Clear and thorough throughout, this textbook covers the major sub-disciplines of modern chemical technology?chemistry, thermal and mechanical unit operations, chemical reaction engineering, and general chemical technology?alongside raw materials, energy sources and detailed descriptions of 24 important industrial processes and products. It brings information on energy and raw material consumption and production data of chemicals up to date and offers not just improved and extended chapters, but completely new ones as well.
This new edition of Chemical Technology: From Principles to Products features a new chapter illustrating the global economic map and its development from the 15th century until today, and another on energy consumption in human history. Chemical key technologies for a future sustainable energy system such as power-to-X and hydrogen storage are now also examined. Chapters on inorganic products, material reserves, and water consumption and resources have been extended, while another presents environmental aspects of plastic pollution and handling of plastic waste. The book also adds four important processes to its pages: production of titanium dioxide, silicon, production and chemical recycling of polytetrafluoroethylene, and fermentative synthesis of amino acids.
-Provides comprehensive coverage of chemical technology?from the fundamentals to 24 of the most important processes
-Intertwines the four disciplines of chemical technology: chemistry, thermal and mechanical unit operations, chemical reaction engineering and general chemical technology
-Fully updated with new content on: power-to-X and hydrogen storage; inorganic products, including metals, glass, and ceramics; water consumption and pollution; and additional industrial processes
-Written by authors with extensive experience in teaching the topic and helping students understand the complex concepts
Chemical Technology: From Principles to Products, Second Edition is an ideal textbook for advanced students of chemical technology and will appeal to anyone in chemical engineering.
Table of Contents
Preface of First Edition (and Guidelines How to Use This Textbook) xvii
Why a Second Edition? xviii
Notation xxi
1 Introduction 1
1.1 What is Chemical Technology? 1
1.2 The Chemical Industry 2
1.3 The Changing Global Economic Map 6
2 Chemical Aspects of Industrial Chemistry 19
2.1 Stability and Reactivity of Chemical Bonds 19
2.1.1 Factors that Influence the Electronic Nature of Bonds and Atoms 19
2.1.2 Steric Effects 20
2.1.3 Classification of Reagents 21
2.2 General Classification of Reactions 21
2.2.1 Acid-Base-Catalyzed Reactions 22
2.2.2 Reactions via Free Radicals 23
2.2.3 Nucleophilic Substitution Reactions 24
2.2.4 Reactions via Carbocations 24
2.2.5 Electrophilic Substitution Reactions at Aromatic Compounds 25
2.2.6 Electrophilic Addition Reactions 27
2.2.7 Nucleophilic Addition Reactions 27
2.2.8 Asymmetric Synthesis 28
2.3 Catalysis 30
2.3.1 Introduction and General Aspects 30
2.3.2 Homogeneous, Heterogeneous, and Biocatalysis 35
2.3.3 Production and Characterization of Heterogeneous Catalysts 38
2.3.4 Deactivation of Catalysts 41
2.3.5 Future Trends in Catalysis Research 43
3 Thermal and Mechanical Unit Operations 45
3.1 Properties of Gases and Liquids 46
3.1.1 Ideal and Real Gas 46
3.1.2 Heat Capacities and the Joule-Thomson Effect 50
3.1.3 Physical Transformations of Pure Substances: Vaporization and Melting 53
3.1.4 Transport Properties (Diffusivity, Viscosity, Heat Conduction) 58
3.2 Heat and Mass Transfer in Chemical Engineering 69
3.2.1 Heat Transport 69
3.2.2 Mass Transport 86
3.3 Thermal Unit Operations 93
3.3.1 Heat Exchangers (Recuperators and Regenerators) 94
