Worldwide Refinery Processing Review - 2Q2013 by Hydrocarbon Publishing Company

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

Second Quarter 2013 Hydrocracking and Catalytic Reforming Plus

Latest Refining Technology Developments & Licensing

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

Second Quarter 2013 Hydrocracking and Catalytic Reforming Plus Latest Refining Technology Developments & Licensing

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WORLDWIDE REFINERY PROCESSING REVIEW is published by Hydrocarbon Publishing Co. every quarter. Copyright 2007-2013. All rights reserved. No part of this publication may be reproduced, stored in a retrieval system or transmitted in any form or translated into any language or by any means—electronic, mechanical, photocopying, recording or otherwise—without prior written permission of Hydrocarbon Publishing Company. P.O. Box 661, Southeastern, PA 19399 (USA). Tel: (610) 408-0117, Fax: (610) 408-0118. E-mail: review@hydrocarbonpublishing.com

Abbreviations 1Q, 2Q, 3Q, 4Q .. (the) first, second, third, and fourth quarters, respectively AAA ................... American Automobile Association (US) ANS .................... Alaskan North Slope crude API...................... American Petroleum Institute (US) ARA.................... Antwerp, Rotterdam, Amsterdam ASTM ................. American Society for Testing & Materials b or bbl................ barrel(s) B ......................... billion boe ...................... barrel(s) of oil equivalent CA ...................... California CAA.................... Clean Air Act (US) CARB ................. California Air Resources Board cf ......................... cubic foot, cubic feet cfr........................ cost and freight cif ........................ cost, insurance, and freight Concawe ............. Conservation of Clean Air and Water Europe CIS ...................... Commonwealth of Independent States CNG.................... compressed natural gas cst........................ centistoke d .......................... day DOE .................... Department of Energy EEC .................... European Economic Community EIA ....................... US Energy Information Administration EPA .................... US Environmental Protection Agency EPC(M) .............. engineering, procurement, and construction (management) EU15 ................... 15 original EU members EU25 ................... EU15 and the 10 new members admitted in May 2004 EUROPIA ........... European Petroleum Industry Association (Brussels) FCV .................... fuel cell vehicle fd......................... free delivered FEED .................. front-end engineering design fob....................... free on board gal ....................... gallon GTL .................... gas to liquid(s) h .......................... hour H1 or H2 ............. first or second half of the year ICE...................... Int'l Commodity Exchange (UK— formerly Int'l Petroleum Exchange) IEA ..................... Int'l Energy Agency (Paris-based)

IPAA ................... Independent Petr. Assoc. of America IPO...................... initial public offering j.v. ....................... joint venture LPG .................... liquefied petroleum gas K ......................... thousand kL........................ kiloliter lb ......................... pound(s) METI .................. Ministry of Economy, Trade and Industry (Japan) MM ..................... million MOU ................... memorandum of understanding mpg ..................... miles per gallon mt ........................ metric ton MW ..................... megawatt N.A. .................... not applicable or not available NAAQS .............. national ambient air quality standards NESCAUM ........ Northeast States for Coordinated Air Use Management NG ...................... natural gas NGL .................... natural gas liquid NPRA ................. National Petrochemical & Refiners Association (US) NWE ................... Northwest Europe NYMEX ............. New York Mercantile Exchange (US) OECD ................. Organization for Economic Cooperation & Development OPEC .................. Organization of the Petroleum Exporting Countries OSHA ................. Occupational, Safety and Health Administration (US) PC ....................... petrochemical(s) PM ...................... particulate matter RBOB ................. RFG before oxygenate blending RFG .................... reformulated gasoline RMT ..................... refining, marketing, and transportation RVP .................... Reid vapor pressure SCAQMD ........... South Coast Air Quality Management District (California) VLCC ................. very large crude carrier WTI .................... West Texas Intermediate y .......................... year ¢ .......................... US cent(s) € .......................... EU euro(s) £ .......................... UK pound(s) $ .......................... US dollar(s) ¥ .......................... Japanese yen

Please note that other international currencies are abbreviated using International Standards Organization codes, which can be found at www.xe.com.

