Contents

Foreword ......................................................................................................... IX
Nomenclature................................................................................................ XXlll

Abbreviations and Acronyms ................................................................. XXXlll

Chapter 1 The Basics of Separation Operations ......................... 1

1.1 Function of Separation Operations in Refining ........................... 1
1.2 Main Separation Operations .......................................................... 3
1.3 lmplementation of Separation Processes ..................................... 7
1.3.1 Thermodynamic Equilibrium and Kinetic Factors .... 7
1.3.2 Contact between Phases ............................................... 9
1.3.3 Fixed Bed Adsorption Operations ............................... 12
1.3.4 Membrane Separations .................................................. 13
1.4 Recent Progress in Separation Processes .................................... 13

Chapter 2 Thermodynamics: Phase Equilibria ........................... 15

Introduction ................................................................................................. 15
2.1 Vapor-Liquid Equilibria................................................................... 16
2.1.1 General Description ....................................................... 17
2.1.2 Equilibrium Condition and Generalized Variance...... 29
2.1.3 “Heterogeneous” Methods Applied to Calculate the
K Value ............................................................................. 33
2.1.4 “Homogeneous” Methods Applied to the Calculation
of the K Value .................................................................. 46
XIV CONTENTS

2.1.5 Relations between UHomogeneous”and

“Heterogeneous” Methods ............................................ 59
2.1.6 Calculation Algorithms .................................................. 60
2.2 Liquid-Liquid Equilibria .................................................................. 63
2.2.1 General Description ....................................................... 65
2.2.2 Calculation of Liquid-Liquid and Liquid-Liquid-Vapor
Equilibria ......................................................................... 70
2.3 Solid-Liquid Equilibria ..................................................................... 73
2.3.1 General Description ....................................................... 73
2.3.2 Calculation of Solid-Liquid Equilibria .......................... 75
2.4 Complex Mixtures ............................................................................ 78
2.4.1 Lumping ........................................................................... 78
2.4.2 Continuous Thermodynamics ...................................... 79
2.5 Conclusion ........................................................................................ 79

Chapter 3 Mass Transfer and Efficiency of Separation

Operations ............................................................................. 81
3.1 Introduction ...................................................................................... 81
3.2 Diffusion in a Homogeneous Phase ............................................... 81
3.3 Transfer between Phases ............................................................... 84
3.4 Predicting Transfer Coefficients .................................................... 86
3.5 Relationship between Efficiency and Transfer Coefficient ........ 89

Chapter 4 Distillation. Absorption and Stripping..................... 93

4.1 Introduction ...................................................................................... 93
4.2 The Basics of Distillation ................................................................ 96
4.2.1 Phase Equilibria .............................................................. 96
4.2.2 Separating Power of a Vapor-Liquid Equilibrium
and Distillation ................................................................ 97
4.2.3 Continuous Binary Distillation . The McCabe and
Thiele Method ................................................................. 103
4.2.4 Limits of the McCabe and Thiele Method .
Other Calculation Methods for Binary Distillation .... 114
4.3 Theoretical Trays. Real Contacting Equipment .......................... 115
4.3.1 Trays ................................................................................ 118
4.3.2 Packing............................................................................. 125
4.3.3 Comparison between Packing and Trays .................... 127
4.4 Distilling Complex Mixtures ........................................................... 128
CONTENTS XV

4.4.1 Number of Degrees of Freedom .................................... 129

4.4.2 Distributed and Nondistributed Substances ............. 129
4.4.3 Minimum Reflux.............................................................. 130
4.4.4 Total Reflux ..................................................................... 131
4.4.5 Gilliland Relation . Simplified Study of a Distillation
Column ............................................................................. 133
4.4.6 Advantage of Simplified Methods ................................ 135
4.5 Calculation Methods for Distillation Columns ............................ 136
4.5.1 Static Simulation of Distillation Columns.................... 136
4.5.2 Dynamic Simulation of Distillation Columns .............. 153
4.6 Designing a Distillation Separation Unit ....................................... 158
4.6.1 Reminder of the Pinch Method .................................... 161
4.6.2 Integration of a Distillation Column in a Process .
Choosing Pressure ......................................................... 163
4.6.3 Estimating Investments. Seeking Optimum Sizing ..... 168
4.6.4 Controlling a Distillation Column ................................. 169
4.6.5 Designing a Separation Flowsheet ............................... 179
4.7 Batch Distillation ............................................................................. 189
4.7.1 Principal Balances in a Batch Distillation Column .... 190
4.7.2 Applying the McCabe and Thiele Method .................. 192
4.7.3 Simplified Design Methods ........................................... 192
4.7.4 Rigorous Calculation Methods ..................................... 195
4.8 Absorption . Stripping...................................................................... 197
4.8.1 Absorption ...................................................................... 197
4.8.2 Stripping .......................................................................... 200
4.9 Extractive and Azeotropic Distillation .......................................... 201
4.9.1 Extractive Distillation .................................................... 202
4.9.2 Azeotropic Distillation ................................................... 202
4.9.3 Heteroazeotropic Distillation ........................................ 216
4.10 Reactive Distillation ........................................................................ 216
4.10.1 Batch Coupling of a Reactor and a Rectifying Zone .. 218
4.10.2 Catalytic Distillation ....................................................... 218

