Supercritical transesterification of beef tallow for biodiesel production in a batch reactor
Keywords:
Biodiesel, Transesterification, Vegetable oils, Fatty acids, Hydrotreating, Glycerol
Abstract
Supercritical transesterification experiments of beef tallow with ethanol were carried out in a batch reactor in order to assess the effect of temperature (350 - 400°C), reactant molar ratio (9:1 - 15:1) and reac-tion time (8 - 40 min). Composition of the produced biofuel was assessed in terms of the percentage of peak area of the long chain Fatty Acid Ethyl Esters (FAEEs) identified, including also the decomposition products generated as a result of thermal cracking or cis-trans isomerization reactions. Thermal decomposi-tion of FAEEs produced from beef tallow included short chain ethyl esters (C8 - C13), ethyl pentadecanoate (C15:0), heptadecanoate (C17:0), not initially present or prevalent in triglycerides sources, as well as ethyl stearate (C18:0) and n-alkanes. Glycerol decomposition reactions were also verified by the presence of glycerol ethers and water content in the produced biodiesel. The highest conversion of triglycerides was verified at 400°C, 15:1 triglycerides to ethanol molar ratio and 40-minute reaction time. At these conditions, ethyl oleate (C18:1) decomposed completely to form cis-trans isomers as well as ethyl octadecanoate (C18:0), which was attributed to double bond hydrogenation reactions. Short chain ethyl esters and glycerol decomposition products have the potential to benefit certain properties of the fuel such as viscosity and cold flow.
References
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https://doi.org/10.1021/ie800542k
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https://doi.org/10.1016/j.fuel.2009.06.029
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https://doi.org/10.1016/j.supflu.2010.11.016
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https://doi.org/10.1016/j.biortech.2011.08.105
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https://doi.org/10.1016/j.biombioe.2010.02.001
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https://doi.org/10.1016/j.jaap.2011.07.003
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https://doi.org/10.1016/j.fuel.2011.06.049
Sun, Y., Reddy, H. K., Muppaneni, T., Ponnusamy, S., Patil, P. D., Li, C., Jiang, L & Deng, S. (2014). A comparative study of direct transesterification of camelina oil under supercritical methanol, ethanol and 1-butanol conditions. Fuel, 135: 530-536.
https://doi.org/10.1016/j.fuel.2014.06.070
Tan, K. T., Lee, K. T. & Mohamed, A. R. (2010). Effects of free fatty acids, water content and co-solvent on biodiesel production by supercritical methanol reaction. J. Supercrit. Fluids, 53(1-3), 88-91.
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https://doi.org/10.1016/j.biombioe.2009.12.007
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https://doi.org/10.1021/ef800175e
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https://doi.org/10.1016/j.rser.2014.01.038
Becerra, Y. V. & Ramírez, N. E. (2013). Estudio experimental de la utilización de sebo vacuno para la producción de biodiesel por medio del proceso de transesterificación supercrítica. Tesis de Grado, Ingenieria Ambiental y Sanitaria. Universidad de La Salle. Bogotá. 79pp.
Bertoldi, C., Da Silva, C., Bernardon, J. P., Corazza, M. L., Filho, L. C., Oliveira, J. V., & Corazza, F. C. (2009). Continuous production of biodiesel from soybean oil in supercritical ethanol and carbon dioxide as cosolvent. Energy Fuels, 23(10), 5165-5172.
https://doi.org/10.1021/ef900402r
Biktashev, S. A., Usmanov, R. A., Gabitov, R. R., Gazizov, R. A., Gumerov, F. M., Gabitov, F. R., Abdulagatov, I. M., Yarullin, R. S. & Yakushev, I. A. (2011). Transesterifica- tion of rapeseed and palm oils in supercritical methanol and ethanol. Biomass Bioenerg., 35(7), 2999-3011.
https://doi.org/10.1016/j.biombioe.2011.03.038
Bunyakiat, K., Makmee, S., Sawangkeaw, R. & Ngamprasertsith, S. (2006). Continuous production of biodiesel via transesterification from vegetable oils in supercritical methanol. Energy Fuels, 20(2), 812-817.
https://doi.org/10.1021/ef050329b
Chakraborty, R., Gupta, A. K. & Chowdhury, R. (2014). Conversion of slaughterhouse and poultry farm animal fats and wastes to biodiesel: Parametric sensitivity and fuel quality assessment. Renew. Sust. Energ. Rev., 29: 120-134.
https://doi.org/10.1016/j.rser.2013.08.082
Da Cunha, M. E., Krause, L. C., Moraes, M. S. A., Faccini, C. S., Jacques, R. A., Almeida, S. R., Rodrigues, M. R. A & Caramão, E. B. (2009). Beef tallow biodiesel produced in a pilot scale. Fuel Process. Technol., 90(4), 570-575.
https://doi.org/10.1016/j.fuproc.2009.01.001
Gui, M. M., Lee, K. T. & Bhatia, S. (2009). Supercritical ethanol technology for the production of biodiesel: Process optimization studies. J. Supercrit. Fluids, 49(2), 286-292.
