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1 Refining strategy of IDEMITSU for Environment-Friendly Fuels Production Technology & Engineering Department Petroleum Refining Technology Center Idemitsu Kosan Co., Ltd. 1

2 CONTENTS Chapter 1 Outline of IKC s strategy 1-1 IKC S S refineries 1-2 Crude source in IKC 1-3 Efforts for eco-friendly products 1-4 Major reforms in refineries Chapter 2 Major accomplishments 2-1 Energy conservation 2-2 Sulfur Free Gasoline and Diesel 2-3 Conclusions 2-4 Challenge in the future 2

3 Chapter 1 Outline of IKC s Strategy 3

4 1-1 IKC s Refineries Aichi / Since 1975 CDU Diesel-HDS Resid-HDS RFCC ALKY : 160 kbpsd : 33 kbpsd : 55 kbpsd : 50 kbpsd : 10 kbpsd Hokkaido / Since 1973 CDU Diesel-HDS/HDW :CFI Process Resid-HDS RFCC : 140 kbpsd : 25 kbpsd : 42 kbpsd : 33 kbpsd Tokuyama / Since 1957 Petrochemical complex CDU Diesel-HDS FCC : 120 kbpsd : 20 kbpsd : 25 kbpsd Chiba / Since 1963 Petrochemical complex Lubricants CDU Diesel-HDS Resid-HDS FCC : 220 kbpsd : 60 kbpsd : 40 kbpsd : 45 kbpsd 4

5 1-22 Crude source in IKC *API of crude oil is rising slightly to meet the reduction heavy oil demand in recent years. (Average API=around 35 ) *Crude oil source is mainly the Middle East with minimal amount of Asian and African crudes. 5

6 1-3 Efforts for eco-friendly products 1967~ ARDS unit was installed at Chiba Refinery in 1967 for the first time in the world. (Followed by Aichi in 1975, Hokkaido in 1994) 1975~ Unleaded Gasoline 1997~ Low Sulfur Diesel, 500ppm 1993~ Low Benzene Gasoline, 1% or less 2005~ Ultra Low Sulfur Gasoline and Diesel Essentially sulfur free, 10ppm or less 6

7 1-4 Major reforms in refineries (1) Initial figure (1975) ; Aichi Refinery Ave. API:37 Crude Crude Distillation (130,000 BPSD) Naphtha-HDS (26,000 BPSD) Kerosene,Diesel-HDS (48,000 BPSD) LPG Recovery (550 TONS/D) Platformer (16,000 BPSD) LPG Naphtha Gasoline Jet Kerosene Hydrogen (1,800 KNm3/D) Resid-HDS (50,000 BPSD) Light gas oil A Fuel oil C Fuel oil 7

8 (2) Installation of bottom upgrading units(1986~) : New Unit Ave.API:37 34 Crude Hydrogen (1,800 KNm3/D) Demetalization Unit 1987~ Crude Distillation (160,000 BPSD) O C R Resid-HDS (60,000 BPSD) Vacuum Distillation (16,000 BPSD) Naphtha-HDS (30,000 BPSD) Kerosene,Diesel-HDS (49,000 BPSD) 2004~ 1987~ LPG Recovery (550 TONS/D) Resid Fluid Catalytic Cracking (50,000 BPSD) Propylene Platformer (20,000 BPSD) Alkylation (10,000 BPSD) 1986~ Acrylic Acid (50,000 t/y) Power Generation (252 MW) 2004~ 1991~ LPG Naphtha Gasoline Jet Kerosene Light gas oil A Fuel oil C Fuel oil Propylene Acrylic Acid Power 8

9 (3) Units installation for Sulfur-free free (Present) : New Unit Low Benzene Unit 1993~ Crude Hydrogen (1,800 KNm3/D) Crude Distillation (160,000 BPSD) O C R Vacuum Distillation (16,000 BPSD) Naphtha-HDS (30,000 BPSD) Kerosene,Diesel-HDS (49,000 BPSD) Resid-HDS (60,000 BPSD) Diesel-HDS (34,000 BPSD) Propylene LPG Recovery (550 TONS/D) 1996~ Resid Fluid Catalytic Cracking (50,000 BPSD) Platformer (20,000 BPSD) Alkylation (10,000 BPSD) Gasoline-HDS (15,700 BPSD) Acrylic Acid (50,000 t/y) Power (252 MW) P R 2004~ LPG Naphtha Gasoline Jet Kerosene Light gas oil A Fuel oil C Fuel oil Propylene Acrylic Acid Power 9

