FAME Blended Diesel Fuel Specification in Japan Vehicle Fuel Quality Workshop Petron Mega Plaza Makati City, Metro Manila Katsuro FURUI Fuel & Lubricant committee Japan Automobile Manufacturers Association

Outline Fuel Quality Impact on Vehicle Characteristics of FAME FAME and Diesel Fuel Specification in Europe METI FAME Conformity Tests 4.1 Properties of Test FAME 4.2 FAME Properties to be remarked 4.3 Summary of Test Results 4.4 Key Properties 4.5 Development of New Oxidation Stability Tests 4.6 Remained Issues Fuel Regulation for B5 in Japan Future Plan of METI

1. Fuel Quality Impact on Vehicle Safety Corrosion and degradation of rubber material Fuel leakage Damage to fuel system and engine Sudden stop and Engine broken Environment Damage on After treatment System, Impacts on Air Fuel Management and Deposits etc. Emission Increase Performance Impacts on Air Fuel Management and deposits etc. Poor driveability and Engine stall

2. Characteristics of FAME Difference of Raw Material Impacts of Refining Process Quality after blending is different by base diesel fuels and FAME to be blended. Remaining Glyceride by insufficient Refining Easy to oxidize Easy to produce Sludge Remaining Methanol, water, metals etc Not to remove agricultural chemical Easy to form Wax Bio Diesel (FAME) is mixture of many components like Olein and Stearine. Characteristics of FAME depend on raw materials and refining process. Each specification of FAME should be decided based on the relation between each property and vehicle performance. Both FAME to be blended and base diesel fuel affects quality of FAME blended diesel fuel.

3. FAME Specification in Europe (EN14214)

Diesel Fuel Specification in Europe (EN590) Definition of FAME is EN14214. EN590 just refers EN14214 and does not have properties related to FAME characteristics like methanol and glycerides.

4. METI FAME Conformity Tests 4.1 Properties of Test FAME unit g/cm3 ℃ mass% ppm hrs. Metal Na K Ca Mg P ｍ㎡ /s mgKOH/g mg/100ml Tri-glyceride Free glycerol Total glycerol Methanol Content Linolenic acid methyl ester Mono-glyceride Di-glyceride Total Contamination Sulfated Ash Content Copper Corrosion Ester Content Iodine Number Sulfur Content Kinematic Viscosity Total Acid Number Cetane Number 10% Carbon Residue Water Content Oxidation Stability (EN14112) Property Density Flash Point CFPP EN14214 Limits 0.860 - 0.900 120 min - 51 min 0.3 max 500 max 6 min 120 max 10 max 3.5 - 5.0 0.5 max 24 max 0.02 max 1 max 95.5 min 0.2 max 12 max 0.8 max 0.25 max Na+K 5 max Test FAME 0.8768 182.0 +8 57.5 0.15 140 6.33 74.1 <1 <3 4.355 0.11 1.5 <0.001 1a 99.8 0.03 3.2 0.12 0.046 0.072 0.005 0.048 Ca+Mg Note) Test FAME consists of PME:RME:SME=60:38:2 and is blended in commercial diesel fuel by 5v%.

4.2 FAME Properties to be remarked in order to prevent trouble in the market Estimated Trouble Damage on Fuel Line Parts Metal corrosion, Rubber Swell etc. Acid Value Methanol Oxidation Stability Poly unsaturated fatty acid methyl ester content Ester content Tri-glyceride Mono-glyceride Di-glyseride Glycerine Solid foreign material water Cold performance (PP, CFPP, CP) Metals Phosporous Pump Failure sticking adhesive material Filter plugging Engine stop by stopping fuel supply Worsen exhaust gas Hard start at low temperature Deterioration of after treatment system

4.3 Summary of Conformity Tests Little Impact with up to 10v% Pass Emission Test Observation of no trouble with B5 Vehicle Durability Test (LDV, IDI) Flow loss and Wear in Injectors with B5 Fail HD, DI LD, DI LD, ID Wear in Injectors with B5 FIE Durability Test Same as diesel fuel with B5 Fuel Hose Test Fuel Pipe Test Corrosion and melting plating in Tern Sheet and Bonde Fuel Tank Test Fuel Filter Test Slight Degradation Long Storage Test Poor Startability － Cold Performance Corrosion in Tern Sheet Material Compatibility Summary Results Test Items Metals Rubber & Plastics No effects of Ester as far as less than 5v% Fuel Line Parts Test Engine Durability Test

