Comparison of non-isothermal and isothermal cycles in a novel methane-assisted two-step thermochemical process

Abstract

As driven by thermodynamics and reaction kinetics considerations, conventional two-step solar thermochemical processes typically rely on non-isothermal cycling conditions to effectively couple the endothermic reduction and exothermic oxidation reactions. Nevertheless, recent discussions on isothermal cycles based on thermodynamics simulation and material characterization have sparked dissenting opinions, as certain reaction processes operating under isothermal cycling conditions have demonstrated the possibility of achieving higher energy conversion efficiency. To delve further into such phenomenon and potentially unveil the underlying scientific principles, this study conducts a reaction kinetic analysis and lab-scale systematic experiments on a novel methane-assisted two-step thermochemical process using iron-based oxygen carriers. Despite the fact that the reaction kinetics analysis of iron oxides indicates that isothermal cycles at reaction temperatures of 573–1173 K do not provide significant advantages in terms of energy conversion efficiency, surprisingly, the experiments conducted with the prepared cobalt–nickel ferrite materials conclude oppositely. More specifically, the observed increase in material reactivity with rising oxidation temperature contributes to an approximately two-fold enhancement in the CO yield under isothermal conditions, as well as a noteworthy improvement of about 15% in solar-to-fuel efficiency. This energy efficiency improvement could be attributed, at least in part, to the stable reaction temperature during isothermal cycling, which effectively mitigates the challenges associated with solid-phase sensible heat recovery caused by significant temperature fluctuations, particularly when operating at high feed flow rates. Accordingly, the applicability of isothermal cycles is linked to two crucial factors: the reactivity of the oxygen carrier and the specific operating conditions employed. The experiments herein conducted showed that the catalytic activity of the material reached a relatively stable state after 24 h of reaction, resulting in a peak CO yield of 20.5 mL min${}^{-1}$ g⁻¹ and a CO${}_2$ conversion exceeding 90%. Thorough analyses reveal several optimization measures for enhancing efficiency under the setting of the reaction system.