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Title: Understanding zeolite-catalyzed benzene methylation reactions by methanol and dimethyl ether at operating conditions from first principle microkinetic modeling and experiments

Abstract

In methanol-to-hydrocarbon chemistry, methanol and dimethyl ether (DME) can act as methylating agents. Therefore, in this paper we focus on the different reactivity of methanol and DME towards benzene methylation in H-ZSM-5 at operating conditions by combining first principles microkinetic modeling and experiments. Methylation reactions are known to follow either a concerted reaction path or a stepwise mechanism going through a framework-bound methoxide. By constructing a DFT based microkinetic model including the concerted and stepwise reactions, product formation rates can be calculated at conditions that closely mimic the experimentally applied conditions. Trends in measured rates are relatively well reproduced by our DFT based microkinetic model. We find that benzene methylation with DME is faster than with methanol but the difference decreases with increasing temperature. At low temperatures, the concerted mechanism dominates, however at higher temperatures and low pressures the mechanism shifts to the stepwise pathway. This transition occurs at lower temperatures for methanol than for DME, resulting in smaller reactivity differences between methanol and DME at high temperature. Finally, our theory-experiment approach shows that the widely assumed rate law with zeroth and first order in oxygenate and hydrocarbon partial pressure is not generally applicable and depends on the applied temperature,more » pressure and feed composition.« less

Authors:
ORCiD logo [1];  [2];  [3];  [4];  [4];  [3]
  1. SLAC National Accelerator Lab., Menlo Park, CA (United States). SUNCAT Center for Interface Science and Catalysis; Stanford Univ., CA (United States). Dept. of Chemical Engineering; Ghent Univ. (Belgium). Center for Molecular Modeling
  2. Univ. of Oslo (Norway). Centre for Materials Science and Nanotechnology. Dept. of Chemistry; Haldor Topsøe A/S, Kongens Lyngby (Denmark)
  3. SLAC National Accelerator Lab., Menlo Park, CA (United States). SUNCAT Center for Interface Science and Catalysis; Stanford Univ., CA (United States). Dept. of Chemical Engineering
  4. Univ. of Oslo (Norway). Centre for Materials Science and Nanotechnology. Dept. of Chemistry
Publication Date:
Research Org.:
SLAC National Accelerator Lab., Menlo Park, CA (United States); Ghent Univ. (Belgium); Univ. of Oslo (Norway)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES); Belgian American Educational Foundation (BAEF); Research Foundation - Flanders (FWO) (Belgium); European Union (EU)
OSTI Identifier:
1461966
Alternate Identifier(s):
OSTI ID: 1591661
Grant/Contract Number:  
AC02-76SF00515; 606965
Resource Type:
Accepted Manuscript
Journal Name:
Catalysis Today
Additional Journal Information:
Journal Volume: 312; Journal ID: ISSN 0920-5861
Publisher:
Elsevier
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; zeolites; methanol-to-hydrocarbons; microkinetic modeling; methylation; methanol; dimethyl ether

Citation Formats

De Wispelaere, Kristof, Martinez-Espin, Juan S., Hoffmann, Max J., Svelle, Stian, Olsbye, Unni, and Bligaard, Thomas. Understanding zeolite-catalyzed benzene methylation reactions by methanol and dimethyl ether at operating conditions from first principle microkinetic modeling and experiments. United States: N. p., 2018. Web. https://doi.org/10.1016/j.cattod.2018.02.042.
De Wispelaere, Kristof, Martinez-Espin, Juan S., Hoffmann, Max J., Svelle, Stian, Olsbye, Unni, & Bligaard, Thomas. Understanding zeolite-catalyzed benzene methylation reactions by methanol and dimethyl ether at operating conditions from first principle microkinetic modeling and experiments. United States. https://doi.org/10.1016/j.cattod.2018.02.042
De Wispelaere, Kristof, Martinez-Espin, Juan S., Hoffmann, Max J., Svelle, Stian, Olsbye, Unni, and Bligaard, Thomas. Sat . "Understanding zeolite-catalyzed benzene methylation reactions by methanol and dimethyl ether at operating conditions from first principle microkinetic modeling and experiments". United States. https://doi.org/10.1016/j.cattod.2018.02.042. https://www.osti.gov/servlets/purl/1461966.
@article{osti_1461966,
title = {Understanding zeolite-catalyzed benzene methylation reactions by methanol and dimethyl ether at operating conditions from first principle microkinetic modeling and experiments},
author = {De Wispelaere, Kristof and Martinez-Espin, Juan S. and Hoffmann, Max J. and Svelle, Stian and Olsbye, Unni and Bligaard, Thomas},
abstractNote = {In methanol-to-hydrocarbon chemistry, methanol and dimethyl ether (DME) can act as methylating agents. Therefore, in this paper we focus on the different reactivity of methanol and DME towards benzene methylation in H-ZSM-5 at operating conditions by combining first principles microkinetic modeling and experiments. Methylation reactions are known to follow either a concerted reaction path or a stepwise mechanism going through a framework-bound methoxide. By constructing a DFT based microkinetic model including the concerted and stepwise reactions, product formation rates can be calculated at conditions that closely mimic the experimentally applied conditions. Trends in measured rates are relatively well reproduced by our DFT based microkinetic model. We find that benzene methylation with DME is faster than with methanol but the difference decreases with increasing temperature. At low temperatures, the concerted mechanism dominates, however at higher temperatures and low pressures the mechanism shifts to the stepwise pathway. This transition occurs at lower temperatures for methanol than for DME, resulting in smaller reactivity differences between methanol and DME at high temperature. Finally, our theory-experiment approach shows that the widely assumed rate law with zeroth and first order in oxygenate and hydrocarbon partial pressure is not generally applicable and depends on the applied temperature, pressure and feed composition.},
doi = {10.1016/j.cattod.2018.02.042},
journal = {Catalysis Today},
number = ,
volume = 312,
place = {United States},
year = {2018},
month = {2}
}

Journal Article:

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Cited by: 3 works
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Figures / Tables:

Fig. 1 Fig. 1: Schematical representation of the concerted and stepwise methylation mechanisms with MeOH or DME as reactant.

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    Works referencing / citing this record:

    Olefin methylation and cracking reactions in H-SSZ-13 investigated with ab initio and DFT calculations
    journal, January 2018

    • Plessow, Philipp N.; Studt, Felix
    • Catalysis Science & Technology, Vol. 8, Issue 17
    • DOI: 10.1039/c8cy01194j

      Figures/Tables have been extracted from DOE-funded journal article accepted manuscripts.