Batch Ethanolysis Reaction of Palm Olein Assisted by Ultrasonication
Abstract
In present work, the batch ethanolysis of an ethanal/palm olein molar ratio of 6:1, KC2H4OH as catalyst (1.55 wt.% of oil) at 60 oC synthesizing ethyl ester (POEE) and glycerol using ultrasonic irradiation was investigated. The reaction was activated by sets of various percentages of amplitude and pulse cycles. The mixture temperature, at 37.96 W/kg, was increased from 60.00 oC to 60.30 oC, 60.50 oC, 61.00 oC and 62.00 oC at 0.25, 0.50, 1.00, and 3.00 minutes, respectively. More than 96.5 % ethyl ester were produced between 3 minutes (at 640.58 W/kg) and 9 minutes (37.96 W/kg). This ethanolysis reaction followed the pseudo first-order kinetic model and the reaction rate constant was increased from 1.4036 min-1 at 20 % amplitude to 2.3664 min-1 at 100 % amplitude during continuous ultrasonication. At 100 % amplitude, as decreasing the pulse cycle from 1.00 to 0.90, 0.70, 0.50 and 0.30, the reaction rate constant was decreased from 2.3664 to 2.1252, 1.9857, 1.9123 and 1.8980 min-1, respectively. The kinetic model indicated very high reaction rate within the first minute and slow down toward equilibrium within 10-15 minutes. It was found that the reaction time to synthesize the same percentage of yield would decrease as increasing the electrical energy per mass. For example, the reaction time for 91.94 %Yield was reduced from 9.0 minutes to 5.8, 5.4 and 3.0 minutes as increasing the electrical power consumption from 37.96 W/kg to 75.92, 188.22 and 352.22 W/kg, respectively. Keywords : biodiesel, ethyl ester, ultrasonic, ultrasonicationReferences
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Azam, N. A. M., Uemura, Y., Kusakabe, K., & Bustam, M. A. (2016). Biodiesel production from palm oil using micro tube reactors: effects of catalyst and residence time. Procedia Engineering, 148, 354-360.
Balat, M., Balat, H., & Oz, C. (2008). Progress in bioethanol processing. Prog. Energy Combust. Sci., 34,
551-573.
Chand, P., Chintareddy, V.R., Verkade J.G., & Grewell, D. (2010). Enhancing biodiesel production from soybean oil using ultrasonics. Energy and Fuels, 24, 2010-2015.
Colucci, J.A., Borrero, E.E., & Alape, F. (2005). Biodiesel from an alkaline transesterification reaction of soybean oil using ultrasonic mixing. Journal of the American Oil Chemists' Society, 82(7), 525-530.
Dorado, M.P., Ballesteros, E., Mittelbach, M., & Lopez, F.J. (2004). Kinetic parameters affecting the alkali-catalyzed transesterification process of used olive oil. Energy and Fuels, 18, 1457-1462.
Eevera, T., Rajendran, K., & Saradha, S. (2009). Biodiesel production process optimization and characterization to assess the suitability of the product for varied environmental conditions. Renewable Energy, 34(3), 762-765.
Encinar, J.M., Gonzalez, J.F., & Reinares, A.R. (2007). Ethanolysis of used frying oil: Biodiesel preparation and characterization. Fuel Proc. Tech., 88(5), 513-522.
Enciner, J.M., Gonzalez, J.F., Rodriguez, J.J., & Tajedor, A. (2002). Biodiesels fuel from vegetable oils: transesterification of Cynara cardunculus L. oils with ethanol. Energy and Fuels, 16(2), 443-450.
Feuge, R.O., & Grose, T. (1949). Modification of vegetable oils. VII. Alkali catalyzed interesterification of peanut oil with ethanol. J. American Oil Chem. Soc., 26(3), 97-102.
Freedman, B., Butterfield, R.O., & Pryde, E.H. (1986). Transesterification kinetics of soybean oil. J. American Oil Chem. Soc., 63(10), 1375-1380.
