Thermodynamic and kinetic aspects of the solvent-free liquid–liquid synthesis of tailor-made glyceride esters
Direct esterification between glycerol and carboxylic acids allows the design of different glycerides according to predetermined applications. Five carboxylic acids (caprylic, capric, lauric, stearic and oleic) which formed a bi-phasic system with glycerol were tested for esterification in a 1:1 M p...
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ftconicet:oai:ri.conicet.gov.ar:11336/202422 2023-10-09T21:45:45+02:00 Thermodynamic and kinetic aspects of the solvent-free liquid–liquid synthesis of tailor-made glyceride esters Santos, Maricel del Valle Velez, Alexis Abburra, Rogelio Ernesto Magario, Ivana application/pdf http://hdl.handle.net/11336/202422 eng eng Elsevier info:eu-repo/semantics/altIdentifier/doi/10.1016/j.fuel.2022.126461 info:eu-repo/semantics/altIdentifier/url/https://www.sciencedirect.com/science/article/pii/S0016236122032859 http://hdl.handle.net/11336/202422 Santos, Maricel del Valle; Velez, Alexis; Abburra, Rogelio Ernesto; Magario, Ivana; Thermodynamic and kinetic aspects of the solvent-free liquid–liquid synthesis of tailor-made glyceride esters; Elsevier; Fuel; 333; 126461; 2-2023; 1-10 0016-2361 CONICET Digital CONICET info:eu-repo/semantics/restrictedAccess https://creativecommons.org/licenses/by-nc-nd/2.5/ar/ CANDIDA ANTARCTICA LIPASE B GLYCERIDE ESTERS LIQUID–LIQUID SYSTEMS UNIFAC https://purl.org/becyt/ford/2.4 https://purl.org/becyt/ford/2 info:eu-repo/semantics/article info:ar-repo/semantics/artículo info:eu-repo/semantics/publishedVersion ftconicet https://doi.org/10.1016/j.fuel.2022.126461 2023-09-24T19:57:45Z Direct esterification between glycerol and carboxylic acids allows the design of different glycerides according to predetermined applications. Five carboxylic acids (caprylic, capric, lauric, stearic and oleic) which formed a bi-phasic system with glycerol were tested for esterification in a 1:1 M proportion. Two strategies were pursued: on one hand, homogeneous acid catalysis using sulfuric acid or p-toluenesulfonic acid at 100 °C and on the other hand, reactions catalyzed by immobilized lipase B from Candida antarctica at 65 °C. The selectivity and yield for MG was higher at lower temperature and with the use of the enzyme. Lauric acid was the carboxylic acid with the higher yield and selectivity to MG despite the catalyst used. The decrease in the mutual solubility between the carboxylic acid and glycerol seems to favor MG formation. The rate of reaction decreased with the increase in the molecular weight of the carboxylic acid used and the introduction of one unsaturation. From caprylic to lauric acid, the catalyst performance was: p-toluenesulfonic acid > lipase > sulfuric acid whereas for stearic and oleic acids the lipase was superior. Reactant accumulation at the interface is proposed to explain these results. The thermodynamic UNIFAC model was applied to calculate the initial activity coefficients and molar fractions in each phase. It was demonstrated that the thermodynamic activity of the species is a more convenient representation of the effective concentration for kinetic description of a liquid–liquid system. The equilibrium constant of lipase reaction was calculated with an expression based on the activity of compounds. The equilibrium constant for diglycerides formation decreased with the carbon chain length. Fil: Santos, Maricel del Valle. Universidad Nacional de Córdoba. Instituto de Investigación y Desarrollo en Ingeniería de Procesos y Química Aplicada. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de ... Article in Journal/Newspaper Antarc* Antarctica CONICET Digital (Consejo Nacional de Investigaciones Científicas y Técnicas) Fuel 333 126461 |
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CONICET Digital (Consejo Nacional de Investigaciones Científicas y Técnicas) |
op_collection_id |
ftconicet |
language |
English |
topic |
CANDIDA ANTARCTICA LIPASE B GLYCERIDE ESTERS LIQUID–LIQUID SYSTEMS UNIFAC https://purl.org/becyt/ford/2.4 https://purl.org/becyt/ford/2 |
spellingShingle |
