MoP/SiO2-TiO2-ZrO2催化喹啉加氢脱氮的反应动力学

 采用共沉淀法和共浸渍法制备了MoP/SiO₂-TiO₂-ZrO₂催化剂。以喹啉为模型化合物，在固定床微反应器中考察了MoP/SiO₂-TiO₂-ZrO₂催化剂的加氢脱氮（HDN）活性；在氢分压2~5 MPa、反应温度300~400℃、氢/油体积比200~800和体积空速2~8 h^-1条件下，建立了其HDN的反应动力学模型。结果表明，MoP/SiO₂-TiO₂-ZrO₂催化喹啉HDN反应中，脱氮率随着反应温度升高先增加后趋于平缓，喹啉转化率则随着反应温度升高略有降低；脱氮率及转化率均随着氢分压增加而增加，随着体积空速增加而降低，而随着氢/油体积比增加变化不大。喹啉HDN的反应动力学模型为带有氮化物吸附的拟一级反应动力学模型，并结合Levenberg-Marquardt(L-M)算法对模型参数进行优化求解。将喹啉HDN反应的脱氮率实验值与模型计算值进行了比较，两者吻合较好，平均相对误差为6.87%。

Reaction Kinetics of Quinoline Hydrodenitrogenation Over MoP/SiO2-TiO2-ZrO2

MoP/SiO2-TiO2-ZrO2 catalyst was prepared by co-precipitation method and co-impregnation method.The performance of MoP/SiO2-TiO2-ZrO2 catalyst in HDN reaction was investigated in a fixed micro-reactor with quinoline as model compound.The kinetic model of HDN at the hydrogen pressure of 2-5 MPa,reaction temperature of 300-400℃,volume ratio of hydrogen/oil of 200-800,and liquid hourly space velocity of 2-8 h-1 was obtained.The results showed that in quinoline HDN reaction the HDN ratio steeply increased,then tended to flatten while the conversion of quinoline decreased slightly with the increase of reaction temperature,both the HDN ratio and the conversion of quinoline increased with the increase of hydrogen partial pressure,decreased with the increase of liquid hourly space velocity,and had little change with the increase of hydrogen/oil volumetric ratio.The kinetic model of quinoline HDN was a pseudo first-order kinetic model with adsorption constant,and the parameters of the kinetic model were calculated by the Levenberg-Marquardt(L-M) method.Comparing the experimental values of HDN ratio of quinoline with the calculated results,it was found that the experimental data were in good agreement with the calculated results with the average relative error of 6.87%.