World Trends of BiodieselWorld Trends of Biodiesel StandardsStandards

世界的生物柴油规格讨论的动向世界的 物柴油规格讨论的动向

China Roundtable 2008China Roundtable 2008Beijing, China

February 13 2008February 13, 2008

K t FURUIKatsuro FURUIFuels and Lubricants Committee

JAMA 1

Japan Automobile Manufactures Association

Bio Diesel in the WorldRape seed esterSunflower esterWaste cooking oil ester

Soy bean esterE-dieselg

Waste cooking oil ester

Crude Palm Oil

Refined Palm Oil

Jatropha Curcas ester

Crude Coconut OilCrude Palm Oil

Palm esterCoconut ester

- Various type of bio diesel is introducing and developing in many countries

JAMA 2

- Various type of bio diesel is introducing and developing in many countries.- Some countries are also planning to introduce bio diesel.- There is no global specification for bio diesels.

Characteristics of FAMECharacteristics of FAMEDifference in raw material & impacts of refining process

Remaining glycerides byEasy tooxidize

Remaining glycerides by insufficient refining Quality after blending

Easy to produce sludge

Easy to form wax

Remaining methanol,

water,Residue of agricultural form wax water,

metals etc chemicals

- Bio diesel is mixture of several types of FAMEs- Characteristics of FAME depend on raw materials and refining process- Both FAME and base diesel fuel affects quality of finished blends

JAMA 3

- Both FAME and base diesel fuel affects quality of finished blends

FAME：Fatty Acid Methyl Ester

Issues in Fuel Distribution SystemFAMEProduction

St T k

Spec. FQMS Many Chance of Quality Change in distribution

StorageO idi tiStorage Tank

Transport

FAMEin distribution •Oxidization

•Moisture

Transport / FuelingBlending•Contamination

PipelineLorryVesselTrain

Transport Transport / Fueling•Contamination(metal, rust, other fuels)•Moisture

•Moisture•Poor mixing

Transport

Train

Lorry, Vessel

Storage TankFAMETerminal

Refinery

Filling Station FQMSDistribution

Fueling

BlendGasOil

In lineblend

Storage

UndergroundStorage Tank

Oil

Gas Bxx Bxx

Storagein vehicle fuel tank

JAMA 4In tank blend Terminal

GasOil

Bxx Bxx StorageTank

FAME Blended Diesel Fuel in JapanConformity tests were also conducted for vehicles that has already been used in the market.Evaluation was conducted with the fuels basedEvaluation was conducted with the fuels based on EN14214 and blended FAME up to B5

Ｃｏｎｆｏｒｍｉｔｙ Ｔｅｓｔｓ

Metal Corrosion

Safety(Oxidation Stability)

Materials CompatibilityＣｏｎｆｏｒｍｉｔｙ Ｔｅｓｔｓ

(Key Issue)

Metal Corrosion,Degradation of Rubbers and Plastics

(Oxidation Stability)

Fuel System Durability

Environment Effect on Emission

y y(Sludge Formation)Wear in Injector

PerformanceExhaust Emission

Effect on Performance

JAMA 5

Drivability, Startability

Materials for FAME

Waste cooking oil / Waste cooking oil / JapanJapanR d S b

Soybean oil / USARapeseed Soybean

Palm Safflower Olive etcPlants Oil

Fat LardAnimals Oil Sardine etcRapeseed oil / EuropeGarbage SeasoningOthers etc

p p

FAME Regulations

Europe ： EN14214 took Rapeseed oil ME into considerarionUSA ： ASTM D6751 for Soybean oil ME

Japan ： Assuming various materials, FAME conformity test fuel was designed to be evaluated against EN14214.

After the tests a neet FAME standard was established

JAMA 6

After the tests, a neet FAME standard was established as JIS K2390.

Summary of Conformity Tests

Corrosion in Tern Sheet (lead-tin alloy)FailMaterial Compatibility

SummaryResultsTest Items

Metals

Slight DegradationPassLong Storage Test

Poor Startability－Cold Performance

Rubber & Plastics Pass No effects of Ester as far as less than 5v%

Corrosion and melting plating in lead-tin alloycoated and electrolytic zinc-coated steel sheetsFailFuel Tank Test

Same as diesel fuel with B5PassFuel Filter TestSlight DegradationPassLong Storage Test

Line

s

Test

Same as diesel fuel with B5PassFuel Hose Test

Same as diesel fuel with B5PassFuel Pipe Test

y

Fuel

LPa

rts

Wears in injector are founded in some cases

Observation of no trouble with B5PassLD ID&DI

-FIE Durability Test

Engine Durability Test

Wears in injector are founded in some cases. However, it was not confirmed that wear caused by FAME.

