Isotopic study of the rates of hydrogen provision vs. methanol synthesis from CO2 over Cu-Ga-Zr catalysts

Autores
Fornero, Esteban Luis; Bonivardi, Adrian Lionel; Baltanas, Miguel Angel
Año de publicación
2015
Idioma
inglés
Tipo de recurso
artículo
Estado
versión publicada
Descripción
Cu/ZrO2 and Ga2O3-promoted Cu/ZrO2, with the same copper loading (2.6 wt.%), were evaluated in a Carberry-type batch-operated microreactor for methanol synthesis using a H2/CO2/He mixture (75/22/3 v/v) at 1.6 MPa and 498 K. The gallia-promoted catalyst was 5-fold more active to methanol production (per catalyst specific surface) than Cu/ZrO2. In addition, after the incorporation of Ga2O3 the selectivity to the alcohol was enhanced by a factor of three. To discern whether different degrees of hydrogen provision were responsible for the dissimilar performances observed, thus affecting the overall reaction rate to methanol (RCH3OH), the ability to activate H2 of the catalysts was assessed – in the same microreactor – by a combination of H2/D2 isotopic equilibration (H2/D2/Ar = 37.5/37.5/25 v/v) and H/D isotopic exchange (D2/Ar = 10/90 v/v) reactions at 0.1 MPa, between 353 and 393 K. The equilibration rate (Requil) was far higher than RCH3OH on both, Cu/ZrO2 and Ga2O3-promoted Cu/ZrO2. In agreement with the property of gallia to dissociate H2, Ga2O3 increased further Requil in the ternary catalyst. Vis-à-vis, the isotopic-exchange reaction rates (Rexchg) were considerably lower than the Requil for each catalyst, more so for the gallium containing one. However, the extrapolation of those Rexchg values to the temperature of methanol synthesis gave always much higher rates than RCH3OH, thus allowing to conclude that the supply of ‘active’ hydrogen is fully secured on these copper-supported (gallium-promoted) catalysts.
Fil: Fornero, Esteban Luis. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Santa Fe. Instituto de Desarrollo Tecnológico para la Industria Química. Universidad Nacional del Litoral. Instituto de Desarrollo Tecnológico para la Industria Química; Argentina
Fil: Bonivardi, Adrian Lionel. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Santa Fe. Instituto de Desarrollo Tecnológico para la Industria Química. Universidad Nacional del Litoral. Instituto de Desarrollo Tecnológico para la Industria Química; Argentina
Fil: Baltanas, Miguel Angel. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Santa Fe. Instituto de Desarrollo Tecnológico para la Industria Química. Universidad Nacional del Litoral. Instituto de Desarrollo Tecnológico para la Industria Química; Argentina
Materia
Methanol Synthesis
Hydrogen Provision
Copper
Zirconia
Galia
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:11336/23075
Acceder
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oai_identifier_str oai:ri.conicet.gov.ar:11336/23075
network_acronym_str CONICETDig
repository_id_str 3498
network_name_str CONICET Digital (CONICET)
spelling Isotopic study of the rates of hydrogen provision vs. methanol synthesis from CO2 over Cu-Ga-Zr catalystsFornero, Esteban LuisBonivardi, Adrian LionelBaltanas, Miguel AngelMethanol SynthesisHydrogen ProvisionCopperZirconiaGaliahttps://purl.org/becyt/ford/2.4https://purl.org/becyt/ford/2Cu/ZrO2 and Ga2O3-promoted Cu/ZrO2, with the same copper loading (2.6 wt.%), were evaluated in a Carberry-type batch-operated microreactor for methanol synthesis using a H2/CO2/He mixture (75/22/3 v/v) at 1.6 MPa and 498 K. The gallia-promoted catalyst was 5-fold more active to methanol production (per catalyst specific surface) than Cu/ZrO2. In addition, after the incorporation of Ga2O3 the selectivity to the alcohol was enhanced by a factor of three. To discern whether different degrees of hydrogen provision were responsible for the dissimilar performances observed, thus affecting the overall reaction rate to methanol (RCH3OH), the ability to activate H2 of the catalysts was assessed – in the same microreactor – by a combination of H2/D2 isotopic equilibration (H2/D2/Ar = 37.5/37.5/25 v/v) and H/D isotopic exchange (D2/Ar = 10/90 v/v) reactions at 0.1 MPa, between 353 and 393 K. The equilibration rate (Requil) was far higher than RCH3OH on both, Cu/ZrO2 and Ga2O3-promoted Cu/ZrO2. In agreement with the property of gallia to dissociate H2, Ga2O3 increased further Requil in the ternary catalyst. Vis-à-vis, the isotopic-exchange reaction rates (Rexchg) were considerably lower than the Requil for each catalyst, more so for the gallium containing one. However, the extrapolation of those Rexchg values to the temperature of methanol synthesis gave always much higher rates than RCH3OH, thus allowing to conclude that the supply of ‘active’ hydrogen is fully secured on these copper-supported (gallium-promoted) catalysts.Fil: Fornero, Esteban Luis. