Engineering Catalysis

Description

The book illuminates various aspects of heterogeneous catalysis engineering, from catalysis design, catalyst preparation and characterization, reaction kinetics, mass transfer, and catalytic reactors to the implementation of catalysts in chemical technology. Aimed at graduate students, it is also a useful resource for professionals working in research and development. Important topic: the production process of nearly every chemical substance or product used today requires a special catalyst. 2nd edition: More coverage of industrial preparation of catalysts and their technological implementations. Cover Half Title Also of interest Engineering Catalysis Copyright To the memory of Elena Murzina Preface to the first edition Preface to the second edition Contents About the author 1. The basics 1.1 Catalytic concepts 1.1.1 Definitions 1.1.2 Length and time scales in catalysis 1.1.3 Catalytic trinity: activity, selectivity, stability 1.1.4 Composition of catalysts 1.2 Reactivity of solids 1.2.1 Physisorption and chemisorption 1.2.2 Basics of chemisorption theory 1.2.3 Surface crystallography 1.2.4 Mechanisms of some catalytic reactions 1.2.4.1 Oxidations 1.2.4.2 Hydrogenation 1.2.4.3 Catalysis by solid acids 1.3 Catalysis in industry and for environmental protection 1.4 Fuel cells and electrocatalysis References 2. Engineering catalysts 2.1 Catalyst design 2.1.1 Being in shape 2.1.2 Catalysis informatics and high-throughput experimentation 2.2 Toolbox in catalysis 2.2.1 General overview of the characterization methods 2.2.2 Adsorption methods 2.2.3 Physisorption methods 2.2.3.1 Surface area determination 2.2.3.2 Determination of pore size and pore size distribution 2.2.4 Chemisorption 2.2.5 Temperature-programmed methods 2.2.5.1 Temperature-programmed reduction 2.2.5.2 Temperature-programmed desorption 2.2.5.3 Temperature programmed oxidation (TPO) 2.2.6 Calorimetry 2.2.7 X-ray diffraction 2.2.8 X-ray photoelectron spectroscopy and X-ray fluorescence 2.2.9 Infrared and Raman spectroscopies 2.2.10 Catalyst particle size measurements 2.2.11 Electron paramagnetic/spin resonance 2.2.12 Mössbauer spectroscopy 2.2.13 X-ray absorption spectroscopy 2.2.14 Nuclear magnetic resonance 2.2.15 Imaging of catalysts 2.2.15.1 Electron microscopy [28, 29] 2.2.15.2 Scanning probe microscopy 2.2.15.3 Electron microprobing 2.2.15.4 Magnetic resonance imaging 2.2.15.5 Positron emission tomography imaging 2.2.15.6 Integrated laser and electron microscopy 2.2.16 Catalytic reactions: product analysis 2.2.16.1 Gas chromatography 2.2.16.2 Liquid chromatography 2.2.17 Theory as a part of a toolbox 2.3 Preparation of catalytic materials 2.3.1 General overview 2.3.1.1 Preparation of the primary solids 2.3.1.2 Treatment of intermediate solids or precursors 2.3.1.3 Forming 2.3.2 Unsupported metals 2.3.2.1 Colloidal catalysts 2.3.2.2 Bulk metal catalysts 2.3.3 Preparation of bulk oxides by precipitation 2.3.4 Heteropoly acids 2.3.5 Catalyst supports 2.3.5.1 Carbon 2.3.5.2 Deposition of metals on carbon and surface charge of supports 2.3.5.3 Transition metal oxides 2.3.5.4 Silica 2.3.5.5 Alumina 2.3.5.6 Zeolites 2.3.5.7 Metal organic frameworks 2.3.5.8 Mesoporous materials 2.3.5.9 Layered compounds 2.3.5.10 Ceramic and metallic monoliths and foams as catalyst supports 2.3.6 Supported catalysts 2.3.6.1 Adsorption 2.3.6.2 Impregnation and drying 2.3.6.3 Multiple adsorption and impregnation 2.3.6.4 