Liquid transportation fuels from biomass-derived oxygenates: Gas-phase 2-hexanol upgrading on Cu-based mixed oxides

Autores
Luggren, Pablo Jorge; Apesteguia, Carlos Rodolfo; Di Cosimo, Juana Isabel
Año de publicación
2015
Idioma
inglés
Tipo de recurso
artículo
Estado
versión publicada
Descripción
The gas-phase upgrading of 2-hexanol, a model molecule of the primary conversion of sugars, toward higher molecular weight compounds of application as liquid transportation fuels was investigated on Cu-MI-MII mixed oxides (MI, MII: Mg2+, Al3+, Ce4+) at 573K and 101.3 kPa. Catalysts were prepared by coprecipitation and characterized by several techniques such as BET surface area, XRD, TPD of CO2 and NH3, TPR and N2O decomposition. The bifunctional metal-base catalytic process occurs through a series of sequential steps comprising dehydrogenation, C-C coupling, dehydration and hydrogenation reactions. Nano-sized Cu0 particles promote dehydrogenation and hydrogenation steps whereas acid-base sites provided by MI(MII)-O pairs participate in the C-C coupling reaction. In general, main products were C9-C12 compounds that represented ~60% of the product pool. Branched C9-C24 compounds such as ketones, alcohols and alkanes were obtained with yields of up to 91% on a Cu-Mg-Al mixed oxide with 8wt.% Cu (catalyst 8.0CuMgAl). This catalyst presented well dispersed Cu0 particles and a high number of base sites with moderate basic properties as well as a low number of acid sites. The rate-limiting step of the bifunctional process leading to C9-C24 products on catalyst 8.0CuMgAl was the metal-promoted hydrogenation step, but the reaction can be controlled by the C-C bond formation step on less basic catalysts. By carrying out experiments under different reaction atmospheres (N2 or H2) and at different contact times, a reaction pathway leading to formation of odd carbon atom number products (C9, C15 and C21) is postulated in contrast to the conventional aldol condensation pathway toward even carbon atom number products (C12, C18 and C24). The former prevails under conditions at which the catalyst surface is deprived of hydrogen atoms.
Fil: Luggren, Pablo Jorge. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Santa Fe. Instituto de Investigaciones en Catálisis y Petroquímica "Ing. José Miguel Parera". Universidad Nacional del Litoral. Instituto de Investigaciones en Catálisis y Petroquímica "Ing. José Miguel Parera"; Argentina
Fil: Apesteguia, Carlos Rodolfo. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Santa Fe. Instituto de Investigaciones en Catálisis y Petroquímica "Ing. José Miguel Parera". Universidad Nacional del Litoral. Instituto de Investigaciones en Catálisis y Petroquímica "Ing. José Miguel Parera"; 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 "Ing. José Miguel Parera". Universidad Nacional del Litoral. Instituto de Investigaciones en Catálisis y Petroquímica "Ing. José Miguel Parera"; Argentina
Materia
2-HEXANOL
ALDOL CONDENSATION
DEHYDROGENATION
HYDROGENATION
COPPER
MIXED OXIDES
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:11336/113457
Acceder
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oai_identifier_str oai:ri.conicet.gov.ar:11336/113457
network_acronym_str CONICETDig
repository_id_str 3498
network_name_str CONICET Digital (CONICET)
spelling Liquid transportation fuels from biomass-derived oxygenates: Gas-phase 2-hexanol upgrading on Cu-based mixed oxidesLuggren, Pablo JorgeApesteguia, Carlos RodolfoDi Cosimo, Juana Isabel2-HEXANOLALDOL CONDENSATIONDEHYDROGENATIONHYDROGENATIONCOPPERMIXED OXIDEShttps://purl.org/becyt/ford/2.4https://purl.org/becyt/ford/2The gas-phase upgrading of 2-hexanol, a model molecule of the primary conversion of sugars, toward higher molecular weight compounds of application as liquid transportation fuels was investigated on Cu-MI-MII mixed oxides (MI, MII: Mg2+, Al3+, Ce4+) at 573K and 101.3 kPa. Catalysts were prepared by coprecipitation and characterized by several techniques such as BET surface area, XRD, TPD of CO2 and NH3, TPR and N2O decomposition. The bifunctional metal-base catalytic process occurs through a series of sequential steps comprising dehydrogenation, C-C coupling, dehydration and hydrogenation reactions. Nano-sized Cu0 particles promote dehydrogenation and hydrogenation steps whereas acid-base sites provided by MI(MII)-O pairs participate in the C-C coupling reaction. In general, main products were C9-C12 compounds that represented ~60% of the product pool. Branched C9-C24 compounds such as ketones, alcohols and alkanes were obtained with yields of up to 91% on a Cu-Mg-Al mixed oxide with 8wt.% Cu (catalyst 8.0CuMgAl). This catalyst presented well dispersed Cu0 particles and a high number of base sites with moderate basic properties as well as a low number of acid sites. The rate-limiting step of the bifunctional process leading to C9-C24 products on catalyst 8.0CuMgAl was the metal-promoted hydrogenation step, but the reaction can be controlled by the C-C bond formation step on less basic catalysts. By carrying out experiments under different reaction atmospheres (N2 or H2) and at different contact times, a reaction pathway leading to formation of odd carbon atom number products (C9, C15 and C21) is postulated in contrast to the conventional aldol condensation pathway toward even carbon atom number products (C12, C18 and C24). The former prevails under conditions at which the catalyst surface is deprived of hydrogen atoms.Fil: Luggren, Pablo Jorge. