Preface ...................................................................... iii Part I. Feedstock Terminology, Availability, and Evaluation Chapter 1. Definitions and Terminology ......................................... 1 1. Introduction ............................................................... 1 2. Native Materials ........................................................... 3 2.1 Petroleum .............................................................. 3 2.2 Heavy Oil .............................................................. 6 2.3 Bitumen ................................................................ 7 2.4 Bituminous Rock and Bituminous Sand .................................... 8 2.5 Natural Gas ............................................................ 9 2.6 Wax ................................................................... 10 2.7 Kerogen ............................................................... 10 3. Derived Materials ......................................................... 11 4. Manufactured Materials .................................................... 13 4.1 Residuum (Residua) .................................................... 13 4.2 Asphalt ............................................................... 20 4.3 Coke .................................................................. 22 4.4 Wax ................................................................... 22 4.5 Synthetic Crude Oil ................................................... 22 4.6 Coal Liquids .......................................................... 23 4.7 Shale Oil ............................................................. 23 References ................................................................ 24 Chapter 2. Occurrence and Availability ........................................ 25 1. Introduction .............................................................. 25 2. Reserves .................................................................. 29 2.1 Conventional Petroleum ................................................ 31 2.2 Natural Gas ........................................................... 33 2.3 Heavy Oil ............................................................. 36 2.4 Bitumen (Extra Heavy Oil) ............................................. 37 References ................................................................ 39 Chapter 3. Composition ........................................................ 41 1. Introduction .............................................................. 41 2. Ultimate (Elemental) Composition .......................................... 42 3. Chemical Composition ...................................................... 44 4. Bulk (Fractional) Composition ............................................. 50 4.1 Solvent Treatment ..................................................... 53 4.2 Adsorption Methods .................................................... 58 4.3 Chemical Methods ...................................................... 63 5. Use of the Data ........................................................... 65 References ................................................................ 69 Chapter 4. Testing and Evaluation ............................................. 73 1. Introduction .............................................................. 73 2. Physical Properties ....................................................... 75 2.1 Elemental (Ultimate) Analysis ......................................... 75 2.2 Density and Specific Gravity .......................................... 76 2.3 Viscosity ............................................................. 78 3. Thermal Properties ........................................................ 82 3.1 Volatility ............................................................ 83 3.2 Liquefaction and Solidification ....................................... 91 3.3 Carbon Residue ........................................................ 92 3.4 Aniline Point ......................................................... 94 3.5 Heat of Combustion .................................................... 95 3.6 Pressure-Volume-Temperature Relationships ............................. 95 3.7 Critical Properties ................................................... 96 4. Use of the Data ........................................................... 98 References ............................................................... 100 Part II. Engineering Aspects of Refining Chapter 5. Reaction Stoichiometry ............................................ 102 1. Introduction ............................................................. 102 2. Stoichiometry of Chemical Reactions ...................................... 102 3. Stoichiometrically Independent Reactions ................................. 104 4. Material Balance for a Single Reaction ................................... 104 5. Measure of Concentration ................................................. 105 6. Concentration Changes with a Single Reaction ............................. 106 7. Conversion ............................................................... 108 8. Concentration Changes with Several Reactions ............................. 109 9. Reaction Rate ............................................................ 110 10. Concentration Changes in Continuous Mixtures ............................. 112 References ............................................................... 113 Chapter 6. Chemical Kinetics ................................................. 114 1. Introduction ............................................................. 114 2. Chemical Kinetics ........................................................ 115 3. Thermodynamics and Reaction Kinetics ..................................... 116 4. Reaction Rates and Chemical Equilibrium .................................. 120 5. Steady-State Approximation and Catalysis ................................. 122 6. Concentration Change Measurements and Reaction Rates ..................... 125 7. Reaction Severity ........................................................ 127 8. Propagation, Branching, and Autocatalysis ................................ 128 9. Arrhenius Relation and Its Importance .................................... 129 References ............................................................... 131 Chapter 7. Thermochemistry and Chemical Equilibrium .......................... 132 1. Introduction ............................................................. 132 2. Heat of Formation and Heat of Reaction ................................... 