Worldwide Refinery Processing Review - 4Q2011 by Hydrocarbon Publishing Company

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

Fourth Quarter 2011 Fluid Catalytic Cracking and Light Olefins Production Plus

Latest Refining Technology Developments & Licensing

HYDROCARBON PUBLISHING COMPANY Translating Knowledge into Profitability

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Review@Hydrocarbonpublishing.com

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

Fourth Quarter 2011 Fluid Catalytic Cracking and Light Olefins Production Plus Latest Refining Technology Developments & Licensing

http://www.hydrocarbonpublishing.com

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.

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4Q 2011 Hydrocarbon Publishing Co./Copyright Protected

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TABLE OF CONTENTS 4Q 2011 Review Fluid Catalytic Cracking and Light Olefins Production 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............................................................... 8 2.1.2.1.2 Expanding the Share of Diesel in Bunker Fuel Markets ........................................... 9 2.1.2.1.3 Growing Propylene Consumption ........................................................................... 10 2.1.2.1.4 Seeking Outlets for Slurry Oil ................................................................................. 12 2.1.2.2 FCC Capacity and Expansion ................................................................................................... 14 2.1.2.3 New Units Oriented Towards Changes in Feeds, Products ...................................................... 15 2.1.2.4 Fuel Specifications and Unit Emissions Considerations .......................................................... 16 2.1.2.4.1 Transportation Fuels ................................................................................................ 16 2.1.2.4.2 FCC Unit Emissions ................................................................................................ 18 2.1.2.5 Current Status of FCC Catalyst Market .................................................................................... 20 2.1.2.5.1 FCC Catalyst Demand Trends ................................................................................. 21 2.1.2.5.2 Focus on Rare Earth ................................................................................................ 22 2.1.2.5.2.1 Supply, Demand, and Skyrocketing Prices ....................................... 22 2.1.2.5.2.2 Rare Earth Functionality and Usage ................................................. 25 2.1.2.5.2.3 Options for Reducing Rare Earth Use and Costs .............................. 26 2.1.2.5.3 Looking Ahead ........................................................................................................ 28 2.1.3 Technology Directions, Competition, and Future Prospects .................................................................. 29 2.1.3.1 Producing High-quality Gasoline and Increasing Yield ........................................................... 32 2.1.3.2 Light Olefins Production Enhancement .................................................................................... 33 2.1.3.3 Boosting LCO Yield and Quality ............................................................................................. 35 2.1.3.4 Improving Operational Flexibility in Gasoline/Propylene and LCO Production Modes ......... 38 2.1.3.5 Processing Resid and Biofeeds ................................................................................................. 39 2.1.3.6 Regenerator Pollution Abatement and GHG Concerns ............................................................ 41 2.1.3.7 Process Modeling, Monitoring, and Control ............................................................................ 43 2.1.4 Conclusion .............................................................................................................................................. 44 STATE-OF-THE-ART TECHNOLOGY ..................................................................................................................... 46 2.2.1 Introduction ............................................................................................................................................ 46 2.2.2 Commercial Processes and Hardware ................................................................................................... 47 2.2.2.1 ExxonMobil/KBR ..................................................................................................................... 47 2.2.2.1.1 Flexicracking III ...................................................................................................... 47 2.2.2.1.2 Orthoflow ................................................................................................................ 50 2.2.2.1.3 Propylene Production .............................................................................................. 53 2.2.2.2 Lummus Technology ................................................................................................................ 53 2.2.2.2.1 Fuels Production ...................................................................................................... 53 2.2.2.2.2 Indmax FCC (I-FCC) .............................................................................................. 55 2.2.2.3 Nippon/Saudi Aramco .............................................................................................................. 56 2.2.2.4 Petrobras ................................................................................................................................... 60 2.2.2.4.1 Fuels Production ...................................................................................................... 60 2.2.2.4.2 Propylene Production .............................................................................................. 62