10 Chapter 2 Major Accomplishments 10

11 2-1 Energy conservation Japan COP3 requires CO2 reduction by 6% in 2010 from 1990 levels Petroleum Assosiation By 2010, 10% reduction in unit energy consumption at refineries from 1990 levels IDEMITSU By 2008, 20% reduction in unit energy consumption at refineries from 1990 levels IKC s Policy IKC exerts its best effort to maintain and improve the environment and contributes to the society. (1) Energy conservation Activity until 1998 Extensive energy saving was performed in each unit of each refinery. This approach had reached the saturation and activity got stagnant. (2) Current energy conservation activity All-company base activity to replace each refinery base Improvement of management - Strict watch of energy consumption of each unit and whole refinery - Hare of the idea and the theme by staffs of all refineries, and application to all refineries 11

12 (1) Total energy consumption in each refinery FOE-KL 各所燃料使用実績 (H17 年度 ) Purchase Gas Turbine Boiler Refining Unit Hokkaido Chiba Aichi Tokuyama Which refinery is consuming more energy? Which sector is consuming more energy at each refinery? 12

13 (2) Energy Consumption of Each Unit (KL/D) TOP( 通油量 ) 17 年 4 月 18 年 4 月 北海道千葉愛知徳山 (L/KL) TOP( 燃料原単位 ) 17 年 4 月 18 年 4 月 (%) (KL/D) VAC( 通油量 ) TOP( 加熱炉 O2%( 平均 )) (KL/D) 北海道 千葉 愛知 徳山 北海道 50 千葉愛知徳山 17 年 4 月 18 年 4 月 北海道千葉愛知徳山 ( ) 北海道 千葉 愛知 100 徳山 50 0 (L/KL) VAC( 燃料原単位 ) 30 DH( 燃料原単位 ) TOP( 加熱炉排ガス温度 ( 平均 )) 20 (L/KL) 10 北海道 12 千葉 愛知 徳山 年 4 月 5 月 7 月 9 月 11 月 1 月 3 月 18 年 4 月 5 月 7 月 9 月 11 月 1 月 3 月 17 年 4 月 18 年 4 月 17 年 4 月 17 年 4 月 18 年 4 月 (%) (KL/D) VAC( 加熱炉 O2%) PL( 通油量 ) 50 北海道 千葉 愛知 徳山 (2H) 徳山 (3H) 北海道 千葉 愛知 徳山 17 年 4 月 18 年 4 月 北海道千葉愛知徳山 ( ) (L/KL) VAC( 加熱炉排カ ス温度 ) CDU PL( 燃料原単位 ) 17 年 4 月 18 年 4 月 ( ) 北海道 350 千葉愛知徳山 300 VDU 17 年 4 月 18 年 4 月 17 年 4 月 18 年 4 月 (%) PL( 加熱炉 O2%( 平均 )) DH( 通油量 ) 北海道千葉愛知徳山 17 年 4 月 18 年 4 月 北海道千葉愛知徳山 ( ) PL( 加熱炉排ガス温度 ( 平均 )) 17 年 4 月 5 月 7 月 9 月 11 月 1 月 3 月 18 年 4 月 5 月 7 月 9 月 11 月 1 月 3 月 北海道千葉愛知徳山 PLAT 18 年 4 月 17 年 4 月 5 月 7 月 9 月 11 月 1 月 3 月 18 年 4 月 5 月 7 月 9 月 11 月 1 月 3 月 (%) DH( 加熱炉 O2%( 平均 )) 北海道千葉愛知徳山 (2H) 徳山 (3H) 17 年 4 月 18 年 4 月 北海道千葉愛知徳山 (2H) 徳山 (3H) DH( 加熱炉排カ ス温度 ) 年 4 月 5 月 7 月 9 月 11 月 1 月 3 月 18 年 4 月 5 月 7 月 9 月 11 月 1 月 3 月 0 Draw data of the same unit of each refinery The data shows the superiority or inferiority of the role of each office. 北海道千葉愛知徳山 (2H) 徳山 (3H) DH

