The impact of zeolite pore structure on the catalytic behavior of CuZnAl/zeolite hybrid catalysts for the direct DME synthesis

[EN] In this work, the influence of the pore structure of 10-ring zeolites used as the methanol dehydration func-tion in CuZnAl(CZA)/zeolite hybrid catalysts was studied for the direct dimethyl ether (DME) synthesis. Tothis purpose, six different 10-ring H-zeolites (ZSM-5, FER, IM-5, TNU-9, MCM-22,...

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Authors: García Trenco, Andrés, Valencia Valencia, Susana|||0000-0001-7160-2795, MARTINEZ FELIU, AGUSTIN|||0000-0002-9974-1567
Format: article
Publication Date:2013
Country:España
Institution:Universitat Politècnica de València (UPV)
Repository:RiuNet. Repositorio Institucional de la Universitat Politécnica de Valéncia
Language:English
OAI Identifier:oai:riunet.upv.es:10251/94085
Online Access:https://riunet.upv.es/handle/10251/94085
Access Level:Open access
Keyword:Methanol dehydration
Synthesis gas
Direct DME synthesis
CuZnAl methanol synthesis catalyst
10-ring zeolite
Pore structure
Hybrid catalysts
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network_acronym_str ES
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spelling The impact of zeolite pore structure on the catalytic behavior of CuZnAl/zeolite hybrid catalysts for the direct DME synthesisGarcía Trenco, AndrésValencia Valencia, Susana|||0000-0001-7160-2795MARTINEZ FELIU, AGUSTIN|||0000-0002-9974-1567Methanol dehydrationSynthesis gasDirect DME synthesisCuZnAl methanol synthesis catalyst10-ring zeolitePore structureHybrid catalysts[EN] In this work, the influence of the pore structure of 10-ring zeolites used as the methanol dehydration func-tion in CuZnAl(CZA)/zeolite hybrid catalysts was studied for the direct dimethyl ether (DME) synthesis. Tothis purpose, six different 10-ring H-zeolites (ZSM-5, FER, IM-5, TNU-9, MCM-22, ITQ-2) with alike bulkSi/Al ratios (in the 9 14 range) were employed. Additionally, the effect of crystallite size (for ZSM-5) andselective surface dealumination by treatment with oxalic acid (for MCM-22) was also investigated. Whilethe initial activity of the zeolites for methanol dehydration was driven by the concentration of strongBrønsted acid sites, the extent of decay was dictated by the pore structure, which determined the amountand nature of the formed carbon species. When evaluated for direct DME synthesis under methanolsynthesis-controlled conditions, all CZA/zeolite hybrid catalysts (prepared by grinding, CZA:zeolite massratio of 2:1) experienced a decline of CO conversion (and DME yield) with time-on-stream (TOS) due toa gradual loss of the methanol synthesis activity of the Cu-based component. Interestingly, the stabilitywith TOS was the lowest for the hybrid catalysts comprising zeolites with large external surface areas(Sext) such as ITQ-2 and MCM-22. Moreover, for zeolites with similar Sext, the deactivation extent of thehybrid catalysts increased with the concentration of surface Al species (from XPS) in the zeolite. Thus,the delaminated ITQ-2 zeolite (Si/Alsurf= 10.6, Sext= 324 m2/g) produced the less stable hybrid while thatcomprising zeolite TNU-9 (Si/Alsurf= 17.9, Sext= 12 m2/g) displayed the highest stability during the syngas-to-DME experiments. These results suggest that the deterioration of the methanol synthesis activity ofthe CZA catalyst in the hybrid catalysts prepared by grinding is produced by detrimental interactionsbetween zeolitic Al species and Cu sites at the surface-contact between zeolite and CZA particleFinancial support by the Comision Interministerial