioethanol Science and Technology Laboratory (CTBE, Brazil), in the Chemical and Biological Engineering Department at the University of British Columbia (Canada), CIEMAT- Renewable Energy Division, Biofuels Unit (Spain), University of Jaén (Spain), Sadar Swaran Singh National Institute of Bio-Energy (India), Tokyo Institute of Technology (Japan).He has authored or co-authored several research publications with an H factor of 14 (Google Scholar Citations). Currently, Dr. Ruiz is Editor-in-Chief of Bioethanol Journal (De Gruyter Open, since 2014), Associate Editor of BioEnergy Research Journal (Springer, since 2015) and participates in the Editorial Advisory Board of the Industrial Crops and Products (Elsevier, since 2013) and Biofuel Research Journal. Dr. Ruiz was awarded with the Prize "Dr. Carlos Casas Campillo" of the Mexican Society of Biotechnology and Bioengineering in 2016. This award aims to give recognition and encourage young researchers for their contribution to the development of biotechnology and bioengineering in Mexico.Dr. Mette Hedegaard Thomsen, PhD, Assistant Professor, has worked with utilization of waste products and aquatic biomass for bio-fuels and green chemicals for more than 10 years. Dr. Thomsen has worked closely with European, American, and Middle Eastern industry to develop and scale up biorefinery processes, and has PI experience from several national research and international projects. Dr. Thomsen is author and co-author of more than 60 scientific papers including 38 ISI journal papers, five book chapters, and several conference contributions in areas related mainly to bio-energy and bio-chemicals production. Major contributions in the field of biorefineries: i) Application of amylolytic lactic acid bacteria in production of bio-polymers, ii) Part of team that developed acidification process for grass juice as substrate to produce l-lysine, iii) Part of team that developed demonstration scale hydrothermal treatment of wheat straw, iv) Chemical characterization and development of conversion processes for many different biomasses, v) Progress in biomass to ethanol fermentation technology, and vi) Isolation and application of natural antibiotics.Dr. Heather L. Trajano is an Assistant Professor in Chemical and Biological Engineering at the University of British Columbia in Vancouver, Canada.  She obtained her Ph.D. in Chemical Engineering at the University of California Riverside.  Dr. Trajano’s focus is to explore and harness fundamental knowledge of biomass fractionation and conversion for maximum economic and environmental benefit.  Specific research interests include i) Fundamentals of biomass deconstruction to separate carbohydrates from lignin, ii) Recovery and purification of extractives and iii) Heterogeneous catalysis for chemical production.  Dr. Trajano searches for biorefining opportunities that complement existing forestry operations by utilizing waste streams and by-products in collaboration with leading Canadian forestry companies.  Dr. Trajano has published numerous articles on biomass pretreatment and enzymatic hydrolysis in leading biorefining journals including: Biotechnology and Bioengineering, Biotechnology for Biofuels, Bioresource Technology, and Biofuels, Bioproducts and Biorefining.

Preface and Editorial 5
Acknowledgments 9
About This Book 10
Contents 11
Contributors 14
About the Authors 20
Chapter 1: How the Severity Factor in Biomass Hydrolysis Came About 23
Chapter 2: Effect of Hydrothermal Pretreatment on Lignin and Antioxidant Activity 26
