Industrial Catalysis: Chemistry and Mechanism

Description

Industrial Catalysis: Chemistry and Mechanism is an essential textbook for upper-level undergraduate and graduate students with an interest in the underlying concepts of catalysis, industrial organic chemistry and the mechanism of catalysis. For undergraduates it provides an introduction to the basic catalytic principles and industrial processes. Graduate students will find that the book gives an in-depth understanding of the mechanism of catalytic surface intermediates and the practice of modern catalysis research. For the post graduate and industrial chemist involved in catalysis research, it is a valuable reference text as a compendium of mechanisms by which major industrial catalytic processes operate. This unique book fills the gap between basic organic chemistry and fundamental chemical principles of catalysis, and is a must read for students and researchers in the field. Cover Half Title Industrial Catalysis: Chemistry and Mechanism Copyright Dedication Contents Foreword 1. An Introduction to Industrial Catalysis 1.1 Historical Background 1.1.1 Early Catalysis Examples 1.1.2 Highlights of Catalysis Technology 1.2 Catalysis Definitions 1.3 Kinetics and Catalysis 1.4 Thermodynamics 1.4.1 Thermodynamic Limitation 1.5 Key Concepts 1.5.1 Activity: Batch Measures 1.5.2 Activity: Space Velocity 1.5.3 Space Velocity Examples 1.5.4 Activity: Turnover Rate 1.5.5 Turnover Example 1.5.6 Selectivity 1.5.7 Selectivity Example 1.5.8 Selectivity Example 2: Formation of Two Products 1.5.9 Catalyst Life 1.6 Catalytic Mechanism 1.6.1 Representing Mechanisms: “Electron Pushing” 1.6.2 Representing Mechanisms: “Name Reaction” Examples 1.6.3 Elementary Catalytic Reaction Steps 1.6.4 Representing Catalytic Mechanisms: The “Tolman Formalism” 1.6.5 Catalytic Mechanism Example: Hydroformylation of Olefins 1.7 Homogeneous Versus Heterogeneous Catalysis 1.7.1 Homogeneous Catalysis Example 1.7.2 Heterogeneous Catalysis Example 1.7.3 Advantages of Homogeneous Catalysis 1.7.4 Advantages of Heterogeneous Catalysis 1.8 Major Industrial Catalytic Process Types 1.8.1 Industrial Examples 1.9 Problems 1.10 Answers to Problems 2. Acid Catalysis 2.1 Basic Concepts 2.1.1 An Acid Catalyst Periodic Table 2.1.2 pKa Acidity Scale 2.1.3 Ho Acidity Scale for Superacids 2.1.4 Superacid Example: Phosphotungstic Acid 2.1.5 Bronsted Versus Lewis Acidity 2.1.6 Some Common Solid Acid Catalysts 2.1.7 Silica–Alumina SiO2/Al2O3 Solid Acids 2.1.8 Zeolite Synthesis 2.1.9 Zeolite Acid Sites 2.1.10 Bronsted and Lewis Acidity Measurements in Solids 2.1.11 Mechanism of Acid Catalyzed Aromatic Reactions 2.1.12 Thermodynamics 2.2 Elements of Acid Catalyst Design 2.2.1 Active Site Distribution 2.2.2 Zeolites 2.2.3 Other Si/Al Frameworks 2.2.4 Shape Selectivity 2.2.5 Surface Activity Effects 2.2.6 Surface Activity: Small Crystallite Example 2.2.7 Heat Treatment — Phase Formation 2.2.8 Common Catalyst Supports 2.2.9 Catalyst Supports: Hydrophobic Versus Hydrophillic Surfaces 2.3 Major Industrial Processes — Refinery 2.3.1 Catalytic Cracking 2.3.2 