de Ciencia y Tecnologia (CICYT) of Spain through the Project CTQ2010-17988/PPQ is gratefully acknowledged. A. Garcia-Trenco thanks the Ministerio de Economia y Competitividad (former Ministerio de Ciencia e Innovacion) of Spain for a predoctoral (FPI) scholarship.ElsevierInstituto Universitario Mixto de Tecnología QuímicaComisión Interministerial de Ciencia y TecnologíaMinisterio de Economía y CompetitividadRepositorio Institucional de la Universitat Politècnica de València Riunet20132013-01-01journal articlehttp://purl.org/coar/resource_type/c_6501VoRhttp://purl.org/coar/version/c_970fb48d4fbd8a85info:eu-repo/semantics/articleapplication/pdfapplication/pdfhttps://riunet.upv.es/handle/10251/94085reponame:RiuNet. Repositorio Institucional de la Universitat Politécnica de Valénciainstname:Universitat Politècnica de València (UPV)InglésengMinisterio de Ciencia e Innovación http://dx.doi.org/10.13039/501100004837 CTQ2010-17988 CATALIZADORES AVANZADOS PARA LA CONVERSION DE GAS DE SINTESIS EN COMBUSTIBLESopen accesshttp://purl.org/coar/access_right/c_abf2Reserva de todos los derechoshttp://rightsstatements.org/vocab/InC/1.0/info:eu-repo/semantics/openAccessoai:riunet.upv.es:10251/940852026-06-13T07:49:27Z
dc.title.none.fl_str_mv The impact of zeolite pore structure on the catalytic behavior of CuZnAl/zeolite hybrid catalysts for the direct DME synthesis
title The impact of zeolite pore structure on the catalytic behavior of CuZnAl/zeolite hybrid catalysts for the direct DME synthesis
spellingShingle The impact of zeolite pore structure on the catalytic behavior of CuZnAl/zeolite hybrid catalysts for the direct DME synthesis
García Trenco, Andrés
Methanol dehydration
Synthesis gas
Direct DME synthesis
CuZnAl methanol synthesis catalyst
10-ring zeolite
Pore structure
Hybrid catalysts
title_short The impact of zeolite pore structure on the catalytic behavior of CuZnAl/zeolite hybrid catalysts for the direct DME synthesis
title_full The impact of zeolite pore structure on the catalytic behavior of CuZnAl/zeolite hybrid catalysts for the direct DME synthesis
title_fullStr The impact of zeolite pore structure on the catalytic behavior of CuZnAl/zeolite hybrid catalysts for the direct DME synthesis
title_full_unstemmed The impact of zeolite pore structure on the catalytic behavior of CuZnAl/zeolite hybrid catalysts for the direct DME synthesis
title_sort The impact of zeolite pore structure on the catalytic behavior of CuZnAl/zeolite hybrid catalysts for the direct DME synthesis
dc.creator.none.fl_str_mv García Trenco, Andrés
Valencia Valencia, Susana|||0000-0001-7160-2795
MARTINEZ FELIU, AGUSTIN|||0000-0002-9974-1567
author García Trenco, Andrés
author_facet García Trenco, Andrés
Valencia Valencia, Susana|||0000-0001-7160-2795
MARTINEZ FELIU, AGUSTIN|||0000-0002-9974-1567
author_role author
author2 Valencia Valencia, Susana|||0000-0001-7160-2795
MARTINEZ FELIU, AGUSTIN|||0000-0002-9974-1567
author2_role author
author
dc.contributor.none.fl_str_mv Instituto Universitario Mixto de Tecnología Química
Comisión Interministerial de Ciencia y Tecnología
Ministerio de Economía y Competitividad
Repositorio Institucional de la Universitat Politècnica de València Riunet
dc.subject.none.fl_str_mv Methanol dehydration
Synthesis gas
Direct DME synthesis
CuZnAl methanol synthesis catalyst
10-ring zeolite
Pore structure
Hybrid catalysts
topic Methanol dehydration
Synthesis gas
Direct DME synthesis
CuZnAl methanol synthesis catalyst
10-ring zeolite
Pore structure
Hybrid catalysts
