Smith - Chemical Process Design and Integration

Preface xiii

Acknowledgements xv

Nomenclature xvii

References 58

1 The Nature of Chemical Process Design and Integration 1

1.1 Chemical Products 1

1.2 Formulation of Design Problems 3

1.3 Synthesis and Simulation 4

1.4 The Hierarchy of Chemical Process Design and Integration 6

1.5 Continuous and Batch Processes 8

1.6 New Design and Retrofit 11

1.7 Reliability, Availability and Maintainability 11

1.8 Process Control 12

1.9 Approaches to Chemical Process Design and Integration 13

1.10 The Nature of Chemical Process Design and Integration – Summary 16

References 17

2 Process Economics 19

2.1 The Role of Process Economics 19

2.2 Capital Cost for New Design 19

2.3 Capital Cost for Retrofit 25

2.4 Annualized Capital Cost 26

2.5 Operating Cost 27

2.6 Simple Economic Criteria 30

2.7 Project Cash Flow and Economic Evaluation 31

2.8 Investment Criteria 33

2.9 Process Economics–Summary 34

2.10 Exercises 34

References 36

3 Optimization 37

3.1 Objective Functions 37

3.2 Single-Variable Optimization 40

3.3 Multivariable Optimization 42

3.4 Constrained Optimization 45

3.5 Linear Programming 47

3.6 Nonlinear Programming 49

3.7 Structural Optimization 50

3.8 Solution of Equations Using Optimization 54

3.9 The Search for Global Optimality 55

3.10 Optimization – Summary 56

3.11 Exercises 56

4 Chemical Reactors I – Reactor Performance 59

4.1 Reaction Path 59

4.2 Types of Reaction Systems 61

4.3 Measures of Reactor Performance 63

4.4 Rate of Reaction 64

4.5 Idealized Reactor Models 65

4.6 Choice of Idealized Reactor Model 73

4.7 Choice of Reactor Performance 76

4.8 Reactor Performance – Summary 77

4.9 Exercises 78

References 79

5 Chemical Reactors II – Reactor Conditions 81

5.1 Reaction Equilibrium 81

5.2 Reactor Temperature 85

5.3 Reactor Pressure 92

5.4 Reactor Phase 93

5.5 Reactor Concentration 94

5.6 Biochemical Reactions 99

5.7 Catalysts 99

5.8 Reactor Conditions – Summary 102

5.9 Exercises 103

References 105

6 Chemical Reactors III – Reactor Configuration 107

6.1 Temperature Control 107

6.2 Catalyst Degradation 111

6.3 Gas–Liquid and Liquid–Liquid Reactors 112

6.4 Reactor Configuration 116

6.5 Reactor Configuration For Heterogeneous Solid-Catalyzed Reactions 121

6.6 Reactor Configuration – Summary 122

6.7 Exercises 122

References 123

7 Separation of Heterogeneous Mixtures 125

7.1 Homogeneous and Heterogeneous Separation 125

7.2 Settling and Sedimentation 126

7.3 Inertial and Centrifugal Separation 130

7.4 Electrostatic Precipitation 131

7.5 Filtration 133

7.6 Scrubbing 134

7.7 Flotation 135

7.8 Drying 136

7.9 Separation of Heterogeneous Mixtures – Summary 137

7.10 Exercises 137

References 138

8 Separation of Homogeneous Fluid Mixtures I – Distillation 139

8.1 Vapor–Liquid Equilibrium 139

8.2 Calculation of Vapor-Liquid Equilibrium 141

8.3 Single-Stage Separation 146

8.4 Distillation 146

8.5 Binary Distillation 150

8.6 Total and Minimum Reflux Conditions for Multicomponent Mixtures 155

8.7 Finite Reflux Conditions for Multicomponent Mixtures 162

8.8 Column Dimensions 164

8.9 Conceptual Design of Distillation 174

8.10 Detailed Design of Distillation 176

8.11 Limitations of Distillation 179

8.12 Separation of Homogeneous Fluid Mixtures by Distillation – Summary 180

8.13 Exercises 180

References 183

9 Separation of Homogeneous Fluid Mixtures II – Other Methods 185

9.1 Absorption and Stripping 185

9.2 Liquid–Liquid Extraction 189

9.3 Adsorption 196

9.4 Membranes 199

9.5 Crystallization 211

9.6 Evaporation 215

9.7 Separation of Homogeneous Fluid Mixtures by Other Methods – Summary 217

9.8 Exercises 217

References 219

10 Distillation Sequencing 221

10.1 Distillation Sequencing using Simple Columns 221

10.2 Practical Constraints Restricting Options 221

10.3 Choice of Sequence for Simple Nonintegrated Distillation Columns 222

10.4 Distillation Sequencing using Columns With More Than Two Products 229

10.5 Distillation Sequencing using Thermal Coupling 231

10.6 Retrofit of Distillation Sequences 236

