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Chemical Process Design and Integration
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Preface xiii Acknowledgements xv Nomenclature xvii 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 References 58 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 SteamSystems andCogeneration - 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

About the Author

Professor Robin Smith is Head of the Centre for Process Integration at the University of Manchester Institute of Science and Technology (UMIST) in the United Kingdom. Before joining UMIST he had extensive industrial experience with Rohm & Haas in process investigation and process design, and with ICI in computer-aided design and process integration. He was a member of the ICI Process Integration Team that pioneered the first industrial applications of process integration design methods. Since joining UMIST he has acted extensively as a consultant in process integration projects. He has published widely in the field of chemical process design and integration, and is a Fellow of the Royal Academy of Engineering, a Fellow of the Institution of Chemical Engineers in the UK and a chartered engineer. In 1992 he was awarded the Hanson Medal of the Institution of Chemical Engineers in the UK for his work on clean process technology.

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