Adsorption of furan, hexanoic acid, and alkanes in a hierarchical zeolite at reaction conditions: Insights from molecular simulations

Josephson, Tyler R.; Dauenhauer, Paul J.; Tsapatsis, Michael; Siepmann, J. Ilja

doi:10.1016/j.jocs.2020.101267

Adsorption of furan, hexanoic acid, and alkanes in a hierarchical zeolite at reaction conditions: Insights from molecular simulations

Journal Article · Fri Nov 27 04:00:00 EST 2020 · Journal of Computational Science

DOI:https://doi.org/10.1016/j.jocs.2020.101267· OSTI ID:1771017

^[1]; Dauenhauer, Paul J. ^[2]; Tsapatsis, Michael ^[3]; Siepmann, J. Ilja ^[2]

Univ. of Minnesota, Minneapolis, MN (United States); University of Minnesota
Univ. of Minnesota, Minneapolis, MN (United States)
Univ. of Minnesota, Minneapolis, MN (United States); Johns Hopkins Univ., Baltimore, MD (United States)

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.

View Accepted Manuscript (DOE)

Research Organization:: Univ. of Minnesota, Minneapolis, MN (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: SC0008688

OSTI ID:: 1771017

Alternate ID(s):: OSTI ID: 1809792

Journal Information:: Journal of Computational Science, Journal Name: Journal of Computational Science Vol. 48; ISSN 1877-7503

Publisher:: ElsevierCopyright Statement

Country of Publication:: United States

Language:: English

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