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  • 1. Epoxidation of Castor oil fatty acid methylesters (COFAME) as a lubricant base stock using heterogeneous Ion-Exchange resin (IR-120) as a catalyst Venu Babu B Research Scholar Dr Vaibhav V Goud Asst Professor Department of Chemical Engineering Indian Institute of Technology Guwahati
  • 2. PRESENTATION PLAN  Introduction  Materials & Methods  Objectives  Experimental work  Results & Discussions  References 10-Dec-2013 Synthesis of Bio-Lubricant from Castor Oil Methyl Esters via Epoxidation 2
  • 3. PRESENTATION PLAN  Introduction  Literature review  Knowledge gap  Objectives  Preliminary Studies  Future Work Plan Lubricant  References December 10, 10-Dec-13 2013 3
  • 4. INTRODUCTION What is Lubricant ? “Lubricant (Base stock oil + Additives) is a substance introduced between two moving surfaces to reduce the friction between them, improving the efficiency (lifespan), and reducing wear (stress)”  Conventional lubricant base-stocks are originated from Fossil fuels- Contains hydrocarbons, S, N and other metals Courtesy: Jumat salimon et.al, Eur.J.Lipid Sci. Technol. 2010, 112, 519-530 10-Dec-13 Synthesis of Bio-Lubricant from Castor Oil Methyl Esters via Epoxidation 4
  • 5. Current Status 40 25 MMT 35 20 21.9 30 15 36.2 Lubrication Purpose Energy Transfer 16.4 10 5 5.3 4.4 3.5 3.2 2.8 2.2 1.9 1.9 0 Higher quality and need for longer life products 3.3% per year by 2014 10-Dec-13 Courtesy: India’s Lubricant consumption is on the rise, 2011 by Geeta Agashe, Vice President - Energy http://blogs.klinegroup.com/2011/03/31/india_lubricant_1/ 5 Synthesis of Bio-Lubricant from Castor Oil Methyl Esters via Epoxidation
  • 6. End up in Environment 50% world wide Environmental Effects Volatility Toxicity, Accidental Spills Troubles Total loss Non-recoverable usage non-biodegradable, threat to ecology, Surface and ground water, contamination air pollution, soil contamination, agricultural product and food contamination Courtesy: Savita Kaul et.al, Renewable and sustainable energy reviews 16, 2012, 764-774 10-Dec-13 Synthesis of Bio-Lubricant from Castor Oil Methyl Esters via Epoxidation 6
  • 7. Contd… Food Contamination Soil ,Water Contamination 10-Dec-13 www.thehindu.comSynthesis of Bio-Lubricant from Castor Oil Methyl Esters via Epoxidation 7
  • 8. Contd… 10-Dec-13 8
  • 9. Alternative Resources  Edible  Non-edible  Fats  Used Cooking Oils 10-Dec-13 9
  • 10. Historical Development 19th Centaury Abundance and Low cost of Petroleum 10-Dec-13 10 Courtesy: Biobased Lubricants and Greases by Lou A.T Honary, Erwin Rechter
  • 11. Advantages Environmental friendly Easily biodegradable (90-98%) Renewable raw materials Low cost and Readily available High viscosity Low volatility, Good anticorrosion, Higher flash points (3000 C), Higher freezing points and Display better tribological properties Good lubricity Courtesy: Rafael Garces et.al, Grasa Y Aceites, 62 (1), ENERO-MARZO, 21-28, 2011 10-Dec-13 Synthesis of Bio-Lubricant from Castor Oil Methyl Esters via Epoxidation 11
  • 12. Applications of Bio-lubricants  Saw chains and blades,  Railway points,  Conveyers,  Two-stroke engines,  Between gears,  Automobile Gears  Hydraulic and transmission systems  Plasticizers  Polymer Stabilizers  Functional Coatings Courtesy: Savita Kaul et.al, Renewable and sustainable energy reviews 16, 2012, 764-774: Shangde sun et.al, Industrial Crops and Products 33, 2011, 676-682 10-Dec-13 Synthesis of Bio-Lubricant from Castor Oil Methyl Esters via Epoxidation 12
  • 13. Hydraulic Lubricants Applications Hydraulic Break System 10-Dec-13 Synthesis of Bio-Lubricant from Castor Oil Methyl Esters via Epoxidation 13
  • 14. Materials Annual production 790,000 Metric tones in India Only 10-15% is utilizing properly in various applications such as Adhesives, coatings, paints, lubricant and dyes Castor Oil (CO) Courtesy: Borugadda V B et.al, Rev Sust ene rev. 2012, 16, 4763-4784 10-Dec-13 Synthesis of Bio-Lubricant from Castor Oil Methyl Esters via Epoxidation 14
