Enhanced performance of chemical looping combustion of methane by combining oxygen carriers via optimizing the stacking sequences

Abstract

Combination of different types of oxides is a general strategy to prepare high performance oxygen carriers (OCs) for chemical looping combustion (CLC) technology. However, the possible chemical interactions among different components during the long-term redox cycling may reduce the stability of OCs. In the present work, we physically combine different types of OC sticks (i.e., CuO/SiO2, Fe2O3/Al2O3, Mn2O3/ZrO2 and NiO/ZrO2) in particular stacking sequences in a fixed bed reactor to improve the CLC performance. The reaction between methane and CuO is exothermic and the CuO/SiO2 OC exhibits very high activity for methane oxidation and superior resistance to carbon deposition. It is suitable to place the CuO/SiO2 in the front of the sequence which can sufficiently convert methane, and the heat releasing from this reaction will promote the following endothermic reactions. NiO/ZrO2 OC also represents very high activity for CH4 oxidation but results in serious carbon deposition. Since the reduced metallic Ni is an active catalyst for methane activation, it is suggested to place NiO/ZrO2 in the middle of the sequence to enhance the further conversion of methane and to provide enough space to remove the carbon deposition via the gasification by CO2 or H2O generated from the front reaction. Mn2O3/ZrO2 OC possesses poor activity for methane conversion but high resistance to carbon deposition, which can be used to convert unreacted methane in the end of the sequence. Fe2O3/Al2O3 OC is not an important issue due to the low activity and reaction rate. As a result, the combined OCs with a stacking sequence of CuNiFeMn or FeCuNiMn show high performance in CH4 conversion (>97%), CO2 selectivity (>96%), redox stability and resistance to carbon deposition. These results make a certain reference for using the combined OCs in the large-scale CLC system.