4.7 Article

Hydrodeoxygenation of phenol and biomass fast pyrolysis oil (bio-oil) over Ni/WO3-ZrO2 catalyst

Journal

CATALYSIS TODAY
Volume 366, Issue -, Pages 57-67

Publisher

ELSEVIER
DOI: 10.1016/j.cattod.2020.08.029

Keywords

Hydrodeoxygenation (HDO); Phenol; Catalytic fast pyrolysis oil (bio-oil); Ni/ZrO2 and Ni/WO3-ZrO2 catalysts; Cycloalkanes

Funding

  1. European Union (European Social Fund ESF)
  2. Greek national funds through the Operational Program Education and Lifelong Learning of the National Strategic Reference Framework (NSRF) -Research Funding Program THALES (CAT-BIOFUEL project)

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The study investigated the hydrodeoxygenation of pure phenol and catalytic biomass fast pyrolysis oil over 10%Ni/ZrO2 and 10%Ni/WO3-ZrO2 catalysts. It was found that the addition of WO3 improved the catalytic activity, especially in the complete hydrodeoxygenation of phenol to cyclohexane. The 10%Ni/WO3-ZrO2 catalyst showed high activity and selectivity in both phenol and bio-oil hydrodeoxygenation reactions.
The hydrodeoxygenation of pure phenol in hexane solution and of catalytic biomass fast pyrolysis oil (bio-oil) over 10 %Ni/ZrO2 and 10 %Ni/WO3-ZrO2 catalysts was investigated in the present study, at relatively mild conditions (ca. 50 250 degrees C, 30 bar H-2) in a continuous flow high-pressure fixed bed reactor. The catalysts were characterized for their structural, porosity, redox and acidic/basic properties which were used to rationalize the observed catalytic performance. The 10 %Ni/ZrO2 catalyst was very active and selective towards cyclohexanol in the phenol HDO experiments (100 % conversion and selectivity at 110 degrees C) but the enhanced acidity offered by the addition WO3 in ZrO2 was necessary to succeed a complete hydrodeoxygenation of phenol to cyclohexane at the low temperature of 150.C with the 10 %Ni/WO3-ZrO2 catalyst. This catalyst was also proven very active in the hydrodeoxygenation of the catalytic bio-oil which consisted of mono-aromatics (i.e. alkyl-benzenes) and PAHs (mainly naphthalenes and indenes), and fewer oxygenated compounds (i.e. alkyl-phenols and benzofurans), providing a product oil containing mainly alkyl-cycloalkanes and fewer alkyl-benzenes, at the mild conditions of 210 degrees C and 30 bar H-2.

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