2.1 Introduction 26
2.2 Effect of Treatment Conditions in Lignin Solubilization 27
2.3 Phenolic Composition of Autohydrolysis Liquors from LCM 31
2.4 Antioxidant Activity 47
2.4.1 Relevance and Type of Antioxidants 47
2.4.2 Mechanism of Action 48
2.4.3 Methodologies to Evaluate the Antioxidant Capacity 48
2.4.3.1 Chemical-Based Assays 49
2.4.3.2 Measurement of Antioxidant Activity in Biological Model Systems 51
2.4.4 Natural Antioxidants 51
2.5 Examples of Crude Antioxidant Extracts from Autohydrolysis of LCM 52
2.6 Conclusions and Future Perspectives 57
References 57
Chapter 3: Effect of Hydrothermal Processing on Hemicellulose Structure 65
3.1 Introduction 66
3.2 Hemicellulose Structure 68
3.2.1 Hardwood Hemicelluloses 69
3.2.1.1 Glucuronoxylan 69
3.2.1.2 Glucomannan 72
3.2.1.3 Xyloglucan 72
3.2.2 Softwood Hemicelluloses 73
3.2.2.1 Galactoglucomannans 73
3.2.2.2 Arabinoglucuronoxylan 73
3.2.2.3 Arabinogalactan 73
3.2.3 Gramineae Hemicelluloses 74
3.2.3.1 Arabinoxylan 74
3.2.3.2 beta-(13, 14)-Glucans 75
3.2.3.3 Homoxylan 75
3.3 Fundamentals of the Hydrothermal Processing of Lignocellulose 76
3.3.1 Characteristics of Hydrothermal Processing 76
3.3.1.1 Autohydrolysis/Hot Water Pretreatment 76
3.3.1.2 Steam Explosion 78
3.3.2 Reactions and Mechanisms 80
3.3.3 Severity Factor 83
3.3.4 Kinetic Models of Hemicellulose Hydrolysis 84
3.3.4.1 Pseudohomogeneous Kinetic Models 84
3.3.4.2 Kinetic Models with Fast- and Slow-Reacting Xylan 84
3.3.4.3 Kinetic Models Including Oligomer Concentrations 85
3.3.4.4 Kinetic Models Including Intermediates 86
3.4 Analysis and Structural Characterization of Hemicelluloses Before and After Hydrothermal Processing 86
3.4.1 Chromatographic Analysis 86
3.4.1.1 HPAEC 86
3.4.1.2 HPLC 89
3.4.1.3 GPC 90
3.4.1.4 MALDI-TOF MS 91
3.4.2 Spectroscopic Analysis 93
3.4.2.1 FT-IR 93
3.4.2.2 NMR 94
3.4.2.3 Glycome Profiling 96
3.4.2.4 Immunogold Localization 98
3.4.2.5 SEM 99
3.5 Concluding Remarks 100
References 101
Chapter 4: Response of Biomass Species to Hydrothermal Pretreatment 115
4.1 Introduction 115
4.1.1 History, Current State of the Art, and Future Development 115
4.1.2 Feedstock Crop, Production, and Utilization 116
4.1.2.1 Wood 116
4.1.2.2 Bamboo 117
4.1.2.3 Agricultural Residues 117
4.1.2.4 Agave and Agave Bagasse 118
4.2 Structure and Chemical Composition Analysis of Raw Biomass 118
4.2.1 Ultrastructure of Lignocellulosic Biomass 118
4.2.2 Compositional Analysis of Biomass 124
4.2.2.1 Wood 125
4.2.2.2 Bamboo and Agricultural Residues 125
4.2.2.3 Agave and AGB 126
4.3 Response of Biomass to Hydrothermal Treatment 126
4.3.1 Reactions in Acidic Condition 127
4.3.1.1 Hydrolysis Mechanism in Acidic Condition 127
4.3.1.2 Hemicellulose 128
4.3.1.3 Cellulose 131
4.3.1.4 Lignin 133
4.3.1.5 Ash 134
4.3.1.6 Extractives 134
4.3.1.7 Ultrastructure 135
4.3.1.8 Summary of Acid Pretreatment on Biomass Solids 135
4.3.2 Reactions in Alkaline Condition 136
4.3.2.1 Hydrolysis Mechanism in Alkaline Condition 136
4.3.2.2 Hemicellulose 137
4.3.2.3 Cellulose 140
4.3.2.4 Lignin 141
4.3.2.5 Ash 142
4.3.2.6 Extractives 142
4.3.2.7 Ultrastructure 142
4.3.2.8 Summary of Alkaline Pretreatment on Biomass Solids 143
4.4 Influencing Factors 148
4.4.1 Effects of Temperature and Time 148
4.4.2 Effects of Particle Size and Solid Loading 148
4.4.3 Effects of Reactor Type 149
4.4.4 Summary of Influencing Factors 150
4.5 Conclusion 150
References 151
Chapter 5: Kinetic Modeling, Operational Conditions, and Biorefinery Products from Hemicellulose: Depolymerization and Solubil... 161
5.1 Introduction 161