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TABLE OF CONTENTS 2.2.2.5 Shaw Group/Axens ................................................................................................................... 62 2.2.2.5.1 Fuels Production ...................................................................................................... 62 2.2.2.5.2 Propylene Production ............................................................................................... 67 2.2.2.6 Shell Global Solutions .............................................................................................................. 68 2.2.2.6.1 FCC .......................................................................................................................... 68 2.2.2.6.2 MILOS ..................................................................................................................... 72 2.2.2.6.3 Propylene Production ............................................................................................... 73 2.2.2.7 Sinopec ...................................................................................................................................... 73 2.2.2.7.1 Clean Gasoline and Propylene ................................................................................. 74 2.2.2.7.2 Maximizing Iso-paraffins......................................................................................... 76 2.2.2.7.3 Flexible Dual-riser Fluid Catalytic Cracking ........................................................... 77 2.2.2.7.4 Maximum Gas and Diesel ........................................................................................ 79 2.2.2.7.5 Maximum Liquefied Gas and High-octane Gasoline ............................................... 80 2.2.2.7.6 Propylene Production ............................................................................................... 81 2.2.2.8 UOP........................................................................................................................................... 81 2.2.2.8.1 FCC .......................................................................................................................... 81 2.2.2.8.2 MSCC ...................................................................................................................... 87 2.2.2.8.3 Propylene Production ............................................................................................... 88 2.2.2.9 Summary of Commercial FCC Processes and Hardware .......................................................... 89 2.2.3 Other Commercial Hardware ................................................................................................................. 96 2.2.3.1 Fisher-Klosterman ..................................................................................................................... 96 2.2.3.2 Koch-Glitsch ............................................................................................................................. 96 2.2.3.3 Lawrence Pumps ....................................................................................................................... 97 2.2.4 Commercial Catalysts and Additives....................................................................................................... 97 2.2.4.1 Albemarle .................................................................................................................................. 98 2.2.4.1.1 Cracking Catalysts to Increase Liquid Products ...................................................... 99 2.2.4.1.2 Gasoline Olefins Reduction Formulations ............................................................. 106 2.2.4.1.3 Gasoline Sulfur Reduction Formulations ............................................................... 107 2.2.4.1.4 SOX Reduction Additives....................................................................................... 109 2.2.4.1.5 Bottoms Cracking Additives .................................................................................. 110 2.2.4.1.6 Microfine Reduction Catalyst Technology ............................................................ 113 2.2.4.1.7 Catalyst Circulation Improvement Additives ......................................................... 113 2.2.4.1.8 Combustion Promoters........................................................................................... 114 2.2.4.1.9 Propylene Production ............................................................................................. 114 2.2.4.2 Ambur Chemical Co. .............................................................................................................. 115 2.2.4.3 BASF Catalysts ....................................................................................................................... 115 2.2.4.3.1 Cracking Catalysts to Increase Liquid Products .................................................... 117 2.2.4.3.2 Co-catalysts ............................................................................................................ 121 2.2.4.3.3 Gasoline Sulfur Reduction Formulations ............................................................... 123 2.2.4.3.4 SOX Reduction Additives....................................................................................... 124 2.2.4.3.5 Microfine Reduction Catalyst Technology ............................................................ 124 2.2.4.3.6 Catalyst Circulation Improvement Additive .......................................................... 125 2.2.4.3.7 Combustion Promoters........................................................................................... 125 2.2.4.3.8 Propylene Production ............................................................................................. 125 2.2.4.4 Grace Davison ......................................................................................................................... 125 2.2.4.4.1 Cracking Catalysts to Increase Liquid Products .................................................... 128 2.2.4.4.2 Gasoline Olefins Reduction Catalysts .................................................................... 139 2.2.4.4.3 Gasoline Sulfur Reduction Formulations ............................................................... 139 2.2.4.4.4 SOX Reduction Additives....................................................................................... 141 2.2.4.4.5 Bottoms Cracking Additives .................................................................................. 142 2.2.4.4.6 Combustion Promoters........................................................................................... 143 2.2.4.4.7 Propylene Production ............................................................................................. 145 2.2.4.5 Inst. Mexicano del Petr贸leo..................................................................................................... 145

