Worldwide Refinery Processing Review by Hydrocarbon Publishing Company

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

Fourth Quarter 2012 Fluid Catalytic Cracking and Gas Processing Plus

Latest Refining Technology Developments & Licensing

HYDROCARBON PUBLISHING COMPANY Translating Knowledge into Profitability

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

Fourth Quarter 2012 Fluid Catalytic Cracking and Gas Processing Plus Latest Refining Technology Developments & Licensing

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WORLDWIDE REFINERY PROCESSING REVIEW is published by Hydrocarbon Publishing Co. every quarter. Copyright 2007-2012. 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.

TABLE OF CONTENTS 4Q 2012 Review Fluid Catalytic Cracking and Gas Processing 1. Introduction ..................................................................................................................................... 1 2. Fluid Catalytic Cracking ................................................................................................................ 5 2.1

2.2

MARKET/TECHNOLOGY TRENDS & OPPORTUNITIES ............................................................................................. 5 2.1.1 Introduction .............................................................................................................................................. 5 2.1.2 Market Conditions and Outlook................................................................................................................ 5 2.1.2.1 Worldwide Transportation Fuel Demand ................................................................................... 5 2.1.2.1.1 Dieselization vs. Falling Gasoline Demand............................................................. 11 2.1.2.1.2 Expanding the Share of Diesel in Bunker Fuel Markets ......................................... 15 2.1.2.1.3 Growing Propylene Consumption ........................................................................... 16 2.1.2.2 FCC Capacity and Expansion ................................................................................................... 20 2.1.2.3 New Units Oriented Towards Changes in Feeds, Products ...................................................... 22 2.1.2.4 Fuel Specifications and Unit Emissions Considerations .......................................................... 23 2.1.2.4.1 Transportation Fuels ................................................................................................ 23 2.1.2.4.2 FCC Unit Emissions ................................................................................................ 26 2.1.2.5 Current Status of FCC Catalyst Market .................................................................................... 28 2.1.2.5.1 FCC Catalyst Demand Trends ................................................................................. 29 2.1.2.5.2 Focus on Rare Earth ................................................................................................ 29 2.1.2.5.2.1 Supply, Demand, and Prices ............................................................. 29 2.1.2.5.2.2 Rare Earth Functionality and Usage ................................................. 32 2.1.2.5.2.3 Options for Reducing Rare Earth Use and Costs .............................. 33 2.1.2.5.3 Looking Ahead ........................................................................................................ 36 2.1.3 Technology Directions, Competition, and Future Prospects .................................................................. 37 2.1.3.1 Producing High-quality Gasoline and Increasing Yield ........................................................... 40 2.1.3.2 Light Olefins Production Enhancement .................................................................................... 42 2.1.3.3 Boosting LCO Yield and Quality ............................................................................................. 45 2.1.3.4 Improving Operational Flexibility in Gasoline/Propylene and LCO Production Modes ......... 47 2.1.3.5 Processing Resid and Biofeeds ................................................................................................. 49 2.1.3.6 Regenerator Pollution Abatement and GHG Concerns ............................................................ 51 2.1.3.7 Process Modeling, Monitoring, and Control ............................................................................ 53 2.1.4 Conclusion .............................................................................................................................................. 54 STATE-OF-THE-ART TECHNOLOGY ..................................................................................................................... 56 2.2.1 Introduction ............................................................................................................................................ 56 2.2.2 Commercial Processes and Hardware ................................................................................................... 57 2.2.2.1 ExxonMobil/KBR ..................................................................................................................... 57 2.2.2.1.1 Flexicracking III ...................................................................................................... 57 2.2.2.1.2 Orthoflow ................................................................................................................ 60 2.2.2.1.3 Propylene Production .............................................................................................. 63 2.2.2.2 Lummus Technology ................................................................................................................ 64 2.2.2.2.1 Fuels Production ...................................................................................................... 64 2.2.2.2.2 Indmax FCC (I-FCC) .............................................................................................. 67 2.2.2.3 Nippon/Saudi Aramco .............................................................................................................. 67 2.2.2.4 Petrobras ................................................................................................................................... 72 2.2.2.4.1 Fuels Production ...................................................................................................... 72 2.2.2.4.2 Propylene Production .............................................................................................. 74