3.3.2 Distillation 99
3.3.3 Absorption (Gas Scrubbing) 110
3.3.4 Liquid-Liquid Extraction 118
3.3.5 Adsorption 122
3.3.6 Fluid-Solid Extraction 136
3.3.7 Crystallization 139
3.3.8 Separation by Membranes 141
3.4 Mechanical Unit Operations 149
3.4.1 Conveyance of Fluids 149
3.4.2 Contacting and Mixing of Fluids 159
3.4.3 Crushing and Screening of Solids 160
3.4.4 Separation of Solids from Fluids 164
4 Chemical Reaction Engineering 171
4.1 Main Aspects and Basic Definitions of Chemical Reaction Engineering 171
4.1.1 Design Aspects and Scale-up Dimensions of Chemical Reactors 172
4.1.2 Speed of Chemical and Biochemical Reactions 172
4.1.3 Influence of Reactor Type on Productivity 174
4.1.4 Terms Used to Characterize the Composition of a Reaction Mixture 174
4.1.5 Terms Used to Quantify the Result of a Chemical Conversion 175
4.1.6 Reaction Time and Residence Time 175
4.1.7 Space Velocity and Space-Time Yield 176
4.2 Chemical Thermodynamics 177
4.2.1 Introduction and Perfect Gas Equilibria 177
4.2.2 Real Gas Equilibria 184
4.2.3 Equilibrium of Liquid-Liquid Reactions 186
4.2.4 Equilibrium of Gas-Solid Reactions 188
4.2.5 Calculation of Simultaneous Equilibria 190
4.3 Kinetics of Homogeneous Reactions 192
4.3.1 Rate Equation: Influence of Temperature and Reaction Order 192
4.3.2 Parallel Reactions and Reactions in Series 197
4.3.3 Reversible Reactions 200
4.3.4 Reactions with Varying Volume (for the Example of a Batch Reactor) 203
4.4 Kinetics of Fluid-Fluid Reactions 204
4.4.1 Mass Transfer at a Gas-Liquid Interface (Two-Film Theory) 205
4.4.2 Mass Transfer with (Slow) Homogeneous Reaction in the Bulk Phase 207
4.4.3 Mass Transfer with Fast or Instantaneous Reaction near or at the Interface 208
4.5 Kinetics of Heterogeneously Catalyzed Reactions 213
4.5.1 Spectrum of Factors Influencing the Rate of Heterogeneously Catalyzed Reactions 213
4.5.2 Chemical Reaction Rate: Surface Kinetics 217
4.5.3 Reaction on a Solid Catalyst and Interfacial Transport of Mass and Heat 222
4.5.4 Chemical Reaction and Internal Transport of Mass and Heat 232
4.5.5 Simultaneous Occurrence of Interfacial and InternalMass Transport Effects 240
4.5.6 Influence of External and Internal Mass Transfer on Selectivity 245
4.6 Kinetics of Gas-Solid Reactions 253
4.6.1 Spectrum of Factors Influencing the Rate of Gas-Solid Reactions 254
4.6.2 Reaction of a Gas with a Nonporous Solid 255
4.6.3 Reaction of a Gas with a Porous Solid 260
4.7 Criteria Used to Exclude Interphase and Intraparticle Mass and Heat Transport Limitations in Gas-Solid Reactions and Heterogeneously Catalyzed Reactions 265
4.7.1 External Mass Transfer Through Boundary Layer 265
4.7.2 External Heat Transfer 266
4.7.3 Internal Mass Transfer 266
4.7.4 Internal Heat Transfer 266
4.8 Kinetics of Homogeneously or Enzyme-catalyzed Reactions 269
4.8.1 Homogeneous and Enzyme Catalysis in a Single-Phase System 269
4.8.2 Homogeneous Two-Phase Catalysis 271
4.9 Kinetics of Gas-Liquid Reactions on Solid Catalysts 273
4.9.1 Introduction 273
4.9.2 High Concentration of Liquid Reactant B (or Pure B) and Slightly Soluble Gas 275
4.9.3 Low Concentration of Liquid Reactant B and Highly Soluble Gas and/or High Pressure 275
4.10 Chemical Reactors 276
4.10.1 Overview of Reactor Types and Their Characteristics 277
4.10.2 Ideal Isothermal Reactors 284
4.10.3 Non-isothermal Ideal Reactors and Criteria for Prevention of Thermal Runaway 294
4.10.4 Non-ideal Flow and Residence Time Distribution 310
4.10.5 Tanks-in-Series Model 313
4.10.6 Dispersion Model 315
4.10.7 Modeling of Fixed Bed Reactors 325
4.10.8 Novel Developments in Reactor Technology 336
4.11 Measurement and Evaluation of Kinetic Data 344
4.11.1 Principal Methods for Determining Kinetic Data 345
