Upgrading of diols by gas-phase dehydrogenation and dehydration reactions on bifunctional Cu-based oxides

Autores
Torresi, Pablo Antonio; Diez, Veronica Karina; Luggren, Pablo Jorge; Di Cosimo, Juana Isabel
Año de publicación
2014
Idioma
inglés
Tipo de recurso
artículo
Estado
versión publicada
Descripción
Biomass-derived short chain polyols can be transformed in valuable oxygenates used as building blocks. The gas phase conversion of a model molecule of 1,3-diols (1,3-butanediol) was studied on bifunctional Cu-Mg, Cu-Al and Cu-Mg-Al mixed oxide catalysts that combine surface Cu0 particles and acid-base properties. A series of ZCuMgAl catalysts (Z=0.3-61.2 wt.% Cu, Mg/Al=1.5 molar ratio) was prepared by coprecipitation and thoroughly characterized by several techniques such as BET surface area, TPR-N2O chemisorption, XRD and TPD of CO2. The ZCuMgAl catalysts promote the upgrading of the diol by a series of dehydrogenation and/or dehydration reactions proceeding at reaction rates that depend on the copper content (Z). The overall activity increases linearly with the amount of surface Cu0 species thereby confirming participation of metallic sites in rate-limiting steps. Besides, surface Cu0 sites favor the reaction pathway toward 1,3-butanediol dehydrogenation. Thus, the dehydrogenation/dehydration selectivity ratio increases with Z as a result of the enhanced amount of exposed Cu0 particles. ZCuMgAl catalysts with Z < 8wt.% dehydrogenate-dehydrate-hydrogenate the diol at low rates giving mainly C4 ketones and break the intermediates forming C1-C3 oxygenates; catalysts with Z > 8wt.% are more active and yield valuable multifunctional C4 oxygenates such as hydroxyketones and to a lesser extent, unsaturated alcohols and ketones. A strongly basic Cu-Mg catalyst promotes the C-C bond cleavage reaction giving short carbon chain oxygenates at low rates; an acidic Cu-Al catalyst converts the diol into the C4 saturated ketone and olefins.
Fil: Torresi, Pablo Antonio. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Santa Fe. Instituto de Investigaciones en Catálisis y Petroquímica ; Argentina
Fil: Diez, Veronica Karina. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Santa Fe. Instituto de Investigaciones en Catálisis y Petroquímica ; Argentina
Fil: Luggren, Pablo Jorge. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Santa Fe. Instituto de Investigaciones en Catálisis y Petroquímica ; Argentina
Fil: Di Cosimo, Juana Isabel. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Santa Fe. Instituto de Investigaciones en Catálisis y Petroquímica ; Argentina
Materia
Dehydration
Dehydrogenation
Diols
Acid-Base Catalyst
Copper
Nivel de accesibilidad
acceso abierto
Condiciones de uso
https://creativecommons.org/licenses/by-nc-sa/2.5/ar/
Repositorio
CONICET Digital (CONICET)
Institución
Consejo Nacional de Investigaciones Científicas y Técnicas
OAI Identificador
oai:ri.conicet.gov.ar:11336/31112
Acceder
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oai_identifier_str oai:ri.conicet.gov.ar:11336/31112
network_acronym_str CONICETDig
repository_id_str 3498
network_name_str CONICET Digital (CONICET)
spelling Upgrading of diols by gas-phase dehydrogenation and dehydration reactions on bifunctional Cu-based oxidesTorresi, Pablo AntonioDiez, Veronica KarinaLuggren, Pablo JorgeDi Cosimo, Juana IsabelDehydrationDehydrogenationDiolsAcid-Base CatalystCopperhttps://purl.org/becyt/ford/2.4https://purl.org/becyt/ford/2Biomass-derived short chain polyols can be transformed in valuable oxygenates used as building blocks. The gas phase conversion of a model molecule of 1,3-diols (1,3-butanediol) was studied on bifunctional Cu-Mg, Cu-Al and Cu-Mg-Al mixed oxide catalysts that combine surface Cu0 particles and acid-base properties. A series of ZCuMgAl catalysts (Z=0.3-61.2 wt.% Cu, Mg/Al=1.5 molar ratio) was prepared by coprecipitation and thoroughly characterized by several techniques such as BET surface area, TPR-N2O chemisorption, XRD and TPD of CO2. The ZCuMgAl catalysts promote the upgrading of the diol by a series of dehydrogenation and/or dehydration reactions proceeding at reaction rates that depend on the copper content (Z). The overall activity increases linearly with the amount of surface Cu0 species thereby confirming participation of metallic sites in rate-limiting steps. Besides, surface Cu0 sites favor the reaction pathway toward 1,3-butanediol dehydrogenation. Thus, the dehydrogenation/dehydration selectivity ratio increases with Z as a result of the enhanced amount of exposed Cu0 particles. ZCuMgAl catalysts with Z < 8wt.% dehydrogenate-dehydrate-hydrogenate the diol at low rates giving mainly C4 ketones and break the intermediates forming C1-C3 oxygenates; catalysts with Z > 8wt.% are more active and yield valuable multifunctional C4 oxygenates such as hydroxyketones and to a lesser extent, unsaturated alcohols and ketones. A strongly basic Cu-Mg catalyst promotes the C-C bond cleavage reaction giving short carbon chain oxygenates at low rates; an acidic Cu-Al catalyst converts the diol into the C4 saturated ketone and olefins.Fil: Torresi, Pablo Antonio. