catalytic naphtha reforming

Catalytic Naphtha Reforming, Second Edition......Page 1
Preface to the Second Edition......Page 3
Preface to the First Edition......Page 5
Contributors......Page 9
Contents......Page 7
1 INTRODUCTION......Page 11
Table of Contents......Page 0
2.1 Origin from Crude Oil Distillation and Processing......Page 12
Hydrocarbons......Page 13
Heteroatomic Organic Compounds, Water, and Metallic Constituents......Page 14
3.1 Gasoline Quality Requirements......Page 20
3.2 The Octane Number......Page 21
3.3 Catalytic Reforming Process......Page 23
Effect of Naphtha Hydrocarbon Composition......Page 26
Effect of Naphtha Boiling Range......Page 27
Effect of Naphtha Sulfur Content......Page 31
4.1 Hydrocarbon Composition......Page 32
4.3 Sulfur and Nitrogen Analysis......Page 37
4.4 Octane Number Determination......Page 40
REFERENCES......Page 43
1 INTRODUCTION......Page 44
2 POSSIBLE MECHANISMS OF THE REACTIONS......Page 45
3 CATALYSTS AND THEIR ACTIVE SITES......Page 50
4 RELATIONSHIP BETWEEN REACTANT STRUCTURE AND REACTIVITY......Page 59
5 EFFECT OF SECOND COMPONENTS ON THE ACTIVE SITES OF THE CATALYSTS......Page 60
5.1 Metallic Components......Page 61
Sulfur and Nitrogen......Page 63
Carbon......Page 65
Oxygen......Page 70
Hydrogen......Page 71
REFERENCES......Page 76
1 INTRODUCTION......Page 84
2.2 Equilibrium Constant......Page 85
2.4 Influence of Total Pressure and Composition on Equilibrium......Page 87
3 REACTIONS......Page 90
4.1 Classical Metal–Acid Bifunctional Reaction Mechanism......Page 93
Intermediates, Reaction Sequences, and Conversions......Page 95
Thermodynamics......Page 99
Mass Transport......Page 100
Selectivity......Page 101
4.2 Other Metal–Acid Bifunctional Reaction Mechanisms......Page 105
4.3 Other Types of Bifunctional Catalysts......Page 111
REFERENCES......Page 112
1 INTRODUCTION......Page 114
1.2 Cracked Naphthas......Page 116
FCC Naphtha......Page 118
Hydrocracked Naphtha......Page 122
1.3 Sulfur Species in Naphthas......Page 123
3.1 Hydrotreating Reactions and Reactivities......Page 126
Hydrodesulfurization......Page 128
Hydrodenitrogenation......Page 130
Recombination Reaction......Page 132
3.3 Reaction Kinetics......Page 134
4.1 Active Components......Page 135
4.2 Catalyst Structure......Page 137
Arsenic......Page 138
Hydrogen Sulfide......Page 139
4.4 Catalyst Regeneration......Page 140
5.1 Process Flow Scheme......Page 141
5.2 Operating Parameters......Page 143
Temperature......Page 144
Space Velocity......Page 145
6 FUTURE OUTLOOK......Page 147
REFERENCES......Page 148
1 INTRODUCTION......Page 150
2.1 y- and n-Al2O3......Page 151
2.3 Influence of Halogen on Alumina Acidity......Page 154
2.4. Forming of Alumina Macroparticles......Page 155
3.1 Key Features......Page 156
3.2 Industrial Impregnation......Page 157
Fundamental Phenomena of Impregnation......Page 158
Coordination Chemistry of Dissolved and Adsorbed Pt Complexes from CPA......Page 175
Pt uptake in Zeolites and MAPSO and SAPO Zeotypes......Page 185
3.4 Drying, Oxidation, and Reduction of the Impregnated Support......Page 188
Mineral Compounds......Page 189
Organometallic Compounds......Page 190
4.2 Platinum–Tin......Page 191
Alumina-Supported Tin Oxide Preparation......Page 192
Coimpregnation......Page 193
4.3 Platinum–Iridium......Page 194
4.5 Other Bimetallic and Multimetallic Catalysts......Page 195
5 METAL PROFILES IN CATALYST PELLETS......Page 196
6 CONCLUSION......Page 198
REFERENCES......Page 201
1 INTRODUCTION......Page 208
2.1 Surface Area and Porosity......Page 209
2.2 Acidity......Page 213
Infrared Spectroscopy......Page 214
2.3 Chlorided Catalysts......Page 219
2.4 Fluorided Alumina......Page 221
3 PLATINUM–ALUMINA CATALYSTS......Page 223
3.2 X-ray Diffraction......Page 224
3.3 Transmission Electron Microscopy......Page 225
3.4 Chemisorption Techniques......Page 226
3.5 Titration Methods......Page 229
3.6 Small-Angle X-ray Scattering......Page 230
Extended XAFS......Page 233
X-ray Absorption Near-Edge Structure......Page 236
3.8 Nuclear Magnetic Resonance......Page 237
3.10 X-ray or Ultraviolet Photoelectron Spectroscopy; Electron Spectroscopy for Chemical Analysis (ESCA)......Page 241