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TABLE OF CONTENTS 2Q 2013 Review Hydrocracking and Catalytic Reforming 1. Introduction ..................................................................................................................................... 1 2. Hydrocracking ................................................................................................................................ 5 2.1

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 Transportation Fuels .................................................................................................. 6 2.1.2.1.2 Bunker Fuels.............................................................................................................. 8 2.1.2.2 Refined Products Demand .......................................................................................................... 9 2.1.2.3 Increasing Middle Distillate Production ................................................................................... 14 2.1.2.3.1 Diesel Supply and Demand ..................................................................................... 14 2.1.2.3.1.1 United States ..................................................................................... 14 2.1.2.3.1.2 European Union ................................................................................ 15 2.1.2.3.1.3 Russia ............................................................................................... 16 2.1.2.3.1.4 Middle East ....................................................................................... 17 2.1.2.3.1.5 Asia-Pacific ...................................................................................... 17 2.1.2.3.2 Renewable and Bio-based Diesel and Jet Fuel ........................................................ 18 2.1.2.3.2.1 Renewable Diesel and Bio-based Diesel .......................................... 18 2.1.2.3.2.1.1 United States ............................................................... 19 2.1.2.3.2.1.2 Europe and Middle East .............................................. 20 2.1.2.3.2.1.3 Asia-Pacific................................................................. 21 2.1.2.3.2.2 Renewable Jet Fuel and Bio-based Jet Fuel...................................... 21 2.1.2.3.2.2.1 United States ............................................................... 21 2.1.2.3.2.2.2 Europe and Africa ....................................................... 22 2.1.2.3.2.2.3 Asia-Pacific................................................................. 23 2.1.2.4 Shifting Crude Slate.................................................................................................................. 25 2.1.2.4.1 Opportunity Crudes ................................................................................................. 25 2.1.2.4.2 Shale or Tight Oil .................................................................................................... 28 2.1.2.5 Hydrogen Demand .................................................................................................................... 30 2.1.2.6 Capacity Expansion .................................................................................................................. 31 2.1.2.7 Construction Projects and Unit Revamps ................................................................................. 32 2.1.2.8 Hydrocracking Catalyst Market ................................................................................................ 33 2.1.3 Technology Competition, Direction, and Future Prospects ................................................................... 36 2.1.3.1 Market Layout and Strategic Alliances .................................................................................... 36 2.1.3.2 Latest R&D Trends ................................................................................................................... 41 2.1.3.3 Recent Technology Developments ........................................................................................... 42 2.1.3.3.1 Catalyst Developments ............................................................................................ 42 2.1.3.3.2 Process and Hardware Developments ..................................................................... 44 2.1.3.3.3 Conventional and Mild Hydrocracking ................................................................... 45 2.1.3.3.4 Resid Hydrocracking ............................................................................................... 46 2.1.3.3.5 Alternative Feed Hydrocracking ............................................................................. 48 2.1.3.3.6 Revamp and Integration Options ............................................................................. 50 2.1.4 Conclusion .............................................................................................................................................. 51

