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Chemical Process Technology 2/e

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ÁöÀºÀÌ :  Mouljin
¹ßÇàÀÏ :  2013 ³â
ISBN :  9781444320251
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ÃâÆÇ»ç :  Wiley

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Future Energy
Process Intensification for Green Chemistry: Engineering Solutions for Sustainable Chemical Processing

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Chemical Process Technology brings together in one text, a variety of different processes, drawn from chemical and biotechnological disciplines. Readers are able to integrate knowledge of the basic disciplines, to understand the most important chemical processes and to apply this knowledge and understanding to industrial processes.

Features:
 A comprehensive balanced introduction
 Problems with their solutions to encourage a fuller understanding of the subject
 Many examples and case studies taken from a variety of modern industries
 Richly illustrated chapters, with many clearly developed flow diagrams and numerous

Author Biography: Jacob Moulijn, Michiel Makkee, Annelies van Diepen, Delft University of Technology

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JACOB A. MOULIJN, MICHIEL MAKKEE and ANNELIES E. VAN DIEPEN
Catalysis Engineering, Delft University of Technology, The Netherlands
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Preface xiii

1 Introduction 1

References 6

General Literature 6

2 The Chemical Industry 7

2.1 A Brief History 7

2.1.1 Inorganic Chemicals 7

2.1.2 Organic Chemicals 10

2.1.3 The Oil Era 11

2.1.4 The Age of Sustainability 12

2.2 Structure of the Chemical Industry 13

2.3 Raw Materials and Energy 16

2.3.1 Fossil Fuel Consumption and Reserves 16

2.3.2 Biomass as an Alternative for Fossil Fuels 19

2.3.3 Energy and the Chemical Industry 21

2.3.4 Composition of Fossil Fuels and Biomass 23

2.4 Base Chemicals 35

2.5 Global Trends in the Chemical Industry 37

References 39

General Literature 40

3 Processes in the Oil Refinery 41

3.1 The Oil Refinery − An Overview 41

3.2 Physical Processes 42

3.2.1 Desalting and Dehydration 42

3.2.2 Crude Distillation 43

3.2.3 Propane Deasphalting 45

3.3 Thermal Processes 46

3.3.1 Visbreaking 46

3.3.2 Delayed Coking 47

3.3.3 Flexicoking 48

3.4 Catalytic Processes 49

3.4.1 Octane and Cetane Numbers 49

3.4.2 Catalytic Cracking 51

3.4.3 Catalytic Reforming 63

3.4.4 Alkylation 69

3.4.5 Hydroprocessing 76

3.5 Current and Future Trends in Oil Refining 91

3.5.1 Stricter Environmental Regulations 92

3.5.2 Refinery Configurations 94

References 96

4 Production of Light Alkenes 99

4.1 Introduction 99

4.2 Cracking Reactions 100

4.2.1 Thermodynamics 100

4.2.2 Mechanism 101

4.2.3 Kinetics 102

4.3 The Industrial Process 103

4.3.1 Influence of Feedstock on Steam Cracker Operation and Products 103

4.3.2 Cracking Furnace 106

4.3.3 Heat Exchanger 109

4.3.4 Coke Formation 110

4.4 Product Processing 111

4.5 Novel Developments 113

4.5.1 Selective Dehydrogenation of Light Alkanes 114

4.5.2 Metathesis of Alkenes 116

4.5.3 Production of Light Alkenes from Synthesis Gas 118

4.5.4 Dehydration of Bioethanol 121

4.5.5 Direct Conversion of Methane 122

References 123

5 Production of Synthesis Gas 127

5.1 Introduction 127

5.2 Synthesis Gas from Natural Gas 129

5.2.1 Reactions and Thermodynamics 129

5.2.2 Steam Reforming Process 131

5.2.3 Autothermal Reforming Process 137

5.2.4 Novel Developments 139

5.3 Coal Gasification 142

5.3.1 Gasification Reactions 142

5.3.2 Thermodynamics 143

5.3.3 Gasification Technologies 146

5.3.4 Recent Developments in Gasification Technology 151

5.3.5 Applications of Coal Gasification 154

5.3.6 Integrated Gasification Combined Cycle 156

5.3.7 Why Gasify, Not Burn for Electricity Generation? 158

5.3.8 Carbon Capture and Storage (CCS) 159

5.4 Cleaning and Conditioning of Synthesis Gas 161

5.4.1 Acid Gas Removal 161

