Fuel Production Technologies from High Sulfur Content Crude Oil of Middle East
NOC Nippon Oil Corporation Central Technical Research Laboratory Refining Process R&D Group Manager Minoru Hatayama Nov. 2006

Yield, vol%

100 80
Content wt% 0.03 0.01 0.13
Relative Reactor Volume @ Gas Oil HDS Unit 0.05% 1.34%

Yieldvol%

0.01 1.34 0.05 2.24 0.07

3.02 0.08 4.34 0.19

Yield Pattern, vol%

Crude API LPG

AL 33.5 3.9 16.7 18.5 19.1 3.3 24.0 14.4
AM 30.7 1.6 17.1 17.3 18.3 2.0 23.6 20.1
SL 34.4 0.2 8.2 13.5 19.6 3.8 33.1 21.6
32.6 0.4 7.6 10.4 15.8 3.1 31.2 31.5
(14) (5150) (150250) (250360) (360380) (380565) (565+)

Kero LGO HGO VGO VR

Sulfur Content, wt%

Crude API

(5150)
AL 33.5 0.03 0.13 1.34 2.24 3.02 4.34
AM 30.7 0.04 0.23 1.55 2.57 3.00 5.51
SL 34.4 0.01 0.01 0.05 0.07 0.08 0.19
32.6 0.00 0.02 0.04 0.06 0.11 0.20
(150250) (250360) (360380) (380565) (565+)
Changes of oil demand structure in Japan
Japan-development in oil product demand

300,000

250,000
200,000 Naphtha (Mkl) 150,000 Gasoline Jet/Kero Diesel 100,000 Fuel

50,000

Japan-development in oil Product demand
Heavy oil demand (Fuel oil, Asphalt) Light oil demand (Gasoline, Kerosene etc.)

decreasing

increasing
Refining Flow Chart (Negishi Refinery Base)

Crude Oil

LPG Recovery Unit 50(2) Catalytic Reforming Unit 23(2) Kerosene Hydrotreater 142(5) Gas Oil Hydrotreater 72(2) VGO HDC Isomax Unit 10(1) 9(1) Alkylation Unit
SHU* : Butadiene Selective Hydrogenation

kBPSD(Units)

Naphtha
Gasoline Blending Facilities
69.5(2) Naphtha Hydrotreater Crude Distillation Unit

Gasoline Benzene

8.8(1)

Benzene Splitter

Sulfolane

8(1) Isomerization

Jet Fuel Kerosene

Diesel Gas Oil

340(3)
85(2) Vacuum Flashing Unit
81(2) Fluid Catalytic Cracking Unit

ROKFiner

35(1) Residue Desulfurizing Unit
Fuel Oil Blending Facilities

Fuel Oil

37(1) Vacuum Distillation Unit 5.1(1) Propane Deasphalting Unit 13.5(1) Furfural Extraction Unit 8.2(1) Lube Oil Hydrotreater 8.2(1) MEK Dewaxing Unit Lube Oil Blending Facilities
Asphalt Lube Oil Paraffin

Features of HDC Catalyst

Amorphous Cracking activity Middle distillates selectivity Low Zeolite High

Zeolite Y

Tetrahedral Al

Octahedral Al

Change the amount of octahedral Al

Octahedral US-Y A Al

21.6% US-Y B 12.9%

US-Y C 10.6%

Chemical Shiftppm
Al-MASNMR Spectra of Three Zeolites

Yieldmass%

+4.0 +2.0 Base -2.0 -4.0 -6.0

Gas Oil

Octahedral Al ratio% Relationship Between Octahedral Al Ratio and Middle Distillate Selectivity
Cracking Catalyst Preparation US-Y A / Support / Metals US-Y B / Support / Metals US-Y C / Support / Metals Catalyst Evaluation
Feedstock: Density 0.93 S 2.0 mass% N 0.12mass% Pretreatment catalyst 12MPa LHSV 0.4

Cracking catalyst

Pretreatment / Cracking = 100ml / 200ml

80 Naphtha 60

Kerosene

Gas oil 0

Amorphous

(conventional)

Zeolite

(developed)

Product Distribution60% conversion
Developed zeolite-containing catalyst

Amorphous catalyst

Reaction Temperature
Initial Activity (bench scale test)

Kerosene yield, mass%

+20 Amorphous catalyst Base Developed zeolite-containing catalyst Base +40

Conversion rate, mass%

Kerosene Selectivity (bench scale test)
Catalyst average temperature, 0C
Developed zeolite-containing catalyst NCH97-200

Operation days

Catalyst Life Test (bench scale)

Muroran

Toyama Mizushima

Sendai Negishi

Osaka Marifu
Location of Nippon Oil Corporations Refineries
Configuration of the Hydrocracking Catalyst
Feed Pre-treatment Cracking

Product

Muroran Ref. Hydrocracking Unit
+40 14% Conversion rate, % +20 Base Amorphous NCH97-13

Trend of Conversion Rate

Accumulated cracked product volumes Million BL
3.7MillionBL 370 NCH97-13
Accumulated Cracked Product Volumes

