体相加氢精制催化剂的硫化工艺

Sulfurization technology for bulk phase hydrotreating catalyst

分别以CS2和甲硫醚(DMS)为硫化剂对氧化态体相Ni-Mo-W加氢催化剂进行预硫化得到硫化态催化剂,通过XRD、HRTEM、XPS等方法分析了不同硫化剂对催化剂结构和性能的影响,并考察了不同硫化工艺条件对硫化态催化剂加氢脱硫性能的影响。实验结果表明,以DMS为硫化剂时,催化剂中金属硫化物的结晶度较高,MoS2/WS2片层堆积层数较多、长度较短,催化剂中低价态的 Mo^4+和 W^4+较多,催化剂的硫化效果较好;适宜的硫化条件为330 ℃、6 MPa、空速 3 h^-1、氢油体积比 600∶1,在该条件下硫化后的催化剂在 340 ℃、6 MPa、空速 2 h^-1、氢油体积比 600∶1 的反应条件下,对高硫高氮柴油的脱硫率和脱氮率均可达到 99.5%以上。

The sulfided Ni-Mo-W bulk phase hydrotreating catalysts were obtained by presulfurization of the oxide catalysts using CS2 or dimethyl sul de(DMS) as sulfurizing agent,and characterized by XRD,HRTEM and XPS. The effects of sulfurizing agent and sulfurization conditions on catalyst structure and hydrogen desulfurization performance were studied. It revealed that the sul de catalyst showed more highly-crystallized metal sul des,more stacked and shorter MoS2/WS2 layers when DMS was used as the sulfurizing agent. More Mo^4+ and W^4+ with lower valence were detected in the catalyst sul ded by DMS,which further showed DMS was a more effective sulfurizing agent. The optimum sulfurization conditions were 330 ℃,6 MPa,LHSV 3 h^-1 and H2/oil volume ratio 600. Under the above conditions,the sulfur and nitrogen removal ef ciency was above 99.5% for diesel oil with high sulfur and nitrogen content when the reaction conditions were 340 ℃,6 MPa,LHSV 2 h^-1 and H2/oil volume ratio 600.