WORLDWIDE REFINERY PROCESSING REVIEW - 3Q2011 by Hydrocarbon Publishing Company

WORLDWIDE REFINERY PROCESSING REVIEW Monitoring Technology Development and Competition in a Single Source

Third Quarter 2011 Hydrocracking and Hydrogen Production, Purification, and Recovery Plus

Latest Refining Technology Developments & Licensing

HYDROCARBON PUBLISHING COMPANY Translating Knowledge into Profitability

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TABLE OF CONTENTS 3Q 2011 Review Hydrocracking and Hydrogen Production, Purification, and Recovery 1. Introduction ..................................................................................................................................... 1 2. Hydrocracking ................................................................................................................................ 5 2.1

2.2

MARKET/TECHNOLOGY TRENDS & OPPORTUNITIES ............................................................................................. 5 2.1.1 Introduction .............................................................................................................................................. 5 2.1.2 Market Conditions and Outlook................................................................................................................ 6 2.1.2.1 Refined Products Legislation ...................................................................................................... 6 2.1.2.1.1 Gasoline and Diesel ................................................................................................... 6 2.1.2.1.2 Bunker Fuels.............................................................................................................. 7 2.1.2.2 Fuel Demand and Dieselization .................................................................................................. 9 2.1.2.3 Increasing Middle Distillate Production ................................................................................... 12 2.1.2.4 Hydrogen Demand .................................................................................................................... 14 2.1.2.5 Capacity Expansion .................................................................................................................. 15 2.1.2.6 Hydrocracking Catalyst Market ................................................................................................ 17 2.1.3 Technology Competition, Direction, and Future Prospects ................................................................... 20 2.1.3.1 Market Layout and Strategic Alliances .................................................................................... 20 2.1.3.2 Conventional and Mild Hydrocracking .................................................................................... 21 2.1.3.3 Resid Hydrocracking ................................................................................................................ 30 2.1.3.4 Alternative Feed Hydrocracking............................................................................................... 31 2.1.3.5 Revamp and Integration Options .............................................................................................. 33 2.1.4 Conclusion .............................................................................................................................................. 35 STATE-OF-THE-ART TECHNOLOGY ..................................................................................................................... 36 2.2.1 Introduction ............................................................................................................................................ 36 2.2.2 Commercial Process Technology............................................................................................................ 37 2.2.2.1 Axens ........................................................................................................................................ 38 2.2.2.1.1 Mild Hydrocracking ................................................................................................ 38 2.2.2.1.1.1 Mild-HCK ......................................................................................... 38 2.2.2.1.1.2 HyC-10/HyC-10+ ............................................................................. 39 2.2.2.1.2 H-OilDC .................................................................................................................... 43 2.2.2.1.3 HyTail ...................................................................................................................... 44 2.2.2.1.4 Medium-pressure Hydrocracking ............................................................................ 45 2.2.2.1.5 Conventional (High-pressure) Hydrocracking ........................................................ 45 2.2.2.1.6 Reactor Internals ...................................................................................................... 49 2.2.2.2 Chevron Lummus Global ......................................................................................................... 49 2.2.2.2.1 ISOCRACKING ...................................................................................................... 49 2.2.2.2.1.1 Single-Stage Once Through and Single-Stage Recycle .................... 50 2.2.2.2.1.2 Two-Stage Recycle ........................................................................... 51 2.2.2.2.1.3 Optimized Partial Conversion........................................................... 55 2.2.2.2.1.4 Selective Staging .............................................................................. 57 2.2.2.2.1.5 Split-feed Injection ........................................................................... 60 2.2.2.2.1.6 Single-stage Reaction Sequencing .................................................... 61 2.2.2.2.2 ISOFLEX................................................................................................................. 61 2.2.2.2.3 Reactor Internals ...................................................................................................... 63 2.2.2.3 DuPont Clean Technologies ..................................................................................................... 64

