Design of Separation Processes Contents Contributors ................................................................................ vii Preface ....................................................................................... ix Part 1. General Principles ........................................................ 1 1. Phase Equilibria ............................................................................ 3 1.1 Introduction ................................................................... 3 1.2 Thermodynamic Framework for Phase Equilibria .......... 4 1.3 Fugacity Coefficients .................................................... 12 1.4 Activity Coefficients ....................................................... 24 1.5 Vapor-Liquid Equilibria and Liquid-Liquid Equilibria ....................................................................... 34 1.6 Fluid-Solid Equilibrium .................................................. 45 1.7. High Pressure Vapor-Liquid Equilibria .......................... 51 1.8 Summary ...................................................................... 54 Notation .................................................................................. 54 References ............................................................................. 57 2. Mass Transfer Principles ............................................................... 60 2.1 Introduction ................................................................... 60 2.2 Conservation Laws ....................................................... 61 2.3 Molecular Diffusion ....................................................... 70 2.4 Mass Transfer in Turbulent Flow ................................... 100 2.5 Notation ........................................................................ 121 References ............................................................................. 123 3. Phase Segregation ........................................................................ 129 3.1 Basic Mechanisms and Analogies ................................. 129 3.2 Gas-Liquid Segregation ................................................ 132 3.3 Immiscible Liquid Segregation ...................................... 148 xiv Contents This page has been reformatted by Knovel to provide easier navigation. 3.4 Liquid-Solid Segregation ............................................... 157 3.5 Gas-Solid Segregation .................................................. 176 Notation .................................................................................. 193 References ............................................................................. 195 4. General Processing Considerations ............................................. 197 4.1 Methods of Operation ................................................... 197 4.2 Process Synthesis ........................................................ 204 4.3 Control of Separation Processes .................................. 218 4.4 Special Problems .......................................................... 220 References ............................................................................. 222 Part 2. Individual Separation Processes ................................ 227 5. Distillation ...................................................................................... 229 5.1 Introduction ................................................................... 229 5.2 Phase Equilibrium ......................................................... 231 5.3 Equilibrium Stages ........................................................ 238 5.4 Specification of Variables .............................................. 258 5.5 Special Distillations ....................................................... 261 5.6 Transfer Units ............................................................... 275 5.7 Tray-Type Distillation Columns ..................................... 276 5.8 Packed-Type Distillation Columns ................................ 295 5.9 Mass Transfer in Tray Columns .................................... 312 5.10 Mass Transfer in Packed Columns ............................... 323 5.11 Distillation Column Control ............................................ 328 Notation .................................................................................. 331 References ............................................................................. 335 6. Absorption and Stripping ............................................................... 340 6.1 Basic Concepts ............................................................. 340 6.2 Multistage Contactors ................................................... 354 6.3 Differential Contactors .................................................. 364 6.4 Predicting Contactor Performance ................................ 379 Notation .................................................................................. 400 References ............................................................................. 402 Contents xv This page has been reformatted by Knovel to provide easier navigation. 7. Extraction – Organic Chemicals Processing ................................ 405 7.1 Diffusion and Mass Transfer ......................................... 405 7.2 Equilibrium Considerations ........................................... 414 7.3 Stagewise and Differential Contacting Calculation Methods ........................................................................ 415 7.4 Stagewise Contact in Perforated Plate Columns ........... 432 7.5 Stagewise Contact in Mixer-Settlers ............................. 434 7.6 Mechanically Agitated Columns .................................... 438 7.7 Performance and Efficiency of Selected Contactors .................................................................... 441 7.8 Solvent and Process Selection ..................................... 445 Notation .................................................................................. 456 References ............................................................................. 461 8. Extraction – Metals Processing ..................................................... 467 8.1 Introduction ................................................................... 467 8.2 Extraction Chemistry and Reagents .............................. 467 8.3 Phase Equilibria ............................................................ 477 8.4 Extraction Kinetics ........................................................ 486 8.5 Contacting Equipment and Design Calculations ........... 490 8.6 Process Design and Engineering .................................. 495 8.7 Summary ...................................................................... 496 References ............................................................................. 