A comprehensive reference to the use of innovative catalysts and processes to turn biomass into value-added chemicals Chemical Catalysts for Biomass Upgrading offers detailed descriptions of catalysts and catalytic processes employed in the synthesis of chemicals and fuels from the most abundant and important biomass types. The contributors?noted experts on the topic?focus on the application of catalysts to the pyrolysis of whole biomass and to the upgrading of bio-oils. The authors discuss catalytic approaches to the processing of biomass-derived oxygenates, as exemplified by sugars, via reactions such as reforming, hydrogenation, oxidation, and condensation reactions. Additionally, the book provides an overview of catalysts for lignin valorization via oxidative and reductive methods and considers the conversion of fats and oils to fuels and terminal olefins by means of esterification/transesterification, hydrodeoxygenation, and decarboxylation/decarbonylation processes. The authors also provide an overview of conversion processes based on terpenes and chitin, two emerging feedstocks with a rich chemistry, and summarize some of the emerging trends in the field. This important book: -Provides a comprehensive review of innovative catalysts, catalytic processes, and catalyst design -Offers a guide to one of the most promising ways to find useful alternatives for fossil fuel resources -Includes information on the most abundant and important types of biomass feedstocks -Examines fields such as catalytic cracking, pyrolysis, depolymerization, and many more Written for catalytic chemists, process engineers, environmental chemists, bioengineers, organic chemists, and polymer chemists, Chemical Catalysts for Biomass Upgrading presents deep insights on the most important aspects of biomass upgrading and their various types.
Preface xiii
1 Upgrading of Biomass via Catalytic Fast Pyrolysis (CFP)1Charles A. Mullen
1.1 Introduction 1
1.1.1 Catalytic Pyrolysis Over Zeolites 4
1.1.1.1 Catalytic Pyrolysis Over HZSM-5 4
1.1.1.2 Deactivation of HZSM-5 During CFP 9
1.1.1.3 Modification of ZSM-5 with Metals 13
1.1.1.4 Modifications of ZSM-5 Pore Structure 18
1.1.2 CFP with Metal Oxide Catalysts 20
1.1.3 CFP to Produce Fine Chemicals 24
1.1.4 Outlook and Conclusions 26
References 27
2 The Upgrading of Bio-Oil via Hydrodeoxygenation35Adetoyese O. Oyedun, Madhumita Patel, Mayank Kumar, and Amit Kumar
2.1 Introduction 35
2.2 Hydrodeoxygenation (HDO) 37
2.2.1 Hydrodeoxygenation of Phenol as a Model Compound 38
2.2.1.1 HDO of Phenolic (Guaiacol) Model Compounds 38
2.2.1.2 HDO of Phenolic (Anisole)Model Compounds 40
2.2.1.3 HDO of Phenolic (Cresol) Model Compounds 40
2.2.2 Hydrodeoxygenation of Aldehyde Model Compounds 41
2.2.3 Hydrodeoxygenation of Carboxylic Acid Model Compounds 43
2.2.4 Hydrodeoxygenation of Alcohol Model Compounds 44
2.2.5 Hydrodeoxygenation of Carbohydrate Model Compounds 44
2.3 Chemical Catalysts for the HDO Reaction 45
2.3.1 Catalyst Promoters for HDO 48
2.3.2 Catalyst Supports for HDO 49
2.3.3 Catalyst Selectivity for HDO 49
2.3.4 Catalyst Deactivation During HDO 50
2.4 Research Gaps 51
2.5 Conclusions 52
Acknowledgments 52
References 53
3 Upgrading of Bio-oil via Fluid Catalytic Cracking61Idoia Hita, Jose Maria Arandes, and Javier Bilbao
3.1 Introduction 61
3.2 Bio-oil 63
3.2.1 Bio-oil Production via Fast Pyrolysis 63
3.2.2 General Characteristics, Composition, and Stabilization of Bio-oil 63
3.2.2.1 Adjustment of Bio-oil Composition Through Pyrolytic Strategies 65