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STATE-OF-THE-ART TECHNOLOGY ...................................................................................................................... 53 2.2.1 Introduction ............................................................................................................................................. 53 2.2.2 Commercial Process Technology ............................................................................................................ 55 2.2.2.1 Axens ........................................................................................................................................ 55 2.2.2.1.1 Mild Hydrocracking ................................................................................................. 56 2.2.2.1.1.1 Mild-HCK ......................................................................................... 56 2.2.2.1.1.2 HyC-10/HyC-10+.............................................................................. 56 2.2.2.1.2 H-OilDC..................................................................................................................... 60 2.2.2.1.3 HyTail ...................................................................................................................... 61 2.2.2.1.4 Medium-pressure Hydrocracking ............................................................................ 63 2.2.2.1.5 Conventional (High-pressure) Hydrocracking ......................................................... 63 2.2.2.1.6 Reactor Internals ...................................................................................................... 66 2.2.2.2 Chevron Lummus Global .......................................................................................................... 67 2.2.2.2.1 ISOCRACKING ...................................................................................................... 67 2.2.2.2.1.1 Single-stage Once Through and Single-stage Recycle ..................... 68 2.2.2.2.1.2 Two-stage Recycle ............................................................................ 69 2.2.2.2.1.3 Optimized Partial Conversion ........................................................... 73 2.2.2.2.1.4 Selective Staging ............................................................................... 75 2.2.2.2.1.5 Split-feed Injection ............................................................................ 78 2.2.2.2.1.6 Single-stage Reaction Sequencing .................................................... 79 2.2.2.2.2 ISOFLEX ................................................................................................................. 80 2.2.2.2.3 Reactor Internals ...................................................................................................... 82 2.2.2.3 DuPont Clean Technologies...................................................................................................... 83 2.2.2.4 ExxonMobil .............................................................................................................................. 85 2.2.2.4.1 Single-stage MPHC ................................................................................................. 86 2.2.2.4.2 MPHC-PTU ............................................................................................................. 91 2.2.2.4.3 MPHC-LCO ............................................................................................................. 92 2.2.2.4.4 Two-stage MPHC .................................................................................................... 94 2.2.2.4.5 Spider-Vortex Reactor Internals .............................................................................. 96 2.2.2.5 Haldor Topsøe ........................................................................................................................... 96 2.2.2.5.1 Mild Hydrocracking ................................................................................................. 96 2.2.2.5.1.1 Staged Partial Conversion Hydrocracking ........................................ 99 2.2.2.5.1.2 Back-End Shift (BES) Process ........................................................ 100 2.2.2.5.2 Conventional (High-pressure) Hydrocracking ....................................................... 100 2.2.2.5.3 Reactor Internals .................................................................................................... 101 2.2.2.6 Shell Global Solutions ............................................................................................................ 103 2.2.2.6.1 Mild Hydrocracking ............................................................................................... 103 2.2.2.6.2 Conventional Hydrocracking ................................................................................. 105 2.2.2.6.3 Reactor Internals .................................................................................................... 108 2.2.2.7 Sinopec .................................................................................................................................... 111 2.2.2.7.1 Flexible Hydrotreating/Mild Hydrocracking ......................................................... 111 2.2.2.7.2 Medium-pressure Hydro-Upgrading ...................................................................... 112 2.2.2.7.3 Moderate-pressure Hydrocracking......................................................................... 115 2.2.2.7.4 High-pressure Hydrocracking ................................................................................ 115 2.2.2.7.4.1 Single-stage Hydrocracking ............................................................ 116 2.2.2.7.4.2 Single-stage in Series Hydrocracking ............................................. 116 2.2.2.7.4.3 Single-stage, Double-catalyst Hydrocracking ................................. 118 2.2.2.7.4.4 Two-stage Hydrocracking ............................................................... 118 2.2.2.7.4.5 Flexible Hydrocracking................................................................... 119 2.2.2.8 UOP......................................................................................................................................... 120 2.2.2.8.1 MHC Unicracking .................................................................................................. 120 2.2.2.8.2 Unicracking ............................................................................................................ 122 2.2.2.8.2.1 Single-stage Once Through or with Recycle................................... 122