4.11.2 Evaluation of Kinetic Data (Reaction Orders, Rate Constants) 347
4.11.3 Laboratory-Scale Reactors for Kinetic Measurements 350
4.11.4 Transport Limitations in Experimental Catalytic Reactors 351
4.11.5 Case Studies for the Evaluation of Kinetic Data 356
5 Raw Materials, Products, Environmental Aspects, and Costs of Chemical Technology 371
5.1 Raw Materials of Industrial Organic Chemistry and Energy Sources 372
5.1.1 Energy Consumption, Reserves, and Resources of Fossil Fuels and Renewables 373
5.1.2 Composition of Fossil Fuels and Routes for the Production of Synthetic Fuels 403
5.1.3 Natural Gas and Other Technical Gases 403
5.1.4 Crude Oil and Refinery Products 410
5.1.5 Coal and Coal Products 418
5.1.6 Renewable Raw Materials 422
5.1.7 Energy Consumption in Human History 429
5.1.8 Power-to-X and Hydrogen Storage Technologies 434
5.2 Inorganic Products and Raw Materials 448
5.2.1 Nonmetallic Inorganic Materials 448
5.2.2 Metals 453
5.3 Organic Intermediates and Final Products 469
5.3.1 Alkanes and Syngas 469
5.3.2 Alkenes, Alkynes, and Aromatic Hydrocarbons 472
5.3.3 Organic Intermediates Functionalized with Oxygen, Nitrogen, or Halogens 479
5.3.4 Polymers 495
5.3.5 Detergents and Surfactants 503
5.3.6 Fine Chemicals 507
5.4 Environmental Aspects of Chemical Technology 512
5.4.1 Air Pollution 512
5.4.2 Water Consumption and Water Footprint 515
5.4.3 Plastic Production, Pollution, and Recycling of Plastic Waste 523
5.4.4 “Green Chemistry” and Quantifying the Environmental Impact of Chemical Processes 527
5.5 Production Costs of Fuels and Chemicals Manufacturing 530
5.5.1 Price of Chemical Products 530
5.5.2 Investment Costs 530
5.5.3 Variable Costs 532
5.5.4 Operating Costs (Fixed and Variable Costs) 533
6 Examples of Industrial Processes 537
6.1 Ammonia Synthesis 537
6.1.1 Historical Development of Haber-Bosch Process 537
6.1.2 Thermodynamics of Ammonia Synthesis 539
6.1.3 Kinetics and Mechanism of Ammonia Synthesis 540
6.1.4 Technical Ammonia Process and Synthesis Reactors 542
6.2 Syngas and Hydrogen 547
6.2.1 Options to Produce Syngas and Hydrogen (Overview) 547
6.2.2 Syngas from Solid Fuels (Coal, Biomass) 551
6.2.3 Syngas by Partial Oxidation of Heavy Oils 560
6.2.4 Syngas by Steam Reforming of Natural Gas 562
6.3 Sulfuric Acid 565
6.3.1 Reactions and Thermodynamics of Sulfuric Acid Production 565
6.3.2 Production of SO2 566
6.3.3 SO2 Conversion into SO3 567
6.3.4 Sulfuric Acid Process 572
6.4 Nitric Acid 573
6.4.1 Reactions and Thermodynamics of Nitric Acid Production 574
6.4.2 Kinetics of Catalytic Oxidation of Ammonia 576
6.4.3 NO Oxidation 587
6.4.4 Nitric Acid Processes 588
6.5 Coke and Steel 591
6.5.1 Steel Production (Overview) 591
6.5.2 Production of Blast Furnace Coke 593
6.5.3 Production of Pig Iron in a Blast Furnace 599
6.6 Basic Chemicals by Steam Cracking 609
6.6.1 General and Mechanistic Aspects 609
6.6.2 Factors that Influence the Product Distribution 612
6.6.3 Industrial Steam Cracker Process 613
6.6.4 Economic Aspects of the Steam Cracker Process 617
6.7 Liquid Fuels by Cracking of Heavy Oils 618
6.7.1 Thermal Cracking (Delayed Coking) 619
6.7.2 Fluid Catalytic Cracking (FCC Process) 622
6.8 Clean Liquid Fuels by Hydrotreating 625
6.8.1 History, Current Status, and Perspective of Hydrotreating 625
6.8.2 Thermodynamics and Kinetics of Hydrodesulfurization (HDS) 626
6.8.3 Hydrodesulfurization Process and Reaction Engineering Aspects 629
6.9 High-Octane Gasoline by Catalytic Reforming 633
6.9.1 Reactions and Thermodynamics of Catalytic Reforming 633
6.9.2 Reforming Catalyst 635
6.9.3 Process of Catalytic Reforming 635
6.9.4 Deactivation and Regeneration of a Reforming Catalyst 638
6.10 Refinery Alkylation 649
