Chemical Technology

Andreas Jess, PhD is Professor of Chemical Engineering at the University of Bayreuth since 2001. His research interests are the optimization and modeling of catalytic processes, utilization of ionic liquids, and processes for production of fuels and chemicals from fossil and renewable resources. Peter Wasserscheid, PhD, is Professor of Chemical Engineering at the University of Erlangen-Nuremberg. He is also a founding member of the Solvent Innovation GmbH and acts as its scientific supervisor. His research focuses on highly selective catalytic processes.

• Preface of First Edition (and Guidelines How to Use This Textbook) xviiWhy a Second Edition? xviiiNotation xxi1 Introduction 11.1 What is Chemical Technology? 11.2 The Chemical Industry 21.3 The Changing Global Economic Map 62 Chemical Aspects of Industrial Chemistry 192.1 Stability and Reactivity of Chemical Bonds 192.1.1 Factors that Influence the Electronic Nature of Bonds and Atoms 192.1.2 Steric Effects 202.1.3 Classification of Reagents 212.2 General Classification of Reactions 212.2.1 Acid–Base-Catalyzed Reactions 222.2.2 Reactions via Free Radicals 232.2.3 Nucleophilic Substitution Reactions 242.2.4 Reactions via Carbocations 242.2.5 Electrophilic Substitution Reactions at Aromatic Compounds 252.2.6 Electrophilic Addition Reactions 272.2.7 Nucleophilic Addition Reactions 272.2.8 Asymmetric Synthesis 282.3 Catalysis 302.3.1 Introduction and General Aspects 302.3.2 Homogeneous, Heterogeneous, and Biocatalysis 352.3.3 Production and Characterization of Heterogeneous Catalysts 382.3.4 Deactivation of Catalysts 412.3.5 Future Trends in Catalysis Research 433 Thermal and Mechanical Unit Operations 453.1 Properties of Gases and Liquids 463.1.1 Ideal and Real Gas 463.1.2 Heat Capacities and the Joule–Thomson Effect 503.1.3 Physical Transformations of Pure Substances: Vaporization and Melting 533.1.4 Transport Properties (Diffusivity, Viscosity, Heat Conduction) 583.2 Heat and Mass Transfer in Chemical Engineering 693.2.1 Heat Transport 693.2.2 Mass Transport 863.3 Thermal Unit Operations 933.3.1 Heat Exchangers (Recuperators and Regenerators) 943.3.2 Distillation 993.3.3 Absorption (Gas Scrubbing) 1103.3.4 Liquid–Liquid Extraction 1183.3.5 Adsorption 1223.3.6 Fluid–Solid Extraction 1363.3.7 Crystallization 1393.3.8 Separation by Membranes 1413.4 Mechanical Unit Operations 1493.4.1 Conveyance of Fluids 1493.4.2 Contacting and Mixing of Fluids 1593.4.3 Crushing and Screening of Solids 1603.4.4 Separation of Solids from Fluids 1644 Chemical Reaction Engineering 1714.1 Main Aspects and Basic Definitions of Chemical Reaction Engineering 1714.1.1 Design Aspects and Scale-up Dimensions of Chemical Reactors 1724.1.2 Speed of Chemical and Biochemical Reactions 1724.1.3 Influence of Reactor Type on Productivity 1744.1.4 Terms Used to Characterize the Composition of a Reaction Mixture 1744.1.5 Terms Used to Quantify the Result of a Chemical Conversion 1754.1.6 Reaction Time and Residence Time 1754.1.7 Space Velocity and Space–Time Yield 1764.2 Chemical Thermodynamics 1774.2.1 Introduction and Perfect Gas Equilibria 1774.2.2 Real Gas Equilibria 1844.2.3 Equilibrium of Liquid–Liquid Reactions 1864.2.4 Equilibrium of Gas–Solid Reactions 1884.2.5 Calculation