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2.2.2.8.2.2 Two-stage ....................................................................................... 124 2.2.2.8.3 Partial-conversion Unicracking ............................................................................. 128 2.2.2.8.4 Dieselmax .............................................................................................................. 133 2.2.2.8.5 HyCycle Unicracking ............................................................................................ 134 2.2.2.8.6 Advanced Partial Conversion Unicracking ........................................................... 136 2.2.2.8.7 HPNA Removal Systems....................................................................................... 137 2.2.2.8.8 Reactor Internals .................................................................................................... 138 2.2.2.9 Velocys ................................................................................................................................... 139 2.2.2.10 Summary of Hydrocracking Process Technologies ................................................................ 140 2.2.3 Commercial Catalysts ........................................................................................................................... 144 2.2.3.1 Albemarle ............................................................................................................................... 145 2.2.3.2 Axens ...................................................................................................................................... 146 2.2.3.3 Chevron Lummus Global ....................................................................................................... 147 2.2.3.4 Criterion Catalysts & Technologies ........................................................................................ 153 2.2.3.5 Haldor Topsøe ........................................................................................................................ 158 2.2.3.6 JGC Catalysts & Chemicals .................................................................................................... 160 2.2.3.7 Sinopec ................................................................................................................................... 160 2.2.3.8 UOP ........................................................................................................................................ 161 2.2.3.9 Summary of Commercially Available Hydrocracking Catalysts ............................................ 165 2.2.4 Auxiliary Catalyst Technology .............................................................................................................. 167 2.2.4.1 Axens ...................................................................................................................................... 167 2.2.4.2 Crystaphase Products .............................................................................................................. 168 2.2.4.3 Eurecat .................................................................................................................................... 168 2.2.4.4 TRICAT .................................................................................................................................. 169 2.2.5 Control and Optimization Systems........................................................................................................ 169 2.2.6 Resid Hydrocracking ............................................................................................................................ 173 2.2.7 Renewable Hydrocracking .................................................................................................................... 179 PLANT OPERATIONS AND PRACTICES ................................................................................................................ 184 2.3.1 General Hydrocracking Operations ..................................................................................................... 184 2.3.1.1 Feed Considerations, Operational Variables, Process Configurations, and Hardware ........... 185 2.3.1.1.1 Feedstock Characterization.................................................................................... 185 2.3.1.1.2 Upgrading Tight Oil .............................................................................................. 185 2.3.1.1.3 Upgrading LCO and/or HCO in Hydrocrackers .................................................... 185 2.3.1.1.4 Undercutting LVGO to Increase Hydrocracker Utilization................................... 186 2.3.1.1.5 Optimizing Operational Variables ......................................................................... 187 2.3.1.1.5.1 Recycle Rate in Two-stage Units.................................................... 187 2.3.1.1.5.2 Setting Operational Pressure........................................................... 188 2.3.1.1.6 Reactor Configuration ........................................................................................... 189 2.3.1.1.7 Optimized Hydrocracker Reactor Internals ........................................................... 190 2.3.1.1.8 Changing Unit Configuration to Boost Yields and Process Alternative Feeds ..... 192 2.3.1.1.9 Large Single Process Train vs. Smaller Parallel Trains in Hydrocrackers ............ 193 2.3.1.1.10 Reactor Fabrication and Metallurgy ...................................................................... 193 2.3.1.1.11 Comparison of Quench Systems............................................................................ 195 2.3.1.1.12 Hydrocracker Stripper Revamp: From Packing to Trays ...................................... 195 2.3.1.1.13 Hydrocracker Pump Selection ............................................................................... 196 2.3.1.1.14 Membranes for H2 Recovery from Hydrocrackers ................................................ 196 2.3.1.2 Fouling, Particulate Deposition, and Corrosion...................................................................... 197 2.3.1.2.1 Causes of Hydroprocesser Fouling and Possible Treatments ................................ 197 2.3.1.2.2 Ammonium Chloride Fouling in Effluent Exchangers .......................................... 199 2.3.1.2.3 Elimination of Polynuclear Aromatics (PNA) Buildup ......................................... 200 2.3.1.2.4 Iron Sulfide Buildup in VGO Hydrocrackers ........................................................ 201 2.3.1.2.5 Feed Filter Operation ............................................................................................. 204