Observation of no trouble with B5PassVehicle Durability Test (LDV, IDI)

Flow loss and Wear in Injectors with B5FailHD, DI

Observation of no trouble with B5PassLD, ID&DI

JAMA 7

Little Impact with up to 10v%PassEmission Test

Note) Test FAME consists of PME:RME:SME=60:38:2 and is blended in commercial diesel fuel by 5%.

Effects of Improved Oxidation Stability F l T k C ion Fuel Tank CorrosionTest Fuel:

Commercial diesel fuel blended with the FAME meeting EN14214 by 5vol%

Oxy. Stabof B100: 6 Hrs

Test Fuel: Same FAME as above with 400ppm of anti-oxidant (20ppm as B5)pp ( pp )

Oxy. Stabyof B100: 10 Hrs

JAMA 8Source:METI FAME conformity Test

Oxidation Stability and Fuel Tank Corrosion

15at 15R

anci

ma

Test FAME(Pass)

10

Hr b

y R Test FAME

(Failed)

5tabi

lity,

Improved oxidation stability (10Hrs10Hrs)No CorrosionNo Corrosion

5

atio

n St

Oxidation stability limit of EN14214 (66HrsHrs)heavy corrosionheavy corrosion in fuel tank test

200 400 600 80000O

xida heavy corrosionheavy corrosion in fuel tank test

JAMA 9

Dosage of Anti-Oxidant Agent, ppm (as B100)Source:METI FAME conformity Test

Fuel Tank Materials in Asia

Europe North America Asia

About 80% is metal tank in Asia

100%Europe North America Asia

Fuel TankMaterial

MetalPlastic

50%

0%0%

1993

1996

2000

2003

2006

1993

1996

2000

2003

2006

1993

1996

2000

2003

2006

JAMA 10Source: Data from Website of Plastics Fuel Systems Manufactures Association and

in-house information of a material company.

Specification of FAME in JapanJIS K2390

Limit Test methodSpecification

Items

JIS K2390

Agreement between producers and distributors

mass%g/ml

mm2/sDeg.C

Limit Test method96.5 min

0.86 - 0.903.5 - 5.0120 min10

EN 14103JIS K 2249JIS K 2283JIS K 2265JIS K 2541 1 2 6 7

Ester contentDensityKinematic ViscosityFlash PointS lf distributors.

（ Must meet diesel fuel specification after blending FAME ）

ppmmass%

mass%ppm

10 max0.3 max51 min

0.02 max500 max

JIS K 2541-1, -2, -6 or-7JIS K 2270JIS K 2280JIS K 2272JIS K 2275

Sulfur10% Carbon ResidueCetane IndexSulfated AshWater blending FAME ）ppm

mgKOH/g

gI/100g

24 max1 max

0.5 max

120 max

EN 12662JIS K 2513JIS K 2501, JIS K0070

JIS K 0070

Total contaminationCopper CorrosionAcid valueOxidation StabilityIodine Number gI/100g

mass%mass%mass%mass%mass%

120 max12.0 max0.20 max0.80 max0.20 max0 20

JIS K 0070EN 14103JIS K 2536, EN14110EN 14105EN 14105EN 14105

Iodine NumberLinolenic acid methyl esterMethanolMono glycerideDi glycerideTri gl ceride

10 Hrs minimum of Oxidation Stability is

mass%mass%mass%

ppmppm

0.20 max0.02max0.25 max

5max5 max

EN 14105EN 14105, EN14106EN 14105EN 14108, EN 14109prEN 14538

Tri glycerideFree glycerineTotal glycerineMetals (Na + K)Metals (Ca + Mg)

ynecessary for preventing corrosion in fuel line of vehicle.