5.2 Depolymerization and Solubilization Effect on Hemicellulose 165
5.2.1 Fundamentals of the Hydrothermal Processing 165
5.2.2 Operational and Bioreactors Strategies in Hydrothermal Processing 166
5.3 Mathematical Modeling Using Hydrothermal Processing 168
5.4 Importance of High Value-Added Compounds from Hemicellulose 170
5.5 Conclusion and Final Remarks 176
References 177
Chapter 6: Combined Severity Factor for Predicting Sugar Recovery in Acid-Catalyzed Pretreatment Followed by Enzymatic Hydroly... 181
6.1 Introduction 181
6.2 Dilute Acid Pretreatment of Cellulosic Biomass 183
6.3 Simple First-Order Kinetic Models of Dilute Acid Hydrolysis of Biomass Hemicellulose 184
6.4 Derivation of Combined Severity Factor from Simple First-Order Kinetic Models 186
6.5 Correlation of Pretreatment Xylose Yields to Combined Severity Factor 189
6.6 Correlation of Enzymatic Hydrolysis Glucose Yields to Combined Severity Factor 192
6.7 Correlation of Glucose Plus Xylose Yields from Pretreatment Plus Hydrolysis 195
6.8 Extension of Combined Severity Factor to Dilute Acid Hydrolysis of Xylooligomers 196
6.9 Conclusions 197
References 199
Chapter 7: Hydrothermal Pretreatment of Lignocellulosic Biomass for Bioethanol Production 201
7.1 Introduction 201
7.2 Hydrothermal Pretreatments 205
7.3 Liquid Hot Water Pretreatment 206
7.4 Severity 209
7.5 Pretreatment-Derived Inhibitors 213
7.6 Potential Application of Hydrothermally Pretreated Biomass as a Renewable Feedstock for Enzyme Production 215
7.7 Concluding Remarks 218
References 219
Chapter 8: Hydrothermal Pretreatment: Process Modeling and Economic Assessment Within the Framework of Biorefinery Processes 226
8.1 Introduction 226
8.2 Process Description 228
8.2.1 Implementation of the PFD in a Process Simulator 232
8.3 Data Used for Modeling 234
8.3.1 Modeling of Biomass and Biomass-Derived Compounds 234
8.3.2 Modeling of Chemical Reactions: Stoichiometry 240
8.3.3 Modeling of Chemical Reactions: Kinetics 243
8.4 Economics of Hydrothermal Pretreatment 245
8.4.1 Calculation of Capital and Operational Costs 246
8.4.2 Economic Evaluation of Biomass-Based Processes 247
8.4.3 Comparison of Economics for Different Hydrothermal Processes 249
8.5 Conclusions 250
References 251
Chapter 9: Bioethanol Production from Pretreated Solids Using Hydrothermal Processing 255
9.1 Introduction 255
9.2 Effect of the Hydrothermal Pretreatment on the Lignocellulosic Biomass 256
9.3 Examples of Hydrothermally Pretreated Biomass Used as Bioethanol Feedstocks 259
9.3.1 Energy Crops 259
9.3.2 Agricultural Residues 263
9.3.2.1 Date Palm Tree Fronds 263
9.3.3 Extremophiles 265
9.4 Conclusion 268
References 268
Chapter 10: Production and Emerging Applications of Bioactive Oligosaccharides from Biomass Hemicelluloses by Hydrothermal Pro... 271
10.1 Introduction 272
10.2 Production of Hemicellulosic Oligosaccharides by Hydrothermal Processing Within the Biorefinery Framework 274
10.2.1 Operational Conditions in the Hydrothermal Treatments 275
10.2.2 Reactor Configurations 276
10.2.3 Mathematical Modeling for the Autohydrolysis 277
10.2.4 Biomass-Derived Oligosaccharides: XOS Production 279
10.3 Refining of Autohydrolysis Media Containing the Solubilization Products from Hemicelluloses 281
10.4 Chemical and Structural Characterization of Hemicellulosic Oligosaccharides Obtained by Autohydrolysis 285
10.4.1 Chromatographic Techniques 285
10.4.2 Spectroscopic Analysis 288
10.5 Applications of Hemicellulosic Oligomers Obtained from Hydrothermal Processes 290
10.6 Concluding Remarks 291