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TABLE OF CONTENTS 2.2.2.4 ExxonMobil .............................................................................................................................. 67 2.2.2.4.1 Single-stage MPHC ................................................................................................. 67 2.2.2.4.2 MPHC-PTU ............................................................................................................. 71 2.2.2.4.3 MPHC-LCO ............................................................................................................. 72 2.2.2.4.4 Two-stage MPHC .................................................................................................... 74 2.2.2.4.5 Spider-Vortex Reactor Internals .............................................................................. 76 2.2.2.5 Haldor Topsøe ........................................................................................................................... 77 2.2.2.5.1 Mild Hydrocracking ................................................................................................. 77 2.2.2.5.1.1 Staged Partial Conversion Hydrocracking ........................................ 78 2.2.2.5.1.2 Back-End Shift (BES) Process .......................................................... 80 2.2.2.5.2 Conventional (High-pressure) Hydrocracking ......................................................... 80 2.2.2.5.3 Reactor Internals ...................................................................................................... 80 2.2.2.6 Shell Global Solutions .............................................................................................................. 82 2.2.2.6.1 Mild Hydrocracking ................................................................................................. 83 2.2.2.6.2 Conventional Hydrocracking ................................................................................... 84 2.2.2.6.3 Reactor Internals ...................................................................................................... 85 2.2.2.7 Sinopec ...................................................................................................................................... 88 2.2.2.7.1 Flexible Hydrotreating/Mild Hydrocracking ........................................................... 88 2.2.2.7.2 Medium-pressure Hydro-Upgrading ........................................................................ 90 2.2.2.7.3 Moderate-pressure Hydrocracking........................................................................... 92 2.2.2.7.4 High-pressure Hydrocracking .................................................................................. 92 2.2.2.7.4.1 Single-stage Hydrocracking .............................................................. 93 2.2.2.7.4.2 Single-stage in Series Hydrocracking ............................................... 93 2.2.2.7.4.3 Single-stage, Double-catalyst Hydrocracking ................................... 95 2.2.2.7.4.4 Two-stage Hydrocracking ................................................................. 96 2.2.2.7.4.5 Flexible Hydrocracking..................................................................... 96 2.2.2.8 UOP........................................................................................................................................... 97 2.2.2.8.1 MHC Unicracking .................................................................................................... 98 2.2.2.8.2 Unicracking .............................................................................................................. 99 2.2.2.8.2.1 Single-stage Once Through or with Recycle..................................... 99 2.2.2.8.2.2 Two-stage Unicracking ................................................................... 102 2.2.2.8.3 Partial-conversion Unicracking ............................................................................. 106 2.2.2.8.4 Dieselmax .............................................................................................................. 110 2.2.2.8.5 HyCycle Unicracking............................................................................................. 112 2.2.2.8.6 Advanced Partial Conversion Unicracking ............................................................ 113 2.2.2.8.7 HPNA Removal Systems ....................................................................................... 115 2.2.2.8.8 Reactor Internals .................................................................................................... 115 2.2.2.9 Velocys ................................................................................................................................... 116 2.2.2.10 Summary of Hydrocracking Process Technologies ................................................................ 117 2.2.3 Commercial Catalysts ........................................................................................................................... 122 2.2.3.1 Albemarle ................................................................................................................................ 122 2.2.3.2 Axens ...................................................................................................................................... 123 2.2.3.3 Chevron Lummus Global ........................................................................................................ 124 2.2.3.4 Criterion Catalysts & Technologies ........................................................................................ 129 2.2.3.5 Haldor Topsøe ......................................................................................................................... 132 2.2.3.6 JGC Catalysts & Chemicals .................................................................................................... 133 2.2.3.7 Sinopec .................................................................................................................................... 134 2.2.3.8 UOP......................................................................................................................................... 134 2.2.3.9 Summary of Commercially Available Hydrocracking Catalysts ............................................ 138

