含助剂Ni(Co)磷化钨催化剂柴油加氢精制性能

HYDROTREATING PERFORMANCE OF DIESEL OIL OVER TUNGSTEN PHOSPHIDE CATALYSTS CONTAINING PROMOTER OF NICKLE AND COBALT

采用共浸渍和氢气程序升温还原的方法,以γ-Al2O3为载体,分别制备了WO3负载量为30%的含助剂Ni、Co和Ni/Co双助剂的磷化钨催化剂,对催化剂进行了XRD、BET和TG表征,评价了催化剂的柴油HDS和HDN活性。结果表明,Co和Ni均对磷化钨催化剂催化柴油HDS反应有助催化作用;而加入Co和适量的Ni对磷化钨催化剂催化柴油HDN反应有利。反应温度为360℃时,分别加有5%质量分数助剂Ni和助剂Co的2个磷化钨催化剂上柴油HDS率分别为59.15%和58.24%,而其上柴油HDN率分别为55.41%和66.79%。Ni、Co质量分数分别为3%和1%的双助剂磷化钨催化剂具有相对最高的柴油HDS和HDN活性,反应温度为360℃时,其HDS与HDN率分别达到62.44%和57.61%。催化剂对柴油的HDS和HDN催化活性不仅与载体表面W物种的磷化程度及活性组分的分散度有关,具有类似-Al-O-W-P结构的物种可能也是影响反应性能的一个重要因素。

With γ-Al2O3 as support, WP catalysts containing Ni, Co promoter or Ni/Co double promoter and WO3 loading of 30% were prepared by impregnation and temperature programmed reduction method, respectively. The WP catalyst samples were characterized by XRD, BET and TG. The HDS and HDN reaction of diesel oil over these WP catalysts were performed in a highpressure micro reactor to evaluate their catalytic activity. It was found that WP catalyst with Co promoter showed higher BET surface area than that with Ni promoter. The WP catalysts with Ni or Co promoter were all favor to HDS reaction of diesel oil, while the WP catalysts with Co promoter or some content of Ni promoter had a positive effect on the HDN reaction of diesel oil. The WP catalysts of Cat-Ni-5 （Containing 5% mass fraction of Ni） and Cat-Co-5 （Containing 5% mass fraction of Co） gave 59.15% and 58.24% of HDS rate, and 55.41% and 66.79% of HDN rate of diesel oil at 360℃, respectively. It was indicated that hydrotreating performance of catalyst containing Ni/Co double promoter was significantly related to the content of Ni and Co. WP catalyst possessing 3% mass fraction of Ni and 1% mass fraction of Co gave 62.44% and 57.61% of HDS and HDN rate of diesel oil at 360℃, respectively. The HDS and HDN activities of WPcatalyst for diesel oil were not only related to the phosphiding extent of W species and dispersion of active species, but also probably related to the mater with similar structure of-Al-O-W-P.