https://doi.org/10.1016/j.supflu.2008.12.014
Karmakar, A., Karmakar, S. & Mukherjee, S. (2010). Properties of various plants and animals feedstocks for biodiesel production. Bioresour. Technol., 101(19), 7201-7210.
https://doi.org/10.1016/j.biortech.2010.04.079
Kusdiana, D. & Saka, S. (2004). Effects of water on biodiesel fuel production by supercritical methanol treatment. Bioresour. Technol., 91(3), 289-295.
https://doi.org/10.1016/S0960-8524(03)00201-3
Lee, W. J., Liu, Y. C., Mwangi, F. K., Chen, W. H., Lin, S. L., Fukushima, Y., Liao, C. N. & Wang, L. C. (2011). Assessment of energy performance and air pollutant emissions in a diesel engine generator fueled with water-containing ethanol-biodiesel-diesel blend of fuels. Energy, 36(9), 5591-5599.
https://doi.org/10.1016/j.energy.2011.07.012
Lin, R., Zhu, Y. & Tavlarides, L. L. (2013). Mechanism and kinetics of thermal decomposition of biodiesel fuel. Fuel, 106: 593-604.
https://doi.org/10.1016/j.fuel.2012.12.013
Lin, R., Zhu, Y. & Tavlarides, L. L. (2014). Effect of ther- mal decomposition on biodiesel viscosity and cold flow property. Fuel, 117: 981-988.
https://doi.org/10.1016/j.fuel.2013.10.034
Marulanda, V. F. (2012). Biodiesel production by supercriti- cal methanol transesterification: Process simulation and potential environmental impact assessment. J. Cleaner Production, 33: 109-116.
https://doi.org/10.1016/j.jclepro.2012.04.022
Marulanda, V. F., Anitescu, G. & Tavlarides, L. L. (2010a). Biodiesel fuels through a continuous flow process of chicken fat supercritical transesterification. Energy Fuels, 24(1), 253-260.
https://doi.org/10.1021/ef900782v
Marulanda, V. F., Anitescu, G. & Tavlarides, L. L. (2010b). Investigations on supercritical transesterification of chicken fat for biodiesel production from low-cost lipid feedstocks. J. Supercrit. Fluids, 54(1), 53-60.
https://doi.org/10.1016/j.supflu.2010.04.001
Mendow, G., Veizaga, N. S., Sánchez, B. S. & Querini, C. A. (2011). Biodiesel production by two-stage transesterification with ethanol. Bioresour. Technol., 102(22), 10407-10413.
https://doi.org/10.1016/j.biortech.2011.08.052
Moraes, M. S. A., Krause, L. C., Da Cunha, M. E., Faccini, C. S., de Menezes, E. W., Veses, R. C., Rodrigues, M. R. A. & Caramão, E. B. (2008). Tallow biodiesel: Properties evaluation and consumption tests in a diesel engine. Energy Fuels, 22(3), 1949-1954.
https://doi.org/10.1021/ef7006535
Muppaneni, T., Reddy, H. K., Patil, P. D., Dailey, P., Aday, C. & Deng, S. (2012). Ethanolysis of camelina oil under supercritical condition with hexane as a co-solvent. Appl. Energ., 94: 84-88.
https://doi.org/10.1016/j.apenergy.2012.01.023
Muppaneni, T., Reddy, H. K., Ponnusamy, S., Patil, P. D., Sun, Y., Dailey, P. & Deng, S. (2013). Optimization of biodiesel production from palm oil under super- critical ethanol conditions using hexane as co-solvent: A response surface methodology approach. Fuel, 107: 633-640.
https://doi.org/10.1016/j.fuel.2012.11.046
Nan, Y., Liu, J., Lin, R. & Tavlarides, L. L. (2015). Production of biodiesel from microalgae oil (Chlorella protothecoides) by non-catalytic transesterification in supercritical methanol and ethanol: Process optimization. J. Supercrit. Fluids, 97: 174-182.
https://doi.org/10.1016/j.supflu.2014.08.025
Pinnarat, T. & Savage, P. E. (2008). Assessment of non- catalytic biodiesel synthesis using supercritical reaction conditions. Ind. Eng. Chem. Res., 47(18), 6801-6808.
https://doi.org/10.1021/ie800542k
Qi, D. H., Chen, H., Matthews, R. D. & Bian, Y. Z. (2010). Combustion and emission characteristics of ethanol- biodiesel-water micro-emulsions used in a direct injection compression ignition engine. Fuel, 89(5), 958-964.
https://doi.org/10.1016/j.fuel.2009.06.029
Quesada-Medina, J. & Olivares-Carrillo, P. (2011). Evidence of thermal decomposition of fatty acid methyl esters during the synthesis of biodiesel with supercritical methanol. J. Supercrit. Fluids, 56(1), 56-63.
https://doi.org/10.1016/j.supflu.2010.11.016
Rahmat, N., Abdullah, A. Z. & Mohamed, A. R. (2010). Recent progress on innovative and potential technologies for glycerol transformation into fuel additives: A critical review. Renew. Sust. Energ. Rev., 14(3), 987-1000.