Detail and Estimated Cause Engine durability Tests (HDE) Flow loss FIE durability tests Abrasive wear in Injectors (Both Bosch and DENSO) Fuel tank tests and metal dipping tests Melting plating, Corrosion Poor oxidation stability Organic acids present Test Observations Possible cause injectors The cause of the wear is unclear. Hard solid particulates (SiO2 ?) or FAME itself ? － － under examination Review of the requirements on Oxidation stability and Acidity Is necessary.

Example of Test Results - Fuel Tank Tests - Test Fuel: Commercial diesel fuel blended the FAME meets EN14214 by 5vol% Fuel Tank Lower Fuel Tank Upper

4.4 Key Properties Through the conformity tests, oxidation stability and Total Acid Value (TAN) are specially reviewed as key properties. Oxidation Stability Corrosion was observed in fuel tank test though FAME used in the tests meets EN14214. The cause is lack of oxidation stability. Oxidized FAME produced organic acid during tests. Base diesel fuels also affect oxidation stability after blending FAME. It means oxidation stability should be set in the diesel fuel specification. Diesel fuel oxidation stability test (ISO 12205, ASTM D2274) can not discriminate as being blended poor quality FAME. It is essential to develop new test method for oxidation stability of diesel fuel.

4.4 Key Properties (cont,) TAN Relation between Corrosion and TAN is not linear. Lighter molecule organic acids like formic acid, acetic acid and propionic acid shows higher corrosivity. Lighter molecule organic acids corrode metals at low acid. Lighter molecule acids are produced by oxidization of FAME during storage. Both TAN and high corrosive individual organic acids should be set in the FAME blended diesel fuel specification. Acid type of Lubricity Improver (LI) increases TAN of base diesel fuel. This should be considered. In Japan, all acid type LI contains corrosion inhibitor, so no corrosion by LI was observed.

Key Properties - Oxidation Stability Test Fuel: Commercial diesel fuel blended the FAME meets EN14214 by 5vol% Test Fuel: Same FAME above with 400ppm of anti-oxidant (20ppm as B5)

Key Properties – Oxidation Stability 200 400 600 800 5 10 15 Dosage of Anti-Oxidant Agent, ppm (as B100) Oxidation Stability, Hr by Ranchimat Test FAME (Fail) (Pass)

Key Properties – Individual Organic Acid Test Condition 80 80 deg.C deg.C Fuel Fuel Cup Cup FAME 5% TAN 0.088 mgKOH/g Acetic Acid 30 ppm Oleic Acid 300 ppm No Corrosion after 384 Hrs 5% 0.107 mgKOH/g 50 ppm 300 ppm Pitting Corrosion after 120 Hrs

Adaptation of B100 Oxidation Stability Test (Rancimat method) to B5 4.5 Development of New Oxidation Stability Tests Adaptation of B100 Oxidation Stability Test (Rancimat method) to B5 PME 5% PME blended Diesel Fuel No clear clipping point in B5 is observed. It will be difficult to adapt the rancimat test method that is for B100 to B5.

4.5 Development of New Oxidation Stability Tests (Cont,) Current diesel fuel oxidation stability test (ISO 12205, ASTM D2274) shows poor discrimination performance. 30 25 g/m3 max (EN590) 20 Sludge of B5, g/m3 10 FAME Test FAME Test FAME w/anti oxidant Wasted Cooking oil ME SME Oxidation Stability of FAME, Hr 6.3 9.8 3.8 0.5 * FAME was blended into JIS No.2 diesel fuel by 5v%

4.5 Development of New Oxidation Stability Tests (Cont,) Temperature is key parameter as acceleration condition. New test method is almost same as current test method but the temperature is changed to 115 deg.C from 95 deg.C. Test Condition : ASTM D2274 Test duration : 16 Hrs Test temperature : 100 – 120 deg.C 1 2 3 4 5 6 7 95 100 105 110 115 120 125 Testing Temperature, deg.C TAN ,mgKOH.g No difference In samples Wasted cooking oil ME(3%) + SME(2%) Wasted cooking oil ME(5%) Palm oil ME(5%) JIS No.2 Diesel fuel

