Ni-P/TiO2非晶态催化剂对α-蒎烯加氢的性能  

Study on the properties of amorphous catalyst Ni-P/TiO2 for hydrogenation of α-pinene

作　　者：蒋丽红[1] 宋爽爽 潘登[1,2] 王亚明 刘坤[1] 郑燕娥[1] JIANG Lihong;SONG Shuangshuang;PAN Deng;WANG Yaming;LIU Kun;ZHENG Yan’e(Faculty of Chemical Engineering,Kunming University of Science and Technology,Kunming 650500,Yunnan,China;CSPC Zhongqi Pharmaceutical Technology Co.,Ltd.,Shijiazhuang 050051,Hebei,China)

机构地区：[1]昆明理工大学化学工程学院,云南昆明650500 [2]石药集团中奇制药技术有限公司,河北石家庄050051

出　　处：《化工进展》2019年第6期2768-2775,共8页Chemical Industry and Engineering Progress

基　　金：国家自然科学基金(21266012);国家自然科学基金联合重点支持项目(U1202265)

摘　　要：采用化学还原法制备Ni-P/TiO2非晶态催化剂,以α-蒎烯加氢反应为探针反应,考察了催化剂制备条件对其催化性能的影响,得到适宜的制备条件为载体与NiCl2·6H2O质量比为3∶1,P/Ni摩尔比为2.5∶1,反应温度为25℃,pH为11。结果表明:该条件下制备的催化剂对α-蒎烯加氢具有较高的催化活性,α-蒎烯转化率为99.89%,顺式蒎烷选择性为98.48%,收率为98.37%,且可重复使用8次。以XRD、BET、DSC、XPS、TEM为表征手段,对催化剂失活前后的结构及形貌进行了分析,结果表明:新鲜催化剂为粒径均一的球形颗粒,粒径约为100nm,分散性较好,引入TiO2有效提高了Ni-P粒子的热稳定性,将其晶化温度分别提高了78℃、190℃和115.1℃,而失活催化剂的分散度、Ni^0含量均有下降,出现了活性组分流失、氧化及团聚等现象,这可能是导致催化剂失活的主要原因。Ni-P/TiO2 amorphous catalyst was prepared by chemical reduction method. By taking the α-pinene hydrogenation as a probe reaction, the effects of the preparation conditions on the catalytic properties were investigated. The suitable preparation conditions were as follows: TiO2/NiCl2·6H2O mass ratio 3∶1, P/Ni molar ratio 2.5∶1, reaction temperature 25℃ and pH 11. Under these conditions, the catalyst showed excellent catalytic activity in the hydrogenation of α-pinene. The conversion of α-pinene,the enantioselective of cis-pinane and were 99.89%, 98.48% and 98.37%, respectively. And the catalyst could be reused for 8 times. XRD, BET, DSC, XPS and TEM were employed to investigate the structure difference of the catalysts before and after deactivation. The results showed that the fresh catalyst was spherical and well dispersed with uniform particle size of about 100 nm. The introduction of TiO2 effectively had improved the thermal stability of the Ni-P particles. The crystallization temperature increased by 78℃, 190℃ and 115.1℃. However, the deactivated catalysts exhibited deteriorated dispersion, and reduced content of Ni^0, which was considered as the main reasons for the deactivation.

关 键 词：非晶态催化剂 Ni-P/TiO2 Α-蒎烯 加氢 选择性 失活 

分 类 号：TQ333[化学工程—橡胶工业]