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TABLE OF CONTENTS 2.2.2.5 Shaw Group/Stone & Webster and Axens ................................................................................ 74 2.2.2.5.1 Fuels Production ...................................................................................................... 75 2.2.2.5.2 Propylene Production ............................................................................................... 80 2.2.2.6 Shell Global Solutions .............................................................................................................. 81 2.2.2.6.1 FCC .......................................................................................................................... 81 2.2.2.6.2 MILOS ..................................................................................................................... 86 2.2.2.7 Sinopec ...................................................................................................................................... 87 2.2.2.7.1 Clean Gasoline and Propylene ................................................................................. 88 2.2.2.7.2 Maximizing Iso-paraffins......................................................................................... 90 2.2.2.7.3 Flexible Dual-riser Fluid Catalytic Cracking ........................................................... 90 2.2.2.7.4 Maximum Gas and Diesel ........................................................................................ 93 2.2.2.7.5 Maximum Liquefied Gas and High-octane Gasoline ............................................... 94 2.2.2.7.6 Propylene Production ............................................................................................... 94 2.2.2.8 UOP........................................................................................................................................... 95 2.2.2.8.1 FCC .......................................................................................................................... 95 2.2.2.8.2 MSCC .................................................................................................................... 103 2.2.2.8.3 Propylene Production ............................................................................................. 104 2.2.2.9 Summary of Commercial FCC Processes and Hardware ........................................................ 105 2.2.3 Other Commercial Hardware ............................................................................................................... 112 2.2.3.1 Fisher-Klosterman ................................................................................................................... 112 2.2.3.2 Koch-Glitsch ........................................................................................................................... 112 2.2.3.3 Lawrence Pumps ..................................................................................................................... 113 2.2.4 Commercial Catalysts and Additives..................................................................................................... 113 2.2.4.1 Albemarle ................................................................................................................................ 114 2.2.4.1.1 Cracking Catalysts to Increase Liquid Products .................................................... 116 2.2.4.1.2 Gasoline Olefins and Octane Additives ................................................................. 124 2.2.4.1.3 SOX Reduction Additives....................................................................................... 125 2.2.4.1.4 Bottoms Cracking Additives .................................................................................. 126 2.2.4.1.5 Microfine Reduction Catalyst Technology ............................................................ 129 2.2.4.1.6 Catalyst Circulation Improvement Additives ......................................................... 129 2.2.4.1.7 Combustion Promoters........................................................................................... 130 2.2.4.1.8 Propylene Production ............................................................................................. 131 2.2.4.2 Ambur Chemical Co. .............................................................................................................. 133 2.2.4.3 BASF Catalysts ....................................................................................................................... 133 2.2.4.3.1 Cracking Catalysts to Increase Liquid Products .................................................... 136 2.2.4.3.2 Co-catalysts ............................................................................................................ 139 2.2.4.3.3 Gasoline Sulfur Reduction Formulations ............................................................... 141 2.2.4.3.4 SOX Reduction Additives....................................................................................... 142 2.2.4.3.5 Microfine Reduction Catalyst Technology ............................................................ 142 2.2.4.3.6 Catalyst Circulation Improvement Additive .......................................................... 143 2.2.4.3.7 Combustion Promoters........................................................................................... 143 2.2.4.3.8 Propylene Production ............................................................................................. 144 2.2.4.4 Grace ....................................................................................................................................... 144 2.2.4.4.1 Cracking Catalysts to Increase Liquid Products .................................................... 148 2.2.4.4.2 Gasoline Sulfur Reduction Formulations ............................................................... 161 2.2.4.4.3 SOX Reduction Additives....................................................................................... 163 2.2.4.4.4 Catalyst Circulation Improvement Additive .......................................................... 165 2.2.4.4.5 Combustion Promoters........................................................................................... 166 2.2.4.4.6 Propylene Production ............................................................................................. 168 2.2.4.5 Inst. Mexicano del Petróleo..................................................................................................... 169 2.2.4.6 INTERCAT ............................................................................................................................. 169 2.2.4.6.1 Gasoline Olefins Reduction Additives ................................................................... 170

