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Transient kinetic studies and microkinetic modeling of primary olefin formation from dimethyl ether over ZSM‐5 catalysts
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Omojola, Toyin, Lukyanov, Dmitry B. and van Veen, André C. (2019) Transient kinetic studies and microkinetic modeling of primary olefin formation from dimethyl ether over ZSM‐5 catalysts. International Journal of Chemical Kinetics, 51 (7). pp. 528-537. doi:10.1002/kin.21275 ISSN 0538-8066.
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WRAP-transient-kinetic-studies-microkinetic-modeling-primary-olefin-formation-dimethyl-ether-ZSM‐5-catalysts-vanVeen-2019.pdf - Accepted Version - Requires a PDF viewer. Download (1399Kb) | Preview |
Official URL: http://dx.doi.org/10.1002/kin.21275
Abstract
The formation of primary olefins from dimethyl ether (DME) was studied over ZSM-5 catalysts at 300°C using a novel step response methodology in a temporal analysis of products (TAP) reactor. For the first time, the TAP reactor framework was used to conduct single- and multiple-step response cycles of DME (balance argon) over a shallow bed with the continuous flow panel. Propylene is the major primary olefin and portrays an S-shaped profile with a preceding induction period when it is not observed in the gas phase. Methanol and water portray overshoot profiles due to their different rates of generation and consumption. DME effluent shows a rapid rise halfway to its steady-state value leading to a slow rise thereafter because of its high desorption rates followed by subsequent reactions involving DME in further steps during the induction period. To analyze the experimental data quantitatively, nine reaction schemes were compared, and kinetic parameters were obtained by solving a transient plug flow reactor model with coupled dispersion, convection, adsorption, desorption, and reaction steps. The methoxymethyl pathway involving dimethoxyethane and methyl propenyl ether gives the closest match to experimental data in agreement with recent density functional theory studies. Gaseous dispersion coefficients of ca. 10−9 m2 s−1 were obtained in the TAP reactor. The novel experimental data validated against the transient kinetic model suggests that after the formation of initial species, the bottleneck in propylene formation is the transformation of the initial C–C bond, that is dimethoxyethane formed initially from DME and methoxymethyl groups. DME adsorption on ZSM-5 catalyst generates surface methoxy groups, which further react with the feed to give methoxymethyl groups. These methoxymethyl groups are regenerated through a series of reactions involving intermediates such as dimethoxymethane and methyl propenyl ether before propylene formation.
Item Type: | Journal Article | ||||||||||||
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Subjects: | Q Science > QD Chemistry T Technology > TP Chemical technology |
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Divisions: | Faculty of Science, Engineering and Medicine > Engineering > Engineering | ||||||||||||
Library of Congress Subject Headings (LCSH): | Alkenes, Propene, Methyl ether | ||||||||||||
Journal or Publication Title: | International Journal of Chemical Kinetics | ||||||||||||
Publisher: | Wiley | ||||||||||||
ISSN: | 0538-8066 | ||||||||||||
Official Date: | July 2019 | ||||||||||||
Dates: |
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Volume: | 51 | ||||||||||||
Number: | 7 | ||||||||||||
Page Range: | pp. 528-537 | ||||||||||||
DOI: | 10.1002/kin.21275 | ||||||||||||
Status: | Peer Reviewed | ||||||||||||
Publication Status: | Published | ||||||||||||
Reuse Statement (publisher, data, author rights): | This is the peer reviewed version of the following article: Omojola, T, Lukyanov, DB, Veen, AC. Transient kinetic studies and microkinetic modeling of primary olefin formation from dimethyl ether over ZSM‐5 catalysts. Int J Chem Kinet. 2019; 51: 528– 537. https://doi.org/10.1002/kin.21275, which has been published in final form at http://dx.doi.org/10.1002/kin.21275. This article may be used for non-commercial purposes in accordance with Wiley Terms and Conditions for Use of Self-Archived Versions. | ||||||||||||
Access rights to Published version: | Restricted or Subscription Access | ||||||||||||
Date of first compliant deposit: | 22 May 2019 | ||||||||||||
Date of first compliant Open Access: | 8 April 2020 | ||||||||||||
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RIOXX Funder/Project Grant: |
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