Hydrogen Recovery by Mixed Matrix Membranes Made from 6FCl-APAF HPA with Different Contents of a Porous Polymer Network and Their Thermal Rearrangement

Mixed matrix membranes (MMMs) consisting of a blend of a hydroxypolyamide (HPA) matrix and variable loads of a porous polymer network (PPN) were thermally treated to induce the transformation of HPA to polybenzoxazole (β-TR-PBO). Here, the HPA matrix was a hydroxypolyamide having two hexafluoropropy...

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Autores: Soto, Cenit, Torres-Cuevas, Edwin S., González-Ortega, Alfonso, Palacio, Laura, Prádanos, Pedro, Freeman, Benny D., Lozano López, Ángel Emilio, Hernández, Antonio
Tipo de recurso: artículo
Estado:Versión publicada
Fecha de publicación:2021
País:España
Institución:Consejo Superior de Investigaciones Científicas (CSIC)
Repositorio:DIGITAL.CSIC. Repositorio Institucional del CSIC
OAI Identifier:oai:digital.csic.es:10261/257355
Acceso en línea:http://hdl.handle.net/10261/257355
Access Level:acceso abierto
Palabra clave:Mixed matrix membranes
Gas separation
Hydrogen separation
Thermal rearrangement
Porous polymer network
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spelling Hydrogen Recovery by Mixed Matrix Membranes Made from 6FCl-APAF HPA with Different Contents of a Porous Polymer Network and Their Thermal RearrangementSoto, CenitTorres-Cuevas, Edwin S.González-Ortega, AlfonsoPalacio, LauraPrádanos, PedroFreeman, Benny D.Lozano López, Ángel EmilioHernández, AntonioMixed matrix membranesGas separationHydrogen separationThermal rearrangementPorous polymer networkMixed matrix membranes (MMMs) consisting of a blend of a hydroxypolyamide (HPA) matrix and variable loads of a porous polymer network (PPN) were thermally treated to induce the transformation of HPA to polybenzoxazole (β-TR-PBO). Here, the HPA matrix was a hydroxypolyamide having two hexafluoropropyilidene moieties, 6FCl-APAF, while the PPN was prepared by reacting triptycene (TRP) and trifluoroacetophenone (TFAP) in a superacid solution. The most probable size of the PPN particles was 75 nm with quite large distributions. The resulting membranes were analyzed by SEM and AFM. Up to 30% PPN loads, both SEM and AFM images confirmed quite planar surfaces, at low scale, with limited roughness. Membranes with high hydrogen permeability and good selectivity for the gas pairs H2/CH4 and H2/N2 were obtained. For H2/CO2, selectivity almost vanished after thermal rearrangement. In all cases, their hydrogen permeability increased with increasing loads of PPN until around 30% PPN with ulterior fairly abrupt decreasing of permeability for all gases studied. Thermal rearrangement of the MMMs resulted in higher permeabilities but lower selectivities. For all the membranes and gas pairs studied, the balance of permeability vs. selectivity surpassed the 1991 Robeson’s upper bound, and approached or even exceeded the 2008 line, for MMMs having 30% PPN loads. In all cases, the HPA-MMMs before thermal rearrangement provided good selectivity versus permeability compromise, similar to their thermally rearranged counterparts but in the zone of high selectivity. For H2/CH4, H2/N2, these nonthermally rearranged MMMs approach the 2008 Robeson’s upper bound while H2/CO2 gives selective transport favoring H2 on the 1991 Robeson’s bound. Thus, attending to the energy cost of thermal rearrangement, it could be avoided in some cases especially when high selectivity is the target rather than