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Control of the Reaction Mechanism of Alkylaromatics Transalkylation by Means of Molecular Confinement Effects Associated to Zeolite Channel Architecture

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Control of the Reaction Mechanism of Alkylaromatics Transalkylation by Means of Molecular Confinement Effects Associated to Zeolite Channel Architecture

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dc.contributor.author Margarit Benavent, Vicente Juan es_ES
dc.contributor.author OSMAN, MOGAHID es_ES
dc.contributor.author Al-Khattaf, Sulaiman es_ES
dc.contributor.author Martínez, Cristina es_ES
dc.contributor.author Boronat Zaragoza, Mercedes es_ES
dc.contributor.author Corma Canós, Avelino es_ES
dc.date.accessioned 2020-09-24T12:30:36Z
dc.date.available 2020-09-24T12:30:36Z
dc.date.issued 2019-07-05 es_ES
dc.identifier.issn 2155-5435 es_ES
dc.identifier.uri http://hdl.handle.net/10251/150681
dc.description "This document is the Accepted Manuscript version of a Published Work that appeared in final form in ACS Catalysis, copyright © American Chemical Society after peer review and technical editing by the publisher. To access the final edited and published work see https://doi.org/10.1021/acscatal.9b00763" es_ES
dc.description.abstract [EN] Transalkylation of alkylaromatics catalyzed by acid zeolites is a process widely employed in the petrochemical industry for upgrading aromatic fractions. The reaction mechanism is complex as it can proceed either by intermolecular alkyl-transfer involving dealkylation-alkylation steps with surface alkoxy species as reaction intermediates or through the formation of bulkier diaryl intermediates. We have investigated how the possible formation of such bulky intermediates in the microporous channel system of different zeolite structures, together with their stabilization by confinement effects, can determine the preferential mechanism and, therefore, the selectivity of ethylbenzene disproportionation into benzene and diethylbenzene. For testing the concept, four zeolites, MCM-22 (3D MWW) with 1OR pores, 12R cavities and external 12R hemicavities or "cups", DS-ITQ2, (2D MWW) with the same 1OR channels as MCM-22, no 12R cavities and much larger proportion of external "cups", a 10R ZSM-5 (MFI) and a 12R mordenite (MOR) have been used. The higher activity of DS-ITQ2 and MCM-22 as compared to ZSM-5 at low temperature (573 K) and the high selectivity to diethylbenzene of the bidimensional material under all reaction conditions considered have been explained by means of DFT calculations. Contrary to what could be expected according to the available space at the external "cups" and at the lOR channels of the MWW structure, the bulkier diaryl intermediates are better stabilized within the lOR channel system than at the "cups" open at the external surface of the MWW materials. We show from this perspective how the channel structure and molecular confinement stabilization also explain the operating reaction mechanism in ZSM-5 and mordenite. es_ES
dc.description.sponsorship This work was supported by the Spanish Government through "Severo Ochoa Program" (SEV 2012-0267; SEV-2016-0683), RTI2018-101033-B-I00 and MAT2017-82288-C2-1-P, by the Fundacion Ramon Areces through a research contract of the "Life and Materials Science" program, and by the European Union through ERC-AdG-2014-671093 (SynCatMatch). Red Espanola de Supercomputacion (RES) and Centre de Calcul de la Universitat de Valencia are gratefully acknowledged for computational resources and technical support. We thank the Electron Microscopy Service of the UPV for their help in sample characterization. es_ES
dc.language Inglés es_ES
dc.publisher American Chemical Society es_ES
dc.relation.ispartof ACS Catalysis es_ES
dc.rights Reserva de todos los derechos es_ES
dc.subject Zeolites es_ES
dc.subject MWW structure es_ES
dc.subject Molecular confinement es_ES
dc.subject Ethylbenzene transalkylation es_ES
dc.subject DFT es_ES
dc.subject Transalkylation mechanism es_ES
dc.subject.classification QUIMICA ORGANICA es_ES
dc.title Control of the Reaction Mechanism of Alkylaromatics Transalkylation by Means of Molecular Confinement Effects Associated to Zeolite Channel Architecture es_ES
dc.type Artículo es_ES
dc.identifier.doi 10.1021/acscatal.9b00763 es_ES
dc.relation.projectID info:eu-repo/grantAgreement/EC/H2020/671093/EU/MATching zeolite SYNthesis with CATalytic activity/ es_ES
dc.relation.projectID info:eu-repo/grantAgreement/MINECO//SEV-2012-0267/ es_ES
dc.relation.projectID info:eu-repo/grantAgreement/MINECO//CTQ2015-70126-R/ES/DISEÑO DE CATALIZADORES ZEOLITICOS PARA LA OPTIMIZACION DE PROCESOS QUIMICOS DE INTERES INDUSTRIAL/ es_ES
dc.relation.projectID info:eu-repo/grantAgreement/AEI/Plan Estatal de Investigación Científica y Técnica y de Innovación 2013-2016/MAT2017-82288-C2-1-P/ES/MATERIALES HIBRIDOS MULTIFUNCIONALES BASADOS EN NANO-UNIDADES ESTRUCTURALES ACTIVAS/ es_ES
dc.relation.projectID info:eu-repo/grantAgreement/AEI/Plan Estatal de Investigación Científica y Técnica y de Innovación 2017-2020/RTI2018-101033-B-I00/ES/DISEÑO DE CATALIZADORES MULTIFUNCIONALES PARA LA CONVERSION EFICIENTE DE BIOGAS Y GAS NATURAL A HIDROCARBUROS DE INTERES INDUSTRIAL/ es_ES
dc.relation.projectID info:eu-repo/grantAgreement/MINECO//SEV-2016-0683/ es_ES
dc.rights.accessRights Abierto es_ES
dc.contributor.affiliation Universitat Politècnica de València. Departamento de Química - Departament de Química es_ES
dc.contributor.affiliation Universitat Politècnica de València. Instituto Universitario Mixto de Tecnología Química - Institut Universitari Mixt de Tecnologia Química es_ES
dc.description.bibliographicCitation Margarit Benavent, VJ.; Osman, M.; Al-Khattaf, S.; Martínez, C.; Boronat Zaragoza, M.; Corma Canós, A. (2019). Control of the Reaction Mechanism of Alkylaromatics Transalkylation by Means of Molecular Confinement Effects Associated to Zeolite Channel Architecture. ACS Catalysis. 9(7):5935-5946. https://doi.org/10.1021/acscatal.9b00763 es_ES
dc.description.accrualMethod S es_ES
dc.relation.publisherversion https://doi.org/10.1021/acscatal.9b00763 es_ES
dc.description.upvformatpinicio 5935 es_ES
dc.description.upvformatpfin 5946 es_ES
dc.type.version info:eu-repo/semantics/publishedVersion es_ES
dc.description.volume 9 es_ES
dc.description.issue 7 es_ES
dc.relation.pasarela S\409685 es_ES
dc.contributor.funder Fundación Ramón Areces es_ES
dc.contributor.funder Ministerio de Economía y Competitividad es_ES
dc.contributor.funder Agencia Estatal de Investigación es_ES


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