原油深度加氢复合多金属硫化物催化剂的制备方法

Preparation methods of mixed metal sulfide catalysts for deep hydrogenation of crude oils

复合多金属硫化物(MMS)催化剂主要用于原油的深度加氢,用于生产高十六烷值、低硫和低芳族化合物柴油。MMS催化剂包含Ni Mo S、Ni WS、Ni Mo O、Ni WO、Ni Mo WS和Zn Mo WS催化剂等。综述MMS催化剂中二元复合金属硫化物催化剂和三元复合金属硫化物催化剂的制备方法,采用二步法即添加有机物作孔成形剂先制得催化剂前驱体,再由前驱体制得的MMS催化剂结构更松散,具有较大的比表面积(90 m2·g-1)和大孔容(大于0.3 cm3·g-1),因而具有更好的催化活性。对比不同MMS催化剂对重质柴油、焦油等的加氢裂解、加氢脱硫和加氢脱氮性能,认为Ni Mo W三元复合金属硫化物催化剂(50%Ni25%Mo25%W)的活性最优。

Mixed metal sulfide catalyst（ MMS） catalysts are mainly used for deep hydroprocessing of refractory crudes to produce diesel oil with higher cetane number,lower sulfur and lower aromatic compounds. MMS catalysts include Ni Mo S,Ni WS,Ni Mo O,Ni WO,Ni Mo WS and Zn Mo WS,etc. The preparation methods of MMS catalysts,including bi-metallic sulfide catalysts and tri-metallic sulfide catalysts,were summarized in this paper. The catalyst precursors were prepared by adding organic compounds as pore forming agents,and then the catalysts were prepared. The catalysts prepared by the two-steps method possessed dispersive structure. The attained catalyst with BET specific surface area of90 m2·g-1and pore volume of 0. 3 cm3·g-1exhibited better catalytic activity. Compared with other several MMS catalysts,the hydrocracking,hydrodesulfurization and hydrodenitrification activities of Ni Mo W（ 50mol% Ni,25mol% Mo,25mol% W） tri-metallic sulfide catalysts for processing heavy diesel oil and tar were the best.