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2.2.4 Auxiliary Catalyst Technology .............................................................................................................. 140 2.2.4.1 Albemarle ............................................................................................................................... 140 2.2.4.2 Axens ...................................................................................................................................... 141 2.2.4.3 Crystaphase Products .............................................................................................................. 141 2.2.4.4 Eurecat .................................................................................................................................... 141 2.2.4.5 TRICAT .................................................................................................................................. 142 2.2.5 Control and Optimization Systems........................................................................................................ 142 2.2.6 Resid Hydrocracking ............................................................................................................................ 146 2.2.7 Renewable Hydrocracking .................................................................................................................... 152 PLANT OPERATIONS AND PRACTICES ................................................................................................................ 156 2.3.1 General Hydrocracking Operations ..................................................................................................... 156 2.3.1.1 Feed Considerations, Operational Variables, Process Configurations, and Hardware ........... 157 2.3.1.1.1 Feedstock Characterization.................................................................................... 157 2.3.1.1.2 Upgrading LCO and/or HCO in Hydrocrackers .................................................... 157 2.3.1.1.3 Undercutting LVGO to Increase Hydrocracker Utilization................................... 157 2.3.1.1.4 Optimizing Operational Variables ......................................................................... 158 2.3.1.1.4.1 Recycle Rate in Two-stage Units.................................................... 158 2.3.1.1.4.2 Setting Operational Pressure........................................................... 159 2.3.1.1.5 Reactor Configuration ........................................................................................... 160 2.3.1.1.6 Changing Unit Configuration to Boost Yields and Process Alternative Feeds ..... 161 2.3.1.1.7 Large Single Process Train vs. Smaller Parallel Trains in Hydrocrackers ............ 162 2.3.1.1.8 Reactor Fabrication and Metallurgy ...................................................................... 163 2.3.1.1.9 Comparison of Quench Systems............................................................................ 164 2.3.1.1.10 Hydrocracker Stripper Revamp: From Packing to Trays ...................................... 165 2.3.1.1.11 Hydrocracker Pump Selection ............................................................................... 165 2.3.1.2 Fouling, Particulate Deposition, and Corrosion...................................................................... 166 2.3.1.2.1 Causes of Hydroprocesser Fouling and Possible Treatments ................................ 166 2.3.1.2.2 Elimination of Polynuclear Aromatics (PNA) Buildup ......................................... 167 2.3.1.2.3 Iron Sulfide Buildup in VGO Hydrocrackers ........................................................ 168 2.3.1.2.4 Feed Filter Operation ............................................................................................. 170 2.3.1.2.5 Fouling in Furnace Tubes ...................................................................................... 171 2.3.1.2.6 Corrosion in Overhead System .............................................................................. 172 2.3.1.2.7 Corrosion in Auxiliary Equipment ........................................................................ 172 2.3.1.3 Operational Problems ............................................................................................................. 173 2.3.1.3.1 Increased Yield Using Multivariable Predictive Control (MPC) .......................... 173 2.3.1.3.2 Improving Hydrocracker Temperature Control ..................................................... 176 2.3.1.3.3 Detecting Radial Temperature Spread and Preventing Reactor Runaway ............ 178 2.3.1.3.4 Hydrocracker Furnace Operations ......................................................................... 180 2.3.1.3.5 Causes of Overcracking ......................................................................................... 181 2.3.1.3.6 Preventing Off-color Naphtha Product .................................................................. 182 2.3.1.3.7 Reducing the Level of Sulfur in Naphtha at EOR Conditions............................... 182 2.3.1.3.8 Limiting Ammonia Concentration in the Cold High-pressure Separator Overhead.... .............................................................................................................................. 182 2.3.1.3.9 Inline Hydrocracker Cleaning System ................................................................... 183 2.3.1.3.10 Preventing Surges in the Recycle Gas Compressor ............................................... 183 2.3.1.4 Catalyst Management ............................................................................................................. 184 2.3.1.4.1 Selection Process for Hydrocracking Catalysts ..................................................... 184 2.3.1.4.2 Measuring Hydrocracking Catalyst Activity ......................................................... 184 2.3.1.4.3 Catalyst for Processing Various Feeds .................................................................. 185 2.3.1.4.4 Effects of a Catalyst Change on Gasoline Quality ................................................ 186

