ZSM-5分子筛催化1-己烯生成cis-2-己烯的理论研究

doi:10.3866/PKU.WHXB20110516

Abstract

Abstract:

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 good 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.

Key words: ZSM-5, Active site, Hexene, Density functional theory, Double-bond isomerization

MSC2000:

O641

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 Phys. -Chim. Sin., 2011, 27(05): 1081-1088.

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

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