Solvent effect on the activity of Ru-Co3O4 catalyst for liquid-phase hydrogenation of CO2 into methane
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摘要: 采用共沉淀法制备了Ru-Co3O4催化剂,考察了其在液相体系的CO2加氢制甲烷催化性能,并与浸渍法制备的Ru基催化剂(Ru/SiO2、Ru/CeO2、Ru/ZrO2、Ru/TiO2)进行了对比,探讨了不同溶剂(水、正丁醇、1, 4-丁内酯、DMF、十氢萘、环己烷、异辛烷)对催化性能的影响规律。发现Ru-Co3O4具有较高的加氢催化活性和产物选择性,十氢萘和异辛烷作溶剂显示出良好的催化性能。在200 °C及H2/CO2 = 3∶1(v/v, 4 MPa)条件下,CO2转化率达45.6%,CH4的选择性约97%。同位素标记实验和原位漫反射红外光谱结果表明,十氢萘和异辛烷中的叔碳离子可以起到较强的供氢作用,从而提高了催化活性。Abstract: Ru-Co3O4 catalyst was prepared by the co-precipitation method. Its catalytic performance in liquid-phase hydrogenation of CO2 into methane was investigated, and compared with those of the conventional Ru-based catalysts (Ru/SiO2, Ru/CeO2, Ru/ZrO2, Ru/TiO2) prepared by impregnation method. The solvents including H2O, n-butanol, 1,4-butyrolactone, DMF, n-nonane, decalin, cyclohexane and isooctane had significant solvent effects on the catalytic performance. Compared with other solvents, the catalyst showed higher activity and selectivity catalytic performance when decalin and isooctane was applied as the solvent. At 200 °C and H2/CO2=3:1 (v/v, 4 MPa) and with decalin as the solvent, the conversion of CO2 and the selectivity of CH4 reached 45.6% and 97%, respectively. The isotope labeling experiments and in-situ diffuse reflectance infrared spectra showed that the hydrogen atoms of the tertiary carbon in decalin and isooctane were active for CO2 hydrogenation reaction, thus improving the catalytic activity.
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Key words:
- carbon dioxide /
- liquid-phase hydrogenation /
- methane /
- solvent effect /
- hydrogen supply
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图 5 Ru-Co3O4催化剂表面CO2加氢的漫反射红外谱图:(a) 200 °C; (b) 不同温度下
Figure 5 DRIFTS spectra of CO2 hydrogenation to CH4 at 200 oC on Ru-Co3O4 in CO2, decalin, (CO2+decalin), and DRIFTS spectrum of standard CH4 (from the bottom to the top direction) (a); and DRIFTS spectra of CO2 hydrogenation to CH4 at 200 oC on Ru-Co3O4 in (CO2+decalin) at different reaction temperatures (b)
表 1 不同Ru-基催化剂液相CO2加氢制甲烷的催化性能
Table 1 Catalytic results of various supported Ru catalysts for liquid-phase hydrogenation of CO2 to CH4
Entry Catalyst CO2
conversion
/%Selectivity of
hydrocarbons/mol%CH4 C2−5 CO 1 Ru/SiO2 2.3 97.1 2.9 0 2 Ru/CeO2 5.4 98.8 1.2 0 3 Ru/ZrO2 11.3 97.9 2.1 0 4 Ru/TiO2 15.2 97.1 2.9 0 5 Ru-Co3O4 45.6 97.0 2.9 0.1 6 Co3O4 34.0 97.7 2.2 0.1 reaction conditions: 100 mg of catalyst, 5 g decalin, 200 °C, initial pressure: 4 MPa of H2/CO2 gas (v/v = 3∶1), 1 h 表 2 不同溶剂中Ru-Co3O4催化剂上CO2液相加氢制甲烷性能的影响a
Table 2 Catalytic results of Ru-Co3O4 for liquid-phase hydrogenation of CO2 to CH4 in different solventsa
Solvent CO2 conversion/% Product selectivity/% Solubility b/(mmol·L−1) CH4 C2−5 Water 8.3 88.7 11.0 28.9 Butyl alcohol 21.4 88.7 11.1 87.2 1,4- butyrolactone 26.2 95.7 4.2 42.6 DMF 31.0 89.4 10.4 43.2 n-Nonane 31.9 98.5 1.5 93.5 Decalin 45.6 97.0 3.0 67.5 Cyclohexane 34.0 98.8 1.2 Isooctane 42.0 98.2 1.7 a: reaction conditions: 100 mg of 1% Ru-Co3O4,5 g of solvent,200 °C,initial pressure: 4 MPa of H2/CO2 gas (v/v=3/1), 1 h; b: calculated by considering H2 filled in the reactor as standard gas -
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