Bio-additives from glycerol acetylation with acetic acid: chemical equilibrium model

Autores
Pérez, Federico Martín; Gatti, Martín Nicolás; Nichio, Nora Nancy; Pompeo, Francisco
Año de publicación
2022
Idioma
inglés
Tipo de recurso
artículo
Estado
versión publicada
Descripción
In this work, the chemical equilibrium of glycerol (G) acetylation with acetic acid (AA) to form mono- (MAG), di- (DAG) and tri- (TAG) acetylglycerols has been studied. These compounds are biodegradable and renewable options as high-quality bio-additives to improve the antiknock properties and the viscosity of fuels and biofuels. Due to the absence of thermodynamic data, the physicochemical and thermodynamic properties of the compounds were determined, such as the specific heat, and the enthalpy and entropy of formation, by employing a second-order group-additivity predictive method. The values obtained were validated with few experimental data available in the literature (298 K, 101.325 kPa), showing differences in the range 0.2–8.9%. The compositions at equilibrium were calculated by minimizing the total Gibbs free energy of the system and considering the non-ideality of the liquid phase. For this purpose, different temperatures (350–500 K), reactant molar ratios (1–12) and initial water contents (0 and 40 wt%) were studied. The results revealed the global exothermicity of the system, showing that total glycerol conversion (~100%) and high yields to TAG (>90%) can be achieved in the 350–500 K range by employing AA:G molar ratios between 9 and 12. As the presence of water in the glycerol solution produces a decrease of the glycerol conversion and selectivity to TAG, its removal from the reaction medium should be considered. A comparison between our results with the reported data based on different catalytic systems indicates that this model could successfully describe the chemical equilibrium of the system.
Centro de Investigación y Desarrollo en Ciencias Aplicadas
Materia
Ingeniería Química
Química
Biomass
Glycerol
Acetic acid
Esterification
Chemical equilibrium
Gibbs free energy minimization
Nivel de accesibilidad
acceso abierto
Condiciones de uso
http://creativecommons.org/licenses/by-nc-nd/4.0/
Repositorio
SEDICI (UNLP)
Institución
Universidad Nacional de La Plata
OAI Identificador
oai:sedici.unlp.edu.ar:10915/160430

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network_name_str SEDICI (UNLP)
spelling Bio-additives from glycerol acetylation with acetic acid: chemical equilibrium modelPérez, Federico MartínGatti, Martín NicolásNichio, Nora NancyPompeo, FranciscoIngeniería QuímicaQuímicaBiomassGlycerolAcetic acidEsterificationChemical equilibriumGibbs free energy minimizationIn this work, the chemical equilibrium of glycerol (G) acetylation with acetic acid (AA) to form mono- (MAG), di- (DAG) and tri- (TAG) acetylglycerols has been studied. These compounds are biodegradable and renewable options as high-quality bio-additives to improve the antiknock properties and the viscosity of fuels and biofuels. Due to the absence of thermodynamic data, the physicochemical and thermodynamic properties of the compounds were determined, such as the specific heat, and the enthalpy and entropy of formation, by employing a second-order group-additivity predictive method. The values obtained were validated with few experimental data available in the literature (298 K, 101.325 kPa), showing differences in the range 0.2–8.9%. The compositions at equilibrium were calculated by minimizing the total Gibbs free energy of the system and considering the non-ideality of the liquid phase. For this purpose, different temperatures (350–500 K), reactant molar ratios (1–12) and initial water contents (0 and 40 wt%) were studied. The results revealed the global exothermicity of the system, showing that total glycerol conversion (~100%) and high yields to TAG (>90%) can be achieved in the 350–500 K range by employing AA:G molar ratios between 9 and 12. As the presence of water in the glycerol solution produces a decrease of the glycerol conversion and selectivity to TAG, its removal from the reaction medium should be considered. A comparison between our results with the reported data based on different catalytic systems indicates that this model could successfully describe the chemical equilibrium of the system.Centro de Investigación y Desarrollo en Ciencias Aplicadas2022info:eu-repo/semantics/articleinfo:eu-repo/semantics/publishedVersionArticulohttp://purl.org/coar/resource_type/c_6501info:ar-repo/semantics/articuloapplication/pdfhttp://sedici.unlp.edu.ar/handle/10915/160430enginfo:eu-repo/semantics/altIdentifier/issn/2590-1230info:eu-repo/semantics/altIdentifier/doi/10.1016/j.rineng.2022.100502info:eu-repo/semantics/openAccesshttp://creativecommons.org/licenses/by-nc-nd/4.0/Creative Commons Attribution-NonCommercial-NoDerivatives 4.0 International (CC BY-NC-ND 4.0)reponame:SEDICI (UNLP)instname:Universidad Nacional de La Platainstacron:UNLP2025-09-03T11:13:56Zoai:sedici.unlp.edu.ar:10915/160430Institucionalhttp://sedici.unlp.edu.ar/Universidad públicaNo correspondehttp://sedici.unlp.edu.ar/oai/snrdalira@sedici.unlp.edu.arArgentinaNo correspondeNo correspondeNo correspondeopendoar:13292025-09-03 11:13:56.807SEDICI (UNLP) - Universidad Nacional de La Platafalse
dc.title.none.fl_str_mv Bio-additives from glycerol acetylation with acetic acid: chemical equilibrium model
title Bio-additives from glycerol acetylation with acetic acid: chemical equilibrium model
spellingShingle Bio-additives from glycerol acetylation with acetic acid: chemical equilibrium model
Pérez, Federico Martín
Ingeniería Química
Química
Biomass
Glycerol
Acetic acid
Esterification
