Introduction to Catalysis and Industrial Catalytic Processes

Robert J. Farrauto, PHD, is Professor of Practice in the Earth and Environmental Engineering Department at Columbia University in the City of New York. He retired from BASF (formerly Engelhard) as a Research Vice President after 37 years of service. He has over 40 years industrial experience in catalysis and has commercialized a number of technologies in the environmental, chemical and alternative energy fields. He holds 58 US patents and over 115 peer-reviewed journal publications. He teaches graduate and undergraduate courses focusing on catalysis. He is a co-author of Fundamentals of Industrial Catalytic Processes, 2nd Edition and Catalytic Air Pollution Control: Commercial Technology, 3rd Edition.Lucas Dorazio, PhD is a Research Chemical Engineer at BASF Corporation, Iselin, NJ where he is engaged in reforming and environmental technology. He is also Adjunct assistant professor at New Jersey Institute of Technology where he teaches environmental and industrial catalysis.  Calvin H. Bartholomew, PhD is Emeritus Professor at Brigham Young University. He continues to conduct catalysis research, is active in consulting and does specialized teaching for AICHE short courses in catalysis. He has been principal investigator or co-investigator on over 60 grants and contracts and has supervised more than 175 research students. He is the author or co-author of 5 books and 120 peer-reviewed papers and reviews with emphasis on catalysis.

• Preface xvAcknowledgments xviiList of Figures xixNomenclature xxviiChapter 1 Catalyst Fundamentals of Industrial Catalysis 11.1 Introduction 11.2 Catalyzed versus Noncatalyzed Reactions 11.2.1 Example Reaction: Liquid-Phase Redox Reaction 21.2.2 Example Reaction: Gas-Phase Oxidation Reaction 41.3 Physical Structure of a Heterogeneous Catalyst 61.3.1 Active Catalytic Species 71.3.2 Chemical and Textural Promoters 71.3.3 Carrier Materials 81.3.4 Structure of the Catalyst and Catalytic Reactor 81.4 Adsorption and Kinetically Controlled Models for Heterogeneous Catalysis 101.4.1 Langmuir Isotherm 111.4.2 Reaction Kinetic Models 131.4.2.1 Langmuir–Hinshelwood Kinetics for CO Oxidation on Pt 141.4.2.2 Mars–van Krevelen Kinetic Mechanism 171.4.2.3 Eley–Rideal (E–R) Kinetic Mechanism 181.4.2.4 Kinetic versus Empirical Rate Models 181.5 Supported Catalysts: Dispersed Model 191.5.1 Chemical and Physical Steps Occurring during Heterogeneous Catalysis 191.5.2 Reactant Concentration Gradients within the Catalyzed Material 221.5.3 The Rate-Limiting Step 221.6 Selectivity 241.6.1 Examples of Selectivity Calculations for Reactions with Multiple Products 251.6.2 Carbon Balance 261.6.3 Experimental Methods for Measuring Carbon Balance 27Questions 27Bibliography 29Chapter 2 The Preparation of Catalytic Materials 312.1 Introduction 312.2 Carrier Materials 322.2.1 Al2O3 322.2.2 SiO2 342.2.3 TiO2 342.2.4 Zeolites 352.2.5 Carbons 372.3 Incorporating the Active Material into the Carrier 372.3.1 Impregnation 372.3.2 Incipient Wetness or Capillary Impregnation 382.3.3 Electrostatic Adsorption 382.3.4 Ion Exchange 382.3.5 Fixing the Catalytic Species 392.3.6 Drying and Calcination 392.4 Forming the Final Shape of the Catalyst 402.4.1 Powders 402.4.1.1 Milling and Sieving 412.4.1.2 Spray Drying 422.4.2 Pellets, Pills, and Rings 432.4.3 Extrudates 432.4.4 Granules 442.4.5 Monoliths 442.5 Catalyst Physical Structure and Its