Introduction to Catalysis and Industrial Catalytic Processes

PREFACE XV ACKNOWLEDGMENTS XVII LIST OF FIGURES XIX NOMENCLATURE XXVII CHAPTER 1 CATALYST FUNDAMENTALS OF INDUSTRIAL CATALYSIS 1 1.1 Introduction 1 1.2 Catalyzed versus Noncatalyzed Reactions 1 1.3 Physical Structure of a Heterogeneous Catalyst 6 1.4 Adsorption and Kinetically Controlled Models for Heterogeneous Catalysis 10 1.5 Supported Catalysts: Dispersed Model 19 1.6 Selectivity 24 Questions 27 Bibliography 29 CHAPTER 2 THE PREPARATION OF CATALYTIC MATERIALS 31 2.1 Introduction 31 2.2 Carrier Materials 32 2.3 Incorporating the Active Material into the Carrier 37 2.4 Forming the Final Shape of the Catalyst 40 2.5 Catalyst Physical Structure and Its Relationship to Performance 45 2.6 Nomenclature for Dispersed Catalysts 45 Questions 46 Bibliography 46 CHAPTER 3 CATALYST CHARACTERIZATION 48 3.1 Introduction 48 3.2 Physical Properties of Catalysts 49 3.3 Chemical and Physical Morphology Structures of Catalytic Materials 54 3.4 Spectroscopy 65 Questions 66 Bibliography 67 CHAPTER 4 REACTION RATE IN CATALYTIC REACTORS 69 4.1 Introduction 69 4.2 Space Velocity, Space Time, and Residence Time 69 4.3 Definition of Reaction Rate 71 4.4 Rate of Surface Kinetics 72 4.5 Rate of Bulk Mass Transfer 78 4.6 Rate of Pore Diffusion 80 4.7 Apparent Activation Energy and the Rate-Limiting Process 82 4.8 Reactor Bed Pressure Drop 83 4.9 Summary 84 Questions 84 Bibliography 87 CHAPTER 5 CATALYST DEACTIVATION 88 5.1 Introduction 88 5.2 Thermally Induced Deactivation 88 5.3 Poisoning 96 5.4 Coke Formation and Catalyst Regeneration 99 Questions 101 Bibliography 103 CHAPTER 6 GENERATING HYDROGEN AND SYNTHESIS GAS BY CATALYTIC HYDROCARBON STEAM REFORMING 104 6.1 Introduction 104 6.2 Large-Scale Industrial Process for Hydrogen Generation 105 6.3 Hydrogen Generation for Fuel Cells 121 6.4 Summary 126 Questions 127 Bibliography 128 CHAPTER 7 AMMONIA, METHANOL, FISCHER-TROPSCH PRODUCTION 129 7.1 Ammonia Synthesis 129 7.2 Methanol Synthesis 134 7.3 Fischer-Tropsch Synthesis 140 Questions 144 Bibliography 145 CHAPTER 8 SELECTIVE OXIDATIONS 146 8.1 Nitric Acid 146 8.2 Hydrogen Cyanide 151 8.3 The Claus Process: Oxidation of H2S 154 8.4 Sulfuric Acid 155 8.5 Ethylene Oxide 159 8.6 Formaldehyde 160 8.7 Acrylic Acid 164 8.8 Maleic Anhydride 166 8.9 Acrylonitrile 166 Questions 168 Bibliography 169 CHAPTER 9 HYDROGENATION, DEHYDROGENATION, AND ALKYLATION 171 9.1 Introduction 171 9.2 Hydrogenation 171 9.3 Hydrogenation Reactions and Catalysts 177 9.4 Dehydrogenation 185 9.5 Alkylation 187 Questions 188 Bibliography 189 CHAPTER 10 PETROLEUM PROCESSING 190 10.1 Crude Oil 190 10.2 Distillation 191 10.3 Hydrodemetalization and Hydrodesulfurization 193 10.4 Hydrocarbon Cracking 197 10.5 Naphtha Reforming 200 Questions 202 Bibliography 203 CHAPTER 11 HOMOGENEOUS CATALYSIS AND POLYMERIZATION CATALYSTS 205 11.1 Introduction to Homogeneous Catalysis 205 11.2 Hydroformylation: Aldehydes from Olefins 206 11.3 Carboxylation: Acetic Acid Production 208 11.4 Enzymatic Catalysis 209 11.5 Polyolefins 210 Questions 213 Bibliography 213 CHAPTER 12 CATALYTIC TREATMENT FROM STATIONARY SOURCES: HC, CO, NOX, AND O3 215 12.1 Introduction 215 12.2 Catalytic Incineration of Hydrocarbons and Carbon Monoxide 216 12.3 Food Processing 225 12.4 Nitrogen Oxide (NOx) Reduction from Stationary Sources 226 12.5 CO2 Reduction 230 Questions 231 Bibliography 233 CHAPTER 13 CATALYTIC ABATEMENT OF GASOLINE ENGINE EMISSIONS 235 13.1 Emissions and Regulations 235 13.2 Catalytic Reactions Occurring During Catalytic Abatement 238 13.3 First-Generation Converters: Oxidation Catalyst 239 13.4 The Failure of Nonprecious Metals: A Summary of Catalyst History 240 13.5 Supporting the Catalyst in the Exhaust 242 13.6 Preparing the Monolith Catalyst 246 13.7 Rate Control Regimes in Automotive Catalysts 247 13.8 Catalyzed Monolith Nomenclature 248 13.9 Precious Metal Recovery from Catalytic Converters 248 13.10 Monitoring Catalytic Activity in a Monolith 248 13.11 The Failure of the Traditional Beaded (Particulate) Catalysts for Automotive Applications 250 13.12 NOx, CO and HC Reduction: The Three-Way Catalyst 251 13.13 Simulated Aging Methods 255 13.14 Close-Coupled Catalyst 256 13.15 Final Comments 258 Questions 259 Bibliography 261 CHAPTER 14 DIESEL ENGINE EMISSION ABATEMENT 262 14.1 Introduction 262 14.2 Catalytic Technology for Reducing Emissions from Diesel Engines 265 Questions 272 Bibliography 273 CHAPTER 15 ALTERNATIVE ENERGY SOURCES USING CATALYSIS: BIOETHANOL BY FERMENTATION, BIODIESEL BY TRANSESTERIFICATION, AND H2-BASED FUEL CELLS 274 15.1 Introduction: Sources of Non-Fossil Fuel Energy 274 15.2 Sources of Non-Fossil Fuels 276 15.3 Fuel Cells 279 15.4 Types of Fuel Cells 283 15.5 The Ideal Hydrogen Economy 293 Questions 294 Bibliography 295 INDEX 297