Chemical equilibrium
Gibbs free energy minimization
title_short Bio-additives from glycerol acetylation with acetic acid: chemical equilibrium model
title_full Bio-additives from glycerol acetylation with acetic acid: chemical equilibrium model
title_fullStr Bio-additives from glycerol acetylation with acetic acid: chemical equilibrium model
title_full_unstemmed Bio-additives from glycerol acetylation with acetic acid: chemical equilibrium model
title_sort Bio-additives from glycerol acetylation with acetic acid: chemical equilibrium model
dc.creator.none.fl_str_mv Pérez, Federico Martín
Gatti, Martín Nicolás
Nichio, Nora Nancy
Pompeo, Francisco
author Pérez, Federico Martín
author_facet Pérez, Federico Martín
Gatti, Martín Nicolás
Nichio, Nora Nancy
Pompeo, Francisco
author_role author
author2 Gatti, Martín Nicolás
Nichio, Nora Nancy
Pompeo, Francisco
author2_role author
author
author
dc.subject.none.fl_str_mv Ingeniería Química
Química
Biomass
Glycerol
Acetic acid
Esterification
Chemical equilibrium
Gibbs free energy minimization
topic Ingeniería Química
Química
Biomass
Glycerol
Acetic acid
Esterification
Chemical equilibrium
Gibbs free energy minimization
dc.description.none.fl_txt_mv In this work, the chemical equilibrium of glycerol (G) acetylation with acetic acid (AA) to form mono- (MAG), di- (DAG) and tri- (TAG) acetylglycerols has been studied. These compounds are biodegradable and renewable options as high-quality bio-additives to improve the antiknock properties and the viscosity of fuels and biofuels. Due to the absence of thermodynamic data, the physicochemical and thermodynamic properties of the compounds were determined, such as the specific heat, and the enthalpy and entropy of formation, by employing a second-order group-additivity predictive method. The values obtained were validated with few experimental data available in the literature (298 K, 101.325 kPa), showing differences in the range 0.2–8.9%. The compositions at equilibrium were calculated by minimizing the total Gibbs free energy of the system and considering the non-ideality of the liquid phase. For this purpose, different temperatures (350–500 K), reactant molar ratios (1–12) and initial water contents (0 and 40 wt%) were studied. The results revealed the global exothermicity of the system, showing that total glycerol conversion (~100%) and high yields to TAG (>90%) can be achieved in the 350–500 K range by employing AA:G molar ratios between 9 and 12. As the presence of water in the glycerol solution produces a decrease of the glycerol conversion and selectivity to TAG, its removal from the reaction medium should be considered. A comparison between our results with the reported data based on different catalytic systems indicates that this model could successfully describe the chemical equilibrium of the system.
Centro de Investigación y Desarrollo en Ciencias Aplicadas
description In this work, the chemical equilibrium of glycerol (G) acetylation with acetic acid (AA) to form mono- (MAG), di- (DAG) and tri- (TAG) acetylglycerols has been studied. These compounds are biodegradable and renewable options as high-quality bio-additives to improve the antiknock properties and the viscosity of fuels and biofuels. Due to the absence of thermodynamic data, the physicochemical and thermodynamic properties of the compounds were determined, such as the specific heat, and the enthalpy and entropy of formation, by employing a second-order group-additivity predictive method. The values obtained were validated with few experimental data available in the literature (298 K, 101.325 kPa), showing differences in the range 0.2–8.9%. The compositions at equilibrium were calculated by minimizing the total Gibbs free energy of the system and considering the non-ideality of the liquid phase. For this purpose, different temperatures (350–500 K), reactant molar ratios (1–12) and initial water contents (0 and 40 wt%) were studied. The results revealed the global exothermicity of the system, showing that total glycerol conversion (~100%) and high yields to TAG (>90%) can be achieved in the 350–500 K range by employing AA:G molar ratios between 9 and 12. As the presence of water in the glycerol solution produces a decrease of the glycerol conversion and selectivity to TAG, its removal from the reaction medium should be considered. A comparison between our results with the reported data based on different catalytic systems indicates that this model could successfully describe the chemical equilibrium of the system.
publishDate 2022
dc.date.none.fl_str_mv 2022
dc.type.none.fl_str_mv info:eu-repo/semantics/article
info:eu-repo/semantics/publishedVersion
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info:ar-repo/semantics/articulo
format article
status_str publishedVersion
dc.identifier.none.fl_str_mv http://sedici.unlp.edu.ar/handle/10915/160430
url http://sedici.unlp.edu.ar/handle/10915/160430
dc.language.none.fl_str_mv eng
language eng
dc.relation.none.fl_str_mv info:eu-repo/semantics/altIdentifier/issn/2590-1230
info:eu-repo/semantics/altIdentifier/doi/10.1016/j.rineng.2022.100502
dc.rights.none.fl_str_mv info:eu-repo/semantics/openAccess
http://creativecommons.org/licenses/by-nc-nd/4.0/
Creative Commons Attribution-NonCommercial-NoDerivatives 4.0 International (CC BY-NC-ND 4.0)
eu_rights_str_mv openAccess
rights_invalid_str_mv http://creativecommons.org/licenses/by-nc-nd/4.0/
Creative Commons Attribution-NonCommercial-NoDerivatives 4.0 International (CC BY-NC-ND 4.0)
dc.format.none.fl_str_mv application/pdf
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instname:Universidad Nacional de La Plata
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