133 3. First Law of Thermodynamics .............................................. 136 4. Second Law of Thermodynamics: Chemical Equilibrium ....................... 138 References ............................................................... 144 Chapter 8. Kinetic Measurements and Data Analysis ............................ 146 1. Introduction ............................................................. 146 2. Kinetic Models and Calculation of Rate Constants ......................... 147 3. Kinetic Rate Constants in Gas-Solid Reactions ............................ 152 4. Material Balances for Different Types of Reactors ........................ 154 4.1 Batch Reactor ........................................................ 154 4.2 Continuous Flow Stirred Tank Reactor ................................. 155 4.3 Plug Flow Tubular Reactor ............................................ 156 4.4 Axially Dispersed Tubular Reactor .................................... 157 5. Experimental Errors ...................................................... 158 6. Correction Calculations .................................................. 159 References ............................................................... 161 Chapter 9. Reactor Design .................................................... 162 1. Introduction ............................................................. 162 2. Continuous Flow Stirred Tank Reactors .................................... 163 2.1 Mass Balance for Continuous Flow Stirred Tank Reactors ............... 164 2.2 Reactor Volume and Reactor Optimization .............................. 165 2.3 Independence of Material Balances .................................... 169 2.4 Energy Balance for Continuous Flow Stirred Tank Reactors ............. 169 2.5 Reactor Design and Reactor Stability for Continuous Flow Stirred Tank Reactors ........................................................ 171 2.6 Stability Analysis for Continuous Flow Stirred Tank Reactors ......... 176 3. Batch Reactors ........................................................... 180 3.1 Mass Balance for Batch Reactors ...................................... 180 3.2 Energy Balance for Batch Reactors .................................... 181 4. Plug Flow Tubular Reactors ............................................... 184 4.1 Mass Balance for Plug Flow Tubular Reactors .......................... 184 4.2 Energy Balance for Plug Flow Tubular Reactors ........................ 187 5. Axially Dispersed Tubular Reactors ....................................... 188 5.1 Mass Balance for Axially Dispersed Tubular Reactors .................. 188 5.2 Energy Balance for Axially Dispersed Tubular Reactors ................ 191 References ............................................................... 192 Chapter 10. Mixing in Flow Systems and Reactors .............................. 193 1. Introduction ............................................................. 193 2. Residence Time Distribution .............................................. 193 3. Ideal Flow Systems ....................................................... 196 3.1 Continuous Flow Stirred Tank Reactors with Perfect Mixing ............ 196 3.2 Piston Flow Tubular Reactors ......................................... 198 4. Mean, Moments, and Distribution Functions ................................ 199 5. Residence Time Distribution Measurement Techniques ....................... 201 6. Residence Time Distribution Models ....................................... 202 7. Dispersion Models for Tubular Reactors ................................... 205 8. Dispersion Models for Axial Distribution Tubular Reactors ................ 207 References ............................................................... 209 Chapter 11. Transport Phenomena .............................................. 210 1. Introduction ............................................................. 210 2. Formulation of Property Balance Equations ................................ 211 3. Momentum Transfer (Fluid Dynamics) ....................................... 213 3.1 General Properties of the Navier-Stokes Equation and Its Solutions ... 214 3.2 Exact Solutions (Laminar Viscous Flow) ............................... 218 3.3 Approximate Solutions ................................................ 222 3.4 Turbulent Flow ....................................................... 234 4. Heat Transfer ............................................................ 249 4.1 Energy Balance (Equation of Energy) .................................. 249 4.2 Integration of the Thermal Energy Equation ........................... 251 4.3 Steady-State Heat Conduction ......................................... 251 4.4 Unsteady-State Heat Conduction ....................................... 257 4.5 Convective Heat Transfer in Laminar Flow ............................. 260 5. Mass Transfer ............................................................ 267 5.1 Equation of Changes in Multicomponent Systems ........................ 269 5.2 Similarity in Mass, Momentum, and Energy Transfer .................... 273 5.3 Forced Convective Mass Transfer in Laminar Viscous Flow .............. 274 5.4 Forced Convective Mass Transfer in Turbulent Flow .................... 277 6. Computational Fluid Dynamics ............................................. 279 References ............................................................... 280 Chapter 12. Heterogeneous Gas-Solid Reactions and Heterogeneous Catalysis .... 282 1. Introduction ............................................................. 282 2. Reaction Regimes in Heterogeneous Gas-Solid Reactions .................... 283 3. Combustion and Gasification .............................................. 288 4. Heterogeneous Catalysts .................................................. 291 5. Interaction of Reactants with Heterogeneous Catalysts .................... 292 6. Mechanism of Heterogeneous Catalysis ..................................... 294 6.1 Active Sites ......................................................... 295 6.2 Selectivity and Catalytic Activity ................................... 295 6.3 Thermodynamics of Adsorption ......................................... 297 6.4 Reaction Pathways in Heterogeneous Catalysis ......................... 298 7. Adsorption ............................................................... 299 8. Chemisorption and Reaction Rate in Heterogeneous Catalysts ............... 304 8.1 Langmuir-Hinshelwood Model ........................................... 304 8.2 Apparent Activation Energies ......................................... 