環境問題に対する出光の取組み

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Refining strategy of IDEMITSU for

Environment-Friendly Fuels Production

Technology & Engineering Department Petroleum Refining Technology Center

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CONTENTS

Chapter 1 Outline of IKC’s strategy 1

1--11 IKCIKC’’S refineriesS refineries 1

1--22 Crude source in IKC Crude source in IKC 1

1--33 Efforts for ecoEfforts for eco--friendly productsfriendly products 1

1--44 Major reforms in refineriesMajor reforms in refineries Chapter 2 Major accomplishments

2

2--11 Energy conservationEnergy conservation 2

2--22 Sulfur Free Gasoline and DieselSulfur Free Gasoline and Diesel 2

2--33 ConclusionsConclusions 2

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Chapter 1

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

1-1 IKC’s Refineries

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1

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2 Crude source in IKC

＊

＊_{API of crude oil is rising}_{API of crude oil is rising} slightly to meet the

slightly to meet the

reduction heavy oil

demand in recent years.

(Average API=around 35 )

＊

＊Crude oil source is mainly_{Crude oil source is mainly}

the Middle East with

minimal amount of Asian

and African

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3 Efforts for eco

Efforts for eco

-

friendly products

•

• 1967~ 1967~ ARDS unit was installed at Chiba Refinery ARDS unit was installed at Chiba Refinery in 1967 for the first time in the world.

in 1967 for the first time in the world.

(Followed by Aichi in 1975, Hokkaido in 1994)

(Followed by Aichi in 1975, Hokkaido in 1994) •

• 1975~ 1975~ Unleaded GasolineUnleaded Gasoline

•

• 1997~ Low Sulfur Diesel , 500ppm1997~ Low Sulfur Diesel , 500ppm

•

• 1993~ 1993~ Low Benzene Gasoline, 1% or lessLow Benzene Gasoline, 1% or less

•

• 2005~ 2005~ Ultra Low Sulfur Gasoline and DieselUltra Low Sulfur Gasoline and Diesel Essentially sulfur free, 10ppm or less

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7 Crude Distillation (130,000 BPSD) LPG Recovery (550 TONS/D) Platformer (16,000 BPSD) Naphtha-HDS (26,000 BPSD) Crude A Fuel oil Kerosene Jet Gasoline Naphtha

Light gas oil LPG

Hydrogen

(1,800 KNm3/D)

C Fuel oil

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4 Major reforms in refineries

Major reforms in refineries

(1) Initial figure (1975) ; Aichi Refinery

Ave. API：37

Kerosene,Diesel-HDS (48,000 BPSD)

Resid-HDS (50,000 BPSD)

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8 Crude Distillation (160,000 BPSD) LPG Recovery (550 TONS/D) Platformer (20,000 BPSD) Resid-HDS (60,000 BPSD) Naphtha-HDS (30,000 BPSD) Crude A Fuel oil Kerosene Jet Gasoline Naphtha

Light gas oil LPG Hydrogen (1,800 KNm3/D) C Fuel oil Kerosene,Diesel-HDS (49,000 BPSD)

(2) Installation of bottom upgrading units(1986~)

Vacuum Distillation (16,000 BPSD) Power Generation (252 MW) Power 2004~ 2004~ Propylene Ave.API：37⇒34 : New Unit : New Unit O C R Demetalization Unit 1987~ Alkylation (10,000 BPSD) Acrylic Acid

(50,000 ｔ/y) Acrylic Acid

Resid Fluid Catalytic Cracking (50,000 BPSD) 1991~ 1986~ Propylene 1987~

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9 Crude Distillation (160,000 BPSD) LPG Recovery (550 TONS/D) Platformer (20,000 BPSD) Alkylation (10,000 BPSD) Naphtha-HDS (30,000 BPSD) Crude A Fuel oil Kerosene Jet Gasoline Naphtha

Light gas oil LPG Hydrogen (1,800 KNm3/D) Vacuum Distillation (16,000 BPSD) Power (252 MW) Power Acrylic Acid

(50,000 ｔ/Y) Acrylic Acid C Fuel oil

Propylene Propylene

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Units installation for Sulfur

-

free (Present)

