Synthesising unsaturated fatty alcohols from fatty methyl esters using catalysts based on ruthenium and tin supported on alumina
Síntesis de alcoholes grasos insaturados a partir de metilésteres grasos usando catalizadores a base de rutenio y estaño soportados sobre alúmina
DOI:
https://doi.org/10.15446/ing.investig.v31n1.20528Keywords:
fatty alcohol, hydrogenation, methyl ester, palm oil, heterogeneous catalysis. (en)alcoholes grasos, hidrogenación, metilésteres, aceite de palma, catálisis heterogénea. (es)
Downloads
Most promising catalysts for synthesising unsaturated fatty alcohols are based on group 8 metals with a promoter like tin, because the process can be carried out in moderate conditions, and these metals are less toxic than chromium. There have been no reports about the use of this catalyst to date using raw materials like methyl ester blends or evaluation reusing catalysts. This paper presents the hydrogenation of methyl esters from palm oil and commercial methyl oleate with Ru-Sn/Al2O3 catalysts prepared by impregnation, at moderate pressure and temperature (5 MPa and 270°C). Greater selectivity to unsaturated alcohol and the less selectivity to methyl stearate was found for an optimal Sn:Ru=2 ratio. Hydrogenation of palm oil methyl esters with this catalyst produced a mixture of oleyl alcohol, saturated alcohols having 16-18 carbon atoms and heavy esters. Raw material had no great effect on catalyst activity. However, the catalyst showed deactivation through several uses due to decreased catalytic area.
Los sistemas más promisorios para la síntesis de alcoholes grasos mediante hidrogenación catalítica son los basados en metales del grupo VIII con un promotor como el estaño, debido a que permiten realizar el proceso bajo condiciones moderadas, además que son menos tóxicos que los basados en cromo. A la fecha no se han realizado estudios de estos catalizadores con materias primas como mezclas de metil-ésteres o evaluaciones de la reutilización de ellos. En este artículo se estudia la hidrogenación de metilésteres derivados del aceite de palma y de metiloleato comercial con catalizadores de Ru-Sn/Al2O3 preparados por impregnación, a presión y temperatura moderadas (5 Mpa y 270 °C). Se encuentra que para una relación óptima Sn/Ru = 2 se obtiene mayor selectividad hacia el alcohol insaturado y menos hacia metilestearato. La hidrogenación de metilésteres del aceite de palma con este catalizador da lugar a una mezcla de alcoholes insaturados y de saturados de 16 y 18 carbonos, además de ésteres pesados. El tipo de materia prima no tiene un efecto muy significativo sobre la actividad del catalizador; sin embargo, éste presenta desactivación a lo largo de varios ensayos debido a la pérdida de área catalítica.
References
Adkins, H., Sauer, J., The selective hydrogenation of unsaturated esters to unsaturated alcohols., Journal of the American Chemical Society, Vol. 59, No. 1, Ene.,1937, pp.1-3.
Cheah, K.Y., Tang, T.S., Mizukami, F., Niwa, S., Toba, M., Choo, Y.M., Selective hydrogenation of oleic acid to 9-octadecen-1-ol: catalysts preparation and optimum reaction conditions., Journal of the American Oil Chemists’ Society, Vol. 69, No. 5, May.,1992, pp.410-416.
Cheah, K.Y., Tang, T.S., Mizukami, F, Niwa, S, Toba, M., Hydrogenation of 9-octadecenoic acid by Ru-Sn-Al2O3 catalysts: effects of catalyst preparation method., Journal of the American Oil Chemists’ Society, Vol. 71 No. 5, May.,1994, pp. 501-506.
Echeverri, D.A., Marín, J. M., Restrepo, G. M., Rios, L.A., Characterization and carbonylic hydrogenation of methyl oleate over Ru-Sn/Al2O3: Effects of metal precursor and chlorine removal., Applied Catalysis A: General, Vol 366, No 2, Sept., 2009, pp. 342-347.
Echeverri, D.A., Marín, J. M., Ríos, L.A., Hidrogenación de Metil Oleato con Catalizadores de Ru-Sn/Al2O3: Método Sol-gel vs. Impregnación., Información Tecnológica, Vol. 21, No 3, May., 2010, pp. 77-86.
Egan, R., Earl, G.W., Ackerman, J., Properties and uses of some unsaturated fatty alcohols and their derivatives., Journal of the American Oil Chemists´ Society, Vol. 61, No.2, Feb., 1984; pp. 324-329.