14 (3) Target and accomplished value of energy consumption エConsumption/ throughput ネルギー消費原単位 % +5% 11.0 Base % -10% % % % 8.0 Accomplished in 2005 Consumption -17% 省エネ活動総括 Energy Saving H2 H3 H4 H5 H6 H7 H8 H9 H10 H11 H12 H13 H14 H15 H16 H17 H18 H19 H20 H21 H22 省エネ計画 PLAN(Vt.2000) (H12 起点 ) 省エネ実績 見込 ACTUAL(vt.2000) (H12 起点 ) 目標 TARGET 実績 見込み ACTUAL (L/KL) (FOE-KL/Y) 省エ200 ネ Target -20% 50 - Total Energy Saving 14

15 2-2 Sulfur Free Gasoline and Diesel (1) Ultra low sulfur, 10ppm, gasoline production ⅰ. Background Necessity of Sulfur free gasoline Greenhouse gas (CO2) reduction target has been set at COP3 - New engine(direct Injection / Lean burn) are promising technologies for fuel consumption improvement. - NOx reduction catalyst for lean burn engine tends to be poisoned by sulfur in Gasoline. Sulfur free gasoline (S=10ppm or less) is required for better performance of New-engine. - Idemitsu and other Japanese oil companies started supplying sulfur free gasoline in January Three years in advance of Government regulation 15

16 ⅱ. Where does Sulfur come from Blending ratio of regular gasoline Sulfur originated from 100% 100% 50% 50% 0% 0% LPG Reformate Straightrun FCC- Gasoline LPG Reformate Straightrun FCC- Gasoline Desulfurization of FCC gasoline is necessary for producing sulfur free gasoline. 16

17 ⅲ. HDS of FCC gasoline Feature of FCC Gasoline 50% Sulfur distribution Light Heavy 50% Olefin distribution Light Heavy 0% Mercaptan Thiophene Alkyl-Th Benzo-Th 0% Carbon Number Sulfur Olefin RON Light fraction low high high Heavy fraction high low low 17

18 HDS of FCC gasoline (Cont d) Optimum process flow scheme 45~55 55vol% FCC Gasoline Light fraction SPLITTER Caustic wash Desulfurized FCC Gasoline Heavy fraction HDS unit Advantage of splitting into 2 fractions (1) Maintain high octane number of Light fraction (2) Focus on desulfurization of high sulfur Heavy fraction (3) Minimize HDS unit capacity & Maximize the utilization of existing unit 18

19 ⅳ. Revamp in IKC Hokkiado / Aichi (AR conversion type refineries) Resid HDS RFCC Light Splitter Heavy Caustic wash (Existing) HDS unit (New) Desulfurized FCC Gasoline (1) Installation of FCC gasoline HDS unit - Utilize existing caustic wash - Install HDS unit (Prime-G+) 19

20 Revamp in IKC (Cont( Cont d) Light FCC gasoline sulfur:10 10~15ppm15ppm High octane value gasoline material Middle east crude oil Crude unit FCC gasoline sulfur:35 35~65ppm Splitter Caustic wash Light FCC gasoline sulfur:8~13ppm AR sulfur 3.0~4.5w% 4.5w% ARDS unit RFCC unit Splitter Gasoline HDS DSAR sulfur 0.25~0.55wt% 0.55wt% HDS heavy FCC gasoline sulfur:8~13ppm FCC gasoline sulfur 45~75ppm 75ppm(before) 8~13ppm(after) 20

21 ⅴ. Performance of FCC gasoline HDS unit Product quality and Octane loss FCC Gasoline Sulfur [wtppm] Base Days on stream Octane loss [-] - Achieved to produce low sulfur FCC Gasoline - Acceptable Octane loss. 21