CANDIDA ANTARCTICA LIPASE B GLYCERIDE ESTERS LIQUID–LIQUID SYSTEMS UNIFAC https://purl.org/becyt/ford/2.4 https://purl.org/becyt/ford/2 Santos, Maricel del Valle Velez, Alexis Abburra, Rogelio Ernesto Magario, Ivana Thermodynamic and kinetic aspects of the solvent-free liquid–liquid synthesis of tailor-made glyceride esters |
topic_facet |
CANDIDA ANTARCTICA LIPASE B GLYCERIDE ESTERS LIQUID–LIQUID SYSTEMS UNIFAC https://purl.org/becyt/ford/2.4 https://purl.org/becyt/ford/2 |
description |
Direct esterification between glycerol and carboxylic acids allows the design of different glycerides according to predetermined applications. Five carboxylic acids (caprylic, capric, lauric, stearic and oleic) which formed a bi-phasic system with glycerol were tested for esterification in a 1:1 M proportion. Two strategies were pursued: on one hand, homogeneous acid catalysis using sulfuric acid or p-toluenesulfonic acid at 100 °C and on the other hand, reactions catalyzed by immobilized lipase B from Candida antarctica at 65 °C. The selectivity and yield for MG was higher at lower temperature and with the use of the enzyme. Lauric acid was the carboxylic acid with the higher yield and selectivity to MG despite the catalyst used. The decrease in the mutual solubility between the carboxylic acid and glycerol seems to favor MG formation. The rate of reaction decreased with the increase in the molecular weight of the carboxylic acid used and the introduction of one unsaturation. From caprylic to lauric acid, the catalyst performance was: p-toluenesulfonic acid > lipase > sulfuric acid whereas for stearic and oleic acids the lipase was superior. Reactant accumulation at the interface is proposed to explain these results. The thermodynamic UNIFAC model was applied to calculate the initial activity coefficients and molar fractions in each phase. It was demonstrated that the thermodynamic activity of the species is a more convenient representation of the effective concentration for kinetic description of a liquid–liquid system. The equilibrium constant of lipase reaction was calculated with an expression based on the activity of compounds. The equilibrium constant for diglycerides formation decreased with the carbon chain length. Fil: Santos, Maricel del Valle. Universidad Nacional de Córdoba. Instituto de Investigación y Desarrollo en Ingeniería de Procesos y Química Aplicada. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de ... |
format |
Article in Journal/Newspaper |
author |
Santos, Maricel del Valle Velez, Alexis Abburra, Rogelio Ernesto Magario, Ivana |
author_facet |
Santos, Maricel del Valle Velez, Alexis Abburra, Rogelio Ernesto Magario, Ivana |
author_sort |
Santos, Maricel del Valle |
title |
Thermodynamic and kinetic aspects of the solvent-free liquid–liquid synthesis of tailor-made glyceride esters |
title_short |
Thermodynamic and kinetic aspects of the solvent-free liquid–liquid synthesis of tailor-made glyceride esters |
title_full |
Thermodynamic and kinetic aspects of the solvent-free liquid–liquid synthesis of tailor-made glyceride esters |
title_fullStr |
Thermodynamic and kinetic aspects of the solvent-free liquid–liquid synthesis of tailor-made glyceride esters |
title_full_unstemmed |
Thermodynamic and kinetic aspects of the solvent-free liquid–liquid synthesis of tailor-made glyceride esters |
title_sort |
thermodynamic and kinetic aspects of the solvent-free liquid–liquid synthesis of tailor-made glyceride esters |
publisher |
Elsevier |
url |
http://hdl.handle.net/11336/202422 |
genre |
Antarc* Antarctica |
genre_facet |
Antarc* Antarctica |
op_relation |
info:eu-repo/semantics/altIdentifier/doi/10.1016/j.fuel.2022.126461 info:eu-repo/semantics/altIdentifier/url/https://www.sciencedirect.com/science/article/pii/S0016236122032859 http://hdl.handle.net/11336/202422 Santos, Maricel del Valle; Velez, Alexis; Abburra, Rogelio Ernesto; Magario, Ivana; Thermodynamic and kinetic aspects of the solvent-free liquid–liquid synthesis of tailor-made glyceride esters; Elsevier; Fuel; 333; 126461; 2-2023; 1-10 0016-2361 CONICET Digital CONICET |
op_rights |
info:eu-repo/semantics/restrictedAccess https://creativecommons.org/licenses/by-nc-nd/2.5/ar/ |
op_doi |
https://doi.org/10.1016/j.fuel.2022.126461 |
container_title |
Fuel |
container_volume |
333 |
container_start_page |
126461 |
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1779321403309293568 |