  • 15. Composition All the disadvantages due to the presence of unsaturation, i.e. by What it Contains Esters of glycerol with fatty the presence of double bonds in the fatty acid chain between ‘C=C’ atoms acids (85 %) with different degrees of unsaturation Palmetic Acid (chain length, C12-C22) Stearic Acid Disadvantages poor oxidative, Oleic Acid Poor thermal stability, poor cold flow behavior Linoleic Acid Linolenic Acid Courtesy: Nazim M K et.al, NCON-PGR, Malaysia 2009 10-Dec-13 Synthesis of Bio-Lubricant from Castor Oil Methyl Esters via Epoxidation 15 15
  • 16. How and which Route By elimination of unsaturated bonds C=C would improve the thermal and oxidative stability of base stock Structural Modification Genetic Modification Blending with additives Courtesy: Savita Kaul et.al, Renewable and sustainable energy reviews 16, 2012, 764-774 10-Dec-13 Synthesis of Bio-Lubricant from Castor Oil Methyl Esters via Epoxidation 16
  • 17. OBJECTIVES Synthesis of methyl esters of CO using KOH catalyst Structural modification of COFAME via epoxidation reaction and product confirmation Determining the required physico-chemical properties of epoxidised COFAME and comparison with conventional servo hydraulic lube oil 10-Dec-13 Synthesis of Bio-Lubricant from Castor Oil Methyl Esters via Epoxidation 17
  • 18. Synthesis of COFAME Base Catalysed Transesterification Reaction Conditions Run No 1 2 3 4 5 6 Oil to alcohol Temperature molar ratio (mol) (oC) 1:6 1:6 1:6 1:9 1:9 1:9 Catalyst Loading (wt %) 60 55 65 60 55 60 1 1 1 1 0.5 0.5 Thin Layer Chromatograms (TLC) of prepared methylesters from CO at various reaction conditions. Oil : Alcohol (Methanol)-1:6 mol Catalyst Loading (KOH)- 1 wt% Reaction time – 90 min Reaction Temperature – 60 oC 10-Dec-13 Transesterification Mechanism 18
  • 19. Structural Modification Mechanism Raw Materials Castor Oil Fatty Acid Methyl Esters (COFAME) Acetic Acid (Oxygen Carrier) 0.5 mol Hydrogen Peroxide (Oxygen Donor) 1.5 mol Ion-exchange resin heterogeneous acidic catalyst (IR-120) 15wt% CH3COOH + H2O2 Epoxidation reaction Reaction Time: 10 h Reaction Temperature : 60 oC CH3COOOH + H2O o CH3COOOH + R1-CH= CH-R2 R1-CH- CH-R2 + CH3COOOH 10-Dec-13 19 Synthesis of Bio-Lubricant from Castor Oil Methyl Esters via Epoxidation
  • 20. Product Confirmation by 1H-NMR Castor Oil Other Ways Iodine Value Oxirane Value Castor oil fatty acid methyl ester (COFAME) Epoxidised castor oil fatty acid methyl ester (epCOFAME) 10-Dec-13 20 Synthesis of Bio-Lubricant from Castor Oil Methyl Esters via Epoxidation
  • 21. Thermal Stability by TGA 180 oC 260 oC COFAME TGA, DTG@10C in N2 340 oC Servo Hydraulic grade Lube oil TGA, DTG@10C in N2 Ability of a material to withstand the higher temperature in inert atmosphere epCOFAME TGA, DTG@10C in N2 Synthesis of Bio-Lubricant from Castor Oil Methyl Esters via Epoxidation 21
  • 22. Oxidative Stability by TGA 155 oC 250 oC COFAME TGA, DTG@10C in O2 305 oC Servo Hydraulic Grade Lube oil TGA, DTG@10C in O2 Ability of a material to withstand the higher temperature in oxygen atmosphere epCOFAME TGA, DTG@10C in O2 22 Synthesis of Bio-Lubricant from Castor Oil Methyl Esters via Epoxidation
  • 23. Physico-chemical Characterization Properties COFAME epCOFAME Method Acid Value (mg KOH/g) 1.65 1.08 AOCS (Te 1a-64, 1997) Density (kg/m3) 930 956 ASTM D 4052-91 Iodine Value (gI2/100g of oil) 84.6 1.27 AOCS (Tg 1-64, 1997) Kinematic Viscosity (CSt) at 40 oC 59.49 263.6 ASTM D-445 Pour Point (oC) -6 8 Specific Gravity 0.94 0.96 ASTM D854-10 Oxirane Content (Experimental) - 4.86 AOCS Cd-9, 120 Oxirane Content (Theoretical) - 5.06 - Relative percentage - 96.04 - ASTM D97 conversion of oxirane (%) 10-Dec-13 23 Synthesis of Bio-Lubricant from Castor Oil Methyl Esters via Epoxidation