308 References ............................................................... 309 Part III. Refining Chapter 13. Pretreatment and Distillation .................................... 310 1. Introduction ............................................................. 310 2. Pretreatment ............................................................. 312 3. Distillation ............................................................. 319 3.1 Atmospheric Distillation ............................................. 324 3.2 Vacuum Distillation .................................................. 331 4. Other Processes .......................................................... 336 4.1 Stripping ............................................................ 336 4.2 Rerunning ............................................................ 337 4.3 Stabilization and Light End Removal .................................. 337 4.4 Superfractionation ................................................... 340 4.5 Azeotropic Distillation and Extractive Distillation .................. 340 References ............................................................... 342 Chapter 14. Thermal Cracking ................................................. 344 1. Introduction ............................................................. 344 2. Thermal Cracking ......................................................... 350 3. Visbreaking .............................................................. 351 4. Coking ................................................................... 368 4.1 Delayed Coking ....................................................... 369 4.2 Fluid Coking and Flexicoking ......................................... 374 5. Other Processes .......................................................... 385 References ............................................................... 386 Chapter 15. Catalytic Cracking ............................................... 388 1. Introduction ............................................................. 388 2. Fixed-Bed Processes ...................................................... 394 3. Moving-Bed Processes ..................................................... 396 4. Fluid-Bed Processes ...................................................... 400 5. Process Variables ........................................................ 406 5.1 Feedstock Quality ................................................... 406 5.2 Feedstock Preheating ................................................ 411 5.3 Feedstock Pressure .................................................. 412 5.4 Feedstock Conversion ................................................ 413 5.5 Reactor Temperature ................................................. 414 5.6 Recycle Rate ........................................................ 414 5.7 Space Velocity ...................................................... 415 5.8 Catalyst Activity ................................................... 415 5.9 Catalyst/Oil Ratio .................................................. 416 5.10 Regenerator Temperature ............................................. 417 5.11 Regenerator Air Rate ................................................ 417 6. Catalysts ................................................................ 418 6.1 Catalyst Types ....................................................... 418 6.2 Catalyst Manufacture ................................................. 420 6.3 Catalyst Selectivity ................................................. 421 6.4 Catalyst Deactivation ................................................ 422 6.5 Catalyst Stripping ................................................... 423 6.6 Catalyst Treatment ................................................... 424 References ............................................................... 437 Chapter 16. Hydrotreating .................................................... 439 1. Introduction ............................................................. 439 2. Hydrodesulfurization ..................................................... 449 2.1 Process Configuration ................................................ 451 2.2 Downflow Fixed-Bed Reactor ........................................... 451 2.3 Upflow Expanded-Bed Reactor .......................................... 453 2.4 Demetallization Reactor (Guard Bed Reactor) .......................... 454 2.5 Catalysts ............................................................ 455 3. Distillate Hydrodesulfurization .......................................... 456 3.1 Processes ............................................................ 456 3.2 Process Parameters ................................................... 461 4. Residuum Hydrodesulfurization ............................................ 466 4.1 Processes ............................................................ 466 4.2 Process Parameters ................................................... 473 References ............................................................... 484 Chapter 17. Hydrocracking .................................................... 485 1. Introduction ............................................................. 485 2. Processes and Process Design ............................................. 496 2.1 CANMET Process ...................................................... 499 2.2 Gulf HDS Process .................................................... 501 2.3 H-G Hydrocracking Process ........................................... 502 2.4 H-Oil Process ....................................................... 503 2.5 IFP Hydrocracking Process ........................................... 504 2.6 Isocracking Process ................................................. 506 2.7 LC-Fining Process ................................................... 508 2.8 MAKfining HDC Process ............................................... 511 2.9 Microcat-RC Process ................................................. 511 2.10 Mild Hydrocracking Process .......................................... 513 2.11 MRH Process ......................................................... 516 2.12 RCD Unibon (BOC) Process ............................................ 517 2.13 Residfining Process ................................................. 519 2.14 Residue Hydroconversion Process ..................................... 520 2.15 Unicracking Process ................................................. 520 2.16 Veba Combi-Cracking Process ......................................... 523 3. Catalysts ................................................................ 