JDF Developments & Industry Initiatives

Kaoru FujimotoChairman

Japan DME Forum (JDF)

4th International DME Conference

Hilton Stockholm Slussen, Stockholm, 6-9 September 2010

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Contents

・ Japanese Government Policies related to DME

・ Organizations and its Activities for DME

・ DME Production Technology Update

・ DME Utilization Technology Update

・ DME Promoting Activities

・ Conclusion

Government Policies related to DME

Organizations and its Activities for DME• Public organization conducting R&D on DME

• Private organization for DME promotion

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Governmental Policies related to DMEGHG emission reduction target in 2020 has been enforced in September 2009.(exPM Hatoyama)• 25 % reduction target of GHG emission in 1990 has been announced in COP15 in Copenhagen. Law Concerning Promotion of the Development and Introduction of Alternative Energy has been amended in August 2009.(METI)• Electricity, City gas and Petroleum industries are obliged to introduce non-fossil energy. For the moment, this obligation is not applied to LPG industry.Environmental quality standards for PM2.5 is effective since September 2009.(MOE)• Annual standard for PM2.5 is less than 15.0 g/m3 and 24 hour standard less than 35g/m3. Achievement date is not yet fixed.

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Public Organizations conducting R&D on DMENTSEL(National Traffic Safety and Environment Laboratory)• For promotion of practical use of DME vehicles, Public road running tests being conducted to evaluate durability and reliability, and to collect data for a technical guideline.AIST(National Institute of Advanced Industrial Science and Technology)• Promote Technology developments of DME fueled engine and prototype vehicle, Standardization of DME.• Research for effect of lubricity improver and impurities on engine performance.LPG Center of Japan • Promote R&D for practical use of fuel grade DME mainly in LPG market of household and commercial use. • DME/LPG mixture combustion test by existing home appliances specified to LPG.

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Private Organizations for DME promotionJapan DME Forum• established in 2000. 36 corporate and 40 individual members.• Promote Awareness of DME and Information exchange from production to utilization of DME, Economic evaluation and LCA study, and Standardization work of fuel DME. • International activities with IDA,CDA,KDA,etc.DME Promotion Center• established in 2004 by 11 private companies(upstream).• Study of DME introduction scenario into Japan market for short- and long-terms.• Operation of a governmental subsidy program for DME boiler investment. DME Vehicle Promotion Committee• established in 2006 by 17 private companies(upstream & downstream).• Promotion of R&D for practical use of DME vehicle, DME supply infrastructure and safety tests, Standardization of DME filling station for vehicles and Deregulation for distribution network.• Study of Bio-DME production and its use for vehicle.

DME Production Technology Update

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DME Production Technology (1)• Fuel DME product Co. (Japan) has constructed 80 Kt/y commercial plant at Niigata Japan, supplying Fuel DME to customers in near region.

Plant OutlinePlant OutlineProducts: Fuel grade DME

Purity 99% (according to JIS TS)Annual Production Capacity:80,000ton

expandable to approx. 100,000tonPlant Construction Amount:

Approx. 2.5billions Japanese YenFeedstock: Imported Methanol

Transportation by pipeline form Mitsubishi Gas Chemical (MGC)’s owned existing Methanolimport terminal at Niigata East Port to MGCNiigata Factory

Production Process: MGC Methanol Dehydration Process(commercially established technology)

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DME Production Technology (2)

”DME Direct Slurry Process”(ex JFE process: one-step DME synthesis process)

Licensor: Total, Inpex, Japex, Toyota Tsusho

Originally developed by JFE, then demonstrated through multiple-year operation of 100 t/d demonstration plant by a consortium of 10 companies*, this technology is now owned jointly by the above 4 companies who are willing to work with potential partners for a commercial utilization. * the demonstration project was completed

and the plant no longer exists

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DME Production from Multi-resourcesDME can be produced from such stranded resources as;• CO2 rich natural gas• Coal (Sub-bituminous to Lignite)

DME produced from coal emits 1.5 times CO2 by calorie of coal, but if DME is used at home as cooking fuel, life cycle CO2 is even less than coal fired cooking stove. CO2 sequestration should be integrated to DME production in future.

• Biomass Bio-DME is a Second generation Biomass fuel which has no conflict

with food supply.• Remote renewable electricity resources as Wind, Solar, Hydro power,etc.

DME has a big potential as energy carrier from remote resources.

