Pd助剂用于Ni基环戊二烯加氢催化剂的研究

Study on Pd auxiliary used in Ni-based cyclopentadiene hydrogenation catalyst

采用等体积浸渍法制备了以Al_(2)O_(3)-TiO_(2)复合氧化物为载体、Ni为主活性组分、Pd为助活性组分的负载型催化剂Pd-Ni/Al_(2)O_(3)-TiO_(2)。利用N2吸附-脱附、XRD、H_(2)-TPR、SEM等方法对催化剂进行表征,并在固定床微反实验装置上考察了Ni基催化剂助剂、Pd源、Pd负载量等对环戊二烯选择加氢制环戊烯反应性能的影响。实验结果表明,催化剂的Ni含量为17.5%(w)、Pd含量为0.3%(w)、比表面积为89 m^(2)/g、孔体积为0.35 mL/g、最可几孔径为12.6 nm时,Pd-Ni/Al_(2)O_(3)-TiO_(2)具有最佳反应性能;在反应温度40℃、反应压力0.40 MPa、氢/烃摩尔比1.2、新鲜进料体积空速1.5 h^(-1)的工艺条件下,环戊二烯转化率为95.4%,环戊烯选择性为94.5%,催化剂具有良好的加氢活性和稳定性。

In this paper,a supported catalyst Pd-Ni/Al_(2)O_(3)-TiO_(2)was prepared by equal volume impregnation method using Al_(2)O_(3)-TiO_(2)composite oxide as the carrier,Ni as the main active component,and Pd as the auxiliary active component.The catalyst was characterized through N2 adsorption-desorption,XRD,H_(2)-TPR,SEM,and the effects of Ni-based catalyst auxiliary,Pd source,and Pd loading amount on the reaction of selective hydrogenation of cyclopentadiene to cyclopentene were investigated on a fixed bed micro-reaction device.The experimental results show that when the Ni content is 17.5%(w),the Pd content is 0.3%(w),the specific surface area is 89 m^(2)/g,the pore volume is 0.35 mL/g,and the maximum pore size is 12.6 nm,Pd-Ni/Al_(2)O_(3)-TiO_(2)has the best reaction performance.Under the process condition of reaction temperature 40℃,reaction pressure 0.40 MPa,hydrogen/hydrocarbon molar ratio 1.2,and volume space velocity of fresh feed 1.5 h^(-1),the conversion of cyclopentadiene is 95.4%and the selectivity of cyclopentene is 94.5%,indicating that the catalyst has good hydrogenation activity and stability.