Chapter 5 Distillation. Absorption and Stripping in the

Petroleum Industry ........................................................... 221
5.1 Atmospheric Distillation of Crude Oil (Topping) ........................ 221
5.1.1 Description of the Process ............................................ 222
5.1.2 Fractionation Quality ..................................................... 224
5.1.3 Calculation and Simulation of Topping Columns ....... 228
XVI CONTENTS

5.1.4 Technology ...................................................................... 234

5.1.5 Process Variations.......................................................... 234
5.1.6 Crude Oil Desalting ........................................................ 236
5.1.7 Corrosion and Erosion ................................................... 254
5.1.8 Energy Consumption ...................................................... 258
5.1.9 Advanced Control. Maintenance . Type of Effluents .. 263
5.2 Vacuum Distillation of the Atmospheric Residue ....................... 264
5.2.1 Fractionation ................................................................... 265
5.2.2 Examples of Specifications for a Distillate Sent to
Catalytic Cracking .......................................................... 268
5.2.3 Definition of Terms Specific to Vacuum Distillation .. 268
5.2.4 Description of the Atmospheric Residue Vacuum
Distillation Process ........................................................ 269
5.2.5 Description of the Vacuum Distillation Column ......... 272
5.2.6 Choosing the Type of Vacuum Distillation.................. 274
5.2.7 Calculating and Simulating an Atmospheric Residue
Vacuum Distillation Unit ................................................ 274
5.2.8 Vacuum Distillation Column Technology .................... 274
5.2.9 Specifics on Atmospheric Residue Vacuum
Distillation ....................................................................... 277
5.2.10 Integrated Topping and Vacuum Distillation Units.... 278
5.3 Gasoline Distillation and Gas Fractionation ................................ 279
5.3.1 Position of the Unit in the Refinery Flow Scheme ..... 279
5.3.2 Description of the Gasoline Distillation and Gas
Fractionation Process .................................................... 279
5.4 Distillation. Absorption and Stripping Column Internals........... 283
5.4.1 Definition of Efficiency. Capacity and Flexibility of
Fractionation Column Internals.................................... 284
5.4.2 General Presentation of Fractionation Column
Internals ........................................................................... 286
5.4.3 Applications .................................................................... 300

Chapter 6 Liquid0Liquid Extraction................................................ 319

6.1 Introduction ...................................................................................... 319
6.2 Conventions and Notations ............................................................ 320
6.2.1 General Notations ........................................................... 320
6.2.2 Representation of Equilibria......................................... 321
6.3 OneStage Extraction ....................................................................... 322
6.4 Crosscurrent Extraction ................................................................. 324
CONTENTSXVll

6.5 Single Countercurrent Extraction .................................................. 327

6.5.1 Material Balance Relations ........................................... 328
6.5.2 Graphic Solution ............................................................. 329
6.5.3 Special Cases................................................................... 336
6.5.4 Limits of Single Countercurrent Extraction ................ 337
6.6 Countercurrent Extraction with Reflux ........................................ 337
6.6.1 Conditions Favorable to Establishing a Reflux .......... 337
6.6.2 Balances........................................................................... 339
6.6.3 Graphic Solution ............................................................. 342
6.6.4 Relationship between the Reflux Ratio and the
Number of Stages ........................................................... 344
6.6.5 Induced Reflux ................................................................ 345
6.7 Dual Solvent Extraction .................................................................. 345
6.7.1 Graphic Solution ............................................................. 347
6.7.2 Analytic Solution ............................................................ 352
6.8 Multicomponent Feeds: Numerical Calculation of Extraction .. 354
6.9 Solvent Characteristics ................................................................... 355
6.9.1 Solvent Properties .......................................................... 355
6.9.2 Physical Properties ........................................................ 356
6.9.3 Other Properties ............................................................. 356
6.9.4 Antisolvent ...................................................................... 357