Resid Fluid Catalytic Cracking (50,000 BPSD) Gasoline-HDS (15,700 BPSD) 2004~ Resid-HDS (60,000 BPSD) O C R :

: New UnitNew Unit Low Benzene _{Unit 1993~}

P R Kerosene,Diesel-HDS (49,000 BPSD) Diesel-HDS (34,000 BPSD) 1996~

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Chapter 2

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COP3 requires CO2 reduction by 6% in 2010 from 1990 levels By 2010, 10% reduction in unit energy consumption at refineries from 1990 levels

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

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1 Energy conservation

Energy conservation

Petroleum Assosiation

IDEMITSU

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(1) Total energy consumption in each refinery

各所燃料使用実績（Ｈ１７年度）

Hokkaido Chiba Aichi Tokuyama FOE-KL

Purchase Gas Turbine Boiler

Refining Unit

Which refinery is consuming more energy?

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13 ＴＯＰ（通油量） 0 5000 10000 15000 20000 25000 30000 35000 40000 １７年４月６月８月 _１０月 _１２月２月１８年４月 _６月 _８月１０月１２月２月 (KL/D) 北海道千葉愛知徳山ＴＯＰ（燃料原単位） 6 7 8 9 10 11 12 １７年４月６月８月 _１０月 _１２月２月１８年４月 _６月 _８月１０月１２月２月 (L/KL) 北海道千葉愛知徳山ＴＯＰ（加熱炉Ｏ２％（平均）） 0 1 2 3 4 １７年４月 _６月 _８月１０月１２月２月１８年４月 _６月 _８月１０月１２月２月 (％) 北海道千葉愛知徳山ＴＯＰ（加熱炉排ガス温度（平均）） 0 50 100 150 200 250 300 350 １７年４月 _６月 _８月１０月１２月２月１８年４月 _６月 _８月１０月１２月２月 (℃) 北海道千葉愛知徳山 VAC（通油量） 0 1000 2000 3000 4000 5000 6000 7000 8000 9000 １７年４月５月６月７月８月９月１０月１１月１２月１月２月３月１８年４月５月６月７月８月９月１０月１１月１２月１月２月３月 (KL/D) 北海道千葉愛知徳山 VAC（燃料原単位） 0 2 4 6 8 10 12 14 16 １７年４月６月８月 _１０月 _１２月２月１８年４月 _６月 _８月１０月１２月２月 (L/KL) 北海道千葉愛知徳山 VAC（加熱炉Ｏ２％） 0 0.5 1 1.5 2 2.5 3 3.5 4 4.5 １７年４月 _６月 _８月１０月１２月２月１８年４月 _６月 _８月１０月１２月２月 (％) 北海道千葉愛知徳山 VAC（加熱炉排ｶﾞｽ温度） 0 50 100 150 200 250 １７年４月６月８月 _１０月 _１２月２月１８年４月 _６月 _８月１０月１２月２月 (℃) 北海道千葉愛知徳山

(2) Energy Consumption of Each Unit

CDU VDU PL（通油量） 0 500 1000 1500 2000 2500 3000 3500 4000 １７年４月 _６月 _８月１０月１２月２月１８年４月 _６月 _８月１０月１２月２月 (KL/D) 北海道千葉愛知徳山 PL（燃料原単位） 0 10 20 30 40 50 60 １７年４月６月８月 _１０月 _１２月２月１８年４月６月８月 _１０月 _１２月２月 (L/KL) 北海道千葉愛知徳山 PL（加熱炉O2％（平均）） 0 1 2 3 4 5 6 7 １７年４月 _６月 _８月１０月１２月２月１８年４月６月８月 _１０月 _１２月２月 (％) 北海道千葉愛知徳山 PL（加熱炉排ガス温度（平均）） 0 50 100 150 200 250 300 350 400 450 １７年４月５月６月７月８月９月１０月１１月１２月１月２月３月１８年４月５月６月７月８月９月１０月１１月１２月１月２月３月 (℃) 北海道千葉愛知徳山 PLAT DH（通油量） 0 1000 2000 3000 4000 5000 6000 7000 8000 １７年４月５月６月７月８月９月１０月１１月１２月１月２月３月１８年４月５月６月７月８月９月１０月１１月１２月１月２月３月 (KL/D) 北海道千葉愛知徳山 (2H) 徳山 (3H) DH（燃料原単位） 0 2 4 6 8 10 12 １７年４月６月８月 _１０月 _１２月２月１８年４月６月８月 _１０月 _１２月２月 (L/KL) 北海道千葉愛知徳山 (2H) 徳山 (3H) DH（加熱炉O2％（平均）） 0 1 2 3 4 5 6 7 8 １７年４月６月８月 _１０月 _１２月２月１８年４月６月８月 _１０月 _１２月２月 (％) 北海道千葉愛知徳山 (2H) 徳山 (3H) DH（加熱炉排ｶﾞｽ温度） 0 50 100 150 200 250 300 350 １７年４月５月６月７月８月９月１０月１１月１２月１月２月３月１８年４月５月６月７月８月９月１０月１１月１２月１月２月３月 (℃) 北海道千葉愛知徳山 (2H) 徳山 (3H) DH