496 9. Leaching – Metals Applications .................................................... 500 9.1 Introduction ................................................................... 500 9.2 Leaching Practice ......................................................... 504 9.3 Thermodynamics of Leaching ....................................... 522 9.4 Kinetics of Leaching ...................................................... 529 Notation .................................................................................. 536 References ............................................................................. 536 10. Leaching – Organic Materials ....................................................... 540 10.1 Definition of Process ..................................................... 540 10.2 Contacting Methods ...................................................... 540 10.3 Industrial Leaching Equipment ...................................... 541 xvi Contents This page has been reformatted by Knovel to provide easier navigation. 10.4 Products, Raw Materials, and Extraction Conditions ..................................................................... 550 10.5 Phase Equilibrium ......................................................... 550 10.6 Multistage Equilibrium Countercurrent Extraction ......... 550 10.7 Ficks's Laws ................................................................. 554 10.8 Unsteady-State Batch Extraction .................................. 555 10.9 Solute Diffusivities ........................................................ 557 10.10 Fixed Beds .................................................................... 558 10.11 Axial Dispersion and Flow Maldistribution ..................... 560 10.12 Superposition-Multistage Countercurrent Extraction ..................................................................... 563 10.13 Continuous Countercurrent Extraction .......................... 564 10.14 Diffusion Batteries Performance ................................... 566 10.15 Differential Extraction .................................................... 566 10.16 Reflux Extractors .......................................................... 566 10.17 Solubilization ................................................................ 567 10.18 Solvent Selection .......................................................... 567 10.19 Equipment Selection ..................................................... 568 10.20 Solids Feed Preparation ............................................... 568 10.21 Spent Solids Treatment ................................................ 569 10.22 Hydrodynamic Considerations ...................................... 569 10.23 Solid-Liquid Heat Exchange .......................................... 569 Notation .................................................................................. 570 References ............................................................................. 573 11. Crystallization Operations ............................................................. 578 11.1 Introductory Comments ................................................. 578 11.2 Fundamentals ............................................................... 580 11.3 Solution Crystallization ................................................. 606 11.4 Melt Crystallization ........................................................ 626 11.5 General Design and Operational Considerations .......... 635 Notation .................................................................................. 638 References ............................................................................. 639 General Bibliography .............................................................. 642 Contents xvii This page has been reformatted by Knovel to provide easier navigation. 12. Adsorption ..................................................................................... 644 12.1 Introduction ................................................................... 644 12.2 Adsorbents ................................................................... 645 12.3 Criteria for Adsorption Use ............................................ 653 12.4 Basic Adsorption Cycles ............................................... 654 12.5 Process Flowsheets ...................................................... 659 12.6 Selecting a Process ...................................................... 668 12.7 Process-Design Considerations .................................... 669 12.8 Future Directions for Adsorption Technology and Uses ............................................................................. 690 References ............................................................................. 691 13. Ion Exchange ................................................................................ 697 13.1 Principles of Ion Exchange ........................................... 697 13.2 Applications of Ion Exchange ........................................ 711 13.3 Equipment for Ion Exchange ......................................... 717 13.4 Recent Developments in Ion Exchange ........................ 726 Notation .................................................................................. 729 References ............................................................................. 730 14. Large-Scale Chromatography ....................................................... 733 14.1 Theory .......................................................................... 733 14.2 Scale-Up of Elution Chromatography ............................ 739 14.3 Countercurrent and Simulated Countercurrent Systems ........................................................................ 745 14.4 Hybrid Systems ............................................................. 751 14.5 Other Alternatives ......................................................... 753 14.6 System Comparisons .................................................... 756 Acknowledgment .................................................................... 756 References ............................................................................. 757 15. Separation Processes Based on Reversible Chemical Complexation ................................................................................ 760 Summary ................................................................................ 760 15.1 Introduction ................................................................... 761 15.2 Specific Examples ........................................................ 764 xviii Contents This page has been reformatted by Knovel to provide easier navigation. References ............................................................................. 772 16. Bubble and Foam Separations – Ore Flotation ............................ 