10.7 Crude Oil Distillation 237

10.8 Structural Optimization of Distillation Sequences 239

10.9 Distillation Sequencing – Summary 242

10.10 Exercises 242

References 245

11 Distillation Sequencing for Azeotropic Distillation 247

11.1 Azeotropic Systems 247

11.2 Change in Pressure 247

11.3 Representation of Azeotropic Distillation 248

11.4 Distillation at Total Reflux Conditions 250

11.5 Distillation at Minimum Reflux Conditions 255

11.6 Distillation at Finite Reflux Conditions 256

11.7 Distillation Sequencing Using an Entrainer 259

11.8 Heterogeneous Azeotropic Distillation 264

11.9 Entrainer Selection 267

11.10 Multicomponent Systems 270

11.11 Trade-Offs in Azeotropic Distillation 270

11.12 Membrane Separation 270

11.13 Distillation Sequencing for Azeotropic Distillation – Summary 271

11.14 Exercises 272

References 273

12 Heat Exchange 275

12.1 Overall Heat Transfer Coefficients 275

12.2 Heat Exchanger Fouling 279

12.3 Temperature Differences in Shell-and-Tube Heat Exchangers 281

12.4 Heat Exchanger Geometry 288

12.5 Allocation of Fluids in Shell-and-Tube Heat Exchangers 294

12.6 Heat Transfer Coefficients and Pressure Drops in Shell-and-Tube Heat Exchangers 294

12.7 Rating and Simulation of Heat Exchangers 301

12.8 Heat Transfer Enhancement 307

12.9 Retrofit of Heat Exchangers 313

12.10 Condensers 316

12.11 Reboilers and Vaporizers 321

12.12 Other Types of Heat Exchangers 326

12.13 Fired Heaters 328

12.14 Heat Exchange – Summary 345

12.15 Exercises 346

References 348

13 Pumping and Compression 349

13.1 Pressure Drops in Process Operations 349

13.2 Pressure Drops in Piping Systems 349

13.3 Pump Types 355

13.4 Centrifugal Pump Performance 356

13.5 Compressor Types 363

13.6 Reciprocating Compressors 366

13.7 Dynamic Compressors 367

13.8 Staged Compression 369

13.9 Compressor Performance 370

13.10 Process Expanders 372

13.11 Pumping and Compression –

Summary 374

13.12 Exercises 374

References 375

14 Continuous Process Recycle Structure 377

14.1 The Function of Process Recycles 377

14.2 Recycles with Purges 382

14.3 Hybrid Reaction and Separation 385

14.4 The Process Yield 386

14.5 Feed, Product and Intermediate Storage 388

14.6 Continuous Process Recycle Structure – Summary 389

14.7 Exercises 389

References 391

15 Continuous Process Simulation and Optimization 393

15.1 Physical Property Models for Process Simulation 393

15.2 Unit Models for Process Simulation 394

15.3 Flowsheet Models 400

15.4 Simulation of Recycles 400

15.5 Convergence of Recycles 402

15.6 Design Specifications 408

15.7 Flowsheet Sequencing 408

15.8 Model Validation 408

15.9 Process Optimization 408

15.10 Continuous Process Simulation and Optimization – Summary 413

15.11 Exercises 413

References 416

16 Batch Processes 417

16.1 Characteristics of Batch Processes 417

16.2 Batch Reactors 417

16.3 Batch Distillation 420

16.4 Batch Crystallization 431

16.5 Batch Filtration 432

16.6 Batch Heating and Cooling 433

16.7 Optimization of Batch Operations 436

16.8 Gantt Charts 442

16.9 Production Schedules for Single Products 442

16.10 Production Schedules for Multiple Products 444

16.11 Equipment Cleaning and Material Transfer 445

16.12 Synthesis of Reaction and Separation Systems for Batch Processes 446

16.13 Storage in Batch Processes 452

16.14 Batch Processes – Summary 452

16.15 Exercises 452

References 455

17 Heat Exchanger Networks I – Network Targets 457

17.1 Composite Curves 457

17.2 The Heat Recovery Pinch 461

17.3 Threshold Problems 464

17.4 The Problem Table Algorithm 466

17.5 Non-global Minimum Temperature Differences 472

17.6 Process Constraints 473

17.7 Utility Selection 475

17.8 Furnaces 477

17.9 Cogeneration (Combined Heat and Power Generation) 480

17.10 Integration of Heat Pumps 485

17.11 Number of Heat Exchange Units 486

17.12 Heat Exchange Area Targets 489

17.13 Sensitivity of Targets 493

17.14 Capital and Total Cost Targets 493

17.15 Heat Exchanger Network Targets –

Summary 496

17.16 Exercises 496

References 499