JAMA 11

ppmDeg.CDeg.C

10 max EN 14107

Meet diesel fuel specification

PhospourusPour pointCFPP

Specification of Diesel Fuel in JapanItems

SulfurLevel

10 ppm max

ertie

sCetane IndexT90FAME contentFAME content

45 min360 deg.C max5 mass% max5 mass% max

ted

Prop

FAME contentFAME contentMethanolMethanolTriglycerideTriglyceride

5 mass% max5 mass% max0.01 mass% max0.01 mass% max0.01 mass% max0.01 mass% max

ME

rela

t

TAN TAN Individual Organic AcidIndividual Organic AcidOxi Stability (Acid)Oxi Stability (Acid)

0.13 mgKOH/g max0.13 mgKOH/g max30 ppm max 30 ppm max 0 12 mgKOH/g max0 12 mgKOH/g max

Monitor for refining level of FAME.If FAME t JIS K2390/EN14214

This level of oxidation stability is ti l t t t l i

FAMOxi. Stability (Acid) Oxi. Stability (Acid) 0.12 mgKOH/g max0.12 mgKOH/g max

If FAME meets JIS K2390/EN14214, B5 will meet these requirements.Triglyceride is also a monitor for blending cr de oil and/or cooking oil

essential to prevent metal corrosion.Even though FAME has 6 Hrs of oxidation stability, B5 will not be able to meet this req irement

JAMA 12

blending crude oil and/or cooking oil. to meet this requirement.

Fuel Regulation

Europe Japan.Difference between Europe and Japan

SulfurDensity :

SulfurCetane IndexT90

Spec

:

FAME 5v% max *)T90FAME 5w% maxOxi Stabilityl F

uel

5 % a

*) FAME must meet EN14214

Oxi. StabilityGriceride

:Five propertiesrelated to FAMED

iese

l

EN14214 JIS K2390ec.

refer

Ester 96.5 v% minTAN :

Ester 96.5 v% minTAN :M

E Sp

e

JAMA 13

::

::FA

M Voluntary Spec.Voluntary Spec.

International Approach for Harmonization International Approach for Harmonization of Biofuel Specificationof Biofuel Specification

EU USAEU/US/Brazil Bio Fuel Standardization for Trading

pp

WWFCCEN ACEAACEA AAMAAM

EMAEMARevision of EN14214

JAMAJAMAERIA

ASTM

JPNERIA

BrazilAAF/TC3AAF/TC3

JAMA 14ISO

International Approach for International Approach for H i ti f Bi f l S ifi tiH i ti f Bi f l S ifi ti

（（11）） Tripartite Task ForceTripartite Task Force ( B il EU US )

Harmonization of Biofuel SpecificationHarmonization of Biofuel Specification

（（11）） Tripartite Task ForceTripartite Task ForceWhite Paper on Internationally Compatible Biofuel Standards

( Brazil, EU, US )

（（22）） ISO / TC28 / SC7 Liquid BiofuelsISO / TC28 / SC7 Liquid BiofuelsInternational Organization for StandardizationInternational Organization for Standardization

To harmonize the specifications and test methods of biofuels in case of the increase of trade between markets world wide.

（（33）） ERIA Energy ProjectERIA Energy ProjectEconomic Research Institute for ASEAN and East AsiaEconomic Research Institute for ASEAN and East Asia

Working Group for the Standardization of Biodiesel Fuel in East Asia.Members；

JAMA 15

Australia, China, India, Indonesia, Malaysia, New Zealand, Philippines, Singapore, South Korea, Thailand, Vietnam and Japan

WWFC: Worldwide Fuel Charter

WWFCWWFC Th bj tiTh bj tiWWFC WWFC --The objectiveThe objectiveThe objective of the global fuels harmonization effort is to develop common world-wideeffort is to develop common, world wide recommendations for ‘quality fuels’, taking into consideration customer requirements and vehicle emission technologies.

The 4th edition WWFCThe 4th edition WWFC is is

g

available in following sites.available in following sites.www.autoalliance.org

bwww.acea.be

www.jama-english.jpwww.enginemanufacturers.org

JAMA 16

WWFC CommitteeWWFC Committee

Countries represented:Countries represented:Brazil (ANFAVEA)Canada (AIAMC CVMA)

Malaysia (MAA) Mexico (AMIA)Canada (AIAMC, CVMA)

China (CAAM)Europe (ACEA)I di (SIAM)

Mexico (AMIA) Philippines (CAMPI)South Africa (NAAMSA)India (SIAM)

Indonesia (IAF)Japan (JAMA)

( )Thailand (TAIA)US (Alliance, EMA)Vi t (VAMA)

p ( )Korea (KAMA) Vietnam (VAMA)

Red:Committee menbers Gray:Associate menbers

JAMA 17Supporting: International (OICA)

WWFC WWFC ；； Biofuel GuidelinesBiofuel Guidelines

E100 & B100 guidelines for E10 & B5 will be published soon.

