1

Partially Hydrogenated FAME (H-FAME) as a New Alternative Biodiesel”

H-FAME: New alternative biodiesel superior in ox idation and thermal stabilit ies, and produced after the partial hydrogenation of the current FAME. H-FAME is monoene-rich FAME.

Dr. Yuji YOSHIMURA

Leader/Research Director of Thailand-Japan SATREPS Project, National Institute of Advanced Industrial Science and Technology

(AIST), Japan

Dr. Nuwong CHOLLACOOP Research Leader of Thailand-Japan SATREPS Project,

National Metal and Materials Technology Center (MTEC), Thailand

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KMUTNB

Kingdom of Thailand

Thailand-Japan collaboration SATREPS PJ of “Innovation on production and automotive utilization of biofuels from non-food biomass” (FY2010-FY2015)

Science and Technology Research Partnership for Sustainable Development

Japan

• National Institute of Advanced Industrial Science and Technology (AIST)• Waseda University

Japan Science and Technology Agency

Japan International Cooperation Agency

H-FAME technology is developed through

2

• National Science and Technology Development Agency (NSTDA)•Thailand Institute of Scientific and Technological Research (TISTR)•King Mongkut’s University of Technology NB

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Fuel from oil

Fuel from residues Evaluation of

engine and environment compatibilities

Market use of new fuels

（Toxic non-food biomass )

Bio-oil production/ upgrading

LCA, Capacity building and Technology transfer

Jatropha fruit

H-FAME

Gasoline, etc.

FAME production/ upgrading

New FAME (H-FAME: Partially Hydrogenated FAME)

2nd generation biofuel

Outline of JST-JICA SATREPS project

On-road tests

R&D of Jatropha to transportation fuels

3

1st gen. non-food biomass

will develop the novel biofuels production technology from Jatropha oil and residues to enhance its over-all utilization efficiency.

will contribute to the sustainable introduction of high-quality biofuels (H-FAME) into the transportation sector, in particular for the higher blending.

Demands for biofuels from non-food biomass: Energy security; CO2 reduction; Growth of agricultural/forestry industries; Minimizing the conflict with food, etc.

Applicable to all of FAMEs

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Pilot plant study of H-FAME production

Degumming apparatus

FAME production PP (1 ton/day) @ TISTR

FAME partial hydrogenation PP

H-FAME

Jatropha oil

Conventional FAME

H-FAME (Partially Hydrogenated FAME):New high-quality FAME which is produced after the partial hydrogenation

(EEBS):2008WWFC

Advantages of H-FAME

High ox idation/ thermal stability Possible higher blending up to

B20 Low amounts of SMG and SG, Very lower cost-up for H-FAME

production, etc.

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Pilot plant study of bio-oil production

Jatropha residues

Pyrolysis PP (Circulating Fluidized Bed Pyrolyzer)

Bio oil Stabilization /Separation

Hydrotreating (Mild)

Hydrotreating/ Co-processing

(Severe)

Gasoline/Diesel/

Jet

Water soluble/ Water insoluble fractions

Size: ~ 20 kg/h (biomass residues base)

Continuous flow high-pressure reactors

Catalytic pyrolysis

HDO/HDS (HDN)

Catalytic cracking/deoxyge -nation/coking

5

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1. Background and motivation

2. What is H-HAME ? How to produce H-FAME ? Partially Hydrogenated FAME (H-FAME) as a new alternative biodiesel

3. Properties and advantages of H-FAME

4. Feasibility of H-FAME

5. On-road durability tests by using B10 fuel blended with Jatropha H-FAME, and B20 with Palm H-FAME

6. Future plan for H-FAME technology

7. Conclusions

Contents

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1. Importance of quality assurance at the market

7

Bx

B100,Bx

Fresh B100, and Bx

Storage/delivery Vehicle use

Thai standard,

(EEBS):2008 WWFC B100 spec for B5, B7,

etc., e.g., 1,000 ppm BHT in B100 for B7.

Bx (FAME blended diesel) spec..

Lower blending Bx (x7 vol% ), several damages w ill appear on engine systems etc.

Quality assurance

FAME as an alternative fuel, and used as a diesel blend stock, but easy to be oxidized…..

Bx: X vol % FAME and (100-x) vol % petrodiesel

(Mercedes-Benz Biodiesel Brochure)

e.g., engine oil sludging due to biodiesel aging in engine oil

e.g. precipitates/ filter plugging via. saturated MG (sterol glycoside)

Antioxidants

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O

OCH3

O

OCH3

e.g., C18:n FAME molecule

C18:0

C18:1

C18:2

C18:3

1-1. Properties of unsaturated FAME molecules

Methyl ester group

O

OCH3

O

OCH3 (98*)

(41)

(1)

(

9

1-2. Key compounds for FAME upgrading

O

OCH3

O

OCH3

O

O

HO

HO

FAME is mixtures of several types of fatty acid methyl esters, and polyunsaturated FAMEs are key components to determine the oxidative/thermal stabilities of FAME.

