二甲基二硫醚对Ni/Al<sub>2</sub>O<sub>3</sub>催化剂加氢性能的影响

冯军鹏; 张晔; 吕占军; 李学宽

二甲基二硫醚对Ni/Al₂O₃催化剂加氢性能的影响

1.
中国科学院山西煤炭化学研究所, 山西太原 030001;
2.
中国科学院大学, 北京 100049

基金项目: 中国科学院战略性先导科技专项（A类）（XDA07020400）；中国科学院山西煤炭化学研究所知识创新工程（ylsc5c1581）。

详细信息

通讯作者:
李学宽，张晔，Tel：0351-4046547，Fax：0351-4041153，E-mail：lxk@sxicc.ac.cn。

中图分类号: TQ426.95
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出版历程
- 收稿日期: 2014-01-28
- 修回日期: 2014-03-31
- 刊出日期: 2014-07-30

Study of poisoning effect of dimethyl disulfide on Ni/Al₂O₃ catalyst for hydrogenation

1.
Institute of Coal Chemistry, Chinese Academy of Sciences, Taiyuan 030001, China;
2.
University of Chinese Academy of Sciences, Beijing 100049, China

摘要

摘要: 考察了二甲基二硫醚（CH₃SSCH₃）对Ni/Al₂O₃催化剂上苯、环己烯和苯乙烯加氢活性的影响，并采用BET、XRD、H₂-TPR、XPS、SEM和EA等手段对催化剂进行表征。实验结果表明，在CH₃SSCH₃存在下，Ni/Al₂O₃催化剂对苯和环己烯加氢迅速失活，且环己烯加氢对CH₃SSCH₃的耐硫性要略强于苯加氢，而苯乙烯中共轭烯烃的加氢转化率则维持100%长时间不变。CH₃SSCH₃的影响顺序为芳环>单烯烃>共轭烯烃。此外，通过设计实验研究了CH₃SSCH₃对催化剂的毒化机理，发现CH₃SSCH₃分子首先吸附在催化剂的表面，并发生氢解生成甲烷随尾气逸出，故CH₃SSCH₃分子中碳对催化剂的失活影响较小，而留下的硫原子则与镍活性组分发生相互作用，毒化催化剂。
- 二甲基二硫醚 /
- Ni/Al₂O₃ /
- 加氢反应 /
- 失活机理
Abstract: Poisoning effect of dimethyl disulfide (CH₃SSCH₃) on Ni/Al₂O₃ catalysts for hydrogenation of benzene, cyclohexene and styrene was studied. The structures and properties of the catalysts were investigated by means of BET, XRD, H₂-TPR, XPS, SEM and EA. Results indicated that with the existence of CH₃SSCH₃, Ni/Al₂O₃ catalysts quickly deactivated for benzene and cyclohexene hydrogenation, while the activity for styrene hydrogenation remained well. The sulfur tolerance of Ni/Al₂O₃ catalysts for cyclohexene hydrogenation was little better than that of benzene hydrogenation. The conversion of conjugated double bond of styrene can keep 100% for a long time. For hydrogenation reactions, the poisoning effects of CH₃SSCH₃ over Ni/Al₂O₃ were in the order of aromatic nucleus>monoene>conjugated alkene. In addition, poisoning mechanism of CH₃SSCH₃ for Ni/Al₂O₃ catalyst was also discussed. CH₃SSCH₃ molecules were firstly adsorbed on the surface of catalyst and then dissociated to CH₄ under the function of hydrogen and catalyst. It is concluded that the toxicity of carbon in CH₃SSCH₃ for catalysts is neglectful and remaining sulfur is the dominant poisoning factor by the interaction with active component.
- dimethyl disulfide /
- Ni/Al₂O₃ /
- hydrogenation /
- poison

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