JAMA 18

Requirement from Automakers for BiodieselRequirement from Automakers for BiodieselFAME has poor oxidation stability, and might cause troubles in the fuel system when fuel quality cannot y q ybe secured.Adequate Specifications, Use of Anti-Oxidant, GoodAdequate Specifications, Use of Anti Oxidant, Good house keeping and Fuel quality monitoring systemfor FAME blended Biodiesel are necessary.It will be more preferable to utilize “BTL （Biomass To Liquid” or “Hydrogenated Biodiesel” as compared to the use of FAME from the technical view points.

Biomass to Liq idBiomass to Liq idBiomass to LiquidBiomass to LiquidHydrogenated BiodieselHydrogenated Biodiesel

JAMA 19

FAMEFAME

Next Generation Bio Diesel in the World

NExBTLNExBTL

Green Diesel

BHD

PTT

H-BIOBiodiesel

JAMA 20

HydroHydro--treating of Vegetable Oiltreating of Vegetable Oilyy g gg gCH3 CO-O-CH23 O 2

Vegetable OilCH3 CO-O-CH-

Vegetable Oil

CH3 CO-O-CH2

Hydro-treating FAME- 2

+CH3OH+H2

3 HC CH33 HC CH3 HC CO O CH

Double bondHydrogenated

3 HC CH33 HC CH3

＋ H2O＋ H2O

3 HC CO-O-CH3

CH2OHCH2OH

＋ CO2, CH4＋

22

CH3-CH2-CH3＋

＋ CH OH2

CH2OHCH OH

2

CH2OH(glycerin)

JAMA 21Source : Nippon Oil / TOYOTA JSAE Nov.29, 2006

(glycerin)

Character of Next Generation Bio Diesel

Pure hydrocarbon fuel－ Hydrogenated biodiesel －

Pure hydrocarbon fuelsame handling as diesel fuelNo limit of blend ratio as far as meeting dieselNo limit of blend ratio as far as meeting diesel fuel specification

Good properties as diesel fuelGood properties as diesel fuelHigh cetaneZero aromaticsZero aromaticsZero sulfurBetter oxidation stability than FAMEBetter oxidation stability than FAME

Lower CO2 production than fossil diesel fueland same level as FAME

JAMA 22

and same level as FAME Cost ?

ConclusionThe specifications of EN14214 are almost enough for B100 except the following;

Oxidation stability requirement in EN14214, that is 6 hrs minimum with Rancimat method, is not enough for

B100 except the following;

preventing metal corrosion.

If the regulation of B5 specification can be set, it g p ,would be desirable to adopt Japanese B5 specification. If not, specifications for B100 should

f

Q lit t l i di t ib ti t t b t k

include oxidation stability specification which is not less than 10 hrs. Quality control in distribution system must be taken care by distributors. BTL d/ H d t d bi di l d i bl

JAMA 23

BTL and/or Hydrogenated biodiesel are desirable as discussing more than 5% of FAME.

JAMA’s position on BiofuelsJAMA’s position on BiofuelsJAMA s position on BiofuelsJAMA s position on Biofuels

JAMA positively corresponds to introduction of biofuels from view point pof energy security and CO2 reduction.

Issues to be solved;Quality control at pump to prevent problem- Quality control at pump to prevent problem

- Competition with food, land development andwater pollution

- Cost, etc.

JAMA 24

承蒙垂听、不胜感谢 !