Georgogianni, K.G., Kontominas, M.G., Pomonis, P.J., Avlonitis, D., & Gergis, V. (2008). Alkaline conventional and in situ transesterification of cottonseed oil for the production of biodiesel. Energy Fuels, 22, 2110-2115.
Gogate, P.R. (2008). Cavitational reactors for process intensification of chemical processing applications: A critical review. Chemical Engineering and Processing: Process Intensification, 47, 515-527.
Gogate, P.R., Tayal, R.K., Pandit, A.B. (2006). Cavitation: A technology on the horizon. Current Science, 91, 35-46.
Guan, G., Teshima, M., Sato, C., Son, S. M., Irfan, M.F., Kusakabe, K., Ikeda, N., & Lin, T. (2010). Two-phase flow behavior in microtube reactor during biodiesel production from waste cooking oil. AIChE, 56, 1383-1390.
Guo, Z., Jones, A.G., & Li, N. (2006). The effect of ultrasound on the homogeneous nucleation of BaSO4 during reactive crystallization. Chem. Eng., Sci. 61, 1617-1626.
Gupta, P.K., Kumar, R., Panesar, P.S., & Thapar, V.K. (2007). Parametric studies on bio-diesel prepared from rice bran oil. Agricultural Engineering International: the CIGR Ejournal, 9, (1-12).
Issariyakul, T, Kulkarni, M.G., Dalai, A.K., & Bakhshi, N.N. (2007). Production of biodiesel from waste fryer grease using mixed methanol/ethanol system. Fuel Proc. Tech., 88, 429-436.
Jittrong, T. (2015). Ethanolysis of palm olein using ultrasonic. Master of Engineering Thesis, Burapha
University. (in Thai).
Joelianingsih, Maeda, H., Hagiwara, S., Nabetani, H., Sagara, Y., Soerawidjaya, T.H., Tambunan, A.H., & Abdullah, K. (2008). Biodiesel fuels from palm oil via the non-catalytic transesterification in a bubble column reactor at atmospheric pressure: Kinetic study. Renewable Energy, 33(7), 1629-1636.
Joshi, H., Moser, B.R., Toler, J., & Walker, T. (2010). Preparation and fuel properties of mixtures of soybean oil methyl and ethyl esters. Biomass and Bioenergy, 34, 14-20.
Kalva, A., Sivavsankar, T., & Moholkar, V. (2009). Physical mechanism of Ultrasound-assisted synthesis of biodiesel. Ind. Eng. Chem. Rev., 48, 534-544.
Kulkarni M.G., Dalai, A.K., & Bakhshi, N.N. (2007) Transesterification of canola oil in mixed methanol/ethanol system and use of esters as lubricity additive. Bioresource Technology, 98(10), 2027-2033.
Kumar, D., Kumar, G., & Singh, C.P. (2010). Fast, easy ethanolysis of coconut oil for biodiesel production assisted by ultrasonication. Ultrasonics Sonochemistry, 17, 555-559.
Kumar, D., Kumar, G., Poonam, & Singh, C.P. (2010). Ultrasonic-assisted transesterification of Jatropha curcus oil using solid catalyst, Na/SiO2, Ultrasonics Sonochemistry, 17, 839-844
Leonelli C., & Mason T.J. (2010). Microwave and ultrasonic processing: Now a realistic option for industry. Chem. Eng. Proc., 49, 885-900.
Mahamuni, N.N., & Adewuyi, Y.G. (2009). Optimization of the synthesis of biodiesel via ultrasound-enhanced base-catalyzed transesterification of soybean oil using a multifrequency ultrasonic reactor. Energy and Fuels, 23, 2757-2766.
Marjanovic, A.V., Stamenkovic, O.S., Todorovic, Z.B., Lazic, M.L., & Veljkovic, V.B. (2010). Kinetics of the base-catalyzed sunflower oil ethanolysis. Fuel, 89, 665-671.
Meneghetti, S.M. P., Meneghetti, M.R., Wolf, C.R., Silva, E.C., Lima, G.E.S., Silva, L.D.L., Serra, T.M., Cauduro, F., & Oliveira, L.G.D. (2006). Biodiesel from castor oil: A comparison of ethanolysis versus methanolysis. Energy & Fuels, 20, 2262-2265.