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2.3.1.4.5 Catalyst Structure: Homogeneous vs. Stacked....................................................... 186 2.3.1.4.6 Ex-Situ Presulfiding of Hydrocracking Catalysts .................................................. 187 2.3.1.4.7 Ammoniation Passivation during Startup .............................................................. 188 2.3.1.4.8 Disproportionate Catalyst Deactivation in the First Bed of a Hydrocracker ......... 189 2.3.1.4.9 Asphaltene Contribution to Catalyst Deactivation ................................................. 190 2.3.1.4.10 Regenerated Hydrocracking Catalyst Use ............................................................. 190 2.3.1.4.11 Recovering Spent Hydroprocessing Catalysts ....................................................... 192 2.3.1.5 Reducing Hydrocracker Energy Use ....................................................................................... 193 2.3.1.5.1 Modeling ................................................................................................................ 193 2.3.1.5.2 Cleaning ................................................................................................................. 193 2.3.1.5.3 Heat Integration ..................................................................................................... 194 2.3.1.5.4 Power Recovery ..................................................................................................... 194 2.3.1.5.5 Impact of Catalysts................................................................................................. 194 2.3.1.6 Hydrocracker Safety ............................................................................................................... 195 2.3.1.6.1 Hydrocracker Safety Incidents ............................................................................... 195 2.3.1.6.2 Emergency Depressurization: Triggering Criteria, Rates, and Modes ................... 196 2.3.1.6.3 Operational Status of Emergency Depressurizing Valves and Interlocks.............. 198 2.3.2 Mild Hydrocracking (MHC) .................................................................................................................. 198 2.3.2.1 Mild Hydrocracking: Feedstock, Conversion, and Product Quality ....................................... 198 2.3.2.2 Converting a Cat Feed Hydrotreater to a Mild Hydrocracker ................................................. 199 2.3.2.3 Options for Improving the Cycle Length of Mild Hydrocrackers........................................... 201 2.3.3 Distillate Hydrocracking ....................................................................................................................... 201 2.3.3.1 Shifting from Maximum Naphtha to Maximum Middle Distillate Yields .............................. 201 2.3.3.2 Maximizing Diesel Production in VGO Hydrocrackers ......................................................... 203 2.3.3.3 Benefits of Moderate Pressure Hydrocracking (MPHC) in Clean Diesel Production ............ 205 2.3.3.4 Reactor Revamp to Improve ULSD Production ..................................................................... 206 2.3.3.5 Loading Hydrocracking Catalyst in the Last Bed of a ULSD Unit......................................... 207 2.3.3.6 Process Revamp for Added H2S Removal to Meet ULSD Standards ..................................... 208 2.3.3.7 Hydrocracking Catalysts for Cold Flow Property Improvements ........................................... 208 2.3.4 Integrated Processing Schemes ............................................................................................................. 209 2.3.4.1 Delayed Coker with Hydrocracker.......................................................................................... 209 2.3.4.2 Solvent Deasphalting with Hydrocracker ............................................................................... 210 2.3.4.3 Mild Hydrocracker with FCC ................................................................................................. 211 REFINING R&D ALERT! ..................................................................................................................................... 212 2.4.1 Introduction ........................................................................................................................................... 212 2.4.2 General Hydrocracking ......................................................................................................................... 216 2.4.2.1 Process .................................................................................................................................... 216 2.4.2.1.1 Patents .................................................................................................................... 216 2.4.2.1.2 Research ................................................................................................................. 218 2.4.2.2 Catalyst.................................................................................................................................... 219 2.4.2.2.1 Patents .................................................................................................................... 219 2.4.2.2.2 Research ................................................................................................................. 225 2.4.2.3 Hardware ................................................................................................................................. 229 2.4.2.4 Integrated Operations (Conventional Feeds) .......................................................................... 230 2.4.3 Product Selective Hydrocracking .......................................................................................................... 233 2.4.3.1 Diesel ...................................................................................................................................... 233 2.4.3.1.1 Patents .................................................................................................................... 233 2.4.3.1.2 Research ................................................................................................................. 234 2.4.3.2 Gasoline .................................................................................................................................. 235 2.4.3.2.1 Patents .................................................................................................................... 235 2.4.3.2.2 Research ................................................................................................................. 235 2.4.4 Resid Hydrocracking ............................................................................................................................. 236 2.4.4.1 Process .................................................................................................................................... 236

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2.5 2.6 2.7

2.4.4.2 Catalyst ................................................................................................................................... 242 2.4.4.2.1 Patents ................................................................................................................... 242 2.4.4.2.2 Research ................................................................................................................ 244 2.4.5 Hydrocracking Alternative Feedstocks ................................................................................................. 245 2.4.5.1 Fischer-Tropsch Liquids ......................................................................................................... 245 2.4.5.1.1 Process ................................................................................................................... 245 2.4.5.1.2 Catalyst .................................................................................................................. 247 2.4.5.1.2.1 Patents............................................................................................. 247 2.4.5.1.2.2 Research.......................................................................................... 250 2.4.5.2 Renewable Feedstocks ............................................................................................................ 251 2.4.5.2.1 Patents ................................................................................................................... 251 2.4.5.2.2 Research ................................................................................................................ 254 2.4.6 Miscellaneous ....................................................................................................................................... 255 2.4.6.1 Patents..................................................................................................................................... 255 2.4.6.2 Research.................................................................................................................................. 256 WORLDWIDE INSTALLED CAPACITY.................................................................................................................. 256 CONSTRUCTION ................................................................................................................................................. 259 2.6.1 Recent Construction Activity ................................................................................................................. 259 2.6.2 Completed Construction Projects ......................................................................................................... 265 REFERENCES ..................................................................................................................................................... 277

3. Hydrogen Production, Purification, and Recovery ................................................................. 299 3.1