775 16.1 Introduction ................................................................... 775 16.2 Flotation Techniques .................................................... 775 16.3 Physicochemical Principles ........................................... 779 16.4 Flotaids ......................................................................... 792 16.5 Variables in Flotation .................................................... 796 References ............................................................................. 800 17. Bubble and Foam Separations – Waste Treatment ..................... 806 17.1 Background .................................................................. 806 17.2 Theory of Separation .................................................... 809 17.3 Laboratory Studies ........................................................ 814 17.4 Role of Column Design ................................................. 818 17.5 Larger-Scale Studies .................................................... 818 17.6 Applications .................................................................. 822 17.7 Conclusions .................................................................. 822 References ............................................................................. 823 18. Ultrafiltration and Reverse Osmosis ............................................. 826 18.1 Ultrafiltration ................................................................. 826 18.2 Reverse Osmosis ......................................................... 836 References ............................................................................. 839 Bibliography ............................................................................ 839 19. Recent Advances in Liquid Membrane Technology ..................... 840 19.1 Introduction ................................................................... 840 19.2 General Description of Liquid Membranes .................... 840 19.3 Principles of Separation ................................................ 841 19.4 Practical Applications for Liquid Membranes ................. 845 19.5 Conclusions .................................................................. 858 References ............................................................................. 858 20. Separation of Gaseous Mixtures Using Polymer Membranes ................................................................................... 862 20.1 Introduction ................................................................... 862 Contents xix This page has been reformatted by Knovel to provide easier navigation. 20.2 General Design Procedures and Application Examples ...................................................................... 872 20.3 Measurement and Phenomenological Description of Gas Sorption and Transport in Polymers .................. 883 20.4 Fundamentals of Sorption and Transport Processes in Polymers ................................................. 896 20.5 Characterization of Asymmetric Membranes ................. 916 20.6 Modeling and Design Considerations ............................ 920 Notation .................................................................................. 944 References ............................................................................. 944 21. Membrane Processes – Dialysis and Electrodialysis ................... 954 21.1 Dialysis ......................................................................... 954 21.2 Electrodialysis ............................................................... 968 Notation for Section 21.1 ........................................................ 977 References ............................................................................. 978 22. Selection of a Separation Process ................................................ 982 22.1 Introduction ................................................................... 982 22.2 Initial Screening ............................................................ 982 22.3 Choosing the Base Case .............................................. 992 22.4 Process Simulation ....................................................... 992 22.5 Process Synthesis ........................................................ 993 Notation .................................................................................. 994 References ............................................................................. 995 Index .......................................................................................... 997
Contents
Contributors ................................................................................ vii
Preface ....................................................................................... ix
Part 1. General Principles ........................................................ 1
1. Phase Equilibria ............................................................................ 3
1.1 Introduction ................................................................... 3
1.2 Thermodynamic Framework for Phase Equilibria .......... 4
1.3 Fugacity Coefficients .................................................... 12
1.4 Activity Coefficients ....................................................... 24
1.5 Vapor-Liquid Equilibria and Liquid-Liquid
Equilibria ....................................................................... 34
1.6 Fluid-Solid Equilibrium .................................................. 45
1.7. High Pressure Vapor-Liquid Equilibria .......................... 51
1.8 Summary ...................................................................... 54
Notation .................................................................................. 54
References ............................................................................. 57
2. Mass Transfer Principles ............................................................... 60
2.1 Introduction ................................................................... 60
2.2 Conservation Laws ....................................................... 61
2.3 Molecular Diffusion ....................................................... 70
2.4 Mass Transfer in Turbulent Flow ................................... 100
2.5 Notation ........................................................................ 121
References ............................................................................. 123
3. Phase Segregation ........................................................................ 129
3.1 Basic Mechanisms and Analogies ................................. 129
3.2 Gas-Liquid Segregation ................................................ 132
3.3 Immiscible Liquid Segregation ...................................... 148
xiv Contents
This page has been reformatted by Knovel to provide easier navigation.