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Santa Fe. Instituto de Investigaciones en Catálisis y Petroquímica ; ArgentinaFil: Diez, Veronica Karina. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Santa Fe. Instituto de Investigaciones en Catálisis y Petroquímica ; ArgentinaFil: Luggren, Pablo Jorge. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Santa Fe. Instituto de Investigaciones en Catálisis y Petroquímica ; ArgentinaFil: Di Cosimo, Juana Isabel. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Santa Fe. Instituto de Investigaciones en Catálisis y Petroquímica ; ArgentinaRoyal Society of Chemistry2014-06info:eu-repo/semantics/articleinfo:eu-repo/semantics/publishedVersionhttp://purl.org/coar/resource_type/c_6501info:ar-repo/semantics/articuloapplication/pdfapplication/pdfapplication/pdfapplication/pdfapplication/pdfapplication/pdfapplication/pdfapplication/pdfapplication/pdfhttp://hdl.handle.net/11336/31112Torresi, Pablo Antonio; Diez, Veronica Karina; Luggren, Pablo Jorge; Di Cosimo, Juana Isabel; Upgrading of diols by gas-phase dehydrogenation and dehydration reactions on bifunctional Cu-based oxides; Royal Society of Chemistry; Catalysys Science and Technology; 4; 9; 6-2014; 3203-32132044-4761CONICET DigitalCONICETenginfo:eu-repo/semantics/altIdentifier/doi/10.1039/C4CY00639Ainfo:eu-repo/semantics/altIdentifier/url/http://pubs.rsc.org/en/content/articlelanding/2014/cy/c4cy00639a/unauth#!divAbstractinfo:eu-repo/semantics/openAccesshttps://creativecommons.org/licenses/by-nc-sa/2.5/ar/reponame:CONICET Digital (CONICET)instname:Consejo Nacional de Investigaciones Científicas y Técnicas2025-09-10T13:22:07Zoai:ri.conicet.gov.ar:11336/31112instacron: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:34982025-09-10 13:22:07.486CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicasfalse
dc.title.none.fl_str_mv Upgrading of diols by gas-phase dehydrogenation and dehydration reactions on bifunctional Cu-based oxides
title Upgrading of diols by gas-phase dehydrogenation and dehydration reactions on bifunctional Cu-based oxides
spellingShingle Upgrading of diols by gas-phase dehydrogenation and dehydration reactions on bifunctional Cu-based oxides
Torresi, Pablo Antonio
Dehydration
Dehydrogenation
Diols
Acid-Base Catalyst
Copper
title_short Upgrading of diols by gas-phase dehydrogenation and dehydration reactions on bifunctional Cu-based oxides
title_full Upgrading of diols by gas-phase dehydrogenation and dehydration reactions on bifunctional Cu-based oxides
title_fullStr Upgrading of diols by gas-phase dehydrogenation and dehydration reactions on bifunctional Cu-based oxides
title_full_unstemmed Upgrading of diols by gas-phase dehydrogenation and dehydration reactions on bifunctional Cu-based oxides
title_sort Upgrading of diols by gas-phase dehydrogenation and dehydration reactions on bifunctional Cu-based oxides
dc.creator.none.fl_str_mv Torresi, Pablo Antonio
Diez, Veronica Karina
Luggren, Pablo Jorge
Di Cosimo, Juana Isabel
author Torresi, Pablo Antonio
author_facet Torresi, Pablo Antonio
Diez, Veronica Karina
Luggren, Pablo Jorge
Di Cosimo, Juana Isabel
author_role author
author2 Diez, Veronica Karina
Luggren, Pablo Jorge
Di Cosimo, Juana Isabel
author2_role author
author
author
dc.subject.none.fl_str_mv Dehydration
Dehydrogenation
Diols
Acid-Base Catalyst
Copper
topic Dehydration
Dehydrogenation
Diols
Acid-Base Catalyst
Copper
purl_subject.fl_str_mv https://purl.org/becyt/ford/2.4
https://purl.org/becyt/ford/2
dc.description.none.fl_txt_mv Biomass-derived short chain polyols can be transformed in valuable oxygenates used as building blocks. The gas phase conversion of a model molecule of 1,3-diols (1,3-butanediol) was studied on bifunctional Cu-Mg, Cu-Al and Cu-Mg-Al mixed oxide catalysts that combine surface Cu0 particles and acid-base properties. A series of ZCuMgAl catalysts (Z=0.3-61.2 wt.% Cu, Mg/Al=1.5 molar ratio) was prepared by coprecipitation and thoroughly characterized by several techniques such as BET surface area, TPR-N2O chemisorption, XRD and TPD of CO2. The ZCuMgAl catalysts promote the upgrading of the diol by a series of dehydrogenation and/or dehydration reactions proceeding at reaction rates that depend on the copper content (Z). The overall activity increases linearly with the amount of surface Cu0 species thereby confirming participation of metallic sites in rate-limiting steps. Besides, surface Cu0 sites favor the reaction pathway toward 1,3-butanediol dehydrogenation. Thus, the dehydrogenation/dehydration selectivity ratio increases with Z as a result of the enhanced amount of exposed Cu0 particles. ZCuMgAl catalysts with Z < 8wt.% dehydrogenate-dehydrate-hydrogenate the diol at low rates giving mainly C4 ketones and break the intermediates forming C1-C3 oxygenates; catalysts with Z > 8wt.% are more active and yield valuable multifunctional C4 oxygenates such as hydroxyketones and to a lesser extent, unsaturated alcohols and ketones. A strongly basic Cu-Mg catalyst promotes the C-C bond cleavage reaction giving short carbon chain oxygenates at low rates; an acidic Cu-Al catalyst converts the diol into the C4 saturated ketone and olefins.