3.2

MARKET/TECHNOLOGY TRENDS & OPPORTUNITIES ......................................................................................... 299 3.1.1 Introduction .......................................................................................................................................... 299 3.1.2 Market Conditions and Outlook............................................................................................................ 300 3.1.2.1 Refinery Hydrogen Demand ................................................................................................... 300 3.1.2.2 Production Capacity and Market Supply ................................................................................ 300 3.1.2.3 Impact of Opportunity Crudes Processing on Hydrogen Demand ......................................... 302 3.1.2.4 Onsite Production vs. Over-the-fence Supply ........................................................................ 305 3.1.2.5 Feedstock Choices .................................................................................................................. 305 3.1.2.6 Environmental Factors ............................................................................................................ 307 3.1.3 Technology Competition, Directions, and Future Prospects ................................................................ 310 3.1.3.1 Evaluation of Technology Offerings ...................................................................................... 310 3.1.3.2 Hydrogen Production .............................................................................................................. 312 3.1.3.2.1 Steam Reforming/Autothermal Reforming ........................................................... 312 3.1.3.2.2 Membrane Reactors ............................................................................................... 315 3.1.3.2.3 Renewable Feed Reforming .................................................................................. 315 3.1.3.3 H2 Purification, Recovery, and Management ......................................................................... 316 3.1.4 Conclusion ............................................................................................................................................ 317 STATE-OF-THE-ART TECHNOLOGY ................................................................................................................... 318 3.2.1 Introduction .......................................................................................................................................... 318 3.2.2 Commercial and Near-commercial Process Technologies ................................................................... 323 3.2.2.1 H2 Production ......................................................................................................................... 323 3.2.2.1.1 Caloric Anlagenbau ............................................................................................... 323 3.2.2.1.1.1 HC Process ..................................................................................... 323 3.2.2.1.1.2 HM Process..................................................................................... 324 3.2.2.1.1.3 HC Economy Ultra Process ............................................................ 325 3.2.2.1.2 CB&I ..................................................................................................................... 326 3.2.2.1.2.1 Steam Reforming ............................................................................ 326 3.2.2.1.2.2 Autothermal Reforming .................................................................. 328

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TABLE OF CONTENTS 3.2.2.1.3 Davy Process Technology...................................................................................... 328 3.2.2.1.3.1 CRG Prereforming .......................................................................... 328 3.2.2.1.3.2 Compact Reformer .......................................................................... 329 3.2.2.1.4 Foster Wheeler ....................................................................................................... 330 3.2.2.1.5 Haldor Topsøe........................................................................................................ 333 3.2.2.1.5.1 Feed Purification ............................................................................. 333 3.2.2.1.5.2 Prereforming ................................................................................... 333 3.2.2.1.5.3 Side-fired Tubular Reformer ........................................................... 334 3.2.2.1.5.4 High Flux Reformer ........................................................................ 335 3.2.2.1.5.5 Haldor Topsøe Convection Reformer ............................................. 335 3.2.2.1.5.6 Haldor Topsøe Exchange Reformer ................................................ 338 3.2.2.1.5.7 Haldor Topsøe Bayonet Reformer .................................................. 341 3.2.2.1.5.8 Methanol-to-Shift Process............................................................... 341 3.2.2.1.5.9 Methanol Decomposition-based H2 Plants ...................................... 342 3.2.2.1.6 JGC Corp. .............................................................................................................. 343 3.2.2.1.7 Johnson Matthey Catalysts..................................................................................... 343 3.2.2.1.8 KBR ....................................................................................................................... 346 3.2.2.1.9 Linde BOC Process Plants ..................................................................................... 347 3.2.2.1.9.1 Prereformer ..................................................................................... 348 3.2.2.1.9.2 Steam Reformer .............................................................................. 348 3.2.2.1.9.3 Gas Heated Reformer ...................................................................... 349 3.2.2.1.10 Lurgi....................................................................................................................... 350 3.2.2.1.10.1 Pretreatment .................................................................................... 350 3.2.2.1.10.2 Prereforming ................................................................................... 350 3.2.2.1.10.3 Steam Reforming Process ............................................................... 351 3.2.2.1.10.4 Lurgi Autothermal Catalytic Reforming Process ............................ 352 3.2.2.1.10.5 Lurgi CO Shift Process ................................................................... 353 3.2.2.1.11 Praxair .................................................................................................................... 354 3.2.2.1.12 Shell ....................................................................................................................... 357 3.2.2.1.13 Technip .................................................................................................................. 357 3.2.2.1.13.1 Steam Reforming ............................................................................ 358 3.2.2.1.13.2 ART Process ................................................................................... 360 3.2.2.1.13.3 Enhanced Heat Transfer Reformer.................................................. 360 3.2.2.1.14 Toyo Engineering Corp.......................................................................................... 361 3.2.2.1.15 Uhde ....................................................................................................................... 362 3.2.2.1.15.1 Feed Preparation ............................................................................. 363 3.2.2.1.15.2 Prereforming ................................................................................... 363 3.2.2.1.15.3 Steam Reforming ............................................................................ 363 3.2.2.1.15.4 CO Shift .......................................................................................... 364 3.2.2.1.15.5 Autothermal Reforming .................................................................. 365 3.2.2.1.15.6 Combined Autothermal Reforming Process.................................... 365 3.2.2.1.15.7 Convective Reformer ...................................................................... 365 3.2.2.2 H2 Recovery and Purification.................................................................................................. 365 3.2.2.2.1 Advanced Extraction Technologies ....................................................................... 366 3.2.2.2.2 Air Liquide ............................................................................................................. 367 3.2.2.2.2.1 PSA ................................................................................................. 368 3.2.2.2.2.2 Cryogenic System ........................................................................... 368 3.2.2.2.2.3 MEDAL Membrane Technology .................................................... 368 3.2.2.2.3 Air Products and Chemicals ................................................................................... 369 3.2.2.2.3.1 Gemini Hyco Adsorption Systems .................................................. 370 3.2.2.2.3.2 Prism PSA Units ............................................................................. 370 3.2.2.2.3.3 Prism Membrane Systems ............................................................... 372

