WORLDWIDE REFINERY PROCESSING REVIEW Monitoring Technology Development and Competition in One Single Source Fourth Quarter 2017 Fluid Catalytic Cracking Plus Latest Refining Technology Developments & Licensing HYDROCARBON PUBLISHING COMPANY Translating Knowledge into Profitability P.O. Box 815, Paoli, PA 19301-0815 (U.S.A.) Phone: (610) 408-0117/ Fax: (610) 408-0118 Review@Hydrocarbonpublishing.com
Review Fluid Catalytic Cracking 1. INTRODUCTION...1 2. FLUID CATALYTIC CRACKING...5 2.1 MARKET/TECHNOLOGY TRENDS & OPPORTUNITIES... 5 2.1.1 Introduction... 5 2.1.2 Market Conditions and Outlook... 6 2.1.2.1 Worldwide Product Demand... 6 2.1.2.1.1 Global Light Distillates Demand... 7 2.1.2.1.1.1 North America... 8 2.1.2.1.1.2 Europe... 9 2.1.2.1.1.3 Asia Pacific... 10 2.1.2.1.2 Global Middle Distillates Demand... 11 2.1.2.1.2.1 North America... 12 2.1.2.1.2.2 Europe... 14 2.1.2.1.2.3 Asia Pacific... 15 2.1.2.1.3 Global Petrochemicals Demand... 16 2.1.2.1.3.1 2.1.2.1.3.2 Expanding Propylene Consumption... 17 Bright Prospects in Aromatics... 19 2.1.2.1.4 Global Transportation Fuels Specifications... 20 2.1.2.1.4.1 2.1.2.1.4.2 Motor Gasoline... 21 Middle Distillates... 23 2.1.2.1.5 FCCU Emissions... 26 2.1.2.2 2.1.2.3 FCC Capacity Expansion on a Global Scale... 27 Current Status of FCC Catalyst Market... 28 2.1.3 Technology Directions, Competition, and Future Prospects... 29 2.1.3.1 Layout of Current Technology Competition... 29 2.1.3.2 Notable Trends in Current and Future Technological Offerings... 33 2.1.3.2.1 Processing Tight Oil... 33 2.1.3.2.2 Processing Resid Feeds... 36 2.1.3.2.3 2.1.3.2.4 Processing Biofeeds... 38 Producing High quality Gasoline and Increasing Yield... 39 2.1.3.2.5 Boosting LCO Yield and Quality... 41 2.1.3.2.6 Light Olefins Production Enhancement... 44 2.1.3.2.6.1 Propylene Production... 45 2.1.3.2.6.2 Butylene Production... 47 2.1.3.2.7 Aromatics Production... 48 2.1.3.2.8 2.1.3.2.9 Regenerator Pollution Abatement and GHG Concerns... 49 Process Modeling, Monitoring, and Control... 49 2.1.3.2.10 Benchmarking FCCUs for Optimum Performance... 50 2.1.3.3 2.1.3.4 FCCU Revamps for the Optimum Return on Investment... 51 Current R&D Trends... 51 2.1.4 Conclusion... 53 2.2 STATE OF THE ART TECHNOLOGY... 55 2.2.1 Introduction... 55 2.2.2 Commercial Processes and Hardware... 56 2.2.2.1 Axens... 56 2.2.2.2 CB&I /Lummus Technology... 57 2.2.2.2.1 2.2.2.2.2 Fuels Production... 57 Indmax FCC (I FCC)... 60 i
2.2.2.3 ExxonMobil/KBR... 62 2.2.2.3.1 Flexicracking III... 62 2.2.2.3.2 2.2.2.3.3 Orthoflow... 64 MAXDIESEL... 68 2.2.2.3.4 Propylene Production... 69 2.2.2.4 Petrobras... 69 2.2.2.4.1 Fuels Production... 69 2.2.2.4.2 Propylene Production... 71 2.2.2.5 Shell Global Solutions... 71 2.2.2.5.1 FCC... 72 2.2.2.5.2 MILOS... 79 2.2.2.6 Sinopec... 80 2.2.2.6.1 Clean Gasoline and Propylene... 80 2.2.2.6.2 2.2.2.6.3 Maximizing Iso paraffins... 82 Flexible Dual riser Fluid Catalytic Cracking... 83 2.2.2.6.4 Maximum Gas and Diesel... 