Draw data of the same unit of each refinery

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14 省エネ活動総括 8.0 8.5 9.0 9.5 10.0 10.5 11.0 11.5 H2 H3 H4 H5 H6 H7 H8 H9 H10 H11 H12 H13 H14 H15 H16 H17 H18 H19 H20 H21 H22 -50 100 150 200 250 300 350 省エネ計画（Ｈ１２起点）省エネ実績・見込（Ｈ１２起点）目標実績・見込み

(3) Target and accomplished value of energy consumption

エネルギー消費原単位省エネ (L/KL) (FOE-KL/Ｙ) Accomplished in 2005 Energy Saving ＰＬＡＮ（Ｖｔ．２０００）ＴＡＲＧＥＴＡＣＴＵＡＬ（ｖｔ.２０００）ＡＣＴＵＡＬ 90 91 92 93 94 95 96 97 98 99 00 01 02 03 04 05 06 07 08 09 10 Consumption -17% +10% +5% Base -10% -15% -5% -20% -25% Consumption/ throughput -20% Target

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- 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.

- Idemitsu and other Japanese oil companies started supplying sulfur free gasoline in January 2005.

- Three years in advance of Government regulation

Greenhouse gas (CO2) reduction target has been set at COP3

Sulfur free gasoline (S=10ppm or less) is required for

better performance of New-engine.

(1) Ultra low sulfur, 10ppm, gasoline production

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2 Sulfur Free Gasoline and Diesel

Sulfur Free Gasoline and Diesel

ⅰ

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Blending ratio of regular gasoline Sulfur originated from

Desulfurization of FCC gasoline is necessary for

producing sulfur free gasoline.

ⅱ

_.

_{Where does Sulfur come from}

0% 50% 100% LP G Str a ig h t-ru n Re fo rm a te F CC-G aso li n e 0% 50% 100% LP G St ra ig h t-ru n Re fo rm a te FC C -G aso li n e

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17 0% 50% 4 5 6 7 8 9 10 11 12 13 Carbon Number 0% 50% Me rcapt an Thio phen e Alkyl -Th Benz o-Th Feature of FCC Gasoline Light Heavy

Sulfur distribution Olefin distribution

ⅲ

_.

_{HDS of FCC gasoline}

Sulfur Olefin RON

Light fraction low high high

Heavy fraction high low low

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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 Heavy fraction HDS unit Desulfurized FCC Gasoline Light fraction FCC Gasoline Caustic wash

Optimum process flow scheme

SPLITTER

HDS of FCC gasoline (Cont

’

d)

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19 Resid HDS RFCC Caustic wash (Existing) HDS unit (New) Light Heavy Desulfurized FCC Gasoline

Hokkiado / Aichi (AR conversion type refineries)(AR conversion type refineries)

(1) Installation of FCC gasoline HDS unit

- Utilize existing caustic wash

- Install HDS unit (Prime-G+)

ⅳ

_.