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TABLE OF CONTENTS 2.3.1.2.6 Mitigating High Temperature Hydrogen Attack .................................................... 204 2.3.1.2.7 Fouling in Furnace Tubes ...................................................................................... 205 2.3.1.2.8 Corrosion in Overhead System .............................................................................. 206 2.3.1.2.9 Corrosion in Auxiliary Equipment ......................................................................... 206 2.3.1.3 Operational Problems .............................................................................................................. 207 2.3.1.3.1 Increased Yield Using Multivariable Predictive Control (MPC) ........................... 207 2.3.1.3.2 Improving Hydrocracker Temperature Control ..................................................... 210 2.3.1.3.3 Detecting Radial Temperature Spread and Preventing Reactor Runaway ............. 213 2.3.1.3.4 Hydrocracker Furnace Operations ......................................................................... 215 2.3.1.3.5 Causes of Overcracking ......................................................................................... 215 2.3.1.3.6 Improving the Performance of a Debutanizer ........................................................ 216 2.3.1.3.7 Preventing Off-color Naphtha Product .................................................................. 219 2.3.1.3.8 Reducing the Level of Sulfur in Naphtha at EOR Conditions ............................... 219 2.3.1.3.9 Limiting Ammonia Concentration in the Cold High-pressure Separator Overhead .... 220 2.3.1.3.10 Inline Hydrocracker Cleaning System ................................................................... 220 2.3.1.3.11 Improving Recycle Gas Compressor Operation .................................................... 221 2.3.1.4 Catalyst Management .............................................................................................................. 222 2.3.1.4.1 Selection Process for Hydrocracking Catalysts ..................................................... 222 2.3.1.4.2 Measuring Hydrocracking Catalyst Activity ......................................................... 223 2.3.1.4.3 Catalysts for Processing Various Feeds ................................................................. 223 2.3.1.4.4 Replacing a Noble Metal Catalyst with a Base Metal Catalyst .............................. 224 2.3.1.4.5 Catalyst Structure: Homogeneous vs. Stacked....................................................... 225 2.3.1.4.6 Ex-Situ Sulfiding (Presulfiding) of Hydrocracking Catalysts ............................... 225 2.3.1.4.7 Ammoniation Passivation during Startup .............................................................. 227 2.3.1.4.8 Disproportionate Catalyst Deactivation in the First Bed of a Hydrocracker ......... 227 2.3.1.4.9 Asphaltene Contribution to Catalyst Deactivation ................................................. 228 2.3.1.4.10 Impact of HPNAs on Catalyst Activity and Stability ............................................ 229 2.3.1.4.11 Regenerated Hydrocracking Catalyst Use ............................................................. 229 2.3.1.4.12 Recovering Spent Hydroprocessing Catalysts and Metal Reclamation ................. 231 2.3.1.5 Reducing Hydrocracker Energy Use ....................................................................................... 232 2.3.1.5.1 Modeling ................................................................................................................ 233 2.3.1.5.2 Cleaning ................................................................................................................. 233 2.3.1.5.3 Heat Integration ..................................................................................................... 233 2.3.1.5.4 Power Recovery ..................................................................................................... 234 2.3.1.5.5 Process Heaters ...................................................................................................... 234 2.3.1.5.6 Impact of Catalysts................................................................................................. 234 2.3.1.6 Hydrocracker Safety ............................................................................................................... 235 2.3.1.6.1 Hydrocracker Safety Incidents ............................................................................... 235 2.3.1.6.2 Emergency Depressurization: Triggering Criteria, Rates, and Modes ................... 237 2.3.1.6.3 Operational Status of Emergency Depressurizing Valves and Interlocks.............. 239 2.3.1.6.4 Safely Performing Inter-reactor Sampling in Hydrocrackers ................................ 240 2.3.2 Mild Hydrocracking (MHC) .................................................................................................................. 240 2.3.2.1 Mild Hydrocracking: Feedstock, Conversion, and Product Quality ....................................... 240 2.3.2.2 Converting a Cat Feed or Distillate Hydrotreater to a Mild Hydrocracker ............................. 241 2.3.2.3 Options for Improving the Cycle Length of Mild Hydrocrackers........................................... 244 2.3.3 Distillate Hydrocracking ....................................................................................................................... 245 2.3.3.1 Shifting from Maximum Naphtha to Maximum Middle Distillate Yields .............................. 245 2.3.3.2 Maximizing Diesel Production in VGO Hydrocrackers ......................................................... 247 2.3.3.3 Benefits of Moderate Pressure Hydrocracking (MPHC) in Clean Diesel Production ............ 249 2.3.3.4 Adjusting CAT to Maximize Diesel Production ..................................................................... 251 2.3.3.5 Reactor Revamp to Improve ULSD Production ..................................................................... 252 2.3.3.6 Loading Hydrocracking Catalyst in the Last Bed of a ULSD Unit......................................... 253 2.3.3.7 Process Revamp for Added H2S Removal to Meet ULSD Standards ..................................... 253