of Simultaneous Equilibria 1904.3 Kinetics of Homogeneous Reactions 1924.3.1 Rate Equation: Influence of Temperature and Reaction Order 1924.3.2 Parallel Reactions and Reactions in Series 1974.3.3 Reversible Reactions 2004.3.4 Reactions with Varying Volume (for the Example of a Batch Reactor) 2034.4 Kinetics of Fluid–Fluid Reactions 2044.4.1 Mass Transfer at a Gas–Liquid Interface (Two-Film Theory) 2054.4.2 Mass Transfer with (Slow) Homogeneous Reaction in the Bulk Phase 2074.4.3 Mass Transfer with Fast or Instantaneous Reaction near or at the Interface 2084.5 Kinetics of Heterogeneously Catalyzed Reactions 2134.5.1 Spectrum of Factors Influencing the Rate of Heterogeneously Catalyzed Reactions 2134.5.2 Chemical Reaction Rate: Surface Kinetics 2174.5.3 Reaction on a Solid Catalyst and Interfacial Transport of Mass and Heat 2224.5.4 Chemical Reaction and Internal Transport of Mass and Heat 2324.5.5 Simultaneous Occurrence of Interfacial and InternalMass Transport Effects 2404.5.6 Influence of External and Internal Mass Transfer on Selectivity 2454.6 Kinetics of Gas–Solid Reactions 2534.6.1 Spectrum of Factors Influencing the Rate of Gas–Solid Reactions 2544.6.2 Reaction of a Gas with a Nonporous Solid 2554.6.3 Reaction of a Gas with a Porous Solid 2604.7 Criteria Used to Exclude Interphase and Intraparticle Mass and Heat Transport Limitations in Gas–Solid Reactions and Heterogeneously Catalyzed Reactions 2654.7.1 External Mass Transfer Through Boundary Layer 2654.7.2 External Heat Transfer 2664.7.3 Internal Mass Transfer 2664.7.4 Internal Heat Transfer 2664.8 Kinetics of Homogeneously or Enzyme-catalyzed Reactions 2694.8.1 Homogeneous and Enzyme Catalysis in a Single-Phase System 2694.8.2 Homogeneous Two-Phase Catalysis 2714.9 Kinetics of Gas–Liquid Reactions on Solid Catalysts 2734.9.1 Introduction 2734.9.2 High Concentration of Liquid Reactant B (or Pure B) and Slightly Soluble Gas 2754.9.3 Low Concentration of Liquid Reactant B and Highly Soluble Gas and/or High Pressure 2754.10 Chemical Reactors 2764.10.1 Overview of Reactor Types and Their Characteristics 2774.10.2 Ideal Isothermal Reactors 2844.10.3 Non-isothermal Ideal Reactors and Criteria for Prevention of Thermal Runaway 2944.10.4 Non-ideal Flow and Residence Time Distribution 3104.10.5 Tanks-in-Series Model 3134.10.6 Dispersion Model 3154.10.7 Modeling of Fixed Bed Reactors 3254.10.8 Novel Developments in Reactor Technology 3364.11 Measurement and Evaluation of Kinetic Data 3444.11.1 Principal Methods for Determining Kinetic Data 3454.11.2 Evaluation of Kinetic Data (Reaction Orders, Rate Constants) 3474.11.3 Laboratory-Scale Reactors for Kinetic Measurements 3504.11.4 Transport Limitations in Experimental Catalytic Reactors 3514.11.5 Case Studies for the Evaluation of Kinetic Data 3565 Raw Materials, Products, Environmental Aspects, and Costs of Chemical Technology 3715.1 Raw Materials of Industrial Organic Chemistry and Energy Sources 3725.1.1 Energy Consumption, Reserves, and Resources of Fossil Fuels and Renewables 3735.1.2 Composition of Fossil Fuels and Routes for the Production of Synthetic Fuels 4035.1.3 Natural Gas and Other Technical Gases 4035.1.4 Crude Oil and Refinery Products 4105.1.5 Coal and Coal Products 4185.1.6 Renewable Raw Materials 