串联双釜连续反应装置中Ru-Co-B/ZrO_2上苯选择加氢制环己烯  

Selective hydrogenation of benzene to cyclohexene in continuous reaction device with two reaction reactors in serie over Ru-Co-B/ZrO_2 catalysts

作　　者：孙海杰[1,2] 李帅辉[1] 张元馨[1] 江厚兵[1] 曲良龙 刘寿长[1] 刘仲毅[1] 

机构地区：[1]郑州大学化学与分子工程学院,河南郑州450001 [2]郑州师范学院化学系,环境与催化工程研究所,河南郑州450044 [3]北京安耐吉能源工程技术有限公司,北京100190

出　　处：《催化学报》2013年第8期1482-1488,共7页

基　　金：国家自然科学基金(21273205);国家科技型中小企业创新基金(10C26214104505);中国博士后科学基金(2012M511125);郑州大学优秀博士论文培育基金~~

摘　　要：采用化学还原法制备了苯选择加氢制环己烯催化剂Ru-B/ZrO2, 考察了Cr, Mn, Fe, Co, Ni, Cu和Zn等过渡金属的添加对Ru-B/ZrO2催化剂性能的影响. 结果表明, 这些过渡金属的添加均可提高Ru-B/ZrO2催化剂中的B含量. B的修饰及第二种金属或金属氧化物的集团效应和配位效应导致Ru-B/ZrO2催化剂活性降低和环己烯选择性升高. 当Co/Ru原子比为0.06时, Ru-Co-B/ZrO2催化剂上反应25 min苯转化率为75.8%时, 环己烯选择性和收率分别为82.8%和62.8%. 在双釜串联连续反应器中和优化反应条件下, Ru-Co-B/ZrO2催化剂使用419 h内苯转化率稳定在40%左右, 环己烯选择性和收率分别稳定在73%和30%左右.A Ru‐B/ZrO2 catalyst for selective hydrogenation of benzene to cyclohexene was prepared using a chemical reduction method.The effects of transition metals such as Cr,Mn,Fe,Co,Ni,Cu,and Zn on the performance of the Ru‐B/ZrO2 catalyst were investigated.It was found that the addition of these transition metals all increased the B content of the Ru‐B/ZrO2 catalyst.The modification of B,the ensemble effect,and the ligand effect of the second metal or metal oxide resulted in a decrease in the activity and an increase in the selectivity for cyclohexene of the Ru‐B/ZrO2 catalyst.When the atomic ratio of Co/Ru was 0.06,the Ru‐Co‐B/ZrO2 catalyst gave a selectivity for cyclohexene of 82.8% and a cyclohexene yield of 62.8% at a benzene conversion of 75.8% at 25 min.Moreover,the benzene conversion was stable at around 40%,and the selectivity for cyclohexene and the cyclohexene yields stabilized at around 73% and 30%,respectively,in 419 h under the optimum reaction conditions in a continuous device with two reactors in series.

关 键 词：苯 选择加氢 环己烯 钌 过渡金属 硼 

分 类 号：TQ231.2[化学工程—有机化工]