5.4.2 Water–Gas Shift Reaction 163

5.4.3 Methanation 166

References 168

6 Bulk Chemicals and Synthetic Fuels Derived from Synthesis Gas 171

6.1 Ammonia 171

6.1.1 Background Information 171

6.1.2 Thermodynamics 173

6.1.3 Commercial Ammonia Synthesis Reactors 175

6.1.4 Ammonia Synthesis Loop 178

6.1.5 Integrated Ammonia Plant 180

6.1.6 Hydrogen Recovery 182

6.1.7 Production of Urea 185

6.2 Methanol 191

6.2.1 Background Information 191

6.2.2 Reactions, Thermodynamics, and Catalysts 192

6.2.3 Synthesis Gas for Methanol Production 195

6.2.4 Methanol Synthesis 196

6.2.5 Production of Formaldehyde 199

6.3 Synthetic Fuels and Fuel Additives 201

6.3.1 Fischer–Tropsch Process 202

6.3.2 Methanol-to-Gasoline (MTG) Process 212

6.3.3 Recent Developments in the Production of Synthetic Fuels 214

6.3.4 Fuel Additives − Methyl Tert-Butyl Ether 215

References 218

7 Processes for the Conversion of Biomass 221

7.1 Introduction 221

7.2 Production of Biofuels 223

7.2.1 Bioethanol and Biobutanol 224

7.2.2 Diesel-Type Biofuels 226

7.3 Production of Bio-based Chemicals 231

7.3.1 Ethanol 232

7.3.2 Glycerol 233

7.3.3 Succinic Acid 234

7.3.4 Hydroxymethylfurfural (HMF) 236

7.4 The Biorefinery 236

7.4.1 Biorefinery Design Criteria and Products 236

7.4.2 Biorefinery Concepts 238

7.4.3 Core Technologies of a Thermochemical Biorefinery 239

7.4.4 Existing and Projected Biorefineries 243

7.4.5 Possibility of Integrating a Biorefinery with Existing Plants 243

7.4.6 Biorefinery versus Oil Refinery 245

7.5 Conclusions 246

References 246

8 Inorganic Bulk Chemicals 249

8.1 The Inorganic Chemicals Industry 249

8.2 Sulfuric Acid 250

8.2.1 Reactions and Thermodynamics 252

8.2.2 SO2 Conversion Reactor 252

8.2.3 Modern Sulfuric Acid Production Process 254

8.2.4 Catalyst Deactivation 256

8.3 Sulfur Production 256

8.4 Nitric Acid 260

8.4.1 Reactions and Thermodynamics 260

8.4.2 Processes 262

8.4.3 NOx Abatement 266

8.5 Chlorine 268

8.5.1 Reactions for the Electrolysis of NaCl 269

8.5.2 Technologies for the Electrolysis of NaCl 270

References 274

9 Homogeneous Transition Metal Catalysis in the Production of Bulk Chemicals 275

9.1 Introduction 275

9.2 Acetic Acid Production 278

9.2.1 Background Information 278

9.2.2 Methanol Carbonylation – Reactions, Thermodynamics, and Catalysis 281

9.2.3 Methanol Carbonylation – Processes 284

9.3 Hydroformylation 286

9.3.1 Background Information 286

9.3.2 Thermodynamics 288

9.3.3 Catalyst Development 289

9.3.4 Processes for the Hydroformylation of Propene 292

9.3.5 Processes for the Hydroformylation of Higher Alkenes 294

9.3.6 Comparison of Hydroformylation Processes 296

9.4 Ethene Oligomerization and More 297

9.4.1 Background Information 297

9.4.2 Reactions of the SHOP Process 298

9.4.3 The SHOP Process 299

9.5 Oxidation of p-Xylene: Dimethyl Terephthalate and Terephthalic Acid Production 301

9.5.1 Background Information 301

9.5.2 Conversion of p-Toluic Acid Intermediate 302

9.5.3 Processes 303

9.5.4 Process Comparison 305

9.6 Review of Reactors Used in Homogeneous Catalysis 305

9.6.1 Choice of Reactor 306

9.6.2 Exchanging Heat 308

9.7 Approaches for Catalyst/Product Separation 308

9.7.1 Biphasic Catalyst Systems 309

9.7.2 Immobilized Catalyst Systems 309

References 311

10 Heterogeneous Catalysis – Concepts and Examples 313

10.1 Introduction 313

10.2 Catalyst Design 314

10.2.1 Catalyst Size and Shape 314

10.2.2 Mechanical Properties of Catalyst Particles 316

10.3 Reactor Types and Their Characteristics 316

10.3.1 Reactor Types 316

10.3.2 Exchanging Heat 319

10.3.3 Role of Catalyst Deactivation 321

10.3.4 Other Issues 322

10.4 Shape Selectivity − Zeolites 323

10.4.1 Production of Isobutene 325

10.4.2 Isomerization of Pentanes and Hexanes 328

10.4.3 Production of Ethylbenzene 330

10.5 Some Challenges and (Unconventional) Solutions 334

10.5.1 Adiabatic Reactor with Periodic Flow Reversal 334

10.5.2 Highly Exothermic Reactions with a Selectivity Challenge − Selective Oxidations 338