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Santa Fe. Instituto de Investigaciones en Catálisis y Petroquímica "Ing. José Miguel Parera". Universidad Nacional del Litoral. Instituto de Investigaciones en Catálisis y Petroquímica "Ing. José Miguel Parera"; ArgentinaFil: Apesteguia, Carlos Rodolfo. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Santa Fe. Instituto de Investigaciones en Catálisis y Petroquímica "Ing. José Miguel Parera". Universidad Nacional del Litoral. Instituto de Investigaciones en Catálisis y Petroquímica "Ing. José Miguel Parera"; 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 "Ing. José Miguel Parera". Universidad Nacional del Litoral. Instituto de Investigaciones en Catálisis y Petroquímica "Ing. José Miguel Parera"; ArgentinaElsevier Science2015-01info:eu-repo/semantics/articleinfo:eu-repo/semantics/publishedVersionhttp://purl.org/coar/resource_type/c_6501info:ar-repo/semantics/articuloapplication/pdfapplication/pdfapplication/pdfapplication/pdfhttp://hdl.handle.net/11336/113457Luggren, Pablo Jorge; Apesteguia, Carlos Rodolfo; Di Cosimo, Juana Isabel; Liquid transportation fuels from biomass-derived oxygenates: Gas-phase 2-hexanol upgrading on Cu-based mixed oxides; Elsevier Science; Applied Catalysis A: General; 504; 1-2015; 256-2650926-860XCONICET DigitalCONICETenginfo:eu-repo/semantics/altIdentifier/doi/10.1016/j.apcata.2015.01.010info:eu-repo/semantics/openAccesshttps://creativecommons.org/licenses/by-nc-sa/2.5/ar/reponame:CONICET Digital (CONICET)instname:Consejo Nacional de Investigaciones Científicas y Técnicas2025-10-29T11:56:44Zoai:ri.conicet.gov.ar:11336/113457instacron: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:34982025-10-29 11:56:44.456CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicasfalse
dc.title.none.fl_str_mv Liquid transportation fuels from biomass-derived oxygenates: Gas-phase 2-hexanol upgrading on Cu-based mixed oxides
title Liquid transportation fuels from biomass-derived oxygenates: Gas-phase 2-hexanol upgrading on Cu-based mixed oxides
spellingShingle Liquid transportation fuels from biomass-derived oxygenates: Gas-phase 2-hexanol upgrading on Cu-based mixed oxides
Luggren, Pablo Jorge
2-HEXANOL
ALDOL CONDENSATION
DEHYDROGENATION
HYDROGENATION
COPPER
MIXED OXIDES
title_short Liquid transportation fuels from biomass-derived oxygenates: Gas-phase 2-hexanol upgrading on Cu-based mixed oxides
title_full Liquid transportation fuels from biomass-derived oxygenates: Gas-phase 2-hexanol upgrading on Cu-based mixed oxides
title_fullStr Liquid transportation fuels from biomass-derived oxygenates: Gas-phase 2-hexanol upgrading on Cu-based mixed oxides
title_full_unstemmed Liquid transportation fuels from biomass-derived oxygenates: Gas-phase 2-hexanol upgrading on Cu-based mixed oxides
title_sort Liquid transportation fuels from biomass-derived oxygenates: Gas-phase 2-hexanol upgrading on Cu-based mixed oxides
dc.creator.none.fl_str_mv Luggren, Pablo Jorge
Apesteguia, Carlos Rodolfo
Di Cosimo, Juana Isabel
author Luggren, Pablo Jorge
author_facet Luggren, Pablo Jorge
Apesteguia, Carlos Rodolfo
Di Cosimo, Juana Isabel
author_role author
author2 Apesteguia, Carlos Rodolfo
Di Cosimo, Juana Isabel
author2_role author
author
dc.subject.none.fl_str_mv 2-HEXANOL
ALDOL CONDENSATION
DEHYDROGENATION
HYDROGENATION
COPPER
MIXED OXIDES
topic 2-HEXANOL
ALDOL CONDENSATION
DEHYDROGENATION
HYDROGENATION
COPPER
MIXED OXIDES
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 gas-phase upgrading of 2-hexanol, a model molecule of the primary conversion of sugars, toward higher molecular weight compounds of application as liquid transportation fuels was investigated on Cu-MI-MII mixed oxides (MI, MII: Mg2+, Al3+, Ce4+) at 573K and 101.3 kPa. Catalysts were prepared by coprecipitation and characterized by several techniques such as BET surface area, XRD, TPD of CO2 and NH3, TPR and N2O decomposition. The bifunctional metal-base catalytic process occurs through a series of sequential steps comprising dehydrogenation, C-C coupling, dehydration and hydrogenation reactions. Nano-sized Cu0 particles promote dehydrogenation and hydrogenation steps whereas acid-base sites provided by MI(MII)-O pairs participate in the C-C coupling reaction. In general, main products were C9-C12 compounds that represented ~60% of the product pool. Branched C9-C24 compounds such as ketones, alcohols and alkanes were obtained with yields of up to 91% on a Cu-Mg-Al mixed oxide with 8wt.% Cu (catalyst 8.0CuMgAl). This catalyst presented well dispersed Cu0 particles and a high number of base sites with moderate basic properties as well as a low number of acid sites. The rate-limiting step of the bifunctional process leading to C9-C24 products on catalyst 8.0CuMgAl was the metal-promoted hydrogenation step, but the reaction can be controlled by the C-C bond formation step on less basic catalysts. By carrying out experiments under different reaction atmospheres (N2 or H2) and at different contact times, a reaction pathway leading to formation of odd carbon atom number products (C9, C15 and C21) is postulated in contrast to the conventional aldol condensation pathway toward even carbon atom number products (C12, C18 and C24). The former prevails under conditions at which the catalyst surface is deprived of hydrogen atoms.
