Chemical Process Technology

JACOB A. MOULIJN, MICHIEL MAKKEE and ANNELIES E. VAN DIEPENCatalysis Engineering, Delft University of Technology, The Netherlands

“In conclusion, this excellent textbook is highly recommended to those readers wishing to have up-to-date knowledge of the chemical industry and its processes. Organic chemists, in particular, will learn the chemical engineer’s approach to process design and process development and will appreciate the differences and hopefully understand how the methods used for bulk chemicals can be used for more complex molecules book.”  (Organic Process Research & Development, 1 September 2014)“The book could serve as a valuable text for lower-level chemical engineering students, but it could also be useful to professionals in biotechnology and industrial chemistry.  Summing Up: Recommended.  All academic, two-year technical program, and professional engineering collections.”  (Choice, 1 December 2013)

• Preface xiii1 Introduction 1References 6General Literature 62 The Chemical Industry 72.1 A Brief History 72.1.1 Inorganic Chemicals 72.1.2 Organic Chemicals 102.1.3 The Oil Era 112.1.4 The Age of Sustainability 122.2 Structure of the Chemical Industry 132.3 Raw Materials and Energy 162.3.1 Fossil Fuel Consumption and Reserves 162.3.2 Biomass as an Alternative for Fossil Fuels 192.3.3 Energy and the Chemical Industry 212.3.4 Composition of Fossil Fuels and Biomass 232.4 Base Chemicals 352.5 Global Trends in the Chemical Industry 37References 39General Literature 403 Processes in the Oil Refinery 413.1 The Oil Refinery − An Overview 413.2 Physical Processes 423.2.1 Desalting and Dehydration 423.2.2 Crude Distillation 433.2.3 Propane Deasphalting 453.3 Thermal Processes 463.3.1 Visbreaking 463.3.2 Delayed Coking 473.3.3 Flexicoking 483.4 Catalytic Processes 493.4.1 Octane and Cetane Numbers 493.4.2 Catalytic Cracking 513.4.3 Catalytic Reforming 633.4.4 Alkylation 693.4.5 Hydroprocessing 763.5 Current and Future Trends in Oil Refining 913.5.1 Stricter Environmental Regulations 923.5.2 Refinery Configurations 94References 964 Production of Light Alkenes 994.1 Introduction 994.2 Cracking Reactions 1004.2.1 Thermodynamics 1004.2.2 Mechanism 1014.2.3 Kinetics 1024.3 The Industrial Process 1034.3.1 Influence of Feedstock on Steam Cracker Operation and Products 1034.3.2 Cracking Furnace 1064.3.3 Heat Exchanger 1094.3.4 Coke Formation 1104.4 Product Processing 1114.5 Novel Developments 1134.5.1 Selective Dehydrogenation of Light Alkanes 1144.5.2 Metathesis of Alkenes 1164.5.3 Production of Light Alkenes from Synthesis Gas 1184.5.4 Dehydration of Bioethanol 1214.5.5 Direct Conversion of Methane 122References 1235 Production of Synthesis Gas 1275.1 Introduction 1275.2 Synthesis Gas from Natural Gas 1295.2.1 Reactions and Thermodynamics 1295.2.2 Steam Reforming Process 1315.2.3 Autothermal Reforming Process 1375.2.4 Novel Developments 1395.3 Coal Gasification 1425.3.1 Gasification Reactions 1425.3.2 Thermodynamics 1435.3.3 Gasification Technologies 1465.3.4 Recent Developments in Gasification Technology 1515.3.5 Applications of Coal Gasification 1545.3.6 Integrated Gasification Combined Cycle 1565.3.7 Why Gasify, Not Burn for Electricity Generation? 