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2.2.4.6.2 Gasoline Sulfur Reduction Additives .................................................................... 170 2.2.4.6.3 SOX Reduction Additives ...................................................................................... 171 2.2.4.6.4 Bottoms Cracking Additives ................................................................................. 172 2.2.4.6.5 Catalyst Enhancement Additives ........................................................................... 174 2.2.4.6.6 Combustion Promoters .......................................................................................... 175 2.2.4.7 JGC Catalysts and Chemicals ................................................................................................. 176 2.2.4.8 Nalco Energy Services/Refining Process Services ................................................................. 177 2.2.4.8.1 MVP ...................................................................................................................... 177 2.2.4.8.2 NPP ........................................................................................................................ 179 2.2.4.9 Sinopec ................................................................................................................................... 179 2.2.4.9.1 Diesel Maximizing Catalysts ................................................................................. 180 2.2.4.9.2 Gasoline Olefins Reduction Formulations............................................................. 181 2.2.4.9.3 Gasoline Sulfur Reduction Additives .................................................................... 182 2.2.4.9.4 Propylene Production ............................................................................................ 182 2.2.4.10 Summary of Commercially Available FCC Catalysts ............................................................ 182 2.2.4.11 Summary of Commercially Available FCC Additives ........................................................... 183 2.2.5 Alternative Catalyst Technologies ........................................................................................................ 185 2.2.5.1 Albemarle ............................................................................................................................... 185 2.2.5.2 Grace....................................................................................................................................... 186 2.2.5.3 INTERCAT ............................................................................................................................ 186 2.2.5.4 KBR ........................................................................................................................................ 188 2.2.5.5 Nippon Oil .............................................................................................................................. 189 2.2.6 Advanced Process Control Systems ...................................................................................................... 189 2.2.6.1 ABB ........................................................................................................................................ 190 2.2.6.2 AspenTech .............................................................................................................................. 190 2.2.6.3 Cutler Technology Corp. ........................................................................................................ 190 2.2.6.4 Expertune ................................................................................................................................ 191 2.2.6.5 Honeywell Industry Solutions ................................................................................................ 192 2.2.6.6 Invensys .................................................................................................................................. 192 2.2.6.7 Petrocontrol ............................................................................................................................ 193 2.2.6.8 Yokogawa ............................................................................................................................... 193 2.2.6.9 Summary of Commercially Available Advanced Control Systems ........................................ 194 2.2.7 Process Models and Simulation ............................................................................................................ 196 2.2.7.1 AspenTech .............................................................................................................................. 197 2.2.7.2 Computational Particle Fluid Dynamics ................................................................................. 198 2.2.7.3 Eurotek Refining Services ...................................................................................................... 199 2.2.7.4 KBC Advanced Technologies ................................................................................................ 199 2.2.7.5 Petrobras ................................................................................................................................. 199 2.2.7.6 Shell ........................................................................................................................................ 200 2.2.7.7 Topnir Systems ....................................................................................................................... 200 2.2.7.8 Summary of Commercially Available Process Models and Simulation Software .................. 201 2.2.8 Resid Fluid Catalytic Cracking............................................................................................................. 202 2.2.9 Renewable Fluid Catalytic Cracking .................................................................................................... 211 PLANT OPERATIONS AND PRACTICES ................................................................................................................ 213 2.3.1 Feed Considerations ............................................................................................................................. 213 2.3.1.1 Effect of FCC Feed Contaminants on Unit Operation ............................................................ 213 2.3.1.2 Impact of VGO Hydrogen Content on FCC Operation .......................................................... 215 2.3.1.3 Minimizing Diesel-range Material in FCC Feed .................................................................... 216 2.3.1.4 Optimizing FCC Feed Preheat Temperature........................................................................... 218 2.3.2 Improving FCC Gasoline Output and Quality ...................................................................................... 219 2.3.2.1 Enhancing Gasoline Octane .................................................................................................... 220 2.3.2.2 FCC Gasoline Sulfur Reduction ............................................................................................. 220 2.3.2.3 Lowering FCC Gasoline Olefinicity ....................................................................................... 221