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2.3

2.2.4.6 INTERCAT ............................................................................................................................ 145 2.2.4.6.1 Gasoline Olefins Reduction Additives .................................................................. 146 2.2.4.6.2 Gasoline Sulfur Reduction Additives .................................................................... 146 2.2.4.6.3 SOX Reduction Additives ...................................................................................... 147 2.2.4.6.4 Bottoms Cracking Additives ................................................................................. 148 2.2.4.6.5 Catalyst Enhancement Additives ........................................................................... 150 2.2.4.6.6 Combustion Promoters .......................................................................................... 151 2.2.4.7 JGC Catalysts and Chemicals ................................................................................................. 152 2.2.4.8 Nalco Energy Services/Refining Process Services ................................................................. 153 2.2.4.8.1 MVP ...................................................................................................................... 153 2.2.4.8.2 NPP ........................................................................................................................ 154 2.2.4.9 Sinopec ................................................................................................................................... 155 2.2.4.9.1 Diesel Maximizing Catalysts ................................................................................. 155 2.2.4.9.2 Gasoline Olefins Reduction Formulations............................................................. 156 2.2.4.9.3 Gasoline Sulfur Reduction Additives .................................................................... 157 2.2.4.9.4 Propylene Production ............................................................................................ 158 2.2.4.10 Summary of Commercially Available FCC Catalysts ............................................................ 158 2.2.4.11 Summary of Commercially Available FCC Additives ........................................................... 159 2.2.5 Alternative Catalyst Technologies ........................................................................................................ 161 2.2.5.1 Albemarle ............................................................................................................................... 161 2.2.5.2 Grace Davison ........................................................................................................................ 161 2.2.5.3 INTERCAT ............................................................................................................................ 161 2.2.5.4 KBR ........................................................................................................................................ 163 2.2.5.5 Nippon Oil .............................................................................................................................. 164 2.2.6 Advanced Process Control Systems ...................................................................................................... 164 2.2.6.1 ABB ........................................................................................................................................ 165 2.2.6.2 AspenTech .............................................................................................................................. 165 2.2.6.3 Cutler Technology Corp. ........................................................................................................ 165 2.2.6.4 Expertune ................................................................................................................................ 166 2.2.6.5 Honeywell Industry Solutions ................................................................................................ 167 2.2.6.6 Invensys .................................................................................................................................. 167 2.2.6.7 Petrocontrol ............................................................................................................................ 168 2.2.6.8 Yokogawa ............................................................................................................................... 168 2.2.6.9 Summary of Commercially Available Advanced Control Systems ........................................ 169 2.2.7 Process Models and Simulation ............................................................................................................ 171 2.2.7.1 AspenTech .............................................................................................................................. 172 2.2.7.2 Computational Particle Fluid Dynamics ................................................................................. 173 2.2.7.3 Eurotek Refining Services ...................................................................................................... 174 2.2.7.4 KBC Advanced Technologies ................................................................................................ 174 2.2.7.5 Petrobras ................................................................................................................................. 174 2.2.7.6 Shell ........................................................................................................................................ 175 2.2.7.7 Topnir Systems ....................................................................................................................... 175 2.2.7.8 Summary of Commercially Available Process Models and Simulation Software .................. 176 2.2.8 Resid Fluid Catalytic Cracking............................................................................................................. 177 2.2.9 Renewable Fluid Catalytic Cracking .................................................................................................... 185 PLANT OPERATIONS AND PRACTICES ................................................................................................................ 188 2.3.1 Feed Considerations ............................................................................................................................. 188 2.3.1.1 Effect of FCC Feed Contaminants on Unit Operation ............................................................ 188 2.3.1.2 Minimizing Diesel-range Material in FCC Feed .................................................................... 189 2.3.1.3 Optimizing FCC Feed Preheat Temperature........................................................................... 190 2.3.2 Improving FCC Gasoline Output and Quality ...................................................................................... 191 2.3.2.1 Enhancing Gasoline Octane .................................................................................................... 192 2.3.2.2 FCC Gasoline Sulfur Reduction ............................................................................................. 192