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3.2.2.2.3.4 Selective Surface Flow Membranes ............................................... 373 3.2.2.2.3.5 Cryogenic Systems ......................................................................... 373 3.2.2.2.3.6 ACORN Methane Wash Units........................................................ 375 3.2.2.2.3.7 ACORN Partial Condensation Units .............................................. 375 3.2.2.2.4 CB&I ..................................................................................................................... 376 3.2.2.2.5 Costain Oil, Gas & Process ................................................................................... 377 3.2.2.2.6 CRI/Criterion Catalysts & Technologies ............................................................... 377 3.2.2.2.7 ExxonMobil ........................................................................................................... 378 3.2.2.2.8 Linde ...................................................................................................................... 379 3.2.2.2.9 Membrane Technology Research .......................................................................... 379 3.2.2.2.10 Pall Corp. ............................................................................................................... 381 3.2.2.2.11 Toyo Engineering .................................................................................................. 381 3.2.2.2.12 UOP ....................................................................................................................... 382 3.2.2.2.12.1 Polybed PSA Systems..................................................................... 383 3.2.2.2.12.2 Polysep Membrane Systems ........................................................... 385 3.2.3 Commercial Catalysts ........................................................................................................................... 387 3.2.3.1 BASF Catalysts....................................................................................................................... 387 3.2.3.2 Haldor Topsøe ........................................................................................................................ 388 3.2.3.2.1 Feed Purification ................................................................................................... 388 3.2.3.2.2 Prereforming .......................................................................................................... 389 3.2.3.2.3 Steam Reforming ................................................................................................... 389 3.2.3.2.4 Shift Conversion .................................................................................................... 390 3.2.3.2.5 Methanation ........................................................................................................... 391 3.2.3.3 Johnson Matthey Catalysts ..................................................................................................... 391 3.2.3.3.1 Feed Purification ................................................................................................... 391 3.2.3.3.2 Steam Reforming ................................................................................................... 392 3.2.3.3.3 Shift Conversion .................................................................................................... 394 3.2.3.3.4 Methanation ........................................................................................................... 395 3.2.3.4 Süd-Chemie ............................................................................................................................ 395 3.2.3.4.1 Pretreatment ........................................................................................................... 395 3.2.3.4.2 Prereforming .......................................................................................................... 396 3.2.3.4.3 Steam Reforming ................................................................................................... 396 3.2.3.4.4 Shift Conversion .................................................................................................... 397 3.2.3.4.5 Methanation ........................................................................................................... 398 3.2.4 Hydrogen Management, Advanced Process Control, Simulation, and Monitoring.............................. 398 3.2.4.1 Hydrogen Management .......................................................................................................... 398 3.2.4.1.1 Air Liquide ............................................................................................................ 398 3.2.4.1.2 Axens ..................................................................................................................... 399 3.2.4.1.3 Foster Wheeler ...................................................................................................... 400 3.2.4.1.4 Technip .................................................................................................................. 401 3.2.4.1.5 UOP ....................................................................................................................... 403 3.2.4.2 Advanced Process Control, Monitoring, and Simulation ....................................................... 404 3.2.4.2.1 AspenTech ............................................................................................................. 404 3.2.4.2.2 Johnson Matthey.................................................................................................... 405 3.2.4.2.3 H2Scan ................................................................................................................... 405 3.2.4.2.4 Honeywell Industry Solutions ............................................................................... 405 3.2.5 Summary of Commercially Available Hydrogen Technologies ............................................................ 406 3.2.6 Comparison of Commercial H2 Production Catalysts .......................................................................... 412 PLANT OPERATIONS AND PRACTICES ................................................................................................................ 414 3.3.1 Meeting Rising Hydrogen Demand ....................................................................................................... 414 3.3.1.1 Sourcing Hydrogen for Plant Expansion ................................................................................ 414 3.3.1.2 Expanding Hydrogen Plant Capacity via Revamps ................................................................ 414