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2.3.3 2.3.4

2.3.5

2.3.6

2.3.7

2.3.8

2.3.2.4 Lowering the Benzene Content of FCC Gasoline ................................................................... 222 2.3.2.5 Variables Influencing Gasoline Aromatics Content ................................................................ 223 2.3.2.6 FCC Gasoline Stability ........................................................................................................... 223 2.3.2.7 Effect of Long-term Storage on FCC Gasoline Quality .......................................................... 224 Increasing FCC LCO Production ......................................................................................................... 224 2.3.3.1 Catalyst Modifications to Improve FCC LCO Yields ............................................................. 229 2.3.3.2 Improving LCO Recovery from the Main Fractionator Bottoms Product .............................. 232 Increasing Production of Light Olefins in the FCCU ........................................................................... 233 2.3.4.1 Improving FCC Propylene Production.................................................................................... 233 2.3.4.2 Managing Revamp Costs for Producing/Recovering Higher Yields of FCC Propylene ........ 239 2.3.4.3 Balancing Propylene Production with FCC Fuel Products ..................................................... 241 2.3.4.4 Increasing FCC Isobutane and Isobutylene Production .......................................................... 243 2.3.4.5 Factors Influencing the FCC Propylene-to-Butylene Production Ratio .................................. 243 Resid Fluid Catalytic Cracking ............................................................................................................. 244 2.3.5.1 Responding to Opportunity Crudes......................................................................................... 244 2.3.5.2 Fouling Prevention for Resid Processing ................................................................................ 246 2.3.5.3 Proper Feed Injection System Design for RFCCUs ................................................................ 247 2.3.5.4 Dual Regenerator Designs for RFCCUs ................................................................................. 248 2.3.5.5 Running an RFCCU on Lighter Feeds: Maintaining Regenerator Temperature ..................... 249 Operational Monitoring and Process Simulation ................................................................................. 250 2.3.6.1 Monitoring Fresh Feed Flowrate ............................................................................................. 250 2.3.6.2 Monitoring Entrained Oxygen Sources in FCC Fuel Gas ....................................................... 250 2.3.6.3 Monitoring Bottoms Level in the Main Fractionator .............................................................. 251 2.3.6.4 Measuring Cyanide Content in CO2 Rich FCCU Flue Gas..................................................... 252 2.3.6.5 Inspecting and Monitoring Expansion Joints in Catalyst Standpipes ..................................... 253 2.3.6.6 Vapor Line Sampling .............................................................................................................. 254 2.3.6.7 Applying Advanced Simulation Techniques........................................................................... 254 Fouling, Degradation, and Erosion Problems ...................................................................................... 256 2.3.7.1 Slurry Exchanger Fouling ....................................................................................................... 256 2.3.7.2 Fouling in Main Air Blower.................................................................................................... 257 2.3.7.3 Refractory Material Degradation in FCCU Catalyst Transfer Lines....................................... 257 2.3.7.4 Hot Spots in FCCU Piping and Transfer Lines ....................................................................... 258 2.3.7.5 Mitigating Erosion Problems in FCC Cyclones ...................................................................... 259 FCCU Hardware Considerations and Improvements ........................................................................... 262 2.3.8.1 Reactor .................................................................................................................................... 262 2.3.8.1.1 Reactor Design ....................................................................................................... 262 2.3.8.1.2 Optimizing Riser Mixing ....................................................................................... 262 2.3.8.1.3 Improving Air-Steam Distribution ......................................................................... 263 2.3.8.1.4 Minimizing Coke Buildup in the Reactor .............................................................. 264 2.3.8.1.5 Methods to Control Secondary Cracking in the FCC Reactor ............................... 265 2.3.8.2 Regenerator ............................................................................................................................. 266 2.3.8.2.1 Available Configurations for Catalyst Regeneration ............................................. 266 2.3.8.2.2 Meeting Regenerator Temperature Constraints ..................................................... 267 2.3.8.2.3 Regenerator Combustion Mode: Effect on Contaminant Mobility and Activity ... 268 2.3.8.2.4 Operating Partial Burn Regenerators in Total Combustion Mode ......................... 269 2.3.8.2.5 Benefits and Drawbacks of Oxygen Enrichment in Regenerators ......................... 269 2.3.8.2.6 Minimizing Inerts Entrained in Catalyst Exiting the Regenerator ......................... 272 2.3.8.3 Stripper Vessel ........................................................................................................................ 272 2.3.8.3.1 Improving Stripper Performance ........................................................................... 272 2.3.8.3.2 Measuring Stripper Efficiency ............................................................................... 273 2.3.8.4 Main Fractionator .................................................................................................................... 274 2.3.8.4.1 Overhead Line Coking and Corrosion ................................................................... 274