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2.3.3

2.3.4

2.3.5

2.3.6

2.3.7

2.3.8

2.3.2.3 Lowering FCC Gasoline Olefinicity ....................................................................................... 193 2.3.2.4 Lowering the Benzene Content of FCC Gasoline ................................................................... 194 2.3.2.5 Variables Influencing Gasoline Aromatics Content ................................................................ 195 2.3.2.6 FCC Gasoline Stability ........................................................................................................... 195 2.3.2.7 Effect of Long-term Storage on FCC Gasoline Quality .......................................................... 196 Increasing FCC LCO Production ......................................................................................................... 197 2.3.3.1 Catalyst Modifications to Improve FCC LCO Yields ............................................................. 199 2.3.3.2 Improving LCO Recovery from the Main Fractionator Bottoms Product .............................. 200 Resid Fluid Catalytic Cracking ............................................................................................................. 201 2.3.4.1 Responding to Opportunity Crudes......................................................................................... 202 2.3.4.2 Fouling Prevention for Resid Processing ................................................................................ 204 2.3.4.3 Proper Feed Injection System Design for RFCCUs ................................................................ 204 2.3.4.4 Running an RFCCU on Lighter Feeds: Maintaining Regenerator Temperature ..................... 205 Operational Monitoring and Process Simulation ................................................................................. 206 2.3.5.1 Monitoring Fresh Feed Flowrate ............................................................................................. 206 2.3.5.2 Monitoring Entrained Oxygen Sources in FCC Fuel Gas ....................................................... 207 2.3.5.3 Monitoring Bottoms Level in the Main Fractionator .............................................................. 208 2.3.5.4 Measuring Cyanide Content in CO2 Rich FCCU Flue Gas..................................................... 209 2.3.5.5 Inspecting and Monitoring Expansion Joints in Catalyst Standpipes ..................................... 210 2.3.5.6 Vapor Line Sampling .............................................................................................................. 211 2.3.5.7 Applying Advanced Simulation Techniques........................................................................... 211 Fouling, Degradation, and Erosion Problems ...................................................................................... 212 2.3.6.1 Slurry Exchanger Fouling ....................................................................................................... 212 2.3.6.2 Refractory Material Degradation in FCCU Catalyst Transfer Lines....................................... 213 2.3.6.3 Hot Spots in FCCU Piping and Transfer Lines ....................................................................... 214 2.3.6.4 Mitigating Erosion Problems in FCC Cyclones ...................................................................... 214 FCCU Hardware Considerations and Improvements ........................................................................... 217 2.3.7.1 Reactor .................................................................................................................................... 217 2.3.7.1.1 Reactor Design ....................................................................................................... 217 2.3.7.1.2 Optimizing Riser Mixing ....................................................................................... 218 2.3.7.1.3 Improving Air-Steam Distribution ......................................................................... 218 2.3.7.1.4 Minimizing Coke Buildup in the Reactor .............................................................. 219 2.3.7.1.5 Methods to Control Secondary Cracking in the FCC Reactor ............................... 220 2.3.7.2 Regenerator ............................................................................................................................. 220 2.3.7.2.1 Available Configurations for Catalyst Regeneration ............................................. 220 2.3.7.2.2 Meeting Regenerator Temperature Constraints ..................................................... 221 2.3.7.2.3 Regenerator Combustion Mode: Effect on Contaminant Mobility and Activity ... 223 2.3.7.2.4 Operating Partial Burn Regenerators in Total Combustion Mode ......................... 224 2.3.7.2.5 Benefits and Drawbacks of Oxygen Enrichment in Regenerators ......................... 224 2.3.7.2.6 Minimizing Inerts Entrained in Catalyst Exiting the Regenerator ......................... 226 2.3.7.3 Stripper Vessel ........................................................................................................................ 227 2.3.7.3.1 Improving Stripper Performance ........................................................................... 227 2.3.7.3.2 Measuring Stripper Efficiency ............................................................................... 227 2.3.7.4 Main Fractionator .................................................................................................................... 228 2.3.7.4.1 Overhead Line Coking and Corrosion ................................................................... 228 2.3.7.4.2 Avoiding Salt Deposition Problems ....................................................................... 229 2.3.7.4.3 Dealing with High Ash Content ............................................................................. 230 2.3.7.4.4 Benefits of a Staged Revamp on a FCCU Main Fractionator ................................ 231 2.3.7.4.5 Isolation Valve Considerations .............................................................................. 232 Catalyst Management ............................................................................................................................ 232 2.3.8.1 Reducing Rare Earth Use ........................................................................................................ 232 2.3.8.2 Evaluating FCC Catalyst Selection ......................................................................................... 233 2.3.8.3 Additives for Feed Flexibility ................................................................................................. 236