Not yet standardized in FAME specifications, but .. Saturated monoglyceride (SMG) will precipitate even at higher temperature than cloud point, mainly after blending of FAME with petrodiesel (Bx).

Sterol glucoside (SG) will Precipitate during the storageof FAME, mainly for B100 FAME.

Phorbol ester should be removed for the safe handling.

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2. What is H-FAME ?

FAME H-FAME

Hydrogen

Hydrogenation catalysts

FAME + Hydrogen = H-FAME

O

OCH3

O

OCH3C18:0

C18:1

C18:2

C18:3

O

OCH3

O

OCH3e.g., C18:n FAME molecule

T

11

Vegetable/Plant oils,

etc.

Esterification/Transesteri-fication

FAME H-FAME

Hydrodeoxy-genation Isomerization

Gas (C3H8, H2O, CO2, CO, etc.)

Gasoline

HVO,BHD

MeOH Catalyst(H2SO4/KOH)

Glycerin

CatalystH2

CatalystH2 CatalystH2

Current biodiesel production process

2-1. How to produce the H-FAME ?

Partial hydrogenation

Conventional FAME

antioxidant < B5-B7

< B10-B20

Incidental facility

High-pressure and high-temperature facility (e.g., P>5 MPa, T>280 ºC)

Large plant size to get a scale merit Very high hydrogen consumption

H-FAME is a friendly fuel to the current biodiesel companies: P

Main reaction

Reaction Conditions

Oil (Triglyceride)

Hydrocarbons

High pressure (>5MPa)High temperature (>280ºC)

Mono/Polyunsaturated FAME

Monounsaturated FAME

Low pressure (atmospheric~0.5MPa)Low temperature (80~140ºC)

Hydrogen consumption Partial hydrogenation : 3H2

Hydrogenolysis/hydrogenation: 18H2Decarboxylation: 9H2 More hydrogen for the isomerization reaction

H-FAME BHD/HVO

Comparison between H-FAME and HVO/BHD

OOOOOO

OOCH3

OOCH3

OOCH3

OOCH3

12

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Bx

13

FAMEPlant

FAME producers A

FAME (B100)

FAMEPlant

FAME producer A

FAME (B100)

H-FAME Plant

H-FAME (B100)

FAME Plant

FAME producer AFAME (B100)

H-FAME Plant

H-FAME (B100)

FAME Plant

FAME producer BFAME (B100)

H-FAME producer

Extension facility

Exclusive facility

H-FAME Plant

H-FAME (B100)

Refinery Petrodiesel Biodisel Blend（Bx)

Refinery

Extension in refinery

Case 2: H-FAME Plant at the Joint Venture’s site

Case 3: H-FAME Plant at the petroleum refinery site

Case 1: H-FAME Plant at FAME production site

Current delivery chain for Bx:X% of FAME blended w ith (100-x)% petrodiesel

Possible plant sites for producing H-FAME

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Biodiesel blended with petroleum diesel (Bx*)B5 B10 B15O

xida

tion

sta

bilit

y of

B10

0 (h

)

5

10

15

40

B20

60

80

Palm MERapeseed ME

Jatropha MESoybean ME

HVO, BHD, etc.(Hydrocarbons and not FAME)

Thai standard of 10 h

0

Conventional FAME

1st gen.

Hydrogen ~3 wt%/VO

Hydrogen ~0.1-0.2 wt%/FAME

*X vol% of biodiesel and (100-X) vol% of petroleum diesel

Blending limitation of FAME (B5-B7)

Very reliable fuel, but relatively higher cost-increase

Reliable and affordable fuel

2-2. Positioning of H-FAME in biodiesels

JAMA’s recommendation

Pro

duct

ion

cost

for

B10

0

H-FAME

//

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EU Japan WWFC TISR's PPEN14214:2003 JIS K2390:2008 March, 2009 Product BDF

Ester content mass% 96.5 min. 96.5 min. 96.5 min. 96.5 min. 99.7Density kg/m3 860-900 860-900 860-900 Report 876Viscosity mm2/s 3.50-5.00 3.50-5.00 2.00-5.00 2.0-5.0 5.0Flashpoint deg. C 120 min. 120 min. 100 min. 100 min. 186Sulfur content mass% 0.0010 max. 0.0010 max. 0.0010 max. 0.0010 max. 0.00025Distillation, T90 deg. C - - - - -Carbon residue (100%) orCarbon residue (10%) mass%

-0.30 max.

-0.3 max.

0.05 max.0.3 max.