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2.5 2.6

2.7

2.3.3.8 Improving Diesel Cetane from Hydrocrackers ....................................................................... 254 2.3.3.9 Hydrocracking Catalysts for Cold Flow Property Improvements .......................................... 255 2.3.4 Integrated Processing Schemes ............................................................................................................ 256 2.3.4.1 Delayed Coker with Hydrocracker ......................................................................................... 256 2.3.4.2 Solvent Deasphalting with Hydrocracker ............................................................................... 259 2.3.4.3 Mild Hydrocracker with FCC ................................................................................................. 261 REFINING R&D ALERT! .................................................................................................................................... 262 2.4.1 Introduction .......................................................................................................................................... 262 2.4.2 General Hydrocracking ........................................................................................................................ 266 2.4.2.1 Process .................................................................................................................................... 266 2.4.2.1.1 Patents ................................................................................................................... 266 2.4.2.1.2 Research ................................................................................................................ 268 2.4.2.2 Catalyst ................................................................................................................................... 268 2.4.2.2.1 Patents ................................................................................................................... 268 2.4.2.2.2 Research ................................................................................................................ 272 2.4.2.3 Hardware ................................................................................................................................ 273 2.4.2.4 Integrated Operations (Conventional Feeds) .......................................................................... 274 2.4.3 Product Selective Hydrocracking ......................................................................................................... 275 2.4.3.1 Middle Distillates.................................................................................................................... 275 2.4.3.1.1 Patents ................................................................................................................... 275 2.4.3.1.1.1 Process ............................................................................................ 275 2.4.3.1.1.2 Catalyst ........................................................................................... 278 2.4.3.1.2 Research ................................................................................................................ 280 2.4.3.2 Naphtha................................................................................................................................... 282 2.4.3.2.1 Patents ................................................................................................................... 282 2.4.3.2.2 Research ................................................................................................................ 283 2.4.3.3 BTX ........................................................................................................................................ 283 2.4.4 Resid Hydrocracking ............................................................................................................................ 284 2.4.4.1 Process .................................................................................................................................... 284 2.4.4.1.1 Patents ................................................................................................................... 284 2.4.4.1.2 Research ................................................................................................................ 288 2.4.4.2 Catalyst ................................................................................................................................... 289 2.4.4.2.1 Patents ................................................................................................................... 289 2.4.4.2.2 Research ................................................................................................................ 290 2.4.5 Hydrocracking Alternative Feedstocks ................................................................................................. 294 2.4.5.1 Fischer-Tropsch Liquids ......................................................................................................... 294 2.4.5.1.1 Process ................................................................................................................... 294 2.4.5.1.1.1 Patents............................................................................................. 294 2.4.5.1.1.2 Research.......................................................................................... 297 2.4.5.1.2 Catalyst .................................................................................................................. 297 2.4.5.1.2.1 Patents............................................................................................. 297 2.4.5.1.2.2 Research.......................................................................................... 298 2.4.5.2 Renewable Feedstocks ............................................................................................................ 299 2.4.5.2.1 Patents ................................................................................................................... 299 2.4.5.2.2 Research ................................................................................................................ 301 WORLDWIDE INSTALLED CAPACITY.................................................................................................................. 303 CONSTRUCTION ................................................................................................................................................. 306 2.6.1 Recent Construction Activity ................................................................................................................. 306 2.6.2 Completed Construction Projects ......................................................................................................... 311 REFERENCES ..................................................................................................................................................... 323

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TABLE OF CONTENTS 3. Catalytic Reforming ................................................................................................................... 347 3.1

3.2

MARKET/TECHNOLOGY TRENDS & OPPORTUNITIES .......................................................................................... 347 3.1.1 Introduction ........................................................................................................................................... 347 3.1.2 Market Conditions and Outlook ............................................................................................................ 348 3.1.2.1.1 Refined Product Supply and Demand .................................................................... 348 3.1.2.1.1.1 Gasoline .......................................................................................... 349 3.1.2.1.1.2 Rise of Aromatics (BTX) ................................................................ 351 3.1.2.1.1.3 Pricing Trends ................................................................................. 353 3.1.2.1.1.4 Reforming Catalyst Market ............................................................. 354 3.1.2.1.2 New Construction and Expansion .......................................................................... 355 3.1.2.1.3 Catalytic Reforming Capacity ................................................................................ 355 3.1.3 Technology Competition, Directions, and Future Prospects ................................................................ 356 3.1.3.1 Process and Catalyst Advancements ....................................................................................... 356 3.1.3.1.1 Process and Hardware Improvements .................................................................... 357 3.1.3.1.2 Catalyst Innovations............................................................................................... 359 3.1.3.2 Trends in R&D ........................................................................................................................ 359 3.1.4 Conclusion ............................................................................................................................................. 362 STATE-OF-THE-ART TECHNOLOGY .................................................................................................................... 363 3.2.1 Introduction ........................................................................................................................................... 363 3.2.2 Commercial Process Technology .......................................................................................................... 363 3.2.2.1 Axens ...................................................................................................................................... 365 3.2.2.1.1 Semi-regenerative .................................................................................................. 365 3.2.2.1.2 Octanizing .............................................................................................................. 366 3.2.2.1.3 Aromizing .............................................................................................................. 368 3.2.2.1.4 Dualforming/Dualforming Plus ............................................................................. 369 3.2.2.2 Chevron Phillips Chemical ..................................................................................................... 370 3.2.2.3 UOP......................................................................................................................................... 371 3.2.2.3.1 Platforming ............................................................................................................ 372 3.2.2.3.2 CCR Platforming ................................................................................................... 372 3.2.2.3.3 RZ Platforming ...................................................................................................... 375 3.2.2.3.4 CycleX ................................................................................................................... 376 3.2.2.3.5 Chlorsorb ............................................................................................................... 378 3.2.2.4 Zeosit....................................................................................................................................... 378 3.2.3 Summary of Commercial Process Technology ...................................................................................... 380 3.2.4 Commercial Catalysts ........................................................................................................................... 383 3.2.4.1 Axens ...................................................................................................................................... 384 3.2.4.1.1 CCR Catalysts ........................................................................................................ 385 3.2.4.1.2 Fixed-bed Catalysts ................................................................................................ 387 3.2.4.2 BASF Catalysts ....................................................................................................................... 391 3.2.4.3 ExxonMobil ............................................................................................................................ 391 3.2.4.4 Indian Petrochemical Corp. ..................................................................................................... 391 3.2.4.5 Sinopec .................................................................................................................................... 391 3.2.4.5.1 CCR Catalysts ........................................................................................................ 391 3.2.4.5.2 Fixed-bed Catalysts ................................................................................................ 392 3.2.4.6 UOP......................................................................................................................................... 392 3.2.4.6.1 CCR Catalysts ........................................................................................................ 392 3.2.4.6.2 Fixed-bed Catalysts ................................................................................................ 395 3.2.5 Comparison of Commercially Available Catalysts ............................................................................... 398 3.2.6 Additional Catalyst and Adsorbent Technology .................................................................................... 400 3.2.6.1 Axens ...................................................................................................................................... 400 3.2.6.2 Johnson Matthey Catalysts ...................................................................................................... 400 3.2.6.3 Süd-Chemie ............................................................................................................................. 401

