Esterification of Levulinic Acid to Methyl Levulinate over Zr-MOFs Catalysts

Autores
Bravo Fuchineco, Daiana Antonella; Heredia, Angelica Constanza; Mendoza, Sandra Marina; Rodríguez Castellón, Enrique; Crivello, Mónica Elsie
Año de publicación
2022
Idioma
inglés
Tipo de recurso
artículo
Estado
versión publicada
Descripción
At present, the trend towards partial replacement of petroleum‐derived fuels by those from the revaluation of biomass has become of great importance. An effective strategy for pro-cessing complex biomass feedstocks involves prior conversion to simpler compounds (platform molecules) that are more easily transformed in subsequent reactions. This study analyzes the met-al–organic frameworks (MOFs) that contain Zr metal clusters formed by ligands of terephthalic acid (UiO‐66) and aminoterephthalic acid (UiO‐66‐NH2), as active and stable catalysts for the esterification of levulinic acid with methanol. An alternative synthesis is presented by means of ultrasonic stirring at room temperature and 60 °C, in order to improve the structural properties of the catalysts. They were analyzed by X‐ray diffraction, scanning electron microscopy, infrared spectroscopy, X‐ray photoelectron spectroscopy, microwave plasma atomic emission spectroscopy, acidity measurement, and N2 adsorption. The catalytic reaction was carried out in a batch system and under pressure in an autoclave. Its progress was followed by gas chromatography and mass spectrometry. Parameters such as temperature, catalyst mass, and molar ratio of reactants were optimized to improve the catalytic performance. The MOF that presented the highest activity and selectivity to the desired product was obtained by synthesis with ultrasound and 60 °C with ami-noterephthalic acid. The methyl levulinate yield was 67.77% in batch at 5 h and 85.89% in an auto-clave at 1 h. An analysis of the kinetic parameters of the reaction is presented. The spent material can be activated by ethanol washing allowing the catalytic activity to be maintained in the recycles.
Fil: Bravo Fuchineco, Daiana Antonella. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Centro de Investigación y Tecnología Química. Universidad Tecnológica Nacional. Facultad Regional Córdoba. Centro de Investigación y Tecnología Química; Argentina
Fil: Heredia, Angelica Constanza. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Centro de Investigación y Tecnología Química. Universidad Tecnológica Nacional. Facultad Regional Córdoba. Centro de Investigación y Tecnología Química; Argentina
Fil: Mendoza, Sandra Marina. Universidad Tecnológica Nacional. Facultad Regional Reconquista; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba; Argentina
Fil: Rodríguez Castellón, Enrique. Dpto. Química Inorgánica, Cristalografía y Mineralogía; España
Fil: Crivello, Mónica Elsie. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Centro de Investigación y Tecnología Química. Universidad Tecnológica Nacional. Facultad Regional Córdoba. Centro de Investigación y Tecnología Química; Argentina
Materia
BATCH AND PRESSURE REACTIONS
ESTERIFICATION KINETICS
LEVULINIC ACID
METHYL LEVULINATE
UIO‐66
UIO‐66‐NH2
Nivel de accesibilidad
acceso abierto
Condiciones de uso
https://creativecommons.org/licenses/by/2.5/ar/
Repositorio
CONICET Digital (CONICET)
Institución
Consejo Nacional de Investigaciones Científicas y Técnicas
OAI Identificador
oai:ri.conicet.gov.ar:11336/163282
Acceder
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oai_identifier_str oai:ri.conicet.gov.ar:11336/163282
network_acronym_str CONICETDig
repository_id_str 3498
network_name_str CONICET Digital (CONICET)
