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Valorization of Vegetable Oils
Natural oils and fats are predominantly composed of triglycerides (esters of glycerol) of carboxylic acids of long chain lengths. They are important sources both for nutrition and as raw materials in the oleochemical industry to produce surfactants, cosmetics, resins, biodiesel and lubricants, as well as polymers for specialty applications. Plant oils offer also important alternatives for obtaining propanediols, polyols, acrylic acid, dicarboxylic acids, and other oxo chemicals, thus enabling to substitute petrochemicals. The total production of vegetable oils worldwide amounted to about 204 million tons in 2018/19, and about one-sixth is consumed by the chemical industry. Oleochemical products have a good biodegradability, do not contribute to a net increase in the amount of CO2 in the atmosphere and to acidification of soil and water, and contain low sulfur levels. The major part of all oleochemical reactions of fatty acid esters are carried out at the ester function. However, transformations by reaction of the carbon-carbon double bond in the alkyl chain of unsaturated fatty acid esters, such as epoxidation, metathesis, ozonolysis, and dimerization, are becoming increasingly important industrially.
Reactions:
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Valorization of vegetable oils by metathesis reactions
Vegetable oils are renewable raw materials for producing fatty acid methyl esters (FAME) that may be converted into fine chemicals via metathesis reactions. The presence of an ester group in the FAME molecule requires a catalyst that tolerates functional groups and is active at moderate reaction temperatures in the liquid phase. Our research focuses in the development of active and stable solid catalysts for the cross-metathesis of FAME with functionalized olefins such as nitriles, aldehydes, and alcohols. Reaction products are valuable chemicals are used for the synthesis of pheromones and in polymer, pharmaceutical and fragrance industries. -
Synthesis of monoglycerides
Our research focuses on the catalytic valorization of chemical compounds resulting from vegetable oil processing such as FAME and glycerin. In particular, we investigate the glycerolysis of FAME on solid basic catalysts to produce monoglycerides that are widely used as emulsifiers in food, pharmaceutical and cosmetic industries. -
Synthesis of healthy oils
With the aim of obtaining healthier edible oils, we investigate the partial conversion of triglycerides with glycerol to diglycerides on basic catalysts. Specifically, the goal is to produce diglyceride-rich oils because the human metabolism of 1,3-diglyceride occurs through a pathway that avoids re-synthesis of triglycerides and the consequent fat deposit in the body tissues -
Synthesis of fatty alcohols
Fatty alcohols are aliphatic alcohols with straight-chain length ranging from 6 to 22 carbon atoms and a single functional OH group attached to the terminal carbon. They are mainly used in the production of detergents and surfactants, but are also employed in the manufacture of solvents, plasticizers, lubricants, cosmetics, and foods. Fatty alcohols are usually obtained by hydrogenation of FAME, at relatively high temperatures and H2 pressures. We investigate an alternative synthesis route of fatty alcohols by liquid-phase reduction of FAME via hydride and hydrogen transfer. Metal hydrides and short-chain alcohols are used as donors of hydride and hydrogen, respectively.
Publicaciones recientes
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Reduction of vegetable oil-derived fatty acid methyl esters toward fatty alcohols without the supply of gaseous H2, A. Vallejo Orrego, C.A. Ferretti, V.K. Díez, JAOCS, 97(9), 1029-1042 (2020)
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Valorisation of plant oil derivatives via metathesis reactions: study of the cross-metathesis of methyl oleate with cinnamaldehyde. P.D. Nieres, A.F. Trasarti, C.R. Apesteguia, Molec. Catal., 481, 100612, 1-6 (2020).
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Synthesis of edible vegetable oils enriched with healthy 1,3-diglycerides using crude glycerol and homogeneous/heterogeneous catalysis, L.A. Dosso, P.J.Luggren, J.I. Di Cosimo, JAOCS, 97(5), 551-561, (2020).
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Plant oil valorization by cross-metathesis reactions: synthesis of fine chemicals from methyl oleate, A.F. Trasarti, E. Gonzalez, P.D. Nieres, C.R. Apesteguía, Latinam. Appl. Res., 50(2), 139-144 (2020).
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Equilibrium data for the cross-metathesis of fatty acid methyl esters with functionalized olefins: The case of methyl oleate with cinnamaldehyde, P.D. Nieres, A.F. Trasarti, C.R. Apesteguia, Data in Brief, 20, 190-195 (2018).
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Diglyceride-rich oils from glycerolysis of edible vegetable oils, C.A. Ferretti, M.L. Spotti, J.I. Di Cosimo, Catal. Today, 302, 233-241 (2018).
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Valorisation of vegetable oils by heterogeneous catalysis via metathesis reactions, P.D. Nieres, J. Zelin, A.F. Trasarti, C.R. Apesteguia, Curr. Opin. Green Sustain. Chem., 10, 1-5 (2018).
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Healthy oils: A process to obtain diglyceride-rich edible vegetable oils, C.A. Ferretti, M.L. Spotti, J.I. Di Cosimo, International News on Fats, Oils and Related Materials, 29, 14-17 (2018).
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Heterogeneous catalysis for valorisation of vegetable oils via metathesis reactions: Ethenolysis of methyl oleate, P.D. Nieres, J. Zelin, A.F. Trasarti, C.R. Apesteguía, Catal. Sci. Technol., 6, 6561- 6568 (2016).
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Catalytic valorisation of vegetable oils: Cross-metathesis of methyl oleate with 3-pentenenitrile, P.D. Nieres, J. Zelin, A.F. Trasarti, C.R. Apesteguía, Eur. J. Lipid Sci. Technol., 118, 1722-1729 (2016).
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Glycerolysis of methyl oleate on MgO: experimental and theoretical study of the reaction, P.G. Belelli, C.A. Ferretti, C.R. Apesteguía, R.M. Ferullo, J.I. Di Cosimo, J. Catal., 323, 132-144 (2015).
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Valorisation of vegetable oils via metathesis reactions on solid catalysts: Cross-metathesis of methyl oleate with 1-hexene, J. Zelin, P.D. Nieres, A.F. Trasarti, C.R. Apesteguía, Appl. Catal. A: General, 502, 410-417 (2015).
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Self-metathesis of methyl oleate on silica-supported Hoveyda-Grubbs catalysts, J. Zelin, A.F. Trasarti, C.R. Apesteguía, Catal. Comm., 42, 84-88 (2013).
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Monoglyceride synthesis by glycerolysis of methyl oleate on MgO: catalytic and DFT study of the active site, C.A. Ferretti, S. Fuente, R. Ferullo, N. Castellani, C.R. Apesteguía, J.I. Di Cosimo, Appl. Catal. A: General, 413-414, 322-331 (2012).