Kerocene Yield vol%

+30 NCH97-13 Base
Amorphous Base Conversion ratevol% +40

Kerosene Selectivity in a Commercial Operation
NCH97-13 +10 Amorphous Base Base Conversion ratevol% +40

Gas oil Yield

Gas oil selectivity in a commercial operation
Corrected catalyst average temperature

+60 +40 +20 Base

NHC97-13

500 Operation days

Trend of Catalyst Average Temperature
Refining Flow Chart (Negishi Refinery Base) : Butadiene Selective Hydrogenation SHU
Deregulation of electric power market
Merit of IPP business for NOC (1) Utilizing excess heavy oil (2) A new source of income (3) Taking advantage of existing infrastructure and expertise on power plants
NOC entered the IPP business
Deregulation of electric power market List of NOCs IPP plants
Refineries Capacity/Sales Type Fuel OSAKA 149MW/130MW BTG Asphalt YOKOHAMA 57MW/49MW GTG LCO (Light Cycle Oil) NEGISHI 431MW/342MW IGCC Asphalt MARIFU 149MW/132.3MW BTG Cokes & Asphalt MURORAN 99MW/50MW BTG Asphalt Total 885MW/703.3MW (note) BTG: Boiler and Turbine generation GTG: Gas Turbine Generation IGCC: Integrated Gasification Combined Cycle
IGCC (Integrated Gasification Combined Cycle)

IGCC Major Flow

AIR SEPARATION UNIT

NITROGEN

OXYGEN STEAM TANK (VR) GAS VR+STEAM+OXYGEN SYNTHESIS GAS (H2,CO) SYNTHESIS GAS
TOKYO ELECTRIC POWER COMPANY SUB STATION 342MW GAS TUEBINE/STEAM TURBINE COMBINED CYCLE GENERATION UNIT

GENERATOR

GAS TREATER GT AIR ST TRANSFORMER
STEAM WASTE WATER TREATING UNIT EXHAUST GAS OF GT
WASTE HEAT BOILER DENOX UNIT
First plant in Japan The first plant in Japan applies the latest technology. (gasification of asphalt). Low environmental impact SOx emission NOx emission Particulate matters emission below 2.0 volppm below 2.6 volppm below 1.4 mg/Nm3
Efficient power generation 46% of high efficiency has been accomplished.
Specifications of Negishi IGCC
Plant Electric power output 431,000kW synthesis capacity at generating end (Efficiency: 46%) Net Power output Gasification system Gasified fuel Fuel consumption Power generation method 342,000kW (Efficiency: 36%) The partial oxidizing method Vacuum residual oil (VR: Vacuum Residue) 50,000ton/month Integrated gasification combined cycle (Single shaft)
Gas Turbine Main fuel Synthesis gas Main ingredients:CO,H2 1350oC 570oC Air cooling system High:9.8MPaG Middle:2.9MPaG Low:0.7MPaG

Steam Turbine

Combustion temperature Temperature of exhaust gas Cooling system for hot parts Input steam pressure
Refining Flow Chart (Negishi Refinery)

Fuel Oil Asphalt

Coking Unit
13.5(1) Furfural Extraction Unit 8.2(1) Lube Oil Hydrotreater 8.2(1) MEK Dewaxing Unit Lube Oil Blending Facilities

37(1) Vacuum Distillation Unit 5.1(1) Propane Deasphalting Unit

Lube Oil Paraffin

Coking Unit Major Flow
CDU Crude V/F VGO HDS Unit gas Naphtha Kerosene Gas oil FCC Unit CLO gas Naphtha Coking Unit Gas oil VGO Cokes gas Gasoline LCO

HDS Unit

Flowchart of Coking Unit

gas 6wt% 4wt%

Temp.100110 Press.0.25 MPa
Density Carbon residue Sulfur 1010 kg/mwt% 3.3 wt%
Naphtha17wt% Foul Water Gas oil 22wt% Fuel oil 25wt% Cokes 26wt%

Press.0.330.36 MPa

Coke Drum

1.081.12

Temp.498502

Feed Specifications

VR Dens. Sulfur g/cm3 mass% 1.011.04 2.55.0 0.1628 VR 0. 95 0.2 0.12.5 Feed 1.001.02 3.23.4 0.1621
Nitrogen mass% Ni C.R. massppm mass %
Blend ratio of each feed VR would be changed according to the sulfur content of ME VR.

Product Specifications

Yield Dens. Dist. wt% g/cm3 5% 95% mass% 6

(MW22)

Naphtha Fuel oil 4 0.51 17 0.165 0.22 0.330 1.25 0.510 2.2 2500
Sulfur Nitrogen massppm Sulfur Nitrogen VM V
mass% mass% mass% mass ppm

Cokes 5.05.280

Next operation
amine treator aminesoda treator HDS Unit HDS Unit HDC Unit

Utilization

Self-Consumption
Naphtha Gas oil Fuel oil Cokes
Feed for Reformer Gas oil Feed for Unit Sale