86 2.2.2.6.5 2.2.2.6.6 Maximum Liquefied Gas and High octane Gasoline... 87 Propylene Production... 87 2.2.2.7 TechnipFMC/Axens... 88 2.2.2.7.1 2.2.2.7.2 Fuels Production... 88 Propylene Production... 92 2.2.2.8 UOP... 98 2.2.2.8.1 FCC... 98 2.2.2.8.2 MSCC... 107 2.2.2.8.3 Propylene Production... 108 2.2.2.9 Summary of Commercial FCC Processes and Hardware... 110 2.2.3 Other Commercial Hardware... 116 2.2.3.1 Beijing Huiersanji Green Chem Co.... 116 2.2.3.2 Blasch Precision Ceramics... 117 2.2.3.3 Cat' Fine Management Technologies LLC... 117 2.2.3.4 ClearStak... 117 2.2.3.5 Fisher Klosterman... 118 2.2.3.6 2.2.3.7 Koch Glitsch... 118 Lawrence Pumps... 119 2.2.3.8 Tracerco/Johnson Matthey... 119 2.2.4 Commercial Catalysts and Additives... 120 2.2.4.1 Albemarle... 121 2.2.4.1.1 Cracking Catalysts to Increase Liquid Products... 122 2.2.4.1.2 Gasoline Olefins and Octane Additives... 133 2.2.4.1.3 Gasoline Sulfur Reduction... 134 2.2.4.1.4 Tight Oil Processing... 134 2.2.4.1.4.1 ACTION T... 134 2.2.4.1.4.2 AMBER T/UPGRADER T... 136 2.2.4.1.5 SO X Reduction Additives... 137 2.2.4.1.6 Bottoms Cracking Additives... 139 2.2.4.1.7 Microfine Reduction Catalyst Technology... 143 2.2.4.1.8 Catalyst Circulation Improvement Additives... 143 2.2.4.1.9 Combustion Promoters... 144 2.2.4.1.10 Light Olefins Production... 145 2.2.4.2 Ambur Chemical Co.... 149 2.2.4.3 BASF Catalysts... 149 2.2.4.3.1 Cracking Catalysts to Increase Liquid Products... 153 2.2.4.3.2 Co catalysts... 158 2.2.4.3.3 2.2.4.3.4 Tight Oil Processing... 161 Gasoline Sulfur Reduction Formulations... 163 2.2.4.3.5 SO X Reduction Additives... 164 2.2.4.3.6 Microfine Reduction Catalyst Technology... 165 ii
2.2.4.3.7 Catalyst Circulation Improvement Additive... 166 2.2.4.3.8 Combustion Promoters... 166 2.2.4.3.9 Light Olefins Production... 167 2.2.4.4 Grace Catalysts Technologies... 169 2.2.4.4.1 Cracking Catalysts to Increase Liquid Products... 173 2.2.4.4.2 Gasoline Sulfur Reduction Formulations... 190 2.2.4.4.3 Tight Oil Processing... 194 2.2.4.4.4 SO X Reduction Additives... 196 2.2.4.4.5 NO X Reduction Additive... 197 2.2.4.4.6 Catalyst Circulation Improvement Additive... 198 2.2.4.4.7 2.2.4.4.8 Bottoms Cracking Additive... 199 Combustion Promoters... 199 2.2.4.4.9 Light Olefins Production... 201 2.2.4.5 2.2.4.6 Inst. Mexicano del Petróleo... 206 JGC Catalysts and Chemicals... 206 2.2.4.7 Johnson Matthey Process Technologies/INTERCAT JM... 207 2.2.4.7.1 2.2.4.7.2 Gasoline Olefins and Octane Additives... 207 Gasoline Sulfur Reduction Additives... 209 2.2.4.7.3 SO X Reduction Additives... 209 2.2.4.7.4 2.2.4.7.5 Tight Oil Processing... 212 Bottoms Cracking Additives... 214 2.2.4.7.6 2.2.4.7.7 Combustion Promoters... 216 Light Olefins Production... 217 2.2.4.7.8 Delta Coke Reduction... 220 2.2.4.8 Nalco Energy Services/Refining Process Services... 220 2.2.4.8.1 MVP... 221 2.2.4.8.2 NPP... 222 2.2.4.9 Rive Technology, Inc... 223 2.2.4.10 Sinopec Catalyst Co.... 226 2.2.4.10.1 2.2.4.10.2 Diesel Maximizing Catalysts... 