Environmental Controls by Hydrocarbon Publishing Company

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

Second Quarter 2012 Environmental Controls Plus

Latest Refining Technology Developments & Licensing

HYDROCARBON PUBLISHING COMPANY Translating Knowledge into Profitability

P.O. Box 661 Southeastern, PA 19399 (U.S.A.)

Phone: (610) 408-0117/ Fax: (610) 408-0118

Review@Hydrocarbonpublishing.com

TABLE OF CONTENTS 2Q 2012 Review Environmental Controls 3. Environmental Controls ............................................................................................................. 413 3.1

3.2

MARKET/TECHNOLOGY TRENDS & OPPORTUNITIES ......................................................................................... 413 3.1.1 Introduction .......................................................................................................................................... 413 3.1.2 Market Conditions and Outlook............................................................................................................ 414 3.1.2.1 Refinery Emissions Considerations ........................................................................................ 414 3.1.2.1.1 Refinery Unit Emissions ........................................................................................ 414 3.1.2.1.2 Flaring ................................................................................................................... 416 3.1.2.1.3 GHG Emissions ..................................................................................................... 418 3.1.2.2 Compliance Costs ................................................................................................................... 419 3.1.2.3 Effect of Rare Earth Materials on FCC SOX Reduction Additives ......................................... 421 3.1.3 Technology Directions, Competition, and Future Prospects ................................................................ 423 3.1.3.1 General Pollution Control Technologies ................................................................................ 424 3.1.3.1.1 Flue Gas Scrubbing for SOX and PM Control ....................................................... 424 3.1.3.1.2 Electrostatic Precipitators for PM Control ............................................................ 425 3.1.3.1.3 Selective Catalytic Reduction for NOX Control .................................................... 426 3.1.3.1.4 Selective Non-catalytic Reduction for NOX Control ............................................. 426 3.1.3.1.5 Low and Ultra-low NOX Burners for NOX Control ............................................... 427 3.1.3.1.6 Flaring for VOCs Control ...................................................................................... 428 3.1.3.2 Unit Specific Pollution Control Technologies ........................................................................ 429 3.1.3.2.1 FCC ....................................................................................................................... 429 3.1.3.2.2 Sulfur Plant ............................................................................................................ 430 3.1.3.2.2.1 Acid Gas Removal .......................................................................... 431 3.1.3.2.2.2 Claus Process .................................................................................. 432 3.1.3.2.2.3 Tailgas Treating .............................................................................. 433 3.1.4 Conclusion ............................................................................................................................................ 434 STATE-OF-THE-ART TECHNOLOGY ................................................................................................................... 435 3.2.1 Introduction .......................................................................................................................................... 435 3.2.2 Commercial Processes and Hardware for General Pollution Control................................................. 436 3.2.2.1 Flue Gas Scrubbing for SOX and PM Control ........................................................................ 436 3.2.2.1.1 CANSOLV ............................................................................................................ 436 3.2.2.1.2 DuPont Clean Technologies .................................................................................. 437 3.2.2.1.2.1 EDV ................................................................................................ 437 3.2.2.1.2.2 LABSORB ...................................................................................... 439 3.2.2.1.3 ExxonMobil ........................................................................................................... 440 3.2.2.1.4 Fischer-Klosterman ............................................................................................... 442 3.2.2.1.5 Haldor Topsøe ....................................................................................................... 442 3.2.2.1.6 MECS .................................................................................................................... 444 3.2.2.1.7 Marsulex Environmental Technologies ................................................................. 446 3.2.2.1.7.1 Wet Flue Gas Scrubbing ................................................................. 446 3.2.2.1.7.2 Regenerable Scrubbing ................................................................... 447 3.2.2.1.8 Met-Pro .................................................................................................................. 448 3.2.2.1.9 Pollution Systems .................................................................................................. 448 3.2.2.1.10 Tri-Mer .................................................................................................................. 449 3.2.2.1.10.1 Cloud Chamber Scrubber ............................................................... 449 3.2.2.1.10.2 Tri-NOX .......................................................................................... 451 3.2.2.2 Electrostatic Precipitators for PM Control.............................................................................. 451 3.2.2.2.1 Buell ...................................................................................................................... 454

