NiAlCe mixed oxides obtained from layered double hydroxides applied to anisole hydrodeoxygenation

Abstract

Bio-oil derived from the pyrolysis of lignocellulosic biomass residues cannot be used directly as biofuel due to the high content of oxygenated compounds. As an alternative, bio-oil must undergo a deoxygenation process, such as catalytic hydrodeoxygenation (HDO). In this sense, this work studied the effect of different concentrations of Ce3+ and Ce4+ in layered double hydroxides (LDHs) in order to obtain mixed oxide catalysts containing NiAlCe (NiO-NiAl2O4-CeO2) with low cost and high performance for the hydrodeoxygenation of anisole as a model bio-oil compound. Mixed oxides were obtained from the thermal decomposition of layered double hydroxides (LDHs) by using terephthalic acid as compensation anion, with molar ratio: Ni2+/(Al3++ M) = 1.0, where M = Ce3+; Ce4+ or Ce3+-Ce4+; and Al/Ce ratios of 9 and 1. Characterization analyses confirmed the formation of LDHs for all materials, although at lower Al/Ce ratio it is observed a loss of crystallinity, due to a greater repulsion and distortion of the layer structure caused by the incorporation, in greater amount, of cations with a high ionic radius. The increase in the content of cerium in mixed oxides also led to an increase in the acidity of the catalysts, in addition to a reduction in the surface area, justified by the pore blockage by CeO2 on the catalyst surface. The greater structural and thermal stability was evidenced in the LDHs derived from Ce4+, as well as a greater dispersion of the NiO phase in the corresponding mixed oxides, and therefore presenting greater anisole conversion. The obtained data indicated that the presence of Ce4+ ions on the catalyst surface was decisive in the conversion of anisole to cyclohexane, the main deoxygenated product, obtained via the direct deoxygenation and hydrogenation mechanism.