Disproportionation of Aromatics 2.3.3 Isobutane/isobutylene Alkylation (Octane) 2.3.4 Methyl–tert–butyl ether Synthesis 2.3.5 Methanol-to-Gasoline (MTG) 2.4 Major Industrial Processes — Chemical 2.4.1 Benzene Ethylation 2.4.2 Cumene 2.4.3 Beckman Isomerization 2.4.4 Esterification 2.5 Trends in Acid Catalysis 2.6 Problems 2.7 Answers to Problems 3. Oxidation Catalysis 3.1 Concepts 3.1.1 Oxidation Catalyst Periodic Table 3.1.2 Oxidation Thermodynamics 3.1.3 Recognizing Organic Oxidation States 3.1.4 Oxidation Catalysis Concepts — Homogeneous 3.1.5 Oxidation Catalysis Concepts — Heterogeneous 3.1.6 Elementary Reaction Steps 3.1.7 Homogeneous Oxidation Catalysis 3.1.7.1 Homogeneous molecular 3.1.7.2 Homogeneous free radical 3.1.8 Hetereogeous Oxidation 3.1.8.1 Hetereogeous surface oxidation 3.1.8.2 Hetereogeous bulk (Mars-van krevelen) oxidation 3.2 Elements of Oxidation Catalyst Design 3.2.1 Metals Substitution 3.2.2 Active Site Isolation 3.2.3 Surface Versus Bulk Composition 3.2.4 Promoters 3.2.5 Oxidation Catalyst Synthesis 3.3 Major Industrial Processes 3.3.1 Epoxidation — Styrene Monomer Propylene Oxide Process 3.3.2 Acrylonitrile 3.3.3 Vinyl Acetate/Wacker Oxidation 3.3.4 Cyclohexanol/One — Cyclohexane Oxidation 3.3.5 Adipic Acid/Nylon 6,6 3.3.6 Maleic Anhydride 3.3.6.1 Maleic anhydride mechanism 3.3.6.2 O-utilization 3.3.7 Aromatic Oxidation — Terephthalic Acid 3.3.8 Phthalic Anhydride 3.3.9 Aromatic Oxidation — Cumene to Phenol/Acetone 3.4 Problems 3.5 Answers to Problems 4. Polymerization Catalysis 4.1 Concepts 4.1.1 Polymerization Catalyst Periodic Table 4.1.2 Thermodynamics 4.1.3 Polymer Molecular Weight 4.1.4 Polymerization Reaction Mechanisms 4.1.5 Polymerization Mechanisms: Elementary Steps 4.1.6 Anionic Polymerization 4.1.7 Cationic Polymerization 4.1.8 Metal Oxide/Coordination Catalysis 4.1.9 Coordination Catalysis: Ziegler–Natta 4.1.10 Coordination Catalysis: Metallocene 4.1.11 Free Radical Polymerization 4.1.12 Living Polymerization 4.1.13 Living Polymerization: TEMPO Initiator 4.2 Polymerization Catalyst Design 4.2.1 Metals Substitution: PP Isomers 4.2.2 V-Based Polypropylene Catalysts: Syndiotactic 4.2.3 Ti-Based PP Catalysts: Isotactic 4.2.4 Ligand Effect: Constrained Geometry Metallocenes 4.2.5 Isotactic from Cp* Catalyst 4.2.6 Non-Coordinating Anions 4.2.6.1 Activation of catalytic cation 4.2.6.2 Effect on reaction path 4.2.7 Effect of Solvents: Butadiene Example 4.2.8 Ziegler–Natta Catalyst Synthesis: Particle Microreactor 4.2.9 Single Versus Multiple Site Polyolefin Catalysts 4.3 Major Industrial Processes 4.3.1 Polyethylene and Isotactic Polypropylene: TiCl4/AlEt2Cl/MgCl2 4.3.1.1 Ziegler-Natta catalyst synthesis particle "Microreactor" 4.3.1.2 Polyethylene and isotactic polypropylene: donor molecule improvement 4.3.2 Ethylene/Propylene Copolymers (EPC) 4.3.2.1 General 4.3.2.2 Mechanism 4.3.3 Higher Olefins: Shell Higher Olefin Process (SHOP) 4.3.4 Styrene/Butadiene Emulsion Polymerization (SBR) 4.3.4.1 General 4.3.4.2 SBR mechanism 4.3.5 Polyethoxylates (Anionic Polymerization) 4.3.6 Polyisobutylene 4.3.6.1 General 4.3.6.2 Mechanism 4.4 Future