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3.4

3.2.6.4 UOP ........................................................................................................................................ 401 3.2.7 Comparison of Commercially Available Advanced Control and Optimization Systems ...................... 401 PLANT OPERATIONS AND PRACTICES ................................................................................................................ 406 3.3.1 Feedstock Management ........................................................................................................................ 406 3.3.1.1 Product Slate and Feed Type .................................................................................................. 406 3.3.1.2 Feedrate Considerations.......................................................................................................... 408 3.3.1.3 Sulfur Management ................................................................................................................ 408 3.3.1.4 Iron ......................................................................................................................................... 410 3.3.1.5 Nitrogen .................................................................................................................................. 410 3.3.1.6 Mercury .................................................................................................................................. 411 3.3.2 Operational Challenges and Mitigation Strategies .............................................................................. 411 3.3.2.1 Problems Encountered when Processing Non-straight Run Naphthas ................................... 411 3.3.2.2 Chloride, Water, and Fouling Monitoring and Control .......................................................... 414 3.3.2.3 Red Oil in the Reformer ......................................................................................................... 416 3.3.2.4 High Temperature Hydrogen Attack (HTHA)........................................................................ 417 3.3.2.5 Problems in the Catalyst Circulation Loop ............................................................................. 417 3.3.2.6 Preventing Failure in Reactor Internals .................................................................................. 418 3.3.3 Catalyst Management ........................................................................................................................... 419 3.3.3.1 Justifying a Change of Catalyst .............................................................................................. 419 3.3.3.2 Tracking Coke on Catalyst ..................................................................................................... 420 3.3.3.3 Separating Useable Catalyst Pills from Fines ......................................................................... 420 3.3.3.4 Using Pre-reduced and Pre-sulfided Catalyst ......................................................................... 421 3.3.3.5 Platinum Losses from Reforming Catalyst ............................................................................. 421 3.3.3.6 Catalyst Modeling for Improved Unit Performance ............................................................... 422 3.3.3.7 Catalyst Improvements for Extending Semi-regenerative Reformer Cycle Length ............... 422 3.3.3.8 In-situ Regeneration and its Importance for Reclamation ...................................................... 423 3.3.4 Process Control and Modeling ............................................................................................................. 424 3.3.4.1 Model-based Inferential Properties......................................................................................... 424 3.3.4.2 Advanced Process Control in Catalytic Reforming Units ...................................................... 425 3.3.4.3 Online Measuring Tools: NMR Spectroscopy and Gas Chromatography .............................. 426 3.3.5 Product Slate......................................................................................................................................... 427 3.3.5.1 Reformate Benzene and Aromatics Reduction ....................................................................... 427 3.3.5.2 Maximizing Hydrogen Production ......................................................................................... 429 3.3.5.3 Aromatics Production in Catalytic Reforming ....................................................................... 430 3.3.5.4 Flexibility in Naphtha Conversion for Integration with Petrochemical Plants ....................... 430 3.3.6 Revamp Strategies ................................................................................................................................. 431 3.3.6.1 Revamping Fixed-bed Units to CCR Reformers or Hybrid Units .......................................... 431 3.3.6.2 Revamping Semi-regenerative Reformers to Low-pressure Operations ................................ 433 3.3.7 Improving Energy Efficiency and Reducing CO2 Emissions ................................................................ 433 3.3.7.1 Reformer Heat Exchanger Types............................................................................................ 434 3.3.7.1.1 Welded Plate.......................................................................................................... 435 3.3.7.1.2 Twisted Tube ......................................................................................................... 438 3.3.7.1.3 Rod Baffle ............................................................................................................. 438 3.3.7.2 Fired Heater Capacity and Efficiency ..................................................................................... 439 3.3.7.2.1 General Strategies .................................................................................................. 439 3.3.7.2.2 CCR Reformer Furnace Upgrade .......................................................................... 439 3.3.7.2.3 Ceramic Refractory Coating .................................................................................. 440 3.3.7.2.4 Rebalancing heat load among furnaces for CCR Platforming ............................... 441 REFINING R&D ALERT! .................................................................................................................................... 442 3.4.1 Introduction .......................................................................................................................................... 442 3.4.2 Product Selective Cat Reforming .......................................................................................................... 446 3.4.2.1 Aromatics................................................................................................................................ 446 3.4.2.1.1 Patents ................................................................................................................... 446 3.4.2.1.2 Research ................................................................................................................ 450 3.4.2.2 Reformate Octane ................................................................................................................... 452

