Pressure‐Induced Enhancement in Chemical Looping Reforming of CH4: A Thermodynamic Analysis with Fe‐Based Oxygen Carriers

Abstract Chemical looping reforming of methane (CLRM) with Fe‐based oxygen carriers is widely acknowledged as an environmentally friendly and cost‐effective approach for syngas production, however, sintering‐caused deactivate of oxygen carriers at elevated temperatures of above 900 °C is a longstanding issue restricting the development of CLRM. Here, in order to reduce the reaction temperature without compromising the chemical‐looping CH 4 conversion efficiency, we proposed a novel operation scheme of CLRM by manipulating the reaction pressure to shift the equilibrium of CH 4 partial oxidation towards the forward direction based on the Le Chatelier's principle. The results from thermodynamic simulations showed that, at a fixed reaction temperature, the reduction in pressure led to the increase in CH 4 conversion, H 2 and CO selectivity, as well as carbon deposition rate of all investigated oxygen carriers. The pressure‐negative CLRM with Fe 3 O 4 , Fe 2 O 3 and MgFe 2 O 4 could reduce the reaction temperature to below 700 °C on the premise of a satisfactory CLRM performance. In a comprehensive consideration of the CLRM performance, energy consumption, and CH 4 requirement, NiFe 2 O 4 was the Fe‐based OCs best available for pressure‐negative CLRM, especially for an excellent syngas yield of 23.08 mmol/g OC . This study offered a new strategy to address sintering‐caused deactivation of materials in chemical looping from the reaction thermodynamics point of view.