Chemical Catalysts for Biomass Upgrading

Mark Crocker is Associate Director at the University of Kentucky Center for Applied Energy Research, where he leads the Biofuels and Environmental Catalysis research program, and Professor of Chemistry at the University of Kentucky. Eduardo Santillan-Jimenez is Principal Research Scientist at the University of Kentucky Center for Applied Energy Research. His current work focuses on the application of heterogeneous catalysis to the production of renewable fuels and chemicals.

• Preface xiii1 Upgrading of Biomass via Catalytic Fast Pyrolysis (CFP) 1Charles A. Mullen1.1 Introduction 11.1.1 Catalytic Pyrolysis Over Zeolites 41.1.1.1 Catalytic Pyrolysis Over HZSM-5 41.1.1.2 Deactivation of HZSM-5 During CFP 91.1.1.3 Modification of ZSM-5 with Metals 131.1.1.4 Modifications of ZSM-5 Pore Structure 181.1.2 CFP with Metal Oxide Catalysts 201.1.3 CFP to Produce Fine Chemicals 241.1.4 Outlook and Conclusions 26References 272 The Upgrading of Bio-Oil via Hydrodeoxygenation 35Adetoyese O. Oyedun, Madhumita Patel, Mayank Kumar, and Amit Kumar2.1 Introduction 352.2 Hydrodeoxygenation (HDO) 372.2.1 Hydrodeoxygenation of Phenol as a Model Compound 382.2.1.1 HDO of Phenolic (Guaiacol) Model Compounds 382.2.1.2 HDO of Phenolic (Anisole)Model Compounds 402.2.1.3 HDO of Phenolic (Cresol) Model Compounds 402.2.2 Hydrodeoxygenation of Aldehyde Model Compounds 412.2.3 Hydrodeoxygenation of Carboxylic Acid Model Compounds 432.2.4 Hydrodeoxygenation of Alcohol Model Compounds 442.2.5 Hydrodeoxygenation of Carbohydrate Model Compounds 442.3 Chemical Catalysts for the HDO Reaction 452.3.1 Catalyst Promoters for HDO 482.3.2 Catalyst Supports for HDO 492.3.3 Catalyst Selectivity for HDO 492.3.4 Catalyst Deactivation During HDO 502.4 Research Gaps 512.5 Conclusions 52Acknowledgments 52References 533 Upgrading of Bio-oil via Fluid Catalytic Cracking 61Idoia Hita, Jose Maria Arandes, and Javier Bilbao3.1 Introduction 613.2 Bio-oil 633.2.1 Bio-oil Production via Fast Pyrolysis 633.2.2 General Characteristics, Composition, and Stabilization of Bio-oil 633.2.2.1 Adjustment of Bio-oil Composition Through Pyrolytic Strategies 653.2.2.2 Bio-oil Stabilization 663.2.3 Valorization Routes for Bio-oil 693.2.3.1 Hydroprocessing 693.2.3.2 Steam Reforming 703.2.3.3 Extraction of Valuable Components from Bio-oil 713.3 Catalytic Cracking of Bio-oil: Fundamental Aspects 713.3.1 The FCC Unit 713.3.2 Cracking Reactions and Mechanisms 733.3.3 Cracking of Oxygenated Compounds 743.3.4 Cracking of Bio-oil 763.4 Bio-oil Cracking in the FCC Unit 783.4.1 Cracking of Model Oxygenates 783.4.2 Coprocessing of Oxygenates and Their Mixtures with Vacuum Gas Oil (VGO) 783.4.3 Cracking of Bio-oil and Its Mixtures with VGO 793.5 Conclusions and Critical Discussion 86References 884 Stabilization of Bio-oil via Esterification 97Xun Hu4.1 Introduction 974.2 Reactions of the Main Components of Bio-Oil Under Esterification Conditions 1024.2.1 Sugars 1024.2.2 Carboxylic Acids 1094.2.3 Furans 1134.2.4 Aldehydes and Ketones 1144.2.5 Phenolics 1164.2.6 Other Components 1174.3 Processes