Ni–Fe catalysts derived from hydrotalcite-like precursors for hydrogen production by ethanol steam reforming Original Research Article

Nickel–iron mixed oxides derived from reevesite, a hydrotalcite-type compound, were tested in steam reforming of ethanol for hydrogen production. The influence of iron content (Ni/Fe ranging from 3 to 1) and the calcination temperature of the catalyst precursor (773 and 1073 K) on the catalytic performance were investigated. Both parameters were essential to optimize the reforming performance. Increasing the amount of iron in the reevesite precursors affected both the chemical and activity properties of the derived mixed oxide catalysts. Iron displays a positive role in nickel-based catalysts due to the enhancement of catalytic activity and hydrogen selectivity induced by the improved dispersion of nickel and the alleviation in carbon deposition. The calcination temperature led to variations in phase composition consisting of Ni(Fe)Ox solid solution and NiFe2O4, which affected the final size and dispersion of nickel species formed during the reaction. The best catalyst, with a Ni/Fe ratio of 1 and calcined at 773 K, rendered high and stable hydrogen and carbon dioxide selectivity of up to ca. 60% and 40%, respectively, low methane content, and consisted of a Ni(Fe)Ox + NiFe2O4 mixture with high surface area and small Ni0 crystallites. A higher percentage of crystalline NiFe2O4 attained at high calcination temperature (1073 K) associated with a lower carbon deposition resistance and probably Ni0 sintering brings about lower activity and fast deactivation. The improved performance over catalysts calcined at lower temperature and with lower Ni/Fe ratio is motivated by the effect of iron on the structural and electronic properties of the mixed oxides, thus inducing a slow formation of metallic nickel particles and coke deposits. Features like high surface area, higher iron content, lower reducibility of nickel species and small nickel crystallite size well dispersed on the surface of the catalyst with high iron content lead to a higher activity in ethanol dehydrogenation, acetaldehyde decarbonylation and reforming, and WGS.