新型柴油HDN催化剂的制备与性能研究

Preparation and performance evaluation of a new type of catalysts for the hydrodenitrogenation of diesel

采用改进的溶胶凝胶法制备的TiO2-ZrO2-SiO2三元复合载体并负载磷化钼制备了MoP/TiO2-ZrO2-SiO2新型加氢脱氮催化剂.以喹啉为模型化合物,考察催化剂的加氢脱氮性能,得出n(Ti)∶n(Zr)∶n(Si)为6∶1∶10时复合载体催化剂的催化性能最好.由BET的结果可知,T6Z1S10复合载体具有较大的比表面积和孔径.XRD衍射峰中锐钛矿特征峰宽而尖锐,趋于完善.确定了反应的最佳工艺条件:温度380℃,空速2.0 h-1,压力3.0 MPa,φ(氢)∶φ(油)为500.原位还原法制备磷化钼催化剂,还原条件对加氢活性影响较大,确定最佳原位还原条件为:升温速率2℃.m in-1,还原气流速60 mL.m in-1,还原压力为0.5 MPa,还原终温为600℃.

The ternary composite oxide TiO2-ZrO2-SiO2 is prepared by sol-gel method,and it loads molybdenum phosphide to form a new type of hydrodenitrogenation catalysts.Using quinoline as the objective compound,the hydrodenitrogenation performance of the catalysts is evaluated by laboratory experiments.The results show that of the catalysts,the hydrodenitrogenation performance of the composite carrier T6Z1S10 is the best,in which the substance amount ratio of Ti,Zr to Si is 6∶1∶10.The BET result shows that T6Z1S10 is of larger specific surface area and pore diameter.XRD analysis shows that there is the characteristic peak of anatase phase in the XRD of all the composite catalysts,and it is wide and sharp.The optimal dydrodenitrogenation reaction conditions are determined:the reaction temperature of 380 ℃,LHSV of 2 h-1,the reaction pressure of 3.0MPa,and the volume ratio of hydrocarbon to oil of 500.The optimal in-situ reduction conditions are the heating rate of 2 ℃/min,the H2 flow rate of 60 mL/min,the reduction pressure of 0.5 MPa,and the reduction temperature of 600 ℃.