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dc.contributor.author
Belelli, Patricia Gabriela
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dc.contributor.author
Ferretti, Cristián Alejandro
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dc.contributor.author
Apesteguia, Carlos Rodolfo
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dc.contributor.author
Ferullo, Ricardo
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dc.contributor.author
Di Cosimo, Juana Isabel
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dc.date.available
2016-07-15T18:29:59Z
dc.date.issued
2015-01
dc.identifier.citation
Belelli, Patricia Gabriela; Ferretti, Cristián Alejandro; Apesteguia, Carlos Rodolfo; Ferullo, Ricardo; Di Cosimo, Juana Isabel; Glycerolysis of methyl oleate on MgO: experimental and theoretical study of the reaction selectivity; Elsevier; Journal of Catalysis; 323; 1-2015; 132-144
dc.identifier.issn
0021-9517
dc.identifier.uri
http://hdl.handle.net/11336/6534
dc.description.abstract
The liquid-phase MgO-promoted glycerolysis of methyl oleate, a fatty acid methyl ester (FAME), to give acylglycerol products was studied both, experimentally and by density functional theory (DFT). Catalytic results showed that strongly basic low coordination O2− surface sites participate in kinetically relevant steps of the glycerolysis reaction. Changes in the selectivity toward the different mono- and diglyceride isomers were investigated by varying the reaction conditions. The main product was always α-glyceryl monooleate (α-MG), a monoglyceride with the ester fragment at one of the terminal positions of the glycerol molecule; the β-MG isomer, with the ester substituted at position 2 was obtained in much lower amounts.
The molecular modeling of glycerol (Gly) and FAME adsorptions as well as of the glycerolysis reaction was carried out using periodic DFT calculations and a model of stepped MgO surface. Results indicated that FAME was more weakly adsorbed than Gly; the latter adsorbs on a coordinatively unsaturated surface O2− site with Osingle bondH bond breaking at position 2 of the Gly molecule, giving therefore a surface β-glyceroxide species. Calculations explained the apparent contradiction between the preferential formation of the α-MG isomer and the energetically favored dissociation of the secondary OH group of Gly that leads to the β-glyceroxide species. They predict that the β-glyceroxide species participates in the pathways conducting to both, α- and β-MG isomers. Synthesis of α-MG occurs by Csingle bondO coupling of β-glyceroxide with FAME at one of the two primary OH groups of the β-glyceroxide species. Two transition states (TS) and a tetrahedral intermediate (TI) are involved in both, α-MG and β-MG isomer formation. However, the pathway toward β-MG is limited by the large sterical effects associated to the TI formation. Contrarily, the TI leading to α-MG is relatively easy to form.
dc.format
application/pdf
dc.language.iso
eng
dc.publisher
Elsevier
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dc.rights
info:eu-repo/semantics/openAccess
dc.rights.uri
https://creativecommons.org/licenses/by-nc-nd/2.5/ar/
dc.subject
Mgo
dc.subject
Fatty Acid
dc.subject
Glycerolysis
dc.subject
Dft
dc.subject.classification
Química Orgánica
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dc.subject.classification
Ciencias Químicas
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dc.subject.classification
CIENCIAS NATURALES Y EXACTAS
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dc.title
Glycerolysis of methyl oleate on MgO: experimental and theoretical study of the reaction selectivity
dc.type
info:eu-repo/semantics/article
dc.type
info:ar-repo/semantics/artículo
dc.type
info:eu-repo/semantics/publishedVersion
dc.date.updated
2016-02-29T13:25:43Z
dc.journal.volume
323
dc.journal.pagination
132-144
dc.journal.pais
Países Bajos
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dc.journal.ciudad
Amsterdam
dc.description.fil
Fil: Belelli, Patricia Gabriela. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Bahía Blanca. Instituto de Física del Sur; Argentina
dc.description.fil
Fil: Ferretti, Cristián Alejandro. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Santa Fe. Instituto de Investigaciones en Catálisis y Petroquímica; Argentina
dc.description.fil
Fil: Apesteguia, Carlos Rodolfo. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Santa Fe. Instituto de Investigaciones en Catálisis y Petroquímica; Argentina
dc.description.fil
Fil: Ferullo, Ricardo. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Bahía Blanca. Instituto de Química del Sur; Argentina
dc.description.fil
Fil: Di Cosimo, Juana Isabel. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Santa Fe. Instituto de Investigaciones en Catálisis y Petroquímica; Argentina
dc.journal.title
Journal of Catalysis
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dc.relation.alternativeid
info:eu-repo/semantics/altIdentifier/url/http://www.sciencedirect.com/science/article/pii/S0021951715000032
dc.relation.alternativeid
info:eu-repo/semantics/altIdentifier/doi/10.1016/j.jcat.2015.01.001
dc.relation.alternativeid
info:eu-repo/semantics/altIdentifier/doi/http://dx.doi.org/10.1016/j.jcat.2015.01.001
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