Monnier, H., Wilhelm, A. M., & Delmas, H. (1999). The influence of ultrasound on micromixing in a semi-batch reactor. Chem. Eng. Sci., 54(13-14), 2953-2961.
Noipin, K., & Kumar, S. (2014). Optimization of ethyl ester production from palm oil. Petroleum&Coal, 56, 249-258.
Patchana, N., & Santikunaporn, M. (2012). Biodiesel production by transesterification of palm oil with ethanol. In Proceeding of the 1st Conference on Graduate Student Network of Thailand. Thammasat University, Thailand. (in Thai)
Refaat, A.A. (2010). Different techniques for the production of biodiesel from waste vegetable oil. Int. J. Env. Sci. & Tech., 7, 183-213.
Richard, R., Dubreuil, B., Prat, L., & Thiebaud-roux, S. (2013). Development of continuous processes for vegetable oil alcoholysis in microfluidic devices. OCL, 20(1), 23-32.
Sakthivel, G., Nagarajan, G., Ilangkumaran, M., & Gaikwad, A.B. (2014). Comparative analysis of performance, emission and combustion parameters of diesel engine fuelled with ethyl ester of fish oil and its diesel blends. Fuel, 132, 116-124.
Sanaz, S., Gek, C.N., & Rozita, Y. (2012). The evaluation of various kinetic models for base-catalyzed ethanolysis of palm oil. Bioresource Technology.104, 1-5.
Silva, N.D.L.D., Batistella, C.B., Filho, R.M., & Maciel, M.R.W. (2009). Biodiesel production from castor oil: Optimization of alkaline ethanolysis. Energy Fuels, 23, 5636-5642.
Singh, A.K., Fernando, S.D., & Hernandez, R. (2007). Base-catalyzed fast transesterification of soybean oil using ultrasonication, Energy and Fuels, 21, 1161-1164.
Tiwari, A., Rajest, V.M., & Yadav, S. (2018). Biodiesel production in micro-reactors: A review. Energy Sustain. Dev., 43, 143-161.
Venkateswara, R.P. (2016). Performance analysis of c i engine fuelled with diesel-biodiesel (methyl/ethyl esters) blend of non-edible oil. International Journal of Research-Granthaalayah, 4(7), 20-26.
Virone, C., Kramer, H.J.M., van Rosmale, G.M., Stoop, A.H., & Bakker, T.W. (2006). Primary nucleation induced by ultrasonic cavitation. J. Crys. Growth., 294, 9-15.
Wu, P., Yang, Y., Colucci, J.A., & Grulke, E.A. (2007). Effect of ultrasonication on droplet size in biodiesel mixtures. J. American Oil Chem. Soc., 84(9), 877-884.
Yin, X., Ma, H., You, Q., Wang, Z., & Chang, J. (2012). Comparison of four different enhancing methods for preparing biodiesel through transesterification of sunflower oil. Applied Energy, 91, 320-325.
Azam, N. A. M., Uemura, Y., Kusakabe, K., & Bustam, M. A. (2016). Biodiesel production from palm oil using micro tube reactors: effects of catalyst and residence time. Procedia Engineering, 148, 354-360.
Balat, M., Balat, H., & Oz, C. (2008). Progress in bioethanol processing. Prog. Energy Combust. Sci., 34,
551-573.
Chand, P., Chintareddy, V.R., Verkade J.G., & Grewell, D. (2010). Enhancing biodiesel production from soybean oil using ultrasonics. Energy and Fuels, 24, 2010-2015.
Colucci, J.A., Borrero, E.E., & Alape, F. (2005). Biodiesel from an alkaline transesterification reaction of soybean oil using ultrasonic mixing. Journal of the American Oil Chemists' Society, 82(7), 525-530.
Dorado, M.P., Ballesteros, E., Mittelbach, M., & Lopez, F.J. (2004). Kinetic parameters affecting the alkali-catalyzed transesterification process of used olive oil. Energy and Fuels, 18, 1457-1462.
