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Title: Diffusion of aromatic hydrocarbons in hierarchical mesoporous H-ZSM-5 zeolite

Abstract

Hierarchical mesoporous zeolites exhibit higher catalytic activities and longer lifetime compared to the traditional microporous zeolites due to improved diffusivity of substrate molecules and their enhanced access to the zeolite active sites. Understanding diffusion of biomass pyrolysis vapors and their upgraded products in such materials is fundamentally important during catalytic fast pyrolysis (CFP) of lignocellulosic biomass, since diffusion makes major contribution to determine shape selectivity and product distribution. However, diffusivities of biomass relevant species in hierarchical mesoporous zeolites are poorly characterized, primarily due to the limitations of the available experimental technology. In this work, molecular dynamics (MD) simulations are utilized to investigate the diffusivities of several selected coke precursor molecules, benzene, naphthalene, and anthracene, in hierarchical mesoporous H-ZSM-5 zeolite. The effects of temperature and size of mesopores on the diffusivity of the chosen model compounds are examined. The simulation results demonstrate that diffusion within the microspores as well as on the external surface of mesoporous H-ZSM-5 dominates only at low temperature. At pyrolysis relevant temperatures, mass transfer is essentially conducted via diffusion along the mesopores. Furthermore, the results illustrate the heuristic diffusion model, such as the extensively used Knudsen diffusion, overestimates the diffusion of bulky molecules in the mesopores, thusmore » making MD simulation a powerful and compulsory approach to explore diffusion in zeolites.« less

Authors:
 [1];  [1];  [1];  [1]
  1. National Renewable Energy Lab. (NREL), Golden, CO (United States)
Publication Date:
Research Org.:
National Renewable Energy Lab. (NREL), Golden, CO (United States)
Sponsoring Org.:
USDOE Office of Energy Efficiency and Renewable Energy (EERE), Transportation Office. Bioenergy Technologies Office
OSTI Identifier:
1424576
Alternate Identifier(s):
OSTI ID: 1591656
Report Number(s):
NREL/JA-2700-71045
Journal ID: ISSN 0920-5861; TRN: US1801924
Grant/Contract Number:  
AC36-08GO28308
Resource Type:
Accepted Manuscript
Journal Name:
Catalysis Today
Additional Journal Information:
Journal Volume: 312; Journal Issue: C; Journal ID: ISSN 0920-5861
Publisher:
Elsevier
Country of Publication:
United States
Language:
English
Subject:
09 BIOMASS FUELS; diffusion; mesoporous zeolite; H-ZSM-5; molecular dynamics; coke precursor; Knudsen diffusion

Citation Formats

Bu, Lintao, Nimlos, Mark R., Robichaud, David J., and Kim, Seonah. Diffusion of aromatic hydrocarbons in hierarchical mesoporous H-ZSM-5 zeolite. United States: N. p., 2018. Web. https://doi.org/10.1016/j.cattod.2018.02.012.
Bu, Lintao, Nimlos, Mark R., Robichaud, David J., & Kim, Seonah. Diffusion of aromatic hydrocarbons in hierarchical mesoporous H-ZSM-5 zeolite. United States. https://doi.org/10.1016/j.cattod.2018.02.012
Bu, Lintao, Nimlos, Mark R., Robichaud, David J., and Kim, Seonah. Thu . "Diffusion of aromatic hydrocarbons in hierarchical mesoporous H-ZSM-5 zeolite". United States. https://doi.org/10.1016/j.cattod.2018.02.012. https://www.osti.gov/servlets/purl/1424576.
@article{osti_1424576,
title = {Diffusion of aromatic hydrocarbons in hierarchical mesoporous H-ZSM-5 zeolite},
author = {Bu, Lintao and Nimlos, Mark R. and Robichaud, David J. and Kim, Seonah},
abstractNote = {Hierarchical mesoporous zeolites exhibit higher catalytic activities and longer lifetime compared to the traditional microporous zeolites due to improved diffusivity of substrate molecules and their enhanced access to the zeolite active sites. Understanding diffusion of biomass pyrolysis vapors and their upgraded products in such materials is fundamentally important during catalytic fast pyrolysis (CFP) of lignocellulosic biomass, since diffusion makes major contribution to determine shape selectivity and product distribution. However, diffusivities of biomass relevant species in hierarchical mesoporous zeolites are poorly characterized, primarily due to the limitations of the available experimental technology. In this work, molecular dynamics (MD) simulations are utilized to investigate the diffusivities of several selected coke precursor molecules, benzene, naphthalene, and anthracene, in hierarchical mesoporous H-ZSM-5 zeolite. The effects of temperature and size of mesopores on the diffusivity of the chosen model compounds are examined. The simulation results demonstrate that diffusion within the microspores as well as on the external surface of mesoporous H-ZSM-5 dominates only at low temperature. At pyrolysis relevant temperatures, mass transfer is essentially conducted via diffusion along the mesopores. Furthermore, the results illustrate the heuristic diffusion model, such as the extensively used Knudsen diffusion, overestimates the diffusion of bulky molecules in the mesopores, thus making MD simulation a powerful and compulsory approach to explore diffusion in zeolites.},
doi = {10.1016/j.cattod.2018.02.012},
journal = {Catalysis Today},
number = C,
volume = 312,
place = {United States},
year = {2018},
month = {2}
}

Journal Article:

Citation Metrics:
Cited by: 17 works
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Figures / Tables:

Figure 1 Figure 1: Constructing the mesoporous H-ZSM-5 zeolites with pore size of 60 Å.

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