Chemical Catalysts for Biomass Upgrading

Cover......Page 1
Title Page......Page 5
Copyright......Page 6
Contents......Page 7
Preface......Page 15
 1.1 Introduction......Page 17
   1.1.1.1 Catalytic Pyrolysis Over HZSM‐5......Page 20
   1.1.1.2 Deactivation of HZSM‐5 During CFP......Page 25
   1.1.1.3 Modification of ZSM‐5 with Metals......Page 29
   1.1.1.4 Modifications of ZSM‐5 Pore Structure......Page 34
  1.1.2 CFP with Metal Oxide Catalysts......Page 36
  1.1.3 CFP to Produce Fine Chemicals......Page 40
  1.1.4 Outlook and Conclusions......Page 42
 References......Page 43
 2.1 Introduction......Page 51
 2.2 Hydrodeoxygenation (HDO)......Page 53
   2.2.1.1 HDO of Phenolic (Guaiacol) Model Compounds......Page 54
   2.2.1.3 HDO of Phenolic (Cresol) Model Compounds......Page 56
  2.2.2 Hydrodeoxygenation of Aldehyde Model Compounds......Page 57
  2.2.3 Hydrodeoxygenation of Carboxylic Acid Model Compounds......Page 59
  2.2.5 Hydrodeoxygenation of Carbohydrate Model Compounds......Page 60
 2.3 Chemical Catalysts for the HDO Reaction......Page 61
  2.3.1 Catalyst Promoters for HDO......Page 64
  2.3.3 Catalyst Selectivity for HDO......Page 65
  2.3.4 Catalyst Deactivation During HDO......Page 66
 2.4 Research Gaps......Page 67
 Acknowledgments......Page 68
 References......Page 69
 3.1 Introduction......Page 77
  3.2.2 General Characteristics, Composition, and Stabilization of Bio‐oil......Page 79
   3.2.2.1 Adjustment of Bio‐oil Composition Through Pyrolytic Strategies......Page 81
   3.2.2.2 Bio‐oil Stabilization......Page 82
   3.2.3.1 Hydroprocessing......Page 85
   3.2.3.2 Steam Reforming......Page 86
  3.3.1 The FCC Unit......Page 87
  3.3.2 Cracking Reactions and Mechanisms......Page 89
  3.3.3 Cracking of Oxygenated Compounds......Page 90
  3.3.4 Cracking of Bio‐oil......Page 92
  3.4.2 Coprocessing of Oxygenates and Their Mixtures with Vacuum Gas Oil (VGO)......Page 94
  3.4.3 Cracking of Bio‐oil and Its Mixtures with VGO......Page 95
 3.5 Conclusions and Critical Discussion......Page 102
 References......Page 104
 4.1 Introduction......Page 113
  4.2.1 Sugars......Page 118
  4.2.2 Carboxylic Acids......Page 125
  4.2.3 Furans......Page 129
  4.2.4 Aldehydes and Ketones......Page 130
  4.2.5 Phenolics......Page 132
  4.2.6 Other Components......Page 133
  4.3.2 Removal of the Water in Bio‐oil to Enhance Conversion of Carboxylic Acids......Page 137
  4.3.5 Esterification Coupled with Hydrogenation......Page 139
  4.3.6 Steric Hindrance in Bio‐oil Esterification......Page 140
  4.3.7 Coking in Esterification of Bio‐oil......Page 141
  4.3.8 Effects of Bio‐oil Esterification on the Subsequent Hydrotreatment......Page 145
 4.4 Catalysts......Page 148
 4.5 Summary and Outlook......Page 152
 References......Page 153
 5.1 Introduction......Page 161
 5.2 Catalytic Transformation of C5–C6 Sugars......Page 162
  5.2.1 Isomerization Catalysts......Page 163
   5.2.1.1 Zeolites......Page 165
   5.2.1.2 Hydrotalcites......Page 167
  5.2.2 Dehydration Catalysts......Page 170
   5.2.2.1 Zeolitic and Mesoporous Brønsted Solid Acids......Page 172
   5.2.2.2 Sulfonic Acid Functionalized Hybrid Organic–Inorganic Silicas......Page 175
   5.2.2.3 Metal–Organic Frameworks......Page 179
   5.2.2.4 Supported Ionic Liquids......Page 180