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2.4

2.3.8.4 Effect of Changing Catalyst Formulation on FCC Performance ............................................ 237 2.3.8.5 Catalyst Losses from the FCCU ............................................................................................. 237 2.3.8.6 Catalyst Circulation Problems ................................................................................................ 242 2.3.8.7 Preventing Catalyst Backflow ................................................................................................ 244 2.3.8.8 Maintaining FCC Ecat Activity .............................................................................................. 244 2.3.8.9 Disposing of FCC Ecat ........................................................................................................... 246 2.3.9 Energy Efficiency and Environmental Emissions ................................................................................. 246 2.3.9.1 Improving FCC Energy Efficiency ......................................................................................... 246 2.3.9.1.1 Key FCC Variables to Monitor for Energy Efficiency Improvements .................. 246 2.3.9.1.2 Heat Recovery in the Main Fractionator for Propylene Recovery ........................ 247 2.3.9.1.3 Installation of a Power Recovery System .............................................................. 248 2.3.9.2 Reducing Environmental Emissions from the FCCU ............................................................. 249 2.3.9.2.1 Use of Electrostatic Precipitators to Reduce FCC Emissions ................................ 250 2.3.9.2.2 Effect of FCC Operating Variables on SOX Emissions ......................................... 251 2.3.9.2.3 Flue Gas Scrubbers to Reduce FCC SOX Emissions ............................................. 252 2.3.9.2.4 Effect of Regenerator Operations on NOX Emissions ........................................... 254 2.3.9.2.5 Effect of O2 Availability and Discharge Design on Regenerator NOX Emissions 255 2.3.9.2.6 Selective Catalytic Reduction Units for NOX Reduction ...................................... 255 2.3.9.2.7 Options to Reduce Particulate Matter Emissions from Regenerators .................... 258 2.3.10 FCCU Safety Considerations ................................................................................................................ 259 2.3.10.1 Preventing Vapor Over-pressure Events during Startup ........................................................ 259 2.3.10.2 Emergency Shutdowns ........................................................................................................... 260 2.3.10.3 Operating in Dry Circulation Mode ........................................................................................ 261 2.3.10.4 Improving Catalyst Slide Valve Design to Improve Unit Safety............................................ 261 2.3.10.5 Relief Valves in the FCCU ..................................................................................................... 262 REFINING R&D ALERT! .................................................................................................................................... 262 2.4.1 Introduction .......................................................................................................................................... 262 2.4.2 Gasoline Reformulation and Yield Enhancement ................................................................................. 268 2.4.2.1 Process .................................................................................................................................... 268 2.4.2.1.1 Reduction of Sulfur and Benzene .......................................................................... 268 2.4.2.1.2 Yield Enhancement ............................................................................................... 269 2.4.2.2 Catalysts.................................................................................................................................. 271 2.4.3 LCO Yield ............................................................................................................................................. 272 2.4.3.1 Patents..................................................................................................................................... 272 2.4.3.2 Research.................................................................................................................................. 274 2.4.4 Light Olefin Yield Maximization ........................................................................................................... 274 2.4.4.1 Process .................................................................................................................................... 274 2.4.4.1.1 Patents ................................................................................................................... 274 2.4.4.1.2 Research ................................................................................................................ 276 2.4.4.2 Catalysts.................................................................................................................................. 277 2.4.4.2.1 Patents ................................................................................................................... 277 2.4.4.2.2 Research ................................................................................................................ 279 2.4.5 Bottoms Cracking and Resid Feedstock................................................................................................ 280 2.4.5.1 Process .................................................................................................................................... 280 2.4.5.2 Catalysts and Additives .......................................................................................................... 280 2.4.5.2.1 Patents ................................................................................................................... 280 2.4.5.2.2 Research ................................................................................................................ 283 2.4.6 Biofeeds ................................................................................................................................................. 283 2.4.6.1 Patents..................................................................................................................................... 283 2.4.6.2 Research.................................................................................................................................. 285 2.4.7 Preparation of Catalysts and Additives ................................................................................................ 285 2.4.7.1 Patents..................................................................................................................................... 285 2.4.7.2 Research.................................................................................................................................. 290

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2.5 2.6

2.7

2.4.8 General Application: Process and Hardware ....................................................................................... 291 2.4.8.1 Feed Injection Nozzles ............................................................................................................ 291 2.4.8.2 Multi-stage and Dual Riser Processes ..................................................................................... 292 2.4.8.3 Catalyst Injection .................................................................................................................... 295 2.4.8.4 Catalyst Separation.................................................................................................................. 296 2.4.8.4.1 Patents .................................................................................................................... 296 2.4.8.4.2 Research ................................................................................................................. 299 2.4.8.5 Catalyst Regeneration ............................................................................................................. 300 2.4.8.5.1 Patents .................................................................................................................... 300 2.4.8.5.2 Research ................................................................................................................. 303 2.4.8.6 Power Recovery ...................................................................................................................... 304 2.4.8.7 Catalyst Coolers ...................................................................................................................... 305 2.4.8.8 Other ....................................................................................................................................... 306 2.4.9 NOX, SOX, CO, and PM Emissions Additives ........................................................................................ 307 2.4.9.1 Patents ..................................................................................................................................... 307 2.4.9.2 Research .................................................................................................................................. 309 2.4.10 Process Monitoring, Control, and Optimization ................................................................................... 309 2.4.10.1 Patents ..................................................................................................................................... 309 2.4.10.2 Research .................................................................................................................................. 312 2.4.11 Integration ............................................................................................................................................. 315 2.4.11.1 Patents ..................................................................................................................................... 315 2.4.11.2 Research .................................................................................................................................. 318 WORLDWIDE INSTALLED CAPACITY .................................................................................................................. 318 CONSTRUCTION ................................................................................................................................................. 322 2.6.1 Recent Construction Activity ................................................................................................................. 322 2.6.2 Completed Construction Projects.......................................................................................................... 328 REFERENCES ...................................................................................................................................................... 342

3. Light Olefins Production ........................................................................................................... 373 3.1