Industrial implementation of impregnation 2.3.6.5 Precipitation 2.3.6.6 Atomic layer deposition 2.3.7 Catalyst forming operations 2.3.7.1 Spray-drying 2.3.7.2 Size reduction and granulation 2.3.7.3 Extrusion 2.3.7.4 Tableting 2.3.7.5 3D printing in catalytic technology 2.3.7.6 Scaling-up catalyst preparation References 3. Engineering reactions 3.1 Introduction 3.2 Thermodynamics 3.3 Kinetics 3.3.1 Definitions 3.3.2 Reaction mechanism 3.4 Kinetics of complex reactions 3.4.1 Theory of complex reactions kinetics 3.4.2 Relationship between thermodynamics and kinetics 3.4.3 Non-ideal surfaces 3.4.4 Kinetic aspects of selectivity 3.4.5 Structure sensitivity 3.4.6 Mechanism-free kinetics – kinetic polynomial 3.4.7 What is behind a rate constant? 3.4.8 Apparent activation energy of complex reactions 3.4.9 Dynamic catalysis and deactivation 3.4.10 Mathematical treatment of experimental data 3.5 Mass transfer 3.5.1 Diffusion effects in heterogeneous catalysis 3.5.2 Reactor dependent external diffusion (interphase mass transfer, film diffusion) 3.5.3 Calculation of diffusion coefficients 3.5.4 Size dependent internal (pore) diffusion 3.5.5 Non-isothermal conditions 3.5.6 Multiple reactions and diffusional limitations 3.5.7 Diffusion in micropores 3.5.8 Criteria for the absence of diffusional limitations 3.6 Catalytic reactors 3.6.1 Laboratory reactors 3.6.2 Industrial reactors 3.6.3 Two-phase reactors 3.6.4 Three-phase catalytic reactors 3.6.4.1 Fixed-bed multiphase reactors 3.6.4.2 Moving-bed multiphase reactors 3.6.4.3 Comparison between various reactor options 3.6.4.3.1 Fischer–Tropsch synthesis 3.6.4.3.2 Methanol synthesis 3.6.5 Reactor modeling 3.6.5.1 Reactor modeling and process development strategy 3.6.5.2 Reactor models: mass and heat balances 3.6.6 Catalyst handing in a plant 3.6.6.1 Delivery to a plant 3.6.6.2 Catalyst charging 3.6.6.3 Catalyst activation, shutdown, restarts and discharging 3.6.6.4 Metal recovery References 4. Engineering technology 4.1 General structures of chemical processes 4.1.1 Safety in design 4.1.2 Conceptual process design: examples 4.1.3 Conceptual process design: general comments 4.1.4 Reactor selection 4.2 (Petro)chemical industry 4.3 Fluid catalytic cracking 4.3.1 Feedstock 4.3.2 Reactions/mechanism 4.3.3 Kinetics/process variables 4.3.4 Catalysts 4.3.5 Technology 4.4 Hydrocracking 4.4.1 Overview of hydrocracking 4.4.2 Hydrocracking catalysts 4.4.3 Hydrocracking technology 4.5 Steam reforming of natural gas 4.5.1 General 4.5.2 Process conditions for sulfur removal and primary reforming 4.5.3 Kinetics and mechanism 4.5.4 Technology 4.5.5 Catalysts 4.6 Ammonia synthesis 4.6.1 General 4.6.2 Thermodynamics 4.6.3 Kinetics 4.6.4 Catalysts 4.6.4.1 Iron 4.6.4.2 Ruthenium 4.6.5 Reactors and process design 4.7 Oxidation 4.7.1 General 4.7.2 Epoxidation of olefins 4.7.2.1 Ethylene oxide 4.7.2.2 Propylene oxide 4.7.3 Oxidation of alkanes to anhydrides 4.7.3.1 Maleic anhydride 4.7.3.2 Phthalic anhydride synthesis 4.7.3.2.1 Feedstock 4.7.3.2.2 Thermodynamics 4.7.3.2.3 Mechanism 4.7.3.2.4 Catalyst 4.7.3.2.5 Kinetics 4.7.3.2.6 Technology, reaction and separation 4.7.4 From alcohols to aldehydes: oxidative dehydrogenation of methanol to formaldehyde 4.7.5 Ammoxidation 4.7.5.1 Acrylic acid 4.7.5.2 Acrylonitrile 4.8 Oxychlorination 4.8.1 Overview 4.8.2 Catalysts and reactors 4.8.3 Reaction network and kinetics 4.8.4 Technology References Acknowledgments Recommended reading Index