18 Heat Exchanger Networks II – Network Design 501

18.1 The Pinch Design Method 501

18.2 Design for Threshold Problems 507

18.3 Stream Splitting 507

18.4 Design for Multiple Pinches 511

18.5 Remaining Problem Analysis 516

18.6 Simulation of Heat Exchanger Networks 518

18.7 Optimization of a Fixed Network Structure 520

18.8 Automated Methods of Heat Exchanger Network Design 523

18.9 Heat Exchanger Network Retrofit with a Fixed Network Structure 525

18.10 Heat Exchanger Network Retrofit through Structural Changes 530

18.11 Automated Methods of Heat Exchanger Network Retrofit 536

18.12 Heat Exchanger Network Design –

Summary 538

18.13 Exercises 539

References 542

19 Heat Exchanger Networks III – Stream Data 543

19.1 Process Changes for Heat Integration 543

19.2 The Trade-Offs Between Process Changes, Utility Selection, Energy Cost and Capital Cost 543

19.3 Data Extraction 544

19.4 Heat Exchanger Network Stream Data – Summary 551

19.5 Exercises 551

References 553

20 Heat Integration of Reactors 555

20.1 The Heat Integration Characteristics of Reactors 555

20.2 Appropriate Placement of Reactors 557

20.3 Use of the Grand Composite Curve for Heat Integration of Reactors 558

20.4 Evolving Reactor Design to Improve Heat Integration 560

20.5 Heat Integration of Reactors – Summary 561

20.6 Exercises 561

Reference 561

21 Heat Integration of Distillation 563

21.1 The Heat Integration Characteristics of Distillation 563

21.2 The Appropriate Placement of Distillation 563

21.3 Use of the Grand Composite Curve for Heat Integration of Distillation 564

21.4 Evolving the Design of Simple Distillation Columns to Improve Heat Integration 564

21.5 Heat Pumping in Distillation 567

21.6 Capital Cost Considerations for the Integration of Distillation 567

21.7 Heat Integration Characteristics of Distillation Sequences 568

21.8 Design of Heat Integrated Distillation Sequences 571

21.9 Heat Integration of Distillation – Summary 572

21.10 Exercises 572

References 575

22 Heat Integration of Evaporators and Dryers 577

22.1 The Heat Integration Characteristics of Evaporators 577

22.2 Appropriate Placement of Evaporators 577

22.3 Evolving Evaporator Design to Improve Heat Integration 577

22.4 The Heat Integration Characteristics of Dryers 579

22.5 Evolving Dryer Design to Improve Heat Integration 579

22.6 A Case Study 581

22.7 Heat Integration of Evaporators and Dryers – Summary 581

22.8 Exercises 582

References 582

23 Steam Systems and Cogeneration 583

23.1 Boiler Feedwater Treatment 585

23.2 Steam Boilers 589

23.3 Gas Turbines 595

23.4 Steam Turbines 602

23.5 Steam Distrubution 609

23.6 Site Composite Curves 612

23.7 Cogeneration Targets 623

23.8 Power Generation and Machine Drives 627

23.9 Utility Simulation 631

23.10 Optimizing Steam Systems 633

23.11 Steam Costs 638

23.12 Steam Systems and Cogeneration – Summary 641

23.13 Exercises 642

References 645

24 Cooling and Refrigeration Systems 647

24.1 Cooling Systems 647

24.2 Once-Through Water Cooling 647

24.3 Recirculating Cooling Water Systems 647

24.4 Air Coolers 650

24.5 Refrigeration 656

24.6 Choice of a Single-Component Refrigerant for Compression Refrigeration 662

24.7 Targeting Refrigeration Power for Pure Component Compression Refrigeration 665

24.8 Heat Integration of Pure Component Compression Refrigeration Processes 669

24.9 Mixed Refrigerants for Compression Refrigeration 673

24.10 Expanders 677

24.11 Absorption Refrigeration 681

24.12 Indirect Refrigeration 682

24.13 Cooling Water and Refrigeration Systems – Summary 682

24.14 Exercises 683

References 685

25 Environmental Design for Atmospheric Emissions 687

25.1 Atmospheric Pollution 687

25.2 Sources of Atmospheric Pollution 688

25.3 Control of Solid Particulate Emissions to Atmosphere 690

25.4 Control of VOC Emissions 690

25.5 Control of Sulfur Emissions 703

25.6 Control of Oxides of Nitrogen Emissions 708

25.7 Control of Combustion Emissions 711

25.8 Atmospheric Dispersion 714

25.9 Environmental Design for Atmospheric Emissions – Summary 716

25.10 Exercises 717