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2.4

2.3.8.4.2 Avoiding Salt Deposition Problems ...................................................................... 274 2.3.8.4.3 Dealing with High Ash Content ............................................................................ 276 2.3.8.4.4 Benefits of a Staged Revamp on a FCCU Main Fractionator................................ 277 2.3.8.4.5 Isolation Valve Considerations .............................................................................. 278 2.3.9 Catalyst Management ........................................................................................................................... 278 2.3.9.1 Reducing Rare Earth Use........................................................................................................ 278 2.3.9.2 Evaluating FCC Catalyst Selection......................................................................................... 281 2.3.9.3 Additives for Feed Flexibility ................................................................................................. 283 2.3.9.4 Effect of Changing Catalyst Formulation on FCC Performance ............................................ 284 2.3.9.5 Catalyst Losses from the FCCU ............................................................................................. 284 2.3.9.6 Catalyst Circulation Problems ................................................................................................ 289 2.3.9.7 Preventing Catalyst Backflow ................................................................................................ 291 2.3.9.8 Diagnosing the Cause of Catalyst Deactivation...................................................................... 291 2.3.9.9 Maintaining FCC Ecat Activity .............................................................................................. 292 2.3.9.10 Disposing of FCC Ecat ........................................................................................................... 293 2.3.10 Energy Efficiency and Environmental Emissions ................................................................................. 294 2.3.10.1 Improving FCC Energy Efficiency ......................................................................................... 294 2.3.10.1.1 Key FCC Variables to Monitor for Energy Efficiency Improvements .................. 294 2.3.10.1.2 Heat Recovery in the Main Fractionator for Propylene Recovery ........................ 295 2.3.10.1.3 Installation of a Power Recovery System .............................................................. 295 2.3.10.2 Reducing Environmental Emissions from the FCCU ............................................................. 297 2.3.10.2.1 FCC Feed Pretreatment ......................................................................................... 298 2.3.10.2.2 Use of Electrostatic Precipitators to Reduce FCC Emissions ................................ 298 2.3.10.2.3 Proper Two-stage Cyclone System Design ........................................................... 299 2.3.10.2.4 Effect of FCC Operating Variables on SOX Emissions ......................................... 300 2.3.10.2.5 Flue Gas Scrubbers to Reduce FCC SOX Emissions ............................................. 301 2.3.10.2.6 SOX Additives to Meet Ultra-low SOX Emission Levels ...................................... 303 2.3.10.2.7 Effect of Regenerator Operations on NOX Emissions ........................................... 304 2.3.10.2.8 Effect of O2 Availability and Discharge Design on Regenerator NOX Emissions 305 2.3.10.2.9 Selective Catalytic Reduction Units for NOX Reduction ...................................... 306 2.3.10.2.10 Utilizing NOX Reduction Additives ..................................................................... 309 2.3.10.2.11 Lowering CO Emissions during FCCU Startup ................................................... 310 2.3.10.2.12 Options to Reduce Particulate Matter Emissions from Regenerators .................. 310 2.3.10.2.13 Preventing Clogging of FCC Flue Gas Equipment .............................................. 312 2.3.10.2.14 Measuring Sulfur Content in FCC Flue Gas ........................................................ 313 2.3.11 FCCU Safety Considerations ................................................................................................................ 314 2.3.11.1 Preventing Vapor Over-pressure Events during Startup ........................................................ 314 2.3.11.2 Emergency and Unplanned Shutdowns .................................................................................. 315 2.3.11.3 Operating in Dry Circulation Mode ........................................................................................ 316 2.3.11.4 Improving Catalyst Slide Valve Design to Improve Unit Safety............................................ 317 2.3.11.5 Relief Valves in the FCCU ..................................................................................................... 318 REFINING R&D ALERT! .................................................................................................................................... 318 2.4.1 Introduction .......................................................................................................................................... 318 2.4.2 Gasoline Reformulation and Yield Enhancement ................................................................................. 323 2.4.2.1 Process .................................................................................................................................... 323 2.4.2.1.1 Reduction of Sulfur and Benzene .......................................................................... 323 2.4.2.1.2 Yield Enhancement ............................................................................................... 325 2.4.2.2 Catalysts.................................................................................................................................. 325 2.4.3 LCO Yield ............................................................................................................................................. 326 2.4.3.1 Patents..................................................................................................................................... 326 2.4.3.2 Research.................................................................................................................................. 328

