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Intrinsic reaction kinetics of P2O5-MoO3/Al2O3 catalyzed 1-butene and hudrogen sulfide to synthesize sec-butyl mercaptan

ZHANG Binhao,ZHANG Zekai,LI Linlin,CHEN Yinfei   

  1. Institute of Catalytic Reaction Engineering,School of Chemical Engineering and Materials Science,Zhejiang University of Technology,Hangzhou 310014,Zhejiang,China
  • Online:2014-02-05 Published:2014-02-05

1-丁烯与H2S反应制备仲丁硫醇动力学研究

张斌浩,张泽凯,李林林,陈银飞   

  1. 浙江工业大学化学工程与材料学院催化反应工程研究所,浙江 杭州 310014

Abstract: P2O5-MoO3/Al2O3 catalyst was prepared by the incipient-wetness impregnation method to catalyze the synthesis reaction of sec-butyl mercaptan from 1-butene and H2S. After eliminating the influence of internal and external diffusion,the intrinsic reaction kinetics of 1-butene and H2S on P2O5-MoO3/Al2O3 catalyst was studied. The effects of reaction temperature,1-butene partial pressure and H2S partial pressure on reaction rate were investigated under the conditions of 120—180 ℃ and 0.2 MPa. The catalytic mechanism of reaction of 1-butene and H2S on the P2O5-MoO3/Al2O3 catalyst was discussed. The intrinsic reaction mechanism of 1-butene and H2S on P2O5-MoO3/Al2O3 catalyst was dual site mechanism. 1-butene and H2S were co-adsorbed on the catalyst surface to react and form sec-butyl mercaptan and the surface reaction step was the rate-limiting step. According to the dual site mechanism the rate of reaction was derived: Pre-exponential factor k0=3.3×109,activation energy Ea=60.78 kJ/mol.

Key words: alumina, catalysis, reaction kinetics, surface reaction, rate limiting step

摘要: 以Al2O3为载体,采用等体积浸渍法制备了P2O5-MoO3/Al2O3催化剂。在排除内外扩散影响的条件下,研究了1-丁烯与H2S在P2O5-MoO3/Al2O3催化剂上反应生成仲丁硫醇反应的本征动力学。在反应温度120~180 ℃、压力0.2 MPa的条件下,考察了反应温度、1-丁烯分压和硫化氢分压对反应速率的影响。对1-丁烯在P2O5-MoO3/ Al2O3催化剂上的催化硫化机理进行了探讨。实验结果表明,1-丁烯与H2S在P2O5-MoO3/Al2O3催化剂上的反应机制是1-丁烯与H2S发生共吸附后由表面反应控制的二级催化反应,根据该机理得到反应动力学方程为 根据实验数据得到其指前因子k0=3.3×109,活化能Ea=60.78 kJ/mol。

关键词: 二氧化二铝, 催化作用, 反应动力学, 表面反应, 速率控制步骤

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