227 Gasoline Olefins Reduction Formulations... 227 2.2.4.10.3 Gasoline Sulfur Reduction Additives... 229 2.2.4.10.4 SO X Reduction Additive... 229 2.2.4.10.5 Light Olefins Production... 229 2.2.4.11 Summary of Commercially Available FCC Catalysts... 229 2.2.4.12 Summary of Commercially Available FCC Additives... 231 2.2.5 Alternative Catalyst Technologies... 233 2.2.5.1 2.2.5.2 Albemarle... 233 Grace Catalysts Technologies... 233 2.2.5.3 Johnson Matthey Process Technologies... 234 2.2.5.4 2.2.5.5 KBR... 239 Nippon Oil... 239 2.2.6 Advanced Process Control Systems... 240 2.2.6.1 ABB... 240 2.2.6.2 AspenTech... 240 2.2.6.3 Cutler Technology Corp.... 241 2.2.6.4 Expertune... 242 2.2.6.5 Honeywell Advanced Solutions... 242 2.2.6.6 2.2.6.7 Invensys... 244 Petrocontrol... 244 2.2.6.8 Yokogawa... 245 2.2.6.9 Summary of Commercially Available Advanced Control Systems... 245 2.2.7 Process Models and Simulation... 247 2.2.7.1 AspenTech... 249 2.2.7.2 BASF... 249 2.2.7.3 2.2.7.4 Computational Particle Fluid Dynamics... 250 Eurotek Refining Services... 251 iii
2.2.7.5 KBC Advanced Technologies... 251 2.2.7.6 Petrobras... 252 2.2.7.7 2.2.7.8 Shell... 252 Topnir Systems... 253 2.2.7.9 Summary of Commercially Available Process Models and Simulation Software... 253 2.2.8 Resid Fluid Catalytic Cracking... 255 2.2.8.1 RFCC Processes... 255 2.2.8.2 RFCC Additives and Catalysts... 257 2.3 PLANT OPERATIONS AND PRACTICES... 274 2.3.1 Feed Considerations... 274 2.3.1.1 Effect of FCC Feed Contaminants on Unit Operation... 274 2.3.1.2 Impact of VGO Hydrogen Content on FCC Operation... 276 2.3.1.3 2.3.1.4 Minimizing Diesel range Material in FCC Feed... 279 Waxy Crudes as FCC Feeds... 280 2.3.1.5 Optimizing FCC Feed Preheat Temperature... 281 2.3.2 Processing Tight Oil... 282 2.3.2.1 2.3.2.2 Expected Changes to Product Slate... 284 Heat Balance Concerns... 287 2.3.2.3 Delta Coke Concerns... 289 2.3.3 Improving FCC Gasoline Output and Quality... 290 2.3.3.1 Enhancing Gasoline Octane... 291 2.3.3.2 FCC Gasoline Sulfur Reduction... 292 2.3.3.3 2.3.3.4 Lowering FCC Gasoline Olefinicity... 295 Lowering the Benzene Content of FCC Gasoline... 296 2.3.3.5 Variables Influencing Gasoline Aromatics Content... 296 2.3.3.6 2.3.3.7 FCC Gasoline Stability... 297 Revamping FCC Naphtha Splitter to Dividing Wall Column Design... 297 2.3.3.8 Effect of Long term Storage on FCC Gasoline Quality... 298 2.3.4 Increasing FCC LCO Production... 299 2.3.4.1 Catalyst Modifications to Improve FCC LCO Yields... 306 2.3.4.2 Improving LCO Recovery from the Main Fractionator... 309 2.3.5 Increasing Production of Light Olefins in the FCCU... 312 2.3.5.1 Improving FCC Propylene Production... 312 2.3.5.2 2.3.5.3 Propylene Production with Resid Streams... 319 Managing Revamp Costs for Producing/Recovering Higher Yields of FCC Propylene... 320 2.3.5.4 Balancing Propylene Production with FCC Fuel Products... 322 2.3.5.5 2.3.5.6 Increasing FCC Isobutane and Isobutylene Production... 324 Factors Influencing the FCC Propylene to Butylene Production Ratio... 