Chapter 7 Solvent Extraction in the Oil Industry..................... 359

Eliminating Aromatic Compounds from Lube Oil Stocks to
Produce Lubricants ......................................................................... 359
7.1.1 Furfural Extraction ......................................................... 363
7.1.2 Flow Scheme of a Furfural Extraction Unit ................. 375
7.1.3 Operating a Furfural Extraction Unit ........................... 381
7.1.4 Operating Costs of a Furfural Extraction Unit ............ 384
7.1.5 NMP Extraction ............................................................... 384
Deasphalting..................................................................................... 388
7.2.1 Purpose and Principle of the Process . Feed
Structure ......................................................................... 388
7.2.2 Feeds and Products........................................................ 394
7.2.3 Solvent Characteristics .................................................. 397
7.2.4 The Deasphalting Process ............................................. 397
7.2.5 Description of a Deasphalting Unit .............................. 408
7.2.6 Solvent Recovery Techniques ...................................... 414
7.2.7 Economics ....................................................................... 417
Aromatics Extraction from Light Oil Cuts .................................... 424
7.3.1 Purpose ............................................................................ 424
7.3.2 Sources of BTX Aromatics ............................................ 424
7.3.3 Product Specifications ................................................... 425
7.3.4 Solvent Properties .......................................................... 426
7.3.5 General Process Flow Scheme ...................................... 430
7.3.6 Industrial Processes ....................................................... 432
7.3.7 Recovery Ratio and Aromatics Purity ......................... 438
7.3.8 Economics ....................................................................... 438
Liquid-Liquid Extraction Equipment Onternals) ......................... 439
7.4.1 General Introduction ...................................................... 439
7.4.2 Static Systems ................................................................. 442
7.4.3 Agitated Systems ............................................................ 447
7.4.4 Conclusion....................................................................... 456

Chapter 8 Crystall~tatfon..................................................................... 457

8.1 Solid-Liquid Equilibria. Equilibrium Deviations .......................... 458
8.2 First Step in the Crystallization Process: Nucleation ................. 458
8.2.1 Kinetics of Primary Nucleation .................................... 460
8.2.2 Kinetics of Secondary Nucleation ................................ 461
8.2.3 Seeding (Tertiary Nucleation) ...................................... 462
8.2.4 Measuring Nucleation Rates ......................................... 462
8.3 Second Step in Crystallization: Crystal Growth .......................... 462
8.3.1 Crystal Growth Rate Governed by Mass Transfer ..... 463
8.3.2 Growth Rate Controlled by Molecule Integration in
the Crystal Lattice .......................................................... 465
8.3.3 Growth Rate Controlled by Both Mass Transfer and
Integration in the Lattice ............................................... 465
8.4 Crystal Agglomeration .................................................................... 468
8.5 Crystal Morphology ........................................................................ 468
8.6 Influence of Crystal Shape on Filtration (Case of n-Paraffins) .. 468
8.6.1 Macroscopic Measurement of Paraffin Cake
Filterability ...................................................................... 469
8.6.2 Measuring Cake Porosity............................................... 470
8.6.3 Crystal Morphology and Cake Texture ....................... 471
8.6.4 Filter Aids ........................................................................ 472
8.7 Reminder of Precautions Recommended to Succeed with a
Crystallization-Filtration Operation .............................................. 473
CONTENTSXIX