spelling Esterification of Levulinic Acid to Methyl Levulinate over Zr-MOFs CatalystsBravo Fuchineco, Daiana AntonellaHeredia, Angelica ConstanzaMendoza, Sandra MarinaRodríguez Castellón, EnriqueCrivello, Mónica ElsieBATCH AND PRESSURE REACTIONSESTERIFICATION KINETICSLEVULINIC ACIDMETHYL LEVULINATEUIO‐66UIO‐66‐NH2https://purl.org/becyt/ford/2.4https://purl.org/becyt/ford/2At present, the trend towards partial replacement of petroleum‐derived fuels by those from the revaluation of biomass has become of great importance. An effective strategy for pro-cessing complex biomass feedstocks involves prior conversion to simpler compounds (platform molecules) that are more easily transformed in subsequent reactions. This study analyzes the met-al–organic frameworks (MOFs) that contain Zr metal clusters formed by ligands of terephthalic acid (UiO‐66) and aminoterephthalic acid (UiO‐66‐NH2), as active and stable catalysts for the esterification of levulinic acid with methanol. An alternative synthesis is presented by means of ultrasonic stirring at room temperature and 60 °C, in order to improve the structural properties of the catalysts. They were analyzed by X‐ray diffraction, scanning electron microscopy, infrared spectroscopy, X‐ray photoelectron spectroscopy, microwave plasma atomic emission spectroscopy, acidity measurement, and N2 adsorption. The catalytic reaction was carried out in a batch system and under pressure in an autoclave. Its progress was followed by gas chromatography and mass spectrometry. Parameters such as temperature, catalyst mass, and molar ratio of reactants were optimized to improve the catalytic performance. The MOF that presented the highest activity and selectivity to the desired product was obtained by synthesis with ultrasound and 60 °C with ami-noterephthalic acid. The methyl levulinate yield was 67.77% in batch at 5 h and 85.89% in an auto-clave at 1 h. An analysis of the kinetic parameters of the reaction is presented. The spent material can be activated by ethanol washing allowing the catalytic activity to be maintained in the recycles.Fil: Bravo Fuchineco, Daiana Antonella. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Centro de Investigación y Tecnología Química. Universidad Tecnológica Nacional. Facultad Regional Córdoba. Centro de Investigación y Tecnología Química; ArgentinaFil: Heredia, Angelica Constanza. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Centro de Investigación y Tecnología Química. Universidad Tecnológica Nacional. Facultad Regional Córdoba. Centro de Investigación y Tecnología Química; ArgentinaFil: Mendoza, Sandra Marina. Universidad Tecnológica Nacional. Facultad Regional Reconquista; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba; ArgentinaFil: Rodríguez Castellón, Enrique. Dpto. Química Inorgánica, Cristalografía y Mineralogía; EspañaFil: Crivello, Mónica Elsie. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Centro de Investigación y Tecnología Química. Universidad Tecnológica Nacional. Facultad Regional Córdoba. Centro de Investigación y Tecnología Química; ArgentinaMDPI2022-03-25info:eu-repo/semantics/articleinfo:eu-repo/semantics/publishedVersionhttp://purl.org/coar/resource_type/c_6501info:ar-repo/semantics/articuloapplication/pdfapplication/pdfhttp://hdl.handle.net/11336/163282Bravo Fuchineco, Daiana Antonella; Heredia, Angelica Constanza; Mendoza, Sandra Marina; Rodríguez Castellón, Enrique; Crivello, Mónica Elsie; Esterification of Levulinic Acid to Methyl Levulinate over Zr-MOFs Catalysts; MDPI; ChemEngineering; 25-3-20222305-7084CONICET DigitalCONICETenginfo:eu-repo/semantics/altIdentifier/doi/10.3390/chemengineering6020026info:eu-repo/semantics/altIdentifier/url/https://www.mdpi.com/2305-7084/6/2/26info:eu-repo/semantics/openAccesshttps://creativecommons.org/licenses/by/2.5/ar/reponame:CONICET Digital (CONICET)instname:Consejo Nacional de Investigaciones Científicas y Técnicas2025-09-29T10:20:33Zoai:ri.conicet.gov.ar:11336/163282instacron:CONICETInstitucionalhttp://ri.conicet.gov.ar/Organismo científico-tecnológicoNo correspondehttp://ri.conicet.gov.ar/oai/requestdasensio@conicet.gov.ar; lcarlino@conicet.gov.arArgentinaNo correspondeNo correspondeNo correspondeopendoar:34982025-09-29 10:20:33.247CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicasfalse