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2.5 2.6

2.7

2.4.4 Light Olefin Yield Maximization ........................................................................................................... 328 2.4.4.1 Process .................................................................................................................................... 328 2.4.4.1.1 Patents .................................................................................................................... 328 2.4.4.1.2 Research ................................................................................................................. 331 2.4.4.2 Catalysts .................................................................................................................................. 332 2.4.4.2.1 Patents .................................................................................................................... 332 2.4.4.2.2 Research ................................................................................................................. 334 2.4.5 Bottoms Cracking and Resid Feedstock ................................................................................................ 336 2.4.5.1 Process .................................................................................................................................... 336 2.4.5.2 Catalysts and Additives ........................................................................................................... 337 2.4.5.2.1 Patents .................................................................................................................... 337 2.4.5.2.2 Research ................................................................................................................. 339 2.4.6 Biofeeds ................................................................................................................................................. 339 2.4.6.1 Patents ..................................................................................................................................... 339 2.4.6.2 Research .................................................................................................................................. 341 2.4.7 Preparation of Catalysts and Additives ................................................................................................. 343 2.4.7.1 Patents ..................................................................................................................................... 343 2.4.7.2 Research .................................................................................................................................. 346 2.4.8 General Application: Process and Hardware ....................................................................................... 348 2.4.8.1 Feed Injection Nozzles ............................................................................................................ 348 2.4.8.2 Multi-stage and Dual Riser Processes ..................................................................................... 348 2.4.8.3 Catalyst Injection .................................................................................................................... 350 2.4.8.4 Catalyst Separation.................................................................................................................. 350 2.4.8.4.1 Patents .................................................................................................................... 350 2.4.8.4.2 Research ................................................................................................................. 353 2.4.8.5 Catalyst Regeneration ............................................................................................................. 354 2.4.8.5.1 Patents .................................................................................................................... 354 2.4.8.5.2 Research ................................................................................................................. 356 2.4.8.6 Power Recovery ...................................................................................................................... 358 2.4.8.7 Catalyst Coolers ...................................................................................................................... 358 2.4.8.8 Other ....................................................................................................................................... 358 2.4.9 NOX, SOX, CO, and PM Emissions Additives ........................................................................................ 359 2.4.9.1 Patents ..................................................................................................................................... 359 2.4.9.2 Research .................................................................................................................................. 362 2.4.10 Process Monitoring, Control, and Optimization ................................................................................... 363 2.4.10.1 Patents ..................................................................................................................................... 363 2.4.10.2 Research .................................................................................................................................. 364 2.4.11 Integration ............................................................................................................................................. 367 2.4.11.1 Patents ..................................................................................................................................... 367 2.4.11.2 Research .................................................................................................................................. 368 WORLDWIDE INSTALLED CAPACITY .................................................................................................................. 369 CONSTRUCTION ................................................................................................................................................. 372 2.6.1 Recent Construction Activity ................................................................................................................. 372 2.6.2 Completed Construction Activity ........................................................................................................... 377 REFERENCES ...................................................................................................................................................... 392

3. Gas Processing ............................................................................................................................ 425 3.1

MARKET/TECHNOLOGY TRENDS & OPPORTUNITIES .......................................................................................... 425 3.1.1 Introduction ........................................................................................................................................... 425 3.1.2 Market Conditions and Outlook ............................................................................................................ 427 3.1.2.1 Liquefied Petroleum Gas......................................................................................................... 427 3.1.2.2 Ethylene .................................................................................................................................. 428 3.1.2.3 Propylene ................................................................................................................................ 429

