摘要
以三氧化钼、硝酸钴、L-半胱氨酸为原料,水热法一步制得分散型Co促进的MoS_(2)(Co-Mo-S)催化剂。采用XRD、XPS、ICP-OES、Raman、N_(2)物理吸附和HRTEM等手段对催化剂进行表征,并在高压釜式反应器中,以二苯并噻吩(DBT)为模型化合物考察了Co-Mo-S催化剂的加氢脱硫性能。结果表明:当Co/Mo摩尔比不大于1时,Co-Mo-S催化剂仍保持2H-MoS_(2)的层状结构,S-Mo(Co)-S片层层间距为0.94 nm,平均层数为4层,部分Co取代S-Mo-S层中的Mo形成“Co-Mo-S”相。相比于水热制备的MoS_(2),钴的加入对S-Mo(Co)-S片层堆积层数没有影响,但片层长度变短。悬浮床加氢评价结果表明:Co-Mo-S-1催化剂上的DBT的转化率和联苯选择性分别为MoS_(2)催化剂上的1.8倍和7.3倍。当Co/Mo摩尔比不大于1时,Co-Mo-S催化剂上DBT的转化率和直接脱硫路径的选择性与“Co-Mo-S”相的含量呈现正相关的关系,说明“Co-Mo-S”相是主要活性位。
Dispersed Co promoted MoS_(2)(Co-Mo-S)catalyst was prepared by hydrothermal method with molybdenum trioxide,cobalt nitrate and L-cysteine as raw materials.The Co-Mo-S catalyst was characterized by XRD,XPS,ICP-OES,Raman,N_(2) physisorption and HRTEM,and the hydrodesulfurization performance was investigated with dibenzothiophene(DBT)as a model compound in the high pressure tank reactor.The results show that when Co/Mo molar ratio is not greater than 1,Co-Mo-S catalyst still maintains the layered structure of 2H-MoS_(2),the S-Mo(Co)-S layer spacing is 0.94 nm,the average layer number is 4,and partial Co replaces Mo in S-Mo-S layer to form“Co-Mo-S”phase.Compared with MoS_(2) prepared by hydrothermal method,the addition of cobalt has no effect on the the stacking layer number of S-Mo(Co)-S,but the length of the lamellar layer becomes shorter.The evaluation results of the slurry bed hydrogenation process reveal that the conversion rate of DBT on Co-Mo-S-1 catalyst and the selectivity of biphenyl are 1.8 and 7.3 times of those on MoS_(2) catalyst,respectively.When the Co/Mo molar ratio is not greater than 1,the conversion rate of DBT on Co-Mo-S catalyst and the selectivity of direct desulfuration path are positively correlated with the content of“Co-Mo-S”phase,indicating that“Co-Mo-S”phase serves as the primary active site.
作者
王小平
马怀军
王冬娥
田志坚
WANG Xiaoping;MA Huaijun;WANG Donge;TIAN Zhijian(Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023, China;College of Chemical Engineering, University of Chinese Academy of Sciences, Beijing 100049, China)
出处
《石油学报（石油加工）》
EI
CAS
CSCD
北大核心
2021年第6期1287-1297,共11页
Acta Petrolei Sinica(Petroleum Processing Section)
基金
新疆自治区重点研发计划项目(2017B02007-1,2017B02007-2)基金资助。