high permeability.This work was supported by the Spanish Government (AEI) through projects PID2019-109403RBC21/AEI/10.13039/501100011033, PID2019-109403RBC22/AEI/10.13039/501100011033 and EQC2019-006481-P, and by the Regional Government of Castilla y León and the EU-FEDER program (CLU2017-09, UIC082, VA088G19 and PhD grant of C.S.). C.S. thanks University of Valladolid for a mobility grant UVa-2019.Peer reviewedMultidisciplinary Digital Publishing InstituteMinisterio de Ciencia, Innovación y Universidades (España)Agencia Estatal de Investigación (España)Junta de Castilla y LeónEuropean CommissionUniversidad de ValladolidConsejo Superior de Investigaciones Científicas [https://ror.org/02gfc7t72]2022202220212022info:eu-repo/semantics/articlehttp://purl.org/coar/resource_type/c_6501Publisher's versioninfo:eu-repo/semantics/publishedVersionapplication/pdfhttp://hdl.handle.net/10261/257355reponame:DIGITAL.CSIC. Repositorio Institucional del CSICinstname:Consejo Superior de Investigaciones Científicas (CSIC)Inglés#PLACEHOLDER_PARENT_METADATA_VALUE##PLACEHOLDER_PARENT_METADATA_VALUE##PLACEHOLDER_PARENT_METADATA_VALUE#info:eu-repo/grantAgreement/AEI/Plan Estatal de Investigación Científica y Técnica y de Innovación 2017-2020/PID2019-109403RB-C21info:eu-repo/grantAgreement/AEI/Plan Estatal de Investigación Científica y Técnica y de Innovación 2017-2020/PID2019-109403RB-C22info:eu-repo/grantAgreement/AIE//EQC2019-006481-Phttps://doi.org/10.3390/polym13244343Síinfo:eu-repo/semantics/openAccessoai:digital.csic.es:10261/2573552026-05-22T06:33:51Z
dc.title.none.fl_str_mv Hydrogen Recovery by Mixed Matrix Membranes Made from 6FCl-APAF HPA with Different Contents of a Porous Polymer Network and Their Thermal Rearrangement
title Hydrogen Recovery by Mixed Matrix Membranes Made from 6FCl-APAF HPA with Different Contents of a Porous Polymer Network and Their Thermal Rearrangement
spellingShingle Hydrogen Recovery by Mixed Matrix Membranes Made from 6FCl-APAF HPA with Different Contents of a Porous Polymer Network and Their Thermal Rearrangement
Soto, Cenit
Mixed matrix membranes
Gas separation
Hydrogen separation
Thermal rearrangement
Porous polymer network
title_short Hydrogen Recovery by Mixed Matrix Membranes Made from 6FCl-APAF HPA with Different Contents of a Porous Polymer Network and Their Thermal Rearrangement
title_full Hydrogen Recovery by Mixed Matrix Membranes Made from 6FCl-APAF HPA with Different Contents of a Porous Polymer Network and Their Thermal Rearrangement
title_fullStr Hydrogen Recovery by Mixed Matrix Membranes Made from 6FCl-APAF HPA with Different Contents of a Porous Polymer Network and Their Thermal Rearrangement
title_full_unstemmed Hydrogen Recovery by Mixed Matrix Membranes Made from 6FCl-APAF HPA with Different Contents of a Porous Polymer Network and Their Thermal Rearrangement
title_sort Hydrogen Recovery by Mixed Matrix Membranes Made from 6FCl-APAF HPA with Different Contents of a Porous Polymer Network and Their Thermal Rearrangement
dc.creator.none.fl_str_mv Soto, Cenit
Torres-Cuevas, Edwin S.
González-Ortega, Alfonso
Palacio, Laura
Prádanos, Pedro
Freeman, Benny D.
Lozano López, Ángel Emilio
Hernández, Antonio
author Soto, Cenit
author_facet Soto, Cenit
Torres-Cuevas, Edwin S.
González-Ortega, Alfonso
Palacio, Laura
Prádanos, Pedro
Freeman, Benny D.
Lozano López, Ángel Emilio
Hernández, Antonio
author_role author
author2 Torres-Cuevas, Edwin S.
González-Ortega, Alfonso
Palacio, Laura
Prádanos, Pedro
Freeman, Benny D.
