Study on the catalytic hydrogenation of methyl levulinate over Ru/organic modified vermiculite
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摘要: 以有机改性蛭石为载体，RuCl3·xH2O为活性组分前驱体，采用吸附-沉淀法制备催化剂Ru/有机改性蛭石（Ru/OV），将其用于乙酰丙酸甲酯（ML）催化加氢反应中。采用X射线衍射（XRD）、N2物理吸附-脱附、透射电镜（TEM）、X射线光电子能谱（XPS）对催化剂进行表征。结合单因素和正交实验考察了反应温度、反应压力、反应时间对乙酰丙酸甲酯加氢效果的影响，在最佳工艺条件下乙酰丙酸甲酯的转化率达84%，γ-戊内酯（GVL）选择性达100%。经重复使用20次后，ML的转化率仍然保持在80%以上，GVL的选择性为100%。Abstract: Organic-pillared vermiculite supported Ru (Ru/OV) was prepared via adsorption-precipitation method, using RuCl3·xH2O as precursor and applied to catalytic hydrogenation of methyl levulinate (ML). The physicochemical properties of the catalysts were investigated by XRD, N2-adsorption-desorption, TEM and XPS. Effects of reaction temperature, pressure, reaction time on the catalytic performance were studied by orthogonal and single factor experiments. Under the optimum conditions, the conversion of ML and the selectivity of γ-valerolactone (GVL) were 84% and 100%, separately. After being recycled for 20 times, the conversion of ML was above 80% and the 100% selectivity of GVL could be obtained.
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Key words:
- Ru /
- organic-pillared vermiculite /
- catalytic hydrogenation /
- methyl levulinate /
- γ-valerolactone
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图 1 催化剂的XRD谱图
Figure 1 XRD patterns of the Ru/OV catalysts with different states
(a): 1°-10°; (b): 5°-80°
图 2 有机改性蛭石和Ru/有机改性蛭石的N2吸附-脱附曲线(嵌图为对应的孔径分布)
Figure 2 N2 adsorption-desorption isotherms of the origanic pillared vermiculite and Ru/origanic pillared vermiculite (the inset is pore size distribution)
图 5 反应压力对乙酰丙酸甲酯加氢的影响
Figure 5 Effect of reaction pressure on the hydrogenation of methyl levulinate
图 6 反应温度对乙酰丙酸甲酯加氢的影响
Figure 6 Effect of reaction temperature on the hydrogenation of methyl levulinte
图 7 反应时间对乙酰丙酸甲酯加氢的影响
Figure 7 Effect of reaction time on the hydrogenation of methyl levulinate
表 1 有机改性蛭石和Ru/有机改性蛭石N2-物理吸附分析
Table 1 N2 physical adsorption-desorption data of the origanic pillared vermiculite and the Ru/origanic pillared vermiculite
Sample Special surface area A/(m2·g-1) Total pore volume v/(cm3·g-1) Average pore diameter d/nm OV 31.0 0.065 4.23 Ru/OV 35.3 0.098 3.83 
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表 2 正交实验安排
Table 2 Orthogonal experimental arrangements
Factor Levels Reaction pressure p/MPa 3.5 4.0 4.5 Reaction temperature t/℃ 110 130 150 Reaction time t/h 4.5 5.0 5.5
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表 3 ML加氢正交试验
Table 3 Orthogonal test results of ML hydrogenation
Sample number A (reaction
pressure p/MPa)B (reaction
temperature t/℃)C (reaction
time t/h)Blank sample
(error)ML conversion
x/%1 3.5 110 4.5 1 60.18 2 3.5 130 5.0 2 75.20 3 3.5 150 5.5 3 62.91 4 4.0 110 5.0 3 66.88 5 4.0 130 5.5 1 80.73 6 4.0 150 4.5 2 65.80 7 4.5 110 5.5 2 80.19 8 4.5 130 4.5 3 77.53 9 4.5 150 5.0 1 72.16 Average value1 66.10 69.08 67.84 71.02 Average value 2 71.14 77.82 71.41 73.73 Average value 3 76.62 66.95 74.61 69.10 Sample limit error 10.53 10.86 6.77 4.63 Optimization levels 3 2 3
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表 4 正交试验方差分析
Table 4 Orthogonal test variance analysis table
Factor Square of
deviance(Si)Degree of
freedom(fi)F critical-
valuesF0.01 F0.05 Significancea Reaction pressure(p) 166.42 2 5.13 10.92 5.14 - Reaction temperature(t) 198.68 2 6.12 10.92 5.14 * Reaction time(t) 69.02 2 2.13 10.92 5.14 - Error 32.46 2 - - - - a: when Fi＞F0.01, it is highly significant, denoted as**; when F0.01＞Fi＞F0.05, it is significant, denoted as*
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表 5 ML加氢验证实验及结果
Table 5 Results of ML hydrogenation verification experiment
Sample code Reaction
pressure p/MPaReaction
temperature t/℃Reaction
time t/hML
conversion x/%Average
value/%1 4.5 130 5.5 84.93 2 4.5 130 5.5 83.95 84.45 3 4.5 130 5.5 84.47
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