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Santa Fe. Instituto de Desarrollo Tecnológico para la Industria Química. Universidad Nacional del Litoral. Instituto de Desarrollo Tecnológico para la Industria Química; ArgentinaFil: Bonivardi, Adrian Lionel. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Santa Fe. Instituto de Desarrollo Tecnológico para la Industria Química. Universidad Nacional del Litoral. Instituto de Desarrollo Tecnológico para la Industria Química; ArgentinaFil: Baltanas, Miguel Angel. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Santa Fe. Instituto de Desarrollo Tecnológico para la Industria Química. Universidad Nacional del Litoral. Instituto de Desarrollo Tecnológico para la Industria Química; ArgentinaAcademic Press Inc Elsevier Science2015-08info:eu-repo/semantics/articleinfo:eu-repo/semantics/publishedVersionhttp://purl.org/coar/resource_type/c_6501info:ar-repo/semantics/articuloapplication/pdfapplication/pdfapplication/pdfhttp://hdl.handle.net/11336/23075Fornero, Esteban Luis; Bonivardi, Adrian Lionel; Baltanas, Miguel Angel; Isotopic study of the rates of hydrogen provision vs. methanol synthesis from CO2 over Cu-Ga-Zr catalysts; Academic Press Inc Elsevier Science; Journal of Catalysis; 330; 8-2015; 302-3100021-9517CONICET DigitalCONICETenginfo:eu-repo/semantics/altIdentifier/doi/10.1016/j.jcat.2015.07.025info:eu-repo/semantics/altIdentifier/url/http://www.sciencedirect.com/science/article/pii/S0021951715002456info:eu-repo/semantics/openAccesshttps://creativecommons.org/licenses/by-nc-sa/2.5/ar/reponame:CONICET Digital (CONICET)instname:Consejo Nacional de Investigaciones Científicas y Técnicas2025-10-22T12:12:55Zoai:ri.conicet.gov.ar:11336/23075instacron: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:34982025-10-22 12:12:55.368CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicasfalse
dc.title.none.fl_str_mv Isotopic study of the rates of hydrogen provision vs. methanol synthesis from CO2 over Cu-Ga-Zr catalysts
title Isotopic study of the rates of hydrogen provision vs. methanol synthesis from CO2 over Cu-Ga-Zr catalysts
spellingShingle Isotopic study of the rates of hydrogen provision vs. methanol synthesis from CO2 over Cu-Ga-Zr catalysts
Fornero, Esteban Luis
Methanol Synthesis
Hydrogen Provision
Copper
Zirconia
Galia
title_short Isotopic study of the rates of hydrogen provision vs. methanol synthesis from CO2 over Cu-Ga-Zr catalysts
title_full Isotopic study of the rates of hydrogen provision vs. methanol synthesis from CO2 over Cu-Ga-Zr catalysts
title_fullStr Isotopic study of the rates of hydrogen provision vs. methanol synthesis from CO2 over Cu-Ga-Zr catalysts
title_full_unstemmed Isotopic study of the rates of hydrogen provision vs. methanol synthesis from CO2 over Cu-Ga-Zr catalysts
title_sort Isotopic study of the rates of hydrogen provision vs. methanol synthesis from CO2 over Cu-Ga-Zr catalysts
dc.creator.none.fl_str_mv Fornero, Esteban Luis
Bonivardi, Adrian Lionel
Baltanas, Miguel Angel
author Fornero, Esteban Luis
author_facet Fornero, Esteban Luis
Bonivardi, Adrian Lionel
Baltanas, Miguel Angel
author_role author
author2 Bonivardi, Adrian Lionel
Baltanas, Miguel Angel
author2_role author
author
dc.subject.none.fl_str_mv Methanol Synthesis
Hydrogen Provision
Copper
Zirconia
Galia
topic Methanol Synthesis
Hydrogen Provision
Copper
Zirconia
Galia
purl_subject.fl_str_mv https://purl.org/becyt/ford/2.4
https://purl.org/becyt/ford/2
dc.description.none.fl_txt_mv Cu/ZrO2 and Ga2O3-promoted Cu/ZrO2, with the same copper loading (2.6 wt.%), were evaluated in a Carberry-type batch-operated microreactor for methanol synthesis using a H2/CO2/He mixture (75/22/3 v/v) at 1.6 MPa and 498 K. The gallia-promoted catalyst was 5-fold more active to methanol production (per catalyst specific surface) than Cu/ZrO2. In addition, after the incorporation of Ga2O3 the selectivity to the alcohol was enhanced by a factor of three. To discern whether different degrees of hydrogen provision were responsible for the dissimilar performances observed, thus affecting the overall reaction rate to methanol (RCH3OH), the ability to activate H2 of the catalysts was assessed – in the same microreactor – by a combination of H2/D2 isotopic equilibration (H2/D2/Ar = 37.5/37.5/25 v/v) and H/D isotopic exchange (D2/Ar = 10/90 v/v) reactions at 0.1 MPa, between 353 and 393 K. The equilibration rate (Requil) was far higher than RCH3OH on both, Cu/ZrO2 and Ga2O3-promoted Cu/ZrO2. In agreement with the property of gallia to dissociate H2, Ga2O3 increased further Requil in the ternary catalyst. Vis-à-vis, the isotopic-exchange reaction rates (Rexchg) were considerably lower than the Requil for each catalyst, more so for the gallium containing one. However, the extrapolation of those Rexchg values to the temperature of methanol synthesis gave always much higher rates than RCH3OH, thus allowing to conclude that the supply of ‘active’ hydrogen is fully secured on these copper-supported (gallium-promoted) catalysts.