JAMA 25

Appendix

JAMA 26

Estimated Trouble Related To DistributionEstimated Trouble Related To Distribution

S •Sludge D it t I j tStorage•Oxidization•Moisture

•Acid

•Sludge •Deposit at Injector

•Deposit in InjectorForming Salt

Transport / Fueling

•Corrosion and Inj. Pump

•Abrasive wear inDistribution system

g

Transport / Fueling•Contamination(metal, rust, other fuels, etc.)Moisture

Abrasive wear in Injector and Inj. Pump

•Moisture•Additives for pipeline

Blending

•Metal CorrosionVehicle Fuel Line

Blending•Contamination(metal, rust, other fuels, etc.)Moist re

•Organic materialCompatibility

JAMA 27

•Moisture•Poor mixing •Fuel Filter Plugging

Outline of The Categories in WWFCOutline of The Categories in WWFCCategory 5Category 5 ??Fuels needed to achieve future emission levelsand emission control

Category 4: EUROCategory 4: EUROⅣⅣ--ⅤⅤFuels for markets with further advanced requirementsfor emission control, to enable sophisticated NOx and PM after-treatment technologies

Category 3: EUROCategory 3: EUROⅢⅢFuels for markets with advanced requirements

Category 2: EUROCategory 2: EUROⅡⅡ--ⅢⅢFuels for markets with stringent requirements

for emission control

Category 1: EUROCategory 1: EUROⅠⅠ

Fuels for markets with stringent requirementsfor emission control

JAMA 28

g yg yFuels for markets with minimal requirementsfor emission control

B100 Specs and Test Methods B100 Specs and Test Methods Property Value Units Test MethodsProperty Value Units Test Methods

Ester content 96.5 min % m/m ISO: EN 14103 mod; EN 14078 Other: ABNT NBR 15342

Linolenic acid methyl ester 12.0 max % m/m ISO: EN 14103 modPolyunsaturated acid methyl ester (≥4 double bonds) 1 max % m/m ISO: prEN 15799ester (≥4 double bonds)Oxidation stability

Induction period 10 min hr ISO: EN 14112 or prEN 15751 as alternative

Insolubles 2.5 max mg/100 mL ISO: EN 12205ASTM: D2274

Iodine number

130 max**May unnecessarily

preclude certain feedstocks.

g I2/100 g ISO: EN 14111 (for use on B100 only, not blends)

ISO: EN 6618, EN 14104ASTM D664 D974Total acid number 0.5 max mg KOH/g ASTM: D664, D974JIS: K 2501Other: ABNT NBR 14448

Methanol 0.20 max % m/mISO: EN 14110JIS: K 2536Other: ABNT NBR 15343Other: ABNT NBR 15343

Glycerides

Mono-glyceride 0.80 max % m/m ISO: EN 14105Other: ABNT NBR 15342

Di-glyceride 0.20 max % m/m ISO: EN 14105Other: ABNT NBR 15342Other: ABNT NBR 15342

Tri-glyceride 0.20 max % m/m ISO: EN 14105Other: ABNT NBR 15342

Glycerin (glycerol)

Free glycerin 0 02 max % m/mISO: EN 14105/14106ASTM: D6584

JAMA 29

Free glycerin 0.02 max % m/m ASTM: D6584Other: ABNT NBR 15341

Total glycerin 0.24 max % m/mISO: EN 14105ASTM: D6584Other: ABNT NBR 15344

Property Value Units Test Methods

B100 Specs and Test Methods (cont’d)Property Value Units Test Methods

Density 0.86 - 0.90 g/ml @15°C

ISO: EN 3675ASTM: D4052JIS: K 2249Other: EN 12185, ABNT NBR 7148/14065ISO: EN 3104

Kinematic viscosity 2.0 - 5.0 mm2/s @40°C ASTM: D445JIS: K2283Other: ABNT NBR 10441

Flash point 100 min °C ISO: 2719ASTM: D93

Cetane number 51 minISO: 5165ASTM: D613JIS: K2280

Water 500 max mg/kg (ppm) ISO: EN 12937Water and Sediment 0.05 max % v/v ASTM: D2709

Total contamination 24 max mg/kg ISO: EN 12662ASTM: D2276, D5452, D6217

Ash content 0.001 max % m/mISO: EN 6245ASTM: D482JIS: K2272

Sulfated ash 0.005 max % m/mISO: EN 3987ASTM: D874Other: ABNT NBR 984

Carbon residue: Ramsbottom, on 100% distillation residue 0.05 max % m/m ASTM: D4530

C i F li ht ti R ti ASTM D665 P d ACorrosion: Ferrous light rusting, max Rating ASTM: D665, Procedure A

