Effect of low-loading of Ni on the activity of La0.9Sr0.1FeO3 perovskites for chemical looping dry reforming of methane

Methane dry reforming (MDR) is a very appealing process to bring back waste CO2 into the chemical production chain. Operating in chemical looping (CL) conditions allows to reduce deactivation by coke deposition and facilitates the use of concentrating solar energy to power this reaction. Perovskites have successfully applied as oxygen carriers for chemical looping, and those of the family La1-xSrxFeO3 with lower Sr content have showed high activity and cycling stability. To further enhance the performance of these oxygen carriers in this work, we evaluate the impact of dispersing Ni in low concentration (<1 mol %) on the performance of La0.9Sr0.1FeO3 for CL-MDR. Simple impregnation allows to distribute evenly the metal, which according to XPS is present as Ni2+ in the fresh material. CH4-TPR reveal that NiOx species are firstly reduced at around 650 ºC and they shift the onset of methane partial oxidation to lower temperatures with regards to the unmodified perovskite. However, during isothermal CL tests at 850 ºC, the presence of Ni does not modify much the syngas production during the methane reforming stage, although the H2/CO ratio increases with the presence of this metal. This indicates an increment in the contribution of methane cracking. In contrast, when feeding CO2, the generation of CO is greatly enhanced by the incorporation of Ni, particularly at a loading of 0.4 mol%, while higher metal concentration are slightly less effective. Higher CO generation is attributed to the promotion of reverse Boudouard reaction, which can remove the coke previously deposited in the methane reforming stage. Accordingly, the Ni/ La0.9Sr0.1FeO3 presents a stable activity during several consecutive cycles.