References 296
Chapter 11: Production of Hemicellulases, Xylitol, and Furan from Hemicellulosic Hydrolysates Using Hydrothermal Pretreatment 302
11.1 Introduction 302
11.2 Structure of Hemicellulose 303
11.2.1 Processing of Hemicellulose 303
11.3 Production of Value-Added Products 306
11.4 Hemicellulases 306
11.4.1 Action Mode 307
11.4.1.1 Endoxylanases and beta-Xylosidases 307
11.4.1.2 ?-l-Arabinofuranosidases, Arabinanases, ?-Glucuronidases, and Galactosidases 307
11.4.1.3 Acetyl Xylan Esterases, Feruloyl Esterases, p-Coumaric Acid Esterases, and Glucuronoyl Esterases 308
11.4.1.4 Other Activities 308
11.4.2 Commercial Hemicellulases 308
11.4.3 Industrial Application and World Market 310
11.4.4 Hemicellulase Production from Hemicellulosic Hydrolysates of Hydrothermal Pretreatment 311
11.5 Xylitol 313
11.5.1 Chemical vs. Microbial Synthesis 314
11.5.2 Use of Engineered Strains for Xylitol Production 315
11.5.3 Xylitol Production from Hemicellulosic Sugars of Hydrothermal Pretreatment 317
11.6 Furan Compounds and Furan Derivatives 317
11.6.1 Furan Compounds Production by Hydrothermal Treatment: Degradation Reactions of Sugars 318
11.6.2 Furfural and HMF: Methods of Production and Applications 319
11.6.2.1 Technology of Production 321
11.6.2.2 Commercial Applications 322
11.6.3 Hydrothermal Treatment as the First Step for Furan Compound Production 323
11.7 Concluding Remarks 324
References 325
Chapter 12: Steam Explosion as a Hydrothermal Pretreatment in the Biorefinery Concept 333
12.1 Introduction 333
12.2 Steam Explosion Biorefinery Technique 334
12.2.1 Multistage Steam Explosion Process 334
12.2.2 Hydrothermal Mechanism of Steam Explosion Technique 336
12.2.3 Advantages of Steam Explosion-Derived Biomass Refining 338
12.3 Novel Steam Explosion-Derived Biorefinery Techniques 339
12.3.1 Steam Explosion and Solvent Extraction Integrated Biorefinery Technique 339
12.3.1.1 Steam Explosion: Ethanol Extraction Combined Pretreatment 339
12.3.1.2 Steam Explosion: High Boiling Organic Solvent Combined Pretreatment 339
12.3.1.3 Steam Explosion: Ionic Liquid Dissolution Combined Pretreatment 340
12.3.1.4 Steam Explosion: Alkaline Peroxide Combined Pretreatment 341
12.3.2 Steam Explosion and Superfine Grinding Integrated Biorefinery Technique 341
12.3.3 Steam Explosion and Mechanical Carding Integrated Biorefinery Technique 342
12.3.4 Two-Stage Steam Explosion and Carding Integrated Biorefinery Technique 343
12.4 Process Integration of Steam Explosion Biorefinery Techniques 344
References 346
Chapter 13: Adaptation of Severity Factor Model According to the Operating Parameter Variations Which Occur During Steam Explo... 349
13.1 Introduction 349
13.2 Steam Explosion: Process Description and Effects on Lignocellulosic Biomass 350
13.3 The Severity Factor: Description of the Model and Limiting Factors 356
13.3.1 Integration of Temperature and pH Variation in Steam Explosion Models 361
13.4 Conclusion 364
References 364
Chapter 14: Hydrothermal Pretreatment Using Supercritical CO2 in the Biorefinery Context 368
14.1 Introduction 368
14.2 Supercritical Fluids 369
14.3 Supercritical CO2: Why Is It so Intriguing Solvent? 370
14.4 Hydrothermal Technologies Catalysed with scCO2 372
14.4.1 Principles 372
14.4.2 Effect of Operational Pretreatment Conditions on Enzymatic Hydrolysis 375
14.4.2.1 CO2 Pressure 375
14.4.2.2 Temperature 376
14.4.2.3 Reaction Time 378
14.4.2.4 Influence of Other Factors 380
ScCO2 Efficiency Dependence on Water Presence 380
Biomass Features 381
14.4.3 Technology Integration 381