1585.3.8 Carbon Capture and Storage (CCS) 1595.4 Cleaning and Conditioning of Synthesis Gas 1615.4.1 Acid Gas Removal 1615.4.2 Water–Gas Shift Reaction 1635.4.3 Methanation 166References 1686 Bulk Chemicals and Synthetic Fuels Derived from Synthesis Gas 1716.1 Ammonia 1716.1.1 Background Information 1716.1.2 Thermodynamics 1736.1.3 Commercial Ammonia Synthesis Reactors 1756.1.4 Ammonia Synthesis Loop 1786.1.5 Integrated Ammonia Plant 1806.1.6 Hydrogen Recovery 1826.1.7 Production of Urea 1856.2 Methanol 1916.2.1 Background Information 1916.2.2 Reactions, Thermodynamics, and Catalysts 1926.2.3 Synthesis Gas for Methanol Production 1956.2.4 Methanol Synthesis 1966.2.5 Production of Formaldehyde 1996.3 Synthetic Fuels and Fuel Additives 2016.3.1 Fischer–Tropsch Process 2026.3.2 Methanol-to-Gasoline (MTG) Process 2126.3.3 Recent Developments in the Production of Synthetic Fuels 2146.3.4 Fuel Additives − Methyl Tert-Butyl Ether 215References 2187 Processes for the Conversion of Biomass 2217.1 Introduction 2217.2 Production of Biofuels 2237.2.1 Bioethanol and Biobutanol 2247.2.2 Diesel-Type Biofuels 2267.3 Production of Bio-based Chemicals 2317.3.1 Ethanol 2327.3.2 Glycerol 2337.3.3 Succinic Acid 2347.3.4 Hydroxymethylfurfural (HMF) 2367.4 The Biorefinery 2367.4.1 Biorefinery Design Criteria and Products 2367.4.2 Biorefinery Concepts 2387.4.3 Core Technologies of a Thermochemical Biorefinery 2397.4.4 Existing and Projected Biorefineries 2437.4.5 Possibility of Integrating a Biorefinery with Existing Plants 2437.4.6 Biorefinery versus Oil Refinery 2457.5 Conclusions 246References 2468 Inorganic Bulk Chemicals 2498.1 The Inorganic Chemicals Industry 2498.2 Sulfuric Acid 2508.2.1 Reactions and Thermodynamics 2528.2.2 SO 2 Conversion Reactor 2528.2.3 Modern Sulfuric Acid Production Process 2548.2.4 Catalyst Deactivation 2568.3 Sulfur Production 2568.4 Nitric Acid 2608.4.1 Reactions and Thermodynamics 2608.4.2 Processes 2628.4.3 No X Abatement 2668.5 Chlorine 2688.5.1 Reactions for the Electrolysis of NaCl 2698.5.2 Technologies for the Electrolysis of NaCl 270References 2749 Homogeneous Transition Metal Catalysis in the Production of Bulk Chemicals 2759.1 Introduction 2759.2 Acetic Acid Production 2789.2.1 Background Information 2789.2.2 Methanol Carbonylation – Reactions, Thermodynamics, and Catalysis 2819.2.3 Methanol Carbonylation – Processes 2849.3 Hydroformylation 2869.3.1 Background Information 2869.3.2 Thermodynamics 2889.3.3 Catalyst Development 2899.3.4 Processes for the Hydroformylation of Propene 2929.3.5 Processes for the Hydroformylation of Higher Alkenes 2949.3.6 Comparison of Hydroformylation Processes 2969.4 Ethene Oligomerization and More 2979.4.1 Background Information 2979.4.2 Reactions of the SHOP Process 2989.4.3 The SHOP Process 2999.5 Oxidation of p-Xylene: Dimethyl Terephthalate and Terephthalic Acid Production 3019.5.1 Background Information 3019.5.2 Conversion of p-Toluic Acid Intermediate 3029.5.3 Processes 3039.5.4 Process Comparison 3059.6 Review of Reactors Used in Homogeneous Catalysis 3059.6.1 Choice of Reactor 3069.6.2 Exchanging Heat 3089.7 Approaches for Catalyst/Product Separation 3089.7.1 Biphasic Catalyst Systems 3099.7.2 Immobilized Catalyst Systems 309References 31110 Heterogeneous Catalysis – Concepts and Examples 31310.1 Introduction 31310.2 Catalyst Design 31410.2.1 Catalyst Size and Shape 31410.2.2 Mechanical Properties of Catalyst Particles 31610.3 Reactor Types and Their Characteristics 31610.3.1 Reactor Types 31610.3.2 Exchanging Heat 31910.3.3 Role of Catalyst Deactivation 32110.3.4 Other Issues 32210.4 Shape Selectivity − Zeolites 32310.4.1 Production of Isobutene 32510.4.2 Isomerization of Pentanes and Hexanes 32810.4.3 Production of Ethylbenzene 33010.5 Some Challenges and (Unconventional) Solutions 33410.5.1 Adiabatic Reactor with Periodic Flow Reversal 33410.5.2 Highly Exothermic Reactions with a Selectivity Challenge − Selective Oxidations 33810.6 Monolith Reactors − Automotive Emission Control 34410.6.1 Exhaust Gas Composition 34610.6.2 Reduction of