Preface... xii Chapter Breakdown... xiii 1. Refinery Distillation... 1 Process Variables... 2 Process Design of a Crude Distillation Tower... 5 Characterization of Unit Fractionation... 11 General Properties of Petroleum Fractions... 14 Atmospheric Distillation Unit... 18 Vacuum Distillation Unit... 20 Crude Desalting... 22 2. Distillate Hydrotreating... 29 Naphtha Hydrodesulfurization Process... 34 Kerosene Hydrotreating... 38 Gas Oil Hydrodesulfurization... 41 Atmospheric Residuum Desulfurization... 50 3. Hydrocracking Processes... 62 Hydrocracking Reactions... 62 Process Configuration... 66 Process Flow Scheme... 69 Operating Conditions... 75 Catalyst Sulfiding and Unit Startup... 88 Shutdown Procedure... 90 vii
viii Catalyst Regeneration... 92 Mild Hydrocracking... 95 Residuum Hydrocracking... 95 4. Gasoline Manufacturing Processes... 109 Catalytic Reforming... 109 Fluid Catalytic Cracking... 114 Alkylation... 128 Isomerization of C 5 /C 6 Normal Paraffins... 136 Methyl Tertiary Butyl Ether... 143 5. Hydrogen Production and Recovery... 153 Natural Gas Desulfurization... 153 Steam Reforming... 156 Carbon Monoxide Conversion... 157 Carbon Dioxide Removal... 158 Methanation... 162 Pressure Swing Adsorption Route... 162 Partial Oxidation Process... 164 Hydrogen Recovery... 170 6. Residuum Processing... 176 Delayed Coking... 176 Visbreaking... 189 Solvent Deasphalting... 197 Bitumen Blowing... 203 7. Treating Processes... 210 General Principles... 210 FCCU Light Gasoline... 211 Jet Fuel (ATK) Sweetening... 214
ix 8. Sulfur Recovery and Pollution Control Processes... 220 Sulfur Recovery from Acid Gas... 220 Claus Tail Gas Treatment... 223 Flue Gas Desulfurization... 228 Amine Treatment... 235 9. Refinery Water Systems... 242 Cooling Water System... 242 Sea Water Cooling System... 243 Cooling Towers... 246 Boiler Feedwater System... 247 Utility Water System... 251 Treatment of Oily Water... 257 Wet Slop Oil System... 260 Treatment of Sanitary Sewage... 261 Sour Water Treatment... 261 10. Refinery Off-site Facilities and Utility Systems... 270 Refinery Tankage... 270 Shipping Terminals and Sea Lines... 272 Refinery Tankage Estimation... 273 Product Blending System... 278 Refinery Flare System... 286 Refinery Steam System... 298 Refinery Fuel System... 303 11. Product Blending... 308 Gasoline Octane Blending... 308 ASTM Distillation Blending... 314 Viscosity Blending... 326
x Pour Point Blending... 330 Flash Point Blending... 331 Reid Vapor Pressure Blending for Gasolines and Naphthas... 339 Aniline Point Blending... 341 Crude Oil Assays... 342 12. Refinery Stock Balancing... 384 Data for Model Building... 385 Calculation Procedure... 386 Refinery Material Balance Spreadsheet Program... 388 13. Refinery Linear Programming Modeling... 415 Overview... 415 Development of the Refinery LP Model... 415 The Structure of a Refinery LP Model... 417 Property Propagation to Other Tables... 430 Blending Specifications... 431 Stream Pooling (Recursion Process)... 431 Distributive Recursion... 436 Objective Function... 439 Optimization Step... 439 Solution Convergence... 440 Interpreting the Solution... 440 Report Writer Programs... 443 Delta-based Modeling... 443 Atmospheric Crude Distillation and VDU Modeling... 447 Single-product LP Blender... 471 14. Pricing Petroleum Products... 476 Netback and Formula Pricing for Crude Oil... 476 Pricing Petroleum Products and Intermediate Stocks... 481
xi Assigned Crude Yields... 488 15. Definitive Operating Plan... 493 DOPs in Joint-ownership Refineries... 498 Fixed- and Balancing-grade Products... 505 Product Equivalencies... 510 Product Equivalency Determination... 514 Crude Oil Equivalency... 518 Equivalency of Slop... 519 16. Product Allocation... 520 Input Data... 521 Forecaster Changes... 521 Rules for Forecaster Changes... 521 Crude Oil Changes... 534 DOP Loss Adjustment... 535 Retrospective DOP... 536 Allocation of Balancing Grades... 536 Reverse Allocation... 537 Final Allocation... 542 Allocation LPs... 545 Process Unit Capacities... 545 Product Prices... 548 Summary of Primary Data Input for LPs... 551 Examination of LP Results... 551 Final Allocation Cycle... 556 Allocation Spreadsheet Program... 561 Product Allocation Problems... 567 17. Available Tankage Capacity... 620 Estimation of Total Available Capacity... 620
xii Minimum and Maximum Inventory (LI and HI)... 621 Allocation of Tankage Capacity... 622 Ullage... 633 Ceding of Refinery Capacity... 635 Ceding of Tankage Capacity... 635 18. Shipping Inventory Forecasts... 638 Weekly Production Estimates... 638 Refinery Estimate Schedule... 639 Procedure... 640 Allocation of Deltas... 641 Inventory and Ullage Forcasting System (Joint Ownership Refineries)... 646 19. Refinery Operating Cost... 681 Allocation of Operating Cost... 682 System Costing Method... 682 Theoretical Sales Realization Valuation Method... 682 Cost Allocation for Actual Usage... 684 Unused Capacity Charge... 684 Appendix: Processing Agreement for Joint-ownership Refinery... 691 Index... 709