Preparation of Al-based layered double hydroxides and corresponding mixed oxides supported Pt catalysts and their performance in the hydrodeoxygenation of p-cresol
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摘要: 采用共沉淀法制备了多种铝基类水滑石，焙烧后得到对应的复合氧化物；以水滑石或复合氧化物为载体，制备了系列Pt基催化剂，研究了该催化剂对甲基苯酚加氢脱氧反应的催化性能。结果表明，Pt基催化剂的性能与载体的组分组成和结构相关；当以不经焙烧的类水滑石做载体时，所制备的Pt基催化剂具有较高的活性。其中，Pt-Ni-Al-H催化剂的加氢脱氧活性最高，对甲基苯酚转化率达到99.8%，甲苯选择性为1.4%，而Pt-Zn-Al-H催化剂的直接脱氧活性最高，在275℃和氢压2MPa下反应1h后，甲苯选择性达到84.1%。研究发现，反应过程中所生成的甲基环己烷可进一步发生脱氢反应转化为甲苯，说明所制备的Pt基催化剂具有较好的脱氢活性，可节省脱氧过程中的氢气消耗量。Abstract: Al-based layered double hydroxides and corresponding mixed oxides were prepared and used as the supports for the Pt based catalysts; their catalytic performance in the hydrodeoxygenation (HDO) of p-cresol was then investigated. The results indicate that the catalytic performance of Pt based catalysts is related to the composition and structure of the support; Pt directly supported on the Al-based layered double hydroxides exhibits higher activity in p-cresol HDO than that supported on corresponding mixed oxides. Especially, for the HDO at 275 ℃ and 2 MPa for 1 h, the conversion of p-cresol over Pt-Ni-Al-H is 99.8%, with a selectivity of 1.4% to toluene, whereas the selectivity to toluene over Pt-Zn-Al-H reaches 84.1%. Moreover, the Pt based catalysts are also active for the dehydrogenation of methylcyclohexane to toluene, which can effectively reduce the hydrogen consumption in HDO.
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Key words:
- Pt /
- hydrodeoxygenation /
- p-cresol /
- layered double hydroxide /
- mixed metal oxides /
- dehydrogenation
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Figure 1 FT-IR spectra of layered double hydroxides and corresponding Pt supported catalysts
Figure 3 XRD patterns of (a) layered double hydroxides, (b) Pt supported on layered double hydroxides, (c) metal mixed oxides and (d) Pt supported on metal mixed oxides
Figure 4 HDO of p-cresol on Pt-Al-H, Pt-Mg-Al-H, Pt-Zn-Al-H, Pt-Co-Al-H and Pt-Ni-Al-H at 275 ℃ and 2 MPa for 1 h
Figure 5 HDO of p-cresol on Pt-Al-O, Pt-Mg-Al-O, Pt-Zn-Al-O, Pt-Co-Al-O and Pt-Ni-Al-O at 275 ℃ and 2 MPa for 8 h
Figure 7 FT-IR spectra of adsorbed pyridine on Pt-Al-H, Pt-Ni-Al-H, Pt-Co-Al-H and Pt-Mg-Al-H
Table 1 Effect of pressure on the HDO of p-cresol on Pt-Ni-Al-H at 275 ℃
Pressure p/MPa Reaction time t/h p-cresol conversion x/% Product selectivity s/% Deoxygenation degree/% 4-methylcyclohexene methylcyclohexane toluene 1.0 1 27.5 1.3 69.3 29.4 25.3 1.0 8 96.5 0.1 51.5 48.4 96.0 2.0 1 99.9 0.1 98.5 1.4 99.9 2.0 8 100 0 64.2 35.8 100 3.0 1 100 0.3 99.3 0.4 100 3.0 8 100 0 80.6 19.4 100 4.0 1 100 0.1 99.8 0.1 100 4.0 8 100 0 88.9 11.1 100 
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