Identifying the ideal thermodynamics of non-stoichiometric oxygen-carrier materials for chemical looping water-gas shift†

With the growth in importance of H₂ both industrially and as a potential energy vector along the pathway to achieving future environmental sustainability, there is an increasing need for cleaner and more efficient methods of H₂ production. One promising short-term solution is to perform the water-gas shift reaction for H₂ production in a chemical looping reactor to produce separate H₂ and CO₂ streams, thereby reducing equipment size and the cost of downstream CO₂ separation. Non-stoichiometric perovskite oxides have been identified as promising oxygen carrier materials (OCMs) for the chemical looping water-gas shift (CLWGS) process as they can be engineered to allow rapid oxygen uptake kinetics, and also benefit from a thermodynamic advantage allowing higher conversions than that of conventional mixed feed reactor systems at the same temperature. The relationship between the oxygen non-stoichiometry of the solid OCM and the equilibrium oxygen partial pressure of the gas phase streams plays an important role in determining the gas conversions and usable oxygen capacity of the OCM. In this work, an optimal relationship between the two material properties in a thermodynamically limited system is proposed, and an equilibrium packed-bed reactor model is used for validation. The effect on conversions was investigated by varying the thermodynamics of the non-stoichiometric material relative to the proposed optimal case. More generally, an analogue of the pinch analysis can be used to analyse chemical looping water-gas shift reactions and similar processes.