FLEXICOKING technology for upgrading heavy oil and utilization of by-products 2007 Japan-China-Korea Petroleum Technology Seminar Tokyo Dec 3-5, 2007 Toa Oil Co.Ltd Kenya Takahashi
Background Driver - Rising Crude Cost - Expanding Spread of Heavy/Light Crude Direction to proceed - Be likely to process lower cost heavier crude, but exploring solution of not reducing hydrocarbon margin Declining Fuel Oil Demand - Aim to move to bottomless / fuel oil free refinery FLEXICOKING Technology is one of the solutions for meeting these requirements. TOA OIL CO. LTD. Keihin Refinery 2
Product Pattern of Resid Conversion Options Specific Yields Depend Upon Feed and Processing Conditions About 1/3 of Feed Converted to High Sulfur / Less valuable By-Products Fuel Gas & LPG (6-12 wt%) Heavy Crudes Resids Delayed or FLUID COKING Moving Bed Hydroconversion Solvent Deasphalting C5+ Liquids (55-65 wt%) Byproduct: ( 30-38 wt%) + Coke + Heavy Bottoms + Pitch FLEXICOKING Technology gives solution for minimizing by-products. TOA OIL CO. LTD. Keihin Refinery 3
FLEXICOKING Produces Clean Fuel Gas Instead of Coke Fluid Bed Coking Integrated With Air & Gasification of Coke Produces Only a Small Amount of Coke (2 4 wt%) Produces a Large Quantity of LCG (220,000 Nm3/h th for 24 kbd unit) (LCG = Low Calorie Gas) Reactor Products to Fractionator Generation Tertiary Cyclones Fines Recovery TO FLEXSORB Gas Treating LCG to be used as Clean Fuel Scrubber Direct Contact Cooler Heavy Feed Reactor Cold Coke Heater Hot Coke Gasifier Coke Fines Air Sour Water Air Blower LCG Users: Pipestill Furnaces Reformer Furnaces Hydrogen Plant Furnaces Superheaters Power Plant Boilers Purge Coke TOA OIL CO. LTD. Keihin Refinery 4
Operating Principles of FLEXICOKING Products LCG 1. Vacuum Resid Feed Pumped to Reactor Scrubber Most resid feed from vacuum distillater directory goes to reactor. Provides rough cut separation at recycle cut point 2. Hot Resid Sprayed With Nozzles Into Fluidized Coke Bed Reactions occur in thin film on small coke particles and product vapors fluidize coke bed Feed R H G 3. Product Vapors Flow Overhead Through Cyclones to Scrubber Cyclones remove bulk of coke particles Scrubber condenses heavy liquids, removes entrained coke dust. Coke free hydrocarbons leave scrubber overhead to product fractionator Purge Coke Air & 4. Hot Fluid Coke Circulates Between Reactor, Heater and Gasifier Heater serves as heat exchanger 5. Coke Gasified with Air and in Fluid Bed Gasifier Vessel Partial combustion provides process heat for both reactor and gasifier Gasification Produces CO/H2 fuel gas stream Heater Overhead Cooled and Cleaned (Particulates and H2S) to produce clean LCG stream 6. Metals in Feed Removed in Purge Coke Solid fuel coke is sold to cement company. 7. Approximately 97% of the Products are Liquids and Gases Minimum production of coke TOA OIL CO. LTD. Keihin Refinery 5
LCG (Low Calorie Gas) Utilization LCG is Rich in CO and H2 Heating Value Reduced by Nitrogen Diluent LCG Amine Gas Treating Reduces Sulfur to Very Low Levels (10 ~ 20 ppm as H2S) Burns Cleanly Low SOx and NOx Burns With Constant Heating Value LCG Burns in a Refinery Furnaces, Boilers Process heaters (pipestill furnace, hydrogen plant furnace, steam superheater) Utility boilers (steam superheater, power plants boiler) Revamp of existing boilers, furnaces for accommodating LCG TOA OIL CO. LTD. Keihin Refinery 6