DME Production from Biomass and its use• Bio DME was produced by bench scale plant of Hiroshima Biomass research center of AIST in the joint research project with DMEVPC. • Eucalyptus chip was gasified with oxygen enriched air(O2 31.5%) in downdraft gasifier and a part of synthesis gas was supplied intosynthesis reactor after gas cleaning. [ presented by Dr.Miyazawa]• Produced DME was mixed with DME from Niigata plant, and used for the first DME truck test run with Bio DME on May 18 at Yokohama LP Gas terminal. [ presented by Mr.Mikita]

Eucalyptus chips Downdraft gasifier DME synthesis equipment

Potential of DME as Energy carrier

Liquid H2 Liquid Ammonia

Methanol DME CO2

Formula H2 NH3 CH3OH CH3OCH3 CO2Liquid density [kg/L] 0.07 0.7 0.795 0.67 1.1Boiling point [℃] @0.1Mpa

－253 －33.4 64.4 －25 (－50)*1

Vapor pressure [Mpa] @25℃

－ 1.02 0.0129 0.53 (0.7)*1

Energy density by Weight [MJ/kg]

120.8 19.2 21.1 28.8 －

Energy density by Volume [MJ/L]

8.5 13.4 16.8 19.3 －

Explosion limit [%] 4～75 15～28 6.7～36 3.4～27 －

Allowable limit of toxicity

－ 25ppm 200ppm － －

*1: Marine transportation condition of liquid CO2

• DME is promising as Energy carrier from remote resource for high energy intensity by volume and safety aspect.

Conversion efficiency estimation from Electricity to DME

(1) Electrolysis of water 6H2O+Electricity→6H2+3O2

(2) Reverse shift 3H2+3CO2→3CO+3H2O(3) DME synthesis 3H2+3CO→CH3OCH3+CO2

(2)+(3) 6H2+2CO2→CH3OCH3+3H2O(4) Total system 3H2O+2CO2 +Electricity→CH3OCH3+3O2

Renewable Electricity

Electrolysis

H2Reverse Shift

CO+H2DME synthesis

DME

0.01Kmol-H2/KW (4KW/H2-Nm3)

1Kmol(CO+H2) /KmolH2

0.15KmolDME/Kmol(CO+H2)

1KW(3.6MJ) (100%)

2.4MJ(67%) 2.6MJ(72%) 2.0MJ(55%)

69g(103mL)CO2 220g(100mL)

( E-mail: ohno@dmeforum.jp )

DME Utilization Technology Update

• DME/LPG Mixture

• DME Vehicle

• DME as Chemical feedstock

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DME/LPG mixture combustion testVaporized gas composition from liquid DME/LPG mixture container• DME concentration in gas is not constant and slightly increases with vaporization. In order to keep lower than 20% in gas, initial DME concentration in liquid should be less than 15%.

Initial liquid DME concentration (wt%)

10 15 20 40

Initial DME concentration in gas (wt%)

9.4 13.7 18.8 33.7

Final DME concentration in gas (wt%)

10.9 17.1 24.8 52.1

Home appliances performance• Up to 20% DME in gas, DME/LPG mixture can be used as same as LPG for Tabletop stove, Infrared stove, Hot-water unit, 40% with minor modification (Nozzle diameter, Air damper opening and so on). • No degradation of performances for 1,000 hours (cumulative combustion time) on these appliances.

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DME/LPG mixture combustion testThermal efficiency of LPG appliances• Thermal efficiency is almost constant, independent on DME concentration of DME/LPG mixture, a little better than that with Propane.

LPG appliance(Maximum output)

DME content in gas (wt%) DME content in liquid (wt%)

0 10 15 20 20 30 40 50

Tabletop gas stove(4.21kw)

54.0 55.7 56.0 55.3 54.8 54.9 56.4 55.3

Tankless gas hot-water heater (10.5kw)

84.2 83.2 84.2 84.5 84.6 84.7 84.4 84.4

Hot-water unit(43.6kw)

77.4 78.1 78.8 77.6 77.9 77.6 77.6 76.8

with small change of equipment

( E-mail: hirohata@lpgc.or.jp )

Developing DME tolerant rubber materials

• Among the versatile rubber materials, EPDM (ethylene propylene diene Monomer) with high Ethylene content has smaller swelling-rate against DME than others.

• By blending above EPDM as base-rubber and low molecular weight Polyethylene, which has well compatibility with EPDM, Japanese firms have succeeded in developing the versatile rubber which is superior in DME tolerance.