description [EN] In this work, the influence of the pore structure of 10-ring zeolites used as the methanol dehydration func-tion in CuZnAl(CZA)/zeolite hybrid catalysts was studied for the direct dimethyl ether (DME) synthesis. Tothis purpose, six different 10-ring H-zeolites (ZSM-5, FER, IM-5, TNU-9, MCM-22, ITQ-2) with alike bulkSi/Al ratios (in the 9 14 range) were employed. Additionally, the effect of crystallite size (for ZSM-5) andselective surface dealumination by treatment with oxalic acid (for MCM-22) was also investigated. Whilethe initial activity of the zeolites for methanol dehydration was driven by the concentration of strongBrønsted acid sites, the extent of decay was dictated by the pore structure, which determined the amountand nature of the formed carbon species. When evaluated for direct DME synthesis under methanolsynthesis-controlled conditions, all CZA/zeolite hybrid catalysts (prepared by grinding, CZA:zeolite massratio of 2:1) experienced a decline of CO conversion (and DME yield) with time-on-stream (TOS) due toa gradual loss of the methanol synthesis activity of the Cu-based component. Interestingly, the stabilitywith TOS was the lowest for the hybrid catalysts comprising zeolites with large external surface areas(Sext) such as ITQ-2 and MCM-22. Moreover, for zeolites with similar Sext, the deactivation extent of thehybrid catalysts increased with the concentration of surface Al species (from XPS) in the zeolite. Thus,the delaminated ITQ-2 zeolite (Si/Alsurf= 10.6, Sext= 324 m2/g) produced the less stable hybrid while thatcomprising zeolite TNU-9 (Si/Alsurf= 17.9, Sext= 12 m2/g) displayed the highest stability during the syngas-to-DME experiments. These results suggest that the deterioration of the methanol synthesis activity ofthe CZA catalyst in the hybrid catalysts prepared by grinding is produced by detrimental interactionsbetween zeolitic Al species and Cu sites at the surface-contact between zeolite and CZA particle
publishDate 2013
dc.date.none.fl_str_mv 2013
2013-01-01
dc.type.none.fl_str_mv journal article
http://purl.org/coar/resource_type/c_6501
VoR
http://purl.org/coar/version/c_970fb48d4fbd8a85
dc.type.openaire.fl_str_mv info:eu-repo/semantics/article
format article
dc.identifier.none.fl_str_mv https://riunet.upv.es/handle/10251/94085
url https://riunet.upv.es/handle/10251/94085
dc.language.none.fl_str_mv Inglés
eng
language_invalid_str_mv Inglés
language eng
dc.relation.none.fl_str_mv Ministerio de Ciencia e Innovación http://dx.doi.org/10.13039/501100004837 CTQ2010-17988 CATALIZADORES AVANZADOS PARA LA CONVERSION DE GAS DE SINTESIS EN COMBUSTIBLES
dc.rights.none.fl_str_mv open access
http://purl.org/coar/access_right/c_abf2
Reserva de todos los derechos
http://rightsstatements.org/vocab/InC/1.0/
dc.rights.openaire.fl_str_mv info:eu-repo/semantics/openAccess
rights_invalid_str_mv open access
http://purl.org/coar/access_right/c_abf2
Reserva de todos los derechos
http://rightsstatements.org/vocab/InC/1.0/
eu_rights_str_mv openAccess
dc.format.none.fl_str_mv application/pdf
application/pdf
dc.publisher.none.fl_str_mv Elsevier
publisher.none.fl_str_mv Elsevier
dc.source.none.fl_str_mv reponame:RiuNet. Repositorio Institucional de la Universitat Politécnica de Valéncia
instname:Universitat Politècnica de València (UPV)
instname_str Universitat Politècnica de València (UPV)
reponame_str RiuNet. Repositorio Institucional de la Universitat Politécnica de Valéncia
collection RiuNet. Repositorio Institucional de la Universitat Politécnica de Valéncia
repository.name.fl_str_mv
repository.mail.fl_str_mv
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score 15,301603

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