Fil: Luggren, Pablo Jorge. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Santa Fe. Instituto de Investigaciones en Catálisis y Petroquímica "Ing. José Miguel Parera". Universidad Nacional del Litoral. Instituto de Investigaciones en Catálisis y Petroquímica "Ing. José Miguel Parera"; Argentina
Fil: Apesteguia, Carlos Rodolfo. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Santa Fe. Instituto de Investigaciones en Catálisis y Petroquímica "Ing. José Miguel Parera". Universidad Nacional del Litoral. Instituto de Investigaciones en Catálisis y Petroquímica "Ing. José Miguel Parera"; 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 "Ing. José Miguel Parera". Universidad Nacional del Litoral. Instituto de Investigaciones en Catálisis y Petroquímica "Ing. José Miguel Parera"; Argentina
description The gas-phase upgrading of 2-hexanol, a model molecule of the primary conversion of sugars, toward higher molecular weight compounds of application as liquid transportation fuels was investigated on Cu-MI-MII mixed oxides (MI, MII: Mg2+, Al3+, Ce4+) at 573K and 101.3 kPa. Catalysts were prepared by coprecipitation and characterized by several techniques such as BET surface area, XRD, TPD of CO2 and NH3, TPR and N2O decomposition. The bifunctional metal-base catalytic process occurs through a series of sequential steps comprising dehydrogenation, C-C coupling, dehydration and hydrogenation reactions. Nano-sized Cu0 particles promote dehydrogenation and hydrogenation steps whereas acid-base sites provided by MI(MII)-O pairs participate in the C-C coupling reaction. In general, main products were C9-C12 compounds that represented ~60% of the product pool. Branched C9-C24 compounds such as ketones, alcohols and alkanes were obtained with yields of up to 91% on a Cu-Mg-Al mixed oxide with 8wt.% Cu (catalyst 8.0CuMgAl). This catalyst presented well dispersed Cu0 particles and a high number of base sites with moderate basic properties as well as a low number of acid sites. The rate-limiting step of the bifunctional process leading to C9-C24 products on catalyst 8.0CuMgAl was the metal-promoted hydrogenation step, but the reaction can be controlled by the C-C bond formation step on less basic catalysts. By carrying out experiments under different reaction atmospheres (N2 or H2) and at different contact times, a reaction pathway leading to formation of odd carbon atom number products (C9, C15 and C21) is postulated in contrast to the conventional aldol condensation pathway toward even carbon atom number products (C12, C18 and C24). The former prevails under conditions at which the catalyst surface is deprived of hydrogen atoms.
publishDate 2015
dc.date.none.fl_str_mv 2015-01
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/11336/113457
Luggren, Pablo Jorge; Apesteguia, Carlos Rodolfo; Di Cosimo, Juana Isabel; Liquid transportation fuels from biomass-derived oxygenates: Gas-phase 2-hexanol upgrading on Cu-based mixed oxides; Elsevier Science; Applied Catalysis A: General; 504; 1-2015; 256-265
0926-860X
CONICET Digital
CONICET
url http://hdl.handle.net/11336/113457
identifier_str_mv Luggren, Pablo Jorge; Apesteguia, Carlos Rodolfo; Di Cosimo, Juana Isabel; Liquid transportation fuels from biomass-derived oxygenates: Gas-phase 2-hexanol upgrading on Cu-based mixed oxides; Elsevier Science; Applied Catalysis A: General; 504; 1-2015; 256-265
0926-860X
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.apcata.2015.01.010
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
dc.publisher.none.fl_str_mv Elsevier Science
publisher.none.fl_str_mv 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 13.10058

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