3.11 Auger Electron Spectroscopy......Page 243
3.13 Infrared Spectroscopy for Metallic Function......Page 244
4 CHARACTERIZATION OF PLATINUM–RHENIUM CATALYST......Page 246
5 CHARACTERIZATION OF PLATINUM–TIN–ALUMINA CATALYSTS......Page 254
6.1 Group VIII or Group VIII/Group IB Bimetallics......Page 258
6.2 Platinum and Partially Reduced Metal......Page 261
7 CHARACTERIZATION OF ALKALINE L-ZEOLITES—Pt......Page 262
9 SUMMARY......Page 267
REFERENCES......Page 271
1 INTRODUCTION......Page 284
1.1 Models of Porous Structures......Page 286
1.2 Optimization of Porous Structure Reported in Literature......Page 287
2 SCOPE OF CHAPTER......Page 288
3.1 Previous Kinetic Modeling......Page 290
3.2 Experiments and Methods......Page 292
Naphtha Fraction (60– 150°C)......Page 296
n-Heptane + Methylcyclohexane......Page 298
3.5 Models Based on an Analytical Description of Time-Related Variations in the Content of Reagents......Page 302
3.6 Summarizing Comments......Page 303
4 DIFFUSION PHENOMENA IN THE BIDISPERSIVE GRAIN OF THE CATALYST......Page 305
4.2 Assumptions in the Description of Diffusion Phenomena......Page 307
Statistical Analysis......Page 310
Properties of Bidispersive Catalytic Systems......Page 314
5 OPTIMIZING THE POROUS STRUCTURE OF THE REFORMING CATALYST......Page 317
5.2 Topological and Geometrical Representation of the Pore Space......Page 318
Diffusion......Page 320
5.4 Method and Scope of Model Analysis......Page 321
Effect of Porous Structure on Grain Performance......Page 322
Statistical Approach to the Results of Model Analysis......Page 331
5.6 Conclusions......Page 332
6.1 Method of Analysis......Page 333
Activity Tests: Dehydrocyclization of n-Heptane......Page 334
6.3 Analysis of Results......Page 335
NOTATION......Page 339
REFERENCES......Page 341
1 INTRODUCTION......Page 344
2 SEMIREGENERATIVE REFORMING CATALYSTS......Page 345
2.2 Process Improvements......Page 348
3.1 Cyclic and Continuous Units......Page 349
3.2 Catalyst Advances......Page 350
Continuous Catalysts......Page 351
3.3. Regenerator Advances......Page 353
3.4 Combining Semiregeneration with Continuous Regeneration......Page 354
4.2 Aromatics from LPG......Page 356
4.3. Aromatics from Naphtha......Page 357
REFERENCES......Page 358
1 INTRODUCTION......Page 361
2 CATALYST PREPARATION AND CHARACTERIZATION......Page 363
3 EVIDENCE OF LD-HBS MECHANISM......Page 371
4 REACTION PATHWAYS IN n-HEXANE TRANSFORMATION......Page 380
5 COMMERCIAL NAPHTHA REFORMING OVER HYBRID CATALYSTS......Page 382
6 HEAT OF REACTION FOR NAPHTHA REFORMING......Page 388
7 DEMONSTRATION UNIT FOR NAPHTHA REFORMING......Page 391
SUBSCRIPTS......Page 395
REFERENCES......Page 396
1 INTRODUCTION......Page 398
2.1 Temperature-Programmed Oxidation......Page 399
2.2 Infrared Spectroscopy......Page 400
2.4 Raman Spectroscopy......Page 402
2.6 Transmission Electronic Microscopy......Page 405
3.2 Coke Distribution Across the Catalyst Pellet......Page 406
3.3 Coke Distribution Along the Catalyst Bed......Page 407
4.1 Metallic Platinum Content, Dispersion, and Ensemble Size......Page 409
4.2 Metallic Additives......Page 410
Tin Addition......Page 411
Interaction Between Platinum and Additives......Page 412
4.3 Catalyst Support......Page 413
4.4 Operating Conditions......Page 414
Circulating Hydrogen......Page 417
Sulfur and Sulfurization......Page 418
Chlorine and Water Content......Page 421
4.6 Feed Compositions......Page 423
5 COKING MECHANISMS......Page 424
6 COKING KINETICS......Page 428
7 EFFECTS OF COKING ON ACTIVITY AND SELECTIVITY......Page 431
8 CONCLUSIONS......Page 432
REFERENCES......Page 433
1 INTRODUCTION......Page 439
2.2 Cyclic Regenerative Process......Page 440
2.3 Continuous Regenerative Process......Page 442
3 CATALYST REGENERATION......Page 446
3.1 Reactor/Catalyst Purge......Page 447
3.2 Coke Burn......Page 448
3.3 Oxidation/Chlorination......Page 449
3.5 Metals Reduction......Page 450
4 CATALYST PROPERTIES INFLUENCING REFORMING CATALYST ACTIVITY AND PERFORMANCE......Page 451
4.1 Surface Area Stability......Page 452
4.2 Catalyst Attrition......Page 454
Particle Crush Strength......Page 455
Rotating Drum Test......Page 457
4.3 Metal Redispersion......Page 458
4.4 Regenerator Troubleshooting......Page 460