22 ⅵ. Conclusion for Gasoline HDS IKC started supplying sulfur free gasoline at all of its four refineries in January Maximum utilization of existing unit capacity and installation of proper process saved initial investment significantly. Operation of FCC gasoline HDS unit is satisfactory. Future optimization will be focused on - Management of catalyst cycle length. - Investigation of optimum operation conditions ex. splitter cut ratio vs. HDS Rx severity 22

23 (2) Catalyst and process for ULSD Production ⅰ. Background The demand to improve diesel-exhaust emissions urged stringent regulation for diesel fuel quality. The quality regulations of diesel fuel in Japan Sulfur content (ppm) ULSD production started earlier than government target Jan <50ppm<10ppm HDS conversion: 80% 95% 99.5% 99.9% ⅱ. Strategy to meet the target Step1: Application of new highly active catalysts without major revamp Step2: Revamps of the unit (ex. Additional reactor) 23

24 ⅲ. Revamp for 50ppm [2003~] Refinery Catalyst Chiba Aichi Tokuyama IKC developed catalyst Revamps No revamp Installation of amine scrubber Increase of MU compressor capacity No revamp Catalyst evaluation technique is one of the keys for saving the cost of revamps and producing high quality fuels. 24

25 ⅳ. Revamp for 10ppm [2005~] Refinery Catalyst Chiba Aichi Tokuyama New highly active catalyst Revamps No revamp Additional Rx. Increase of MU compressor capacity Additional Rx. from a spare unit Increase of MU compressor capacity... etc (Catalyst development had not meet the target for short development period) We can work out more practical and cost effective solution than the licensor, since we, as user of the process, have better understanding of actual operation. 25

26 ⅴ. ULSD unit operation for 40ppm and 10ppm 40ppm 10ppm Rx WAT 26

27 ULSD unit operation for 40ppm and 10ppm (Cont d) Difference of 40ppm and 10 ppm operation Temperature increase is less than 10ºC. Catalyst deactivation rate is almost same. (0.6ºC/month) Hydrogen consumption difference is around 7Nm 3 /KL ( Depend on operating condition and feedstock properties.) 27

28 ⅵ. Conclusions for Diesel HDS Unexpectedly, catalyst deactivation rate in 10 ppm production is almost the same as that in 40 ppm operation. (But deactivation rate depends on feed properties, such as T90 and Nitrogen content.) Hydrogen consumption is higher by 7Nm 3 /KL in 10 ppm operation than 40 ppm case. This must be caused by saturation reaction of aromatics, and make up compressor capacity should be carefully checked before starting 10ppm operation. 28

29 2-3 Conclusions (1) Energy conservation Unit Energy consumption for 2008 is expected to be lowered by 20% from 1990 levels. cf.. Japanese petroleum association s s target :10% (2) Sulfur free gasoline and diesel production Sulfur free gasoline and diesel production had started successfully by Jan.2005 with the combination of - the installation of new process, - revamp and best utilization of existing unit and - catalysts optimization. 29

30 2-4 Challenge in the future Approach for reinforcing competitiveness of refinery (1) Bottom of the barrel technologies Introduction of heavy oil upgrading process Development of catalysts to crack reidue (2) Further energy saving Introduction of new technology Further integration of units (3) Increase of throughput High operating ratio by continuous unit operation Long HDS catalysts life ex. two years to four years for ULSD catalyst 30

31 Thank you for your patience 31

32 OCR OCR 32

33 Hydrodemetalization Unit (OCR:On stream Catalyst Replacement) OCR Outlet to Fixed Bed RDS Rx from Fresh Catalyst Hopper H2 Quench OCR Reactor High Pressure Catalyst Vessel Feed + H2 OCR Reactor system to Spent Catalyst Hopper 33

34 PG Rerun Unit C5- C6 PG 300#STM PGA (C6) 300#STM C6+ PR Simple Flow Diagram PGZ (C7+) 34

5 11 3 1....1 2. 5...4 (1)...5...6...7...17...22 (2)...70...71...72...77...82 (3)...85...86...87...92...97 (4)...101...102...103...112...117 (5)...121...122...123...125...128 1. 10 Web Web WG 5 4 5 ²

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