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TABLE OF CONTENTS 3.2.2.2.2 CoorsTek ................................................................................................................ 455 3.2.2.2.3 Hamon Research-Cottrell ....................................................................................... 455 3.2.2.2.4 Marsulex Environmental Technologies ................................................................. 455 3.2.2.2.5 Nestec..................................................................................................................... 455 3.2.2.2.6 PPC ........................................................................................................................ 455 3.2.2.3 Selective Catalytic Reduction for NOX Control ...................................................................... 455 3.2.2.3.1 BASF ..................................................................................................................... 456 3.2.2.3.2 Clariant................................................................................................................... 457 3.2.2.3.3 Cormetech .............................................................................................................. 457 3.2.2.3.4 Haldor Topsøe........................................................................................................ 458 3.2.2.3.5 Johnson Matthey .................................................................................................... 461 3.2.2.3.6 Mitsubishi Power Systems ..................................................................................... 461 3.2.2.4 Selective Non-catalytic Reduction for NOX Control............................................................... 462 3.2.2.4.1 ExxonMobil ........................................................................................................... 463 3.2.2.5 Low and Ultra-low NOX Burners for NOX Control ................................................................ 463 3.2.2.5.1 Alzeta ..................................................................................................................... 464 3.2.2.5.2 Callidus .................................................................................................................. 464 3.2.2.5.2.1 Low NOX......................................................................................... 464 3.2.2.5.2.2 Ultra-low NOX ................................................................................ 465 3.2.2.5.2.3 CUBL .............................................................................................. 465 3.2.2.5.3 John Zink ............................................................................................................... 466 3.2.2.5.4 NAO ....................................................................................................................... 466 3.2.2.6 Clean Burn Flaring for VOCs Control .................................................................................... 467 3.2.2.6.1 Baker Hughes ......................................................................................................... 467 3.2.2.6.2 John Zink ............................................................................................................... 468 3.2.2.6.2.1 Steam-assisted Flares ...................................................................... 468 3.2.2.6.2.2 Air-assisted Flares ........................................................................... 468 3.2.2.6.2.3 Enclosed Flares ............................................................................... 469 3.2.2.6.3 NAO ....................................................................................................................... 470 3.2.2.7 Other Commercial Processes and Hardware ........................................................................... 471 3.2.2.7.1 DuPont Clean Technologies .................................................................................. 471 3.2.2.7.2 Eco Power Solutions .............................................................................................. 471 3.2.2.8 Summary of Commercially Available Environmental Control Technologies ........................ 472 3.2.3 Unit Specific Pollution Control Technology ......................................................................................... 479 3.2.3.1 FCC ......................................................................................................................................... 479 3.2.3.1.1 FCC Hardware ....................................................................................................... 479 3.2.3.1.1.1 Feed Injection Technology.............................................................. 479 3.2.3.1.1.1.1 ExxonMobil/KBR .................................................... 479 3.2.3.1.1.1.2 Lummus Technology................................................ 480 3.2.3.1.1.2 Third and Fourth Stage Separators.................................................. 481 3.2.3.1.1.2.1 KBR ......................................................................... 481 3.2.3.1.1.2.2 Shell ......................................................................... 481 3.2.3.1.1.2.3 UOP .......................................................................... 482 3.2.3.1.1.3 Low-NOX Regenerators .................................................................. 483 3.2.3.1.1.3.1 KBR ......................................................................... 483 3.2.3.1.1.3.2 Praxair/Shell ............................................................. 484 3.2.3.1.1.3.3 UOP .......................................................................... 486 3.2.3.1.1.4 Other FCC Hardware ...................................................................... 487 3.2.3.1.1.4.1 Fischer-Klosterman .................................................. 487 3.2.3.1.1.4.2 UOP .......................................................................... 487 3.2.3.1.1.4.2.1 RxCat ............................................. 487 3.2.3.1.1.4.2.2 Emergency Interlock System ......... 488