for Esterification of Bio-oil 1214.3.1 Esterification of Bio-oil Under Subcritical or Supercritical Conditions 1214.3.2 Removal of the Water in Bio-oil to Enhance Conversion of Carboxylic Acids 1214.3.3 In-line Esterification of Bio-oil 1234.3.4 Esterification Coupled with Oxidation 1234.3.5 Esterification Coupled with Hydrogenation 1234.3.6 Steric Hindrance in Bio-oil Esterification 1244.3.7 Coking in Esterification of Bio-oil 1254.3.8 Effects of Bio-oil Esterification on the Subsequent Hydrotreatment 1294.4 Catalysts 1324.5 Summary and Outlook 136Acknowledgments 137References 1375 Catalytic Upgrading of Holocellulose-Derived C5 and C6 Sugars 145Xingguang Zhang, Zhijun Tai, Amin Osatiashtiani, Lee Durndell, Adam F. Lee, and Karen Wilson5.1 Introduction 1455.2 Catalytic Transformation of C5–C6 Sugars 1465.2.1 Isomerization Catalysts 1475.2.1.1 Zeolites 1495.2.1.2 Hydrotalcites 1515.2.1.3 Other Solid Catalysts 1545.2.2 Dehydration Catalysts 1545.2.2.1 Zeolitic and Mesoporous Brønsted Solid Acids 1565.2.2.2 Sulfonic Acid Functionalized Hybrid Organic–Inorganic Silicas 1595.2.2.3 Metal–Organic Frameworks 1635.2.2.4 Supported Ionic Liquids 1645.2.3 Catalysts for Tandem Isomerization and Dehydration of C5–C6 Sugars 1655.2.3.1 Bifunctional Zeolites and Mesoporous Solid Acids 1655.2.3.2 Metal Oxides, Sulfates, and Phosphates 1675.2.3.3 Metal–Organic Frameworks 1725.2.4 Catalysts for the Hydrogenation of C5–C6 Sugars 1725.2.4.1 Ni Catalysts 1735.2.4.2 Ru Catalysts 1765.2.4.3 Pt Catalysts 1785.2.4.4 Other Hydrogenation Catalysts 1785.2.5 Hydrogenolysis Catalysts 1795.2.6 Other Reactions 1835.3 Conclusions and Future Perspectives 184References 1866 Chemistry of C—C Bond Formation Reactions Used in Biomass Upgrading: Reaction Mechanisms, Site Requirements, and Catalytic Materials 207Tuong V. Bui, Nhung Duong, Felipe Anaya, Duong Ngo, Gap Warakunwit, and Daniel E. Resasco6.1 Introduction 2076.2 Mechanisms and Site Requirements of C–C Coupling Reactions 2086.2.1 Aldol Condensation: Mechanism and Site Requirement 2086.2.1.1 Base-Catalyzed Aldol Condensation 2086.2.1.2 Acid-Catalyzed Aldol Condensation: Mechanism and Site Requirement 2146.2.2 Alkylation: Mechanism and Site Requirement 2196.2.2.1 Lewis Acid-Catalyzed Alkylation Mechanism 2196.2.2.2 Brønsted Acid-Catalyzed Alkylation Mechanism 2206.2.2.3 Base-Catalyzed Alkylation: Mechanism and Site Requirement 2256.2.3 Hydroxyalkylation: Mechanism and Site Requirement 2256.2.3.1 Brønsted Acid-Catalyzed Mechanism 2276.2.3.2 Site Requirement 2286.2.4 Acylation: Mechanism and Site Requirement 2296.2.4.1 Mechanistic Aspects of Acylation Reactions 2306.2.4.2 Role of Brønsted vs. Lewis Acid in Acylation Over Zeolites 2326.2.5 Ketonization: Mechanism and Site Requirement 2346.2.5.1 Mechanism of Surface Ketonization 2346.2.5.2 Site Requirement 2386.3 Optimization and Design of Catalytic Materials for C–C Bond Forming Reactions 2396.3.1 Oxides 2396.3.1.1 Magnesia (MgO) 2396.3.1.2 Zirconia (ZrO2) 2456.3.2 Zeolites 2486.3.2.1 ZSM-5 2486.3.2.2 HY 2546.3.2.3 HBEA 257References 2597 Downstream Conversion of Biomass-Derived Oxygenates