FLEXICOKING Commercial Units in Operation First Commercial Unit Started Up by TOA Oil in 1976, Expanded in 1993, 1994 Currently 5 Units Operating With a Total Capacity of ~ 200 kb/d New Unit for Hellenic Petroleum Currently in Design Company TOA Oil PDVSA Shell ExxonMobil ExxonMobil Hellenic Location Japan Venezuela California Netherlands Texas Greece Feed Rate (kb/d) 27 65 22 43 42 21 TOA OIL CO. LTD. Keihin Refinery 7
History of TOA Oil CO. LTD 1890 1920 1940 1960 1980 199 0 Chief Shareholder Tokyu Corporation ITOCHU Corporation 2000 Showa Oil Co. (Showa Shell Sekiyu K.K.) Nippon Heavy Oil Co. (Foundation 1924) Sales of imported heavy oil TOA Oil Co.,LTD (Renamed 1942) (1) Imports of (1)Imports of (1)Imports of oil products crude and oil products crude and (2) Sales of (2)Refining oil products oil products (3)Sales of oil (2)Refining products (1)Refining (1)Refining (2)IPP 1965 Foundation Kyodo Oil Co. Sale oil products 1979 Showa Oil Co.(Showa Shell sekiyu K.K.) Crude Processing Arrangement Refinery Kawasaki Refinery 1976 Flexicoking 1968 1962 INTEG 50,000B/D No2 C.D 30,000B/D No1 C.D 6,000B/D 20,000B/D 1955 MizueFactory 65,000B/D 65,000B/D 35,000B/D 1985 Ohgimachi Factory 120,000B/D 1979 1987 FCC,KPL Keihin Refinery 2000 TOA OIL CO. LTD. Keihin Refinery 8
TOA OIL- Keihin Refinery: Location Ohgimachi Ref. KPL Mizue Ref. 2,700 DWT 5,000 DWT 16B 8B,10B,12Bx2 JFE 53,520 DWT EPL 5,000 DWT Includes Ogimachi and Mizue Plants (~ 1.2 km apart) KPL(Kawasaki Pipeline : 5 underground piping) between Mizue/Ohgimachi enables 2 sites to operate as integrated refinery. OET OPL 36B,10Bx2 EOT 1,000 DWT 3,000 DWT 5,000 DWT 2 KEIHIN KAWASAKI SBM 315,000 DWT TOA OIL CO. LTD. Keihin Refinery 9
TOA OIL- 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 Ref. Crude Atmospheric Distillation (120,000) Underground Pipeline Units: BPSD Crude Atmospheric Distillation (65,000) (58,000) Vacuum Fractionation Unit HDS Unit (Light Oil) HDS Unit (Vac. Gas Oil) (42,000) FCC Unit Propylene LPG Gasoline Solvent Kerosene Light Oil Vacuum Residue FLEXICOKING Unit Polymerization Heavy Oil Coke Mizue Ref. (27,000) TOA OIL CO. LTD. Keihin Refinery 10
TOA OIL FLEXICOKING Unit, Japan Started up in 1976 Expanded in 1993, 1994 Current Capacity: 27 KB/SD Fluid Solids Vessels: Gasifier on Left, Heater in Center Reactor on Right Earthquake Proof Structure ExxonMobil Proprietary
TOA FLEXICOKING UNIT FLOW PLAN Three Fluid Solids Vessels: Reactor, Heater, and Gasifier Scrubber / Fractionator Control Recycle and Product Cut Points Air and Gasify Coke to Produce LCG COS Converter & FLEXSORB Amine Treating Reduce Sulfur in LCG to Low Levels Naphtha/Gas Venturi Scrubber COS Converter LCG L't Gas Oil L-FLS H'y Gas Oil Fractionator R-FLS ^ ^ ^ ^^ ~~ ~~ ~~~ ~~~ Scrubber Reactor Slurry Tertiary Coke LCG Absorber Cyclone Condensing Tower Heater Fine Coke Gasifier Feed ~~~~ ~ ~~~~~~~~~ ^ ^ ^^ ^ ^ ^^ Product Coke Air Blower TOA Flexicoker TOA OIL CO. LTD. Keihin Refinery 12
