Introduction of H-FAME Technology

Transcription

1 Introduction of H-FAME Technology H-FAME (Partially Hydrogenated FAME) : New alternative biodiesel superior in oxidation and thermal stabilities, and produced after the partial hydrogenation of the current FAME. H-FAME is monoene-rich FAME. Dr. Yuji YSHIMURA Leader/Research Director of Thailand-Japan SATREPS Project, National Institute of Advanced Industrial Science and Technology (AIST), Japan Dr. Paritud BHANDHUBANYNG Project Director of Thailand-Japan SATREPS Project, Panyapiwat Institute of Management (PIM) -TISTR, Thailand WS on higher blending of biodiesel (17-18, September 1

2 2 H-FAME from Thailand-Japan collaboration H-FAME technology is developed through Thailand-Japan collaboration SATREPS PJ of Innovation on production and automotive utilization of biofuels from non-food biomass (FY2010-FY2015) Japan Kingdom of Thailand Japan Science and Technology Agency Science and Technology Research Partnership for Sustainable Development National Institute of Advanced Industrial Science and Technology (AIST) Waseda University National Science and Technology Development Agency (NSTDA) Thailand Institute of Science and Technological Research (TISTR) King Mongkut s University of Technology NB Japan International Cooperation Agency KMUTNB

3 Contents 3 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. n-road durability tests by using B20 fuel blended with Palm H-FAME 6. Future plan for H-FAME technology 7. Conclusions

4 4 1. Background: Importance of quality assurance FAME as an alternative fuel, and used as a diesel blend stock, but easy to be oxidized.. Bx Fresh B100, and Bx Storage/delivery Vehicle use Lower blending Bx can be used safely Quality assurance in vehicles, if Bx quality is assured. Thai standard, B100, Bx Bx: X vol % FAME and (100-x) vol % petrodiesel (EEBS):2008 WWFC B100 spec for B5, B7, etc., e.g., 1,000 ppm BHT in B100 for B7. Bx (FAME blended diesel) spec.. Antioxidants will retard oxidative degradation of polyunsaturated FAME.

5 Increased cautions for the higher FAME blending With increasing the FAME blending ratio, Fresh B100, and Bx xidation stability High Low Bx Minimum level of quality Storage/ delivery Storage time/oxidation severity enough A More degradation of FAME in fuel station, fuel tank, engine oil pan, etc. via. expirering of antioxidants, metals contaminants assisted oxidation, inappropriate handling/storage, etc. Vehicle use Will cause several damages on engine systems. e.g., engine oil sludging due to biodiesel aging in engine oil (Mercedes-Benz Biodiesel Brochure) 5

6 1-2. Key compounds for FAME upgrading 6 CH 3 <xidative degradation issue> 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. <Precipitation/filter plugging issues> 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 storage of FAME, mainly for B100 FAME. CH 3 H H

7 1-3. Properties of unsaturated FAME molecules 7 C18:3 C18:2 C18:1 C18:0 e.g., C18:n FAME molecule CH 3 (98*) CH 3 CH 3 CH 3 xidation stability Acid corrosion, polymers and sludge formation (41) (1) Peroxide formation Elastomer damage Cold flow property filter plugging Solvency effect cleaning effect (<1) Ease of oxidation: Methyl ester group E.N. Frankel, Lipid xidation, 2005 Monoene (monounsaturated FAME) seems to be reliable component.

8 2. What is H-FAME? H-FAME (Partially Hydrogenated FAME) : New alternative biodiesel superior in oxidation and thermal stabilities, and produced after the partial hydrogenation of the current FAME. H-FAME is monoene (monounsaturated FAME)-rich FAME. FAME Hydrogen Hydrogenation catalysts H-FAME FAME + Hydrogen = H-FAME T<140 ºC P<0.5 MPa But, partial hydrogenation! e.g., C18:n FAME molecule C18:3 CH 3 Degree of hydrogenation C18:2 CH 3 Partial hydrogenation C18:1 CH 3 C18:0 CH 3 Complete hydrogenation 8

9 2-1. How to produce the H-FAME? 9 Current biodiesel production process Vegetable /Plant oils, etc. MeH Catalyst(H 2 S 4 /KH) Esterification /Transesterification Glycerin H 2 FAME Catalyst antioxidant H 2 Catalyst Partial hydrogenation Incidental facility H 2 Catalyst Conventional FAME H-FAME Gas (C3H8, H2, C2, C, etc.) < B5-B7 < B10-B20 H-FAME is a friendly fuel to the current biodiesel companies: P<0.5MPa, T<140 ºC Hydrodeoxy -genation Isomerization 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 Gasoline HV,BHD

10 Comparison between H-FAME and HV/BHD 10 H-FAME BHD/HV Main reaction CH 3 CH 3 CH 3 Mono/Polyunsaturated FAME il (Triglyceride) Reaction Conditions CH 3 Monounsaturated FAME Hydrogen consumption Partial hydrogenation : 3H 2 Low pressure (atmospheric~0.5mpa) Low temperature (80~140ºC) Hydrocarbons Hydrogenolysis/hydrogenation : 18H 2 Decarboxylation: 9H 2 More hydrogen for the isomerization reaction High pressure (>5MPa) High temperature (>280ºC)

11 2-2. Positioning of H-FAME in biodiesels 11 Production cost for B100 xidation stability of B100 (h) Blending limitation of FAME (B5-B7) 1st gen. HV, BHD, etc. (Hydrocarbons and not FAME) Palm ME Rapeseed ME Jatropha ME Soybean ME B5 B10 B15 JAMA s recommendation H-FAME Thai standard of 10 h Conventional FAME B20 Hydrogen ~3 wt%/v Hydrogen ~ wt%/fame Biodiesel blended with petroleum diesel (Bx*) *X vol% of biodiesel and (100-X) vol% of petroleum diesel Very reliable fuel, but relatively higher costincrease Reliable and affordable fuel //