Eevera, T., Rajendran, K., & Saradha, S. (2009). Biodiesel production process optimization and characterization to assess the suitability of the product for varied environmental conditions. Renewable Energy, 34(3), 762-765.
Encinar, J.M., Gonzalez, J.F., & Reinares, A.R. (2007). Ethanolysis of used frying oil: Biodiesel preparation and characterization. Fuel Proc. Tech., 88(5), 513-522.
Enciner, J.M., Gonzalez, J.F., Rodriguez, J.J., & Tajedor, A. (2002). Biodiesels fuel from vegetable oils: transesterification of Cynara cardunculus L. oils with ethanol. Energy and Fuels, 16(2), 443-450.
Feuge, R.O., & Grose, T. (1949). Modification of vegetable oils. VII. Alkali catalyzed interesterification of peanut oil with ethanol. J. American Oil Chem. Soc., 26(3), 97-102.
Freedman, B., Butterfield, R.O., & Pryde, E.H. (1986). Transesterification kinetics of soybean oil. J. American Oil Chem. Soc., 63(10), 1375-1380.
Georgogianni, K.G., Kontominas, M.G., Pomonis, P.J., Avlonitis, D., & Gergis, V. (2008). Alkaline conventional and in situ transesterification of cottonseed oil for the production of biodiesel. Energy Fuels, 22, 2110-2115.
Gogate, P.R. (2008). Cavitational reactors for process intensification of chemical processing applications: A critical review. Chemical Engineering and Processing: Process Intensification, 47, 515-527.
Gogate, P.R., Tayal, R.K., Pandit, A.B. (2006). Cavitation: A technology on the horizon. Current Science, 91, 35-46.
Guan, G., Teshima, M., Sato, C., Son, S. M., Irfan, M.F., Kusakabe, K., Ikeda, N., & Lin, T. (2010). Two-phase flow behavior in microtube reactor during biodiesel production from waste cooking oil. AIChE, 56, 1383-1390.
Guo, Z., Jones, A.G., & Li, N. (2006). The effect of ultrasound on the homogeneous nucleation of BaSO4 during reactive crystallization. Chem. Eng., Sci. 61, 1617-1626.
Gupta, P.K., Kumar, R., Panesar, P.S., & Thapar, V.K. (2007). Parametric studies on bio-diesel prepared from rice bran oil. Agricultural Engineering International: the CIGR Ejournal, 9, (1-12).
Issariyakul, T, Kulkarni, M.G., Dalai, A.K., & Bakhshi, N.N. (2007). Production of biodiesel from waste fryer grease using mixed methanol/ethanol system. Fuel Proc. Tech., 88, 429-436.
Jittrong, T. (2015). Ethanolysis of palm olein using ultrasonic. Master of Engineering Thesis, Burapha
University. (in Thai).
Joelianingsih, Maeda, H., Hagiwara, S., Nabetani, H., Sagara, Y., Soerawidjaya, T.H., Tambunan, A.H., & Abdullah, K. (2008). Biodiesel fuels from palm oil via the non-catalytic transesterification in a bubble column reactor at atmospheric pressure: Kinetic study. Renewable Energy, 33(7), 1629-1636.
Joshi, H., Moser, B.R., Toler, J., & Walker, T. (2010). Preparation and fuel properties of mixtures of soybean oil methyl and ethyl esters. Biomass and Bioenergy, 34, 14-20.
Kalva, A., Sivavsankar, T., & Moholkar, V. (2009). Physical mechanism of Ultrasound-assisted synthesis of biodiesel. Ind. Eng. Chem. Rev., 48, 534-544.
Kulkarni M.G., Dalai, A.K., & Bakhshi, N.N. (2007) Transesterification of canola oil in mixed methanol/ethanol system and use of esters as lubricity additive. Bioresource Technology, 98(10), 2027-2033.
Kumar, D., Kumar, G., & Singh, C.P. (2010). Fast, easy ethanolysis of coconut oil for biodiesel production assisted by ultrasonication. Ultrasonics Sonochemistry, 17, 555-559.