Sulfur 10 max ppmISO: EN 20846/20884ASTM: D5453/D2622JIS: K3541-1, -2, -6 or -7

Phosphorus 4 max ppm ISO: EN 14107ASTM D4951 D3231

JAMA 30

p pp ASTM: D4951, D3231Alkali metals (Na+K) 5 max ppm ISO: EN 14108/14109, EN 14538Alkaline metals (Ca+Mg) 5 max ppm ISO: EN 14538Trace metals no addition ASTM D7111Injector coking 2% max permitted power loss CEC F-98-08

Comparison between WWFC B100 Guideline Comparison between WWFC B100 Guideline and ERIA Benchmark Specsand ERIA Benchmark Specsand ERIA Benchmark Specsand ERIA Benchmark Specs

NotesProperty ERIA WWFC

Methanol presenceFlashpoint 100 min 100 min

Feedstock neutralViscosity 2.0 - 5.0

(deg C)

(mm2/s) 2.0 - 5.0

Methanol presenceFlashpoint

Impact on CCDCarbon residue(100%)

100 min 100 min

0.05 max 0.05 max

(deg.C)

0 3( )or (10%)

Impact on inj. depositsSulfated ash 0.005 max0.02 max

(WWFC only specify 100%)(mass%) 0.3 max

Not harmonizedAsh 0.001 max

Risk of filter pluggingWater & Sediment 0.05 max(not specify)

(not specify)(mass%)

Oxidation stability 10 min 10 min Risk of tank corrosion

p gg gNot harmonized(vol%)

JAMA 31

Oxidation stability 10 min 10 min Risk of tank corrosion (JAMA’s request)(hrs)

Comparison between WWFC B100 Guideline Comparison between WWFC B100 Guideline and ERIA Benchmark Specsand ERIA Benchmark Specs (cont’d)

NotesProperty ERIA WWFC

and ERIA Benchmark Specs and ERIA Benchmark Specs (cont’d)

Not harmonizedReport Risk of sludge formationIodine number 130 max

Risk of sludge formationPoly-unsatulatedFAME Not harmonized

N.D. 1 max(mass%) Not harmonized

Risk of filter pluggingMono-glyceride 0.8 max

(mass%)

( %)0.8 max

Impact on catalystPhosphorous 10 max

Need more discussion

4 max

(mass%)

Not harmonized

Metals (Na + K) 5 max Impact on inj. deposits

(ppm)

5 max

JAMA 32

Metals (Na + K)Metals (Ca + Mg)

5 max5 max

Impact on inj. depositsImpact on catalyst

5 max5 max

Oxidation Stability of Hydrotreated Palm OilNippon Oil/TOYOTA Bio Hydrotreated Diesel

Oxidation Stability of Hydrotreated Palm Oil

12g Before Aging10.4

Poor

8

10

KO

H/g Before Aging

After Aging

A i ditiabili

ty

6

8

mg・

K Aging condition：115deg.C、16hrs、O2blow

tion

Sta

2

4

TAN

Oxi

da

0

20.26 0.060.00Good

JAMA 33

PME HydrotreatedPalm OilSource : Nippon Oil/TOYOTA JSAE Nov.29, 2006

Properties of Hydrotreated Palm OilNippon Oil/TOYOTA Bio Hydrotreated Diesel

Hydrotreated JIS N 2

Properties of Hydrotreated Palm Oil

0.82830.87420.7852g/cm3Density

HydrotreatedPalm Oil

JIS No.2Diesel FuelPME

75180132deg.CFlash Point

0.82830.87420.7852g/cm3Density

4.0635.5104.140mm2/sVis. (30deg.C)

Distrillation 284.5 221.0333.0T10, deg.C

Cetane Number

PropertiesDistrillation

101301.0284.5

6062337.5359.0T90, deg.C221.0333.0, g

0 0590 1

Oxygen <0.1 <0.112mass%

JAMA 34

0.0590.1Iodine Number

Source : Nippon Oil/TOYOTA JSAE Nov.29, 2006

Properties of NExBTLNESTE OIL / NExBTL

Properties of NExBTL

JAMA 35Source : NESTE OIL/SYNBIOS Stockholm, May 19, 2005

B100 Specification in Asia (1)B100 Specification in Asia (1)

JAMA 36

B100 Specification in Asia (2)B100 Specification in Asia (2)

JAMA 37