6.10.1 Reaction and Reaction Mechanism of Refinery Alkylation 649
6.10.2 Alkylation Feedstock and Products 651
6.10.3 Process Variables 651
6.10.4 Commercial Alkylation Processes 652
6.11 Fuels and Chemicals from Syngas: Methanol and Fischer-Tropsch Synthesis 657
6.11.1 Fischer-Tropsch Synthesis 658
6.11.2 Methanol Synthesis 676
6.12 Ethylene and Propylene Oxide 685
6.12.1 Commercial Production of Ethylene Oxide 685
6.12.2 Commercial Production of Propylene Oxide 689
6.13 Catalytic Oxidation of o-Xylene to Phthalic Acid Anhydride 694
6.13.1 Production and Use of Phthalic Anhydride (Overview) 694
6.13.2 Design and Simulation of a Multi-tubular Reactor for Oxidation of o-Xylene to PA 695
6.14 Hydroformylation (Oxosynthesis) 701
6.14.1 Industrial Relevance of Hydroformylation 701
6.14.2 Hydroformylation Catalysis 703
6.14.3 Current Hydroformylation Catalyst and Process Technologies 706
6.14.4 Advanced Catalyst Immobilization Technologies for Hydroformylation Catalysis 714
6.15 Acetic Acid 721
6.15.1 Acetic Acid Synthesis via Acetaldehyde Oxidation 722
6.15.2 Acetic Acid Synthesis via Butane or Naphtha Oxidation 723
6.15.3 Acetic Acid Synthesis via Methanol Carbonylation 724
6.15.4 Other Technologies for the Commercial Production of Acetic Acid 728
6.16 Ethylene Oligomerization Processes for Linear 1-Alkene Production 729
6.16.1 Industrial Relevance of 1-Olefins 729
6.16.2 Aluminum-Alkyl-Based “Aufbaureaktion” (Growth Reaction) 730
6.16.3 Nickel-Catalyzed Oligomerization: Shell Higher Olefin Process (SHOP) 733
6.16.4 Metallacycle Mechanism for Selective Ethylene Oligomerization 735
6.17 Production of Fine Chemicals (ExampleMenthol) 740
6.17.1 Menthol and Menthol Production (Overview) 740
6.17.2 Thermodynamics and Kinetics of Epimerization of Menthol Isomers 741
6.17.3 Influence of Mass Transfer on the Epimerization of Menthol Isomers 744
6.17.4 Epimerization of Menthol Isomers in Technical Reactors 748
6.18 Treatment of Exhaust Gases from Mobile and Stationary Sources 750
6.18.1 Automotive Emission Control 750
6.18.2 Selective Catalytic Reduction (SCR) of NOx from Flue Gas from Power Plants 756
6.19 Industrial Electrolysis 763
6.19.1 Electrochemical Kinetics and Thermodynamics 763
6.19.2 Chlorine and Sodium Hydroxide 768
6.19.3 Electrolysis of Water 773
6.19.4 Electrometallurgy (Purification of Metals by Electrorefining) 778
6.20 Polyethene Production 782
6.20.1 Polyethene Classification and Industrial Use 782
6.20.2 General Characteristics of PE Production Processes 783
6.20.3 Reaction Mechanism and Process Equipment for the Production of LDPE 784
6.20.4 Catalysts for the Production of HDPE and LLDPE 787
6.20.5 Production Processes for HDPE and LLDPE 789
6.20.6 PE Production Economics and Modern Developments in PE Production 792
6.21 Titanium Dioxide 793
6.21.1 Production and Use of Titanium Dioxide (Overview) 793
6.21.2 Sulfate Process for Production of Titanium Dioxide 793
6.21.3 Chloride Process for Production of Titanium Dioxide 795
6.22 Silicon 796
6.22.1 Production and Use of Silicon (Overview) 796
6.22.2 Carbothermic Reduction of Silica 797
6.22.3 Refining, Casting, and Crushing of Metallurgical Grade Silicon 798
6.22.4 Economics of the Metallurgical Grade Silicon Production 798
6.22.5 Production of Photovoltaic Grade Silicon by Purification of Metallurgical Grade Silicon 798
6.23 Polytetrafluoroethylene (PTFE) 801
6.23.1 Production and Use of PTFE (Overview) 801
6.23.2 Process for Production of PTFE 802
6.23.3 Treatment of PTFE Waste 802
6.24 Production of Amino Acids by Fermentation 807
6.24.1 General Aspects 807
6.24.2 Overview of the Methods Applied for Industrial Amino Acid Production 807
6.24.3 Amino Acid Fermentation 810
References 815
Index 841