12 2-3. Palm H-FAME from TISTR s pilot plant 12 Conventional Palm FAME FAME partial hydrogenation PP@TISTR (100 L/batch), H-FAME HYD reaction conditions: Temperature: 80 ºC 140 ºC H2 pressure: < 0.5 MPa Pd-based catalyst:

13 3. Properties of palm H-FAME (Pilot 13 Items Units Thailand EAS-ERIA BDF Std WWFC TISR's PP DEB 2014 (EEBS):2008 March, 2009 H-FAME Density kg/m Report 872 Viscosity mm2/s Flashpoint ºC 120 min. 100 min. 100 min. 168 Sulfated ash mass% 0.02 max max max. <0.001 Ash content mass% max. - Water content mg/kg 500 max. 500 max. 500 max. 375 Total contamination mg/kg 24 max. 24 max. 24 max. 1 xidation stability hrs. 10 min 10.0 min. (**) 10 min Iodine value 120 max. Reported (*) 130 max. 42 Monoglyceride content mass% 0.70 max max max Trace metals - - no addition - Cloud point ºC Report ºC CFPP ºC Report ºC Additive Approval Saturated mass% monoglyceride in MG Sterol glucoside ppm EAS: East Asia Summit ; ERIA: Economic Research Institute for ASEAN and East Asia; WWFC: World Wide Fuel Charter

14 3-1. Advantages of H-FAME and H-FAME process Meets with all of FAME standards 11. No need of high pressure facilities and distillation facilities. 10. Volume-up reaction 9. Make ease of metals removal H-FAME 2. High oxidation stability (>>10h) (less acids/ corrosion) 3. Less peroxides formation (more elastomer tolerance) 4. Decrease in heavier fraction (less polymerization/ deposits) 8. Make ease of sterol glyceride (SG) removal 7. Make ease of removal of saturated fatty acid monoglyceride (SMG) 5. Increase in Cetane number 6. Less sludge formation during oxidative/thermal degradation (less deposits)

15 3-2. Less sludge formation via. H-FAME After oxidation, H-FAME is very effective to minimize the sludge formation! Depth of Hydrogenation light medium deep Diesel (B0) (Japanese EUR V diesel) B20 Current FAME (Thai Palm FAME) Accelerated oxidation condition: Bx=20g, T=135 ºC (>115 ºC*), 2 Flow=100 ml/min, xidation period=16 h. B20 H-FAME B20 H-FAME B20 H-FAME Before oxidation, B0 B20 B20 B20 B20 *Testing condition for oxidation stability in Japanese quality assurance law for B5 (former method). Now PetroXY method is used. 15

16 16 4. Feasibility of H-FAME (affordability) Production cost of several biofuels(us$/ton) 1,800 1,600 1,600 1,400 1,400 1,200 1,200 1,000 1, BDF 100,000 t/y Plant size of 100,000 t/y Palm FAME Petroleum diesel 1 st gen. FAME 1G-BDF (PalmFAME) Less cost-up H-FAME HV FT-BTL 1.5G-BDF (Palm H-FAME) 2G-BDF (Palm NExBTL) Diesel price in Thailand (2011)( ) RI 10% Fixed costs 3G-BDF (BTL) RI 10% Variable 固定費 costs 変動費 RI: Return on investment Market price of Palm oil(us- CIF): 800 US$/ton (2010.Apr). Environmental Research Institute, Waseda University (2011) Small cost up for H-FAME compared with 1 st gen. FAME, but much less than HV (BHD), even after newly installation of an on-site H2 package unit. High proportion of variable costs for FAME, H-FAME and HV. i.e., more than 80 % of the total production cost, so reduction of raw materials costs will be the key to increase its feasibility.

17 17 5. n-road test by using B20 (Palm H-FAME) Verification of automotive compatibility of H-FAME, with the collaboration of Isuzu Thailand group and petroleum company. Testing fuel of B20: 20 vol % of Palm H-FAME blended with 80 vol % of Thai petro-diesel. Testing periods: Jan.5, 2015 Mar ( km). Testing vehicle: ISUZU pick up truck, D-MAX Super Daylight (EURIV) Isuzu D-Max Petroleum diesel (S<50 ppm) B100, Blending & property check H-FAME Successfully finished! Fuel: B20 of Palm H-FAME

18 18 6. Future proposal of demonstration PJ To confirm the process maturity of H-FAME technologies, etc. H-FAME plant package e.g., P<0.5 MPa T<140 ºC WHSV> 20 h -1 Plant capacity : tons of H-FAME /day (1/10-1/30 in size of the commercial FAME plants) Palm FAME Palm H-FAME FAME standards Thai standard, If we will apply for Japanese NED s International Collaboration Project Japanese organization (NED) subsidy MU Tentative Thai organization Japanese private sectors, collaborating with AIST, etc. ID Implementation document Thai private sectors, collaborating with NSTDA/MTEC, TISTR, etc.

19 7. Conclusions Partially hydrogenated FAME (H-FAME) is a new alternative biodiesel, and can be produced from any kinds of FAME, e.g., Palm FAME, Jatropha FAME and Waste cooking oil FAME, etc. 2. H-FAME is a reliable and affordable biodiesel, and can be used as a nation-wide high-speed biodiesel blend stock even at the higher blending use, e.g., up to B20 for Palm H-FAME. 3. H-FAME will support the Thai Alternative Energy Development Action Plan (AEDP) as one of the new alternative biodiesels.

20 20 Acknowledgements Japan Kingdom of Thailand KMUTNB 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

21 The 60 th birthday 21