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Mechanistic investigation of methanol to propene conversion catalyzed by H-beta zeolite: a two-layer ONIOM study

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Abstract

Two-layer ONIOM calculations have been carried out to study methanol to propene (MTP) conversion reactions catalyzed by H-beta zeolite. On the basis of the so-called side-chain hydrocarbon pool (HCP) mechanism, this work proposes the complete catalytic cycle pathway for the MTP reaction. The cycle starts from the methylation of pentamethylbenzene (PMB), which leads to the formation of hexamethylbenzenium ion (hexaMB+). Subsequent steps involving deprotonation, methylation, an internal H-shift, and a unimolecular CH3-shift are required to produce propene and ethene. The calculated activation barriers and reaction energy data indicate that propene is the more favored product, rather than ethene, from both kinetic and thermodynamic perspectives, which is consistent with experimental observations. In addition, the calculations suggest that the activation barriers of the reaction steps decrease in the order: internal H-shift > methylation > unimolecular CH3-shift ≥ deprotonation. In the methylation step, methylation of the exocyclic double bond is easier than methylation of the ring carbons on the aromatic benzene derivative.

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Acknowledgments

This work was funded by the National Science Foundation of China (nos. 21203118), the Training Program for Young College Teachers in Shanghai (ZZyyy12005), and the Scientific Research Foundation of Shanghai Institute of Technology (grant YJ2012-11).

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Authors and Affiliations

  1. School of Chemical and Environmental Engineering, Shanghai Institute of Technology, Shanghai, People’s Republic of China

    Yingxin Sun & Sheng Han

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  1. Yingxin Sun
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  2. Sheng Han
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Correspondence to Yingxin Sun or Sheng Han.

Electronic supplementary material

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894_2013_2030_MOESM1_ESM.doc

Data from S-value testing, activation barriers and reaction energies for the methylation step of HMB and the protonation step of HMMC, optimized structural parameters for the formation and methylation of HMEC, and optimized structural parameters for unimolecular CH3-shift reactions on H-beta zeolite. (DOC 494 kb)

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Sun, Y., Han, S. Mechanistic investigation of methanol to propene conversion catalyzed by H-beta zeolite: a two-layer ONIOM study. J Mol Model 19, 5407–5422 (2013). https://doi.org/10.1007/s00894-013-2030-6

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  • DOI: https://doi.org/10.1007/s00894-013-2030-6

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