3.4 Liquid-Solid Segregation ............................................... 157
3.5 Gas-Solid Segregation .................................................. 176
Notation .................................................................................. 193
References ............................................................................. 195
4. General Processing Considerations ............................................. 197
4.1 Methods of Operation ................................................... 197
4.2 Process Synthesis ........................................................ 204
4.3 Control of Separation Processes .................................. 218
4.4 Special Problems .......................................................... 220
References ............................................................................. 222
Part 2. Individual Separation Processes ................................ 227
5. Distillation ...................................................................................... 229
5.1 Introduction ................................................................... 229
5.2 Phase Equilibrium ......................................................... 231
5.3 Equilibrium Stages ........................................................ 238
5.4 Specification of Variables .............................................. 258
5.5 Special Distillations ....................................................... 261
5.6 Transfer Units ............................................................... 275
5.7 Tray-Type Distillation Columns ..................................... 276
5.8 Packed-Type Distillation Columns ................................ 295
5.9 Mass Transfer in Tray Columns .................................... 312
5.10 Mass Transfer in Packed Columns ............................... 323
5.11 Distillation Column Control ............................................ 328
Notation .................................................................................. 331
References ............................................................................. 335
6. Absorption and Stripping ............................................................... 340
6.1 Basic Concepts ............................................................. 340
6.2 Multistage Contactors ................................................... 354
6.3 Differential Contactors .................................................. 364
6.4 Predicting Contactor Performance ................................ 379
Notation .................................................................................. 400
References ............................................................................. 402
Contents xv
7. Extraction – Organic Chemicals Processing ................................ 405
7.1 Diffusion and Mass Transfer ......................................... 405
7.2 Equilibrium Considerations ........................................... 414
7.3 Stagewise and Differential Contacting Calculation
Methods ........................................................................ 415
7.4 Stagewise Contact in Perforated Plate Columns ........... 432
7.5 Stagewise Contact in Mixer-Settlers ............................. 434
7.6 Mechanically Agitated Columns .................................... 438
7.7 Performance and Efficiency of Selected
Contactors .................................................................... 441
7.8 Solvent and Process Selection ..................................... 445
Notation .................................................................................. 456
References ............................................................................. 461
8. Extraction – Metals Processing ..................................................... 467
8.1 Introduction ................................................................... 467
8.2 Extraction Chemistry and Reagents .............................. 467
8.3 Phase Equilibria ............................................................ 477
8.4 Extraction Kinetics ........................................................ 486
8.5 Contacting Equipment and Design Calculations ........... 490
8.6 Process Design and Engineering .................................. 495
8.7 Summary ...................................................................... 496
References ............................................................................. 496
9. Leaching – Metals Applications .................................................... 500
9.1 Introduction ................................................................... 500
9.2 Leaching Practice ......................................................... 504
9.3 Thermodynamics of Leaching ....................................... 522
9.4 Kinetics of Leaching ...................................................... 529
Notation .................................................................................. 536
References ............................................................................. 536
10. Leaching – Organic Materials ....................................................... 540
10.1 Definition of Process ..................................................... 540
10.2 Contacting Methods ...................................................... 540
10.3 Industrial Leaching Equipment ...................................... 541
xvi Contents
10.4 Products, Raw Materials, and Extraction
Conditions ..................................................................... 550
10.5 Phase Equilibrium ......................................................... 550
10.6 Multistage Equilibrium Countercurrent Extraction ......... 550
10.7 Ficks's Laws ................................................................. 554
10.8 Unsteady-State Batch Extraction .................................. 555
10.9 Solute Diffusivities ........................................................ 557
10.10 Fixed Beds .................................................................... 558
10.11 Axial Dispersion and Flow Maldistribution ..................... 560
10.12 Superposition-Multistage Countercurrent
Extraction ..................................................................... 563
10.13 Continuous Countercurrent Extraction .......................... 564
10.14 Diffusion Batteries Performance ................................... 566
10.15 Differential Extraction .................................................... 566
10.16 Reflux Extractors .......................................................... 566
10.17 Solubilization ................................................................ 567
10.18 Solvent Selection .......................................................... 567
10.19 Equipment Selection ..................................................... 568
10.20 Solids Feed Preparation ............................................... 568
10.21 Spent Solids Treatment ................................................ 569
10.22 Hydrodynamic Considerations ...................................... 569
10.23 Solid-Liquid Heat Exchange .......................................... 569
Notation .................................................................................. 570
References ............................................................................. 573
11. Crystallization Operations ............................................................. 578
11.1 Introductory Comments ................................................. 578
11.2 Fundamentals ............................................................... 580
11.3 Solution Crystallization ................................................. 606
11.4 Melt Crystallization ........................................................ 626
11.5 General Design and Operational Considerations .......... 635