dc.title.none.fl_str_mv Esterification of Levulinic Acid to Methyl Levulinate over Zr-MOFs Catalysts
title Esterification of Levulinic Acid to Methyl Levulinate over Zr-MOFs Catalysts
spellingShingle Esterification of Levulinic Acid to Methyl Levulinate over Zr-MOFs Catalysts
Bravo Fuchineco, Daiana Antonella
BATCH AND PRESSURE REACTIONS
ESTERIFICATION KINETICS
LEVULINIC ACID
METHYL LEVULINATE
UIO‐66
UIO‐66‐NH2
title_short Esterification of Levulinic Acid to Methyl Levulinate over Zr-MOFs Catalysts
title_full Esterification of Levulinic Acid to Methyl Levulinate over Zr-MOFs Catalysts
title_fullStr Esterification of Levulinic Acid to Methyl Levulinate over Zr-MOFs Catalysts
title_full_unstemmed Esterification of Levulinic Acid to Methyl Levulinate over Zr-MOFs Catalysts
title_sort Esterification of Levulinic Acid to Methyl Levulinate over Zr-MOFs Catalysts
dc.creator.none.fl_str_mv Bravo Fuchineco, Daiana Antonella
Heredia, Angelica Constanza
Mendoza, Sandra Marina
Rodríguez Castellón, Enrique
Crivello, Mónica Elsie
author Bravo Fuchineco, Daiana Antonella
author_facet Bravo Fuchineco, Daiana Antonella
Heredia, Angelica Constanza
Mendoza, Sandra Marina
Rodríguez Castellón, Enrique
Crivello, Mónica Elsie
author_role author
author2 Heredia, Angelica Constanza
Mendoza, Sandra Marina
Rodríguez Castellón, Enrique
Crivello, Mónica Elsie
author2_role author
author
author
author
dc.subject.none.fl_str_mv BATCH AND PRESSURE REACTIONS
ESTERIFICATION KINETICS
LEVULINIC ACID
METHYL LEVULINATE
UIO‐66
UIO‐66‐NH2
topic BATCH AND PRESSURE REACTIONS
ESTERIFICATION KINETICS
LEVULINIC ACID
METHYL LEVULINATE
UIO‐66
UIO‐66‐NH2
purl_subject.fl_str_mv https://purl.org/becyt/ford/2.4
https://purl.org/becyt/ford/2
dc.description.none.fl_txt_mv At present, the trend towards partial replacement of petroleum‐derived fuels by those from the revaluation of biomass has become of great importance. An effective strategy for pro-cessing complex biomass feedstocks involves prior conversion to simpler compounds (platform molecules) that are more easily transformed in subsequent reactions. This study analyzes the met-al–organic frameworks (MOFs) that contain Zr metal clusters formed by ligands of terephthalic acid (UiO‐66) and aminoterephthalic acid (UiO‐66‐NH2), as active and stable catalysts for the esterification of levulinic acid with methanol. An alternative synthesis is presented by means of ultrasonic stirring at room temperature and 60 °C, in order to improve the structural properties of the catalysts. They were analyzed by X‐ray diffraction, scanning electron microscopy, infrared spectroscopy, X‐ray photoelectron spectroscopy, microwave plasma atomic emission spectroscopy, acidity measurement, and N2 adsorption. The catalytic reaction was carried out in a batch system and under pressure in an autoclave. Its progress was followed by gas chromatography and mass spectrometry. Parameters such as temperature, catalyst mass, and molar ratio of reactants were optimized to improve the catalytic performance. The MOF that presented the highest activity and selectivity to the desired product was obtained by synthesis with ultrasound and 60 °C with ami-noterephthalic acid. The methyl levulinate yield was 67.77% in batch at 5 h and 85.89% in an auto-clave at 1 h. An analysis of the kinetic parameters of the reaction is presented. The spent material can be activated by ethanol washing allowing the catalytic activity to be maintained in the recycles.