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3.3

3.2.3.1.1.5 Summary of FCC Hardware ........................................................... 489 3.2.3.1.2 Commercial Catalysts and Additives ..................................................................... 491 3.2.3.1.2.1 SOX Reduction Additives ............................................................... 491 3.2.3.1.2.1.1 Albemarle ................................................................ 491 3.2.3.1.2.1.2 Baker Petrolite ......................................................... 492 3.2.3.1.2.1.3 BASF ....................................................................... 492 3.2.3.1.2.1.4 Grace Davison ......................................................... 493 3.2.3.1.2.1.5 INTERCAT.............................................................. 494 3.2.3.1.2.1.6 JGC Catalysts and Chemicals .................................. 496 3.2.3.1.2.2 CO Combustion Promoters ............................................................. 496 3.2.3.1.2.2.1 Albemarle ................................................................ 496 3.2.3.1.2.2.2 Ambur Chemical Co. ............................................... 497 3.2.3.1.2.2.3 BASF ....................................................................... 497 3.2.3.1.2.2.4 Grace Davison ......................................................... 498 3.2.3.1.2.2.5 Inst. Mexicano del Petróleo ..................................... 499 3.2.3.1.2.2.6 INTERCAT.............................................................. 499 3.2.3.1.2.2.7 JGC Catalysts and Chemicals .................................. 500 3.2.3.1.2.3 Microfine Reduction Catalyst Technology ..................................... 500 3.2.3.1.2.3.1 Albemarle ................................................................ 500 3.2.3.1.2.3.2 BASF ....................................................................... 501 3.2.3.1.2.4 Summary of Commercially Available Catalyst and Additive Technologies ................................................................................... 502 3.2.3.2 Sulfur Plant ............................................................................................................................. 503 3.2.3.2.1 Summary of Commercially Available Sulfur Plant Technologies......................... 505 3.2.3.2.2 Summary of Commercially Available Sulfur Plant Catalysts ............................... 515 3.2.4 Advanced Process Control/Process Models and Simulation ................................................................ 516 3.2.4.1 ABB ........................................................................................................................................ 516 3.2.4.2 Computational Particle Fluid Dynamics ................................................................................. 517 PLANT OPERATIONS AND PRACTICES ................................................................................................................ 517 3.3.1 Minimizing Flaring During Unit Startup .............................................................................................. 517 3.3.2 Treating and Recovering VOCs ............................................................................................................ 518 3.3.3 Upgrading to Low or Ultra-low NOX Burners ...................................................................................... 519 3.3.4 Calculating Emissions from Furnace and Heater Stacks ..................................................................... 520 3.3.5 Unit Specific Environmental Considerations ........................................................................................ 521 3.3.5.1 Coker ...................................................................................................................................... 521 3.3.5.1.1 Coke Drum Emission Reduction ........................................................................... 521 3.3.5.1.2 CO2 Emissions Considerations .............................................................................. 521 3.3.5.1.3 Reduce Flaring from Closed Blowdown System................................................... 522 3.3.5.1.4 Minimizing Coke Particulate Emissions................................................................ 522 3.3.5.2 FCC......................................................................................................................................... 523 3.3.5.2.1 FCC Feed Pretreatment ......................................................................................... 523 3.3.5.2.2 Use of Electrostatic Precipitators to Reduce FCC Emissions ................................ 524 3.3.5.2.3 Proper Two-stage Cyclone System Design ........................................................... 526 3.3.5.2.4 Effect of FCC Operating Variables on SOX Emissions ......................................... 526 3.3.5.2.5 Flue Gas Scrubbers to Reduce FCC SOX Emissions ............................................. 527 3.3.5.2.6 Effect of Regenerator Operations on NOX Emissions ........................................... 529 3.3.5.2.7 Effect of O2 Availability and Discharge Design on Regenerator NOX Emissions 530 3.3.5.2.8 Utilizing NOX Reduction Additives ...................................................................... 531 3.3.5.2.9 Lowering CO Emissions During FCCU Startup ................................................... 532 3.3.5.2.10 Options to Reduce Particulate Matter Emissions from Regenerators .................... 532 3.3.5.2.11 Preventing Clogging of FCC Flue Gas Equipment ............................................... 534 3.3.5.2.12 Measuring Sulfur Content in FCC Flue Gas ......................................................... 535 3.3.5.3 Sulfur Plant ............................................................................................................................. 536