Fil: Fornero, Esteban Luis. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Santa Fe. Instituto de Desarrollo Tecnológico para la Industria Química. Universidad Nacional del Litoral. Instituto de Desarrollo Tecnológico para la Industria Química; Argentina
Fil: Bonivardi, Adrian Lionel. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Santa Fe. Instituto de Desarrollo Tecnológico para la Industria Química. Universidad Nacional del Litoral. Instituto de Desarrollo Tecnológico para la Industria Química; Argentina
Fil: Baltanas, Miguel Angel. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Santa Fe. Instituto de Desarrollo Tecnológico para la Industria Química. Universidad Nacional del Litoral. Instituto de Desarrollo Tecnológico para la Industria Química; Argentina
description Cu/ZrO2 and Ga2O3-promoted Cu/ZrO2, with the same copper loading (2.6 wt.%), were evaluated in a Carberry-type batch-operated microreactor for methanol synthesis using a H2/CO2/He mixture (75/22/3 v/v) at 1.6 MPa and 498 K. The gallia-promoted catalyst was 5-fold more active to methanol production (per catalyst specific surface) than Cu/ZrO2. In addition, after the incorporation of Ga2O3 the selectivity to the alcohol was enhanced by a factor of three. To discern whether different degrees of hydrogen provision were responsible for the dissimilar performances observed, thus affecting the overall reaction rate to methanol (RCH3OH), the ability to activate H2 of the catalysts was assessed – in the same microreactor – by a combination of H2/D2 isotopic equilibration (H2/D2/Ar = 37.5/37.5/25 v/v) and H/D isotopic exchange (D2/Ar = 10/90 v/v) reactions at 0.1 MPa, between 353 and 393 K. The equilibration rate (Requil) was far higher than RCH3OH on both, Cu/ZrO2 and Ga2O3-promoted Cu/ZrO2. In agreement with the property of gallia to dissociate H2, Ga2O3 increased further Requil in the ternary catalyst. Vis-à-vis, the isotopic-exchange reaction rates (Rexchg) were considerably lower than the Requil for each catalyst, more so for the gallium containing one. However, the extrapolation of those Rexchg values to the temperature of methanol synthesis gave always much higher rates than RCH3OH, thus allowing to conclude that the supply of ‘active’ hydrogen is fully secured on these copper-supported (gallium-promoted) catalysts.
publishDate 2015
dc.date.none.fl_str_mv 2015-08
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/11336/23075
Fornero, Esteban Luis; Bonivardi, Adrian Lionel; Baltanas, Miguel Angel; Isotopic study of the rates of hydrogen provision vs. methanol synthesis from CO2 over Cu-Ga-Zr catalysts; Academic Press Inc Elsevier Science; Journal of Catalysis; 330; 8-2015; 302-310
0021-9517
CONICET Digital
CONICET
url http://hdl.handle.net/11336/23075
identifier_str_mv Fornero, Esteban Luis; Bonivardi, Adrian Lionel; Baltanas, Miguel Angel; Isotopic study of the rates of hydrogen provision vs. methanol synthesis from CO2 over Cu-Ga-Zr catalysts; Academic Press Inc Elsevier Science; Journal of Catalysis; 330; 8-2015; 302-310
0021-9517
CONICET Digital
CONICET
dc.language.none.fl_str_mv eng
language eng
dc.relation.none.fl_str_mv info:eu-repo/semantics/altIdentifier/doi/10.1016/j.jcat.2015.07.025
info:eu-repo/semantics/altIdentifier/url/http://www.sciencedirect.com/science/article/pii/S0021951715002456
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
dc.publisher.none.fl_str_mv Academic Press Inc Elsevier Science
publisher.none.fl_str_mv Academic Press Inc Elsevier Science
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 12.982451

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