Preparation of Ru/Co-Al-O supported catalysts and its hydrodeoxygenation properties
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摘要: 先采用共沉淀法制备出Co-Al类水滑石, 其经煅烧后形成的复合氧化物用作载体制备出一系列Ru/Co-Al-O负载型催化剂, 并采用XRD、BET、FT-IR等方法对其结构性能进行表征分析, 最后以木质素生物质油的典型含氧化合物对甲基苯酚为模型, 测试所制催化剂的加氢脱氧性能。主要研究了载体中Co/Al物质的量比、催化剂还原温度等因素对催化剂加氢脱氧活性的影响, 并优化了HDO反应温度。结果表明, 当Co/Al物质的量比为3：1, 催化剂还原温度为350 ℃, 反应温度为275 ℃时, 催化剂的加氢脱氧活性最高, 催化对甲基苯酚加氢脱氧反应的转化率和脱氧率都达到了100%。Abstract: Co-Al layered double hydroxides were prepared by co-precipitation method and converted into composite oxides via calcination.The composite oxide were then used to prepare a series of Ru/Co-Al-O supported catalysts.The structures and properties of the catalysts were characterized by XRD, BET and FT-IR.The hydrodeoxygenation (HDO) properties of these catalysts were tested by using 4-methylphenol as a typical oxygen-containing model compound of lignin biomass oil.This study concentrated on the effects of Co/Al molar ratio and the reduction temperature of the catalyst on the hydrodeoxygenation activity of Ru/Co-Al-O and the optimization of HDO temperature.The results showed that when the molar ratio of Co/Al was 3:1, the catalyst reduction temperature was 350℃ and the reaction temperature was 275℃, the HDO activity was the highest:both the conversion and deoxygenation degree in the HDO of p-methyl phenol reached up to 100%.
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Key words:
- hydrodeoxygenation /
- Co-Al layered double hydroxides /
- Ru /
- 4-methylphenol /
- composite oxides
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图 2 不同Co/Al物质的量比催化剂XRD谱图
Figure 2 XRD patterns of the catalysts with different Co/Al molar ratio
图 4 275 ℃下Ru/Co-Al-O催化对甲基苯酚HDO反应2 h后的转化率、产物分布及脱氧率
:conversion; :methylcyclohexane;
:3-methylcyclohexene; :toluene;
:4-methylcyclohexanol;
:4-methylcyclohexanone; :deoxidation rateFigure 4 Catalytic reaction results over different Ru/Co-Al-O catalysts reaction conditions:reaction time:2 h, 275 ℃, 4 MPa
表 1 Ru/Co-Al-O负载型催化剂对应的制备条件及BET分析
Table 1 Ru/Co-Al-O supported catalyst corresponding to the preparation conditions and BET analysis results
Catalyst Co/Al(molar ratio) Reduction temperature t/℃ Specific surface area A/(m2·g-1) Pore volume v/(mL·g-1) Pore diameter d/nm Ru/Co4Al-350 4 350 65 0.22 12.3 Ru/Co3Al-350 3 350 79 0.29 13.4 Ru/Co3Al-500 3 500 48 0.21 16.2 Ru/Co2Al-350 2 350 67 0.31 10.9 Ru/Co1Al-350 1 350 40 0.10 9.4 Ru/Al-350 0 350 194 0.32 5.1 
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表 2 275 ℃反应2 h时不同还原温度的催化剂催化对甲基苯酚HDO产物分布
Table 2 HDO product distribution of the catalysts reduced at different temperatures
Catalyst Ru/Co3Al-350 Ru/Co3Al-500 Conversion rate x/% 100 99.2 Product distribution w/% Methylcyclohexane 92.1 83.8 4-methylcyclohexanol 0 8.5 4-methylcyclohexanone 0 0.3 3-methylcyclohexene 0 0.9 Toluene 7.9 6.5 Deoxidation rate η/% 100 89.6
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表 3 不同温度下Ru/Co3Al-350催化对甲基苯酚HDO反应的转化率、产物分布及脱氧率
Table 3 Effect of reaction temperature on HDO
225 ℃ 250 ℃ 275 ℃ Conversion x/% 56.0 94.6 100 Product distribution w/% Methylcyclohexane 23.7 80.4 92.1 4-methylcyclohexanol 65.3 10.5 0 4-methylcyclohexanone 6.0 1.1 0 3-methylcyclohexene 1.7 1.6 0 Toluene 3.3 6.4 7.9 Deoxidation rate η/% 16.5 82.3 100
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