5 CONCLUSIONS......Page 461
REFERENCES......Page 462
1 INTRODUCTION......Page 464
2 MATERIALS HANDLING AT THE OIL REFINERY......Page 465
3.2. Support Material......Page 467
3.4. Distribution of the Precious Metals......Page 468
4 WEIGHING, SIEVING, AND SAMPLING PROCEDURES......Page 469
5.1. Sample Handling and Analysis......Page 470
6.1. Removal of Halides, Hydrocarbons, and Carbon......Page 473
6.3. Utilization of Leach Products......Page 474
6.4. Smelting......Page 475
7.3. Platinum Metal Production......Page 476
7.4. Recovery Schemes for Palladium and Iridium......Page 477
8.2. Purification of Ammonium Perrhenate and Perrhenic Acid......Page 478
REFERENCES......Page 479
2 PROCESS CLASSIFICATION......Page 481
2.1. Semiregenerative Process......Page 483
2.3. Continuous Catalyst Regeneration Process......Page 484
3 MAJOR REFORMING PROCESSES......Page 485
3.1. UOP Platforming......Page 486
CCR Platforming......Page 487
RZ Platforming......Page 488
3.2. Axens Reforming Technology—Octanizing and Aromizing Processes......Page 489
4.2. Magnaforming Process......Page 492
4.3. Powerforming Process......Page 493
4.5. Ultraforming Process......Page 494
5 COMMERCIAL REFORMING CATALYSTS......Page 495
ACKNOWLEDGMENT......Page 498
REFERENCES......Page 499
1 INTRODUCTION......Page 500
2.1. Basic Regulatory Control Systems......Page 502
Distributed Control Systems......Page 503
Regulatory Controls in a Catalytic Reformer......Page 504
Auxiliary Control System......Page 509
2.3. Emergency Shutdown Systems......Page 512
Logic Tree for a Catalytic Reformer Emergency Shutdown System......Page 513
2.4. Process Equipment Safety Systems......Page 514
2.5. Catalyst Control Functions......Page 515
Catalytic Reformer Performance Indicators......Page 516
3 ADVANCED PROCESS CONTROL OF CATALYTIC REFORMERS......Page 517
3.1. Instrumentation Requirements for APC......Page 518
Reformer Severity Control with APC......Page 520
APC of Reformer Fired Heaters......Page 522
Catalyst Regeneration......Page 524
3.5. Inferred Properties......Page 525
Reid Vapor Pressure......Page 526
Coke Laydown Rate......Page 527
Recycle Hydrogen Purity Analyzers......Page 528
Reformate Octane Analyzers......Page 529
Utility System On-line Analyzers......Page 530
3.7. Benefits from Application of APC to a Catalytic Reformer......Page 531
Benefits from Minimizing Operating Costs with APC in a Reformer Unit......Page 532
Benefits of Reducing Variability with APC in a Reformer Unit......Page 533
4 EXPERT ADVISOR SYSTEMS FOR CATALYTIC REFORMERS......Page 534
4.1. Expert Advisor Functions in Catalytic Reforming......Page 535
4.2. Expert Advisor Integration into the Control System......Page 536
5.1. Defining the Catalytic Reformer Economic Envelope......Page 537
Sources of Benefits......Page 538
Economic Drivers in a Catalytic Reformer......Page 539
The Reformer Optimization Statement......Page 540
Using an LP for Real-Time Optimization......Page 542
Optimization Using Kinetic Models......Page 543
RT-OPT Frequency of Execution......Page 544
5.3. Instrumentation and Analyzer Requirements......Page 545
Operator Training......Page 546
The Danger in Being Overly Conservative in RT-OPT of Reformers......Page 547
Project Analysis......Page 548
Model On-line Implementation......Page 549
6 SUMMARY......Page 550
REFERENCES......Page 551
1 INTRODUCTION......Page 553
2 REFORMING THERMODYNAMIC EQUILIBRIUM CALCULATIONS......Page 554
2.1. Rigorous Methodology......Page 556
2.2. Shortcut Method......Page 557
3 FEED CHARACTERIZATION TECHNIQUE......Page 558
3.1. Feed Characterization Algorithm......Page 559
3.2. NMR On-line Analyzers......Page 561
4 NAPHTHA REFORMING KINETIC MODEL......Page 563
4.1. Reaction Mechanism......Page 567
4.2 Reactor Model......Page 569
Deactivation Function......Page 570
Parameter Estimation......Page 572
5 FLASH DRUM SEPARATOR MODEL......Page 573
6 MODEL APPLICATIONS......Page 574
6.1. Reforming Model Performance......Page 575
6.2. Naphtha Reforming Heat Needs......Page 578
6.3. Benzene Reduction and Reformer Operation Conditions......Page 585
7 CONCLUSION......Page 590
SYMBOLS......Page 591
REFERENCES......Page 592
APPENDIX: FRACTALS AND SURFACES......Page 594