to Fine Chemicals 299Michele Besson, Stephane Loridant, Noemie Perret, and Catherine Pinel7.1 Introduction 2997.2 Selective Catalytic Oxidation 3007.2.1 Introduction 3007.2.2 Catalytic Oxidation of Glycerol 3017.2.2.1 Glycerol to Glyceric Acid (GLYAC) 3017.2.2.2 Glycerol to Tartronic Acid (TARAC) 3047.2.2.3 Glycerol to Dihydroxyacetone (DHA) 3057.2.2.4 Glycerol to Mesoxalic Acid (MESAC) 3057.2.2.5 Glycerol to Glycolic Acid (GLYCAC) 3057.2.2.6 Glycerol to Lactic Acid (LAC) 3067.2.3 Oxidation of 5-Hydroxymethylfurfural (HMF) 3077.2.3.1 HMF to 2,5-Furandicarboxylic Acid (FDCA) 3077.2.3.2 HMF to 2,5-Diformylfuran (DFF) 3097.2.3.3 HMF to 5-Hydroxymethyl-2-furancarboxylic Acid (HMFCA) or 5-Formyl-2-furancarboxylic Acid (FFCA) 3107.3 Hydrogenation/Hydrogenolysis 3107.3.1 Introduction 3107.3.2 Hydrogenolysis of Polyols 3107.3.2.1 Hydrodeoxygenation of Polyols 3117.3.2.2 C–C Hydrogenolysis of Polyols 3147.3.3 Hydrogenation of Carboxylic Acids 3167.3.3.1 Levulinic Acid 3167.3.3.2 Succinic Acid 3187.3.4 Selective Hydrogenation of Furanic Compounds 3207.3.5 Reductive Amination of Acids and Furans 3237.4 Catalyst Design for the Dehydration of Biosourced Molecules 3247.4.1 Introduction 3247.4.2 Glycerol to Acrolein 3257.4.3 Lactic Acid to Acrylic Acid 3287.4.4 Sorbitol to Isosorbide 3307.5 Conclusions and Outlook 331References 3318 Conversion of Lignin to Value-added Chemicals via Oxidative Depolymerization 357Justin K. Mobley8.1 Introduction 3578.1.1 Cautionary Statements 3608.2 Catalytic Systems for the Oxidative Depolymerization of Lignin 3618.2.1 Enzymes and Bio-mimetic Catalysts 3618.2.2 Cobalt Schiff Base Catalysts 3638.2.3 Vanadium Catalysts 3678.2.4 Methyltrioxorhenium (MTO) Catalysts 3688.3 Commercial Products from Lignin 3698.4 Stepwise Depolymerization of β-O-4 Linkages 3698.4.1 Benzylic Oxidation 3698.4.2 Secondary Depolymerization 3768.5 Heterogeneous Catalysts for Lignin Depolymerization 3828.6 Outlook 386Acknowledgments 386References 3869 Lignin Valorization via Reductive Depolymerization 395Yang (Vanessa) Song9.1 Introduction 3959.2 Late-stage Reductive Lignin Depolymerization 3969.2.1 Mild Hydroprocessing 3989.2.2 Harsh Hydroprocessing 4049.2.3 Bifunctional Hydroprocessing 4079.2.4 Liquid Phase Reforming 4109.2.5 Reductive Lignin Depolymerization Using Hydrosilanes, Zinc, and Sodium 4149.3 Reductive Catalytic Fractionation (RCF) 4169.3.1 Reaction Conditions 4179.3.2 Lignocellulose Source 4179.3.3 Applied Catalyst 4279.4 Outlook 428Acknowledgment 429References 42910 Conversion of Lipids to Biodiesel via Esterification and Transesterification 439Amin Talebian-Kiakalaieh and Amin Nor Aishah Saidina10.1 Introduction 43910.2 Different Feedstocks for Biodiesel Production 44110.3 Biodiesel Production 44110.3.1 Algal Biodiesel Production 44210.3.1.1 Nutrients for Microalgae Growth 44310.3.1.2 Microalgae Cultivation System 44410.3.1.3 Harvesting 44410.3.1.4 Drying 44510.3.1.5 Lipid Extraction 44610.4 Catalytic Transesterification 44610.4.1 Homogeneous Catalysts 44610.4.1.1 Alkali Catalysts 44610.4.1.2 Acid Catalysts 44810.4.1.3 Two-step Esterification–Transesterification