B型银催化剂上乙烯环氧化宏观动力学研究-学兔兔 www.xuetutu.com.pdfVIP

学兔兔 石 油 化 工 2015年第44卷第1期 PETR0CHEMICAL TECHNOL0GY ·29· B型银催化剂上乙烯环氧化宏观动力学研究 梁汝军 ，李建伟 (1．北京化工大学 化工资源有效利用国家重点实验室，北京 100029； 2．中国石化 北京北化院燕山分院，北京 102549) [摘要]针对B型银催化剂，提出以表面反应为控制步骤、乙烯与一个活性中心位上非解离吸附氧发生环氧化反应和乙烯与相 邻多个活性中心位上解离吸附氧发生深度氧化反应的乙烯环氧化反应机理；考虑到抑制剂1，2-二氯乙烷的竞争吸附作用，引 入有效总活性位点覆盖率概念，构建包含1，2一二氯乙烷影响因子项的乙烯环氧化宏观动力学模型。采用无梯度反应器进行B 型银催化剂上乙烯环氧化合成环氧乙烷的宏观动力学实验，以单纯形优化方法进行非线性参数估值，建立了与实验数据良好 吻合的B型银催化剂上乙烯环氧化宏观动力学模型。 [关键词]银催化剂；环氧乙烷；乙烯环氧化反应；宏观动力学模型 [文章编号]1000—8144(2015)01—0029—07 [中图分类号]TQ 032．41 [文献标志码]A Maerokineties of Ethylene Epoxidation over B-Type Silver Catalyst Liang Rujun 一．Li Jianwei (1．State Key Laboratory ofChemical Resource Engineering，Beijing University ofChemical Technology，Beijing 100029，China 2．SINOPEC Yanshan Branch of Beijing Research Institute ofChemical Industry，Beijing 102549，China) l Abstract j Possible reaction mechanism for the epoxidation of ethylene to ethylene oxide over the B-type silver catalyst was investigated，in which it was proposed that with the surface chemical reactions as rate—controlling step，the epoxidation reaction would occur between ethylene and non— dissociated adsorbed oxygen on an active site，and the deep oxidation would occur between ethylene and dissociated adsorbed oxygen on the adj acent active sites．Considering the strong competitive adsorption of 1，2-dichloroethane inhibitor，a concept for effective surface coverage was presented and the macro—kinetic model for the ethylene epoxidation over the B-type silver catalyst was established． Macro--kinetic experiments were ca~ied out in a gradientless reactor