The kinetic study of Beckmann rearrangement of cyclohexanone oxime catalyzed by trifluoroacetic acid and acetonitrile in a microreactor is presented in this article. Parametric studies are conducted varying temperature, ratio of trifluoroacetic acid to acetonitrile, and concentration of cyclohexanone oxime. The inhibition effect of ɛ-caprolactam in this reaction system is firstly reported. A comprehensive mathematic kinetic model considering the product inhibition effect of caprolactam has been developed in the temperature range of 368–391 K, which agrees well with the experimental results across a broad experimental parameter space. In addition, kinetic study indicates that the esterification of cyclohexanone oxime and transposition reaction of the intermediate are both supposed to be the rate-determining steps, and in this catalyst system, the ratio of trifluoroacetic acid and acetonitrile mainly influences the reaction rate and the activation energy of the transposition step. The developed model could provide much reliable knowledge for industrial application. © 2017 American Institute of Chemical Engineers AIChE J, 2017

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微反应器中环己酮肟的有机催化贝克曼重排：动力学模型和产物抑制

本文介绍了在微反应器中三氟乙酸和乙腈催化的环己酮肟的贝克曼重排动力学。在不同的温度，三氟乙酸与乙腈的比例以及环己酮肟的浓度下进行参数研究。首次报道了ε-己内酰胺在该反应体系中的抑制作用。在368–391 K的温度范围内，开发了考虑己内酰胺对产物抑制作用的综合数学动力学模型，该模型与广泛的实验参数空间中的实验结果吻合良好。另外，动力学研究表明，环己酮肟的酯化反应和中间体的转座反应均被认为是决定速率的步骤，在该催化剂体系中，三氟乙酸与乙腈的比例主要影响转座步骤的反应速度和活化能。开发的模型可以为工业应用提供可靠的知识。©2017美国化学工程师学会AIChE的Ĵ，2017年