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3.4

3.3.5.3.1 Acid Gas Removal ................................................................................................. 537 3.3.5.3.1.1 Amine Solvent Replacement ........................................................... 537 3.3.5.3.1.2 Optimizing an Amine Unit .............................................................. 538 3.3.5.3.1.3 Amine System Operating Issues ..................................................... 540 3.3.5.3.1.3.1 Wet Acid Gas Corrosion .......................................... 540 3.3.5.3.1.3.2 Amine Solution Corrosion ....................................... 540 3.3.5.3.1.3.3 Foaming.................................................................... 542 3.3.5.3.1.3.4 Amine Losses ........................................................... 542 3.3.5.3.1.3.5 Carbon Filters in Amine Systems ............................. 543 3.3.5.3.1.4 Safe Acid Gas Handling .................................................................. 544 3.3.5.3.1.5 Fuel Gas Sweetening in a Hydrocracker Fractionation Section ...... 545 3.3.5.3.2 Claus Process ......................................................................................................... 546 3.3.5.3.2.1 Increasing Sulfur Recovery Capacity.............................................. 546 3.3.5.3.2.2 The Effects of Extreme Turndowns ................................................ 548 3.3.5.3.2.3 Benefits and Drawbacks of Oxygen Enrichment ............................ 548 3.3.5.3.2.4 Claus Unit Shutdowns ..................................................................... 550 3.3.5.3.2.5 Claus Catalyst Life and Reuse ........................................................ 550 3.3.5.3.2.6 Analyzing Sulfur Content in Claus Tailgas..................................... 551 3.3.5.3.3 Tailgas Treating ..................................................................................................... 552 3.3.5.3.3.1 Experience with Designing a TGTU ............................................... 552 3.3.5.3.3.2 Proper TGT Catalyst Selection ....................................................... 554 REFINING R&D ALERT! ..................................................................................................................................... 554 3.4.1 Introduction ........................................................................................................................................... 554 3.4.2 General Pollution Control Technologies .............................................................................................. 557 3.4.2.1 Flue Gas Scrubbing for SOX and PM Control......................................................................... 557 3.4.2.1.1 Patents .................................................................................................................... 557 3.4.2.1.2 Research ................................................................................................................. 563 3.4.2.2 Selective Catalytic Reduction for NOX Control ...................................................................... 564 3.4.2.2.1 Process ................................................................................................................... 564 3.4.2.2.1.1 Patents ............................................................................................. 564 3.4.2.2.1.2 Research .......................................................................................... 565 3.4.2.2.2 Catalyst .................................................................................................................. 565 3.4.2.2.2.1 Patents ............................................................................................. 565 3.4.2.2.2.2 Research .......................................................................................... 570 3.4.2.3 Selective Non-catalytic Reduction for NOX Control............................................................... 571 3.4.2.3.1 Patents .................................................................................................................... 571 3.4.2.3.2 Research ................................................................................................................. 573 3.4.2.4 Flaring for VOCs Control ....................................................................................................... 573 3.4.3 Unit Specific Control Technologies....................................................................................................... 575 3.4.3.1 FCC ......................................................................................................................................... 575 3.4.3.1.1 Hardware Improvements ........................................................................................ 575 3.4.3.1.1.1 CO Boiler ........................................................................................ 575 3.4.3.1.1.2 Third Stage Separator...................................................................... 575 3.4.3.1.1.3 Catalyst Regeneration ..................................................................... 576 3.4.3.1.1.3.1 Patents ...................................................................... 576 3.4.3.1.1.3.2 Research ................................................................... 578 3.4.3.1.2 Catalyst and Additive Improvements ..................................................................... 578 3.4.3.1.2.1 Attrition Resistant Catalysts ............................................................ 578 3.4.3.1.2.2 SOX Reduction Additives ................................................................ 579 3.4.3.1.2.2.1 Patents ...................................................................... 579 3.4.3.1.2.2.2 Research ................................................................... 581 3.4.3.1.2.3 NOX Reduction Additives ............................................................... 582 3.4.3.1.2.4 CO Combustion Promoters ............................................................. 583

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3.5

3.4.3.1.2.4.1 Patents ...................................................................... 583 3.4.3.1.2.4.2 Research ................................................................... 585 3.4.3.1.2.5 Multipurpose Additives .................................................................. 585 3.4.3.2 Sulfur Plant ............................................................................................................................. 586 REFERENCES ..................................................................................................................................................... 590