金属助剂对Ni/SiO2催化剂苯甲醚加氢脱氧性能的影响

Influence of metallic promoters on the performance of Ni/SiO2 catalyst in the hydrodeoxygenation of anisole

  • 摘要: 采用等体积浸渍法制备了Ni/SiO2及Ni与金属助剂MM=Fe、Co、Cu、Zn及Ga)物质的量比为30的Ni基双金属催化剂(记作Ni30M/SiO2),利用H2-TPR、XRD、H2化学吸附、NH3-TPD以及N2物理吸附-脱附等手段对催化剂进行了结构表征,研究了不同助剂对催化剂结构与苯甲醚加氢脱氧性能影响。结果发现,金属助剂影响了催化剂前驱体中镍物种的还原性能,表明金属助剂及镍之间存在一定相互作用。Ni30M/SiO2中Ni-M双金属晶粒粒径和Ni/SiO2中金属Ni晶粒粒径相近。由于表面张力较低的金属会在双金属晶粒表面富集,Ni30M/SiO2的H2化学吸附量不同程度地低于Ni/SiO2。另外,Ni30M/SiO2催化剂的酸量(尤其较弱酸中心酸量)高于Ni/SiO2。在300℃、常压、苯甲醚质量空速1.0 h-1及H2与苯甲醚物质的量比为25:1条件下考察了各催化剂苯甲醚的加氢脱氧性能。Ni30M/SiO2上苯甲醚转化率不同程度低于Ni/SiO2,原因在于Ni30M/SiO2催化剂H2化学吸附量较低。Ga及Zn改性催化剂上三苯(包括苯、甲苯及二甲苯)选择性分别为81.7%和76.8%,高于Ni/SiO2(71.5%),且Ni30Ga/SiO2及Ni30Zn/SiO2上三苯收率(分别为65.0%及63.8%)高于或接近于Ni/SiO2(63.7%)。Ni/SiO2及Ni30M/SiO2催化剂中,Ni30Zn/SiO2具有较高甲基转移能力及较低C-C键氢解活性。从提高碳收率、降低耗氢量角度而言,Ni30Zn/SiO2具有较佳的加氢脱氧性能,与Ni和Zn之间作用及Zn亲氧性高于Ni有关。

     

    Abstract: Ni/SiO2 and Ni-based bimetallic Ni30M/SiO2 catalysts (with a Ni/M atomic ratio of 30; M=Fe, Co, Cu, Zn and Ga) were prepared by the impregnation method and characterized by the means of H2-TPR, XRD, H2 chemisorption, NH3-TPD and N2 sorption; the effect of M promoters on the structure and performance Ni-based catalysts in the hydrodeoxygenation of anisole was investigated. The results indicated that the metallic promoters have a significant influence on the reducibility of nickel species, due to the interaction between M and Ni species, although the sizes of Ni-M bimetallic crystallites in Ni30M/SiO2 are similar to that of Ni crystallite in Ni/SiO2. Because of the interaction between Ni and M and the enrichment of certain M promoters on the surface of Ni-M bimetallic particles, the adsorption quantity of H2 on Ni30M/SiO2 is lower than that on Ni/SiO2. In addition, the Ni30M/SiO2 catalysts also have more acid sites (especially the weak ones) than Ni/SiO2. For the hydrodeoxygenation of anisole under 300℃, 0.1 MPa, weight hourly space velocity (WHSV) of anisole of 1.0 h-1 and H2/anisole molar ratio of 25, the Ni30M/SiO2 catalysts exhibit lower anisole conversion than Ni/SiO2, probably due to the lower H2 uptakes on the bimetallic catalysts. However, Ni30Ga/SiO2 and Ni30Zn/SiO2 give much higher selectivities to BTX (benzene, toluene and xylene) (81.7% and 76.8%, respectively) than Ni/SiO2 (71.5%). Meanwhile, Ni30Zn/SiO2 exhibits higher activity in methyl transfer and lower activity in C-C bond hydrogenolysis than other catalysts; owing to the high oxophilicity of Zn, from the aspects of increasing carbon yield and reducing H2 consumption, Ni30Zn/SiO2 is probably an appropriate catalyst in hydrodeoxygenation.

     

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