3.2

MARKET/TECHNOLOGY TRENDS & OPPORTUNITIES .......................................................................................... 373 3.1.1 Introduction ........................................................................................................................................... 373 3.1.2 Market Conditions and Outlook ............................................................................................................ 373 3.1.2.1 Propylene Demand and Growth .............................................................................................. 373 3.1.2.2 Polymer-grade Propylene Pricing ........................................................................................... 376 3.1.2.3 Effect of Shale Gas on Coproduct Propylene Supply from Steam Crackers .......................... 377 3.1.2.4 Propylene Capacity and Source Distribution .......................................................................... 379 3.1.2.5 Expansion ................................................................................................................................ 379 3.1.3 Technology Competition, Directions, and Future Prospects ................................................................ 382 3.1.3.1 FCC Technology ..................................................................................................................... 383 3.1.3.1.1 Process Configuration and Operating Conditions .................................................. 385 3.1.3.1.2 Catalyst and Additive Systems............................................................................... 386 3.1.3.1.3 Recovery ................................................................................................................ 387 3.1.3.2 On-purpose Technologies ....................................................................................................... 388 3.1.3.2.1 Cracking Butane and Heavier Olefins ................................................................... 390 3.1.3.2.2 Metathesis .............................................................................................................. 391 3.1.3.2.3 Propane Dehydrogenation ...................................................................................... 392 3.1.3.2.4 Methanol-to-Olefins (MTO) .................................................................................. 394 3.1.4 Conclusion ............................................................................................................................................. 396 STATE-OF-THE-ART TECHNOLOGY .................................................................................................................... 397 3.2.1 Introduction ........................................................................................................................................... 397

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TABLE OF CONTENTS 3.2.2 FCC Technologies ................................................................................................................................ 398 3.2.2.1 Commercial Processes ............................................................................................................ 398 3.2.2.1.1 Axens ..................................................................................................................... 400 3.2.2.1.1.1 PetroRiser ....................................................................................... 400 3.2.2.1.1.2 FlexEne ........................................................................................... 401 3.2.2.1.2 KBR/ExxonMobil.................................................................................................. 402 3.2.2.1.2.1 MAXOFIN ..................................................................................... 403 3.2.2.1.2.2 Advanced Catalytic Olefins (ACO) ................................................ 405 3.2.2.1.3 Lummus Technology ............................................................................................. 407 3.2.2.1.3.1 Selective Component Cracking ...................................................... 407 3.2.2.1.3.2 Indmax FCC (I-FCC)...................................................................... 407 3.2.2.1.4 Nippon Oil Corp./Saudi Aramco ........................................................................... 409 3.2.2.1.5 Petrobras ................................................................................................................ 413 3.2.2.1.5.1 Double Riser FCC .......................................................................... 413 3.2.2.1.5.2 Downflow Reactor .......................................................................... 413 3.2.2.1.6 Shell Global Solutions ........................................................................................... 415 3.2.2.1.7 Sinopec .................................................................................................................. 417 3.2.2.1.7.1 Deep Catalytic Cracking ................................................................. 417 3.2.2.1.7.2 Flexible Dual-riser Fluid Catalytic Cracking .................................. 421 3.2.2.1.7.3 FCC Process for Producing Clean Gasoline and Propylene ........... 424 3.2.2.1.7.4 MIP-CGP ........................................................................................ 425 3.2.2.1.7.5 Maximizing Iso-Olefins .................................................................. 427 3.2.2.1.7.6 Catalytic Pyrolysis Process ............................................................. 427 3.2.2.1.8 UOP ....................................................................................................................... 428 3.2.2.1.8.1 PetroFCC ........................................................................................ 428 3.2.2.1.8.2 RxPro .............................................................................................. 431 3.2.2.2 Commercial Catalysts and Additives ...................................................................................... 433 3.2.2.2.1 Albemarle .............................................................................................................. 433 3.2.2.2.1.1 AFX ................................................................................................ 433 3.2.2.2.1.2 Additives......................................................................................... 435 3.2.2.2.2 BASF Catalysts ..................................................................................................... 437 3.2.2.2.2.1 Maximum Propylene Solution (MPS) ............................................ 437 3.2.2.2.2.2 Additive .......................................................................................... 437 3.2.2.2.3 Grace Davison ....................................................................................................... 438 3.2.2.2.3.1 ProtAgon......................................................................................... 438 3.2.2.2.3.2 NEXUS ........................................................................................... 441 3.2.2.2.3.3 NACER........................................................................................... 441 3.2.2.2.3.4 Additives......................................................................................... 442 3.2.2.2.4 Instituto Mexicano del Petr贸leo ............................................................................. 443 3.2.2.2.5 Indian Oil Corp. ..................................................................................................... 443 3.2.2.2.6 INTERCAT ........................................................................................................... 444 3.2.2.2.7 JGC Catalysts & Chemicals................................................................................... 446 3.2.2.2.8 Sinopec .................................................................................................................. 447 3.2.2.2.8.1 Conventional FCC Catalysts........................................................... 447 3.2.2.2.8.2 FCC Catalysts for Heavy Feeds ...................................................... 448 3.2.2.2.8.3 DCC Catalysts ................................................................................ 448 3.2.2.2.8.4 CPP Catalysts ................................................................................. 448 3.2.2.2.8.5 Additives......................................................................................... 449 3.2.3 Light Olefin Recovery, Separation, and Purification............................................................................ 449 3.2.3.1 Propane-Propylene Splitter for FCCU .................................................................................... 449 3.2.3.1.1 Shaw Group ........................................................................................................... 449 3.2.3.1.2 UOP ....................................................................................................................... 450