   5.2.3.1 Bifunctional Zeolites and Mesoporous Solid Acids......Page 181
   5.2.3.2 Metal Oxides, Sulfates, and Phosphates......Page 183
  5.2.4 Catalysts for the Hydrogenation of C5–C6 Sugars......Page 188
   5.2.4.1 Ni Catalysts......Page 189
   5.2.4.2 Ru Catalysts......Page 192
   5.2.4.4 Other Hydrogenation Catalysts......Page 194
  5.2.5 Hydrogenolysis Catalysts......Page 195
  5.2.6 Other Reactions......Page 199
 5.3 Conclusions and Future Perspectives......Page 200
 References......Page 202
 6.1 Introduction......Page 223
   6.2.1.1 Base‐Catalyzed Aldol Condensation......Page 224
   6.2.1.2 Acid‐Catalyzed Aldol Condensation: Mechanism and Site Requirement......Page 230
   6.2.2.1 Lewis Acid‐Catalyzed Alkylation Mechanism......Page 235
   6.2.2.2 Brønsted Acid‐Catalyzed Alkylation Mechanism......Page 236
  6.2.3 Hydroxyalkylation: Mechanism and Site Requirement......Page 241
   6.2.3.1 Brønsted Acid‐Catalyzed Mechanism......Page 243
   6.2.3.2 Site Requirement......Page 244
  6.2.4 Acylation: Mechanism and Site Requirement......Page 245
   6.2.4.1 Mechanistic Aspects of Acylation Reactions......Page 246
   6.2.4.2 Role of Brønsted vs. Lewis Acid in Acylation Over Zeolites......Page 248
   6.2.5.1 Mechanism of Surface Ketonization......Page 250
   6.2.5.2 Site Requirement......Page 254
   6.3.1.1 Magnesia (MgO)......Page 255
   6.3.1.2 Zirconia (ZrO2)......Page 261
   6.3.2.1 ZSM‐5......Page 264
   6.3.2.2 HY......Page 270
   6.3.2.3 HBEA......Page 273
 References......Page 275
 7.1 Introduction......Page 315
  7.2.1 Introduction......Page 316
   7.2.2.1 Glycerol to Glyceric Acid (GLYAC)......Page 317
   7.2.2.2 Glycerol to Tartronic Acid (TARAC)......Page 320
   7.2.2.5 Glycerol to Glycolic Acid (GLYCAC)......Page 321
   7.2.2.6 Glycerol to Lactic Acid (LAC)......Page 322
   7.2.3.1 HMF to 2,5‐Furandicarboxylic Acid (FDCA)......Page 323
   7.2.3.2 HMF to 2,5‐Diformylfuran (DFF)......Page 325
  7.3.2 Hydrogenolysis of Polyols......Page 326
   7.3.2.1 Hydrodeoxygenation of Polyols......Page 327
   7.3.2.2 C–C Hydrogenolysis of Polyols......Page 330
   7.3.3.1 Levulinic Acid......Page 332
   7.3.3.2 Succinic Acid......Page 334
  7.3.4 Selective Hydrogenation of Furanic Compounds......Page 336
  7.3.5 Reductive Amination of Acids and Furans......Page 339
  7.4.1 Introduction......Page 340
  7.4.2 Glycerol to Acrolein......Page 341
  7.4.3 Lactic Acid to Acrylic Acid......Page 344
  7.4.4 Sorbitol to Isosorbide......Page 346
 References......Page 347
 8.1 Introduction......Page 373
  8.1.1 Cautionary Statements......Page 376
  8.2.1 Enzymes and Bio‐mimetic Catalysts......Page 377
  8.2.2 Cobalt Schiff Base Catalysts......Page 379
  8.2.3 Vanadium Catalysts......Page 383
  8.2.4 Methyltrioxorhenium (MTO) Catalysts......Page 384
  8.4.1 Benzylic Oxidation......Page 385
  8.4.2 Secondary Depolymerization......Page 392
 8.5 Heterogeneous Catalysts for Lignin Depolymerization......Page 398
 References......Page 402
 9.1 Introduction......Page 411
 9.2 Late‐stage Reductive Lignin Depolymerization......Page 412
  9.2.1 Mild Hydroprocessing......Page 414
  9.2.2 Harsh Hydroprocessing......Page 420
  9.2.3 Bifunctional Hydroprocessing......Page 423
  9.2.4 Liquid Phase Reforming......Page 426