Notation .................................................................................. 638
References ............................................................................. 639
General Bibliography .............................................................. 642
Contents xvii
12. Adsorption ..................................................................................... 644
12.1 Introduction ................................................................... 644
12.2 Adsorbents ................................................................... 645
12.3 Criteria for Adsorption Use ............................................ 653
12.4 Basic Adsorption Cycles ............................................... 654
12.5 Process Flowsheets ...................................................... 659
12.6 Selecting a Process ...................................................... 668
12.7 Process-Design Considerations .................................... 669
12.8 Future Directions for Adsorption Technology and
Uses ............................................................................. 690
References ............................................................................. 691
13. Ion Exchange ................................................................................ 697
13.1 Principles of Ion Exchange ........................................... 697
13.2 Applications of Ion Exchange ........................................ 711
13.3 Equipment for Ion Exchange ......................................... 717
13.4 Recent Developments in Ion Exchange ........................ 726
Notation .................................................................................. 729
References ............................................................................. 730
14. Large-Scale Chromatography ....................................................... 733
14.1 Theory .......................................................................... 733
14.2 Scale-Up of Elution Chromatography ............................ 739
14.3 Countercurrent and Simulated Countercurrent
Systems ........................................................................ 745
14.4 Hybrid Systems ............................................................. 751
14.5 Other Alternatives ......................................................... 753
14.6 System Comparisons .................................................... 756
Acknowledgment .................................................................... 756
References ............................................................................. 757
15. Separation Processes Based on Reversible Chemical
Complexation ................................................................................ 760
Summary ................................................................................ 760
15.1 Introduction ................................................................... 761
15.2 Specific Examples ........................................................ 764
xviii Contents
References ............................................................................. 772
16. Bubble and Foam Separations – Ore Flotation ............................ 775
16.1 Introduction ................................................................... 775
16.2 Flotation Techniques .................................................... 775
16.3 Physicochemical Principles ........................................... 779
16.4 Flotaids ......................................................................... 792
16.5 Variables in Flotation .................................................... 796
References ............................................................................. 800
17. Bubble and Foam Separations – Waste Treatment ..................... 806
17.1 Background .................................................................. 806
17.2 Theory of Separation .................................................... 809
17.3 Laboratory Studies ........................................................ 814
17.4 Role of Column Design ................................................. 818
17.5 Larger-Scale Studies .................................................... 818
17.6 Applications .................................................................. 822
17.7 Conclusions .................................................................. 822
References ............................................................................. 823
18. Ultrafiltration and Reverse Osmosis ............................................. 826
18.1 Ultrafiltration ................................................................. 826
18.2 Reverse Osmosis ......................................................... 836
References ............................................................................. 839
Bibliography ............................................................................ 839
19. Recent Advances in Liquid Membrane Technology ..................... 840
19.1 Introduction ................................................................... 840
19.2 General Description of Liquid Membranes .................... 840
19.3 Principles of Separation ................................................ 841
19.4 Practical Applications for Liquid Membranes ................. 845
19.5 Conclusions .................................................................. 858
References ............................................................................. 858
20. Separation of Gaseous Mixtures Using Polymer
Membranes ................................................................................... 862
20.1 Introduction ................................................................... 862
Contents xix
20.2 General Design Procedures and Application
Examples ...................................................................... 872
20.3 Measurement and Phenomenological Description
of Gas Sorption and Transport in Polymers .................. 883
20.4 Fundamentals of Sorption and Transport
Processes in Polymers ................................................. 896
20.5 Characterization of Asymmetric Membranes ................. 916
20.6 Modeling and Design Considerations ............................ 920
Notation .................................................................................. 944
References ............................................................................. 944
21. Membrane Processes – Dialysis and Electrodialysis ................... 954
21.1 Dialysis ......................................................................... 954
21.2 Electrodialysis ............................................................... 968
Notation for Section 21.1 ........................................................ 977
References ............................................................................. 978
22. Selection of a Separation Process ................................................ 982
22.1 Introduction ................................................................... 982
22.2 Initial Screening ............................................................ 982
22.3 Choosing the Base Case .............................................. 992
22.4 Process Simulation ....................................................... 992
22.5 Process Synthesis ........................................................ 993
Notation .................................................................................. 994
References ............................................................................. 995
Index .......................................................................................... 997
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