Fil: Bravo Fuchineco, Daiana Antonella. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Centro de Investigación y Tecnología Química. Universidad Tecnológica Nacional. Facultad Regional Córdoba. Centro de Investigación y Tecnología Química; Argentina
Fil: Heredia, Angelica Constanza. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Centro de Investigación y Tecnología Química. Universidad Tecnológica Nacional. Facultad Regional Córdoba. Centro de Investigación y Tecnología Química; Argentina
Fil: Mendoza, Sandra Marina. Universidad Tecnológica Nacional. Facultad Regional Reconquista; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba; Argentina
Fil: Rodríguez Castellón, Enrique. Dpto. Química Inorgánica, Cristalografía y Mineralogía; España
Fil: Crivello, Mónica Elsie. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Centro de Investigación y Tecnología Química. Universidad Tecnológica Nacional. Facultad Regional Córdoba. Centro de Investigación y Tecnología Química; Argentina
description At present, the trend towards partial replacement of petroleum‐derived fuels by those from the revaluation of biomass has become of great importance. An effective strategy for pro-cessing complex biomass feedstocks involves prior conversion to simpler compounds (platform molecules) that are more easily transformed in subsequent reactions. This study analyzes the met-al–organic frameworks (MOFs) that contain Zr metal clusters formed by ligands of terephthalic acid (UiO‐66) and aminoterephthalic acid (UiO‐66‐NH2), as active and stable catalysts for the esterification of levulinic acid with methanol. An alternative synthesis is presented by means of ultrasonic stirring at room temperature and 60 °C, in order to improve the structural properties of the catalysts. They were analyzed by X‐ray diffraction, scanning electron microscopy, infrared spectroscopy, X‐ray photoelectron spectroscopy, microwave plasma atomic emission spectroscopy, acidity measurement, and N2 adsorption. The catalytic reaction was carried out in a batch system and under pressure in an autoclave. Its progress was followed by gas chromatography and mass spectrometry. Parameters such as temperature, catalyst mass, and molar ratio of reactants were optimized to improve the catalytic performance. The MOF that presented the highest activity and selectivity to the desired product was obtained by synthesis with ultrasound and 60 °C with ami-noterephthalic acid. The methyl levulinate yield was 67.77% in batch at 5 h and 85.89% in an auto-clave at 1 h. An analysis of the kinetic parameters of the reaction is presented. The spent material can be activated by ethanol washing allowing the catalytic activity to be maintained in the recycles.
publishDate 2022
dc.date.none.fl_str_mv 2022-03-25
dc.type.none.fl_str_mv info:eu-repo/semantics/article
info:eu-repo/semantics/publishedVersion
http://purl.org/coar/resource_type/c_6501
info:ar-repo/semantics/articulo
format article
status_str publishedVersion
dc.identifier.none.fl_str_mv http://hdl.handle.net/11336/163282
Bravo Fuchineco, Daiana Antonella; Heredia, Angelica Constanza; Mendoza, Sandra Marina; Rodríguez Castellón, Enrique; Crivello, Mónica Elsie; Esterification of Levulinic Acid to Methyl Levulinate over Zr-MOFs Catalysts; MDPI; ChemEngineering; 25-3-2022
2305-7084
CONICET Digital
CONICET
url http://hdl.handle.net/11336/163282
identifier_str_mv Bravo Fuchineco, Daiana Antonella; Heredia, Angelica Constanza; Mendoza, Sandra Marina; Rodríguez Castellón, Enrique; Crivello, Mónica Elsie; Esterification of Levulinic Acid to Methyl Levulinate over Zr-MOFs Catalysts; MDPI; ChemEngineering; 25-3-2022
2305-7084
CONICET Digital
CONICET
dc.language.none.fl_str_mv eng
language eng
dc.relation.none.fl_str_mv info:eu-repo/semantics/altIdentifier/doi/10.3390/chemengineering6020026
info:eu-repo/semantics/altIdentifier/url/https://www.mdpi.com/2305-7084/6/2/26
dc.rights.none.fl_str_mv info:eu-repo/semantics/openAccess
https://creativecommons.org/licenses/by/2.5/ar/
eu_rights_str_mv openAccess
rights_invalid_str_mv https://creativecommons.org/licenses/by/2.5/ar/
dc.format.none.fl_str_mv application/pdf
application/pdf
dc.publisher.none.fl_str_mv MDPI
publisher.none.fl_str_mv MDPI
dc.source.none.fl_str_mv reponame:CONICET Digital (CONICET)
instname:Consejo Nacional de Investigaciones Científicas y Técnicas
reponame_str CONICET Digital (CONICET)
collection CONICET Digital (CONICET)
instname_str Consejo Nacional de Investigaciones Científicas y Técnicas
repository.name.fl_str_mv CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicas
repository.mail.fl_str_mv dasensio@conicet.gov.ar; lcarlino@conicet.gov.ar
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score 13.069144

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