Host in Japan : List of invited researcher:

Transcription

1 Invited Researcher Renewable Energy Laboratory, National Metal and Materials Technology Center (MTEC) National Science and Technology Development Agency (NSTDA), Thailand

2 Host in Japan : List of invited researcher: 1. Teerapong Baitiang, National Metal and Materials Technology Center, Thailand 2. Prapisala Thepsithar, Institute of Environmental Science and Engineering (IESE), Singapore 3. Alvin David Tijing Lim, Department of Energy, Philippines 4. Ricardo Salazar Infante, Department of Energy, Philippines 5. Tirto Prakoso, Bandung Institute of Technology, Indonesia 2

3 Biomass Technical Tours 1.Tokachi Industrial Advancement Centre, Obihiro City Institute 2. Japan Livestock Trading Corp, Obihiro City 3. Obihiro University of Agriculture & Veterinary Medicine,Obihiro City 4. Obihiro University of Agriculture & Veterinary Medicine,Obihiro City 5. Shikaoi Environmental Preservation Centre,Shikaoi-city Institute,Shikaoi City 6. Nakasorachi-city Institute, Nakasorachi City 7. Epoch Service Co.,Shiraoi Town 8. Ryuseki Corporation, Okinawa Prefecture etc. 3

4 Effect of Antioxidants on the Oxidative Stability of Fatty Acid Methyl Ester (FAME) under Different Storage Conditions By: Parncheewa UDOMSAP National Metal and Materials Technology Center (MTEC) National Science and Technology Development Agency (NSTDA), Thailand Technical Advisers: Toshihiro HIROTSU and Shinichi GOTO Research Center for New Fuels and Vehicle Technology (NFV) National Institute of Advance Industrial Science and Technology (AIST), Japan

5 Properties of Biodiesel Feedstock Description Palm oil Soybean oil Rapeseed oil Jatropha oil Coconut oil Area East Asia USA Europe East Asia East Asia Oil productivity (kg/hectare) 5, ,000 3,000 NA Major fatty acid 1. Palmitic 2. Oleic 1. Linoleic 2. Oleic 1. Oleic 2. Linoleic 1. Oleic 2. Linoleic 1. Lauric 2. Myristic Degree of Unsaturation* (DU, %wt.) Iodine value Oxidation stability degree C Flash point Low temperature performance Good; Fair; Poor *DU=(monounsaturated (Cn:1), %wt.)+2(polyunsaturated (Cn:2,3), %wt.) 5 Source: Adapted from Ma and Hanna (1999), Shay, E.G. (1993) and Ramos, M. J. (2009)

6 Mechanism of Oxidation Mechanism of oxidation** Initiation phase: RH R Propagation phase: R + O 2 ROO ROO + RH ROOH + R Termination phase: R + R RR ROO + R ROOR Ester Peroxide Aldehyde Acid Source: * www. Brinkmann.com 6

7 Deterioration of engine 7 Source: NFV laboratory, AIST, Japan.

8 Mechanism of Antioxidants Reaction of antioxidants with radicals: Example of BHA R + AH RH + A RO + AH ROH + A ROO + AH ROOH + A R + A RA RO + A ROA ROO + A ROOA Antioxidants+ O 2 Oxidized - Antioxidant R, RO, ROO = free radical AH = antioxidant Source: 8

9 ..Objective.. 1. To investigate the properties of refined canola oil and waste cooking oil originated from soybean as biodiesel feedstock and its methyl ester. 2. To investigate the effect of antioxidants on the properties of biodiesel. 3. To investigate the effect of storage temperature on the deterioration of biodiesel with and without antioxidants. 9

10 Experiment Methyl ester preparation from two biodiesel feedstock - Refined Canola Oil (RCO) to Canola Methyl Ester (CME) - Waste Cooking Oil originated from soybean (WCO) to Waste Cooking Oil Methyl Ester (WCOME) CME and WCOME Effect of additive: BHT (100,300, 600 ppm) BPH (100, 300,600 ppm) Effect of storage temperature: 20, 40 and 60 o C 10

11 Results and Discussions Part I: Methyl ester preparation from RCO and WCO Table 1: Properties of biodiesel feedstock and its methyl ester Standard Result Properties JIS K2390:2008 EN 14214:2003 ASTM D RCO CME WCO WCOME 1.Oxidation stability (hours) 10 min. 6 min. 3 min Acid value (mg KOH/ g) 0.50 max max max Water content (ppm) 500 max. 500 max. 0.05%v/v max Kinematic viscosity (mm 2 /s) Peroxide value (meq/kg) NA NA NA RCO: refined canola oil, CME: canola methyl ester, WCO: waste cooking oil and WCOME: waste 11 cooking oil methyl ester