TOA OIL FLEXICOKING Reactor Product / Yields Process Long Residue from Both Ohgimachi and Mizue FEED (Vacuum residue) Density 1.01~1.03 Sulfur (wt%) 4.0~4.7 CCR (wt%) 19~22 Ni+V (wtppm) <230 Products GAS & LIQUIDS yield (wt%) Disposition C2-8.5 ~ 10.0 Gas turbine fuel (For power plant) C3/C4 4.8 ~ 6.5 C3H8, C3H6 recovery Feed for Poly Naphtha Plant Naphtha 19.0 ~ 21.0 Light : Caustic treatment for Mogas Heavy : Hydrotreated to be platformer feed Gas Oil FLEXIGAS 36.0 ~ 39.0 Light : Hydrotreated to be diesel oil product Heavy : Hydrotreated to be FCC feed R H Purge Coke G Air & Product Coke yield (wt%) Disposition Total 26 ~ 28 Gasified 23 ~ 27 Converted to Low Calorie Gas Net Product 2 ~ 4 Sales to cement company TOA OIL CO. LTD. Keihin Refinery 13
Refinery Upgrade with Addition of FLEXICOKING & FCC Units Improved Product Pattern CRUDE 70.2% VGO 9.7% L-RE/S-RE 20.1% 1.8 15.0 7.4 3.2 9.7 60.1 TYPICAL PRODUCT PATTERN 3.6 6.6 6.7 8.7 17.0 8.3 16.3 6.2 40.1 4.2 28.9 12.1 15.4 9.6 20.6 35.0 12.9 14.2 13.3 40.8 12.9 14.2 9.8 15.6 4.1 2.5 5.6 3.4 5.9 1.5 2.5 MIZUE Factory LPG Gasoline Kerosene Diesel Oil A-Fuel LSC-Fuel HSC-Fuel Others Loss SKIMMING +FLG +FCC/ FLG +FCC/ FLG (FLG 21,000) (FCC:20,000) (FLG 21,000) (FCC:33,000) (FLG:24,000) FEED BASE:CRUDE(AM),VGO(AL),LONG RE(AL),SHORT RE(AH) 65,000B/D 9,000B/D 14,500B/D 4,100B/D +FCC/ FLG (FCC:42,000) (FLG:24,000) (BPSD) (BPSD) Others: Gas for Sales,Sulfur,Coke, etc. TOA OIL CO. LTD. Keihin Refinery 14
TOA FLEXICOKING Unit Produces Large Amount of LCG LCG is Used as Fuel in Refinery Furnaces, Boilers and Power Plant FEED Capacity: 27 kbpsd (180 t/hr) C&F FLEXIGAS FLEXIGAS Composition (mol%) CO 22-23 H2 12-13 N2 55-57 CO2 6-7 C1,C2 etc 1.9-2.5 Total 100 Heating Value (kcal/nm 3) 1,100 ~ 1,200 Flow rate (NM 3 /hr) 220,000 Flow rate (MW) 280 ~ 310 R H G LCG Users: Purge Coke Air & Refinery Furnaces 50 % Power Plant Boiler 50 % TOA OIL CO. LTD. Keihin Refinery 15
Keihin Refinery Participates in Wholesale Electricity Business Operation Began in 2003 in Co-operation with other electric power company LCG is supplied as Fuel for -Generating Boiler is used for Power Generation and also by Refineries Stable Supply of Electricity and TOA OIL Keihin Refinery Genex (Power-Generating Plant) Products Vacuum Residue Fraction Boiler Frac. L/E Low Calorie Gas (LCG) High Calorie Gas (C1, C2) LPG (C3, C4) Gas Turbine Waste Heat Boiler Refinery furnaces R H G Air & TOA OIL CO. LTD. Keihin Refinery 16
Summary - Key Features of FLEXICOKING FLEXICOKING Produces Valuable Liquids Like Other Conversion Processes Yields are similar to other Coking processes FLEXICOKING Minimizes Product Coke with Integrated Air Gasification Only about ~ 2-4% compared with ~30% for other coking processes FLEXICOKING Produces Large Amount of Clean Fuel Gas Low Calorie Gas (LCG) is mainly composed of CO / H2, with N2. Sulfur content 10 ~ 20 ppm as H2S, 5 ~ 30 ppm as COS Burns cleanly with low SOx and NOx emissions LCG Burns in a Refinery Furnaces, Boilers Process heaters (pipestills, hydrogen plant furnace, crude preheating furnace) Utilities (steam superheaters) Power plant boiler TOA OIL Keihin Refinery has implemented First Commercial Application of FLEXICOKING Technology which has Contributed to Reduce Fuel Oil Production and Enhancement of Hydrocarbon Margin. TOA OIL CO. LTD. Keihin Refinery 17