Adsorption of furan, hexanoic acid, and alkanes in a hierarchical zeolite at reaction conditions: Insights from molecular simulations
Abstract
Hierarchical zeolites containing both micropores and mesopores are valuable catalysts for facilitating reactions of large molecules. Furan acylation by fatty acids is a promising reaction for valorizing biomass, and the self-pillared pentasil (SPP) zeolite was found to perform particularly well for this reaction. To better understand the distribution of molecules in hierarchical zeolites at the elevated temperature (T = 523 K) and the elevated pressure (p >1 bar) associated with typical reaction conditions, unary and binary adsorption were predicted using Monte Carlo simulations in the isothermal–isobaric Gibbs ensemble. Adsorption of six species (furan, hexanoic acid, -hexane, -decane, -tetradecane, and 3,6-diethyloctane) was investigated from vapor, liquid, and supercritical phases, and loadings into the micropores, onto the mesopore surface, and in the mesopore interior of SPP were obtained. As pressure increases, -alkanes fill the micropores before loading the surface and then the interior of the mesopore, while furan and hexanoic acid adsorb strongly to the mesopore surface due to hydrogen bonding interactions with surface silanols. Hydrogen bonding interactions also draw hexanoic acid molecules in the micropore region toward the pore mouths, so their carboxylic acid group forms H-bonds with silanols, while the alkyl tails interact with the micropore walls. Mesopore condensation ismore »
- Authors:
-
[1];
- Univ. of Minnesota, Minneapolis, MN (United States)
- Univ. of Minnesota, Minneapolis, MN (United States); Johns Hopkins Univ., Baltimore, MD (United States)
- Publication Date:
- Research Org.:
- Univ. of Minnesota, Minneapolis, MN (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES)
- OSTI Identifier:
- 1771017
- Alternate Identifier(s):
- OSTI ID: 1809792
- Grant/Contract Number:
- SC0008688; SC0001004
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Journal of Computational Science
- Additional Journal Information:
- Journal Volume: 48; Journal ID: ISSN 1877-7503
- Publisher:
- Elsevier
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Multi-component adsorption; Gibbs ensemble Monte Carlo; Mesopore condensation
Citation Formats
Josephson, Tyler R., Dauenhauer, Paul J., Tsapatsis, Michael, and Siepmann, J. Ilja. Adsorption of furan, hexanoic acid, and alkanes in a hierarchical zeolite at reaction conditions: Insights from molecular simulations. United States: N. p., 2020.
Web. doi:10.1016/j.jocs.2020.101267.
Josephson, Tyler R., Dauenhauer, Paul J., Tsapatsis, Michael, & Siepmann, J. Ilja. Adsorption of furan, hexanoic acid, and alkanes in a hierarchical zeolite at reaction conditions: Insights from molecular simulations. United States. https://doi.org/10.1016/j.jocs.2020.101267
Josephson, Tyler R., Dauenhauer, Paul J., Tsapatsis, Michael, and Siepmann, J. Ilja. Fri .
"Adsorption of furan, hexanoic acid, and alkanes in a hierarchical zeolite at reaction conditions: Insights from molecular simulations". United States. https://doi.org/10.1016/j.jocs.2020.101267. https://www.osti.gov/servlets/purl/1771017.
@article{osti_1771017,
title = {Adsorption of furan, hexanoic acid, and alkanes in a hierarchical zeolite at reaction conditions: Insights from molecular simulations},
author = {Josephson, Tyler R. and Dauenhauer, Paul J. and Tsapatsis, Michael and Siepmann, J. Ilja},
abstractNote = {Hierarchical zeolites containing both micropores and mesopores are valuable catalysts for facilitating reactions of large molecules. Furan acylation by fatty acids is a promising reaction for valorizing biomass, and the self-pillared pentasil (SPP) zeolite was found to perform particularly well for this reaction. To better understand the distribution of molecules in hierarchical zeolites at the elevated temperature (T = 523 K) and the elevated pressure (p >1 bar) associated with typical reaction conditions, unary and binary adsorption were predicted using Monte Carlo simulations in the isothermal–isobaric Gibbs ensemble. Adsorption of six species (furan, hexanoic acid, -hexane, -decane, -tetradecane, and 3,6-diethyloctane) was investigated from vapor, liquid, and supercritical phases, and loadings into the micropores, onto the mesopore surface, and in the mesopore interior of SPP were obtained. As pressure increases, -alkanes fill the micropores before loading the surface and then the interior of the mesopore, while furan and hexanoic acid adsorb strongly to the mesopore surface due to hydrogen bonding interactions with surface silanols. Hydrogen bonding interactions also draw hexanoic acid molecules in the micropore region toward the pore mouths, so their carboxylic acid group forms H-bonds with silanols, while the alkyl tails interact with the micropore walls. Mesopore condensation is observed for molecules below their critical point, and occurs when the Gibbs free energy of transfer into the mesopore interior and onto the mesopore surface converge. When hexanoic acid adsorption occurs in the presence of alkane solvents, then the selectivity and spatial distribution of hexanoic acid in the micropores and on the surface can be tuned by adjusting the fluid pressure and the alkane length and/or branching.},
doi = {10.1016/j.jocs.2020.101267},
journal = {Journal of Computational Science},
number = ,
volume = 48,
place = {United States},
year = {Fri Nov 27 00:00:00 EST 2020},
month = {Fri Nov 27 00:00:00 EST 2020}
}
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