Published
Colombian fusel oil
El aceite de fusel de Colombia
Keywords:
Fuel ethanol, higher alcohols, GC-MS analysis, solid-phase microextraction, TBP (en)Etanol-combustible, alcoholes pesados, análisis GC-MS, micro-extracción en fase sólida, TBP (es)
By-products valorization in bio-fuels industry is an important issue for making the global process more efficient, more profitable and closer to the concept of biorefinery. Fusel oil is a by-product of bioethanol production that can be considered as an inexpensive and renewable raw material for manufacturing value-added products. In this work, results in terms of composition and physicochemical properties of six samples of fusel oil from industrial alcohol facilities are presented. Composition of the main components was established by gas chromatography. Complementary techniques, such as headspace solid-phase microextraction and gas chromatography–mass spectrometry (GC-MS), were used for detection of minor components. Fifty-five compounds were identified. Physicochemical properties such as density, acid value, moisture content and true boiling point curves were determined. Results are useful in the conceptual design of separation strategies for recovering higher alcohols, as well as to consider new options of valorization alternatives for fusel oil.
Los subproductos para valorización en la industria de los biocombustibles es un tema importante para alcanzar un proceso global más eficiente, más rentable y más cerca del concepto de biorrefinería. El aceite de fusel es un subproducto de la producción de bioetanol que se puede considerar como una materia prima barata y renovable para la fabricación de productos de valor agregado. En este trabajo se presentan los resultados en términos de composición y de las propiedades físico-químicas de seis muestras de aceite de fusel de las instalaciones industriales de alcohol. La composición de los componentes principales se estableció mediante cromatografía de gases. Técnicas complementarias, como espacio de cabeza, microextracción en fase sólida, y cromatografía de gasesespectrometría
de masas (GC-MS), fueron utilizadas para la detección de componentes menores. Se identificaron cincuenta y cinco
compuestos. Se determinaron las propiedades físico-químicas, como la densidad, el índice de acidez, el contenido de humedad y las curvas de puntos verdaderos de ebullición. Los resultados son útiles en el diseño conceptual de las estrategias de separación para la recuperación de alcoholes superiores, así como para comprobar las opciones de alternativas de valorización del aceite de fusel
References
Bandres, M., de Caro, P., Thiebaud-Roux, S., & Borredon, M. (2010). Green syntheses of biobased solvents. C. R. Chim., Vol. 14, No. 7-8, 636-646. DOI: 10.1016/j.crci.2010.07.008.
Dörmo, N., Bélafi-Bakó, K., Bartha, L., Ehrenstein, U., & Gubicza, L. (2004). Manufacture of an environmentalsafe biolubricant from fusel oil by enzymatic esterification in solvent-free system. Biochem. Eng. J., Vol. 21, No. 3, 229 - 234. DOI: 10.1016/j.bej.2004.06.011.
Ehrlich, F. (1907). Über die Bedingungen der Fuseölbildung und über ihren Zusammenhang mit dem Eiweissaufbau der Hefe. Berichte Deutsch Chem. Gesellschaft, Vol. 40, No. 1, 1027-1047. DOI: 10.1002/cber.190704001156.
Garcia, M.A., Aramayona, J.J., Bregante, M.A., Fraile, L.J., & Solans, C. (1997). Simultaneous determination of verapamil and norverapamil in biological samples by high-performance liquid chromatography using ultraviolet detection. J. Chromatogr. B., Vol. 693, No. 2, 377-382. DOI: 10.1016/S0378-4347(97)00058-3.
Garcia, V. (2008). Subproduto de destilaria de óleo fúsel: caracterização da composição química e estudo de sua aplicação industrial (Mestre em Engenharia de Processos Químicos e Bioquímicos). Centro Universitário do Instituto Mauá de Tecnologia, São Caetano do Sul: Brasil. Recuperado de http://maua.br/files/dissertacoes/subproduto-de-destilaria-de-oleo-fusel.pdf.
Güvenç, A., Kapucu, N., Kapucu, H., Aydogan, Ö., & Mehmetoglu, Ü. (2007). Enzymatic esterification of isoamyl alcohol obtained from fusel oil: Optimization by response surface methodology. Enzyme Microb. Technol., Vol. 40, No. 4, 778-785. DOI: 10.1016/j.enzmictec.2006.06.010.
Grob, R., & Barry, M. (2004). Modern Practice in Gas Chromatography. Fourth Edition. United States of America: Wiley and Sons Publications. DOI: 10.1002/0471651141.
Hewlett-Packard Co. (1988). Analytical Supplies Catalog and Catalog Reference Guide. West Germany: Hewlett-Packard Co.
Ikeda, R.M., Webb, A.D., & Kepner, R.E. (1956). Comparative analysis of fusel oils from Thompson Seedless, Emperor, and Muscat of Alexandria Wines. J. Agric. Food Chem., Vol. 4, No. 4, 355–363. DOI: 10.1021/jf60062a009.
Klier, K., Beretta, A., Sun, Q., Feeley, O.C., & Herman, R.G. (1997). Catalytic synthesis of methanol, higher alcohols and ethers. Catal. Today, Vol. 36, No. 1, 3-14. DOI: 10.1016/S0920-5861(96)00190-3.
