Selective breaking of C−O bonds in hydrodeoxygenation of 4-methylphenol over CoMoS/ZrO2
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摘要: 采用饱和浸渍法制备了不同Co-Mo原子比（0.25，0.30，0.35，0.40，0.45）和Co-Mo负载量（2.35%，4.36%，7.48%和10.79%）的CoMoS/ZrO2催化剂。用X射线衍射（XRD）、程序升温还原（H2-TPR）、氮气吸附和X射线光电子能谱（XPS）对催化剂进行了表征。以4-甲基苯酚为模型化合物进行加氢脱氧反应。结果表明，当Co-Mo（Co/Co+Mo）原子比为0.30，Mo负载量为4.36%时，催化加氢活性最好，4-甲基苯酚的转化率可达99.86%，直接加氢脱氧产物甲苯的选择性达到87.85%，较高程度保持了芳环。CoMoO4的产生不利于甲苯的生成。Co-Mo和ZrO2之间需要适当的相互作用。Abstract: CoMoS/ZrO2 catalysts with different Co-Mo atomic ratios (0.25, 0.30, 0.35, 0.40 and 0.45) and Co-Mo loading amounts (2.35%, 4.36%, 7.48% and 10.79%) were prepared by incipient wetness impregnation. These catalysts were characterized by X-ray diffraction (XRD), temperature-programmed reduction (H2-TPR), nitrogen adsorption/desorption and X-ray photoelectron spectroscopy (XPS). 4-methylphenol was used as model compound for hydrodeoxygenation reaction. The result showed that when the atomic ratio of Co-Mo (Co/Co + Mo) was 0.30 and the Mo loading amount was 4.36%, the highest hydrogenation activity was observed. The conversion of 4-methylphenol was up to 99.86% and the selectivity of main product toluene reached to 87.85%. The formation of CoMoO4 was unfavourable to the formation of toluene. An appropriate interaction between Co-Mo and ZrO2 was required.
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Key words:
- hydrodeoxygenation /
- phenols /
- 4-methylphenol /
- transition metal sulfides /
- zirconia
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Figure 2 Catalytic performance of CoMoS/ZrO2 catalysts with different Co-Mo atomic ratios for HDO of 4-methyl phenol (3 MPa, 300 ℃ and 8 h)
Figure 3 Catalytic performance of CoMoS/ZrO2 catalysts with different Co-Mo loading amounts for HDO of 4-methyl phenol (3 MPa, 300 ℃ and 8 h)
Figure 4 XRD patterns of catalysts with different Co-Mo atomic ratios
(a): for CoMo/ZrO2; (b): for CoMoS/ZrO2
Figure 6 H2-TPR profiles of CoMo/ZrO2
(a): catalysts with different Co-Mo atomic ratios; (b): catalysts with different Co-Mo loading
Figure 8 XPS spectra of pre-sulfided CoMoS/ZrO2 catalysts with different Co-Mo atomic ratios
Table 1 CoMo/ZrO2 catalysts with different Co-Mo atomic ratios
Catalyst Cobalt
content w/%Molybdenum
conten w/%Co-Mo atomic
ratioCo/(Co+Mo)
(mol ratio)C1.15M5.54-0.25 1.15 5.54 0.25 C1.15M4.36-0.30 1.15 4.36 0.30 C1.15M3.50-0.35 1.15 3.50 0.35 C1.15M2.85-0.40 1.15 2.85 0.40 C1.15M2.35-0.45 1.15 2.35 0.45 
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Table 2 CoMo/ZrO2 catalysts with different Co-Mo loading
Catalyst Cobalt
content w/%Molybdenum
content w/%Co-Mo atomic
ratioCo/(Co+Mo)
(mol ratio)C0.62M2.37-0.30 0.62 2.37 0.30 C1.15M4.36-0.30 1.15 4.36 0.30 C1.97M7.47-0.30 1.97 7.47 0.30 C2.84M10.79-0.30 2.84 10.79 0.30
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