526 References ............................................................... 536 Chapter 18. The Next Generation Process ...................................... 538 1. Introduction ............................................................. 538 2. Thermal (Carbon Rejection) Processes ..................................... 542 2.1 Asphalt Coking Technology Process .................................... 542 2.2 Cherry-P (Comprehensive Heavy Ends Reforming Refinery) Process ....... 544 2.3 Deep Thermal Conversion Process ...................................... 544 2.4 ET-II Process ........................................................ 545 2.5 Eureka Process ....................................................... 547 2.6 Fluid Thermal Cracking Process ....................................... 549 2.7 High Conversion Soaker Cracking Process .............................. 550 2.8 Tervahl Process ...................................................... 552 3. Catalytic Cracking (Carbon Rejection) Processes .......................... 553 3.1 Asphalt Residua Treating Process ..................................... 554 3.2 Heavy Oil Treating Process ........................................... 556 3.3 R2R Process .......................................................... 558 3.4 Reduced Crude Oil Conversion Process ................................. 558 3.5 Residual Fluid Catalytic Cracking Process ............................ 558 3.6 Shell FCC Process .................................................... 564 3.7 S&W Fluid Catalytic Cracking Process ................................. 565 4. Hydrogen Addition Processes .............................................. 566 4.1 Asphaltenic Bottoms Cracking Process ................................. 566 4.2 Hydrovisbreaking (HYCAR) Process ..................................... 570 4.3 Hyvahl F Process ..................................................... 571 5. Solvent Processes ........................................................ 572 5.1 Deasphalting Process ................................................. 572 5.2 Deep Solvent Deasphalting Process .................................... 579 5.3 Demex Process ........................................................ 581 5.4 MDS Process .......................................................... 584 5.5 Residuum Oil Supercritical Extraction Process ........................ 585 5.6 Solvahl Process ...................................................... 587 References ............................................................... 587 Chapter 19. Product Improvement .............................................. 590 1. Introduction ............................................................. 590 2. Desulfurization and Heteroatom Removal ................................... 593 2.1 Hydrotreating ........................................................ 595 2.2 Hydrogen Sulfide Removal ............................................. 596 3. Reforming ................................................................ 598 3.1 Thermal Reforming .................................................... 598 3.2 Catalytic Reforming .................................................. 602 3.3 Dehydrogenation ...................................................... 621 3.4 Catalysts ............................................................ 622 4. Isomerization ............................................................ 623 4.1 Process Types ........................................................ 624 4.2 Commercial Processes ................................................. 624 4.3 Catalysts ............................................................ 628 5. Alkylation ............................................................... 628 5.1 Process Types ........................................................ 629 5.2 Commercial Processes ................................................. 629 5.3 Catalysts ............................................................ 633 6. Polymerization ........................................................... 634 6.1 Process Types ........................................................ 634 6.2 Commercial Processes ................................................. 635 6.3 Catalysts ............................................................ 636 References ............................................................... 637 Chapter 20. Hydrogen Production .............................................. 639 1. Introduction ............................................................. 639 2. Process Variables ........................................................ 645 2.1 Feedstocks ........................................................... 645 2.2 Process Chemistry .................................................... 647 3. Commercial Processes ..................................................... 650 3.1 Heavy Residue Gasification and Combined Cycle Power Generation ....... 650 3.2 Hybrid Gasification Process .......................................... 650 3.3 Hydrocarbon Gasification ............................................. 651 3.4 Hypro Process ........................................................ 651 3.5 Shell Gasification (Partial Oxidation) Process ....................... 651 3.6 Steam-Methane Reforming .............................................. 652 3.7 Steam-Naphtha Reforming .............................................. 653 3.8 Synthesis Gas Generation ............................................. 653 3.9 Texaco Gasification (Partial Oxidation) Process ...................... 655 4. Catalysts ................................................................ 657 4.1 Reforming Catalysts .................................................. 657 4.2 Shift Conversion Catalysts ........................................... 658 4.3 Methanation Catalysts ................................................ 659 5. Hydrogen Purification .................................................... 659 5.1 Wet Scrubbing ........................................................ 660 5.2 Pressure Swing Adsorption Units ...................................... 660 5.3 Membrane Systems ..................................................... 661 5.4 Cryogenic Separation ................................................. 662 References ............................................................... 662 Glossary ..................................................................... 663 Conversion Factors and SI Units .............................................. 693 Index ........................................................................ 695