Deoxygenation of decanoic acid and its main intermediates over unpromoted and promoted sulfided catalysts

The transformation of decanoic acid, used as a model oxygenated compound, was first studied over Mo/Al2O3 at 340 degrees C under 4 MPa of total pressure (H-2 pressure equal to 2.72 MPa) in a fixed-bed reactor. The deoxygenation of decanoic acid is considered to proceed through two main routes: (i) the HDO pathway yielding decenes and decane as ultimate hydrocarbons, oxygen being removed as water; (ii) the DEC pathway involving a decarbonylation reaction and mainly leading to nonene isomers, oxygen being discarded as water and carbon monoxide. Other products such as oygenates (mainly decanal and 1-decanol) and sulfur-containing products (mainly 1-decanethiol) appeared as intermediates of the HDO way. A significant inhibiting effect of carboxylic acid on the deoxygenation of decanal was highlighted. A general reaction scheme of deoxygenation of decanoic acid over sulfided catalysts was established. Considering a sulfur vacancy as an active site, deoxygenation reaction mechanisms were proposed involving a cationic species as a common intermediate between the HDO and the DEC pathways. The effect of Co and Ni on the deoxygenation rate of decanoic acid was measured by using both CoMo/Al2O3 and NiMo/Al2O3. The DEC route was strongly promoted by Co and Ni, whereas an inhibiting effect of Co and Ni was observed on the HDO route. It was assumed that the promoter effect on the DEC route may result from an increase of the basicity of sulfur anions neighbouring of Co or Ni present in the sulfided promoted phase. (C) 2013 Elsevier B.V. All rights reserved.