4225.1.7 Energy Consumption in Human History 4295.1.8 Power-to-X and Hydrogen Storage Technologies 4345.2 Inorganic Products and Raw Materials 4485.2.1 Nonmetallic Inorganic Materials 4485.2.2 Metals 4535.3 Organic Intermediates and Final Products 4695.3.1 Alkanes and Syngas 4695.3.2 Alkenes, Alkynes, and Aromatic Hydrocarbons 4725.3.3 Organic Intermediates Functionalized with Oxygen, Nitrogen, or Halogens 4795.3.4 Polymers 4955.3.5 Detergents and Surfactants 5035.3.6 Fine Chemicals 5075.4 Environmental Aspects of Chemical Technology 5125.4.1 Air Pollution 5125.4.2 Water Consumption and Water Footprint 5155.4.3 Plastic Production, Pollution, and Recycling of Plastic Waste 5235.4.4 “Green Chemistry” and Quantifying the Environmental Impact of Chemical Processes 5275.5 Production Costs of Fuels and Chemicals Manufacturing 5305.5.1 Price of Chemical Products 5305.5.2 Investment Costs 5305.5.3 Variable Costs 5325.5.4 Operating Costs (Fixed and Variable Costs) 5336 Examples of Industrial Processes 5376.1 Ammonia Synthesis 5376.1.1 Historical Development of Haber–Bosch Process 5376.1.2 Thermodynamics of Ammonia Synthesis 5396.1.3 Kinetics and Mechanism of Ammonia Synthesis 5406.1.4 Technical Ammonia Process and Synthesis Reactors 5426.2 Syngas and Hydrogen 5476.2.1 Options to Produce Syngas and Hydrogen (Overview) 5476.2.2 Syngas from Solid Fuels (Coal, Biomass) 5516.2.3 Syngas by Partial Oxidation of Heavy Oils 5606.2.4 Syngas by Steam Reforming of Natural Gas 5626.3 Sulfuric Acid 5656.3.1 Reactions and Thermodynamics of Sulfuric Acid Production 5656.3.2 Production of SO2 5666.3.3 SO2 Conversion into SO3 5676.3.4 Sulfuric Acid Process 5726.4 Nitric Acid 5736.4.1 Reactions and Thermodynamics of Nitric Acid Production 5746.4.2 Kinetics of Catalytic Oxidation of Ammonia 5766.4.3 NO Oxidation 5876.4.4 Nitric Acid Processes 5886.5 Coke and Steel 5916.5.1 Steel Production (Overview) 5916.5.2 Production of Blast Furnace Coke 5936.5.3 Production of Pig Iron in a Blast Furnace 5996.6 Basic Chemicals by Steam Cracking 6096.6.1 General and Mechanistic Aspects 6096.6.2 Factors that Influence the Product Distribution 6126.6.3 Industrial Steam Cracker Process 6136.6.4 Economic Aspects of the Steam Cracker Process 6176.7 Liquid Fuels by Cracking of Heavy Oils 6186.7.1 Thermal Cracking (Delayed Coking) 6196.7.2 Fluid Catalytic Cracking (FCC Process) 6226.8 Clean Liquid Fuels by Hydrotreating 6256.8.1 History, Current Status, and Perspective of Hydrotreating 6256.8.2 Thermodynamics and Kinetics of Hydrodesulfurization (HDS) 6266.8.3 Hydrodesulfurization Process and Reaction Engineering Aspects 6296.9 High-Octane Gasoline by Catalytic Reforming 6336.9.1 Reactions and Thermodynamics of Catalytic Reforming 6336.9.2 Reforming Catalyst 6356.9.3 Process of Catalytic Reforming 6356.9.4 Deactivation and Regeneration of a Reforming Catalyst 6386.10 Refinery Alkylation 6496.10.1 Reaction and Reaction Mechanism of Refinery Alkylation 6496.10.2 Alkylation Feedstock and Products 6516.10.3 Process Variables 6516.10.4 Commercial Alkylation Processes 6526.11 Fuels and Chemicals from Syngas: Methanol and Fischer–Tropsch Synthesis 6576.11.1 Fischer–Tropsch Synthesis 6586.11.2 Methanol Synthesis 6766.12 Ethylene and Propylene Oxide 6856.12.1 Commercial