Super phosphoric acid catalyzed esterification of Palm Fatty Acid Distillate for biodiesel production: physicochemical parameters and kinetics

Metre, Anand V.; Nath, Kaushik

doi:10.1515/pjct-2015-0013

Abstract

In the present study the esterification of palm fatty acid distillate (PFAD), a by-product from palm oil industry, in the presence of super phosphoric acid (SPA) catalyst was studied. The effects of various physico-chemical parameters such as temperature, PFAD to methanol molar ratio and amount of catalyst on the conversion of biodiesel were investigated. The percent conversion of FFA and properties of the biodiesel were determined following standard methodologies. Percent conversion of biodiesel was found to increase with the increase in PFAD to methanol molar ratio and at 1:12 molar ratio and 70°C temperature 95% conversion was achieved. Thermodynamic parameters were also evaluated in terms of Gibbs free energy, enthalpy and entropy at different molar ratio and temperatures. Both pseudo first and second order irreversible kinetics were applied to a wide range of experimental data. However, according to regression coefficient (R2) the second order described better experimental behavior of kinetic data.

References

1. Van, Gerpen, J., Shanks, B., Pruszko, R., Clements, D. & Knothe, G. (2004). Biodiesel production technology NREL/ SR-510-36244. Springfield VA: Iowa State University and Renewable Products Laboratory USDA/NCAUR.
Search in Google Scholar
2. Kiss, A.A., Dimian, A.C. & Rothenberg, G. (2006). Solid Acid Catalysts for Biodiesel Production Towards Sustainable Energy. Adv. Synth. Ccatal. 348 (1-2), 75-81. DOI: 10.1002/ adsc.200505160.10.1002/adsc.200505160
Search in Google Scholar
3. Canakci, M. & Van, Gerpen, J. (1999). Biodiesel production via acid catalysis. Transactions of ASAE 42(5), 1203-1210. DOI: 0001-2351/99/4205-1203.10.13031/2013.13285
Search in Google Scholar
4. Chongkhong, S., Tongurai, C., Chetpattananondh, P. & Bunyakan, C. (2007). Biodiesel production by esterification of palm fatty acid distillate. Biomass and Bioenergy 31(8), 563-568. DOI: 10.1016/j.biombioe.2007.03.001.10.1016/j.biombioe.2007.03.001
Search in Google Scholar
5. Mongkolbovornkij, P., Champreda, V., Sutthisripok, W. & Laosiripojana, N. (2010). Esterification of industrial-grade palm fatty acid distillate over modified ZrO2 (with WO3-, SO4 -and TiO2-): Effects of co-solvent adding and water removal. Fuel Processing Technology 91(11). 1510-1516. DOI: 10.1016/j.fuproc.2010.05.030.10.1016/j.fuproc.2010.05.030
Search in Google Scholar
6. Cho, H.J., Kim, S.H., Hong, S.W. & Yeo, Y.K. (2012). A single step non-catalytic esterification of palm fatty acid distillate (PFAD) for biodiesel production. Fuel 93(1), 373-380. DOI: org/10.1016/j.fuel.2011.08.063.10.1016/j.fuel.2011.08.063
Search in Google Scholar
7. Yujaroen, D., Goto, M., Sasaki, M. & Shotipruk, A. (2009). Esterification of palm fatty acid distillate (PFAD) in supercritical methanol: effect of hydrolysis on reaction activity. Fuel 88(10), 2011-2016. DOI: 10.1016/j.fuel.2009.02.040.10.1016/j.fuel.2009.02.040
Search in Google Scholar
8. Demirbas, A. (2009). Progress and recent trends in biodiesel fuels. Energy Conversion and Management 50(1), 14-34. DOI: 10.1016/j.enconman.2008.09.001.10.1016/j.enconman.2008.09.001
Search in Google Scholar
9. Noureddini, H. & Zhu, D. (1997). Kinetics of transesterification of soybean oil. J. Ame. Oil Chem. Soc., 74(11), 1457-1463. DOI: 10.1007/s11746-997-0254-2.10.1007/s11746-997-0254-2
Search in Google Scholar
10. Vicente, G., Martinez, M., Aracil, J. & Esteban, A. (2005). Kinetics of sunflower oil methanolysis. Industrial & Engineering Chemistry Research 44(15), 5447-5454. DOI: 10.1021/ie040208j.10.1021/ie040208j
Search in Google Scholar
11. Darnoko, D. & Cheryan, M. (2000). Kinetics of palm oil transesterification in a batch reactor. J. Ame. Oil Chem. Soc. 77(12), 1263-1267. DOI: 10.1007/s11746-000-0198-y.10.1007/s11746-000-0198-y
Search in Google Scholar
12. Stamenkovic, O.S., Todorovic, Z.B., Lazic, M.L., Veljkovic, V.B. & Skala, D.U. (2008). Kinetics of sunflower oil methanolysis at low temperatures. Biores. Technol. 99(5), 1131-1140. DOI: 10.1016/j.biortech.2007.02.028.10.1016/j.biortech.2007.02.028
Search in Google Scholar
13. Deshmane, V.G., Gogate, P.R., & Pandit, A.B. (2009). Ultrasound assisted synthesis of isopropyl esters from palm fatty acid distillate. Ultrasonics Sonochemistry 16(3), 345-350. DOI: 10.1016/j.ultsonch.2008.09.004.10.1016/j.ultsonch.2008.09.004