4.6 Remained Issues Through the conformity tests, two issues, Injector wear and developing oxidation stability tests for sludge are remained. Wear of Injectors Injector wear was observed in HD engine durability tests and FIE durability tests. It is estimated that solid contamination caused abrasive wear as FAME was blended. But the mechanism is not clear. It will continue to analyze the mechanism. Developing oxidation stability test for sludge formation Oxidation stability tests to evaluate acid formation and sludge formation would be necessary. For sludge evaluation, the lack of reproducibility was main issue. It will continue to improve the test method.

5. Fuel Regulation for B5 in Japan Six properties related to FAME characteristics were added to the current diesel fuel regulation. That is, Ester content, Triglyceride, Methanol, Total Acid Number (TAN), Individual organic acid (Formic acid, Acetic acid and Propionic acid) and Oxidation stability to evaluate acid formation because these items have a possibility of significant impact on vehicle performance from the viewpoint of safety and environments. B100 specification also develops as JASO standard, that is volantly specification and just a guideline at same time. In addition, for the oxidation stability of FAME blended diesel fuels, new test method was developed because the current oxidation stability, ISO 12205/ASTM D 2275 set in EN590 shows poor discrimination performance.

5. Fuel Regulation for B5 in Japan (Cont,) FAME content Up to 5v%. It means diesel fuel can contain 5v% of FAME as far as meet this regulation. Triglyceride content Less than 0.01 mass%. Triglyceride affects filter plugging, deposit formation in Fuel Injection Equipment (FIE) and Injector nozzle deposits. This requirement is same level as European specification. This requirement plays the role of the indicator to confirm that the adequate quality of FAME meet JASO standard is blended. Methanol content Less than 0.01 mass%. Methanol affects corrosion. Methanol is one of raw material of FAME. As adequate FAME meets JASO standard was blended, methanol content should be less than 0.01 mass%.

5. Fuel Regulation for B5 in Japan (Cont,) TAN 0.13 mgKOH/g max. It was set to prevent corrosion. In 0.13 mgKOH/g of TAN value, “0.03” derives from FAME and “0.10” is from diesel fuel itself. Japan's diesel fuel added lubricity improver (LI). Especially, acid type LI increases TAN of diesel fuel up to “0.10” at maximum case in Japan. However, all Acid type LI in Japan contains corrosion inhibitor. No corrosion by LI with this level of TAN was observed in the conformity test. If Acid type LI does not contain corrosion inhibitor, this figure should be reviewed. The value of “0.03” from FAME is same level as European specification. Individual acid Total amount of Formic acid, Acetic acid and Propionic acid should be less than 30ppmw. These lighter molecule organic acid are produced through oxidation of FAME and are very corrosive. Even TAN lowers 0.13mgKOH/g, corrosion will happen as these acids are contained.

5. Fuel Regulation for B5 in Japan (Cont,) Oxidation stability The limit is 0.12 mgKOH/g max as Acid Value Growth after oxidation stability test. New oxidation stability test to evaluate acid formation was developed because current oxidation stability test of diesel fuel, ISO 12205/ASTM D 2275 that is set in EN590 ( European diesel fuel specification ) shows poor discrimination performance. Main difference between current test and newly developed test is testing temperature. Former is 95 deg.C and the latter is 115 deg.C Sludge produced through the oxidation of FAME also has a significant impact on vehicle performance. So, it should be controlled by the FAME regulation and should be controlled by fuel regulation. The oxidation stability test to evaluate sludge formation was also studied. But it could not be completed. It will be continued to develop and be added in diesel fuel regulation in future.