Klosowski, G., Mikulski, D., Grajewski, J., & Blajet-Kosicka, A. (2010). The influence of raw material contamination with mycotoxins on alcoholic fermentation indicator. Bioresour. Technol., Vol. 101, No. 9, 3147-3152. DOI: 10.1016/j.biortech.2009.12.040.
Liaw, W.J., Ho, S.T., Wang, J.J., Hu, O.Y.P., & Li, J.H. (1998). Determination of morphine by high-performance liquid chromatography with electrochemical detection: application to human and rabbit pharmacokinetic studies. J. Chromatogr. B., Vol. 714, No. 2, 237-245. DOI: 10.1016/S0378-4347(98)00230-8.
Maiorella, B., Wilke, Ch.R., & Blanch, H.W. (1981). Alcohol production and recovery. Adv. Biochem. Eng. Biotechnol., Vol. 20, 43-92. DOI: 10.1007/3-540-11018-6_3.
Marvel, C.S., & Hager, F.D. (1924). Bauer Oil, The High-Boiling Residue From Molasses Fusel Oil. J. Am. Chem. Soc., Vol. 46, No. 3, 726–731. DOI: 10.1021/ja01668a024.
Mitra, A., Subramanian, S., Das, D., Satyanarayana, V.V.C., & Chakrabarty, D.K. (1997). Alkylation of aromatics on zeolite beta. Unusual butylation of benzene with isobutanol. Appl. Catal. A., Vol. 153, No. 1-2, 233-241. DOI: 10.1016/ S0926-860X(96)00321-3.
Nonato, E.A., Carazza, F., Silva, F.C., Ciomara, R., & Cardeal, Z. (2001). A Headspace Solid-Phase Microextraction Method for the Determination of Some Secondary Compounds of
Brazilian Sugar Cane Spirits by Gas Chromatography. J. Agric. Food Chem., Vol. 49, No. 8, 3533-3539. DOI: 10.1021/jf000896r.
Ogonowski, J., & Sikora, E. (2000). Coupling of methanol and isobutanol to ethers over γ-alumina catalyst. Kinetic Study. React. Kinet. Catal. Lett., Vol. 70, No. 2, 235-241. DOI: 10.1023/A:1010320312175.
Özgülsün, A., Karaosmanôglu, F., & Tüter, M. (2000). Esterification reaction of oleic acid with a fusel oil fraction for production of lubricating oil. J. Am. Oil Chem. Soc., Vol. 77, No. 1, 105-109. DOI: 10.1007/s11746-000-0017-5.
Patil, A.G., Koolwal, S.M., & Butala, H.D. (2002). Fusel Oil: Composition, removal and potential utilization. Int. Sugar J., Vol. 104, 51-58.
Penniman, W.B.D., Smith, D.C., & Lawshe, E.I. (1937). Determination of Higher Alcohols in Distilled Liquors. Ind. Eng. Chem. Anal. Ed., Vol. 9, No. 2, 91–95. DOI: 10.1021/ac50106a016.
Pfenninger, H. (1963). Gaschromatographische Untersuchungen von Fuselölen aus verschiedenen Gäsprodukten. Z. Lebensm. Unters. Forsch., Vol. 119, 401-415. DOI: 10.1007/BF01300142.
Restek Corp. (2003). Chromatography Products 2003/2004, Restek Corporation Inc.: United States of America.
Ribereau-Gayon, P., Glories, Y., Maujean, A., & Dubourdieu, D. (2006). Handbook of Enology. The Chemistry of Wine, Vol. 2, John Wiley & Sons Ltd.: Paris.
Roehr, M. (2001). The biotechnology of ethanol. Classical and future applications, Wiley-VCH Verlag GmbH: Weinheim.
Schicktanz, S.T., Etienne, A.D., & Steele, W.I. (1939). Analysis of Fusel Oil by Azeotropic Distillation. Ind. Eng. Chem. Anal. Ed., Vol. 11, No. 8, 420-422. DOI: 10.1021/ac50136a003.
Van Gheluwe, G., Chen, E., & Valyi, Z. (1976). Factors Affecting the Formation of Fusel Alcohols during Fermentation. MBAA Technical Quarterly., Vol. 12, No. 3, 169-175.
Varian Inc. (2004). GC 3380 Documentation: Quick Reference Guide, Varian GC Getting Started & Operator’s Manual, Varian Incorporated: United States of America.
Vaze, A.S., Sawant, S.B., & Pangarkar, V.G. (1997). Electrochemical oxidation of isobutanol to isobutyric acid at nickel oxide electrode: improvement of the anode stability. J. Appl. Electrochem., Vol. 27, No. 7, 584-588. DOI: 10.1023/A:1018406914144.
Webb, A.D., Kepner, R.E., & Ikeda, R.M. (1952). Composition of Typical Grape Brandy Fusel Oil. Anal. Chem., Vol. 24, No. 12, 1944–1949. DOI: 10.1021/ac60072a020.
License
Copyright (c) 2016 Natalia Montoya, Jairo Durán, Fernando Córdoba, Iván Darío Gil, Carlos Alexander Trujillo, Gerardo Rodríguez
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.
