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First principle kinetic studies of zeolite-catalyzed methylation reactions

Veronique Van Speybroeck UGent, Jeroen Van der Mynsbrugge UGent, Matthias Vandichel UGent, Karen Hemelsoet UGent, David Lesthaeghe UGent, An Ghysels UGent, Guy Marin UGent and Michel Waroquier UGent (2011) JOURNAL OF THE AMERICAN CHEMICAL SOCIETY. 133(4). p.888-899
abstract
Methylations of ethene, propene, and butene by methanol over the acidic microporous H-ZSM-5 catalyst are studied by means of state of the art computational techniques, to derive Arrhenius plots and rate constants from first principles that can directly be compared with the experimental data. For these key elementary reactions in the methanol to hydrocarbons (MTH) process, direct kinetic data became available only recently [J. Catal. 2005, 224, 115-123; J. Catal. 2005, 234, 385-400]. At 350 degrees C, apparent activation energies of 103, 69, and 45 kJ/mol and rate constants of 2.6 x 10(-4), 4.5 x 10(-3), and 1.3 x 10(-2) mol/(g h mbar) for ethene, propene, and butene were ;derived, giving following relative ratios for methylation k(ethene)/k(propene)/k(butene) = 1:17:50. In this work, rate constants including pre-exponential factors are calculated which give very good agreement with the experimental data: apparent activation energies of 94, 62, and 37 kJ/mol for ethene, propene, and butene are found, and relative ratios of methylation k(ethene)/k(propene)/k(butene) = 1:23:763. The entropies of gas phase alkenes are underestimated in the harmonic oscillator approximation due to the occurrence of internal rotations. These low vibrational modes were substituted by manually constructed partition functions. Overall, the absolute reaction rates can be calculated with near chemical accuracy, and qualitative trends are very well reproduced. In addition, the proposed scheme is computationally very efficient and constitutes significant progress in kinetic modeling of reactions in heterogeneous catalysis.
Please use this url to cite or link to this publication:
author
organization
year
type
journalArticle (original)
publication status
published
subject
keyword
TO-OLEFIN CONVERSION, DENSITY-FUNCTIONAL THEORY, BLOCK HESSIAN APPROACH, ELASTIC BAND METHOD, AB-INITIO, REACTION-MECHANISM, ACIDIC ZEOLITES, N-ALKANES, MOLECULAR-SIEVES, DIMETHYL ETHER
journal title
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
J. Am. Chem. Soc.
volume
133
issue
4
pages
888 - 899
Web of Science type
Article
Web of Science id
000287295300051
JCR category
CHEMISTRY, MULTIDISCIPLINARY
JCR impact factor
9.907 (2011)
JCR rank
11/149 (2011)
JCR quartile
1 (2011)
ISSN
0002-7863
DOI
10.1021/ja1073992
language
English
UGent publication?
yes
classification
A1
copyright statement
I have transferred the copyright for this publication to the publisher
id
1191987
handle
http://hdl.handle.net/1854/LU-1191987
date created
2011-03-21 10:04:59
date last changed
2011-04-18 14:10:57
@article{1191987,
  abstract     = {Methylations of ethene, propene, and butene by methanol over the acidic microporous H-ZSM-5 catalyst are studied by means of state of the art computational techniques, to derive Arrhenius plots and rate constants from first principles that can directly be compared with the experimental data. For these key elementary reactions in the methanol to hydrocarbons (MTH) process, direct kinetic data became available only recently [J. Catal. 2005, 224, 115-123; J. Catal. 2005, 234, 385-400]. At 350 degrees C, apparent activation energies of 103, 69, and 45 kJ/mol and rate constants of 2.6 x 10(-4), 4.5 x 10(-3), and 1.3 x 10(-2) mol/(g h mbar) for ethene, propene, and butene were ;derived, giving following relative ratios for methylation k(ethene)/k(propene)/k(butene) = 1:17:50. In this work, rate constants including pre-exponential factors are calculated which give very good agreement with the experimental data: apparent activation energies of 94, 62, and 37 kJ/mol for ethene, propene, and butene are found, and relative ratios of methylation k(ethene)/k(propene)/k(butene) = 1:23:763. The entropies of gas phase alkenes are underestimated in the harmonic oscillator approximation due to the occurrence of internal rotations. These low vibrational modes were substituted by manually constructed partition functions. Overall, the absolute reaction rates can be calculated with near chemical accuracy, and qualitative trends are very well reproduced. In addition, the proposed scheme is computationally very efficient and constitutes significant progress in kinetic modeling of reactions in heterogeneous catalysis.},
  author       = {Van Speybroeck, Veronique and Van der Mynsbrugge, Jeroen and Vandichel, Matthias and Hemelsoet, Karen and Lesthaeghe, David and Ghysels, An and Marin, Guy and Waroquier, Michel},
  issn         = {0002-7863},
  journal      = {JOURNAL OF THE AMERICAN CHEMICAL SOCIETY},
  keyword      = {TO-OLEFIN CONVERSION,DENSITY-FUNCTIONAL THEORY,BLOCK HESSIAN APPROACH,ELASTIC BAND METHOD,AB-INITIO,REACTION-MECHANISM,ACIDIC ZEOLITES,N-ALKANES,MOLECULAR-SIEVES,DIMETHYL ETHER},
  language     = {eng},
  number       = {4},
  pages        = {888--899},
  title        = {First principle kinetic studies of zeolite-catalyzed methylation reactions},
  url          = {http://dx.doi.org/10.1021/ja1073992},
  volume       = {133},
  year         = {2011},
}

Chicago
Van Speybroeck, Veronique, Jeroen Van der Mynsbrugge, Matthias Vandichel, Karen Hemelsoet, David Lesthaeghe, An Ghysels, Guy Marin, and Michel Waroquier. 2011. “First Principle Kinetic Studies of Zeolite-catalyzed Methylation Reactions.” Journal of the American Chemical Society 133 (4): 888–899.
APA
Van Speybroeck, V., Van der Mynsbrugge, J., Vandichel, M., Hemelsoet, K., Lesthaeghe, D., Ghysels, A., Marin, G., et al. (2011). First principle kinetic studies of zeolite-catalyzed methylation reactions. JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 133(4), 888–899.
Vancouver
1.
Van Speybroeck V, Van der Mynsbrugge J, Vandichel M, Hemelsoet K, Lesthaeghe D, Ghysels A, et al. First principle kinetic studies of zeolite-catalyzed methylation reactions. JOURNAL OF THE AMERICAN CHEMICAL SOCIETY. 2011;133(4):888–99.
MLA
Van Speybroeck, Veronique, Jeroen Van der Mynsbrugge, Matthias Vandichel, et al. “First Principle Kinetic Studies of Zeolite-catalyzed Methylation Reactions.” JOURNAL OF THE AMERICAN CHEMICAL SOCIETY 133.4 (2011): 888–899. Print.