Relationship to Performance 452.6 Nomenclature for Dispersed Catalysts 45Questions 46Bibliography 46Chapter 3 Catalyst Characterization 483.1 Introduction 483.2 Physical Properties of Catalysts 493.2.1 Surface Area and Pore Size 493.2.1.1 Nitrogen Porosimetry 493.2.1.2 Pore Size by Mercury Intrusion 513.2.2 Particle Size Distribution of Particulate Catalyst 513.2.2.1 Particle Size Distribution 513.2.2.2 Mechanical Strength 533.2.3 Physical Properties of Environmental Washcoated Monolith Catalysts 543.2.3.1 Washcoat Thickness 543.2.3.2 Washcoat Adhesion 543.3 Chemical and Physical Morphology Structures of Catalytic Materials 543.3.1 Elemental Analysis 543.3.2 Thermal Gravimetric Analysis and Differential Thermal Analysis 553.3.3 The Morphology of Catalytic Materials by Scanning Electron Microscopy 563.3.4 Structural Analysis by X-Ray Diffraction 573.3.5 Structure and Morphology of Al2O3 Carriers 583.3.6 Dispersion or Crystallite Size of Catalytic Species 583.3.6.1 Chemisorption 583.3.6.2 Transmission Electron Microscopy 613.3.7 X-Ray Diffraction 623.3.8 Surface Composition of Catalysts by X-Ray Photoelectron Spectroscopy 623.3.9 The Bonding Environment of Metal Oxides by Nuclear Magnetic Resonance 643.4 Spectroscopy 65Questions 66Bibliography 67Chapter 4 Reaction Rate in Catalytic Reactors 694.1 Introduction 694.2 Space Velocity, Space Time, and Residence Time 694.3 Definition of Reaction Rate 714.4 Rate of Surface Kinetics 724.4.1 Empirical Power Rate Expressions 724.4.2 Experimental Measurement of Empirical Kinetic Parameters 734.4.3 Accounting for Chemical Equilibrium in Empirical Rate Expression 774.4.4 Special Case for First-Order Isothermal Reaction 774.5 Rate of Bulk Mass Transfer 784.5.1 Overview of Bulk Mass Transfer Rate 784.5.2 Origin of Bulk Mass Transfer Rate Expression 794.6 Rate of Pore Diffusion 804.6.1 Overview of Pore Diffusion 804.6.2 Pore Diffusion Theory 814.7 Apparent Activation Energy and the Rate-Limiting Process 824.8 Reactor Bed Pressure Drop 834.9 Summary 84Questions 84Bibliography 87Chapter 5 Catalyst Deactivation 885.1 Introduction 885.2 Thermally Induced Deactivation 885.2.1 Sintering of the Catalytic Species 895.2.2 Sintering of Carrier 925.2.3 Catalytic Species–Carrier Interactions 955.3 Poisoning 965.3.1 Selective Poisoning 965.3.2 Nonselective Poisoning or Masking 975.4 Coke Formation and Catalyst Regeneration 99Questions 101Bibliography 103Chapter 6 Generating Hydrogen and Synthesis Gas by Catalytic Hydrocarbon Steam Reforming 1046.1 Introduction 1046.1.1 Why Steam Reforming with Hydrocarbons? 1046.2 Large-Scale Industrial Process for Hydrogen Generation 1056.2.1 General Overview 1056.2.2 Hydrodesulfurization 1066.2.3 Hydrogen via Steam Reforming and Partial Oxidation 1066.2.3.1 Steam Reforming 1066.2.3.2 Deactivation of Steam Reforming Catalyst 1106.2.3.3 Pre-reforming 1116.2.3.4 Partial Oxidation and Autothermal Reforming 1116.2.4 Water Gas Shift 1126.2.4.1 Deactivation of Water Gas Shift Catalyst 1166.2.5 Safety Considerations During Catalyst Removal 1166.2.6 Other CO Removal Methods 1166.2.6.1 Pressure Swing Absorption 1166.2.6.2 Methanation 1176.2.6.3 Preferential Oxidation of CO 1176.2.7 Hydrogen Generation for Ammonia Synthesis 1196.2.8 Hydrogen Generation for Methanol Synthesis 1206.2.9 Synthesis Gas for Fischer–Tropsch Synthesis 1206.3 Hydrogen Generation for Fuel Cells 1216.3.1 New Catalyst and Reactor Designs for the Hydrogen Economy 1226.3.2 