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本文详细地介绍了扩展示踪动力学方法(EKIM),并用此法解析了Bi-Mo-P,Sn-P-Li和Fe-Cr-Zn三种丁烯氧化脱氢催化剂上包括丁烯异构化、选择氧化和全氧化等共13个基元反应的复杂反应网络。求得了选择氧化和全氧化的反应级数以及13个速度常数。从这三种催化剂上的不同动力学特征讨论了在Bi-Mo-P和sn-P-Li上选择氧化的控速步骤为第一个氢原子的解离生成烯丙基,在Fe-Cr-Zn上则第一个氢原子的解离不是选择氧化的控速步骤。本文还讨论了选择氧化和异构化在不同催化剂上的可能机理。
In this paper, the extended tracer kinetic method (EKIM) is introduced in detail. And this method is used to analyze the catalytic performance of three kinds of catalysts for the oxidative dehydrogenation of butenes, including Butene-based catalysts for Bi-Mo-P, Sn-P-Li and Fe-Cr-Zn Structuring, selective oxidation and oxidation of a total of 13 elementary reaction complex reaction network. The reaction order of selective oxidation and total oxidation and 13 velocity constants were obtained. The rate-controlling steps of selective oxidation on Bi-Mo-P and Sn-P-Li are discussed from the different kinetic characteristics of the three catalysts for the dissociation of the first hydrogen atom to form the allyl group. In the Fe-Cr The first hydrogen atom dissociation on -Zn is not a rate-selective step of selective oxidation. This article also discusses possible mechanisms for the selective oxidation and isomerization on different catalysts.