Effect of P/Ni ratio on the structure and hydrodesulfurization performance of nickel phosphide catalyst prepared by the solvothermal method
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摘要: 以三苯基膦(PPh3) 为磷源, 以三正辛胺(TOA) 为液相反应体系, 采用溶剂热法制备了负载型Ni-P (x)/MCM-41催化剂(x为初始P/Ni物质的量比), 并用X射线衍射(XRD)、N2吸附比表面积测定(BET)、CO吸附、X射线光电子能谱(XPS) 和TEM对催化剂进行了结构表征。以含质量分数1%二苯并噻吩(DBT) 的十氢萘溶液为原料, 在连续固定床反应装置上, 研究了初始P/Ni物质的量比对加氢脱硫(HDS) 性能的影响。结果表明, 在初始P/Ni物质的量比为0.5时, 生成的磷化镍物相为以Ni12P5为主, 含有少量Ni2P的混合相; 初始P/Ni物质的量比大于0.5时, 可得到纯Ni2P相, 且随着P/Ni物质的量比的提高, Ni2P晶粒粒径减小, 分散度提高。在反应温度613 K, 压力3.0 MPa, H2/oil体积比500, 质量空速2.0 h-1时, Ni-P (6)/MCM-41和Ni-P (10)/MCM-41催化剂的DBT转化率接近100%。
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关键词:
- 溶剂热法 /
- Ni2P /
- 二苯并噻吩(DBT) /
- 加氢脱硫(HDS)
Abstract: A series of MCM-41-supported NixP catalysts was prepared by the solvothermal method using low-price triphenylphosphine as phosphorus material and tri-n-octylamine as coordinating liquid reaction system. They were characterized with X-ray diffraction, N2 sorption, CO sorption, X-ray photoelectron spectroscopy and transmission electron microscopy techniques. The effects of initial P/Ni molar ratio on their structures and hydrodesulfurization performances were investigated in a lab-scale continuous flow fixed-bed reactor by feeding 1% of dibenzothiophene (DBT) in decahydronaphthalene. It was shown that Ni12P5 was primarily formed with a small amount of Ni2P at the initial P/Ni molar ratio of 0.5. When the initial P/Ni molar ratio was higher than 0.5, pure Ni2P phase was generated, and its crystal size decreased, and thus, its dispersion increased with the increase of initial P/Ni molar ratio. At 613 K, 3.0 MPa, H2/oil ratio of 500 (volume ratio), and weight hourly space velocity of 2.0 h-1, the DBT conversion nearly reached 100% on both the Ni-P (6)/MCM-41 and the Ni-P (10)/MCM-41 samples.-
Key words:
- solvothermal method /
- nickel phosphide /
- dibenzothiophene /
- hydrodesulfurization
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图 1 不同初始P/Ni物质的量比的Ni-P (x)/MCM-41的XRD谱图
Figure 1 XRD patterns of Ni-P (x)/MCM-41 samples
图 2 不同P/Ni物质的量比的Ni-P (x)/MCM-41催化剂的XPS谱图
Figure 2 Ni 2p and P 2p XPS spectra of Ni-P (x)/MCM-41
图 3 Ni-P (x)/MCM-41催化剂的TEM照片
Figure 3 TEM images of the Ni-P (x)/MCM-41 catalysts
(a): Ni-P (0.5)/MCM-41; (b): Ni-P (2)/MCM-41; (c): Ni-P (6)/MCM-41; (d): Ni-P (10)/MCM-41
图 4 不同P/Ni物质的量比催化剂的HDS活性和产物选择性
Figure 4 DBT conversion and BP and CHB selectivity obtained over Ni-P (x)/MCM-41 at different reaction temperatures
(553-613 K, 3.0 MPa, WHSV=2.0 h-1, H2/oil (volume ratio)=500)
■: Ni-P (0.5)/MCM-41; ●: Ni-P (2)/MCM-41; ▲: Ni-P (6)/MCM-41; ▼: Ni-P (10)/MCM-41表 1 Ni-P (x)/MCM-41催化剂及MCM-41载体的性质
Table 1 Textural properties of Ni-P (x)/MCM-41 and MCM-41
Sample ABET/(m2·g-1) vp/(cm3·g-1) dp/nm XRD phase Dca /nm CO uptake m/(μmol·g-1) MCM-41 1 012 0.816 3.2 - - Ni-P (0.5)/MCM-41 712 0.503 2.8 Ni2P+Ni12P5 2(Ni12P5) 156 Ni-P (2)/MCM-41 690 0.472 2.7 Ni2P 10 97 Ni-P (6)/MCM-41 668 0.456 2.7 Ni2P 4 124 Ni-P (10)/MCM-41 613 0.417 2.7 Ni2P 3 132 Dca: calculated from the Dc=Kλ/βcosθ(Scherrer equation) based on the (111) plane of Ni2P or Ni12P5 
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表 2 催化剂的XPS分析得到的光谱学参数
Table 2 XPS data of Ni-P (x)/MCM-41
Sample Binding energy E/eV Superficial molar ratio Ni 2p3/2 P 2p Niδ+ P/Ni Ni2+ satellite Niδ+ P5+ Pδ- Ni Ni-P (0.5)/MCM-41 856.4 861.7 852.7 134.3 129.3 0.321 1.6 Ni-P (2)/MCM-41 856.6 861.8 852.9 134.5 130.1 0.349 2.3 Ni-P (6)/MCM-41 856.7 862.0 853.0 134.4 130.1 0.402 2.4 Ni-P (10)/MCM-41 856.9 862.3 853.2 134.1 129.9 0.393 2.6
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