丁硫醚在Ce-HZSM-5分子筛上的转化反应研究  

Study on transformation reaction of n-butyl sulfide over Ce-modified HZSM-5 zeolite

作　　者：李虎[1] 罗立文[1] 于慧征[1] 吕仁庆[1] 夏道宏[1] 

机构地区：[1]中国石油大学化学化工学院重质油国家重点实验室,山东东营257061

出　　处：《化工科技》2006年第1期5-8,共4页Science & Technology in Chemical Industry

基　　金：重质油国家重点实验室开放课题(E030407-2);教育部优秀青年教师资助计划项目(20011863)。

摘　　要：开发可降硫的催化剂和助剂,既可以降低汽油中硫化物含量,又不损失汽油收率、不降低汽油辛烷值已成为新的研究思路。作者以Ce改性的HZSM-5沸石为催化剂,在固定床微型反应器中研究了丁硫醚的催化转化反应。结果表明:Ce改性后的HZSM-5对丁硫醚的脱除具有较高的活性及稳定性;硫化氢的量得到上升,并趋于稳定;丁硫醚转化率明显提高,在350℃下,Ce3+交换量为1.51%时,丁硫醚基本完全转化;而丁硫醚的裂解副产物四氢噻吩(THT)的量有增大趋势。同时探讨了丁硫醚的反应历程,认为烷基硫醚类化合物裂解过程中,碳硫键的断裂生成类硫醇物种的一步是其裂解关键步骤。To develop the catalysts and additive for decreasing sulfur, which may not only decrease sulfur compounds contents of gasoline, hut also not decrease the yield and octane value of gasoline , had become new research route. The catalytic desulfurization rule of model organic compound n-butyl sulfide over Cemodified HZSM-5 （molar ratio of silica-to-alumina is 25） was studied in fixed bed micro-reactor. The experimental results show that there are higher catalytic activities and stabilities for the desulfurization of n-butyl＂ sulfide, higher hydrogen sulfide and obviously higher n-butyl sulfide conversion when Ce-modified HZSM-5 zeolite catalyst is applied in the experiment; n-butyl sulfide is converted completely into H2S and there is an increase tendency for cracking byproduct tetrahydrothiophene while the reaction temperature is 350 ℃ and the Ce203 content in Ce-HZSM-5 zeolite catalyst is 1.51%. At the same time, reaction mechanism of nbutyl sulfide is investigated, it is found that the key step of cracking reaction is the rupture of S-C bond to create analogous mercaptan intermediate in the cracking course of alkyl-sulfide compounds.

关 键 词：丁硫醚 HZSM-5 Ce改性 脱硫 历程 

分 类 号：TE624[石油与天然气工程—油气加工工程]