在固定床连续微型反应装置上研究了选择性加氢脱硫过程中CoMo/γ-Al2O3催化剂上硫醇的生成反应。考察了不同类型硫化物和烯烃对硫醇生成的影响，研究了催化剂上环己烯与H2S的反应规律。实验结果表明，烯烃与H2S反应只生成了硫醇，没有其他硫化物生成。反应产物中硫醇硫的含量不受原料中硫化物种类的影响，但受烯烃结构的影响。空间位阻大的烯烃与H2S反应生成的硫醇较难加氢脱除，导致产物中硫醇硫含量较高。当H2S含量较低时，H2S通过竞争吸附减少了加氢活性位，阻碍了烯烃的加氢反应，从而抑制了环己烯的加氢饱和。继续增大H2S含量，由于H2S与烯烃反应生成的硫醇易脱除，故对环己烯的加氢饱和起到了促进作用。升高温度和增加V（H2）∶V（油）均有利于减少产物中环己硫醇的生成量。%The production of mercaptans from olefins and H2S in selective hydrodesulfurization(HDS) over CoMo/γ-Al2O3 catalyst in a fixed-bed micro-reactor was studied. The effects of the olefins and sulfur compounds on the reactions were investigated,and the reaction between cyclohexene and H2S was analyzed. It was showed that only mercaptans were produced in the reactions between olefins and H2S. The content of mercaptans in the products was not related to the structure of the sulfur compounds,but was affected by the structure of the olefins. The mercaptans produced from olefins with big steric hindrance were hard to be removed,which lead to the increase of the mercaptan content in the products. H2S had an inhibition effect on the olefin hydrogenation due to competitive adsorption decreasing the active sites for the hydrogenation with a lower H2S content. The hydrogenation of cyclohexene was promoted with further increasing the H2S content because of the easy desulfurization. The content of cyclohexanethiol in the products remarkably decreased when temperature rose andV(H2)∶V(oil) increased.
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