Upgrading of Heavy Oils with FLEXICOKING. ExxonMobil Research & Engineering Company Tim Hilbert

Upgrading of Heavy Oils with FLEXICOKING ExxonMobil Research & Engineering Company Tim Hilbert

FLEXICOKING: Integrated Coking and Gasification FLEXICOKING TM Integrated Coke Gasification Key features of technology Commercial experience FLEXIGAS Utilization - Clean Fuel Gas Utilization in refinery or for power production Rotterdam and TOA Oil FLEXICOKING Experience Commercial operations Expansion and joint venture for power production 1

Coking Process Coking is the Most Widely Used Resid Conversion Approach Worldwide! Delayed Coking Furnace & Drum, Batch Process, Coke Pits FLUID COKING Fluidized Bed, Continuous, Coke Silos and Closed System Environmental considerations important for both Coke by-product Yield Typically 1/3 of Feed Similar amount for other resid conversion processes Heavy Crudes Resids Delayed Coking (several providers) FLUID COKING TM (ExxonMobil) Product: (a) Yield (wt%) Fuel Gas & LPG 10 C5+ Liquids 55 Coke (b) 35 Total 100 Coke Dispositions Can Have A Major Impact on Project Economics! 2

FLUID COKING Technology and Commercial Experience Developed by ExxonMobil Research and Engineering Company (EMRE) as an Extension of FCC Fluid Solids Technology Heavy feed injected into fluidized coke bed with feed rings / nozzles Partial combustion of coke in burner and coke circulation provides heat for reaction Scrubber preheats feed, separates coke fines, and sets recycle cut point Liquid products split in down stream fractionators Coke pneumatically conveyed and stored in silos for fuel coke market Reactor Products to Fractionators Heavy Feed Scrubber Flue Gas to CO Boiler First commercialized in ExxonMobil s Billings, Montana Refinery in 1954! Reactor Burner Cold Coke Hot Coke Product Coke Air Over 420 kb/d of Operating Capacity Worldwide 7 Units with last S/U in 06 - Unit Rates from 10 110 kb/d 3

FLEXICOKING Same Liquid Yields as Fluid or Delayed Coking Coke Gasified in Integrated Steam Air Gasifier Produces Clean CO/H 2 Fuel Gas Product Instead of Coke FLEXSORB Hindered Amine Reduces H 2 S to Low Level Low SO X Nitrogen Diluent Reduces BTU Content, But Low NO X FLEXIGAS Burned in Refinery or Third Party Furnaces / Boilers Reactor Products to Fractionators Heavy Feed Reactor Scrubber Heater Steam Generation Gasifier Tertiary Cyclones Coke Fines Fines Recovery Sour Water TO FLEXSORB Gas Treating Direct Contact Cooler FLEXIGAS Clean Fuel Cold Coke Hot Coke Coke Withdrawal Steam Air Blower Air FLEXIGAS Users: Refinery Third Party Consumers 4

FLEXICOKING: Reactor Product / Yields Similar to Other Coking Processes - Thermal Conversion Feed and Recycle Cut point Differences can complicate Comparisons Gas & Liquids Feed Products FLEXIGAS Wt% FF C2 Fuel Gas 6.7 C3 / C4 LPG 4.4 LV% FF Type VR Total C4-11.1 Nominal cut point, C 565 C5 / 430 F 15.3 20.8 Nominal cut point, F 1050 Feed Properties R H G 430 / 650 F 11.0 12.6 650 / 975 F 32.2 33.2 Gravity, API 6.9 Sulfur, wt% 4.6 Conradson Carbon, wt% 26 Nickel, wppm 18 Vanadium, wppm 108 Air & Steam Total C5+ 58.6 66.6 Coke, Wt% Net Product Coke 1.7 Gasified Coke 28.6 Total 30.3 5

