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Ca Cations Impact the Local Environment inside HZSM-5 Pores during the Methanol-to-Hydrocarbons Reaction
[Image: see text] The methanol-to-hydrocarbons (MTH) process is an industrially relevant method to produce valuable light olefins such as propylene. One of the ways to enhance propylene selectivity is to modify zeolite catalysts with alkaline earth cations. The underlying mechanistic aspects of this...
Autores principales: | , , , , , , , |
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Formato: | Online Artículo Texto |
Lenguaje: | English |
Publicado: |
American Chemical Society
2023
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Acceso en línea: | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC10028611/ https://www.ncbi.nlm.nih.gov/pubmed/36970466 http://dx.doi.org/10.1021/acscatal.3c00059 |
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author | Liutkova, Anna Zhang, Hao Simons, Jérôme F. M. Mezari, Brahim Mirolo, Marta Garcia, Gustavo A. Hensen, Emiel J. M. Kosinov, Nikolay |
author_facet | Liutkova, Anna Zhang, Hao Simons, Jérôme F. M. Mezari, Brahim Mirolo, Marta Garcia, Gustavo A. Hensen, Emiel J. M. Kosinov, Nikolay |
author_sort | Liutkova, Anna |
collection | PubMed |
description | [Image: see text] The methanol-to-hydrocarbons (MTH) process is an industrially relevant method to produce valuable light olefins such as propylene. One of the ways to enhance propylene selectivity is to modify zeolite catalysts with alkaline earth cations. The underlying mechanistic aspects of this type of promotion are not well understood. Here, we study the interaction of Ca(2+) with reaction intermediates and products formed during the MTH reaction. Using transient kinetic and spectroscopic tools, we find strong indications that the selectivity differences between Ca/ZSM-5 and HZSM-5 are related to the different local environment inside the pores due to the presence of Ca(2+). In particular, Ca/ZSM-5 strongly retains water, hydrocarbons, and oxygenates, which occupy as much as 10% of the micropores during the ongoing MTH reaction. This change in the effective pore geometry affects the formation of hydrocarbon pool components and in this way directs the MTH reaction toward the olefin cycle. |
format | Online Article Text |
id | pubmed-10028611 |
institution | National Center for Biotechnology Information |
language | English |
publishDate | 2023 |
publisher | American Chemical Society |
record_format | MEDLINE/PubMed |
spelling | pubmed-100286112023-03-22 Ca Cations Impact the Local Environment inside HZSM-5 Pores during the Methanol-to-Hydrocarbons Reaction Liutkova, Anna Zhang, Hao Simons, Jérôme F. M. Mezari, Brahim Mirolo, Marta Garcia, Gustavo A. Hensen, Emiel J. M. Kosinov, Nikolay ACS Catal [Image: see text] The methanol-to-hydrocarbons (MTH) process is an industrially relevant method to produce valuable light olefins such as propylene. One of the ways to enhance propylene selectivity is to modify zeolite catalysts with alkaline earth cations. The underlying mechanistic aspects of this type of promotion are not well understood. Here, we study the interaction of Ca(2+) with reaction intermediates and products formed during the MTH reaction. Using transient kinetic and spectroscopic tools, we find strong indications that the selectivity differences between Ca/ZSM-5 and HZSM-5 are related to the different local environment inside the pores due to the presence of Ca(2+). In particular, Ca/ZSM-5 strongly retains water, hydrocarbons, and oxygenates, which occupy as much as 10% of the micropores during the ongoing MTH reaction. This change in the effective pore geometry affects the formation of hydrocarbon pool components and in this way directs the MTH reaction toward the olefin cycle. American Chemical Society 2023-02-23 /pmc/articles/PMC10028611/ /pubmed/36970466 http://dx.doi.org/10.1021/acscatal.3c00059 Text en © 2023 The Authors. Published by American Chemical Society https://creativecommons.org/licenses/by/4.0/Permits the broadest form of re-use including for commercial purposes, provided that author attribution and integrity are maintained (https://creativecommons.org/licenses/by/4.0/). |
spellingShingle | Liutkova, Anna Zhang, Hao Simons, Jérôme F. M. Mezari, Brahim Mirolo, Marta Garcia, Gustavo A. Hensen, Emiel J. M. Kosinov, Nikolay Ca Cations Impact the Local Environment inside HZSM-5 Pores during the Methanol-to-Hydrocarbons Reaction |
title | Ca Cations Impact
the Local Environment inside HZSM-5
Pores during the Methanol-to-Hydrocarbons Reaction |
title_full | Ca Cations Impact
the Local Environment inside HZSM-5
Pores during the Methanol-to-Hydrocarbons Reaction |
title_fullStr | Ca Cations Impact
the Local Environment inside HZSM-5
Pores during the Methanol-to-Hydrocarbons Reaction |
title_full_unstemmed | Ca Cations Impact
the Local Environment inside HZSM-5
Pores during the Methanol-to-Hydrocarbons Reaction |
title_short | Ca Cations Impact
the Local Environment inside HZSM-5
Pores during the Methanol-to-Hydrocarbons Reaction |
title_sort | ca cations impact
the local environment inside hzsm-5
pores during the methanol-to-hydrocarbons reaction |
url | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC10028611/ https://www.ncbi.nlm.nih.gov/pubmed/36970466 http://dx.doi.org/10.1021/acscatal.3c00059 |
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