Selective hydrodeoxygenation of lignin-derived phenolics to cycloalkanes over highly stable NiAl2O4 spinel-supported bifunctional catalysts

Hydrodeoxygenation (HDO) of lignin-derived bio-oil offers a promising route for the production of advanced biofuels. However, the conventional HDO of lignin-derived bio-oil faces serious problems, such as low hydrocarbon yield and easy deactivation of catalysts. Herein, a novel reaction system consisting of a highly stable bifunctional catalyst (i.e., Ni−WOx/NiAl2O4) and a dodecane solvent was developed for the HDO of lignin-derived phenolics. The Ni0 species, derived from NiWO4 precursors on the NiAl2O4, were of small crystallite size and high dispersion, together with the strong oxophilicity of W, thereby exhibiting high activity. The use of a highly stable NiAl2O4 spinel support and the replacement of common solid acid with more stable WOx for the cleavage of CO bond accounted for excellent stability. The optimized 10Ni−15WOx/NiAl2O4 exhibited a high guaiacol conversion of 97.8% with a high cycloalkane yield of 83.8% under the optimum conditions (250 °C, 5 MPa H2, and 4 h). Cycloalkanes with a high yield over 90% were also obtained by the HDO of other complex lignin-derived compounds. More importantly, the catalyst always retained its initial activity for the HDO of guaiacol in five runs, with negligible coke formation. Subsequently, the HDO behavior of the bio-oil obtained from walnut shell pyrolysis was also studied. The relative content of cycloalkanes in the products reached 44.3% after the reaction. This study highlights the prospect of a highly stable catalyst consisting of hydrogenation metal and oxophilic promoter, and dodecane solvent to enable efficient production of cycloalkanes from the HDO of lignin-derived phenolics.