RSC Publishing. Thermochemical Conversion of Biomass to Liquid Fuels and Chemicals. Edited by. Mark Crocker. University of Kentucky, Lexington,

Transcription

1 Thermochemical Conversion of Biomass to Liquid Fuels and Chemicals Edited by Mark Crocker Center for Applied Energy Research, KY 40511, USA University of Kentucky, Lexington, RSC Publishing

2 Contents Chapter 1 The Rationale for Biofuels 1 Mark Crocker and Rodney Andrews 1.1 The Rise of Petroleum Worldwide Demand for Liquid Fuels and the Impact of Non-OECD Asia Increasing Price and Decreasing Supply of Petroleum Instability in Supply and Production of Petroleum Forecast for Biofuels Biomass as a Renewable Source of Energy Biomass Composition Energy Density of Biomass Overview of Pathways for Biomass Conversion to Fuels Comparison of Thermochemical and Biological Processes for Biomass Conversion to Fuels Outlook 22 References 23 Chapter 2 Energy Crops for the Production of Biofuels 26 Michael Montross and Czarena Crofcheck 2.1 Biorenewable Resources Definition of Biomass Dedicated Energy Crops Herbaceous Energy Crops Short-Rotation Woody Crops Waste Biomass Resources 28 RSC Energy and Environment Series No. 1 Thermochemical Conversion of Biomass to Liquid Fuels and Chemicals Edited by Mark Crocker Royal Society of Chemistry 2010 Published by the Royal Society of Chemistry, xi

3 Thermochemical xii Contents Biomass Characterization Proximate and Ultimate Analysis Heating Value Additional Processing Characteristics Available Land Resources Biomass Composition and its Effect on Processing Energy Consumption During Establishment and Production Biomass Logistics Biomass Crop Harvesting Woody Crop Harvest Harvesting of Herbaceous Energy Crops Biomass Transportation Storage Summary 42 References 42 Chapter 3 The Biorefinery Concept - Production of Building Blocks and Syngas 46 Birgit Kamm, Mirko Gerhardt and Sebastian Leifi 3.1 Introduction The Lignocellulosic Feedstock Biorefinery Building Blocks by Thermochemical Methods Furfural Levulinic acid Hydroxymethylfurfural Dehydration in Aqueous Milieu Dehydration in Organic Polar Solvents Dehydration in the Two-Phase System Water/Methyl Isobutyl Ketone Dehydration in Ionic Liquids Dehydration Without Solvents Sugar Alcohols Syngas Lactic Acid Outlook 62 References 62

4 Contents xiii Chapter 4 Bioinass Gasification 67 James K. Neathery 4.1 Historical Background Gasification Chemistry and Reaction Stages Gasifier Stages Overall Reaction Simplification and Air-Equivalence Ratio Quantifying Gasifier Performance Gasification Processes Downdraft Gasification Updraft Gasification Fluidized-Bed and Transport-Reactor Gasification Practical Issues of Gasification Fuel Particle Size Fuel Moisture Content Process Control and Automation of Gasifiers Producer-Gas Conditioning Particulate Removal Tar and Oil Removal 91 References 93 Chapter 5 Conversion of Biomass to Liquid Fuels and Chemicals via the Fischer-Tropsch Synthesis Route 95 Gary Jacobs andburtron H. Davis 5.1 Motivation Syngas Derived from Biomass Gasification for Use in Fischer-Tropsch Synthesis Differences Between Co and Fe Fischer-Tropsch Synthesis Catalysts Product Distribution Dependence on Conditions Proposed Mechanisms, Kinetics, and Catalyst Structure-Function Properties Conclusions 119 References 121 Chapter 6 Bioderived Syngas to Alcohols 125 Adefemi Egbebi and James Spivey 6.1 Introduction Syngas to Alcohols: Thermodynamics Hydrogenation of CO Hydrogenation of C02 128

5 xiv Contents Side Reactions Effect of Pressure Catalyst Types Methanol Synthesis Ethanol Synthesis Rh-based Catalysts Modified Methanol Synthesis Catalysts (Based on Cu) Modified Fischer-Tropsch-Type Catalysts Modified (Sulfide and Unsulfided) Mo-based Catalysts Mixed-Alcohol Synthesis Conclusions 140 References 141 Chapter 7 Fast Pyrolysis of Biomass for Energy and Fuels 146 A. V. Bridgwater Introduction Biomass Resources Thermal Conversion Processes Fast Pyrolysis Principles Reactors Bubbling Fluid Beds Circulating Fluid Beds and Transported Bed Ablative Pyrolysis Entrained Flow Rotating Cone Vacuum Pyrolysis Heat Transfer in Fast Pyrolysis Summary and Status of Reactors Char Removal Liquids Collection Byproducts Pyrolysis Liquid Bio-Oil Bio-Oil Characteristics Environment, Health and Safety Bio-Oil Upgrading Physical Upgrading of Bio-Oil Filtration Emulsions Chemical and Catalytic Upgrading of Bio-Oil Hydrotreating 171

