Citation: LI Jun-Nan, PU Min, SU Yong, HE Jing, EVANS David G.. Theoretical Study on the Synthesis of Ethyl Tertiary Butyl Ether over HZSM-5 Zeolite[J]. Acta Physico-Chimica Sinica, ;2012, 28(07): 1630-1636. doi: 10.3866/PKU.WHXB201204171 shu

Theoretical Study on the Synthesis of Ethyl Tertiary Butyl Ether over HZSM-5 Zeolite

1.
State Key Laboratory of Chemical Resource Engineering, Beijing University of Chemical Technology, Beijing 100029, P. R. China

Received Date: 1 December 2011
Available Online: 17 April 2012

The formation mechanism of ethyl tertiary butyl ether (ETBE) from ethanol and isobutene catalyzed by HZSM-5 has been investigated using the ONIOM (B3LYP/6-31G(d,p):UFF) method. The calculation results of the reactants adsorbability reveal that the interaction between ethanol and the acidic sites on HZSM-5 leads to the formation of hydrogen bonds. The interaction between isobutene and Brönsted acidic sites leads to the formation of a π-complex. It is subsequently found that the mechanism of the ETBE formation from ethanol and isobutene catalyzed by HZSM-5 is a concerted reaction, and that the order of reactant adsorption onto HZSM-5 affected the reaction. The favorable pathway is based on the complex formed by the simultaneous adsorption of ethanol and isobutene, in which the H atom of the π-complex is transferred to the C atom of the C＝C in isobutene, and the O atom of the adsorbed ethanol is transferred to the other C atom of the C＝C to form the C－O bond. In this process, the proton of the acidic sites adds to the C＝C bond forming the C－H bond, and the H atom of the ethanol hydroxyl interacts with acidic sites, generating a new proton. The corresponding lowest energy barrier was 25.14 kJ·mol^-1.
- Ethanol,
- Isobutene,
- HZSM-5 zeolite,
- ONIOM,
- Ethyl tertiary butyl ether
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