Chemical catalysts for biomass upgrading

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. 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