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3.2.3.2 Propylene Recovery from Refinery Offgas ............................................................................. 452 3.2.3.2.1 Advanced Extraction Technologies ....................................................................... 452 3.2.3.2.2 Air Products and Chemicals ................................................................................... 453 3.2.3.2.2.1 Cryogenic System ........................................................................... 453 3.2.3.2.2.2 Dephlegmator .................................................................................. 454 3.2.3.2.3 Black & Veatch ...................................................................................................... 455 3.2.3.2.4 Costain Oil, Gas & Process .................................................................................... 457 3.2.3.2.4.1 Light Olefin Recovery .................................................................... 458 3.2.3.2.4.2 LPG Recovery ................................................................................. 461 3.2.3.2.5 Linde Process Plants .............................................................................................. 463 3.2.3.2.6 Shaw Group ........................................................................................................... 467 3.2.3.3 Butene Recovery and Separation ............................................................................................ 467 3.2.3.3.1 Saipem ................................................................................................................... 467 3.2.3.3.2 Uhde ....................................................................................................................... 467 3.2.4 Cracking of Heavier Olefins to Propylene ............................................................................................ 469 3.2.4.1 Asahi Kasei Chemicals ........................................................................................................... 469 3.2.4.2 ExxonMobil ............................................................................................................................ 469 3.2.4.2.1 Mobil Olefins Interconversion (MOI).................................................................... 469 3.2.4.2.2 Propylene Catalytic Cracking (PCC) ..................................................................... 471 3.2.4.3 KBR ........................................................................................................................................ 472 3.2.4.4 Linde/Lurgi ............................................................................................................................. 474 3.2.4.5 Sinopec .................................................................................................................................... 476 3.2.4.6 UOP/Total Petrochemicals ...................................................................................................... 477 3.2.5 Metathesis.............................................................................................................................................. 478 3.2.5.1 Lummus Technology .............................................................................................................. 479 3.2.5.2 Sinopec .................................................................................................................................... 485 3.2.6 Propane Dehydrogenation .................................................................................................................... 485 3.2.6.1 BASF/Linde ............................................................................................................................ 486 3.2.6.2 Lummus Technology .............................................................................................................. 486 3.2.6.3 Saipem/Yarsintez .................................................................................................................... 489 3.2.6.4 Uhde ........................................................................................................................................ 490 3.2.6.5 UOP......................................................................................................................................... 492 3.2.7 Methanol-to-Olefins .............................................................................................................................. 495 3.2.7.1 ExxonMobil ............................................................................................................................ 495 3.2.7.2 JGC Corp./Mitsubishi Chemicals ............................................................................................ 496 3.2.7.3 Lurgi ........................................................................................................................................ 497 3.2.7.4 Lummus Technology/SYN Energy Technology ..................................................................... 498 3.2.7.5 Sinopec .................................................................................................................................... 500 3.2.7.6 UOP/HYDRO ......................................................................................................................... 501 3.2.8 Technology Summary ............................................................................................................................ 502 3.2.8.1 Summary of Commercially Available Processes .................................................................... 502 3.2.8.2 Summary of Commercially Available Catalyst and Additives................................................ 512 PLANT OPERATIONS AND PRACTICES................................................................................................................. 514 3.3.1 Increasing Production of Light Olefins in the FCCU ........................................................................... 514 3.3.1.1 Improving FCC Propylene Production.................................................................................... 514 3.3.1.2 Managing Revamp Costs for Producing/Recovering Higher Yields of FCC Propylene ........ 518 3.3.1.3 Balancing Propylene Production with FCC Fuel Products ..................................................... 520 3.3.1.4 Increasing FCC Isobutane and Isobutylene Production .......................................................... 522 3.3.1.5 Factors Influencing the FCC Propylene-to-Butylene Production Ratio .................................. 523 3.3.2 Improving FCC Propylene Recovery and Purity .................................................................................. 523 3.3.2.1 Holistic Approach to FCC Gas Plant Optimization for Improved Propylene Recovery ......... 523 3.3.2.2 Processes Used to Purify FCC Propylene ............................................................................... 525 3.3.2.3 Control Issues for Propylene-Propane Separators................................................................... 526

