Ghent University Academic Bibliography

Advanced

Effect of zeolite confinement on the conversion of 1-butanol to butene isomers : mechanistic insights from DFT based microkinetic

Mathew John, Konstantinos Alexopoulos, Marie-Françoise Reyniers UGent and Guy Marin UGent (2017) CATALYSIS SCIENCE & TECHNOLOGY. 7(14). p.2978-2977
abstract
Ab initio based microkinetic modelling of 1-butanol dehydration to butene isomers is used to obtain mechanistic insights into the effect of a zeolite framework. A detailed microkinetic model including double bond isomerization, skeletal isomerization and mechanisms for the direct formation of 2t-butene from 1-butanol dimer and di-1-butyl ether (DBE) is considered for the dehydration in H-ZSM-5, H-ZSM-22 and H-FER. HFER favors the production of 2t-butene and H-ZSM-22 achieves thermodynamic equilibrium composition for linear butenes even at low conversion levels, while H-ZSM-5 maximizes 1-butene selectivity. Significant differences are observed in the reaction mechanism leading to formation of 2t-butene. For H-ZSM-5 and H-ZSM-22, the formation of 2-butenes occurs via double bond isomerization of 1-butene produced from butanol dehydration. For the double bond isomerization of 1-butene to 2t-butene, both concerted and 2-butoxide mediated stepwise mechanisms contribute significantly in H-ZSM-5, while only the concerted mechanism is operative in H-ZSM-22. On the other hand, for H-FER, 2t-butene is mainly produced from the butanol dimer via an E1 elimination accompanied by a 1,2-hydride shift. This in turn can be attributed to an increase in enthalpic stabilization of the E1 elimination transition state for the direct formation of 2tbutene from 1-butanol dimer when moving from H-ZSM-5 to H-FER. Isobutene formation is not observed in all three zeolites at the investigated temperature range of 450–500 K.
Please use this url to cite or link to this publication:
author
organization
year
type
journalArticle (original)
publication status
published
keyword
DENSITY-FUNCTIONAL THEORY, DOUBLE-BOND MIGRATION, SKELETAL ISOMERIZATION, AB-INITIO, N-BUTANOL, ADSORPTION THERMODYNAMICS, NMR-SPECTROSCOPY, SILICA-ALUMINA, LINEAR BUTENES, ACID CATALYSIS
journal title
CATALYSIS SCIENCE & TECHNOLOGY
volume
7
issue
14
pages
2978 - 2977
Web of Science type
Article
Web of Science id
000405806900008
ISSN
2044-4753
DOI
10.1039/c7cy00536a
language
English
UGent publication?
yes
classification
A1
id
8536776
handle
http://hdl.handle.net/1854/LU-8536776
date created
2017-11-09 14:58:25
date last changed
2017-11-14 07:50:38
@article{8536776,
  abstract     = {Ab initio based microkinetic modelling of 1-butanol dehydration to butene isomers is used to obtain mechanistic
insights into the effect of a zeolite framework. A detailed microkinetic model including double bond isomerization, skeletal isomerization and mechanisms for the direct formation of 2t-butene from 1-butanol dimer and di-1-butyl ether (DBE) is considered for the dehydration in H-ZSM-5, H-ZSM-22 and H-FER. HFER favors the production of 2t-butene and H-ZSM-22 achieves thermodynamic equilibrium composition for linear butenes even at low conversion levels, while H-ZSM-5 maximizes 1-butene selectivity. Significant differences are observed in the reaction mechanism leading to formation of 2t-butene. For H-ZSM-5 and H-ZSM-22, the formation of 2-butenes occurs via double bond isomerization of 1-butene produced from butanol dehydration. For the double bond isomerization of 1-butene to 2t-butene, both concerted and 2-butoxide mediated stepwise mechanisms contribute significantly in H-ZSM-5, while only the concerted
mechanism is operative in H-ZSM-22. On the other hand, for H-FER, 2t-butene is mainly produced from the butanol dimer via an E1 elimination accompanied by a 1,2-hydride shift. This in turn can be attributed to an increase in enthalpic stabilization of the E1 elimination transition state for the direct formation of 2tbutene from 1-butanol dimer when moving from H-ZSM-5 to H-FER. Isobutene formation is not observed in all three zeolites at the investigated temperature range of 450--500 K.},
  author       = {John, Mathew and Alexopoulos, Konstantinos and Reyniers, Marie-Fran\c{c}oise and Marin, Guy},
  issn         = {2044-4753 },
  journal      = {CATALYSIS SCIENCE \& TECHNOLOGY},
  keyword      = {DENSITY-FUNCTIONAL THEORY,DOUBLE-BOND MIGRATION,SKELETAL ISOMERIZATION,AB-INITIO,N-BUTANOL,ADSORPTION THERMODYNAMICS,NMR-SPECTROSCOPY,SILICA-ALUMINA,LINEAR BUTENES,ACID CATALYSIS},
  language     = {eng},
  number       = {14},
  pages        = {2978--2977},
  title        = {Effect of zeolite confinement on the conversion of 1-butanol to butene isomers : mechanistic insights from DFT based microkinetic },
  url          = {http://dx.doi.org/10.1039/c7cy00536a},
  volume       = {7},
  year         = {2017},
}

Chicago
John, Mathew, Konstantinos Alexopoulos, Marie-Françoise Reyniers, and Guy Marin. 2017. “Effect of Zeolite Confinement on the Conversion of 1-butanol to Butene Isomers : Mechanistic Insights from DFT Based Microkinetic .” Catalysis Science & Technology 7 (14): 2978–2977.
APA
John, M., Alexopoulos, K., Reyniers, M.-F., & Marin, G. (2017). Effect of zeolite confinement on the conversion of 1-butanol to butene isomers : mechanistic insights from DFT based microkinetic . CATALYSIS SCIENCE & TECHNOLOGY, 7(14), 2978–2977.
Vancouver
1.
John M, Alexopoulos K, Reyniers M-F, Marin G. Effect of zeolite confinement on the conversion of 1-butanol to butene isomers : mechanistic insights from DFT based microkinetic . CATALYSIS SCIENCE & TECHNOLOGY. 2017;7(14):2978–2977.
MLA
John, Mathew, Konstantinos Alexopoulos, Marie-Françoise Reyniers, et al. “Effect of Zeolite Confinement on the Conversion of 1-butanol to Butene Isomers : Mechanistic Insights from DFT Based Microkinetic .” CATALYSIS SCIENCE & TECHNOLOGY 7.14 (2017): 2978–2977. Print.