Kumar, D., Kumar, G., Poonam, & Singh, C.P. (2010). Ultrasonic-assisted transesterification of Jatropha curcus oil using solid catalyst, Na/SiO2, Ultrasonics Sonochemistry, 17, 839-844
Leonelli C., & Mason T.J. (2010). Microwave and ultrasonic processing: Now a realistic option for industry. Chem. Eng. Proc., 49, 885-900.
Mahamuni, N.N., & Adewuyi, Y.G. (2009). Optimization of the synthesis of biodiesel via ultrasound-enhanced base-catalyzed transesterification of soybean oil using a multifrequency ultrasonic reactor. Energy and Fuels, 23, 2757-2766.
Marjanovic, A.V., Stamenkovic, O.S., Todorovic, Z.B., Lazic, M.L., & Veljkovic, V.B. (2010). Kinetics of the base-catalyzed sunflower oil ethanolysis. Fuel, 89, 665-671.
Meneghetti, S.M. P., Meneghetti, M.R., Wolf, C.R., Silva, E.C., Lima, G.E.S., Silva, L.D.L., Serra, T.M., Cauduro, F., & Oliveira, L.G.D. (2006). Biodiesel from castor oil: A comparison of ethanolysis versus methanolysis. Energy & Fuels, 20, 2262-2265.
Monnier, H., Wilhelm, A. M., & Delmas, H. (1999). The influence of ultrasound on micromixing in a semi-batch reactor. Chem. Eng. Sci., 54(13-14), 2953-2961.
Noipin, K., & Kumar, S. (2014). Optimization of ethyl ester production from palm oil. Petroleum&Coal, 56, 249-258.
Patchana, N., & Santikunaporn, M. (2012). Biodiesel production by transesterification of palm oil with ethanol. In Proceeding of the 1st Conference on Graduate Student Network of Thailand. Thammasat University, Thailand. (in Thai)
Refaat, A.A. (2010). Different techniques for the production of biodiesel from waste vegetable oil. Int. J. Env. Sci. & Tech., 7, 183-213.
Richard, R., Dubreuil, B., Prat, L., & Thiebaud-roux, S. (2013). Development of continuous processes for vegetable oil alcoholysis in microfluidic devices. OCL, 20(1), 23-32.
Sakthivel, G., Nagarajan, G., Ilangkumaran, M., & Gaikwad, A.B. (2014). Comparative analysis of performance, emission and combustion parameters of diesel engine fuelled with ethyl ester of fish oil and its diesel blends. Fuel, 132, 116-124.
Sanaz, S., Gek, C.N., & Rozita, Y. (2012). The evaluation of various kinetic models for base-catalyzed ethanolysis of palm oil. Bioresource Technology.104, 1-5.
Silva, N.D.L.D., Batistella, C.B., Filho, R.M., & Maciel, M.R.W. (2009). Biodiesel production from castor oil: Optimization of alkaline ethanolysis. Energy Fuels, 23, 5636-5642.
Singh, A.K., Fernando, S.D., & Hernandez, R. (2007). Base-catalyzed fast transesterification of soybean oil using ultrasonication, Energy and Fuels, 21, 1161-1164.
Tiwari, A., Rajest, V.M., & Yadav, S. (2018). Biodiesel production in micro-reactors: A review. Energy Sustain. Dev., 43, 143-161.
Venkateswara, R.P. (2016). Performance analysis of c i engine fuelled with diesel-biodiesel (methyl/ethyl esters) blend of non-edible oil. International Journal of Research-Granthaalayah, 4(7), 20-26.
Virone, C., Kramer, H.J.M., van Rosmale, G.M., Stoop, A.H., & Bakker, T.W. (2006). Primary nucleation induced by ultrasonic cavitation. J. Crys. Growth., 294, 9-15.
Wu, P., Yang, Y., Colucci, J.A., & Grulke, E.A. (2007). Effect of ultrasonication on droplet size in biodiesel mixtures. J. American Oil Chem. Soc., 84(9), 877-884.
Yin, X., Ma, H., You, Q., Wang, Z., & Chang, J. (2012). Comparison of four different enhancing methods for preparing biodiesel through transesterification of sunflower oil. Applied Energy, 91, 320-325.
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2018-10-08
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