325 2.3.5.7 Reducing Acetone in Butylene and Butane Streams... 326 2.3.6 Resid Fluid Catalytic Cracking... 327 2.3.6.1 2.3.6.2 Responding to Opportunity Crudes... 329 Fouling Prevention for Resid Processing... 332 2.3.6.3 Proper Feed Injection System Design for RFCCUs... 332 2.3.6.4 2.3.6.5 Dual Regenerator Designs for RFCCUs... 334 Running an RFCCU on Lighter Feeds: Maintaining Regenerator Temperature... 334 2.3.6.6 Processing Hydrotreated Resid Feeds... 335 2.3.6.7 2.3.6.8 New Method for Feedstock Characterization and Yield Predictions for a RFCCU... 335 RFCC Slurry Pumps Design and Service Life... 336 2.3.6.9 Uses for RFCC Slurry... 337 2.3.6.10 RFCCU Operational Issues and the Lessons Learned... 339 2.3.7 Operational Monitoring, Process Simulation and Unit Optimization... 341 2.3.7.1 Multivariate Statistical Modeling... 341 2.3.7.2 2.3.7.3 Monitoring Fresh Feed Flowrate... 342 Monitoring Entrained Oxygen Sources in FCC Fuel Gas... 342 2.3.7.4 2.3.7.5 Monitoring Bottoms Level in the Main Fractionator... 343 Measuring Cyanide Content in CO 2 Rich FCCU Flue Gas... 344 iv
2.3.7.6 FCCU Health Monitoring... 346 2.3.7.7 Inspecting and Monitoring Expansion Joints in Catalyst Standpipes... 347 2.3.7.8 2.3.7.9 Vapor Line Sampling... 347 Applying Advanced Simulation Techniques... 348 2.3.7.10 Debottlenecking the Gas Concentration Unit of a FCCU... 350 2.3.7.11 Benchmarking FCCUs for Optimum Performance... 351 2.3.8 Fouling, Degradation, and Erosion Problems... 352 2.3.8.1 Slurry Exchanger Fouling... 352 2.3.8.2 Fouling in Main Air Blower... 353 2.3.8.3 Dipleg Plugging and Fouling... 354 2.3.8.4 Coke Deposits in the Reactor Plenum Chamber... 355 2.3.8.5 Refractory Material Degradation in FCCU Catalyst Transfer Lines... 356 2.3.8.6 Hot Spots in FCCU Piping and Transfer Lines... 357 2.3.8.7 2.3.8.8 Mitigating Erosion Problems in FCCUs... 358 Preventing Hydrates Formation in FCC Gas Concentration Equipment... 362 2.3.9 FCCU Hardware Considerations and Improvements... 363 2.3.9.1 Reactor... 363 2.3.9.1.1 Reactor Design... 363 2.3.9.1.2 Riser Nozzle Design and Metallurgy... 364 2.3.9.1.3 2.3.9.1.4 Optimizing Riser Mixing... 365 Improving Air Steam Distribution... 366 2.3.9.1.5 Minimizing Coke Buildup in the Reactor... 367 2.3.9.1.6 Methods to Control Secondary Cracking in the FCC Reactor... 369 2.3.9.1.7 The Lifetime of Reactor Cyclones... 369 2.3.9.2 Regenerator... 370 2.3.9.2.1 Available Configurations for Catalyst Regeneration... 370 2.3.9.2.2 Meeting Regenerator Temperature Constraints... 371 2.3.9.2.3 2.3.9.2.4 Regenerator Combustion Mode: Effect on Contaminant Mobility and Activity... 373 Operating Partial Burn Regenerators in Total Combustion Mode... 374 2.3.9.2.5 Benefits and Drawbacks of Oxygen Enrichment in Regenerators... 374 2.3.9.2.6 Minimizing Inerts Entrained in Catalyst Exiting the Regenerator... 377 2.3.9.3 Reactor and Regenerator Internals... 377 2.3.9.4 Stripper Vessel... 378 2.3.9.4.1 Improving Stripper Performance... 