Methanol synthesis from CO2/H2 using Ga2O3-Pd/silica catalysts: Kinetic modeling

Autores
Chiavassa, Dante Luis; Collins, Sebastián Enrique; Bonivardi, Adrian Lionel; Baltanas, Miguel Angel
Año de publicación
2009
Idioma
inglés
Tipo de recurso
artículo
Estado
versión publicada
Descripción
The synthesis of methanol from CO2/H2 on a Ga2O3?Pd/silica catalyst, together with the reverse water gas shift reaction, was modeled for a wide range of temperatures (508?538 K), pressures (1?4MPa), compositions (H2/CO2 = 1, 3 and 6) and space velocity conditions. The kinetic information was combined with relevant spectroscopic (FT-IR) data. The rate determining steps (rds) of the reactions were the hydrogenation of the formate intermediate, and its decomposition on the gallia surface, respectively.
A competitive adsorption mechanism, where adsorbed atomic hydrogen occupies the same active sites as other oxygenated surface intermediates on the gallia, was found as the most satisfactory, in terms of physicochemical significance of the parameter estimates. Minimal residualswere foundwhenconsidering as kinetically relevant the simultaneous surface occupancy by formate, methylenebisoxy, hydroxyl and atomic hydrogen intermediates.
The deleterious impact of CO for certain process conditions, such as high conversion and/or ternary H2/CO2/CO mixture feeds, was also studied. In these cases, CO competes with H2 on the Pd crystallites, severely limiting the availability of atomic hydrogen to the gallia surface. Using the steady-state approximation, the supply and demand of atomic hydrogen were then balanced to find the best model interpretation of the observed reactivity.
Fil: Chiavassa, Dante 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: Collins, Sebastián Enrique. 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
Co2 Recycling
Methanol Synthesis
Palladium
Kinetic Modeling
Gallium Oxide
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:11336/26137
Acceder
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oai_identifier_str oai:ri.conicet.gov.ar:11336/26137
network_acronym_str CONICETDig
repository_id_str 3498
network_name_str CONICET Digital (CONICET)
spelling Methanol synthesis from CO2/H2 using Ga2O3-Pd/silica catalysts: Kinetic modelingChiavassa, Dante LuisCollins, Sebastián EnriqueBonivardi, Adrian LionelBaltanas, Miguel AngelCo2 RecyclingMethanol SynthesisPalladiumKinetic ModelingGallium Oxidehttps://purl.org/becyt/ford/2.4https://purl.org/becyt/ford/2The synthesis of methanol from CO2/H2 on a Ga2O3?Pd/silica catalyst, together with the reverse water gas shift reaction, was modeled for a wide range of temperatures (508?538 K), pressures (1?4MPa), compositions (H2/CO2 = 1, 3 and 6) and space velocity conditions. The kinetic information was combined with relevant spectroscopic (FT-IR) data. The rate determining steps (rds) of the reactions were the hydrogenation of the formate intermediate, and its decomposition on the gallia surface, respectively.<br />A competitive adsorption mechanism, where adsorbed atomic hydrogen occupies the same active sites as other oxygenated surface intermediates on the gallia, was found as the most satisfactory, in terms of physicochemical significance of the parameter estimates. Minimal residualswere foundwhenconsidering as kinetically relevant the simultaneous surface occupancy by formate, methylenebisoxy, hydroxyl and atomic hydrogen intermediates.<br />The deleterious impact of CO for certain process conditions, such as high conversion and/or ternary H2/CO2/CO mixture feeds, was also studied. In these cases, CO competes with H2 on the Pd crystallites, severely limiting the availability of atomic hydrogen to the gallia surface. Using the steady-state approximation, the supply and demand of atomic hydrogen were then balanced to find the best model interpretation of the observed reactivity.Fil: Chiavassa, Dante 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: Collins, Sebastián Enrique. 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; ArgentinaElsevier Science Sa2009-12info:eu-repo/semantics/articleinfo:eu-repo/semantics/publishedVersionhttp://purl.org/coar/resource_type/c_6501info:ar-repo/semantics/articuloapplication/pdfapplication/pdfapplication/pdfapplication/pdfapplication/pdfhttp://hdl.handle.net/11336/26137Chiavassa, Dante Luis; Collins, Sebastián Enrique; Bonivardi, Adrian Lionel; Baltanas, Miguel Angel; Methanol synthesis from CO2/H2 using Ga2O3-Pd/silica catalysts: Kinetic modeling; Elsevier Science Sa; Chemical Engineering Journal; 150; 1; 12-2009; 204-2121385-8947CONICET DigitalCONICETenginfo:eu-repo/semantics/altIdentifier/doi/10.1016/j.cej.2009.02.013info:eu-repo/semantics/altIdentifier/url/http://www.sciencedirect.com/science/article/pii/S1385894709001144info:eu-repo/semantics/openAccesshttps://creativecommons.org/licenses/by-nc-sa/2.5/ar/reponame:CONICET Digital (CONICET)instname:Consejo Nacional de Investigaciones Científicas y Técnicas2025-11-05T09:55:39Zoai:ri.conicet.gov.ar:11336/26137instacron: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:34982025-11-05 09:55:40.125CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicasfalse
dc.title.none.fl_str_mv Methanol synthesis from CO2/H2 using Ga2O3-Pd/silica catalysts: Kinetic modeling
title Methanol synthesis from CO2/H2 using Ga2O3-Pd/silica catalysts: Kinetic modeling
spellingShingle Methanol synthesis from CO2/H2 using Ga2O3-Pd/silica catalysts: Kinetic modeling