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TABLE OF CONTENTS

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3.4.2.3 Hydrogen................................................................................................................................. 453 3.4.2.3.1 Patents .................................................................................................................... 453 3.4.2.3.2 Research ................................................................................................................. 454 3.4.3 Catalyst Improvements .......................................................................................................................... 455 3.4.3.1 Coking and Deactivation ......................................................................................................... 455 3.4.3.2 Composition ............................................................................................................................ 456 3.4.3.2.1 Patents .................................................................................................................... 456 3.4.3.2.2 Research ................................................................................................................. 458 3.4.3.3 Preparation Method ................................................................................................................. 460 3.4.3.3.1 Patents .................................................................................................................... 460 3.4.3.3.2 Research ................................................................................................................. 462 3.4.4 Process Improvements ........................................................................................................................... 464 3.4.4.1 Design ..................................................................................................................................... 464 3.4.4.2 Energy Efficiency ................................................................................................................... 465 3.4.4.2.1 Patent ..................................................................................................................... 465 3.4.4.2.2 Research ................................................................................................................. 467 3.4.4.3 Reactor Modeling .................................................................................................................... 467 3.4.4.4 Improved Feed Flexibility and Conversion ............................................................................. 469 3.4.4.5 Optimization............................................................................................................................ 470 3.4.5 Other...................................................................................................................................................... 471 WORLDWIDE INSTALLED CAPACITY .................................................................................................................. 473 CONSTRUCTION ................................................................................................................................................. 474 3.6.1 Recent Construction Activity ................................................................................................................. 474 3.6.2 Completed Construction Projects.......................................................................................................... 477 REFERENCES ...................................................................................................................................................... 481

4. Latest Refining Technology Developments & Licensing ........................................................ 497 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 4.15 4.16 4.17 4.18

FLUID CATALYTIC CRACKING ........................................................................................................................... 497 HYDROTREATING (INCLUDING HDS) ................................................................................................................. 499 ISOMERIZATION ................................................................................................................................................. 500 ALKYLATION ..................................................................................................................................................... 500 ETHERIFICATION (E.G. MTBE, ETBE, TAME, DME, SKELETAL ISOMERIZATION) ........................................... 501 CRUDE DISTILLATION ........................................................................................................................................ 501 COKING ............................................................................................................................................................. 501 HEAVY OIL, EXTRA-HEAVY OIL, AND BITUMEN UPGRADING ............................................................................ 502 HYDROGEN PRODUCTION AND PURIFICATION ................................................................................................... 502 SULFUR PLANT .................................................................................................................................................. 503 AROMATICS AND LIGHT OLEFINS PRODUCTION................................................................................................. 503 CATALYST AND CARRIER SUPPORT DEVELOPMENTS ......................................................................................... 504 PROCESS CONTROLS AND SIMULATION ............................................................................................................. 505 XTL .................................................................................................................................................................. 506 BIOFUELS PRODUCTION ..................................................................................................................................... 507 CO2 EMISSIONS (CARBON CAPTURE AND SEQUESTRATION) .............................................................................. 510 Site Emissions ................................................................................................................................................... 511 REFERENCES ...................................................................................................................................................... 512