3.2.2.2 Bio-oil Stabilization 66
3.2.3 Valorization Routes for Bio-oil 69
3.2.3.1 Hydroprocessing 69
3.2.3.2 Steam Reforming 70
3.2.3.3 Extraction of Valuable Components from Bio-oil 71
3.3 Catalytic Cracking of Bio-oil: Fundamental Aspects 71
3.3.1 The FCC Unit 71
3.3.2 Cracking Reactions and Mechanisms 73
3.3.3 Cracking of Oxygenated Compounds 74
3.3.4 Cracking of Bio-oil 76
3.4 Bio-oil Cracking in the FCC Unit 78
3.4.1 Cracking of Model Oxygenates 78
3.4.2 Coprocessing of Oxygenates and Their Mixtures with Vacuum Gas Oil (VGO) 78
3.4.3 Cracking of Bio-oil and Its Mixtures with VGO 79
3.5 Conclusions and Critical Discussion 86
References 88
4 Stabilization of Bio-oil via Esterification97Xun Hu
4.1 Introduction 97
4.2 Reactions of the Main Components of Bio-Oil Under Esterification Conditions 102
4.2.1 Sugars 102
4.2.2 Carboxylic Acids 109
4.2.3 Furans 113
4.2.4 Aldehydes and Ketones 114
4.2.5 Phenolics 116
4.2.6 Other Components 117
4.3 Processes for Esterification of Bio-oil 121
4.3.1 Esterification of Bio-oil Under Subcritical or Supercritical Conditions 121
4.3.2 Removal of the Water in Bio-oil to Enhance Conversion of Carboxylic Acids 121
4.3.3 In-line Esterification of Bio-oil 123
4.3.4 Esterification Coupled with Oxidation 123
4.3.5 Esterification Coupled with Hydrogenation 123
4.3.6 Steric Hindrance in Bio-oil Esterification 124
4.3.7 Coking in Esterification of Bio-oil 125
4.3.8 Effects of Bio-oil Esterification on the Subsequent Hydrotreatment 129
4.4 Catalysts 132
4.5 Summary and Outlook 136
Acknowledgments 137
References 137
5 Catalytic Upgrading of Holocellulose-Derived C5 and C6 Sugars145Xingguang Zhang, Zhijun Tai, Amin Osatiashtiani, Lee Durndell, Adam F. Lee, and Karen Wilson
5.1 Introduction 145
5.2 Catalytic Transformation of C5C6 Sugars 146
5.2.1 Isomerization Catalysts 147
5.2.1.1 Zeolites 149
5.2.1.2 Hydrotalcites 151
5.2.1.3 Other Solid Catalysts 154
5.2.2 Dehydration Catalysts 154
5.2.2.1 Zeolitic and Mesoporous Brønsted Solid Acids 156
5.2.2.2 Sulfonic Acid Functionalized Hybrid OrganicInorganic Silicas 159
5.2.2.3 MetalOrganic Frameworks 163
5.2.2.4 Supported Ionic Liquids 164
5.2.3 Catalysts for Tandem Isomerization and Dehydration of C5C6 Sugars 165
5.2.3.1 Bifunctional Zeolites and Mesoporous Solid Acids 165
5.2.3.2 Metal Oxides, Sulfates, and Phosphates 167
5.2.3.3 MetalOrganic Frameworks 172
5.2.4 Catalysts for the Hydrogenation of C5C6 Sugars 172
5.2.4.1 Ni Catalysts 173
5.2.4.2 Ru Catalysts 176
5.2.4.3 Pt Catalysts 178
5.2.4.4 Other Hydrogenation Catalysts 178
5.2.5 Hydrogenolysis Catalysts 179
5.2.6 Other Reactions 183
5.3 Conclusions and Future Perspectives 184
References 186
6 Chemistry of CC Bond Formation Reactions Used in Biomass Upgrading: Reaction Mechanisms, Site Requirements, and Catalytic Materials207Tuong V. Bui, Nhung Duong, Felipe Anaya, Duong Ngo, Gap Warakunwit, and Daniel E. Resasco
6.1 Introduction 207
6.2 Mechanisms and Site Requirements of CC Coupling Reactions 208
6.2.1 Aldol Condensation: Mechanism and Site Requirement 208
6.2.1.1 Base-Catalyzed Aldol Condensation 208
6.2.1.2 Acid-Catalyzed Aldol Condensation: Mechanism and Site Requirement 214
6.2.2 Alkylation: Mechanism and Site Requirement 219
6.2.2.1 Lewis Acid-Catalyzed Alkylation Mechanism 219
6.2.2.2 Brønsted Acid-Catalyzed Alkylation Mechanism 220
6.2.2.3 Base-Catalyzed Alkylation: Mechanism and Site Requirement 225
6.2.3 Hydroxyalkylation: Mechanism and Site Requirement 225