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3.3.3 Polymer-grade Propylene Compositions .............................................................................................. 527 3.3.4 Benefits of an Integrated Refinery-Olefins Plant .................................................................................. 528 3.3.5 Energy and GHG Emissions Considerations for Light Olefins Production Technologies ................... 531 REFINING R&D ALERT! .................................................................................................................................... 533 3.4.1 Introduction .......................................................................................................................................... 533 3.4.2 FCC Technologies ................................................................................................................................ 537 3.4.2.1 Process .................................................................................................................................... 537 3.4.2.1.1 Multi-stage and Dual Riser .................................................................................... 537 3.4.2.1.1.1 Patents............................................................................................. 537 3.4.2.1.1.2 Research.......................................................................................... 539 3.4.2.1.2 Downflow Reactor................................................................................................. 539 3.4.2.1.3 Biofeeds ................................................................................................................. 540 3.4.2.1.3.1 Patents............................................................................................. 540 3.4.2.1.3.2 Research.......................................................................................... 540 3.4.2.1.4 Miscellaneous ........................................................................................................ 541 3.4.2.1.4.1 Patents............................................................................................. 541 3.4.2.1.4.2 Research.......................................................................................... 543 3.4.2.2 Catalyst ................................................................................................................................... 544 3.4.2.2.1 Pore Structure ........................................................................................................ 544 3.4.2.2.2 ZSM-5 ................................................................................................................... 544 3.4.2.2.2.1 Patents............................................................................................. 544 3.4.2.2.2.2 Research.......................................................................................... 545 3.4.2.2.3 Zeolite .................................................................................................................... 546 3.4.2.2.3.1 Patents............................................................................................. 546 3.4.2.2.3.2 Research.......................................................................................... 548 3.4.2.2.4 Metal Phosphate .................................................................................................... 548 3.4.2.2.5 Metal Oxide ........................................................................................................... 548 3.4.2.2.5.1 Patents............................................................................................. 548 3.4.2.2.5.2 Research.......................................................................................... 549 3.4.2.2.6 Cracking Naphtha to Enhance Propylene .............................................................. 549 3.4.3 Light Olefin Recovery, Separation, and Purification............................................................................ 550 3.4.3.1 Propane-Propylene Splitter ..................................................................................................... 550 3.4.3.1.1 Distillation/Fractionation ....................................................................................... 550 3.4.3.1.2 Adsorption ............................................................................................................. 551 3.4.3.1.3 Membrane .............................................................................................................. 552 3.4.3.1.3.1 Patents............................................................................................. 552 3.4.3.1.3.2 Research.......................................................................................... 552 3.4.4 Cracking of Butane and Heavier Olefins to Propylene ........................................................................ 553 3.4.4.1 Patents..................................................................................................................................... 553 3.4.4.2 Research.................................................................................................................................. 556 3.4.5 Metathesis ............................................................................................................................................. 557 3.4.5.1 Process .................................................................................................................................... 557 3.4.5.2 Catalyst ................................................................................................................................... 559 3.4.5.2.1 Patents ................................................................................................................... 559 3.4.5.2.2 Research ................................................................................................................ 563 3.4.6 Propane Dehydrogenation .................................................................................................................... 565 3.4.6.1 Process .................................................................................................................................... 565 3.4.6.2 Catalyst ................................................................................................................................... 565 3.4.6.2.1 Patents ................................................................................................................... 565 3.4.6.2.2 Research ................................................................................................................ 569 3.4.7 Methanol-to-Olefins .............................................................................................................................. 570 3.4.7.1 Process .................................................................................................................................... 570

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3.4.7.2 Catalysts .................................................................................................................................. 573 3.4.7.2.1 Patents .................................................................................................................... 573 3.4.7.2.2 Research ................................................................................................................. 574 REFERENCES ...................................................................................................................................................... 576

4. Latest Refining Technology Developments & Licensing ........................................................ 593 4.1 4.2 4.3 4.4 4.5 4.6 4.7 4.8 4.9

HYDROTREATING (INCLUDING HDS) ................................................................................................................. 593 ALKYLATION ..................................................................................................................................................... 593 HEAVY OIL, EXTRA-HEAVY OIL, AND BITUMEN UPGRADING ............................................................................ 594 SULFUR PLANT .................................................................................................................................................. 594 PROCESS CONTROLS, MONITORING, AND SIMULATION...................................................................................... 595 XTL (GAS-TO-LIQUID, COAL-TO-LIQUID, AND BIOMASS-TO-LIQUID) ................................................................ 596 BIOFUELS PRODUCTION ..................................................................................................................................... 597 ENERGY MANAGEMENT..................................................................................................................................... 599 REFERENCES ...................................................................................................................................................... 600