12 BHT & BPH Antioxidants BHT BPH 12 Source: UNEP (2002)

13 Effect of antioxidant Oxidation stability (hours) Oxidation stability (hours) Oxidation stability CME WCOME CME-BHT CME-BPH JIS K2390: WCOME-BHT WCOME-BPH JIS K2390: EN 14214: EN 14214: ASTM D BPH : 600 ppm BHT : greater than 600 ppm 4 2 BPH : greater than 600 ppm BHT : greater than 600 ppm ASTM D Concentration of antioxidant (ppm) Concentration of antioxidant (ppm) BPH is more effective than BHT at the same concentration Concentration of antioxidant increase, oxidation stability increase 13

14 Oxidation stability (hours) Oxidation stability (hours) Oxidation stability (hours) Effect of storage temperature Oxidation stability o C o C JIS K2390: JIS K2390: EN 14214: EN 14214: ASTM D ASTM D Storage time (weeks) 60 o C JIS K2390:2008 EN 14214:2003 ASTM D Storage time (weeks) Storage time (weeks) w/o antioxidant BHT100 BHT300 BHT600 BPH300 BPH600 CME WCOME Oxidation stability: decrease 60 ⁰C > 40 ⁰C > 20 ⁰C WCOME > CME Relative rate of oxidation: Oleic < Linoleic < Linolenic (1:41:98) Source: Knothe, G.,Gerpen, J.V. and Krahl, J. The biodiesel handbook (2005). 14

15 Peroxide value (meq./kg) Peroxide value (meq./kg) Peroxide value (meq./kg) Effect of storage temperature Peroxide value o C o C Storage time (weeks) Storage time (weeks) o C w/o antioxidant BHT BHT300 BHT600 BPH300 BPH600 CME WCOME Peroxide value: Increase 60 ⁰C > 40 ⁰C > 20 ⁰C WCOME > CME Storage time (weeks) 15

16 Acid value (mg KOH/g) Acid value (mg KOH/g) Acid value (mg KOH/g) Effect of storage temperature Acid value o C o C 0.5 ASTM D , EN 14214:2003, JIS K2390: ASTM D , EN 14214:2003, JIS K2390: Storage time (weeks) ASTM D , EN 14214:2003, JIS K2390: o C Storage time (weeks) 0 w/o antioxidant BHT100 BHT300 BHT600 BPH300 BPH Storage time (weeks) CME WCOME Acid value: increase 60 ⁰C > 40 ⁰C > 20 ⁰C WCOME > CME 16

17 4) Conclusions Oxidation stability of biodiesel depends on degree of unsaturation fatty acid composition and storage condition. Oxidized biodiesel results in an increasing of acid value, peroxide value and kinematic viscosity, which cause negative effects on engine. The storage temperature should be less than 40 o C to preserve the biodiesel stability. Antioxidant can delay the rate of oxidation. Type of antioxidant: BPH was more effective than BHT Antioxidant concentration: 600 ppm 17

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19 My research was presented in E-NETT 2009 Conference which was selected to publish in International Journal of Renewable Energy, Vol.4, No.2, July

20 share data with Dr. Tirto Prakoso. His research was selected to publish in ITB Journal of Engineering Science, Vol.44, No.3, 2012,

21 Research data was referred for: Investigation on increasing the oxidation resistance of renewable energy such bio-oil, epoxidized palm oil. Towards Stabilization of Bio-oil by Addition of Antioxidants and Solvents, and Emulsification with Conventional Hydrocarbon Fuels The study of degradation and stabilization of epoxidized palm oil Investigation on the effect of antioxidant on engine part and performance of engine. Carbon deposit Lubricity (HFRR) Wear Cetane Number Material compatibility Performance and Emission Data of engine test will be useful for Automobile Industrial 21

22 Acknowledgements NEF: Asia Biomass Researcher Invitation Program 2008 AIST: Dr. Shinichi Goto, Dr. Toshihiro Hirotsu, NFV Reseachers, Technicians, Staffs MTEC: Assoc. Prof. Siriluck Nivitchanyong Dr. Subongkoj Topaiboul, Dr. Nuwong Chollacoop Colleague: Dr. Prapisala Thepsithar (IESE, Singapore) Dr. Tirto Prakoso ( ITB, Indonesia) 22

23 Thank You for Your Attention