磷含量对非负载型Ni-Mo-W加氢处理催化剂性能影响的研究  

Effects of phosphorus content on performance of unsupported Ni-Mo-W hydrotreating catalysts

作　　者：李鹤鸣[1] 李东胜[1] 富玉[1] 李晓鸥[1] 

机构地区：[1]辽宁石油化工大学化学化工与环境学部石油化工学院,辽宁抚顺113001

出　　处：《天然气化工—C1化学与化工》2016年第6期72-77,共6页Natural Gas Chemical Industry

摘　　要：Ni-Mo-W为活性金属组分,采用水热法制备了一系列催化剂前体,然后通过用磷酸二氢铵容液浸渍制得改性的NiMo-W-P催化剂。采用XRD、BET、NH_3-TPD、HRTEM和GC-PFPD等手段对制备的催化剂进行了表征,考察了磷含量对催化剂在裂化柴油加氢处理中的加氢脱硫活性的影响。结果表明,磷的最佳浸渍量为质量分数1.5%,磷改性使L酸B酸酸量增加,金属Mo更容易形成高堆垛层数的MoS_2片晶结构,延长催化剂使用寿命,提高加氢脱硫活性。在T=280℃、p(H_2)=4.0MPa、LHSV=2.0h-1和Vg(H_2)/VL(oil)=500条件下,可将催化裂化柴油中的4-甲基二苯丙噻吩,4,6-二甲基二苯丙噻吩,2,4,6-三甲基二苯丙噻吩深度脱除,加氢脱硫率由93%提高到99.78%,硫含量由4000μg/g降至8.8μg/g。Ni-Mo-W catalysts were prepared by hydrothermal reaction method, which were modified by ammonium dihydrogen phosphate solution impregnation to obtain the Ni-Mo-W-P catalysts. The catalysts were characterized by XRD, BET, NH3-TPD, HRTEM and GC-PFPD, and the effect of phosphorus amount on the activity of catalysts in the hydrodesulfurization of catalytic cracking diesel （FCC） was investigated. The results showed that the optimum phosphorus content was 1.5% by mass. The addition of phosphorus could increase the L and B acid amounts, make the Mo species more easy to form the high stacking layer of MoS2, prolong the service life of catalyst and increase hydrodesulfurization activity. Under the reaction conditions： 280℃, hydrogen pressure of 4MPa, LHSV of 2.0h1 and hydrogen （G）/oil （L） volume ratio of 500, the 4-MDBT, 4,6-DMDBT and 2,4,6-TMDBT in FCC diesel could be depthly removed over the phosphorus modified catalyst, increaing desulfurization rate from 93% to 99.78% and decreasing sulphur content from 4000μg/g to 8.8μg/g.

关 键 词：非负载型催化剂 Ni-Mo-W-P 磷含量 柴油 加氢脱硫 

分 类 号：TQ519[化学工程] TQ426