Catalytic Performance of Lanthanum Promoted Ni/ZrO2 for Carbon Dioxide Reforming of Methane

Abstract

Nickel catalysts supported on zirconium oxide and modified by various amounts of lanthanum with 10, 15, and 20 wt.% were synthesized for CO2 reforming of methane. The effect of La2O3 as a promoter on the stability of the catalyst, the amount of carbon formed, and the ratio of H2 to CO were investigated. In this study, we observed that promoting the catalyst with La2O3 enhanced catalyst activities. The conversions of the feed, i.e., methane and carbon dioxide, were in the order 10La2O3 > 15La2O3 > 20La2O3 > 0La2O3, with the highest conversions being about 60% and 70% for both CH4 and CO2 respectively. Brunauer–Emmett–Teller (BET) analysis showed that the surface area of the catalysts decreased slightly with increasing La2O3 doping. We observed that 10% La2O3 doping had the highest specific surface area (21.6 m2/g) and the least for the un-promoted sample. The higher surface areas of the promoted samples relative to the reference catalyst is an indication of the concentration of the metals at the mouths of the pores of the support. XRD analysis identified the different phases available, which ranged from NiO species to the monoclinic and tetragonal phases of ZrO2. Temperature programmed reduction (TPR) analysis showed that the addition of La2O3 lowered the activation temperature needed for the promoted catalysts. The structural changes in the morphology of the fresh catalyst were revealed by microscopic analysis. The elemental compositions of the catalyst, synthesized through energy dispersive X-ray analysis, were virtually the same as the calculated amount used for the synthesis. The thermogravimetric analysis (TGA) of spent catalysts showed that the La2O3 loading of 10 wt.% contributed to the gasification of carbon deposits and hence gave about 1% weight-loss after a reaction time of 7.5 h at 700 °C.