Improving the Catalytic Stability of Ni/TiO₂ for Ethanol Guerbet Condensation: Influence of Second Metal Component¹

Abstract—Ethanol Guerbet condensation (EGC) is a green process for preparing n-butanol and the development of highly effective solid catalysts is still the bottleneck of this reaction. In this work, a series of multifunctional catalysts Ni–X/TiO₂ (X = Ru, Pt, Ir, Au, Cu, Mn, Co, Fe) were prepared by a co-impregnation method in order to improve the catalytic performance, especially the stability. It was found that the addition of the second metal component changed the acidity and alkalinity of Ni/TiO₂ catalyst. What is more, acid site number affected ethanol conversion while alkali site number affected n-butanol selectivity. Among the Ni–X/TiO₂ catalysts, Ni–Cu/TiO₂ showed the best catalytic performance. The effects of preparation conditions on the catalytic performance of Ni–Cu/TiO₂ were investigated and the results showed that the suitable preparation conditions were as follows: a Ni/Cu mass ratio of 59 : 1, a Ni–Cu loading of 12.5 wt %, a calcination temperature of 450°C, a calcination time of 2 h, a reduction temperature of 400°C, and a reduction time of 4 h. At a 10 wt % of catalyst loading, a reaction temperature of 210°C and a reaction time of 10 h, the ethanol conversion and the selectivity of n-butanol were 47.9 and 44.4%, respectively. Moreover, the stability of Ni–Cu/TiO₂ catalyst was greatly improved due to the interaction between Ni and Cu as compared with the Ni/TiO₂ catalyst: the catalytic activity of Ni–Cu/TiO₂ did not decline significantly for reuse in three cycles.