6 Contents xv Zeolite Cracking Gasification for Synfuels Hydrogen Applications of Bio-Oil Energy Carrier Combustion Cofiring Engines and Turbines Chemicals Chemicals in Bio-Oil Other Potential Products Biorefmery Biorefmery Examples Markets Summary Overall Fast-Pyrolysis System System Components and Integration Barriers Conclusions 186 References 187 Chapter 8 Hydrothermal Processing of Biomass 192 P. E. Savage, R. B. Levine and C. M. Huelsman 8.1 Introduction Background on Hydrothermal Processing Properties of Water Hydrothermal Liquefaction Process-Variable Effects Feedstock Composition Nitrogen Partitioning Reaction Atmosphere Liquefaction Chemistry Cellulose Lignin Lipids Wastes Aquatic Feedstocks Outlook Hydrothermal Gasification Gas-Phase Reactions and Kinetics Regimes in Hydrothermal Gasification Low-Temperature Catalytic Gasification High-Temperature SCWG Hydrothermal Gasification Chemistry 212

7 a xvi Contents Cellulose Lignin Protein Interactions Between Model Compounds Aquatic Feedstocks Outlook 214 References 215 Chapter 9 Lignin Utilization 222 Gunnar Henriksson, Jiching Li, Liming Zhang andmikael E. Lindstrom 9.1 Lignin - Large and Incompletely Utilized Natural Resource Structure, Properties and Biological Function of Lignin Occurrence and Biological Function of Lignin Monomers and Intermonolignol Bonds Covalent Bonds Between Lignin and Polysaccharides Physical and Chemical Properties Biosynthesis Reactions of Lignin During Technical Processes Reactions During Alkaline Pulping Reactions During Neutral and Acidic Sulfite Pulping Reactions During Organosolv Pulping Reactions During Bleaching of Pulp Reactions During Acid Hydrolysis and Steam Explosion Preparation of Technical Lignins Precipitation of Lignin Preparation with Ultrafiltration Preparation of Lignosulfonates Use of Technical Lignins in the Energy Sector Combustion of Technical Lignins Gasification of Lignin Oxygen-Free Pyrolysis of Lignin General Considerations on Converting Technical Lignin into Transportation Fuels Pyrolysis of Technical Lignins in the Presence of Formic Acid Other Technical Uses of Lignin Lignosulfonates as Dispersing Agent 257

8 Contents xvii Manufacture of Vanillin Soil-Improving Agent Manufacture of Carbon Fiber Lignin as Binder in Composite Material and Filler in Polymers Lignin for Dust Control 258 References 259 Chapter 10 Catalysts in Biomass Pyrolysis 263 Angelas A. Lappas, Eleni F. Iliopoulou anclk. Kalogiannis Introduction to Biomass Catalytic Pyrolysis Overview of the Biomass Catalytic Pyrolysis Process Catalyst Effects on Bio-Oil Yield and Quality Microporous Catalysts Mesoporous Acid Catalysts Basic Catalytic Materials Catalysts for Biomass Conversion to Aromatics Recent Developments in Bio-Oil Upgrading Zeolite Upgrading Catalytic Cracking Co-processing of Bio-Oil and Conventional Oil in Refinery Processes Conclusions 283 References 283 Chapter 11 Hydrotreating for Bio-Oil Upgrading 288 Maija L. Honkela, Tuula-Riitta Viljava, Andrea Gutierrez and A. Outi I. Krause 11.1 Introduction Early Hydrodeoxygenation Studies Hydrodeoxygenation Sulfided CoMo and NiMo Catalysts Noble-Metal Catalysts Other Catalysts Studies with Wood-Based Pyrolysis Oil Model Components Phenol Anisole Guaiacols Ketones, Aldehydes, Acids and Carbohydrates Catalyst Comparison and Coking with Model Components and with Pyrolysis Oil 301

