Dry reforming of methane over Ni–Mg–Al and Ni–Ca–Al type hydrotalcite-like catalysts: effects of synthesis route and Ru incorporation

Abstract

Ni-incorporated Mg–Al type hydrotalcite-like catalytic materials were synthesized following impregnation and co-precipitation routes, and their catalytic performances were compared in the dry-reforming reaction of methane. The effects of Ru impregnation on the catalytic performance of Ni-incorporated Mg–Al were also investigated. Results showed that the catalytic performance of the Ni-incorporated Mg–Al type catalyst (NiMgAlO), which was prepared by the co-precipitation route, was highly stable during dry-reforming reaction tests performed at 600 °C, extending up to 24 h. The fractional conversion of CO2 (0.42) was higher than the fractional conversion of CH4 (0.29) due to the contribution of the reverse water gas shift reaction. However, the contribution of the reverse water gas shift reaction to the product distribution was much less with the catalyst prepared following the impregnation route (Ni@MgAlO). This difference was shown to be mainly due to the state of the nickel in the catalyst structures. Ni-impregnated Ca–Al type hydrotalcite-like catalyst (Ni@CaAlO) was also synthesized and tested in dry reforming of methane. Results obtained with the Ni-impregnated Ca–Al type catalyst showed some changes in its structure and the formation of some CaCO3 during the dry reforming reaction. The comparison of the performances of Ni-impregnated Mg–Al and Ca–Al type catalysts showed a higher amount of coke on the surface of Ni@CaAlO than Ni@MgAlO. It was also concluded that significant coke minimization and highly stable catalytic performance could be achieved by the impregnation of 1 % Ru to the NiMgAlO catalyst. The amount of coke deposited on the catalyst decreased from about 30 % to less than 5 %, by Ru impregnation. The decrease of the surface area of the Ru-impregnated catalyst was also only about 3 % after 240 min of reaction time.