https://doi.org/10.1016/j.rser.2009.11.010
Rodríguez-Guerrero, J. K., Rubens, M. F. & Rosa, P. T. V. (2013). Production of biodiesel from castor oil using sub and supercritical ethanol: Effect of sodium hydroxide on the ethyl ester production. J. Supercrit. Fluids, 83: 124-132. Saka, S. & Kusdiana, D. (2001). Biodiesel fuel from rapeseed oil as prepared in supercritical methanol. Fuel, 80(2), 225-231.
https://doi.org/10.1016/j.supflu.2013.08.016
Santana, A., Maçaira, J. & Larrayoz, M. A. (2012). Continuous production of biodiesel from vegetable oil using supercritical ethanol/carbon dioxide mixtures. Fuel Process. Technol., 96: 214-219.
https://doi.org/10.1016/j.fuproc.2011.12.021
Sawangkeaw, R., Bunyakiat, K. & Ngamprasertsith, S. (2010). A review of laboratory-scale research on lipid conversion to biodiesel with supercritical methanol (2001-2009). J. Supercrit. Fluids, 55(1), 1-13.
https://doi.org/10.1016/j.supflu.2010.06.008
Sawangkeaw, R., Teeravitud, S., Bunyakiat, K. & Ngam- prasertsith, S. (2011). Biofuel production from palm oil with supercritical alcohols: Effects of the alcohol to oil molar ratios on the biofuel chemical composition and properties. Bioresour. Technol., 102(22), 10704-10710.
https://doi.org/10.1016/j.biortech.2011.08.105
Sawangkeaw, R., Tejvirat, P., Ngamcharassrivichai, C. & Ngamprasertsith, S. (2012). Supercritical transesterifica- tion of palm oil and hydrated ethanol in a fixed bed reac- tor with a CaO/Al2O3 catalyst. Energies, 5(4), 1062-1080.
https://doi.org/10.3390/en5041062
Seames, W., Luo, Y., Ahmed, I., Aulich, T., Kubátová, A., Št'ávová, J. & Kozliak, E. (2010). The thermal cracking of canola and soybean methyl esters: Improvement of cold flow properties. Biomass Bioenerg., 34(7), 939-946.
https://doi.org/10.1016/j.biombioe.2010.02.001
Shin, H. Y., Lim, S. M., Bae, S. Y. & Oh, S. C. (2011). Thermal decomposition and stability of fatty acid methyl esters in supercritical methanol. J. Anal. Appl. Pyrol., 92(2), 332-338.
https://doi.org/10.1016/j.jaap.2011.07.003
Stamenković, O. S., Veličković, A. V. & Veljković, V. B. (2011). The production of biodiesel from vegetable oils by ethanolysis: Current state and perspectives. Fuel, 90(11), 3141-3155.
https://doi.org/10.1016/j.fuel.2011.06.049
Sun, Y., Reddy, H. K., Muppaneni, T., Ponnusamy, S., Patil, P. D., Li, C., Jiang, L & Deng, S. (2014). A comparative study of direct transesterification of camelina oil under supercritical methanol, ethanol and 1-butanol conditions. Fuel, 135: 530-536.
https://doi.org/10.1016/j.fuel.2014.06.070
Tan, K. T., Lee, K. T. & Mohamed, A. R. (2010). Effects of free fatty acids, water content and co-solvent on biodiesel production by supercritical methanol reaction. J. Supercrit. Fluids, 53(1-3), 88-91.
https://doi.org/10.1016/j.supflu.2010.01.012
Teixeira, L. S. G., Couto, M. B., Souza, G. S., Filho, M. A., Assis, J. C. R., Guimarães, P. R. B., Pontes, L. A. M, Almeida, S. Q. & Teixeira, J. S. R. (2010). Characterization of beef tallow biodiesel and their mixtures with soybean biodiesel and mineral diesel fuel. Biomass Bioenerg., 34(4), 438-441.
https://doi.org/10.1016/j.biombioe.2009.12.007
Velez, A., Soto, G., Hegel, P., Mabe, G. & Pereda, S. (2012). Continuous production of fatty acid ethyl esters from sunflower oil using supercritical ethanol. Fuel, 97: 703-709.
https://doi.org/10.1016/j.fuel.2012.02.024
Vieitez, I., da Silva, C., Borges, G. R., Corazza, F. C., Oliveira, J. V., Grompone, M. A. & Jachmanián, I. (2008). Continuous production of soybean biodiesel in supercritical ethanol-water mixtures. Energy Fuels, 22(4), 2805-2809.
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How to Cite
Marulanda Cardona, V. F., & Marulanda Buitrago, P. A. (2015). Supercritical transesterification of beef tallow for biodiesel production in a batch reactor. CT&F - Ciencia, Tecnología Y Futuro, 6(2), 57–68. https://doi.org/10.29047/01225383.20
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Published
2015-12-15
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Scientific and Technological Research Articles