14.4.4 Comparison to Other Pretreatments 382
14.4.5 Effect on Hydrolysis of Hemicellulose 383
14.4.6 Lignin Processing 386
14.5 Conclusions and Outlook 387
References 388
Chapter 15: Scale-Up Hydrothermal Pretreatment of Sugarcane Bagasse and Straw for Second-Generation Ethanol Production 392
15.1 Hydrothermal Pretreatment 392
15.1.1 Reaction in Laboratory Scale 393
15.2 Mass Balance of Hydrothermal Pretreatment in Pilot Scale 396
15.3 Conclusions 401
References 402
Chapter 16: Pilot Plant Design and Operation Using a Hydrothermal Pretreatment: Bioenercel Experience 404
16.1 Introduction 404
16.2 Pilot Plant Description 405
16.2.1 Pretreatment 407
16.2.2 Disintegration and Conditioning 408
16.2.3 Enzymatic Hydrolysis 409
16.2.3.1 Separate Hydrolysis and Fermentation (SHF) 409
16.2.3.2 Simultaneous Saccharification and Fermentation (SSF) 409
16.2.4 Distillation 410
16.3 Evaluation of the Ethanol Production Process at Pilot Plant Scale 410
16.3.1 Pretreatment 410
16.3.2 Enzymatic Hydrolysis 413
16.3.3 Fermentation 414
16.3.4 Distillation 414
References 415
Chapter 17: Techno-Economic Aspects in the Evaluation of Biorefineries for Production of Second-Generation Bioethanol 416
17.1 Introduction 416
17.1.1 A Quick Glance at 1G and 2G Technologies for Ethanol Production 418
17.1.1.1 Starch-to-Ethanol 419
17.1.1.2 Sugarcane-to-Ethanol 419
17.1.1.3 Lignocellulose-to-Ethanol 421
17.1.2 Flowsheeting 423
17.1.3 Economics of a Process 425
17.1.4 Feedstock Considerations 426
17.1.5 Some Selected Examples of Techno-Economic Simulations 427
17.1.5.1 Integration of 2G Ethanol Production in 1G Plants 429
17.1.5.2 Integration of Process Units 430
17.1.5.3 Integration with Pulp Mills or District Heating Systems 431
17.1.6 Concluding Remarks 432
References 433
Chapter 18: Minimizing Precipitated Lignin Formation and Maximizing Monosugar Concentration by Formic Acid Reinforced Hydrolys... 436
18.1 Introduction 436
18.2 Experimental Methods 438
18.2.1 Procedures 438
18.2.1.1 Chemical Analysis of Wood and Prehydrolysate 439
18.2.1.2 Precipitate Characterization 441
18.2.2 Wood Composition 441
18.3 Results and Discussion 441
18.4 Conclusions 454
References 455
Chapter 19: Microwave-Assisted Hydrothermal Processing of Seaweed Biomass 457
19.1 Introduction 457
19.2 Microwave-Assisted Biorefinery 461
19.3 Microwave-Assisted Hydrothermal Processing of Model Sugars 463
19.4 Microwave-Assisted Hydrothermal Processing of Seaweed Biomass 466
19.5 Dielectric Properties of Seaweed Biomass in Water 468
19.6 Conclusion 470
References 471
Chapter 20: Hydrothermal Processes for Extraction of Macroalgae High Value-Added Compounds 475
20.1 Introduction 475
20.1.1 Brown Macroalgae 476
20.1.2 Green Macroalgae 477
20.1.3 Red Macroalgae 477
20.2 Market and Current Applications 478
20.3 Hydrothermal Process for the Extraction of Macroalgae Bioactive Compounds 479
20.3.1 Hydrothermal Process Applied over Brown Macroalgae 479
20.3.2 Hydrothermal Process Applied over Green Macroalgae 487
20.3.3 Hydrothermal Process Applied over Red Macroalgae 488
20.4 Conventional Extraction Methods 489
20.5 Conclusions and Final Remarks 489
References 492
Chapter 21: Hydrothermal Processing of Microalgae 496
21.1 Introduction 496
21.2 Pretreatments Applied to Microalgae Biomass 500
21.3 Thermal Pretreatments 503
21.3.1 Effect on Microalgae Organic Matter 503
21.3.2 Effect on Biofuels Production 505
21.3.2.1 Bioethanol Production 505
21.3.2.2 Biogas Production 507
21.3.2.3 Bio-Oil Production 508
21.4 Conclusions and Final Remarks 509
References 509
Index 514