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3.1.2.4 Hydrogen ................................................................................................................................ 429 3.1.3 Technology Competition, Directions, and Future Prospects ................................................................ 430 3.1.3.1 LPG and Olefins ..................................................................................................................... 430 3.1.3.2 Hydrogen ................................................................................................................................ 432 3.1.4 Research and Development................................................................................................................... 433 3.1.5 Conclusion ............................................................................................................................................ 435 STATE-OF-THE-ART TECHNOLOGY ................................................................................................................... 436 3.2.1 Introduction .......................................................................................................................................... 436 3.2.2 Gas Plant Configuration ....................................................................................................................... 438 3.2.2.1 Saturated Gas Plant ................................................................................................................. 438 3.2.2.2 Unsaturated Gas Plant ............................................................................................................ 439 3.2.3 Gas Separation Mechanisms................................................................................................................. 440 3.2.4 Commercially Available Process Technology ...................................................................................... 443 3.2.4.1 Advanced Extraction Technologies ........................................................................................ 443 3.2.4.1.1 Light Olefin Recovery ........................................................................................... 443 3.2.4.1.2 LPG Recovery from Saturated Offgas................................................................... 444 3.2.4.1.3 Hydrogen Recovery Unit ....................................................................................... 445 3.2.4.2 Air Liquide ............................................................................................................................. 446 3.2.4.3 Air Products and Chemicals ................................................................................................... 447 3.2.4.3.1 Cryogenic System .................................................................................................. 447 3.2.4.3.2 Dephlegmator ........................................................................................................ 448 3.2.4.3.3 Membrane Technology .......................................................................................... 449 3.2.4.3.3.1 Prism Membrane Systems .............................................................. 449 3.2.4.3.3.2 Selective Surface Flow Membranes ............................................... 450 3.2.4.4 BASF ...................................................................................................................................... 450 3.2.4.5 Black & Veatch ...................................................................................................................... 451 3.2.4.6 Costain Oil, Gas & Process .................................................................................................... 453 3.2.4.6.1 Light Olefins Recovery ......................................................................................... 454 3.2.4.6.2 LPG Recovery ....................................................................................................... 456 3.2.4.7 Eurofilm .................................................................................................................................. 458 3.2.4.7.1 LPG Recovery ....................................................................................................... 458 3.2.4.7.2 Hydrogen Recovery ............................................................................................... 458 3.2.4.8 ExxonMobil ............................................................................................................................ 459 3.2.4.8.1 RCPSA .................................................................................................................. 459 3.2.4.9 Fluor ....................................................................................................................................... 460 3.2.4.9.1 CO2LDSep ............................................................................................................. 460 3.2.4.10 Innovative Gas Systems .......................................................................................................... 461 3.2.4.10.1 H2S Removal ......................................................................................................... 461 3.2.4.10.2 Hydrogen Recovery ............................................................................................... 462 3.2.4.10.2.1 HYDROSWING PSA..................................................................... 462 3.2.4.10.2.2 Membrane Technology ................................................................... 463 3.2.4.11 Linde BOC Process Plants ...................................................................................................... 464 3.2.4.11.1 Light Olefins Recovery ......................................................................................... 464 3.2.4.11.1.1 Cryo-Plus ........................................................................................ 464 3.2.4.11.1.2 Cryo-Plus C2= ................................................................................. 466 3.2.4.11.2 Hydrogen Recovery ............................................................................................... 468 3.2.4.11.2.1 Common PSA ................................................................................. 468 3.2.4.11.2.2 Direct Feed to Reformer ................................................................. 469 3.2.4.11.2.3 Dedicated PSA for ROG................................................................. 469 3.2.4.12 Lummus Technology .............................................................................................................. 470 3.2.4.12.1 Low Pressure Olefin Recovery .............................................................................. 470

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3.3

3.4

3.2.4.13 Membrane Technology and Research. .................................................................................... 471 3.2.4.13.1 VaporSep-H2 .......................................................................................................... 471 3.2.4.13.2 VaporSep-LPG....................................................................................................... 472 3.2.4.14 Shanghai Donghua Environmental Engineering Corp. (SDEEC) ........................................... 473 3.2.4.15 Uhde ........................................................................................................................................ 474 3.2.4.16 UOP......................................................................................................................................... 475 3.2.4.16.1 Propylene Recovery ............................................................................................... 475 3.2.4.16.2 Polybed PSA .......................................................................................................... 476 3.2.4.16.3 Membrane Separation ............................................................................................ 477 3.2.4.17 Xebec Adsorption Inc. ............................................................................................................ 478 3.2.4.18 Other Technologies ................................................................................................................. 479 3.2.5 Summary of Commercially Available Gas Processing Technologies.................................................... 480 PLANT OPERATIONS AND PRACTICES................................................................................................................. 483 3.3.1 General Refinery Offgas Treatment ...................................................................................................... 483 3.3.2 Holistic Approach to FCC Gas Plant Optimization .............................................................................. 485 3.3.3 Improving FCC Propylene Recovery and Purity .................................................................................. 487 3.3.3.1 Propylene Splitter .................................................................................................................... 487 3.3.3.1.1 Economic Feasibility.............................................................................................. 487 3.3.3.1.2 Optimization .......................................................................................................... 488 3.3.3.1.3 Control of Propylene Splitters ............................................................................... 489 3.3.3.1.3.1 Dynamic Simulation........................................................................ 489 3.3.3.1.3.2 Inferential Model............................................................................. 490 3.3.3.1.4 Exotherms Safety ................................................................................................... 491 3.3.3.2 Improving FCC Gas Plant Operations to Increase Propylene Yield ....................................... 491 3.3.3.3 Processes Used to Purify FCC Propylene ............................................................................... 492 3.3.3.4 Control Issues for Propylene-Propane Separators................................................................... 494 3.3.4 Improving Hydrogen Recovery ............................................................................................................. 495 3.3.4.1 Feed Properties That Influence Hydrogen Recovery .............................................................. 495 3.3.4.2 Hydrogen Recovery PSA Configurations ............................................................................... 496 3.3.4.2.1 Combined Feed of Refinery Offgas and Steam Reformer Gas to PSA Unit ......... 496 3.3.4.2.2 Separate PSA Unit for ROG .................................................................................. 496 3.3.4.2.3 Direct ROG Feed to HGU...................................................................................... 496 3.3.4.2.4 PSA with TSA ....................................................................................................... 497 3.3.5 Capacity Limitations Due to Stripper Flooding .................................................................................... 497 3.3.5.1 Process Configuration ............................................................................................................. 498 3.3.5.2 Operating Conditions .............................................................................................................. 499 3.3.5.3 Internals................................................................................................................................... 501 3.3.5.4 HP Receiver ............................................................................................................................ 502 3.3.5.5 Water Draw ............................................................................................................................. 502 3.3.6 Overcoming Hardware Limitations Through Revamp .......................................................................... 503 3.3.7 Controlling LPG Weathering in a Gas Plant ........................................................................................ 504 3.3.8 Decreasing LPG Content in Fuel Gas (Dry Gas) ................................................................................. 505 3.3.9 Optimizing Light Ends Recovery from Refinery Fuel Gas Streams ...................................................... 505 3.3.10 Debottlenecking Debutanizer Feed ....................................................................................................... 508 3.3.11 Pressure Safety Valves for Light Hydrocarbon Separations ................................................................. 509 REFINING R&D ALERT! ..................................................................................................................................... 510 3.4.1 Introduction ........................................................................................................................................... 510 3.4.2 Distillation ............................................................................................................................................. 512 3.4.3 Absorption ............................................................................................................................................. 513 3.4.3.1 Light Hydrocarbons ................................................................................................................ 513