Production of Ethylene Oxide 6856.12.2 Commercial Production of Propylene Oxide 6896.13 Catalytic Oxidation of o-Xylene to Phthalic Acid Anhydride 6946.13.1 Production and Use of Phthalic Anhydride (Overview) 6946.13.2 Design and Simulation of a Multi-tubular Reactor for Oxidation of o-Xylene to PA 6956.14 Hydroformylation (Oxosynthesis) 7016.14.1 Industrial Relevance of Hydroformylation 7016.14.2 Hydroformylation Catalysis 7036.14.3 Current Hydroformylation Catalyst and Process Technologies 7066.14.4 Advanced Catalyst Immobilization Technologies for Hydroformylation Catalysis 7146.15 Acetic Acid 7216.15.1 Acetic Acid Synthesis via Acetaldehyde Oxidation 7226.15.2 Acetic Acid Synthesis via Butane or Naphtha Oxidation 7236.15.3 Acetic Acid Synthesis via Methanol Carbonylation 7246.15.4 Other Technologies for the Commercial Production of Acetic Acid 7286.16 Ethylene Oligomerization Processes for Linear 1-Alkene Production 7296.16.1 Industrial Relevance of 1-Olefins 7296.16.2 Aluminum-Alkyl-Based “Aufbaureaktion” (Growth Reaction) 7306.16.3 Nickel-Catalyzed Oligomerization: Shell Higher Olefin Process (SHOP) 7336.16.4 Metallacycle Mechanism for Selective Ethylene Oligomerization 7356.17 Production of Fine Chemicals (ExampleMenthol) 7406.17.1 Menthol and Menthol Production (Overview) 7406.17.2 Thermodynamics and Kinetics of Epimerization of Menthol Isomers 7416.17.3 Influence of Mass Transfer on the Epimerization of Menthol Isomers 7446.17.4 Epimerization of Menthol Isomers in Technical Reactors 7486.18 Treatment of Exhaust Gases from Mobile and Stationary Sources 7506.18.1 Automotive Emission Control 7506.18.2 Selective Catalytic Reduction (SCR) of NOx from Flue Gas from Power Plants 7566.19 Industrial Electrolysis 7636.19.1 Electrochemical Kinetics and Thermodynamics 7636.19.2 Chlorine and Sodium Hydroxide 7686.19.3 Electrolysis of Water 7736.19.4 Electrometallurgy (Purification of Metals by Electrorefining) 7786.20 Polyethene Production 7826.20.1 Polyethene Classification and Industrial Use 7826.20.2 General Characteristics of PE Production Processes 7836.20.3 Reaction Mechanism and Process Equipment for the Production of LDPE 7846.20.4 Catalysts for the Production of HDPE and LLDPE 7876.20.5 Production Processes for HDPE and LLDPE 7896.20.6 PE Production Economics and Modern Developments in PE Production 7926.21 Titanium Dioxide 7936.21.1 Production and Use of Titanium Dioxide (Overview) 7936.21.2 Sulfate Process for Production of Titanium Dioxide 7936.21.3 Chloride Process for Production of Titanium Dioxide 7956.22 Silicon 7966.22.1 Production and Use of Silicon (Overview) 7966.22.2 Carbothermic Reduction of Silica 7976.22.3 Refining, Casting, and Crushing of Metallurgical Grade Silicon 7986.22.4 Economics of the Metallurgical Grade Silicon Production 7986.22.5 Production of Photovoltaic Grade Silicon by Purification of Metallurgical Grade Silicon 7986.23 Polytetrafluoroethylene (PTFE) 8016.23.1 Production and Use of PTFE (Overview) 8016.23.2 Process for Production of PTFE 8026.23.3 Treatment of PTFE Waste 8026.24 Production of Amino Acids by Fermentation 8076.24.1 General Aspects 8076.24.2 Overview of the Methods Applied for Industrial Amino Acid Production 8076.24.3 Amino Acid Fermentation 810References 815Index 841