Steam Reforming 1236.3.3 Water Gas Shift 1246.3.4 Preferential Oxidation 1256.3.5 Combustion 1256.3.6 Autothermal Reforming for Complicated Fuels 1266.3.7 Steam Reforming of Methanol: Portable Power Applications 1266.4 Summary 126Questions 127Bibliography 128Chapter 7 Ammonia, Methanol, Fischer–Tropsch Production 1297.1 Ammonia Synthesis 1297.1.1 Thermodynamics 1297.1.2 Reaction Chemistry and Catalyst Design 1307.1.3 Process Design 1327.1.4 Catalyst Deactivation 1347.2 Methanol Synthesis 1347.2.1 Process Design 1367.2.1.1 Quench Reactor 1367.2.1.2 Staged Cooling Reactor 1377.2.1.3 Tube-Cooled Reactor 1377.2.1.4 Shell-Cooled Reactor 1387.2.2 Catalyst Deactivation 1397.3 Fischer–Tropsch Synthesis 1407.3.1 Process Design 1427.3.1.1 Bubble/Slurry-Phase Process 1427.3.1.2 Packed Bed Process 1437.3.1.3 Slurry/Loop Reactor (Synthol Process) 1437.3.2 Catalyst Deactivation 143Questions 144Bibliography 145Chapter 8 Selective Oxidations 1468.1 Nitric Acid 1468.1.1 Reaction Chemistry and Catalyst Design 1468.1.1.1 The Importance of Catalyst Selectivity 1478.1.1.2 The PtRh Alloy Catalyst 1478.1.2 Nitric Acid Production Process 1488.1.3 Catalyst Deactivation 1508.2 Hydrogen Cyanide 1518.2.1 HCN Production Process 1528.2.2 Deactivation 1528.3 The Claus Process: Oxidation of H2S 1548.3.1 Clause Process Description 1548.3.2 Catalyst Deactivation 1558.4 Sulfuric Acid 1558.4.1 Sulfuric Acid Production Process 1558.4.2 Catalyst Deactivation 1588.5 Ethylene Oxide 1598.5.1 Catalyst 1598.5.2 Catalyst Deactivation 1608.5.3 Ethylene Oxide Production Process 1608.6 Formaldehyde 1608.6.1 Low-Methanol Production Process 1628.6.1.1 Fe+Mo Catalyst 1628.6.2 High-Methanol Production Process 1638.6.2.1 Ag Catalyst 1648.7 Acrylic Acid 1648.7.1 Acrylic Acid Production Process 1648.7.2 Acrylic Acid Catalyst 1658.7.3 Catalyst Deactivation 1668.8 Maleic Anhydride 1668.8.1 Catalyst Deactivation 1668.9 Acrylonitrile 1668.9.1 Acrylonitrile Production Process 1678.9.2 Catalyst 1688.9.3 Deactivation 168Questions 168Bibliography 169Chapter 9 Hydrogenation, Dehydrogenation, and Alkylation 1719.1 Introduction 1719.2 Hydrogenation 1719.2.1 Hydrogenation in Stirred Tank Reactors 1719.2.2 Kinetics of a Slurry-Phase Hydrogenation Reaction 1749.2.3 Design Equation for the Continuous Stirred Tank Reactor 1769.3 Hydrogenation Reactions and Catalysts 1779.3.1 Hydrogenation of Vegetable Oils for Edible Food Products 1779.3.2 Hydrogenation of Functional Groups 1809.3.3 Biomass (Corn Husks) to a Polymer 1839.3.4 Comparing Base Metal and Precious Metal Catalysts 1839.4 Dehydrogenation 1859.5 Alkylation 187Questions 188Bibliography 189Chapter 10 Petroleum Processing 19010.1 Crude Oil 19010.2 Distillation 19110.3 Hydrodemetalization and Hydrodesulfurization 19310.4 Hydrocarbon Cracking 19710.4.1 Fluid Catalytic Cracking 19710.4.2 Hydrocracking 20010.5 Naphtha Reforming 200Questions 202Bibliography 203Chapter 11 Homogeneous Catalysis and Polymerization Catalysts 20511.1 Introduction to Homogeneous Catalysis 20511.2 Hydroformylation: Aldehydes from Olefins 20611.3 Carboxylation: Acetic Acid Production 20811.4 Enzymatic Catalysis 20911.5 Polyolefins 21011.5.1 Polyethylene 21011.5.2 Polypropylene 212Questions 213Bibliography 213Chapter 12 Catalytic Treatment from Stationary Sources: Hc, Co, Nox, and O3 21512.1 Introduction 21512.2 Catalytic Incineration of Hydrocarbons and Carbon Monoxide 21612.2.1 Monolith (Honeycomb) Reactors 21812.2.2 Catalyzed