Kinetics and mechanism of acetic acid esterification with ethanol on zeolites

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• 作者：Jeremy Bedard ^{beda0040@umn.edu} ; Hsu Chiang ^{chian058@umn.edu} ; Aditya Bhan ; ^{abhan@umn.edu}
• 关键词：Esterification ; Acetic acid ; Ethanol ; Zeolite ; Ethyl acetate ; Reaction kinetics ; Mechanism
• 刊名：Journal of Catalysis
• 出版年：2012
• 期刊代码：97_00219517
• 类别：ce
• 出版时间：June, 2012
• 卷：290
• 期：Complete
• 页码：210-219
• 文件大小：708 K

摘要

Steady-state reaction studies of acetic acid and ethanol were used to identify co-adsorbed acetic acid/ethanol dimers as surface intermediates within specific elementary steps involved in the esterification of acetic acid with ethanol on zeolites. A reaction mechanism involving two dominating surface species, an inactive ethanol dimeric species adsorbed on Br酶nsted sites inhibiting ester formation and a co-adsorbed complex of acetic acid and ethanol on the active site reacting to produce ethyl acetate, is shown to describe the reaction rate as a function of temperature (323-383 K), acetic acid (0.5-6.0 kPa), and ethanol (5.0-13.0 kPa) partial pressure on proton-form BEA, FER, MFI, and MOR zeolites. Measured differences in rates as a function of zeolite structure and the rigorous interpretation of these differences in terms of esterification rate and equilibrium constants is presented to show that the intrinsic rate constant for the activation of the co-adsorbed complex increases in the order FER < MOR < MFI < BEA.