  9.2.5 Reductive Lignin Depolymerization Using Hydrosilanes, Zinc, and Sodium......Page 430
 9.3 Reductive Catalytic Fractionation (RCF)......Page 432
  9.3.2 Lignocellulose Source......Page 433
  9.3.3 Applied Catalyst......Page 443
 9.4 Outlook......Page 444
 References......Page 445
 10.1 Introduction......Page 455
 10.3 Biodiesel Production......Page 457
  10.3.1 Algal Biodiesel Production......Page 458
   10.3.1.1 Nutrients for Microalgae Growth......Page 459
   10.3.1.3 Harvesting......Page 460
   10.3.1.4 Drying......Page 461
   10.4.1.1 Alkali Catalysts......Page 462
   10.4.1.3 Two‐step Esterification–Transesterification Reactions......Page 464
  10.4.2 Heterogeneous Catalysts......Page 466
   10.4.2.2 Solid Base Catalysts......Page 467
  10.4.3 Enzyme‐Catalyzed Transesterification Reactions......Page 469
 10.5 Supercritical Transesterification Processes......Page 470
  10.6.1 Ultrasonic Processes......Page 471
  10.6.2 Microwave‐Assisted Processes......Page 472
 References......Page 475
 11.1 Introduction......Page 485
 11.2 Feedstocks......Page 487
 11.3 Chemistry......Page 488
 11.4 Technologies......Page 491
  11.5.1 Sulfided Catalysts......Page 493
  11.5.2 Metallic Catalysts......Page 496
  11.5.3 Metal Carbide, Nitride, and Phosphide Catalysts......Page 499
 11.6 Conclusions and Outlook......Page 505
 References......Page 506
 12.1 Introduction......Page 513
 12.2 Lipid Feeds......Page 516
 12.3 deCOx Catalysts: Active Phases......Page 518
 12.4 deCOx Catalysts: Support Materials......Page 524
 12.5 Reaction Conditions......Page 525
 12.6 Reaction Mechanism......Page 527
 12.7 Catalyst Deactivation......Page 532
 References......Page 534
 13.2 Terpene Biosynthesis and Structure......Page 545
  13.3.1 Conifers and Other Trees......Page 548
  13.3.2 Essential Oils and Other Extracts......Page 550
  13.4.1 Tapping and Extraction......Page 551
  13.5.1 Adhesives and Turpentine......Page 552
 13.6 Catalytic Methods for Conversion of Terpenes to Fine Chemicals and Materials......Page 553
   13.6.1.1 Hydration and Oxidation Reactions......Page 554
   13.6.1.3 Isomerizations......Page 557
   13.6.1.4 Production of Terpene Carbonates from CO2 and Epoxides......Page 559
   13.6.1.5 Polymers and Other Materials from Terpenes......Page 561
   13.6.1.6 “Click Chemistry” Routes for the Production of Materials and Medicinal Compounds from Terpenes......Page 564
   13.6.2.1 Isomerization and Hydration of α‐Pinene......Page 567
   13.6.2.2 Heterogeneous Catalysts for the Epoxidation of Monoterpenes......Page 569
   13.6.2.4 Vitamins from Terpenes......Page 571
   13.6.2.5 Dehydrogenation and Hydrogenation Reactions of Terpenes......Page 573
   13.6.2.6 Conversion of Terpenes to Fuels......Page 574
 Acknowledgments......Page 576
 References......Page 577
 14.1 Waste Shell Biorefinery......Page 585
  14.2.1 Sugar Amines/Amides......Page 587
  14.2.2 Furanic Amines/Amides......Page 590
  14.2.3 Polyol Amines/Amides......Page 592
 14.3 Production of N‐heterocyclic Compounds from Chitin Biomass......Page 595
 14.4 Production of Carbohydrates and Acetic Acid from Chitin Biomass......Page 597
 14.5 Production of Advanced Products from Chitin Biomass......Page 600
 References......Page 603
Chapter 15 Outlook......Page 607
Index......Page 615
EULA......Page 636