378 2.3.9.4.2 Measuring Stripper Efficiency... 379 2.3.9.5 Main Fractionator... 379 2.3.9.5.1 Overhead Line Coking and Corrosion... 379 2.3.9.5.2 Avoiding Salt Deposition Problems... 380 2.3.9.5.3 Preventing Collector Tray Leaks... 382 2.3.9.5.4 Dealing with High Ash Content... 383 2.3.9.5.5 Benefits of a Staged Revamp on a FCCU Main Fractionator... 385 2.3.9.5.6 Isolation Valve Considerations... 385 2.3.9.5.7 Sulfidation Corrosion of the Bottoms Circuit... 386 2.3.10 Catalyst Management... 386 2.3.10.1 2.3.10.2 Reducing Rare Earth Use... 386 Evaluating FCC Catalyst Selection... 389 2.3.10.3 Additives for Feed Flexibility... 394 2.3.10.4 2.3.10.5 Pre blending of Additives with Catalysts... 395 Effect of Changing Catalyst Formulation on FCC Performance... 395 2.3.10.6 Catalyst Losses from the FCCU... 396 2.3.10.6.1 Diagnosing the Cause... 397 2.3.10.6.2 Catalyst Properties... 399 2.3.10.6.3 2.3.10.6.4 Operating Conditions... 400 Equipment Design... 400 2.3.10.6.5 Mechanical Conditions... 401 2.3.10.6.6 Refinery Experience with Loss Detection and Reduction... 402 2.3.10.7 Catalyst Circulation Problems... 403 v
2.3.10.8 Catalyst Backflow... 406 2.3.10.9 Diagnosing the Cause of Catalyst Deactivation... 407 2.3.10.10 2.3.10.11 Maintaining FCC Ecat Activity... 407 Disposing of FCC Ecat... 409 2.3.10.12 Catalyst Unloading and Impact on Profits... 409 2.3.11 Energy Efficiency and Environmental Emissions... 410 2.3.11.1 Improving FCC Energy Efficiency... 410 2.3.11.1.1 Key FCC Variables to Monitor for Energy Efficiency Improvements... 410 2.3.11.1.2 Heat Recovery in the Main Fractionator for Propylene Recovery... 411 2.3.11.1.3 Recovering H 2 in FCC Offgas... 412 2.3.11.1.4 Installation of a Power Recovery System... 412 2.3.11.2 Reducing Environmental Emissions from the FCCU... 415 2.3.11.2.1 FCC Feed Pretreatment... 416 2.3.11.2.2 2.3.11.2.3 Use of Electrostatic Precipitators to Reduce FCC Emissions... 416 Proper Two stage Cyclone System Design... 418 2.3.11.2.4 Effect of FCC Operating Variables on SO X Emissions... 418 2.3.11.2.5 Hydrocarbons in Flue Gas Stream... 419 2.3.11.2.6 Flue Gas Scrubbers to Reduce FCC SO X Emissions... 419 2.3.11.2.7 SO X Additives to Meet Ultra low SO X Emission Levels... 421 2.3.11.2.8 Effect of Regenerator Operations on NO X and CO Emissions... 422 2.3.11.2.8.1 Effect of O 2 Availability and Discharge Design on Regenerator NO X Emissions... 425 2.3.11.2.8.2 Selective Catalytic Reduction Units for NO X Reduction... 425 2.3.11.2.9 Lowering FCC NO X Emissions... 428 2.3.11.2.10 Nitrates in Purge Water... 430 2.3.11.2.11 2.3.11.2.12 Lowering CO Emissions during FCCU Startup... 430 Options to Reduce Particulate Matter Emissions from Regenerators... 430 2.3.11.2.13 Preventing Clogging of FCC Flue Gas Equipment... 433 2.3.11.2.14 Measuring Sulfur Content in FCC Flue Gas... 434 2.3.12 FCCU Safety Considerations... 435 2.3.12.1 Preventing Vapor Over pressure Events during Startup... 435 2.3.12.2 2.3.12.3 Emergency and Unplanned Shutdowns... 435 Loss of Fractionator Bottoms Cooling... 