Fil: Torresi, Pablo Antonio. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Santa Fe. Instituto de Investigaciones en Catálisis y Petroquímica ; Argentina
Fil: Diez, Veronica Karina. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Santa Fe. Instituto de Investigaciones en Catálisis y Petroquímica ; Argentina
Fil: Luggren, Pablo Jorge. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Santa Fe. Instituto de Investigaciones en Catálisis y Petroquímica ; Argentina
Fil: Di Cosimo, Juana Isabel. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Santa Fe. Instituto de Investigaciones en Catálisis y Petroquímica ; Argentina
description Biomass-derived short chain polyols can be transformed in valuable oxygenates used as building blocks. The gas phase conversion of a model molecule of 1,3-diols (1,3-butanediol) was studied on bifunctional Cu-Mg, Cu-Al and Cu-Mg-Al mixed oxide catalysts that combine surface Cu0 particles and acid-base properties. A series of ZCuMgAl catalysts (Z=0.3-61.2 wt.% Cu, Mg/Al=1.5 molar ratio) was prepared by coprecipitation and thoroughly characterized by several techniques such as BET surface area, TPR-N2O chemisorption, XRD and TPD of CO2. The ZCuMgAl catalysts promote the upgrading of the diol by a series of dehydrogenation and/or dehydration reactions proceeding at reaction rates that depend on the copper content (Z). The overall activity increases linearly with the amount of surface Cu0 species thereby confirming participation of metallic sites in rate-limiting steps. Besides, surface Cu0 sites favor the reaction pathway toward 1,3-butanediol dehydrogenation. Thus, the dehydrogenation/dehydration selectivity ratio increases with Z as a result of the enhanced amount of exposed Cu0 particles. ZCuMgAl catalysts with Z < 8wt.% dehydrogenate-dehydrate-hydrogenate the diol at low rates giving mainly C4 ketones and break the intermediates forming C1-C3 oxygenates; catalysts with Z > 8wt.% are more active and yield valuable multifunctional C4 oxygenates such as hydroxyketones and to a lesser extent, unsaturated alcohols and ketones. A strongly basic Cu-Mg catalyst promotes the C-C bond cleavage reaction giving short carbon chain oxygenates at low rates; an acidic Cu-Al catalyst converts the diol into the C4 saturated ketone and olefins.
publishDate 2014
dc.date.none.fl_str_mv 2014-06
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/11336/31112
Torresi, Pablo Antonio; Diez, Veronica Karina; Luggren, Pablo Jorge; Di Cosimo, Juana Isabel; Upgrading of diols by gas-phase dehydrogenation and dehydration reactions on bifunctional Cu-based oxides; Royal Society of Chemistry; Catalysys Science and Technology; 4; 9; 6-2014; 3203-3213
2044-4761
CONICET Digital
CONICET
url http://hdl.handle.net/11336/31112
identifier_str_mv Torresi, Pablo Antonio; Diez, Veronica Karina; Luggren, Pablo Jorge; Di Cosimo, Juana Isabel; Upgrading of diols by gas-phase dehydrogenation and dehydration reactions on bifunctional Cu-based oxides; Royal Society of Chemistry; Catalysys Science and Technology; 4; 9; 6-2014; 3203-3213
2044-4761
CONICET Digital
CONICET
dc.language.none.fl_str_mv eng
language eng
dc.relation.none.fl_str_mv info:eu-repo/semantics/altIdentifier/doi/10.1039/C4CY00639A
info:eu-repo/semantics/altIdentifier/url/http://pubs.rsc.org/en/content/articlelanding/2014/cy/c4cy00639a/unauth#!divAbstract
dc.rights.none.fl_str_mv info:eu-repo/semantics/openAccess
https://creativecommons.org/licenses/by-nc-sa/2.5/ar/
eu_rights_str_mv openAccess
rights_invalid_str_mv https://creativecommons.org/licenses/by-nc-sa/2.5/ar/
dc.format.none.fl_str_mv application/pdf
application/pdf
application/pdf
application/pdf
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application/pdf
application/pdf
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application/pdf
dc.publisher.none.fl_str_mv Royal Society of Chemistry
publisher.none.fl_str_mv Royal Society of Chemistry
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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