Preparation of Ni/SiO2 by ammonia evaporation method for synthesis of 2-MTHF from 2-MF hydrogenation
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摘要: 以硝酸镍为镍源，碱性硅溶胶为硅源，采用蒸氨法制备了Ni/SiO2催化剂。通过XRD、N2等温吸附脱附、H2-TPR、NH3-TPD、XPS和TG对催化剂进行表征。采用固定床反应器，考察了催化剂焙烧温度及反应条件对催化剂应用于2-甲基呋喃（2-MF）气相加氢合成2-甲基四氢呋喃（2-MTHF）的反应性能。结果表明，蒸氨法制备的Ni/SiO2催化剂在焙烧后均呈现层状硅酸镍结构，还原后保持了该结构，活性组分Ni晶粒尺寸较小、金属载体相互作用较强，从而具有较高的活性。催化剂的焙烧温度影响催化剂Ni晶粒尺寸及催化剂的表面酸性。在500 ℃焙烧条件下制备的催化剂性能最佳，优化反应条件下，2-MF转化率100%，2-MTHF选择性为93.5%，反应15 h内催化性能稳定；含碳的有机物在催化剂表面沉积是催化剂失活的主要原因。Abstract: The Ni/SiO2 catalysts were prepared by ammonia evaporation method, with nickel nitrate as Ni source and silica sol as the SiO2 source, for synthesis of 2-MTHF from 2-MF hydrogenation. The catalytic performance of catalysts prepared at different calcination temperatures were tested on a fixed-bed reactor. XRD, N2 adsorption-desorption, H2-TPR, NH3-TPD, XPS and TG were employed to characterize the structure and surface properties of these catalysts. The effect of calcination temperature on the structure, surface property and catalytic performance of catalysts were investigated. The result indicated that all the catalysts had a phyllosilicate structure after calcination, and maintained the structure after reduction. Ni particles dispersed well with smaller size and strong metal support interaction showed high activity. The surface acidity of catalysts was influenced by the calcination temperature. The maximum catalytic activity and selectivity were obtained on the catalyst calcined by at 500 ℃, which exhibited a 2-MF conversion of 100% and the 2-MTHF selectivity of 93.5% at the optimized condition, due to smaller particle size and suitable surface acidity.
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Key words:
- 2-methylfuran /
- 2-methyltetrahydrofuran /
- ammonia evaporation /
- hydrogenation /
- Ni/SiO2 catalysts
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图 1 不同焙烧温度制备的Ni/SiO2催化剂的N2吸附-脱附等温线（a）和BJH孔径分布（b）
Figure 1 N2 adsorption-desorption isotherms (a) and BJH pore size distributions (b) of Ni/SiO2 catalysts
图 2 不同焙烧温度制备的Ni/SiO2催化剂的XRD谱图
Figure 2 XRD patterns of Ni/SiO2 catalysts prepared at different calcination temperatures
(a): after calcination; (b): after reduction
图 3 不同焙烧温度制备的Ni/SiO2催化剂的H2-TPR谱图
Figure 3 H2-TPR profiles of Ni/SiO2 catalysts prepared at different calcination temperatures
图 4 不同焙烧温度制备的Ni/SiO2催化剂的NH3-TPD谱图
Figure 4 NH3-TPD profiles of Ni/SiO2 catalysts prepared at different calcination temperatures
图 5 不同焙烧温度制备的Ni/SiO2催化剂的性能
Figure 5 Catalytic performance of Ni/SiO2 catalysts prepared at different calcination temperatures
图 6 Ni/SiO2催化剂的稳定性
Figure 6 Stability of Ni/SiO2 catalyst (performance vs. time on stream)
图 7 Ni/SiO2催化剂的XRD谱图
Figure 7 XRD patterns of Ni/SiO2 catalysts
a: after reduction; b: after use
表 1 不同焙烧温度制备的Ni/SiO2催化剂的比表面积、孔容和孔径
Table 1 Specific surface area, pore volume and pore sizes of different catalysts
Catalysts calcination SBET /(m2·g−1) v /(cm3·g−1) d /nm 400 ℃ 391.1 0.510 3.9 500 ℃ 346.7 0.641 3.7 600 ℃ 345.6 0.462 3.9 700 ℃ 296.1 0.486 5.0 
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表 2 不同焙烧温度制备的Ni/SiO2催化剂的酸量
Table 2 Total acidity amount of different catalysts
Catalysts calcination 400 ℃ 500 ℃ 600 ℃ 700 ℃ Total acidity /(mmol $({\rm{NH} }_3)\cdot {\rm{g} }_{\rm{cat} }^{-1}$) 0.519 0.411 0.408 0.369
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表 3 不同反应条件下催化剂的催化性能
Table 3 Catalytic performance of Ni/SiO2 catalyst under different reaction conditions
p/MPa H2/2-MF（molar ratio） LHSV/h−1 t/℃ x（2-MF）/% Selectivity s/% 2-MTHF 2-pentanol amyl alcohol others 1.2 5.4 1.6 120 100 88.1 6.3 4.4 1.2 1.6 5.4 1.6 120 100 89.5 5.9 3.8 0.8 2.0 5.4 1.6 120 100 90.9 7.1 1.5 0.5 1.6 2.7 1.6 120 100 89.1 6.8 2.7 1.4 1.6 10.7 1.6 120 100 92.7 4.1 2.1 1.1 1.6 13.7 1.6 120 100 93.7 3.5 1.9 0.9 1.6 16.1 1.6 120 100 91.2 4.7 2.4 1.7 1.6 13.7 2.7 120 100 89.9 5.4 3.2 1.5 1.6 13.7 4.9 120 100 90.6 6.1 1.8 1.5 1.6 13.7 4.9 110 100 86.2 7.9 4.4 1.5 1.6 13.7 4.9 120 100 89.5 7.1 2.8 0.6 1.6 13.7 4.9 140 100 94.1 3.4 1.8 0.7 1.6 13.7 4.9 160 100 95.3 2.6 1.7 0.4 1.6 13.7 4.9 180 100 93.1 4.1 1.9 0.9
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表 4 Ni/SiO2催化剂表面原子百分比
Table 4 Atom ratio on the surface of Ni/SiO2 catalysts
Atom After reduction /% After use /% C 9.10 26.76 O 57.35 48.62 Ni 7.33 4.30 SiO2 26.22 20.31
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