10.6 Monolith Reactors − Automotive Emission Control 344

10.6.1 Exhaust Gas Composition 346

10.6.2 Reduction of Exhaust Gas Emissions 347

References 354

General Literature 355

11 Production of Polymers − Polyethene 357

11.1 Introduction 357

11.2 Polymerization Reactions 357

11.2.1 Step growth Polymerization 358

11.2.2 Chain growth Polymerization − Radical and Coordination Pathways 360

11.3 Polyethenes – Background Information 363

11.3.1 Catalyst Development 363

11.3.2 Classification and Properties 364

11.3.3 Applications 365

11.4 Processes for the Production of Polyethenes 366

11.4.1 Monomer Production and Purification 366

11.4.2 Polymerization – Exothermicity 367

11.4.3 Production of Polyethenes 367

References 375

12 Production of Fine Chemicals 377

12.1 Introduction 377

12.2 Role of Catalysis 380

12.2.1 Atom Economy 380

12.2.2 Alternative Reagents and Catalysts 381

12.2.3 Novel Reaction Routes 384

12.2.4 Selectivity 384

12.2.5 Biocatalysis 392

12.3 Solvents 394

12.3.1 Conventional Solvents 394

12.3.2 Alternative Solvents 395

12.4 Production Plants 398

12.4.1 Multiproduct and Multipurpose Plants (MMPs) 398

12.4.2 Dedicated Continuous Plants 406

12.5 Batch Reactor Selection 407

12.5.1 Reactors for Liquid and Gas–Liquid Systems 408

12.5.2 Reactors for Gas–Liquid–Solid Systems 409

12.6 Batch Reactor Scale-up Effects 411

12.6.1 Temperature Control 411

12.6.2 Heat Transfer 411

12.6.3 Example of the Scale-up of a Batch and Semi-Batch Reactor 412

12.6.4 Summary of the Scale-up of Batch Reactors 416

12.7 Safety Aspects of Fine Chemicals 416

12.7.1 Thermal Risks 416

12.7.2 Safety and Process Development 417

References 419

13 Biotechnology 423

13.1 Introduction 423

13.2 Principles of Fermentation Technology 424

13.2.1 Mode of Operation 425

13.2.2 Reactor Types 426

13.2.3 Sterilization 432

13.3 Cell Biomass − Bakers¡¯ Yeast Production 433

13.3.1 Process Layout 433

13.3.2 Cultivation Equipment 434

13.3.3 Downstream Processing 434

13.4 Metabolic Products − Biomass as Source of Renewable Energy 435

13.4.1 Bioethanol and Biobutanol 435

13.4.2 Biogas 438

13.5 Environmental Application – Wastewater Treatment 438

13.5.1 Introduction 438

13.5.2 Process Layout 438

13.5.3 Aerobic Treatment Processes 440

13.5.4 Anaerobic Treatment Processes 443

13.6 Enzyme Technology – Biocatalysts for Transformations 445

13.6.1 General Aspects 445

13.6.2 Immobilization of Enzymes 446

13.6.3 Production of L-Amino Acids 447

13.6.4 Production of Artificial Sweeteners 448

References 452

General Literature 453

14 Process Intensification 455

14.1 Introduction 455

14.1.1 What is Process Intensification 455

14.1.2 How to Intensify Processes 457

14.2 Structured Catalytic Reactors 459

14.2.1 Types of Structured Catalysts and Reactors 460

14.2.2 Monoliths 462

14.2.3 Microreactors 468

14.3 Multifunctional Reactors/Reactive Separation 472

14.3.1 Reactive Distillation 473

14.3.2 Coupling Reaction and Membrane Separation 477

14.3.3 Coupling Reaction and Adsorption 481

References 482

15 Process Development 485

15.1 Dependence of Strategy on Product Type and Raw Materials 485

15.2 The Course of Process Development 487

15.3 Development of Individual Steps 489

15.3.1 Exploratory Phase 489

15.3.2 From Process Concept to Preliminary Flow Sheet 489

15.3.3 Pilot Plants/Miniplants 494

15.4 Scale-up 499

15.4.1 Reactors with a Single Fluid Phase 499

15.4.2 Fixed Bed Catalytic Reactors with One or More Fluid Phases 501

15.5 Safety and Loss Prevention 505

15.5.1 Safety Issues 505

15.5.2 Reactivity Hazards 511

15.5.3 Design Approaches to Safety 513

15.6 Process Evaluation 514

15.6.1 Capital Cost Estimation 515

15.6.2 Operating Costs and Earnings 523

15.6.3 Profitability Measures 524

15.7 Current and Future Trends 526

References 528

General Literature 529

Magazines 529

Appendix A Chemical Industry − Figures 531

Appendix B Main Symbols Used in Flow Schemes 535

Index 539