0.05 max.- 0.14

Cetane number 　 51.0 min. 51.0 min. 51.0 min. 51.0 min. 57Sulfated ash mass% 0.02 max. 0.02 max. 0.02 max. 0.005 max. 100>120

硫黄分 イオウブンmass%

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EU Thailand WWFC TISR's PPEN14214:2003 March, 2009 H-FAME

Ester content mass% 96.5 min. 96.5 min. 96.5 min. 96.5 min. 98.9Density kg/m3 860-900 860-900 860-900 Report 872Viscosity mm2/s 3.50-5.00 3.5-5.0 2.00-5.00 2.0-5.0 4.5Flashpoint deg. C 120 min. 120 min. 100 min. 100 min. 168Sulfur content mass% 0.0010 max. 0.0010 max. 0.0010 max. 0.0010 max. 0.0002Distillation, T90 deg. C - - - - 354.5Carbon residue (100%) orCarbon residue (10%) mass%

-0.30 max.

-0.30 max.

0.05 max.0.3 max.

0.05 max.- 0.15

Cetane number 　 51.0 min. 51 min. 51.0 min. 51.0 min. > 64Sulfated ash mass% 0.02 max. 0.02 max. 0.02 max. 0.005 max. 120>100>120

硫黄分 イオウブンmass%

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Thailand WWFC TISR's PPDOEB 2014 March, 2009 H-FAME

Density kg/m3 860-900 860-900 Report 872Viscosity mm2/s 3.50-5.00 2.00-5.00 2.0-5.0 4.5Flashpoint ºC 120 min. 100 min. 100 min. 168Sulfated ash mass% 0.02 max. 0.02 max. 0.005 max. 96.5－>96.5

密度 ミツドkg/m3－0.86-0.9軽油と同等 ケイユドウトウ0.86-0.9

動粘度 ドウネンドmm2/s1.9-6.03.5-5.0軽油と同等 ケイユドウトウ3.5-5.0

引火点 インカテン℃>130>120>100>120

硫黄分 イオウブンmass%

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H-FAME

1. Meets with all of FAME standards

(EN, WWFC, EAS-ERIA, Thai, etc.)

2. High oxidation stability (>>10h） (less acids/ corrosion)

4. Decrease in heavier fraction (less poly-

merization/ deposits)

3. Less peroxides formation (more elastomer tolerance)

3-2. Advantages of H-FAME and H-FAME process

6. Detoxification of Phorbol ester (PE)

5. Increase in Cetane numberCN~65 for Palm H-FAMECN~59 for Jatropha H-FAME

(1/2)

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250

300

350

400

450

500

0 20 40 60 80 100Recovered fraction (mass %)

Tem

pera

ture

(ºC

)

4. Decrease in the amounts of heavier fractions

Tx (ºC): Distillation temperature for x mass % of recovered fraction FBP: final boiling point

T90 T95 T98 FBP

Tem

pera

ture

(ºC

)

356 357 358 358 359377 400

485

Simulated Distillation (SIMDIS) data (ASTM D 2887)

Palm FAME

Palm H-FAME

Palm FAME

Palm H-FAME

The higher in boiling point, the heavier.

Retardation of polymers and sludge formation via. oxidative/thermal degradation of heavier fractions.

High temperature fractions

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Phorbol ester (PE) determination by liquid chromatography system (HPLC)Toxicity test by using Protein Kinase C testkit via. Activation of Protein Kinase C by FAME and H-FAME etc. (MTEC/AIST)

6. Detoxification of Phorbol ester (PE)

OH

HOO

HHO

O

H

O O

O

H

13

16

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H-FAME

7. Less sludge formation during oxidative/thermal degradation(less deposits)

9. Make ease of sterol glyceride(SG) removal

11. Volume-up reaction

3-2. Advantages of H-FAME and H-FAME process

10. Make ease of metals removal

12. No need of high pressure facilities and distillation units

8. Make ease of removal of saturated fatty acid monoglyceride (SMG)

(2/2)

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Diesel (B0) B20Current FAME

(Thai Palm FAME)

B20 H-FAME B20 H-FAME B20 H-FAME

Accelerated oxidation condition:Bx=20g, T=135 ºC (>115 ºC*), O2 Flow=100 ml/min, Oxidation period=16 h.

7. Less sludge formation via. H-FAME

(JapaneseEURO V diesel)

light medium deep

Depth of Hydrogenation

Before oxidation,

*Testing condition for oxidation stability in Japanese quality assurance law for B5 (former method). Now PetroOXY method is used.

B0 B20 B20 B20 B20

After ox idation, H-FAME is very effective to minimize the sludge formation !

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Palm FAME (B100)

Palm H-FAME (B100)

About 2 % increase in volume at the same weights

Partial hydrogenation

11. Volume-gain after partial hydrogenation

Biodiesel (B100) sales are based on the volume of biodieselNAC

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3-2-1. Applicable to all of the FAMEs

Monoene (monounsaturated FAME)-rich H-FAME could be produced from all of the FAMEs after partial hydrogenation.