6.2.3.1 Brønsted Acid-Catalyzed Mechanism 227
6.2.3.2 Site Requirement 228
6.2.4 Acylation: Mechanism and Site Requirement 229
6.2.4.1 Mechanistic Aspects of Acylation Reactions 230
6.2.4.2 Role of Brønsted vs. Lewis Acid in Acylation Over Zeolites 232
6.2.5 Ketonization: Mechanism and Site Requirement 234
6.2.5.1 Mechanism of Surface Ketonization 234
6.2.5.2 Site Requirement 238
6.3 Optimization and Design of Catalytic Materials for CC Bond Forming Reactions 239
6.3.1 Oxides 239
6.3.1.1 Magnesia (MgO) 239
6.3.1.2 Zirconia (ZrO2) 245
6.3.2 Zeolites 248
6.3.2.1 ZSM-5 248
6.3.2.2 HY 254
6.3.2.3 HBEA 257
References 259
7 Downstream Conversion of Biomass-Derived Oxygenates to Fine Chemicals299Michele Besson, Stephane Loridant, Noemie Perret, and Catherine Pinel
7.1 Introduction 299
7.2 Selective Catalytic Oxidation 300
7.2.1 Introduction 300
7.2.2 Catalytic Oxidation of Glycerol 301
7.2.2.1 Glycerol to Glyceric Acid (GLYAC) 301
7.2.2.2 Glycerol to Tartronic Acid (TARAC) 304
7.2.2.3 Glycerol to Dihydroxyacetone (DHA) 305
7.2.2.4 Glycerol to Mesoxalic Acid (MESAC) 305
7.2.2.5 Glycerol to Glycolic Acid (GLYCAC) 305
7.2.2.6 Glycerol to Lactic Acid (LAC) 306
7.2.3 Oxidation of 5-Hydroxymethylfurfural (HMF) 307
7.2.3.1 HMF to 2,5-Furandicarboxylic Acid (FDCA) 307
7.2.3.2 HMF to 2,5-Diformylfuran (DFF) 309
7.2.3.3 HMF to 5-Hydroxymethyl-2-furancarboxylic Acid (HMFCA) or 5-Formyl-2-furancarboxylic Acid (FFCA) 310
7.3 Hydrogenation/Hydrogenolysis 310
7.3.1 Introduction 310
7.3.2 Hydrogenolysis of Polyols 310
7.3.2.1 Hydrodeoxygenation of Polyols 311
7.3.2.2 CC Hydrogenolysis of Polyols 314
7.3.3 Hydrogenation of Carboxylic Acids 316
7.3.3.1 Levulinic Acid 316
7.3.3.2 Succinic Acid 318
7.3.4 Selective Hydrogenation of Furanic Compounds 320
7.3.5 Reductive Amination of Acids and Furans 323
7.4 Catalyst Design for the Dehydration of Biosourced Molecules 324
7.4.1 Introduction 324
7.4.2 Glycerol to Acrolein 325
7.4.3 Lactic Acid to Acrylic Acid 328
7.4.4 Sorbitol to Isosorbide 330
7.5 Conclusions and Outlook 331
References 331
8 Conversion of Lignin to Value-added Chemicals via Oxidative Depolymerization357Justin K. Mobley
8.1 Introduction 357
8.1.1 Cautionary Statements 360
8.2 Catalytic Systems for the Oxidative Depolymerization of Lignin 361
8.2.1 Enzymes and Bio-mimetic Catalysts 361
8.2.2 Cobalt Schiff Base Catalysts 363
8.2.3 Vanadium Catalysts 367
8.2.4 Methyltrioxorhenium (MTO) Catalysts 368
8.3 Commercial Products from Lignin 369
8.4 Stepwise Depolymerization of -O-4 Linkages 369
8.4.1 Benzylic Oxidation 369
8.4.2 Secondary Depolymerization 376
8.5 Heterogeneous Catalysts for Lignin Depolymerization 382
8.6 Outlook 386
Acknowledgments 386
References 386
9 Lignin Valorization via Reductive Depolymerization395Yang (Vanessa) Song
9.1 Introduction 395
9.2 Late-stage Reductive Lignin Depolymerization 396
9.2.1 Mild Hydroprocessing 398
9.2.2 Harsh Hydroprocessing 404
9.2.3 Bifunctional Hydroprocessing 407
9.2.4 Liquid Phase Reforming 410
9.2.5 Reductive Lignin Depolymerization Using Hydrosilanes, Zinc, and Sodium 414
9.3 Reductive Catalytic Fractionation (RCF) 416
9.3.1 Reaction Conditions 417
9.3.2 Lignocellulose Source 417
9.3.3 Applied Catalyst 427
9.4 Outlook 428
Acknowledgment 429
References 429
10 Conversion of Lipids to Biodiesel via Esterification and Transesterification439Amin Talebian-Kiakalaieh and Amin Nor Aishah Saidina
10.1 Introduction 439
10.2 Different Feedstocks for Biodiesel Production 441
10.3 Biodiesel Production 441
10.3.1 Algal Biodiesel Production 442