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3.3.3

3.3.4

3.3.5

3.3.1.3 Hydrogen Management via Pinch Technology and Mathematical Modeling ......................... 418 3.3.1.4 Over-the-fence Hydrogen Supply ........................................................................................... 421 3.3.1.5 Partial Oxidation and Gasification for H2 and Syngas Production ......................................... 423 Steam Reforming ................................................................................................................................... 424 3.3.2.1 Feedstock Flexibility ............................................................................................................... 425 3.3.2.1.1 Natural Gas ............................................................................................................ 425 3.3.2.1.2 Naphtha and Other High-quality Refinery Streams ............................................... 425 3.3.2.1.3 Refinery Fuel Gas .................................................................................................. 426 3.3.2.1.4 Butane .................................................................................................................... 427 3.3.2.2 Processing Heavier Hydrocarbons in Steam Reforming ......................................................... 428 3.3.2.3 Pretreatment Requirements for Steam Reformers ................................................................... 429 3.3.2.4 Feed Header Deposits ............................................................................................................. 430 3.3.2.5 Installing Prereforming Technology ....................................................................................... 431 3.3.2.6 Effect of Reformer Tube Wall Temperature on Tube Life ..................................................... 432 3.3.2.7 Catalyst Tube Outlet Pressure and Heater Outlet Temperature in Steam Reformers.............. 433 Hydrogen Recovery and Purification .................................................................................................... 433 3.3.3.1 Technology Options ................................................................................................................ 434 3.3.3.2 Identifying Recoverable Hydrogen ......................................................................................... 435 3.3.3.3 Configuration Options............................................................................................................. 436 3.3.3.4 Improving PSA Recovery Efficiency...................................................................................... 437 3.3.3.5 Using a Membrane to Recover Hydrogen from Hydrotreaters ............................................... 438 3.3.3.6 Summary and Commercial Experience ................................................................................... 438 Operational Problems ........................................................................................................................... 440 3.3.4.1 Process Variables .................................................................................................................... 440 3.3.4.1.1 Optimizing Steam-to-Carbon Ratio: Flowmeters .................................................. 440 3.3.4.1.2 Reformer Overheating Problems ........................................................................... 441 3.3.4.1.2.1 Startup and Shutdown ..................................................................... 442 3.3.4.1.2.2 Monitoring Temperature ................................................................. 443 3.3.4.1.3 Metal-dusting Corrosion ........................................................................................ 444 3.3.4.1.4 Formic Acid Formation in Shift Converters .......................................................... 445 3.3.4.1.5 Preventing and Detecting Hydrogen Leaks ........................................................... 446 3.3.4.1.6 CO2/CO Slip from the Methanator ......................................................................... 447 3.3.4.1.7 Process Condensate Contamination ....................................................................... 447 3.3.4.2 Process Hardware .................................................................................................................... 448 3.3.4.2.1 Preventing Frequent Pigtail Failures ...................................................................... 448 3.3.4.2.2 Sudden Severe Corrosion and Vanadium Plating in a Benfield Unit .................... 449 3.3.4.2.3 Cold-end Corrosion in Convection Section ........................................................... 449 3.3.4.2.4 Steam Reformer Tubing Metallurgy ...................................................................... 449 3.3.4.2.5 Reformer Tube Failure ........................................................................................... 450 3.3.4.2.6 Improving the Reliability of Hydrogen Reciprocating Compressors ..................... 450 3.3.4.2.7 Best Practices for Inspecting PSA Units ................................................................ 451 Catalyst Considerations and Management ........................................................................................... 451 3.3.5.1 Improving Reliability for Longer Run Lengths ...................................................................... 452 3.3.5.2 Optimize Shape and Size ........................................................................................................ 453 3.3.5.3 Proper Catalyst Loading in the Reformer Tubes ..................................................................... 453 3.3.5.4 Carbon Deposition on Reformer Catalysts.............................................................................. 454 3.3.5.5 Preventing Wetting on the Catalyst......................................................................................... 455 3.3.5.6 Reformer Catalyst Deactivation .............................................................................................. 456 3.3.5.7 Temperature Excursions during Shift Catalyst Reduction ...................................................... 457 3.3.5.7.1 HTS Catalysts ........................................................................................................ 457 3.3.5.7.2 LTS Catalysts ......................................................................................................... 458 3.3.5.7.3 Adsorbents ............................................................................................................. 458