• Based on this technology, they established two kinds of practical blend-rate having different hardness, obtained basic property and carried out tests with actual equipment. Finally, they confirmed that all these rubber materials can be used as DME sealing rubber withoutany problems.

• This result was applied to patent on January 20, 2010 in Japan.

Application No. : 2010-10037 “DME tolerant rubber composition”(E-mail: Yokoi-y@nichias.co.jp )

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DME Diesel Vehicle Public Road Tests• NTSEL: Medium duty truck verification road test for commercial freight

Project sponsorship: Ministry of Land, Infrastructure and TransportProject partners: ISUZU ADVANCED ENGINNERING CENTER., Niigata Prefecture, JAPAN DME, Idemitsu Kosan.Project schedule: November 2009-March 2012, 3 yearsSpecifications of Middle duty-trucks: ISUZU ELF, GVW 7.9 tons, 5.2 litre DME engine, Common rail DME injection system, 2009 H/D regulation compliantVerification road test area: Niigata and Kanto with each DME filling station supplied from Fuel DME Production Co., Ltd.

Project sponsorship: Ministry of Land, Infrastructure and Transport Running test: December 2006 - September 2009Specifications of Light duty-truck: ISUZU ELF, GVW 5.0 tons, 4.8 litre DME NA engine, Common rail DME injection system, In-tank feed pumpRoad test : Test course, high way, urbanDurability: Engine valve seat wear, injector nozzle seat wear and Oxidation catalyst deterioration were found important.Practicality: The use through the season has been confirmed. [presented by Mr.Takase]

• ISUZU: Light duty truck 100,000km without serious trouble.

[ presented by Dr.Sato]

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Fundamental researches for DME EngineEffect of lubricity improver and impurities in DME

[presented by Dr.Oguma]

0

200

400

600

800

1000

0 200 400 600 800 1000

WS1

.4 [μ

m]

Water Contamination ratio [ppm]

Water contaminationwith LI 100 ppm

Average of WS1.4 of diesel fuel: 450μm

• Adding 100ppm of fatty acidbased lubricity improver (LI)gives diesel level lubricity toDME.

• Excess adding fatty acid basedLI increases fuel acid valuewhich is a factor of corrosion.

• Water contamination impact onwear scar of fuel injection parts.

• There is no effect of methanolcontamination on wear scar. DiskDisk

FuelFuelStroke:Stroke:1 mm x 50 Hz1 mm x 50 Hz

Y

X

Y

X

Fundamental researches for DME EnginePM emission from DME engine

• Most of PM from DME engine is generated from oils lubricating engine and injection pump, which are core of PM.

• Nano-particles number emitted from DME engine are very few level with oxidation catalyst.

• Impurities with larger carbon numbers might increase nano-particle numbers. ( E-mail: mitsuru.oguma@aist.go.jp )

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100 120 140 160 180 200

Reference DMEwater5%Methanol5%

CPC

cou

nt [x

109 #/

cm3 ]

Time from test start [sec]

00.20.4

0.60.8

1.0

1.21.4

FAME5%

Propane5%

Developing DME High Speed Filling System

P

Pump

DME Storage Tank Filling Equipment

used for LPG VehicleDME middle/heavy-duty truck with

250 to 600 Liter storage tank

Fuel storage tank

Pressurized Filling

SystemP

Pump

DME Storage Tank Filling Equipment

used for LPG VehicleDME middle/heavy-duty truck with

250 to 600 Liter storage tank

Fuel storage tank

Pressurized Filling

System

Pressure Sensor

Pressure balanced filling systemDME middle/heavy-

duty truck

Filling equipment Integrated nozzle for filling and vapor return lines

FMP

Flow meter for liquid DME

Level sensor

Transmitter/Receiver Communicating

level signalPT2

PT1

Liquid lineVapor line

2-stage cut-off valve

Storage tank

Fuel storage tank

Pressure Sensor

Pressure balanced filling systemDME middle/heavy-

duty truck

Filling equipment Integrated nozzle for filling and vapor return lines

FMP

Flow meter for liquid DME

Level sensor

Transmitter/Receiver Communicating

level signalPT2

PT1

Liquid lineVapor line

2-stage cut-off valve

Storage tank

Fuel storage tank

Necessity to improve filling speed up to the level of Diesel oilNecessity to improve filling speed up to the level of Diesel oil

Present System

20 to 30Liter/Min.