  • 24. Conclusions Studied the structural modification of COFAME (Chemical modification) to use as a Bio Lubricant from renewable raw material Epoxidation reaction was performed to convert the un-saturation into oxirane ring formation (Epoxide) Significant physico-chemical and thermal – oxidative stability of modified epoxide and unmodified COFAME properties were studied thoroughly Finally, it could be concluded that COFAME can be used as a potential high temperature lubricant base-stock Further, cold flow properties can be improved by additivation or extending the chain length by ring opening reaction 10-Dec-13 24 Synthesis of Bio-Lubricant from Castor Oil Methyl Esters via Epoxidation
  • 25. REFERENCES [1] Adhvaryu, A., Liu, Z. and Erhan, S.Z. (2005) Synthesis of novel alkoxylated triacylglycerols and their lubricant base oil properties, Industrial Crops and Products, 21, pp. 113–119. [2] Birova, A., Pavlovicova, A., and Cvengros, J. (2002) Lubricating Oils Based on Chemically Modified Vegetable Oils, Journal of Synthetic.Lubrication, 18, pp. 291-299. [3] Shashidhara, Y.M. and Jayaram, S.R. (2010) Tribological Studies on AISI 1040 with Raw and Modified Versions of Pongam and Jatropha Vegetable Oils as Lubricants, Tribology International, 43,pp. 1073–1081. [4] Yao, L., Earl, G., Hammond., Wang, T., Bhuyan, S. and Sundararajan, S. (2010) Synthesis and physical properties of potential biolubricants based on recinoleic acid, Journal of American oil Chemists society, 87, pp. 937-945. [5] Salih, N., Salimon, J. and Yousif, E. (2011) The physicochemical and tribological properties of oleic acid based trimester biolubricants, Industrial crops and products, 34, pp. 1089-1096. [6] Lathi, P.S. and Mattiasson, B. (2007) Green Approach for the Preparation of biodegradable lubricant base stock from epoxidised vegetable oil, Applied Catalysis B: Environmental, 69, pp. 207-212. [7] Hwang, H.S. and Erhan, S.Z. (2006) Synthetic lubricant basestocks from epoxidized soybean oil and Guerbet alcohols, Industrial Crops and Products,23,pp. 311–317. 10-Dec-13 Synthesis of Bio-Lubricant from Castor Oil Methyl Esters via Epoxidation 25
  • 26. Contd… [8] Salimon, J. and Salih, N. (2010) Chemical Modification of Oleic Acid Oil for Biolubricant Industrial Applications, Australian Journal of Basic and Applied Sciences, 4(7),pp. 1999-2003. [9] Campanella, A., Fontanini, C. and Baltanas, M.A. (2008) High yield epoxidation of fatty acid methyl esters with performic acid generated in situ, Chemical engineering journal,144(3),pp. 466-475. [10] Salimon, J., Salih, N. and Yousif, E. (2012) Biolubricant basestocks from chemically modified ricinoleic acid, Journal of king saud university,24 (1),pp. 11-17. [11] Salimon, J., Salih, N. and Yousif, E. (2011) Synthetic biolubricant basestocks from epoxidised ricinoleic acid:Improved low temperature properties, Chemical Industry,60(3),pp. 127-134. [12] Jin, F.L. and Park S.J. (2008) Thermomechanical behavior of epoxy resins modified with epoxidised vegetable oils, Polymer International, 57,pp. 577-583. [13] Farias, E.A., Leles, M.I.G., Ionashiro, M., Zuppa, T.O. and Filho, N.R.A. (2002) Ecl Quím, 27,pp. 111. [14] Sricharoenchaikul, V. and Atong, D. (2009) Thermal decomposition study on Jatropha curcas L. waste using TGA and fixed bed reactor, Journal of Analytical and Applied Pyrolysis,85,pp. 155–162. [15] Imahara, H., Minami, E., Hari, S. and Saka, S. (2006) Thermal Stability of Biodiesel Fuel as Prepared by Supercritical Methanol Process, The 2nd Joint International Conference on “Sustainable Energy and Environment (SEE 2006)” C-037 (P) 21-23 November 2006, Bangkok, Thailand. 10-Dec-13 Synthesis of Bio-Lubricant from Castor Oil Methyl Esters via Epoxidation 26
  • 27. 10-Dec-13 27

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