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TABLE OF CONTENTS

3.4

3.5 3.6

3.7

3.3.5.8 Preventing Unwanted Side Reactions ..................................................................................... 459 3.3.5.9 Catalyst Support Selection ...................................................................................................... 459 3.3.6 Improving Energy Efficiency and Reducing CO2 Emissions ................................................................ 460 3.3.6.1 Hydrogen Plant Energy Use ................................................................................................... 460 3.3.6.1.1 Energy Characteristics ........................................................................................... 460 3.3.6.1.2 General Improvements .......................................................................................... 460 3.3.6.2 Heat Integrated Steam Reforming Designs............................................................................. 462 3.3.6.3 Maintaining PSA Unit Efficiency and Adsorbent Life ........................................................... 463 3.3.6.4 Reducing Export Steam Production........................................................................................ 464 3.3.6.5 Improving the Performance of CO2 Removal Systems .......................................................... 464 3.3.6.6 Impact of Feed on Steam Reformer CO2 Emissions ............................................................... 465 3.3.6.7 Tri-generation: Hydrogen, Steam, and Power to Lower GHG Emissions .............................. 467 REFINING R&D ALERT! .................................................................................................................................... 468 3.4.1 Introduction .......................................................................................................................................... 468 3.4.2 Hydrogen Production Methods ............................................................................................................. 473 3.4.2.1 Steam Reforming .................................................................................................................... 473 3.4.2.1.1 Process and Hardware ........................................................................................... 473 3.4.2.1.1.1 Patents............................................................................................. 473 3.4.2.1.1.2 Research.......................................................................................... 478 3.4.2.1.2 Catalysts ................................................................................................................ 479 3.4.2.1.2.1 Patents............................................................................................. 479 3.4.2.1.2.2 Research.......................................................................................... 482 3.4.2.2 Autothermal Reforming .......................................................................................................... 485 3.4.2.2.1 Patents ................................................................................................................... 485 3.4.2.2.2 Research ................................................................................................................ 486 3.4.2.3 Partial Oxidation ..................................................................................................................... 488 3.4.2.4 Hybrid Reforming Technologies ............................................................................................ 489 3.4.2.5 Reforming with Membrane Reactors ...................................................................................... 489 3.4.2.5.1 Patents ................................................................................................................... 489 3.4.2.5.2 Research ................................................................................................................ 493 3.4.2.6 Hydrogen Production from Renewable Feeds ........................................................................ 495 3.4.2.6.1 Patents ................................................................................................................... 495 3.4.2.6.2 Research ................................................................................................................ 496 3.4.2.6.2.1 Process ............................................................................................ 496 3.4.2.6.2.2 Catalyst ........................................................................................... 497 3.4.3 Hydrogen Recovery and Purification ................................................................................................... 499 3.4.3.1 Pressure Swing Adsorption .................................................................................................... 499 3.4.3.1.1 Patents ................................................................................................................... 499 3.4.3.1.2 Research ................................................................................................................ 501 3.4.3.2 Membrane Separation ............................................................................................................. 502 3.4.3.2.1 Patents ................................................................................................................... 502 3.4.3.2.2 Research ................................................................................................................ 503 3.4.3.3 Other ....................................................................................................................................... 505 WORLDWIDE INSTALLED CAPACITY.................................................................................................................. 506 CONSTRUCTION ................................................................................................................................................. 510 3.6.1 Recent Construction Activity ................................................................................................................. 510 3.6.2 Completed Construction Projects ......................................................................................................... 515 REFERENCES ..................................................................................................................................................... 535

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TABLE OF CONTENTS 4. Latest Refining Technology Developments & Licensing ........................................................ 553 4.1 4.2 4.3 4.4 4.5 4.6 4.7 4.8 4.9 4.10 4.11 4.12 4.13 4.14

FLUID CATALYTIC CRACKING ........................................................................................................................... 553 HYDROTREATING (INCLUDING HDS) ................................................................................................................. 554 DESULFURIZATION (WITHOUT HYDROGEN) ....................................................................................................... 554 ALKYLATION ..................................................................................................................................................... 555 CRUDE TREATMENT (E.G. DESALTING) .............................................................................................................. 555 COKING ............................................................................................................................................................. 556 DEASPHALTING.................................................................................................................................................. 556 SULFUR PLANT .................................................................................................................................................. 557 AROMATICS AND LIGHT OLEFINS PRODUCTION................................................................................................. 557 PROCESS CONTROLS AND SIMULATION ............................................................................................................. 559 XTL (GAS-TO-LIQUID, COAL-TO-LIQUID, AND BIOMASS-TO-LIQUID) ................................................................ 559 BIOFUELS PRODUCTION ..................................................................................................................................... 562 CO2 EMISSIONS (CARBON CAPTURE AND SEQUESTRATION) .............................................................................. 563 REFERENCES ...................................................................................................................................................... 564