石油炼制与化工 ›› 2013, Vol. 44 ›› Issue (12): 46-50.

• 催化剂 • 上一篇    下一篇

硅、磷复合助剂对MoNiP/Al2O3催化剂性质的影响

张艳侠,包洪洲,高鹏,付秋红   

  1. 中国石化抚顺石油化工研究院
  • 收稿日期:2013-04-16 修回日期:2013-06-28 出版日期:2013-12-12 发布日期:2013-11-20
  • 通讯作者: 张艳侠 E-mail:dcgzyx311117@126.com

EFFCT OF INCORPORATION WAYS OF PROMOTERS ON MoNi HYDROGENATION CATALYSTS

  • Received:2013-04-16 Revised:2013-06-28 Online:2013-12-12 Published:2013-11-20
  • Contact: Yan-xia ZHANG E-mail:dcgzyx311117@126.com

摘要: 采用两种不同方式加入硅、磷复合助剂,即SiO2在干胶粉的制备过程中加入和P2O5在载体的制备过程中引入(方式 ①)、SiO2和P2O5都在载体的制备过程中引入(方式 ②),制备了含硅、磷复合助剂的MoNiP/Al2O3催化剂,对其进行了BET、H2-程序升温还原(H2-TPR)、拉曼光谱、X射线光电子能谱(XPS)等表征,研究了复合助剂加入方式和加入量对催化剂孔性质、活性金属配位结构、还原性质以及金属与载体之间相互作用的影响。同时,以含有一定量噻吩、哌啶和萘的液体石蜡为原料,采用微型反应器对催化剂的加氢活性进行评价。结果表明:在相同复合助剂加入量的条件下,以方式 ② 加入复合助剂制备的MoNiP/Al2O3催化剂的加氢脱硫活性高于以方式 ① 加入复合助剂时制备的催化剂,但催化剂的加氢脱氮活性却相反。当复合助剂中SiO2/P2O5质量比为2.5时,催化剂的加氢活性最好,催化剂中八面体配位的钼物种所占比例最高,H2-TPR还原峰的耗氢量最大,活性金属钼与氧化铝的相互作用最弱。

Abstract: A batch of Mo-Ni catalysts with different contents of promoters was prepared via two different adding methods, i.e. ①Si was introduced during the formation of dry alumina powder and P2O5 in the preparation of catalyst support; ②Si and P2O5 were added together during the carrier preparation procedure. The catalysts were characterized by BET, H2-TPR, Raman, and XPS. The effect of the adding methods of promoters on the microstructure properties of the catalysts, active metal coordination structure and reducibility of the catalysts, interaction between metal and carrier were investigated. The catalytic performance was evaluated using liquid wax feed containing thiophene, piperidine and naphthalene. It is shown that under the same conditions,the HDS activity of Mo-Ni-P catalysts prepared by the second method is higher than the first one, while the HDN activity is just on the contrary. When the ratio of SiO2/P2O5 is 2.5, the hydrogenation activity of the catalysts, the proportion of octahedral coordinated molybdenum species in the catalysts and the hydrogen consumption during H2-TPR reach to the maximum, meanwhile the interaction between active metal molybdenum and aluminum oxide is the weakest.