Atomistic Investigations of the Effects of Si/Al Ratio and Al Distribution on the Adsorption Selectivity of n -Alkanes in Brønsted-Acid Zeolites

Yang, Chi-Ta; Janda, Amber; Bell, Alexis T.; Lin, Li-Chiang

doi:10.1021/acs.jpcc.7b11190

Atomistic Investigations of the Effects of Si/Al Ratio and Al Distribution on the Adsorption Selectivity of n -Alkanes in Brønsted-Acid Zeolites

Journal Article · Wed Jan 03 00:00:00 EST 2018 · Journal of Physical Chemistry. C

DOI:https://doi.org/10.1021/acs.jpcc.7b11190· OSTI ID:1571101

Yang, Chi-Ta ^[1]; ^[2]; ^[3]; ^[1]

The Ohio State Univ., Columbus, OH (United States). William G. Lowrie Dept. of Chemical and Biomolecular Engineering
Univ. of California, Berkeley, CA (United States). Dept. of Chemical and Biomolecular Engineering; Stanford Univ., CA (United States). Dept. of Chemical Engineering
Univ. of California, Berkeley, CA (United States). Dept. of Chemical and Biomolecular Engineering

The adsorption of n-alkanes onto Brønsted-acid sites is a key step in the catalytic cracking of alkanes. Employing configurational-bias Monte Carlo simulations, we have investigated how the ratio of equilibrium adsorption constants for central C-C bonds relative to terminal bonds of n-alkanes (i.e., the adsorption selectivity ratio) in Brønsted-acid zeolites is influenced by the Si/Al ratio and the Al distribution. A new computational approach was implemented, and the developed force field was validated by a comprehensive comparison between simulation results and experimental data for a number of Brønsted-acid zeolites. While the adsorption selectivity seems to be relatively insensitive to the Si/Al ratio, our results reveal that the Al distribution plays a crucial role in determining the adsorption selectivity. Changes in the Al distribution result in a change of as much as 2-fold in the adsorption selectivity ratio for n-hexane. The selectivity generally shows larger variations with respect to Al distribution in zeolites with a larger Si/Al ratio. The two factors identified by this work that substantially influence the selectivity ratio are the siting of Al atoms among T-sites and their spatial proximity, and an atomic-level understanding of each of these effects was achieved. The siting of Al atoms at more or less selective T-sites significantly influences the overall selectivity ratio, and Al atoms in close proximity can synergistically enhance the adsorption of central C-C bonds, leading to a higher selectivity ratio relative to isolated Al atoms. Finally, we anticipate that these results will have important implications for future large-scale computational screenings and the development of advanced synthesis approaches to target certain Al distributions in zeolites.

View Accepted Manuscript (DOE)

Research Organization:: Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)

Sponsoring Organization:: USDOE Office of Science (SC)

Grant/Contract Number:: AC02-05CH11231

OSTI ID:: 1571101

Journal Information:: Journal of Physical Chemistry. C, Journal Name: Journal of Physical Chemistry. C Journal Issue: 17 Vol. 122; ISSN 1932-7447

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

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