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 Direction to proceed

- Rising Crude Cost - Be likely to process lower cost heavier

- Expanding Spread of crude, but exploring solution of not reducing
Heavy/Light Crude 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%)

Delayed or FLUID COKING

Heavy Crudes
Resids Moving Bed Hydroconversion C5+ Liquids (55-65 wt%)

Solvent Deasphalting

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 & Steam 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)
Tertiary Fines
TO FLEXSORB
Reactor Products Cyclones Recovery
Gas Treating
LCG to be used
to Fractionator Steam as Clean Fuel
Generation

Direct
Contact
Scrubber Cooler
Sour
Heavy Coke Water
Fines
Feed Reactor Heater
Gasifier
LCG Users:
Pipestill Furnaces
Reformer Furnaces
Steam
Hydrogen Plant Furnaces
Hot Air Blower
Coke Steam Superheaters
Cold
Coke Air
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 R H

G
Reactions occur in thin film on small coke particles
Feed
Steam and product vapors fluidize coke bed
Air &
3. Product Vapors Flow Overhead Through Cyclones to Scrubber Steam
Cyclones remove bulk of coke particles
Scrubber condenses heavy liquids, removes entrained coke dust. Purge
Coke
Coke free hydrocarbons leave scrubber overhead to product fractionator

4. Hot Fluid Coke Circulates Between Reactor, Heater and Gasifier

Heater serves as heat exchanger

5. Coke Gasified with Air and Steam 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 Location Feed Rate (kB/D)

TOA Oil Japan 27
PDVSA Venezuela 65
Shell California 22
ExxonMobil Netherlands 43
ExxonMobil Texas 42
Hellenic Greece 21

TOA OIL CO. LTD. Keihin Refinery 7

 History of TOA Oil CO. LTD

1920
1890 1940 1960 1980 199 2000
0
Chief Tokyu ITOCHU Showa Oil Co.
Shareholder Corporation Corporation (Showa Shell Sekiyu K.K.)

Nippon Heavy
Oil Co.
TOA Oil Co.,LTD
(Foundation (Renamed 1942)
1924)
(1) Imports of (1)Imports of (1)Imports of (1)Refining (1)Refining
oil products crude and crude and
Sales of oil products (2)IPP
(2) Sales of (2)Refining oil products
imported
oil products (3)Sales of oil (2)Refining
heavy oil
products

1965 1979
Foundation Showa Oil Co.(Showa Shell sekiyu K.K.)
Kyodo Oil Co.
Sale oil products Crude Processing Arrangement

Refinery Kawasaki 1976

Flexicoking
1987
FCC,KPL Keihin Refinery
Refinery
1968 MizueFactory
1962 INTEG 50,000B/D 65,000B/D 65,000B/D
No2 C.D 30,000B/D 35,000B/D
No1 C.D 6,000B/D 20,000B/D 1985 Ohgimachi Factory
1955 120,000B/D
1979 2000
TOA OIL CO. LTD. Keihin Refinery 8
 TOA OIL- Keihin Refinery: Location

Mizue Ref.
Ohgimachi Ref. 2,700 DWT
KPL

5,00
DW 0
5,0
JFE

T
0 DW
T
16B EPL
53,520 DWT
8B,10B,12B2

Includes Ogimachi and Mizue Plants OET EOT

(~ 1.2 km apart)
KPL(Kawasaki Pipeline : 5 underground OPL
36B,10Bx2
piping) between Mizue/Ohgimachi 1,000 DWT
enables 2 sites to operate as integrated 3,000 DWT
refinery. 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.
Units: BPSD
Crude Atmospheric Distillation (120,000)
Underground Pipeline
Propylene
(65,000)
Atmospheric
Distillation

HDS Unit
Crude
(Light Oil) Gasoline
(58,000)
(42,000) Solvent
Vacuum
Fractionation HDS Unit Kerosene
FCC Unit
Unit (Vac. Gas Oil)
Light Oil
Vacuum Heavy Oil
FLEXICOKING Unit Polymerization
Residue
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 Steam Gasify Coke to Produce LCG
COS Converter & FLEXSORB Amine Treating Reduce Sulfur in LCG to Low Levels
Venturi Scrubber COS Converter LCG
Naphtha/Gas

L't Gas Oil L-FLS

H'y Gas Oil Fractionator

R-FLS

Slurry
Steam Coke
Tertiary LCG Absorber
Cyclone Condensing Tower
^^^^^
^^^^^
^ ^ ^ Scrubber
Fine Coke
Reactor
Heater
Gasifier

Feed

Steam
Steam
^ ^
^^
^ ^ Steam
^^ Steam

Steam Air Blower

Steam

Steam
Product Coke TOA Flexicoker

TOA OIL CO. LTD. Keihin Refinery 12

 TOA OIL FLEXICOKING Reactor Product / Yields

Process Long Residue from Both Ohgimachi and Mizue

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 36.0 ~ 39.0 Light : Hydrotreated to be diesel oil product
Products Heavy : Hydrotreated to be FCC feed
FEED (Vacuum residue)
Density 1.01~1.03 FLEXIGAS
Sulfur (wt%) 4.0~4.7
CCR (wt%) 19~22
Ni+V (wtppm) <230

R H
G

Product Coke
Air & yield (wt%) Disposition
Steam Total 26 ~ 28
Purge Gasified 23 ~ 27 Converted to Low Calorie Gas
Coke 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

TYPICAL
TYPICAL PRODUCT
PRODUCT PATTERN
PATTERN
MIZUE Factory
1.8 3.6 6.6 6.7 LPG
8.7
15.0
17.0 Gasoline
7.4 28.9
3.2 8.3 35.0 Kerosene
40.8
CRUDE 9.7
16.3 Diesel Oil
70.2% 12.1
6.2 12.9 A-Fuel
15.4 12.9
60.1 14.2 LSC-Fuel
VGO 40.1 9.6 14.2
HSC-Fuel
9.7% 13.3
L-RE/S-RE
20.6
9.8
15.6 Others
20.1% 4.2 1.5 2.5 3.4 Loss
4.1 5.6 5.9

SKIMMING +FLG +FCC/ FLG +FCC/ FLG +FCC/ FLG

(FCC:20,000) (FCC:33,000) (FCC:42,000) (BPSD)
(FLG 21,000) (FLG 21,000) (FLG:24,000) (FLG:24,000) (BPSD)
Others: Gas for Sales,Sulfur,Coke, etc.
FEED BASECRUDE(AM),VGO(AL),LONG RE(AL),SHORT RE(AH)
65,000B/D 9,000B/D 14,500B/D 4,100B/D

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

FLEXIGAS
Composition (mol%)
CO 22 - 23
H2 12 - 13
N2 55 - 57
CO2 6-7
C1,C2 etc 1.9-2.5
C&F Total 100
3)
FLEXIGAS
Heating Value (kcal/Nm 1,100 ~ 1,200
Flow rate (NM3/hr) 220,000
Flow rate (MW) 280 ~ 310
FEED Capacity:
27 kBPSD (180 t/hr)

R H
G
LCG Users:
Air &
Steam
Refinery Furnaces 50 %
Power Plant Boiler 50 %
Purge
Coke

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 Steam-Generating Boiler
Steam is used for Power Generation and also by Refineries
Stable Supply of Electricity and Steam

TOA OIL Keihin Refinery Genex (Power-Generating Plant)

Vacuum
Products Residue Steam Boiler
Fraction

Low Calorie Gas

(LCG)
Frac.
L/E High Calorie Gas
(C1, C2) Waste Heat
Boiler

(C3, C4) Gas Turbine

Refinery furnaces

R H
G

Air & Steam

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