Monolith (Honeycomb) Structures 21912.2.3 Reactor Sizing 22012.2.4 Catalyst Deactivation 22212.2.5 Regeneration of Deactivated Catalysts 22412.3 Food Processing 22512.3.1 Catalyst Deactivation 22612.4 Nitrogen Oxide (NOx) Reduction from Stationary Sources 22612.4.1 SCR Technology 22712.4.2 Ozone Abatement in Aircraft Cabin Air 22912.4.3 Deactivation 22912.5 CO2 Reduction 230Questions 231Bibliography 233Chapter 13 Catalytic Abatement of Gasoline Engine Emissions 23513.1 Emissions and Regulations 23513.1.1 Origins of Emissions 23513.1.2 Regulations in the United States 23613.1.3 The Federal Test Procedure for the United States 23813.2 Catalytic Reactions Occurring During Catalytic Abatement 23813.3 First-Generation Converters: Oxidation Catalyst 23913.4 The Failure of Nonprecious Metals: A Summary of Catalyst History 24013.4.1 Deactivation and Stabilization of Precious Metal Oxidation Catalysts 24113.5 Supporting the Catalyst in the Exhaust 24213.5.1 Ceramic Monoliths 24213.5.2 Metal Monoliths 24513.6 Preparing the Monolith Catalyst 24613.7 Rate Control Regimes in Automotive Catalysts 24713.8 Catalyzed Monolith Nomenclature 24813.9 Precious Metal Recovery from Catalytic Converters 24813.10 Monitoring Catalytic Activity in a Monolith 24813.11 The Failure of the Traditional Beaded (Particulate) Catalysts for Automotive Applications 25013.12 NOx, CO and HC Reduction: The Three-Way Catalyst 25113.13 Simulated Aging Methods 25513.14 Close-Coupled Catalyst 25613.15 Final Comments 258Questions 259Bibliography 261Chapter 14 Diesel Engine Emission Abatement 26214.1 Introduction 26214.1.1 Emissions from Diesel Engines 26214.1.2 Analytical Procedures for Particulates 26414.2 Catalytic Technology for Reducing Emissions from Diesel Engines 26514.2.1 Diesel Oxidation Catalyst 26514.2.2 Diesel Soot Abatement 26614.2.3 Controlling NOx in Diesel Engine Exhaust 267Questions 272Bibliography 273Chapter 15 Alternative Energy Sources Using Catalysis: Bioethanol by Fermentation, Biodiesel by Transesterification, and H2-Based Fuel Cells 27415.1 Introduction: Sources of Non-Fossil Fuel Energy 27415.2 Sources of Non-Fossil Fuels 27615.2.1 Biodiesel 27615.2.1.1 Production Process 27615.2.2 Bioethanol 27715.2.2.1 Process for Bioethanol from Corn 27815.2.3 Lignocellulose Biomass 27815.2.4 New Sources of Natural Gas and Oil Sands 27915.3 Fuel Cells 27915.3.1 Markets for Fuel Cells 28115.3.1.1 Transportation Applications 28115.3.1.2 Stationary Applications 28215.3.1.3 Portable Power Applications 28215.4 Types of Fuel Cells 28315.4.1 Low-Temperature PEM Fuel Cell 28415.4.1.1 Electrochemical Reactions for H2-Fueled Systems 28415.4.1.2 Mechanistic Principles of the PEM Fuel Cell 28615.4.1.3 Membrane Electrode Assembly 28715.4.2 Solid Polymer Membrane 28815.4.3 PEM Fuel Cells Based on Direct Methanol 28915.4.4 Alkaline Fuel Cell 29015.4.5 Phosphoric Acid Fuel Cell 29015.4.6 Molten Carbonate Fuel Cell 29115.4.7 Solid Oxide Fuel Cell 29315.5 The Ideal Hydrogen Economy 293Questions 294Bibliography 295Index 297

"In less than 300 pages it serves as an excellent introduction to these subjects whether for advanced students or those seeking to learn more about these subjects on their own time...Particularly useful are the succinct summaries throughout the book...excellent detail in the table of contents, a detailed index, key references at the end of each chapter, and challenging classroom questions..." (GlobalCatalysis.com, May 2016)