FLEXICOKING: Produces a Significant Quantity of Valuable Clean Fuel Gas GAS: 23 mtons/hr LIQUIDS: 122 mtons/hr FEED: 208 mtons/hr (31 kb/d) Bold the font in the text boxes FLEXIGAS FLEXIGAS Clean Fuel Gas Composition mol% CO/H 2 40 N 2 48 Other 12 Total 100 Rates Metric English Coke Gasified, mtons / hr 60 FLEXIGAS, mtons / hr 351 Heating Value, kj / kg (BTU / SCF) 4,800 128 Heat Rate, MW (th) (MBTU / hr) 460 158 R H G Air & Steam COKE: 3. mtons/hr FLEXIGAS Users: Pipe still Furnaces Hydrogen Plant Furnaces Reformer Furnaces Steam Superheaters Waste Heat Boilers Power Plant Boilers Third Party Consumers 6

FLEXICOKING: Operating Commercially for 30 Years TOA Oil - First Commercial Unit S/U in 1976, Expanded in 2002 Currently 5 Units Operating With a Total Capacity of ~200 kb/d New Unit for Hellenic Petroleum in Greece under construction New Unit for PetroPeru most recent Licensee COMPANY LOCATION FEED RATE, kb/d TOA Oil Japan 27 PDVSA Venezuela 65 Shell California 22 ExxonMobil Netherlands 42 ExxonMobil Texas 42 Hellenic Greece 21 PetroPeru Peru 22 2010 Middle East Petrotech, Bahrain May 23-26, 2010 7

Processing Configurations Comparable to FLEXICOKING FLEXICOKING Commercially Proven With Integrated Steam / Air Gasification Milder Conditions and Lower Capital Cost than POX FULLY INTEGRATED FLEXICOKING Conversion Step Fluid Bed Coking Gasification Step Fluid Bed Coke Gasification CO / H 2 / N 2 Fuel Gas Steam/Air SEPARATE PROCESS Competing Options Conversion Step Delayed Coking Ebullating Bed SDA Gasification Step Partial Oxidation Gasification CO / H 2 SynGas Air Separation Oxygen 8

FLEXIGAS Utilization FLEXIGAS Fuel is Rich in CO and H 2 Heating value reduced by nitrogen diluents FLEXSORB Amine Gas Treating Reduces Sulfur to Very Low Levels (< 10 ppm H 2 S) Burns very cleanly ultra-low SO x and NO x Burns with constant heating value (unlike refinery fuel gas) FLEXIGAS Burns Very Readily in a Wider Range of Services in a Variety of Commercially Available Burners Process heaters (pipe stills, naphtha reformers, hydrogen plant furnaces) Utility boilers (steam generation, steam super heaters) Over-the-fence sales to power plants or other nearby consumers Burner Conversion and Fuel Distribution Costs Are Low Burners commercially available at same cost as conventional burners Low pressure pipes / ducts Refinery Fuel Balance Planning Important Overall fuel requirements in conversion project Location and size of refinery consumers Third party fuel consumers 9

FLEXICOKING Commercial Experience ExxonMobil Rotterdam Started Up in 1986 Currently 42 kb/d Gasifier in Center (green) Coke Silos on Left Heater and Reactor / Scrubber on Right FLEXICOKING Unit Added in Major Upgrade to Hydroskimming Refinery Refinery has high degree of integration / efficiency Refinery is Entirely Gas Fired Refinery fuel gas FLEXIGAS Supplemental natural gas Real Time Optimization (RTO) Control System Used to Manage Fuel Gas Sources / Balance 10

Rotterdam FLEXIGAS Consumers Large number of Furnaces, Fired Heaters & Boiler On Site Consumers Primary Users Boilers (2) Atmospheric Pipe still Furnace (2) Vacuum Pipe still Furnace Naphtha Reformer Furnace Steam Reforming H 2 Plant Furnace Stabilizer Reboiler Splitter Reboiler Steam Super Heater Furnace / Heaters / Burners Grass Roots Revamp Grass Roots Grass Roots Grass Roots Revamp Revamp Grass Roots 11

Considerations for Use of FLEXIGAS Overall Refinery Fuel Balance and Design of FLEXIGAS Distribution System Consider Refinery Consumers that are Large and Close to FLEXICOKING First Secondary Refinery Consumers Selected Based upon Fuel Savings versus Cost of Burners and Ducts Refinery Scenario Planning to Identify: Source of alternate fuel gas for consumers and dual fired burners for added flexibility Disposition of FLEXIGAS when selected consumers are down Large Nearby Consumer Helps Fuel Balance and Provides Flexibility 12

