Effect of preparation methods on the structure and naphthalene hydrogenation performance of Ni2P/SiO2 catalyst
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摘要: 采用程序升温还原法和次磷酸盐歧化法制备了Ni2P/SiO2催化剂，结合现代仪器分析表征技术，研究了制备方法对Ni2P/SiO2催化剂结构和萘加氢性能的影响。结果表明，两种方法均可制备出仅含Ni2P活性相的Ni2P/SiO2催化剂，在反应温度340℃、氢气压力4 MPa、空速为20.8 h-1下，程序升温还原法制备的Ni2P/SiO2催化剂表现出更高的萘加氢活性，这主要是因为程序还原法制备的Ni2P/SiO2催化剂中有更多Ni2P物种生成，提供了较多的活性位点（CO吸附量21.6 μmol/g）；且催化剂表面弱酸位点多，有利于芳烃吸附。当选用程序升温还原法制备Ni2P/SiO2催化剂时，在保证生成纯相Ni2P的前提下，较低的Ni/P比更有利于合成高加氢活性的Ni2P/SiO2催化剂。Abstract: Ni2P/SiO2 catalysts were prepared by temperature-programmed reduction method and hypophosphite disproportionation method to investigate their naphthalene hydrogenation performance. The prepared catalysts were characterized by ICP-OES, X-ray diffraction, H2 temperature-programmed reduction, N2 adsorption-desorption method and transmission electron microscopy, etc. Results showed that Ni2P/SiO2 catalyst with pure Ni2P crystal phase could be successfully prepared by the temperature-programmed reduction method and hypophosphite disproportionation method. When the naphthalene hydrogenation reaction was performed at 340℃, 4 MPa, H2/oil volume ratio of 600, and a weight hourly space velocity (WHSV) of 20.8 h-1, Ni2P/SiO2 catalyst prepared by the temperature-programmed reduction method possessed superior hydrogenation activity. This result was ascribed to the advantages of temperature-programmed reduction method. It not only installed the higher number of Ni2P species (CO adsorption amount 21.6 μmol/g) over SiO2, but also obtained more weak acid sites on the catalyst surface, which promoted the adsorption of aromatic hydrocarbons and subsequently resulted in the higher hydrogenation activity. Furthermore, when the temperature-programmed reduction method was used to prepare Ni2P/SiO2 catalyst, the lower Ni/P molar ratio was more beneficial to enhance the naphthalene hydrogenation activity of the as-prepared catalyst.
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图 1 Ni2P/SiO2催化剂制备原理示意图
Figure 1 Preparation principle of Ni2P/SiO2 catalysts
(a): catalysts prepared by temperature-programmed reduction; (b): catalyst prepared by hypophosphite disproportionation method
图 2 不同制备方法中P物种迁移路径示意图
Figure 2 P species migration path in different preparation methods
图 3 反应前后不同制备方法所得Ni2P/SiO2催化剂的XRD谱图
Figure 3 XRD patterns of Ni2P/SiO2 catalysts prepared by different preparation methods before and after reaction
图 4 不同制备方法所得Ni2P/SiO2催化剂前驱体的H2-TPR谱图
Figure 4 H2-TPR profiles of Ni2P/SiO2 catalysts prepared by different preparation methods
图 5 不同制备方法所得Ni2P/SiO2催化剂的形貌及其粒径分布
Figure 5 Morphologies and particle size distribution of Ni2P/SiO2 catalysts prepared by different methods
图 6 不同制备方法所得Ni2P/SiO2催化剂的NH3-TPD谱图
Figure 6 NH3-TPD profiles of Ni2P/SiO2 catalysts prepared by different methods
图 7 不同制备方法所得Ni2P/SiO2催化剂中Ni 2p和P 2p的XPS谱图
Figure 7 XPS profiles of Ni 2p and P 2p on Ni2P/SiO2 catalysts prepared by different methods
图 8 不同制备方法所得Ni2P/SiO2催化剂的萘加氢性能
Figure 8 Naphthalene hydrogenation performance of Ni2P/SiO2 catalysts prepared by different methods
表 1 不同制备方法Ni2P/SiO2催化剂的元素组成
Table 1 Element composition of Ni2P/SiO2 catalysts synthesized by different methods
Sample Theory content Actual content Ni w/% P w/% Ni/P (mol ratio) Ni w/% P w/% Ni/P (mol ratio) Cat-D 7.9 8.4 0.5 7.9 5.0 0.8 Cat-T(1) 7.9 4.2 1 8.1 2.5 1.7 Cat-T(1.25) 7.9 3.3 1.25 8.3 3.0 1.4 
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表 2 不同制备方法催化剂的比表面积和孔结构
Table 2 BET specific surface area and pore structure of the Ni2P/SiO2 catalyst synthesized by different methods
Sample BET specific
surface area
A/(m2·g-1)Total pore
volume
v/(cm3·g-1)Most probable
aperture
d/nmSiO2 209.0 2.1 32.8 Cat-D 146.8 0.5 12.5 Cat-T(1) 145.3 0.7 20.1 Cat-T(1.25) 149.5 0.8 22.3
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表 3 不同制备方法所得Ni2P/SiO2催化剂中Ni 2p、P 2p的结合能和Ni/P比
Table 3 Binding energy of Ni 2p and P 2p, the atomic ratio of Ni/P on Ni2P/SiO2 catalysts prepared by different methods
Sample Binding energy E/ eV Ni/P
/(mol ratio)Ni 2p3/2 P 2p3/2 Niδ+ Ni2+ Pδ- PO43- Cat-D 853.42 857.36 129.29 133.84 0.99 Cat-T(1) 853.35 857.26 129.39 133.89 1.05 Cat-T(1.5) 853.31 857.05 129.41 133.84 1.52
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