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Title: Reaction mechanism of dimethyl ether carbonylation to methyl acetate over mordenite – a combined DFT/experimental study

Journal Article · · Catalysis Science and Technology
DOI: https://doi.org/10.1039/c6cy01904h · OSTI ID:1353213
 [1];  [1];  [2];  [3];  [2];  [4];  [5]; ORCiD logo [1]
  1. Technical Univ. of Denmark, Lyngby (Denmark). Dept. of Chemical and Biochemical Engineering
  2. Haldor Topsoe A/S, Lyngby (Denmark)
  3. SLAC National Accelerator Lab., Menlo Park, CA (United States). SUNCAT Center for Interface Science and Catalysis
  4. Technical Univ. of Denmark, Lyngby (Denmark). Dept. of Physics
  5. Technical Univ. of Denmark, Lyngby (Denmark). Centre for Catalysis and Sustainable Chemistry, Dept. of Chemistry
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The reaction mechanism of dimethyl ether carbonylation to methyl acetate over mordenite was studied theoretically with periodic density functional theory calculations including dispersion forces and experimentally in a fixed bed flow reactor at pressures between 10 and 100 bar, dimethyl ether concentrations in CO between 0.2 and 2.0%, and at a temperature of 438 K. The theoretical study showed that the reaction of CO with surface methyl groups, the rate-limiting step, is faster in the eight-membered side pockets than in the twelve-membered main channel of the zeolite; the subsequent reaction of dimethyl ether with surface acetyl to form methyl acetate was demonstrated to occur with low energy barriers in both the side pockets and in the main channel. Here, the present analysis has thus identified a path, where the entire reaction occurs favourably on a single site within the side pocket, in good agreement with previous experimental studies. The experimental study of the reaction kinetics was consistent with the theoretically derived mechanism and in addition revealed that the methyl acetate product inhibits the reaction – possibly by sterically hindering the attack of CO on the methyl groups in the side pockets.

Research Organization:
SLAC National Accelerator Laboratory (SLAC), Menlo Park, CA (United States)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
Grant/Contract Number:
AC02-76SF00515
OSTI ID:
1353213
Journal Information:
Catalysis Science and Technology, Vol. 7, Issue 5; ISSN 2044-4753
Publisher:
Royal Society of ChemistryCopyright Statement
Country of Publication:
United States
Language:
English
Citation Metrics:
Cited by: 51 works
Citation information provided by
Web of Science

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Theoretical Insights into the Effect of the Framework on the Initiation Mechanism of the MTO Process journal February 2018
Exceptionally stable Rh-based molecular catalyst heterogenized on a cationically charged covalent triazine framework support for efficient methanol carbonylation journal January 2018
Mechanistic insights into the catalytic role of various acid sites on ZSM-5 zeolite in the carbonylation of methanol and dimethyl ether journal January 2018
Direct Conversion of CO2 into Dimethyl Ether over Al2O3/Cu/ZnO Catalysts Prepared by Sequential Precipitation journal June 2019

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