Liquid phase in-situ hydrodeoxygenation of bio-derived phenol over Raney Ni and Nafion/SiO2

•Hydrodeoxygenation of phenol is performed on the dual-functional catalyst system.•The in situ hydrogen is from methanol aqueous-phase reforming over Raney Ni.•Raney Ni is also used for hydrogenation and Nafion/SiO2 for dehydration.•Phenol is converted to cyclohexanol first and then to cyclohexene and cyclohexane.•The whole reaction system is performed in the liquid phase.

In this work, we report a novel means, named liquid phase in-situ hydrodeoxygenation of bio-derived phenol to cyclohexene and cyclohexane over Raney Ni and Nafion/SiO2. In this method, producing hydrogen, hydrogenation and dehydration are merged and coupled owing to the close reaction conditions. The overall specific reaction pathway was studied and influences of Nafion loading, temperature, H2O/MeOH ratio and the quantity of catalysts on the reaction were also researched. In terms of 3 g phenol, the suitable operating conditions are drawn as follows: the Nafion loading 13 wt%, the reaction temperature 200 °C, H2O/MeOH ratio 20 mL:15 mL, Raney Ni 1 g, Nafion/SiO2 0.3 g. The conversion rate of phenol and the total yield of cyclohexene and cyclohexane can reach respectively 100% and 87%. The whole reaction system is performed in the liquid phase using in situ hydrogen produced from methanol aqueous-phase reforming, not requiring an external source of hydrogen. The operating conditions are gentle, and the cost is considerably reduced.

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