436 2.3.12.4 2.3.12.5 Operating in Dry Circulation Mode... 437 Improving Catalyst Slide Valve Design to Improve Unit Safety... 438 2.3.12.6 Relief Valves in the FCCU... 438 2.3.12.7 2.3.12.8 Blinds between Reactor and Main Fractionator... 438 Tunable Diode Laser Analyzers in FCCUs... 440 2.3.12.9 Preventing ESP Safety Incidents... 441 2.3.13 FCCU Revamps for the Optimum Return on Investment... 442 2.4 REFINING R&D ALERT!... 444 2.4.1 Introduction... 444 2.4.2 Gasoline Reformulation... 451 2.4.2.1 Patents... 451 2.4.2.2 Research... 452 2.4.3 Gasoline Yield Enhancement... 452 2.4.3.1 Process... 452 2.4.3.2 Catalyst... 454 2.4.3.2.1 Patents... 454 2.4.3.2.2 Research... 455 2.4.4 LCO Yield and Quality... 456 2.4.5 Light Olefins Yield Maximization... 457 2.4.5.1 Process and Unit Design... 457 2.4.5.1.1 2.4.5.1.2 Multi stage Cracking... 457 Non VGO Feedstocks... 457 2.4.5.1.2.1 2.4.5.1.2.2 Patents... 457 Research... 458 vi
2.4.5.1.3 Integrated Process Schemes... 458 2.4.5.1.4 Other... 459 2.4.5.1.4.1 2.4.5.1.4.2 Patents... 459 Research... 460 2.4.5.2 Catalyst... 461 2.4.5.2.1 ZSM 5... 461 2.4.5.2.1.1 Patents... 461 2.4.5.2.1.2 Research... 465 2.4.5.2.2 Other Zeolitic Catalysts... 466 2.4.5.2.2.1 Patents... 466 2.4.5.2.2.2 Research... 468 2.4.5.2.3 Additives... 469 2.4.5.2.4 Other... 471 2.4.6 Heavy Oil and Resid Cracking... 471 2.4.6.1 Process... 471 2.4.6.2 Catalysts and Additives... 477 2.4.7 Aromatics Production... 484 2.4.7.1 Integrated Process Schemes... 484 2.4.7.2 Production of Both Light Aromatics and Light Olefins... 485 2.4.7.2.1 2.4.7.2.2 Process... 485 Catalyst... 487 2.4.8 Biofeeds and Fischer Tropsch Feeds... 488 2.4.8.1 Process... 488 2.4.8.1.1 Patents... 488 2.4.8.1.2 Research... 489 2.4.8.2 Catalyst... 492 2.4.8.2.1 Patents... 492 2.4.8.2.2 Research... 492 2.4.9 NO X, SO X, CO, and PM Emissions Reduction... 496 2.4.9.1 Process... 496 2.4.9.2 Catalyst... 501 2.4.10 Preparation and Properties of Catalysts and Additives... 503 2.4.10.1 Metal resistance Properties... 503 2.4.10.1.1 Patents... 503 2.4.10.1.2 Research... 506 2.4.10.2 Preparation Procedures and Equipment... 506 2.4.10.3 Other... 507 2.4.10.3.1 Patents... 507 2.4.10.3.2 Research... 511 2.4.11 Hardware... 512 2.4.11.1 Injection Devices... 512 2.4.11.2 Separators and Cyclones... 516 2.4.11.3 Stripping Devices... 518 2.4.11.4 Regenerator... 518 2.4.11.4.1 Patents... 518 2.4.11.4.2 Research... 525 2.4.11.5 Fractionation Tower... 525 2.4.11.6 Slurry Oil Equipment and Handling... 527 2.4.11.7 Other... 532 2.4.12 Process Monitoring, Control, and Optimization... 536 2.4.12.1 Patents... 536 2.4.12.2 Research... 537 2.4.13 Other... 540 2.4.13.1 Process Integration... 540 2.4.13.2 Recycle or Disposal of Spent FCC Catalyst... 542 2.4.13.2.1 Patents... 542 vii
2.4.13.2.2 Research... 545 2.4.13.3 Other... 546 2.5 WORLDWIDE INSTALLED CAPACITY... 547 2.6 CONSTRUCTION... 548 2.6.1 Recent Construction Activity... 548 2.6.2 Completed Construction Projects... 553 2.7 REFERENCES... 570 viii