Search in Google Scholar
14. Chin, L.H., Abdullah, A.Z. & Hameed, B.H. (2012). Sugar cane bagasse as solid catalyst for synthesis of methyl esters from palm fatty acid distillate. Chem. Engine. J. 183(1), 104-107. DOI: 10.1016/j.cej.2011.12.028.10.1016/j.cej.2011.12.028
Search in Google Scholar
15. Kelkar, M.A., Gogate, P.R. & Pandit, A.B. (2008). Intensification of esterification of acids for synthesis of biodiesel using acoustic and hydrodynamic cavitation. Ultrasonics Sonochemistry 15(3), 188-194. DOI: 10.1016/j.ultsonch.2007.04.003.10.1016/j.ultsonch.2007.04.003
Search in Google Scholar
16. Wen, B., Eli, W., Xue, Q., Dong, X. & Liu, W. (2007). Ultrasound accelerated esterification of palmitic acid with vitamin C. Ultrasonic Sonochemistry 14(2), 213-218. DOI: 10.1016/j.ultsonch.2006.02.003.10.1016/j.ultsonch.2006.02.003
Search in Google Scholar
17. Freedman, B., Pryde, E.H. & Mounts, T.L. (1984). Variables affecting the yields of fatty esters from transesterified vegetable oils. J. Ame. Oil Chem. Soci. 61(10), 1638-1643. DOI: 10.1007/BF02541649.10.1007/BF02541649
Search in Google Scholar
18. Crabbe, E., Nolasco-Hipolito, C., Kobayashi, G., Sonomoto, K. & Ishizaki, A. (2001). Biodiesel production from crude palm oil and evaluation of butanol extraction and fuel properties. Process Biochem. 37(1), 65-71. DOI:10.1016/S0032-9592(01)00178-9.10.1016/S0032-9592(01)00178-9
Search in Google Scholar
19. Keyes, D.B. (1932). Esterification processes and equipment. Ind. Engine. Chem. Res. 24(10), 1096-1103. DOI: 10.1021/ie50274a003.10.1021/ie50274a003
Search in Google Scholar
20. Sridharan, R. & Mathai, I.M. (1974). Transesterification reactions. J. Sci. Ind. Res. 33, 178-187.
Search in Google Scholar
21. Caetano, C.S., Fonseca, I.M., Ramos, A.M., Vital, J. & Castanheiro, J.E. (2008). Esterification of free fatty acids with methanol using heteropolyacids immobilized on silica. Catalysis Communications 9(10), 1996-1999. DOI: 10.1016/j. catcom.2008.03.036
Search in Google Scholar
22. Berrios, M., Siles, J., Martın, M.A. & Martın, A. (2007). A kinetic study of the esterification of free fatty acids (FFA) in sunflower oil. Fuel 86(15), 2383-2388. DOI: 10.1016/j. fuel.2007.02.002.
Search in Google Scholar
23. Kusdiana, D. & Saka, S. (2004). Effects of water on biodiesel fuel production by supercritical methanol treatment. Bioresource Technology 91(3), 289-295. DOI: 10.1016/S0960-8524(03)00201-3.10.1016/S0960-8524(03)00201-3
Search in Google Scholar
24. Freedman, B., Butterfield, R.O. & Pryde, E.H. (1986). Transesterification kinetics of soybean oil. J. Ame. Oil Chem. Soc. 63(10), 1375-1380. DOI: 10.1007/BF02679606.10.1007/BF02679606
Search in Google Scholar
25. Khan, A.K. (2002). Research into biodiesel kinetics & catalyst development. Uni of Queensland Brisbane Queensland.
Search in Google Scholar
26. Hodl, P. & Schindlbauer, H. (1994). Gas chromatographic determination of free glycerol involving extraction. In Handbook of Analytical Methods for Fatty Acid Methyl Esters used as Diesel Fuel. FICHTE Institute, Vienna.
Search in Google Scholar
27. Mittelbach, M., Pokits, B. & Silberholz, A. (1992). Diesel fuel derived from vegetable oils, IV: production and fuel properties of fatty acid methyl esters from used frying oil. In Liquid Fuels from Renewable Resources, Proc. Alternative Energy Conj, (14-15 December 1992) Ame. Soc. Agric. Eng. Michigan, USA, p. 74.
Search in Google Scholar
28. Boros, L., Batista, M.L.S., Vaz, R.V., Figueiredo, B.R., Fernandes, V.F.S., Costa, M.C., Krhenbuhl, M.A., Meirelles, A.J.A. & Coutinho, J.A.P. (2009). Crystallization behavior of mixtures of fatty acid ethyl esters with ethyl stearate. Energy Fuels 23(9), 4625-4629. DOI: 10.1021/ef900366z.10.1021/ef900366z
Search in Google Scholar
29. Sheehan, J., Camobreco, V., Duffield, J., Graboski, M. & Shapouri, H. (1998). National Renewable Energy Laboratory. Golden, Colorado, 314.
Search in Google Scholar
30. Malvade, A.V. & Satpute, S.T. (2013). Production of Palm fatty acid distillate biodiesel and effects of its blends on performance of single cylinder diesel engine. Procedia Engineering 64(1), 1485-1494. DOI: 10.1016/j.proeng.2013.09.230. 10.1016/j.proeng.2013.09.230
Search in Google Scholar

Super phosphoric acid catalyzed esterification of Palm Fatty Acid Distillate for biodiesel production: physicochemical parameters and kinetics

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