9 xviii Contents 11.6 Outlook Summary 303 References 304 Chapter 12 Ionic Liquids for the Utilization of Lignocellulosics 307 Samuel A. Morton III and Laurel A. Motion 12.1 Introduction to Lignocellulosics Ionic Liquids Classification and Nomenclature Synthesis and Purification Potential Uses Reuse, Recycle, and Stability Toxicity and Biodegradation Ionic Liquids and Lignocellulosics Unrefined Lignocellulosics Cellulose Hemicellulose Lignin Conclusions (Issues that Remain to be Resolved) 336 References 337 Chapter 13 Conversion of Cellulose to Sugars 344 Satnar Kumar Guha, Hirokazu Kobayashi andatsushi Fukuoka 13.1 Introduction Structure and Properties of Cellulose General Properties Crystallinity Index Degree of Polymerization Options for Cellulose Saccharification Cellulose Conversion Methods for the Saccharification of Cellulose Acidic Hydrolysis Enzymatic Hydrolysis Thermochemical Transformation Sub- and Supercritical Water Catalytic Conversion of Cellulose Solid Acid-Catalyzed Reaction Supported Metal-Catalyzed Reaction Other Catalytic Conversions of Cellulose Overview of Routes for Utilization of Sugars Utilization of Glucose Utilization of Fructose Utilization of Sorbitol 357

10 Do Contents xix 13.6 Conclusion 360 References 361 Chapter 14 Conversion of Carbohydrates to Liquid Fuels 365 Geoffrey Akien.Long Qi andlstvan T. Horvdth 14.1 Introduction Carbohydrate-Containing Biomass Potential Biomass-Based Liquid Fuels Conversion of Carbohydrates to Liquid Fuels Strategies Methanol Ethanol Butanol Methyl and Ethyl Tertiary-butyl ether Gamma-Valerolactone Methyl-Tetrahydrofuran Furfural Conclusions - We Have Enough? 377 References 378 Chapter 15 Biodiesel Production and Properties 382 Jon H. Van Gerpen and Brian He 15.1 Introduction Biodiesel Chemistry Biodiesel Feedstocks Fatty-Acid Profiles of Feedstocks for Biodiesel Production Biodiesel Production Effect of Catalyst Mass-Transfer Limitations Processing Technology Purification of Biodiesel High Free Fatty-Acid Feedstocks Biodiesel Fuel Properties as Affected by Fatty-Acid Profiles of Plant Oils and Animals Fats ASTM and EN Standards of Biodiesel Specifications Cold-Flow Properties Oxidative Stability Alkyl Esters and Oxidation Oxidation of Biodiesel Preventing Biodiesel Deterioration Cetane Number 409

11 XX Contents Sterol Glucosides and Their Effects on Cold Soak Filtration Test Plant Sterols Procedure of Cold Soak Filtration Test Summary 412 References 412 Chapter 16 Heterogeneous Catalysts for Biodiesel Production 416 Jean-Philippe Dacquin.Adam F. Lee and Karen Wilson 16.1 Introduction Current Processes for Biodiesel Production Catalysts for Triglyceride Transesterification Solid Base Catalysts Solid Acid Catalysts Catalysts for Free-Fatty-Acid Esterification Effect of Free Fatty Acids on Biodiesel Production Heterogeneous Catalysts for Free-Fatty- Acid Esterification Process Considerations for Biodiesel Production Future Perspectives and Concluding Remarks 429 References 430 Chapter 17 Catalytic Conversion of Glycerol to Valuable Commodity Chemicals 435 Jorge N Beltramini andchun-hui (Clayton) Zhou 17.1 Introduction Selective Oxidation of Glycerol Selective Etherification of Glycerol to Fine Chemicals and Polyglycerols Selective Glycerol Transesterification and Esterification Selective Hydrogenolysis of Glycerol Catalytic Dehydration of Glycerol Gasification of Glycerol Concluding Remarks 462 References 463 Chapter 18 Renewable Diesel and Jet-Fuel Production from Fats and Oils 468 Torn N. Kalnes, Michael M. McCall and David R. Shonnard 18.1 Scope of Chapter and Rationale Overview of Hydroprocessing Chemistry 469

12 Contents xxi 18.3 General Considerations for Commercial Production Feedstock Selection Process Considerations Product Properties and Engine Performance Life-Cycle Assessment Fuel-Production Pathways and Inventory Data Impact Assessment and Comprehensive Assumptions Results and Sensitivity Analysis Commercial Production Status and Perspectives 492 References and Footnote 493 Chapter 19 Catalytic Deoxygenation of Fatty Acids and their Derivatives for the Production of Renewable Diesel 496 Dmitry Yu. Murzin cmdpdivi Maki-Arvela 19.1 Technologies for the Production of Biodiesel Catalytic Liquid-Phase Deoxygenation of Fatty Acids and their Derivatives Catalyst Selection Metal and Support Selection Effect of Metal Dispersion Deoxygenation of Different Feedstocks Deoxygenation of Saturated Fatty Acids and their Esters Deoxygenation of Unsaturated Fatty Acids and their Esters Deoxygenation of Triglycerides Comparison ofdifferent Feedstocks in Catalytic Deoxygenation Deoxygenation of Tall-Oil Fatty Acids Reactor Selection Batch versus Semi-Batch Reactors Continuous Operation Catalyst Deactivation Conclusions 507 References 509 Subject Index 511