Water Splitting by MnOx/Na2CO3 Reversible Redox Reactions

Abstract

Thermal water splitting by redox reactants could contribute to a hydrogen-based energy economy. The authors previously assessed and classified these thermo-chemical water splitting redox reactions. The Mn3O4/MnO/NaMnO2 multi-step redox cycles were demonstrated to have high potential. The present research experimentally investigated the MnOx/Na2CO3 redox water splitting system both in an electric furnace and in a concentrated solar furnace at 775 and 825 °C, respectively, using 10 to 250 g of redox reactants. The characteristics of all reactants were determined by particle size distribution, porosity, XRD and SEM. With milled particle and grain sizes below 1 µm, the reactants offer a large surface area for the heterogeneous gas/solid reaction. Up to 10 complete cycles (oxidation/reduction) were assessed in the electric furnace. After 10 cycles, an equilibrium yield appeared to be reached. The milled Mn3O4/Na2CO3 cycle showed an efficiency of 78% at 825 °C. After 10 redox cycles, the efficiency was still close to 60%. At 775 °C, the milled MnO/Na2CO3 cycles showed an 80% conversion during cycle 1, which decreased to 77% after cycle 10. Other reactant compounds achieved a significantly lower conversion yield. In the solar furnace, the highest conversion (>95%) was obtained with the Mn3O4/Na2CO3 system at 775 °C. A final assessment of the process economics revealed that at least 30 to 40 cycles would be needed to produce H2 at the price of 4 €/kg H2. To meet competitive prices below 2 €/kg H2, over 80 cycles should be achieved. The experimental and economic results stress the importance of improving the reverse cycles of the redox system.