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3.5

3.4.4 Membrane ............................................................................................................................................. 514 3.4.4.1 Light Hydrocarbons ................................................................................................................ 514 3.4.4.1.1 Patents ................................................................................................................... 514 3.4.4.1.2 Research ................................................................................................................ 515 3.4.4.2 Hydrogen ................................................................................................................................ 515 3.4.4.2.1 Patents ................................................................................................................... 515 3.4.4.2.2 Research ................................................................................................................ 516 3.4.4.3 Light Hydrocarbons and Hydrogen ........................................................................................ 516 3.4.5 Adsorption ............................................................................................................................................. 517 3.4.5.1 Hydrogen ................................................................................................................................ 517 3.4.5.1.1 Patents ................................................................................................................... 517 3.4.5.1.2 Research ................................................................................................................ 517 3.4.5.2 Light Hydrocarbons and Hydrogen ........................................................................................ 518 3.4.6 Hybrid Separation (Combination of Absorption, Membrane, and/or Adsorption) ............................... 519 3.4.6.1 Hydrogen ................................................................................................................................ 519 3.4.6.2 Light Hydrocarbons and Hydrogen ........................................................................................ 521 3.4.7 Treating ................................................................................................................................................. 521 3.4.8 Propane/Propylene Splitter .................................................................................................................. 523 3.4.8.1 Patents..................................................................................................................................... 523 3.4.8.2 Research.................................................................................................................................. 524 REFERENCES ..................................................................................................................................................... 528

4. Latest Refining TEchnology Developments & Licensing ........................................................ 535 4.1 4.2 4.3 4.4 4.5 4.6 4.7 4.8 4.9 4.10 4.11

DESULFURIZATION (WITHOUT HYDROGEN) ....................................................................................................... 535 HYDROCRACKING ............................................................................................................................................. 536 HYDROGEN PRODUCTION AND PURIFICATION ................................................................................................... 536 COGENERATION AND INTEGRATED GASIFICATION COMBINED CYCLE .............................................................. 537 SULFUR PLANT .................................................................................................................................................. 537 AROMATICS AND LIGHT OLEFINS PRODUCTION ................................................................................................ 538 PROCESS CONTROLS AND SIMULATION ............................................................................................................. 538 GAS-TO-LIQUID AND COAL-TO-LIQUID .............................................................................................................. 538 BIOFUELS PRODUCTION..................................................................................................................................... 540 CO2 EMISSIONS (CARBON CAPTURE AND SEQUESTRATION) ............................................................................. 542 REFERENCES ..................................................................................................................................................... 543

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