分散型催化剂的硫化对悬浮床加氢裂化反应的影响

INFLUENCE OF SULFURIZATION OF DISPERSED CATALYST ON SLURRY BED HYDROCRACKING

在反应釜中考察了单质Mo的硫化对氘代异丙苯加氢裂化的影响,考察了Ni(NO3)2的硫化对叔丁基苯和正丁基苯加氢裂化的影响和以Ni(NO3)2为主催化剂的分散型催化剂的硫化对渣油悬浮床加氢裂化的影响。结果表明,在Mo作用下,氘代异丙苯侧链上的氢与环境中的氢发生置换的速率较快;而在Mo+CS2作用下,苯环上的氢与环境中的氢发生置换的速率较快。Ni(NO3)2催化剂的硫化对叔丁基苯和正丁基苯分子中氢与环境中氢的置换产生类似的影响。催化剂的硫化对不易发生自由基热反应的氘代异丙苯和叔丁基苯的氢解裂化反应和缩合反应都有促进作用,对易于发生自由基热反应的正丁基苯的缩合反应同样具有促进作用,但对正丁基的自由基裂化反应和氢解裂化反应具有抑制作用。以Ni(NO3)2为主催化剂的分散型催化剂的硫化抑制了渣油的裂化,促进了甲苯不溶物的生成,因此,悬浮床加氢裂化过程中催化剂的硫化并不是必须的过程。

The influences of sulfurization of Ni（NO3）2 sulfurization of Mo on hydrocracking of iso-propylbenzene-D12, on hydrocracking of tert-butylbenzene and butylbenzene, and sulfurization of dispersed catalyst with Ni（NO3）2 as the main component on hydrocracking of two atmospheric residues were examined in the batch reactor. The exchange of branch chain hydrogen in iso-propylbenzene-D12 molecule with atmospheric hydrogen was prompted when Mo was used. The exchange of hydrogen on aromatic ring with atmospheric hydrogen was faster when Mo was sulfurized. The sulfurization of Ni（NO3）2 had the same influence on the exchange of hydrogen in tert-butylbenzene and butylbenzene molecules with atmospheric hydrogen. The results were different according to the molecular structure of reactants. As regards the reactants which were not easy to perform radical thermal cracking reactions, such as iso-propylbenzene and tert-butylbenzene, the sulfurization of catalyst prompted their hydrogenolysis cracking reaction and condensation reaction. Different from tert-butylbenzene, the radical thermal cracking reaction and the hydrogenolysis cracking reaction of butylbenzene were restricted, while the condensation reaction was prompted with the sulfurization of catalyst. On slurry bed hydrocracking of residues, the effect of sulfurization catalyst was similar to that on butylbenzene, that is, the cracking reaction was restricted and the condensation reaction was prompted. Therefore, the sulfurazation process for dispersed catalyst in hydrocracking of residue may be not a necessary procedure.