References 720

26 Water System Design 721

26.1 Aqueous Contamination 724

26.2 Primary Treatment Processes 725

26.3 Biological Treatment Processes 729

26.4 Tertiary Treatment Processes 732

26.5 Water Use 733

26.6 Targeting for Maximum Water Reuse for Single Contaminants for Operations with Fixed Mass Loads 735

26.7 Design for Maximum Water Reuse for Single Contaminants for Operations with Fixed Mass Loads 737

26.8 Targeting for Maximum Water Reuse for Single Contaminants for Operations with Fixed Flowrates 747

26.9 Design for Maximum Water Reuse for Single Contaminants for Operations with Fixed Flowrates 751

26.10 Targeting and Design for Maximum Water Reuse Based on Optimization of a Superstructure 758

26.11 Process Changes for Reduced Water Consumption 760

26.12 Targeting for Minimum Wastewater Treatment Flowrate for Single Contaminants 761

26.13 Design for Minimum Wastewater Treatment Flowrate for Single Contaminants 765

26.14 Regeneration of Wastewater 767

26.15 Targeting and Design for Effluent Treatment and Regeneration Based on Optimization of a Superstructure 772

26.16 Data Extraction 773

26.17 Water System Design – Summary 775

26.18 Exercises 776

References 779

27 Environmental Sustainability in Chemical Production 781

27.1 Life Cycle Assessment 781

27.2 Efficient Use of Raw Materials Within Processes 786

27.3 Efficient Use of Raw Materials Between Processes 792

27.4 Exploitation of Renewable Raw Materials 794

27.5 Efficient Use of Energy 795

27.6 Integration of Waste Treament and Energy Sytems 805

27.7 Renewable Energy 806

27.8 Efficient Use of Water 807

27.9 Sustainability in Chemical Production – Summary 807

27.10 Exercises 808

References 809

28 Process Safety 811

28.1 Fire 811

28.2 Explosion 812

28.3 Toxic Release 813

28.4 Hazard Identification 813

28.5 The Hierarchy of Safety Management 815

28.6 Inherently Safer Design 815

28.7 Layers of Protection 819

28.8 Hazard and Operability Studies 822

28.9 Layer of Protection Analysis 823

28.10 Process Safety – Summary 823

28.11 Exercises 824

References 825

Appendix A Physical Properties in Process Design 827

A. 1 Equations of State 827

A. 2 Phase Equilibrium for Single Components 831

A. 3 Fugacity and Phase Equilibrium 831

A. 4 Vapor–Liquid Equilibrium 831

A. 5 Vapor–Liquid Equilibrium Based on Activity Coefficient Models 833

A. 6 Group Contribution Methods for Vapor–Liquid Equilibrium 835

A. 7 Vapor–Liquid Equilibrium Based on Equations of State 837

A. 8 Calculation of Vapor–Liquid Equilibrium 838

A. 9 Liquid–Liquid Equilibrium 841

A. 10 Liquid–Liquid Equilibrium Activity Coefficient Models 842

A. 11 Calculation of Liquid–Liquid Equilibrium 842

A. 12 Choice of Method for Equilibrium Calculations 844

A. 13 Calculation of Enthalpy 846

A. 14 Calculation of Entropy 847

A. 15 Other Physical Properties 848

A. 16 Physical Properties in Process Design – Summary 850

A. 17 Exercises 851

References 852

Appendix B Materials of Construction 853

B.1 Mechanical Properties 853

B.2 Corrosion 854

B.3 Corrosion Allowance 855

B.4 Commonly Used Materials of Construction 855

B.5 Criteria for Selection 859

B.6 Materials of Construction – Summary 860

References 860

Appendix C Annualization of Capital Cost 861

Reference 861

Appendix D The Maximum Thermal Effectiveness for 1–2 Shell-and-Tube Heat Exchangers 863

References 863

Appendix E Expression for the Minimum Number of 1–2 Shell-and-Tube Heat Exchangers for a Given Unit 865

References 866

Appendix F Heat Transfer Coefficient and Pressure Drop in Shell-and-Tube Heat Exchangers 867

F.1 Heat Transfer and Pressure Drop Correlations for the Tube Side 867

F.2 Heat Transfer and Pressure Drop Correlations for the Shell Side 869

References 873

Appendix G Gas Compression Theory 875

G.1 Modeling Reciprocating Compressors 875

G.2 Modeling Dynamic Compressors 877

G.3 Staged Compression 877

References 879

Appendix H Algorithm for the Heat Exchanger Network Area Target 881

Index 883

Chemical Process Design and Integration

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