Reactions 44810.4.2 Heterogeneous Catalysts 45010.4.2.1 Solid Acid Catalysts 45110.4.2.2 Solid Base Catalysts 45110.4.3 Enzyme-Catalyzed Transesterification Reactions 45310.5 Supercritical Transesterification Processes 45410.6 Alternative Processes for Biodiesel Production 45510.6.1 Ultrasonic Processes 45510.6.2 Microwave-Assisted Processes 45610.7 Summary 459References 45911 Upgrading of Lipids to Hydrocarbon Fuels via (Hydro)deoxygenation 469David Kubièka11.1 Introduction 46911.2 Feedstocks 47111.3 Chemistry 47211.4 Technologies 47511.5 Catalysts 47711.5.1 Sulfided Catalysts 47711.5.2 Metallic Catalysts 48011.5.3 Metal Carbide, Nitride, and Phosphide Catalysts 48311.6 Conclusions and Outlook 489References 49012 Upgrading of Lipids to Fuel-like Hydrocarbons and Terminal Olefins via Decarbonylation/Decarboxylation 497Ryan Loe, Eduardo Santillan-Jimenez, and Mark Crocker12.1 Introduction 49712.2 Lipid Feeds 50012.3 deCOx Catalysts: Active Phases 50212.4 deCOx Catalysts: Support Materials 50812.5 Reaction Conditions 50912.6 Reaction Mechanism 51112.7 Catalyst Deactivation 51612.8 Conclusions and Outlook 518References 51813 Conversion of Terpenes to Chemicals and Related Products 529Anne E. Harman-Ware13.1 Introduction 52913.2 Terpene Biosynthesis and Structure 52913.3 Sources of Terpenes 53213.3.1 Conifers and Other Trees 53213.3.2 Essential Oils and Other Extracts 53413.4 Isolation of Terpenes 53513.4.1 Tapping and Extraction 53513.4.2 Terpenes as a By-product of Pulping Processes 53613.5 Historical Uses of Raw Terpenes 53613.5.1 Adhesives and Turpentine 53613.5.2 Flavors, Fragrances, Therapeutics, and Pharmaceutical Applications 53713.6 Catalytic Methods for Conversion of Terpenes to Fine Chemicals and Materials 53713.6.1 Homogeneous Processes 53813.6.1.1 Hydration and Oxidation Reactions 53813.6.1.2 Homogeneous Catalysis for the Epoxidation of Monoterpenes 54113.6.1.3 Isomerizations 54113.6.1.4 Production of Terpene Carbonates from CO2 and Epoxides 54313.6.1.5 Polymers and Other Materials from Terpenes 54513.6.1.6 “Click Chemistry” Routes for the Production of Materials and Medicinal Compounds from Terpenes 54813.6.2 Heterogeneous Processes 55113.6.2.1 Isomerization and Hydration of α-Pinene 55113.6.2.2 Heterogeneous Catalysts for the Epoxidation of Monoterpenes 55313.6.2.3 Isomerization of α-Pinene Oxide 55513.6.2.4 Vitamins from Terpenes 55513.6.2.5 Dehydrogenation and Hydrogenation Reactions of Terpenes 55713.6.2.6 Conversion of Terpenes to Fuels 558Acknowledgments 560References 56114 Conversion of Chitin to Nitrogen-containing Chemicals 569Xi Chen and Ning Yan14.1 Waste Shell Biorefinery 56914.2 Production of Amines and Amides from Chitin Biomass 57114.2.1 Sugar Amines/Amides 57114.2.2 Furanic Amines/Amides 57414.2.3 Polyol Amines/Amides 57614.3 Production of N-heterocyclic Compounds from Chitin Biomass 57914.4 Production of Carbohydrates and Acetic Acid from Chitin Biomass 58114.5 Production of Advanced Products from Chitin Biomass 58414.6 Conclusion 587References 58715 Outlook 591Eduardo Santillan-Jimenez and Mark CrockerIndex 599