Jaimes, D., Romero, C.A., Narváez, P.C., Principales tecnologías para la elaboración de oleoquímicos a partir de los aceites de palma y palmiste., Palmas, Vol. 25, No.1, Ene., 2004; pp. 47-64.
Kreutzer, U., Manufacture of Fatty Alcohols Based on Natural Fats and Oils., Journal of the American Oil Chemists´ Society, Vol. 61, No.2, Feb., 1984, pp. 343-348.
Monick, J.A., Fatty alcohols, Journal of the American Oil Chemists´ Society., Vol. 56, No.2, Feb., 1979, pp. 853-860 A.
Narasimhan, C.S., Deshpande, V.M., Ramnarayan, K., Studies on ruthenium-tin boride catalysts I. Characterizaction., Journal of Catalysis, Vol.121 No.1, Ene., 1990, pp.165-173.
Narasimhan, C.S., Deshpande, V.M., Ramnarayan, K., Studies on ruthenium-tin boride catalysts II. Hydrogenation of fatty acid esters to fatty alcohols., Journal of Catalysis, Vol. 121, No.1, Ene., 1990, pp.174-182.
Poels, E.K., Sulfur deactivation of fatty esters hydrogenolysis catalysts., Journal of Catalysis, Vol. 186, No.1, Ago., 1999, pp.169-180.
Pouilloux, Y., Autin, F., Guimon, C., Barrault, J., Hydrogenation of fatty acids over ruthenium-tin catalysts; characterization and identification of active centers., Journal of Catalysis, Vol. 176, No.1, May.,1998, pp. 215-224.
Pouilloux, Y., Barrault, J., De Oliveira, K., Selective hydrogenation of methyl oleate into unsaturated alcohols in the presence of cobalt-tin supported over zinc oxide catalysts., Journal of Catalysis, Vol. 204, No.1, Dic., 2001, pp. 230-237.
Ríos, L.A, Franco, A, Echeverri, D.A., Producción de alcoholes grasos a partir de aceites de palma y de palmiste utilizando procesos de hidrogenación catalítica. Una revisión Bibliográfica., Palmas, Vol. 27, No.1, Ene., 2006, pp. 65-76.
Sánchez, M.A., Mazzieri, V.A., Sad, M.R., Grau, R., Pieck, C. L., Influence of preparation method and boron addition on the metal function properties of RuSn catalysts for selective carbonyl hydrogenation., Journal of Chemical Technology & Biotechnology, Vol. 86, No 3, Oct., 2011, pp 447-453.
Tahara, K., Nagahara, E., Itoi, Y., Nishiyama, S., Tsuruya, S., Masai, M., Liquid-phase hydrogenation of carboxylic acid on supported Ru-Sn-alumina catalysts., Applied Catalysis A: General, Vol. 154, No.1, Jun., 1997, pp. 75-86.
Voeste, T., Buchold, H., Production of fatty alcohols from fatty acids., Journal of the American Oil Chemists´ Society, Vol. 61, No.2, Feb.,1984, pp. 350-352.
Dimensions
PlumX
Article abstract page views
Downloads
How to Cite
License
Copyright (c) 2011 David Alexander Echeverri, Luis Alberto Rios, Juan Miguel Marín

This work is licensed under a Creative Commons Attribution 4.0 International License.
The authors or holders of the copyright for each article hereby confer exclusive, limited and free authorization on the Universidad Nacional de Colombia's journal Ingeniería e Investigación concerning the aforementioned article which, once it has been evaluated and approved, will be submitted for publication, in line with the following items:
1. The version which has been corrected according to the evaluators' suggestions will be remitted and it will be made clear whether the aforementioned article is an unedited document regarding which the rights to be authorized are held and total responsibility will be assumed by the authors for the content of the work being submitted to Ingeniería e Investigación, the Universidad Nacional de Colombia and third-parties;
2. The authorization conferred on the journal will come into force from the date on which it is included in the respective volume and issue of Ingeniería e Investigación in the Open Journal Systems and on the journal's main page (https://revistas.unal.edu.co/index.php/ingeinv), as well as in different databases and indices in which the publication is indexed;
3. The authors authorize the Universidad Nacional de Colombia's journal Ingeniería e Investigación to publish the document in whatever required format (printed, digital, electronic or whatsoever known or yet to be discovered form) and authorize Ingeniería e Investigación to include the work in any indices and/or search engines deemed necessary for promoting its diffusion;
4. The authors accept that such authorization is given free of charge and they, therefore, waive any right to receive remuneration from the publication, distribution, public communication and any use whatsoever referred to in the terms of this authorization.