Chiavassa, Dante Luis
Co2 Recycling
Methanol Synthesis
Palladium
Kinetic Modeling
Gallium Oxide
title_short Methanol synthesis from CO2/H2 using Ga2O3-Pd/silica catalysts: Kinetic modeling
title_full Methanol synthesis from CO2/H2 using Ga2O3-Pd/silica catalysts: Kinetic modeling
title_fullStr Methanol synthesis from CO2/H2 using Ga2O3-Pd/silica catalysts: Kinetic modeling
title_full_unstemmed Methanol synthesis from CO2/H2 using Ga2O3-Pd/silica catalysts: Kinetic modeling
title_sort Methanol synthesis from CO2/H2 using Ga2O3-Pd/silica catalysts: Kinetic modeling
dc.creator.none.fl_str_mv Chiavassa, Dante Luis
Collins, Sebastián Enrique
Bonivardi, Adrian Lionel
Baltanas, Miguel Angel
author Chiavassa, Dante Luis
author_facet Chiavassa, Dante Luis
Collins, Sebastián Enrique
Bonivardi, Adrian Lionel
Baltanas, Miguel Angel
author_role author
author2 Collins, Sebastián Enrique
Bonivardi, Adrian Lionel
Baltanas, Miguel Angel
author2_role author
author
author
dc.subject.none.fl_str_mv Co2 Recycling
Methanol Synthesis
Palladium
Kinetic Modeling
Gallium Oxide
topic Co2 Recycling
Methanol Synthesis
Palladium
Kinetic Modeling
Gallium Oxide
purl_subject.fl_str_mv https://purl.org/becyt/ford/2.4
https://purl.org/becyt/ford/2
dc.description.none.fl_txt_mv The synthesis of methanol from CO2/H2 on a Ga2O3?Pd/silica catalyst, together with the reverse water gas shift reaction, was modeled for a wide range of temperatures (508?538 K), pressures (1?4MPa), compositions (H2/CO2 = 1, 3 and 6) and space velocity conditions. The kinetic information was combined with relevant spectroscopic (FT-IR) data. The rate determining steps (rds) of the reactions were the hydrogenation of the formate intermediate, and its decomposition on the gallia surface, respectively.<br />A competitive adsorption mechanism, where adsorbed atomic hydrogen occupies the same active sites as other oxygenated surface intermediates on the gallia, was found as the most satisfactory, in terms of physicochemical significance of the parameter estimates. Minimal residualswere foundwhenconsidering as kinetically relevant the simultaneous surface occupancy by formate, methylenebisoxy, hydroxyl and atomic hydrogen intermediates.<br />The deleterious impact of CO for certain process conditions, such as high conversion and/or ternary H2/CO2/CO mixture feeds, was also studied. In these cases, CO competes with H2 on the Pd crystallites, severely limiting the availability of atomic hydrogen to the gallia surface. Using the steady-state approximation, the supply and demand of atomic hydrogen were then balanced to find the best model interpretation of the observed reactivity.
Fil: Chiavassa, Dante 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: Collins, Sebastián Enrique. 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 The synthesis of methanol from CO2/H2 on a Ga2O3?Pd/silica catalyst, together with the reverse water gas shift reaction, was modeled for a wide range of temperatures (508?538 K), pressures (1?4MPa), compositions (H2/CO2 = 1, 3 and 6) and space velocity conditions. The kinetic information was combined with relevant spectroscopic (FT-IR) data. The rate determining steps (rds) of the reactions were the hydrogenation of the formate intermediate, and its decomposition on the gallia surface, respectively.<br />A competitive adsorption mechanism, where adsorbed atomic hydrogen occupies the same active sites as other oxygenated surface intermediates on the gallia, was found as the most satisfactory, in terms of physicochemical significance of the parameter estimates. Minimal residualswere foundwhenconsidering as kinetically relevant the simultaneous surface occupancy by formate, methylenebisoxy, hydroxyl and atomic hydrogen intermediates.<br />The deleterious impact of CO for certain process conditions, such as high conversion and/or ternary H2/CO2/CO mixture feeds, was also studied. In these cases, CO competes with H2 on the Pd crystallites, severely limiting the availability of atomic hydrogen to the gallia surface. Using the steady-state approximation, the supply and demand of atomic hydrogen were then balanced to find the best model interpretation of the observed reactivity.
publishDate 2009
dc.date.none.fl_str_mv 2009-12
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/11336/26137
Chiavassa, Dante Luis; Collins, Sebastián Enrique; Bonivardi, Adrian Lionel; Baltanas, Miguel Angel; Methanol synthesis from CO2/H2 using Ga2O3-Pd/silica catalysts: Kinetic modeling; Elsevier Science Sa; Chemical Engineering Journal; 150; 1; 12-2009; 204-212
1385-8947
CONICET Digital
CONICET
url http://hdl.handle.net/11336/26137
identifier_str_mv Chiavassa, Dante Luis; Collins, Sebastián Enrique; Bonivardi, Adrian Lionel; Baltanas, Miguel Angel; Methanol synthesis from CO2/H2 using Ga2O3-Pd/silica catalysts: Kinetic modeling; Elsevier Science Sa; Chemical Engineering Journal; 150; 1; 12-2009; 204-212
1385-8947
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.cej.2009.02.013
info:eu-repo/semantics/altIdentifier/url/http://www.sciencedirect.com/science/article/pii/S1385894709001144
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
application/pdf
dc.publisher.none.fl_str_mv Elsevier Science Sa
publisher.none.fl_str_mv Elsevier Science Sa
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 13.082534

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