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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
NAC2016 (31 March 2016 @TSP)
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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%
16
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%
17
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%
18
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
28
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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