Citation: LI Yan-Feng, ZHU Ji-Qin, LIU Hui, HE Peng, WANG Peng, TIAN Hui-Ping. Theoretical Study of the Double-Bond Isomerization of 1-Hexene to cis-2-Hexene over ZSM-5 Zeolite[J]. Acta Physico-Chimica Sinica, ;2011, 27(05): 1081-1088. doi: 10.3866/PKU.WHXB20110516 shu

Theoretical Study of the Double-Bond Isomerization of 1-Hexene to cis-2-Hexene over ZSM-5 Zeolite

LI Yan-Feng ¹ ,
ZHU Ji-Qin ¹ ,
LIU Hui ^1, ,
HE Peng ¹ ,
WANG Peng ² ,
TIAN Hui-Ping ²

1.
1. State Key Laboratory of Chemical Resource Engineering, Beijing University of Chemical Technology, Beijing 100029, P. R. China;
2. Research Institute of Petroleum Processing, SINOPEC, Beijing 100083, P. R. China

Received Date: 6 January 2011
Available Online: 1 April 2011
Fund Project: 国家重点基础研究发展计划项目(973) (2010CB732301)资助 (973) (2010CB732301)

We investigated the double-bond isomerization reaction of 1-hexene to cis-2-hexene on the surface of ZSM-5 zeolite using density functional theory with a 54T cluster model simulating the local structures of zeolite materials. We found that the double-bond isomerization proceeded by a mechanism that did not involve the bifunctional (acid-base) nature of the zeolite active sites but exclusively involved the Brønsted acid sites. According to this mechanism, 1-hexene is the first physically adsorbed onto the zeolite acid site resulting in the formation of a π-complex, and then the acidic proton of the zeolite transfers to a carbon atom of the double bond of the physisorbed 1-hexene. The other carbon atom of the double bond of the physisorbed 1-hexene bonds with the Brønsted host oxygen and yields a stable alkoxy intermediate. Thereafter, the Brønsted host oxygen abstracts a hydrogen atom from the C₆H₁₃ fragment and the C―O bond of the alkoxy intermediate is broken, which restores the zeolite active site and yields physisorbed cis-2-hexene. The proposed reaction pathway competes with the bifunctional pathway. The rate- determining step is the decomposition of the alkoxy intermediate with an activation energy of 134. 64 kJ·mol^-1. The calculated apparent activation energy for the isomerization reaction is 59. 37 kJ·mol^-1, which is in od agreement with the reported experimental value. These results well explain the energetic aspects during the double-bond isomerization and extend the understanding of the nature of zeolite active sites.
- ZSM-5,
- Active site,
- Hexene,
- Density functional theory,
- Double-bond isomerization
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