8.8 Crystallization Techniques ............................................................. 474

8.9 Crystal Purification Techniques .................................................... 475

Chapter 9 Crystallization in the Oil Industry: Solvent

Dewaxing .............................................................................. 477
9.1 Introduction ...................................................................................... 477
9.1.1 Purpose of Dewaxing ..................................................... 477
9.1.2 Feed and Products ......................................................... 477
9.2 Solvent Dewaxing............................................................................. 480
9.2.1 Dewaxing Process Using an MEK-Toluene Mixture as
a Solvent .......................................................................... 482
9.2.2 Influence of the Type of Feed ....................................... 483
9.2.3 Influence of Solvent Composition ................................ 485
9.2.4 Influence of Final Dewaxing Temperature (Equal to
Filtration Temperature) ................................................. 487
9.2.5 Influence of Solvent Ratio and Dilution Distribution
Mode ................................................................................ 491
9.2.6 Influence of Cooling Rate .............................................. 494
9.2.7 Filtration Method ............................................................ 496
9.2.8 Principle of Dual Pass (or Repulping) and Results ... 498
9.2.9 Dewaxing Aids ................................................................. 500
9.3 Description of a Dewaxing Unit Using the MEK-Toluene
Solvent Mixture ................................................................................ 500
9.3.1 General Flow Diagram .................................................... 500
9.3.2 Detailed Description of the Process ............................ 503
9.4 Operating a Solvent Dewaxing Unit .............................................. 517
9.4.1 Feed Train Operation ..................................................... 519
9.4.2 Filter Operation .............................................................. 519
9.4.3 Solvent Quality ............................................................... 520
9.4.4 Temperatures and Pressures of the Solvent
Recovery System ............................................................ 520
9.4.5 Refrigeration Unit Performance ................................... 520
9.4.6 Operation of the Azeotropic System and Solvent
Dehydration Section ...................................................... 520
9.4.7 Solvent Consumption . Environmental Protection ..... 521
9.4.8 Optimizing Dilutions ...................................................... 521
9.5 Economics ........................................................................................ 521
9.5.1 Energy Consumption ...................................................... 521
9.5.2 Operating Costs .............................................................. 522
9.5.3 Cost of Major Equipment (1992 Figures) .................... 522
XX CONTENTS

9.6 Process Developments.................................................................... 522

9.6.1 Applications of Computerized Process Control ......... 522
9.6.2 Other Techniques: Dilchil Process ............................... 523

Chapter 10 Adsorption ............................................................................. 525

10.1 Adsorbents ....................................................................................... 526
10.1.1 Activated Carbon ............................................................ 528
10.1.2 Carbon Molecular Sieve, MSC ....................................... 530
10.1.3 Activated Alumina .......................................................... 532
10.1.4 Silica Gel .......................................................................... 532
10.1.5 Zeolites (Molecular Sieves) ........................................... 532
10.1.6 Natural and Activated Clays ......................................... 534
10.2 Adsorption Thermodynamics ........................................................ 535
10.2.1 Adsorption of Pure Substances .................................... 535
10.2.2 Mixture Adsorption ........................................................ 542
10.2.3 Heat of Adsorption ......................................................... 544
10.3 Transfer Phenomena in Adsorbers ............................................... 545
10.3.1 Balance Equations .......................................................... 545
10.3.2 Transfer Resistance Models.......................................... 551
10.4 Dynamic Adsorber Behavior: Bed Profiles and Breakthrough
Curves ............................................................................................... 554
10.4.1 Equilibrium Theory ........................................................ 555
10.4.2 Modelling Breakthrough Curves .................................. 558
10.5 Different Techniques for Implementing Adsorption ................... 560
10.5.1 Adsorbent Regeneration Methods ............................... 560
10.5.2 Cyclic Processes ............................................................. 561
10.5.3 Continuous Processes: Moving Bed and Simulated
Moving Bed ..................................................................... 567

Chapter 11 Adsorption in the Oil and Gas Industry ................... 573

11.1 Dehydration ...................................................................................... 573
11.2 Desulfurization ................................................................................. 577
11.3 Decarbonation of Gases.................................................................. 581
11.4 Eliminating Oxygenated Products from Hydrocarbon Cuts ...... 581
11.5 Hydrogen Purification ..................................................................... 582
11.6 nllsoparaffin Separation ................................................................. 584
11.6.1 Solvent Production ......................................................... 584
CONTENTS XXI

11.6.2 lmproving the Octane Number of Motor Fuel Stocks 584

11.6.3 Production of C,,-C,, n-Paraffins .................................. 587
11.7 Separation of Olefins ....................................................................... 587
11.8 Separation of Aromatics ................................................................. 588
11.9 Recovery of Hydrocarbon Vapors ................................................. 589
11.10 Clay Treatments ............................................................................... 591

Chapter 12 Membrane Separation...................................................... 593

12.1 Introduction ...................................................................................... 593
12.2 Background Information on Membranes...................................... 594
12.2.1 Principle of Membrane Separations ............................ 594
12.2.2 Membranes...................................................................... 585
12.2.3 Modules ........................................................................... 597
12.2.4 Different Types of Membrane Separation Processes 602
12.3 Applications of Membranes in Refining and Petrochemistry ... 602
12.3.1 Hydrogen Recovery by Gas Permeation ..................... 603
12.3.2 Ultrafiltration .................................................................. 607
12.3.3 Pervaporation ................................................................. 608
12.3.4 Zeolite Membranes......................................................... 611
12.3.5 Membrane Reactors ....................................................... 612

References ....................................................................................................... 615

Index................................................................................................................. 631