_{Revamp in IKC}

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20 Crude unit Crude unit ARDS unit DSAR sulfur DSAR sulfur 0.25 0.25～～0.55wt%0.55wt%

High octane value

gasoline material gasoline material AR sulfur AR sulfur 3.0 3.0～～4.5w%4.5w% RFCC unit Splitter FCC gasoline FCC gasoline sulfur sulfur：：3535～～65ppm65ppm Splitter Gasoline HDS HDS heavy FCC gasoline sulfur：8～13ppm Light FCC gasoline Light FCC gasoline sulfur sulfur：：1010～～15ppm15ppm Ca ustic wash Ca ustic wash FCC gasoline sulfur FCC gasoline sulfur 45 45～～75ppm75ppm（（beforebefore）） 8 8～～13ppm13ppm（（afterafter））

Revamp in IKC (

Cont

’

d

)

Middle east Middle east crude oil crude oil Light FCC gasoline Light FCC gasoline sulfur sulfur：：88～～13ppm13ppm

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- Achieved to produce low sulfur FCC Gasoline - Acceptable Octane loss.

Product quality and Octane loss

ⅴ

_.

_{Performance of FCC gasoline HDS unit}

-10 -5 0 5 10 15 20 0 200 400 600 800 Days on stream F C C G a s o lin e S u lf u r [w tppm ] -2 0 2 4 6 8 10 O c ta n e lo s s [-] Base

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22 •

• IKC started supplying sulfur free gasoline at all of its four IKC started supplying sulfur free gasoline at all of its four refineries in January 2005.

refineries in January 2005.

•

• Maximum utilization of existing unit capacity and Maximum utilization of existing unit capacity and

installation of proper process saved initial investment

significantly.

•

• Operation of FCC gasoline HDS unit is satisfactory. Operation of FCC gasoline HDS unit is satisfactory. Future optimization will be focused on

Future optimization will be focused on

-- Management of catalyst cycle length.Management of catalyst cycle length.

-- Investigation of optimum operation conditions Investigation of optimum operation conditions ex. splitter cut ratio vs. HDS Rx severity

ex. splitter cut ratio vs. HDS Rx severity

ⅵ

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23 ⅰ. Background

• The demand to improve diesel-exhaust emissions urged stringent regulation for diesel fuel quality.

Sulfur content (ppm)

1992

1997

2004

2007

₂₀₀₇

The quality regulations of diesel fuel in Japan

2000 500 50 10

2003

<50ppm

Jan. 2005

<10ppm

HDS conversion: 80% 95% 99.5% 99.9％

ULSD production started earlier than government target.

• Step1: Application of new highly active catalysts without major revamp

ⅱ. Strategy to meet the target

• Step2: Revamps of the unit (ex. Additional reactor)

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24 • Catalyst evaluation technique is one of the keys for saving

the cost of revamps and producing high quality fuels.

Chiba Aichi Tokuyama

Revamps

Catalyst IKC developed catalyst Refinery No revamp No revamp •Installation of amine scrubber •Increase of MU compressor capacity

ⅲ. Revamp for 50ppm [2003~]

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25 • 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 .

Chiba Aichi Tokuyama

Revamps

Catalyst New highly _{active catalyst} Refinery •Additional Rx. No revamp •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）

ⅳ. Revamp for 10ppm [2005~]

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ⅴ

_.

_{ULSD unit operation for 40ppm and 10ppm}

40

40ppmppm 1010ppmppm

Rx WAT

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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 7Nm3/KL

（→ Depend on operating condition and feedstock

properties.）

ULSD unit operation for 40ppm and 10ppm

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ⅵ. Conclusions for Diesel HDS

•

• Unexpectedly, catalyst deactivation rate in 10 ppm

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

Hydrogen consumption is higher by 7Nm

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_{/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.

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3 Conclusions

Conclusions

(1)

Energy conservation

Unit Energy consumption for 2008 is expected to be

lowered by 20% from 1990 levels.

cf

. Japanese petroleum association

’

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

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4 Challenge in the future

Challenge in the future

Approach for reinforcing competitiveness of refinery

(1) Bottom of the barrel technologies

・

Introduction of heavy oil upgrading process

_{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

_{High operating ratio by continuous unit operation}

・

_{Long HDS catalysts life}

ex. two years to four years for ULSD catalyst

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OCR OCR

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OCR Reactor system

Feed + H2 H2 Quench

to Spent Catalyst Hopper

from Fresh Catalyst Hopper High Pressure Catalyst Vessel OCR Reactor OCR Outlet to Fixed Bed RDS Rx (OCR：On stream Catalyst Replacement)

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