Catalysts: Late Transition Metals for Branched Polyethylene 4.4.1 Branched Polyethylene 4.4.2 Branching Mechanism 4.5 Problems 4.6 Answers to Problems 5. Reduction/Hydrogenation Catalysis 5.1 Concepts 5.1.1 Reduction Catalysis Periodic Table 5.1.2 Thermodynamics 5.1.3 H2 activation by Metals/Olefin Hydrogenation 5.1.4 Hydroformylation: CO Insertion 5.1.5 Synthesis Gas Reactions 5.1.6 Synthesis Gas: Non-Dissociative CO Adsorption: MeOH 5.1.7 Synthesis Gas: Dissociative CO Adsorption: Fischer–Tropsch Hydrocarbons 5.1.8 Fischer–Tropsch: Schultz–Flory Distribution 5.1.9 Hydrodesulfurization 5.2 Elements of Catalyst Design 5.2.1 Metal Substitution Effect: Fe Versus Co in FT 5.2.2 Metals/Ligand Effect: Hydroformylation 5.2.3 Hydroformylation Ligand Effects 5.2.3.1 χ and Φ values 5.2.3.2 Electronic(χ) and steric (Φ) effects in hydroformylation 5.2.4 Asymmetric Hydrogenation 5.2.5 Promoters and Poisons: Noble Metals 5.3 Major Industrial Processes 5.3.1 Hydrogenolysis: Hydrocracking and Hydrotreating 5.3.2 Dehydrogenation: Styrene 5.3.3 Hydroformylation/Hydrogenation: Oxo Alcohols 5.3.4 Carbonylation: Methanol to Acetic Acid 5.3.5 Catalytic Reforming 5.3.6 Ammonia Synthesis 5.4 Problems 5.5 Answers to Problems 6. Environmental Catalysis 6.1 Concepts 6.1.2. Thermodynamic Considerations 6.1.3 Exhaust Gas Components 6.1.4 Catalytic Conversion of Exhaust Gas 6.1.5 Catalytic Reactions for Removal of Exhaust Pollutants 6.1.6 Catalysts for Removal of Exhaust Pollutants 6.1.7 Catalyst Components and Functions — 3-Way Catalyst 6.1.8 Catalyst Components and Functions — Lean NOx Catalyst 6.1.9 Catalyst Components and Functions — SCR Catalyst 6.1.10 Catalyst Components and Functions — NOx Absorber 6.1.11 Catalyst Functions and Components — DOC and DPF 6.1.12 Mechanistic Concepts 6.2 Elements of Catalyst Design 6.2.1 Metal Substitution 6.2.2 Promoters and Poisons 6.2.3 Catalyst Synthesis 6.2.4 Engineering Concepts 6.3 Major Catalytic Technologies 6.3.1 Diesel Particulate Trap 6.3.1.1 Diesel particulate trap: mechanisms 6.3.1.2 Duesel particulate filter: sulfur sensitivity 6.3.2 Diesel Oxidation Catalyst 6.3.2.1 Monolith reactions 6.3.2.2 Conversion to CO and hydrocarbon 6.3.3 Diesel NOx Reduction — SCR 6.3.3.1 SCR mechanism 6.3.3.2 SCR with V2O5/TiO2 catalyst 6.3.3.3 SCR: Pt versus V2O5/TiO2 catalysts 6.3.3.4 SCR components 6.3.4 NOx Trap 6.3.5 Gasoline Engines — 3-Way Catalyst 6.3.6 Future Technology: Fuels Cells 6.3.6.1 Fuel cell reactions 6.4 Problems 6.5 Answers to Problems 7. Catalyst Characterization 7.1 Spectroscopic Methods 7.1.1 X-ray Diffraction/X-ray Fluorescence 7.1.2 X-ray Photoelectron Spectroscopy 7.1.3 Extended X-ray Adsorption Fine Structure 7.1.4 Fourier Transform Infrared Spectroscopy 7.1.5 Laser Raman Spectroscopy 7.1.6 Nuclear Magnetic Resonance Spectroscopy 7.1.7 Electron Microscopy 7.1.8 Secondary Ion Mass Spectrometry 7.2 Adsorption Methods 7.2.1 BET Surface Area 7.2.2 Porosimetry — Pore Volume and Pore Size Distribution 7.2.3 Thermogravimetric Analysis/Differential Scanning Calorimetry 7.3 Problems 7.4 Answers to Problems References Index Cover back