10.3.1.1 Nutrients for Microalgae Growth 443
10.3.1.2 Microalgae Cultivation System 444
10.3.1.3 Harvesting 444
10.3.1.4 Drying 445
10.3.1.5 Lipid Extraction 446
10.4 Catalytic Transesterification 446
10.4.1 Homogeneous Catalysts 446
10.4.1.1 Alkali Catalysts 446
10.4.1.2 Acid Catalysts 448
10.4.1.3 Two-step EsterificationTransesterification Reactions 448
10.4.2 Heterogeneous Catalysts 450
10.4.2.1 Solid Acid Catalysts 451
10.4.2.2 Solid Base Catalysts 451
10.4.3 Enzyme-Catalyzed Transesterification Reactions 453
10.5 Supercritical Transesterification Processes 454
10.6 Alternative Processes for Biodiesel Production 455
10.6.1 Ultrasonic Processes 455
10.6.2 Microwave-Assisted Processes 456
10.7 Summary 459
References 459
11 Upgrading of Lipids to Hydrocarbon Fuels via (Hydro)deoxygenation469David Kubika
11.1 Introduction 469
11.2 Feedstocks 471
11.3 Chemistry 472
11.4 Technologies 475
11.5 Catalysts 477
11.5.1 Sulfided Catalysts 477
11.5.2 Metallic Catalysts 480
11.5.3 Metal Carbide, Nitride, and Phosphide Catalysts 483
11.6 Conclusions and Outlook 489
References 490
12 Upgrading of Lipids to Fuel-like Hydrocarbons and Terminal Olefins via Decarbonylation/Decarboxylation497Ryan Loe, Eduardo Santillan-Jimenez, and Mark Crocker
12.1 Introduction 497
12.2 Lipid Feeds 500
12.3 deCOxCatalysts: Active Phases 502
12.4 deCOxCatalysts: Support Materials 508
12.5 Reaction Conditions 509
12.6 Reaction Mechanism 511
12.7 Catalyst Deactivation 516
12.8 Conclusions and Outlook 518
References 518
13 Conversion of Terpenes to Chemicals and Related Products529Anne E. Harman-Ware
13.1 Introduction 529
13.2 Terpene Biosynthesis and Structure 529
13.3 Sources of Terpenes 532
13.3.1 Conifers and Other Trees 532
13.3.2 Essential Oils and Other Extracts 534
13.4 Isolation of Terpenes 535
13.4.1 Tapping and Extraction 535
13.4.2 Terpenes as a By-product of Pulping Processes 536
13.5 Historical Uses of Raw Terpenes 536
13.5.1 Adhesives and Turpentine 536
13.5.2 Flavors, Fragrances, Therapeutics, and Pharmaceutical Applications 537
13.6 Catalytic Methods for Conversion of Terpenes to Fine Chemicals and Materials 537
13.6.1 Homogeneous Processes 538
13.6.1.1 Hydration and Oxidation Reactions 538
13.6.1.2 Homogeneous Catalysis for the Epoxidation of Monoterpenes 541
13.6.1.3 Isomerizations 541
13.6.1.4 Production of Terpene Carbonates from CO2 and Epoxides 543
13.6.1.5 Polymers and Other Materials from Terpenes 545
13.6.1.6 Click Chemistry Routes for the Production of Materials and Medicinal Compounds from Terpenes 548
13.6.2 Heterogeneous Processes 551
13.6.2.1 Isomerization and Hydration of -Pinene 551
13.6.2.2 Heterogeneous Catalysts for the Epoxidation of Monoterpenes 553
13.6.2.3 Isomerization of -Pinene Oxide 555
13.6.2.4 Vitamins from Terpenes 555
13.6.2.5 Dehydrogenation and Hydrogenation Reactions of Terpenes 557
13.6.2.6 Conversion of Terpenes to Fuels 558
Acknowledgments 560
References 561
14 Conversion of Chitin to Nitrogen-containing Chemicals569Xi Chen and Ning Yan
14.1 Waste Shell Biorefinery 569
14.2 Production of Amines and Amides from Chitin Biomass 571
14.2.1 Sugar Amines/Amides 571
14.2.2 Furanic Amines/Amides 574
14.2.3 Polyol Amines/Amides 576
14.3 Production of N-heterocyclic Compounds from Chitin Biomass 579
14.4 Production of Carbohydrates and Acetic Acid from Chitin Biomass 581
14.5 Production of Advanced Products from Chitin Biomass 584
14.6 Conclusion 587
References 587
15 Outlook591Eduardo Santillan-Jimenez and Mark Crocker
Index 599