Exhaust Gas Emissions 347References 354General Literature 35511 Production of Polymers − Polyethene 35711.1 Introduction 35711.2 Polymerization Reactions 35711.2.1 Step growth Polymerization 35811.2.2 Chain growth Polymerization − Radical and Coordination Pathways 36011.3 Polyethenes – Background Information 36311.3.1 Catalyst Development 36311.3.2 Classification and Properties 36411.3.3 Applications 36511.4 Processes for the Production of Polyethenes 36611.4.1 Monomer Production and Purification 36611.4.2 Polymerization – Exothermicity 36711.4.3 Production of Polyethenes 367References 37512 Production of Fine Chemicals 37712.1 Introduction 37712.2 Role of Catalysis 38012.2.1 Atom Economy 38012.2.2 Alternative Reagents and Catalysts 38112.2.3 Novel Reaction Routes 38412.2.4 Selectivity 38412.2.5 Biocatalysis 39212.3 Solvents 39412.3.1 Conventional Solvents 39412.3.2 Alternative Solvents 39512.4 Production Plants 39812.4.1 Multiproduct and Multipurpose Plants (MMPs) 39812.4.2 Dedicated Continuous Plants 40612.5 Batch Reactor Selection 40712.5.1 Reactors for Liquid and Gas–Liquid Systems 40812.5.2 Reactors for Gas–Liquid–Solid Systems 40912.6 Batch Reactor Scale-up Effects 41112.6.1 Temperature Control 41112.6.2 Heat Transfer 41112.6.3 Example of the Scale-up of a Batch and Semi-Batch Reactor 41212.6.4 Summary of the Scale-up of Batch Reactors 41612.7 Safety Aspects of Fine Chemicals 41612.7.1 Thermal Risks 41612.7.2 Safety and Process Development 417References 41913 Biotechnology 42313.1 Introduction 42313.2 Principles of Fermentation Technology 42413.2.1 Mode of Operation 42513.2.2 Reactor Types 42613.2.3 Sterilization 43213.3 Cell Biomass − Bakers’ Yeast Production 43313.3.1 Process Layout 43313.3.2 Cultivation Equipment 43413.3.3 Downstream Processing 43413.4 Metabolic Products − Biomass as Source of Renewable Energy 43513.4.1 Bioethanol and Biobutanol 43513.4.2 Biogas 43813.5 Environmental Application – Wastewater Treatment 43813.5.1 Introduction 43813.5.2 Process Layout 43813.5.3 Aerobic Treatment Processes 44013.5.4 Anaerobic Treatment Processes 44313.6 Enzyme Technology – Biocatalysts for Transformations 44513.6.1 General Aspects 44513.6.2 Immobilization of Enzymes 44613.6.3 Production of L-Amino Acids 44713.6.4 Production of Artificial Sweeteners 448References 452General Literature 45314 Process Intensification 45514.1 Introduction 45514.1.1 What is Process Intensification 45514.1.2 How to Intensify Processes 45714.2 Structured Catalytic Reactors 45914.2.1 Types of Structured Catalysts and Reactors 46014.2.2 Monoliths 46214.2.3 Microreactors 46814.3 Multifunctional Reactors/Reactive Separation 47214.3.1 Reactive Distillation 47314.3.2 Coupling Reaction and Membrane Separation 47714.3.3 Coupling Reaction and Adsorption 481References 48215 Process Development 48515.1 Dependence of Strategy on Product Type and Raw Materials 48515.2 The Course of Process Development 48715.3 Development of Individual Steps 48915.3.1 Exploratory Phase 48915.3.2 From Process Concept to Preliminary Flow Sheet 48915.3.3 Pilot Plants/Miniplants 49415.4 Scale-up 49915.4.1 Reactors with a Single Fluid Phase 49915.4.2 Fixed Bed Catalytic Reactors with One or More Fluid Phases 50115.5 Safety and Loss Prevention 50515.5.1 Safety Issues 50515.5.2 Reactivity Hazards 51115.5.3 Design Approaches to Safety 51315.6 Process Evaluation 51415.6.1 Capital Cost Estimation 51515.6.2 Operating Costs and Earnings 52315.6.3 Profitability Measures 52415.7 Current and Future Trends 526References 528General Literature 529Magazines 529Appendix A Chemical Industry − Figures 531Appendix B Main Symbols Used in Flow Schemes 535Index 539