DevelopedSystem

Secured 80 Liter/Min.

Newly developedHigh SpeedFilling Equipment

Newly developedIntegrated nozzlefor Filling and Vapor lines

(E-mail: amemori@tokicotechno.co.jp )

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New Combined Process of DME to Olefins・CH3OCH3 → X → CnH2n + H2O ・Atmospheric ～ Slightly Pressurized・DME + Diluent : Reaction Control・Solid Catalyst : Zeolite (MFI) + binder + additive

0%

10%

20%

30%

40%

50%

60%

70%

80%

90%

100%

0.04 0.05 0.06 0.07 0.09 0.11 0.12 0.15 0.19 0.37 0.47 0.49 0.75 1.01 1.5 2.5 3

W/F (g・h/mol)

Prod

uct d

istri

butio

n . C

.%

C2=

Ar

C6

C5

C1-4

c-C4=

t-C4=

1-C4=

i-C4=

C3=

Conv.DME0

5

10

15

20

25

30

35

40

45

0 0.5 1 1.5 2 2.5 3

W/F

produ

ct

dist

ribu

tion C

.% C3=

C4=

C1-4

C5

C6

Ar

C2=

DME+MeOH

methylationpolymerization hydrogen transfer

Crackingdesorptionadsorption

＊ adsorbed species

cokes

MeOH DME

C1*

C2*

Zeolite

Aromatics

C4－C2＝ C5－

-H2O

C3－

C3* C4* C5*

CH4

C2－ C3＝ C4＝ C5＝

C5*C6*

C7*

C3＝

C4＝

C5＝

C6*

Reaction model of New Combined Process

Propylene : 45% (one pass)75～80% (recycle)

Ethylene 5～10%Aromatics + paraffin 15～20%・ Catalyst life : > 10,000 hr・ On the way to Industrialization

( E-mail: fujimoto@env.kitakyu-u.ac.jp ) 24

DME reaction Olefins Hi Olefins

Propylene

Total system performance estimation

DME Promoting Activities

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Standardization Activities on DME Fuel• Standardization in Japan• JDF has worked, in 2005, drafted TS(Technical Specification) for DME

standard for industrial and power generation fuel excluding internal combustion equipment as diesel engine.

This TS will be finalized as JIS with ISO’s progress. • Fuel standards for vehicle are under study in JSAE (Society of Automotive

Engineers of Japan, Inc.). As for vehicle use, effects of impurities and additives on durability and

performance of engine are investigated.

• International Standard• JDF is cooperating on International work for DME standard since 2007 in

subcommittee SC4 and SC5 of ISO/TC28. • New committee, “National Committee for DME Fuel Qualitative

Standardization” has established to support PAJ (Petroleum Association of Japan) who is a domestic secretariat of TC28 in DME standardization field.

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Supplementary edition of DME HandbookDME handbook was published in 2006 and its English edition in 2007. Supplementary edition will cover progress since the last publication. Japanese edition will be published in April 2011 and English edition in October 2011 before 7th Asian DME Conference.Ch.1 DME production (Production system from various resources, Production technologies and Projects)

Ch. 2 Residential use of DME (LPG/DME blend use, Seal materials, Sulfur free odorant and Development of residential DME use)

Ch. 3 Industrial use of DME (Distributed energy use and Chemical use)

Ch. 4 Transportation use of DME (Performance of DME vehicles, Effect of impurities, Lubricity improver and Rapid fueling equipment)

Ch.5 Standardization and Legislation (Standard of fuel DME and Standardization of DME utilization/ancillary system)

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7th Asian DME ConferenceOrganizing committee has just started.Date and Venue16-18 November 2011Niigata Toki Messe Convention Center350km from Tokyo (2 hours by Shinkansen)

ConferenceProduction and consumption business Technology progressStrategy

Site visitFuel DME Production Co. 80,000ton/year DME production plantDME consumer factory Commercial-use DME vehicle and Fueling station

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Conclusion• Coal to DME is important to supply DME as clean fuel in energy demand growing countries.

• Bio-DME is a key to open DME market in energy saturated countries as Japan.

• DME diesel vehicle can correspond to much stronger environmental regulation,such as “Particle number regulation” in near future.

• DME is also promising as chemical feedstock.

• As Potential market is so huge, International cooperation such as Standardization,DME vehicle promotion and utilization technologies can contribute to “Low Carbon World”.

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Thank you !!!

A Warm Welcome to Niigata in November 2011!!