TOA Oil Refinery FLEXICOKING Unit TOA Oil Keihin Mizue Ohgimachi 186 kb/d 65 kb/d 120 kb/d Ohgimachi and Mizue Plants ~ 1.2 km Apart KPL (Kawasaki Underground Pipeline (5)) Enables Two Sites to Operate as Integrated Refinery 2010 Middle East Petrotech, Bahrain May 23-26, 2010 13

TOA Keihin Refinery: Process Configuration Vacuum Distillation Unit at Mizue Processes Long Residue from Both Sites and Provides Feed to FLEXICOKING Unit Intermediate / Finished Products Transported Between Plants Through Underground Pipelines Ohgimachi Refinery Crude Atmospheric Distillation (120,000) Underground Pipeline Units: BPSD Crude Atmospheric Distillation Vacuum Residue (65,000) (58,000) Vacuum Fractionation Unit HDS Unit (Light Oil) HDS Unit (Vac. Gas Oil) FLEXICOKING Unit (42,000) FCC Unit Polymerization Propylene LPG Gasoline Solvent Kerosene Light Oil Heavy Oil Coke Mizue Refinery (27,000) 14

TOA Oil FLEXICOKING Unit FLEXICOKING Unit Started up in 1976 (21 kb/sd) Current Capacity: 27 kb/sd Fluid Solids Vessels: Gasifier on Left Heater in Center Reactor on Right Earthquake-Proof Structure FLEXIGAS Users Refinery Furnaces 50% Power Plant Boilers 50% 15

TOA Oil FLEXICOKING Reactor Products / Yields Process Long Residue from Both Ohgimachi and Mizue Also process H-Oil Bottoms from nearby Tonen Kawasaki refinery Feed (Vacuum Residue) Density 1.01 1.03 Sulfur (wt%) 4.0 4.7 CCR (wt%) 19 22 Ni+V (wtppm) <230 PRODUCTS R H Purge Coke FLEXIGAS G Air & Steam C2 8.5 10.0 C3 C4 4.8 6.5 Gas and Liquids Naphtha 19.0 21.0 Gas Oil 36.0 39.0 Yield (wt%) Disposition Gas Turbine Fuel for Power Plant C 3 H 8, C 3 H 6 recovery Feed for Poly Naphtha Plant Light: Caustic Treatment for Mogas Heavy: Hydrotreated for Platformer Feed Light: Hydrotreated to be Diesel Oil Product Heavy: Hydrotreated to be FCC Feed Product Coke Yield (wt%) Disposition Total 26 28 Gasified 23 27 Converted to Low Calorie Gas Net Product 2 4 Sales to Cement Company 16

Keihin Refinery Participates in Wholesale Electricity Business Operation Began in 2003 in Cooperation with Electric Power Company LCG is Supplied as Fuel for Steam-Generating Boiler Steam is Used for Power Generation and Refineries Stable Supply of Electricity and Steam TOA OIL Keihin Refinery Products Vacuum Residue Fraction Genex (Power-Generating Plant) 37 % Steam Boiler Frac. L/E Low Calorie Gas (LCG) High Calorie Gas (C1, C2) FCC HCG Gas LPG (C3, C4) Refinery furnaces 21 % 33 % 9 % 100 % Gas Turbine Waste Heat Boiler R H G Air & Steam Gas Turbine: Steam Turbine: Total ~80 MW ~190 MW ~ 270 MW 17

Major Advantages of FLEXICOKING Technology FLEXICOKING Produces a Large Quantity of Valuable Clean Fuel Gas FLEXIGAS is primarily CO / H 2, with N 2 Sulfur content < 10 ppm H 2 S and burns cleanly with very low SO x and NO x FLEXICOKING Produces Valuable Liquids Like Other Conversion Processes Yields are similar to other coking processes FLEXICOKING Minimizes Product Coke with Integrated Air Gasification Approx. 1-4% compared with approx. 30% for other coking processes FLEXIGAS Burns Readily in a Wide Range of Consumers Process heaters, Utilities, Power Plants or over-the-fence sales FLEXICOKING Fits Best in Locations with Large Demand for Clean Fuel 18

Upgrading of Heavy Oils with FLEXICOKING Questions Sunset at TOA Oil, Keihin Refinery ( Mizue )