Influence of metallic promoters on the performance of Ni/SiO2 catalyst in the hydrodeoxygenation of anisole
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摘要: 采用等体积浸渍法制备了Ni/SiO2及Ni与金属助剂M（M=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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Key words:
- Ni-based catalyst /
- metallic promoter /
- anisole /
- hydrodeoxygenation /
- hydrogenolysis /
- methanation.
1) 本文的英文电子版由 Elsevier 出版社在 ScienceDirect 上出版(http://www.sciencedirect.com/science/journal/18725813). -
图 1 Ni/SiO2及Ni30M/SiO2催化剂前驱体的H2-TPR谱图
Figure 1 H2-TPR profiles of the Ni/SiO2 and Ni30M/SiO2 catalyst precursors
图 2 Ni/SiO2及Ni30M/SiO2催化剂的XRD谱图
Figure 2 XRD patterns of the Ni/SiO2 and Ni30M/SiO2 catalysts
图 3 Ni/SiO2及Ni30M/SiO2催化剂的NH3-TPD谱图
Figure 3 NH3-TPD profiles of the Ni/SiO2 and Ni30M/SiO2
图 5 Ni/SiO2及Ni30M/SiO2催化剂上苯甲醚转化率、三苯收率以及主要产物选择性
Figure 5 Anisole conversion, BTX yield and product selectivity for HDO of anisole on the Ni/SiO2 and Ni30M/SiO2 catalysts
图 6 Ni/SiO2及Ni30M/SiO2催化剂上苯选择性、甲苯和二甲苯总选择性及nB/nTX比值
Figure 6 Selectivity to benzene, selectivity to toluene plus xylenes and nB/nTX ratio for HDO of anisole on the Ni/SiO2 and Ni30M/SiO2 catalysts
图 7 Ni/SiO2及Ni30M/SiO2催化剂上的正己烷选择性
Figure 7 Selectivity to n-hexane for HDO of anisole on the Ni/SiO2 and Ni30M/SiO2 catalysts
图 8 Ni/SiO2及Ni30M/SiO2催化剂上nCH4/n△Anisole及nCO/n△Anisole比值
Figure 8 nCH4/n△Anisole and nCO/n△Anisole mol ratios on the Ni/SiO2 and Ni30M/SiO2 catalysts
表 1 Ni/SiO2及Ni30M/SiO2催化剂物理化学性质
Table 1 Physical-chemical properties of the Ni/SiO2 and Ni30M/SiO2 catalysts
Catalyst ABET/
(m2·g-1)vp/
(cm3·g-1)dp/nm Crystallite
sizea/nmH2 uptake/
(μmol·g-1)TOFb/s-1 Relative acid amountc total acid (Ⅰ) (Ⅱ) nS/nWd Ni/SiO2 314 0.53 5.6 7.2 70 0.04 1.00 0.24 0.76 3.17 Ni30Fe/SiO2 342 0.53 6.6 6.8 1.1 2.46 1.38 0.35 1.03 2.94 Ni30Co/SiO2 330 0.52 6.6 6.7 17 0.12 1.11 0.31 0.81 2.61 Ni30Cu/SiO2 366 0.57 6.6 7.1 7.4 0.27 1.26 0.41 0.85 2.07 Ni30Zn/SiO2 341 0.54 6.6 7.7 44 0.04 1.22 0.51 0.71 1.39 Ni30Ga/SiO2 329 0.56 6.6 6.4 49 0.05 1.46 0.53 0.93 1.79 a: calculated by Scherrer equation based on the reflection of Ni (111); b: calculated from the H2 chemisorption; c: designing the total acid amount of Ni/SiO2 as 1.0 ((Ⅰ) NH3 desorption temperature < 250 ℃; (Ⅱ) NH3 desorption temperature >250 ℃); d: the ratio between the amount of strong acid (NH3 desorption temperature < 250 ℃) and weak acid (NH3 desorption temperature >250 ℃) 
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