Specification of Diesel Fuel in Japan Items Sulfur Cetane Index T90 FAME content Methanol Trigriceride TAN Individual Organic Acid Oxi. Stability (Sludge) Oxi. Stability (Acid) Level 50 ppm max *1) 45 min 360 deg.C max 5 mass% max 0.01 mass% max 0.13 mgKOH/g max 30 ppm max *2) - *3) 0.12 mgKOH/g as growth mandatory To be added *1) 10ppm max from ’07 *2) Total of Formic, Acetic and Propionic acid, *3) Continue to develop new test method

Specification of B100 for Diesel Fuel Blend Limit Test method Ester content mass% 96.5 min EN 14103 Density g/ml 0.86 - 0.90 JIS K 2249 Kinematic Viscosity mm2/s 3.5 - 5.0 JIS K 2283 Flash Point Deg.C 120 min JIS K 2265 Sulfur ppm 10 max JIS K 2541-1, -2, -6 or-7 10% Carbon Residue 0.3 max JIS K 2270 Cetane Index 51 min JIS K 2280 Sulfated Ash 0.02 max JIS K 2272 Water 500 max JIS K 2275 Total contamination 24 max EN 12662 Copper Corrosion 1 max JIS K 2513 Acid value mgKOH/g 0.5 max JIS K 2501, JIS K0070 Oxidation Stability Iodine Number gI/100g 120 max JIS K 0070 Linolenic acid methyl ester 12.0 max Methanol 0.20 max JIS K 2536, EN14110 Mono glyceride 0.80 max EN 14105 Di glyceride Tri glyceride Free glycerine 0.02max EN 14105, EN14106 Total glycerine 0.25 max Metals (Na + K) 5max EN 14108, EN 14109 Metals (Ca + Mg) 5 max prEN 14538 Phospourus EN 14107 Pour point CFPP Specification Agreement between producer and distributor Items Voluntary spec. as JASO/JIS Almost same as EN specification (EN14214) except for oxidation stability and cold performance. Because oxidation stability after blending FAME is quite different by base diesel fuels.

Fuel Regulation Difference between Europe and Japan Europe Japan Sulfur Density : FAME 5v% max *) *) FAME must meet EN14214 Sulfur Density : FAME 5v% max Glyceride Diesel Fuel　Spec. Five properties related to FAME refer EN14214 Ester 96.5 v% min TAN : JASO Ester 96.5 v% min TAN : FAME Spec. Voluntary Spec.

Fuel Regulation Difference between Europe and Japan Europe Japan The government can not discriminate if the FAME meet the EN14214 or not at the pump after the FAME was blended into diesel fuel. It is essential for the quality control of the market fuel that the government must have the regulatory structure to confirm the quality of the FAME before blending and the FAME was blended into diesel fuel. FAME blended diesel fuel is far easily oxidized than normal diesel fuel. Even though the FAME meets the specification, quality of FAME blended diesel will not be controlled. Because the influence of distribution system including storage period and house keeping is not considered. Japan The fuel regulation in Japan can not ensure all of quality in FAME specification after the FAME was blended into diesel fuel. However, the key properties that have significant impacts on vehicle performance from the view point of safety and environments can be controlled at the pump. The limit of glyceride and methanol plays a role of measure for the refining level of FAME.

6. Future Plan of METI Making Regulation Public comment　(JPN): June 22th to July 21th Public comment　(Eng): Aug 1th to Aug 16th http://www.meti.go.jp/english/information/data/0608cPubComBDF.html Notice to WTO : 3 months after Public comment Issues : End of 2006 Enforcement : March 2007 Conformity Test of Distribution System in Japan METI has a plan to evaluate the issues of handling FAME blended diesel fuel in actual distribution system.

JAMA Recommendation Diesel fuel specification blended FAME in Japan was decided based on technical studies for more than two years testing. The expenses for the studies amount to more than 400 million JPY and main research institutes and associations in Japan participated ( METI, AIST, JARI, JAMA, JPI, PAJ ). JAMA strongly recommend the governments to adopt Japanese specification. B100 specification is not enough to ensure the quality of FAME blended diesel fuels at the pump because base diesel fuels also affects oxidation stability of FAME blended diesel fuels.

JAMA Recommendation (Cont,) Good house keeping and management in distribution system would be necessary because FAME blended diesel adsorb moisture and oxidized easily. Japan’s diesel fuel regulation and B100 specification is for up to 5v% of FAME blending. As introduction of more than 5v% of FAME is discussing, both diesel fuel and B100 specification should be reviewed based on technical data. It will be more preferable to utilize "BTL (Biomass To Liquid)" or "Hydrotreated Vegetable Oil" as compared to the use of FAME from the technical view points.