Original feedstock in H-FAME development

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0

200

400

600

800

1,000

1,200

1,400

1,600

1,800

1G-BDF(PalmFAME)

1.5G-BDF(Palm H-FAME)

2G-BDF (Palm NExBTL)

3G-BDF (BTL)

ROI 10％

固定費

変動費

BDF 100,000 t/yPr

oduc

tion

cost

of s

ever

al

biof

uels

（U

S$/to

n)Palm FAME

Petroleum diesel

Plant size of 100,000 t/y

H-FAME HVO FT-BTL

1,800

1,600

1,400

1,200

1,000

800

600

400

200

0

1st gen. FAME

Diesel price in Thailand（2011）( )

Market price of Palm oil（US-CIF)： 800 US$/ton （2010.Apr).

ROI 10% Fixed costs Variable costs

Environmental Research Institute, Waseda University (2011)

ROI: Return on investment

4. Feasibility of H-FAME (affordability)

Less cost-up

High proportion of variable costs for FAME, H-FAME and HVO. i.e., more than 80 % of the total production cost , so reduction of raw materials costs will be the key to increase its feasibility.

Small cost up for H-FAME compared with 1st gen. FAME, but much less than HVO (BHD), even after newly installation of an on-site H2 package unit.

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Isuzu Spark-S (M/T)

Petroleum diesel (S

Testing fuel of B20: 20 vol % of Palm H-FAME blended with 80 vol % of Thai petro-diesel. Testing periods: Jan.5, 2015 〜 Mar. 2015 (50.000 km). Testing vehicle: ISUZU pick up truck, D-MAX Super Daylight (EUROIV)

Verification of automotive compatibility of H-FAME, with the collaboration of Isuzu Thailand group and petroleum company .

5-1. On-road test by using B20 (Palm H-FAME)

Isuzu D-Max

Petroleum diesel (S

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5-3. H-FAME adopted in Thai AEDP (2015-2036)

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I f we w ill apply for Japanese NEDO’s International Collaboration Project

6. Future proposal of demonstration PJ

Thai standard,

FAME standards

H-FAME plant package

Palm FAME Palm H-FAME

Plant capacity : １0-30 tons of H-FAME /day (1/10-1/30 in size of the commercial FAME plants)

To confirm the process maturity of H-FAME technologies, etc.

Japanese organization (NEDO)

Thai organization MOU

Japanese private sectors,collaborating with AIST, etc.

subsidy

Thai private sectors, collaborating with NSTDA/MTEC, TISTR, etc.

ID

Tentative

Implementation document

e.g., P

30

6-1. Technology/knowledge transfer via. TCTP

ASEAN countries

ERIA WG

Phase I

Thailand Japan

JST-JICA Project (on-going)

Biodiesel production technology- FAME (Pilot plant, 1 ton/d)- H-FAME (Pilot plant)- Bio-oil (Pilot plant)

(fast-pyrolysis of biomass) Biodiesel standardization

- Analysis of impurities- Analytical methods

Thailand

JICA training Program (FY2016?~)

Training program for the 3rdcountries (other than Thailand)

Utilization of facilities dispatched by JICA

Phase II

ERIA Project (on-going)

ASEAN’s persons will be invited to Thailand for training in biodiesel productions and standardization. All of the fees for invitation will be supported by JICA and TICA.

(FY2010-2015)

Biodiesel std. of EEBS:2008

H-FAME as a key technology to meet with EEBS:2008

ProductionStandardization

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7. Conclusions1. Jatropha FAME can be upgraded to the nation-

wide automotive biodiesel and can be blended up to 10 vol % (B10) after converting to Partially hydrogenated FAME (H-FAME) .

2. H-FAME can be produced from any kinds of FAME , e.g., Jatropha FAME, Palm FAME and waste cooking oil FAME, etc.

3. H-FAME is a reliable and affordable biodiesel, and can be used as a nation-wide automotive biodiesel blend stock even at the higher blending use, e.g., up to B20 for Palm H-FAME.

4. H-FAME will support the Thai Alternative Energy Development Action Plan (AEDP) as one of the new alternative biodiesels, and will support the safe use of Bx in automotive transportation.

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Acknowledgements

KMUTNB

Japan Kingdom of Thailand

We deeply appreciate JST and JICA for their financial supports.

We also deeply thank all of the research participants of NSTDA/MTEC, TISTR. KMUTNB, WASEDA U. and AIST for their contributions to this Project.

We also deeply thank the ISUZU Thailand group for their kind supports on the on-road tests, and PTT, Bangchak and Thai oil for supplying the FAME(B100) and petro diesel (B0) and for measuring the fuel quality.

Thank you for your kind attention

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