Lozano López, Ángel Emilio
Hernández, Antonio
author2_role author
author
author
author
author
author
author
dc.contributor.none.fl_str_mv Ministerio de Ciencia, Innovación y Universidades (España)
Agencia Estatal de Investigación (España)
Junta de Castilla y León
European Commission
Universidad de Valladolid
Consejo Superior de Investigaciones Científicas [https://ror.org/02gfc7t72]
dc.subject.none.fl_str_mv Mixed matrix membranes
Gas separation
Hydrogen separation
Thermal rearrangement
Porous polymer network
topic Mixed matrix membranes
Gas separation
Hydrogen separation
Thermal rearrangement
Porous polymer network
description Mixed matrix membranes (MMMs) consisting of a blend of a hydroxypolyamide (HPA) matrix and variable loads of a porous polymer network (PPN) were thermally treated to induce the transformation of HPA to polybenzoxazole (β-TR-PBO). Here, the HPA matrix was a hydroxypolyamide having two hexafluoropropyilidene moieties, 6FCl-APAF, while the PPN was prepared by reacting triptycene (TRP) and trifluoroacetophenone (TFAP) in a superacid solution. The most probable size of the PPN particles was 75 nm with quite large distributions. The resulting membranes were analyzed by SEM and AFM. Up to 30% PPN loads, both SEM and AFM images confirmed quite planar surfaces, at low scale, with limited roughness. Membranes with high hydrogen permeability and good selectivity for the gas pairs H2/CH4 and H2/N2 were obtained. For H2/CO2, selectivity almost vanished after thermal rearrangement. In all cases, their hydrogen permeability increased with increasing loads of PPN until around 30% PPN with ulterior fairly abrupt decreasing of permeability for all gases studied. Thermal rearrangement of the MMMs resulted in higher permeabilities but lower selectivities. For all the membranes and gas pairs studied, the balance of permeability vs. selectivity surpassed the 1991 Robeson’s upper bound, and approached or even exceeded the 2008 line, for MMMs having 30% PPN loads. In all cases, the HPA-MMMs before thermal rearrangement provided good selectivity versus permeability compromise, similar to their thermally rearranged counterparts but in the zone of high selectivity. For H2/CH4, H2/N2, these nonthermally rearranged MMMs approach the 2008 Robeson’s upper bound while H2/CO2 gives selective transport favoring H2 on the 1991 Robeson’s bound. Thus, attending to the energy cost of thermal rearrangement, it could be avoided in some cases especially when high selectivity is the target rather than high permeability.
publishDate 2021
dc.date.none.fl_str_mv 2021
2022
2022
2022
dc.type.none.fl_str_mv info:eu-repo/semantics/article
http://purl.org/coar/resource_type/c_6501
Publisher's version
info:eu-repo/semantics/publishedVersion
format article
status_str publishedVersion
dc.identifier.none.fl_str_mv http://hdl.handle.net/10261/257355
url http://hdl.handle.net/10261/257355
dc.language.none.fl_str_mv Inglés
language_invalid_str_mv Inglés
dc.relation.none.fl_str_mv #PLACEHOLDER_PARENT_METADATA_VALUE#
#PLACEHOLDER_PARENT_METADATA_VALUE#
#PLACEHOLDER_PARENT_METADATA_VALUE#
info:eu-repo/grantAgreement/AEI/Plan Estatal de Investigación Científica y Técnica y de Innovación 2017-2020/PID2019-109403RB-C21
info:eu-repo/grantAgreement/AEI/Plan Estatal de Investigación Científica y Técnica y de Innovación 2017-2020/PID2019-109403RB-C22
info:eu-repo/grantAgreement/AIE//EQC2019-006481-P
https://doi.org/10.3390/polym13244343
Sí
dc.rights.none.fl_str_mv info:eu-repo/semantics/openAccess
eu_rights_str_mv openAccess
dc.format.none.fl_str_mv application/pdf
dc.publisher.none.fl_str_mv Multidisciplinary Digital Publishing Institute
publisher.none.fl_str_mv Multidisciplinary Digital Publishing Institute
dc.source.none.fl_str_mv reponame:DIGITAL.CSIC. Repositorio Institucional del CSIC
instname:Consejo Superior de Investigaciones Científicas (CSIC)
instname_str Consejo Superior de Investigaciones Científicas (CSIC)
reponame_str DIGITAL.CSIC. Repositorio Institucional del CSIC
collection DIGITAL.CSIC. Repositorio Institucional del CSIC
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