CAJ | 학술논문

利用等体积浸渍法制备了不同磷含量的预硫化型NiMo/Al2O3催化剂,并利用XRD、BET、TPR和HRTEM等分析方法对其进行了表征,研究了磷对其加氢脱硫脱氮性能的影响.结果表明,由于预硫化型NiMo加氢催化剂上活性组分和载体的相互作用较弱,MoS2或Ni-Mo-S相主要以TypeⅡ形式存在,磷通过增加MoS2的堆积层数、减小片晶长度提高了MoS2的分散度.TPR结果表明磷仅提高了金属硫化物中Ni-Mo-S相的比例,而对Ni-Mo-S相和体相MoS2中的金属-硫键的键合强度没有影响.NiMoP-1.2催化剂(磷负载量为1.2%)表面MoS2的分散度最高,同时也具有最高的加氢脱硫(HDS)选择性和加氢脱氮(HDN)活性;过高磷含量(NiMoP-1.8,磷负载量为1.8%)则造成MoS2分散度降低,催化剂的比表面积、孔径和孔容也减小,导致其HDS和HDN反应性能下降.
이용등체적침지법제비료불동린함량적예류화형NiMo/Al2O3최화제,병이용XRD、BET、TPR화HRTEM등분석방법대기진행료표정,연구료린대기가경탈류탈담성능적영향.결과표명,유우예류화형NiMo가경최화제상활성조분화재체적상호작용교약,MoS2혹Ni-Mo-S상주요이TypeⅡ형식존재,린통과증가MoS2적퇴적층수、감소편정장도제고료MoS2적분산도.TPR결과표명린부제고료금속류화물중Ni-Mo-S상적비례,이대Ni-Mo-S상화체상MoS2중적금속-류건적건합강도몰유영향.NiMoP-1.2최화제(린부재량위1.2%)표면MoS2적분산도최고,동시야구유최고적가경탈류(HDS)선택성화가경탈담(HDN)활성;과고린함량(NiMoP-1.8,린부재량위1.8%)칙조성MoS2분산도강저,최화제적비표면적、공경화공용야감소,도치기HDS화HDN반응성능하강.
Phosphorus promoted presulfided NiMo/Al2O3 catalysts were prepared by successive incipient wetness impregnation and characterized by XRD, N2-physisorption, TPR and HRTEM. The effect of phosphorus on the hydrodesulfurization ( HDS )hydrodenitrogenation (HDN) performance of the presulfided NiMo/Al2O3 catalyst was investigated. The results indicate that the main active phase is type Ⅱ MoS2 or Ni-Mo-S phase because of their weak interaction with the support. The incorporation of phosphorus in the catalyst enhances the dispersion of MoS2 particles by increasing the stacking number and reducing the slab length.Phosphorus has no influence on the metal-sulfur bonding energies in the Ni-Mo-S phases and bulk MoS2 , but it increases the proportion of Ni-Mo-S phases in the metal sulfides. NiMoP-1.2 catalyst ( containing 1.2% phosphorus) exhibits high hydrogenation (HYD) selectivity in the HDS of dibenzothiophene (DBT) and high HDN ratio of quinoline, which can be attributed to its high dispersion of the active phase. The HYD activity in HDS and HDN ratio on NiMoP-1. 8 catalyst with excess phosphorus ( 1.8% ) is declined due to the aggregation of MoS2 particles and the decrease of the catalyst surface area.