Nickel and cobalt as active phase on supported zirconia catalysts for bio-ethanol reforming: Influence of the reaction mechanism on catalysts performance

Steam reforming of ethanol for hydrogen production was investigated on Co/ZrO2 and Ni/ZrO2 catalysts promoted with lanthana. Catalysts were prepared by impregnation method and characterized by XRD and TPR. TPD-R experiments were also carried out to determine the role of active phase on reaction mechanism. The results suggest that adsorbed ethanol is dehydrogenated to acetaldehyde producing hydrogen. Then, the adsorbed acetaldehyde may evolve by different mechanisms, depending on the nature of active phase. On one hand, in cobalt-based catalyst, acetaldehyde could be reformed directly. By acetaldehyde thermal decomposition, methyl and formaldehyde groups are obtained. By coupling of methyl groups, ethane can be obtained. At medium temperature range, WGS reaction contribution is noteworthy.On the other hand, in nickel-based catalyst, acetone was detected in a higher temperature range as the main intermediate reaction product, which indicates that acetaldehyde is transformed into acetone by decarbonylation of acetaldehyde leading to H2 and CO2 formation. In addition, acetone can also be reformed to give both H2 and CO2. Contrary to cobalt-based catalyst, ethylene was detected at intermediate range temperature which suggests that it was formed by ethanol dehydration reaction. Ethylene polymerization could easily explain coke formation, which must be avoided.Steam reforming reaction was studied at S/C ratio of 4.84 and 700 °C, to verify the activity, selectivity and stability of the catalysts. Ethanol conversion reached 100% and catalysts were very stable for almost 50 h on stream. No significant differences were detected in both catalysts. Nevertheless, TPO experiments performed on used samples demonstrate a higher carbon production on nickel based catalyst that can be correlated to ethanol dehydration contribution on it reaction pathway.