Abstract

Water-splitting thermochemical cycles have emerged as a possible solution for the decentralized production of hydrogen using solar energy. A useful tool to select the most promising thermochemical cycles among those proposed in the literature is represented by the exergy analysis. In this context, the exergy and energy analyses of the zinc/zinc oxide thermochemical water-splitting cycle, coupled with the production of electrical energy in a fuel cell, are here carried out and discussed. The aim has been to identify the steps in the process characterized by the highest inefficiencies and to propose possible solutions to increase the overall thermodynamic efficiency. Calculations were carried out using the commercial process simulator PRO/II. The cycle consists of two steps: (i) the endothermic thermal reduction of solid zinc oxide to liquid zinc and oxygen, carried out in a solar thermo-reactor at 2025 °C, and (ii) the non-solar, exothermic hydrolysis of zinc to form hydrogen and solid zinc oxide. This work reports three possible process schemes based on the zinc/zinc oxide redox reactions, each differing from the others in terms of envisaged modes of heat recovery. In addition, the effect of carrying out the hydrolysis step under adiabatic, rather than isothermal conditions, has been analysed. Four values of conversion were considered (1, 0.9. 0.8, and 0.7) and the effect on fuel cell power generation, utility consumption, and energy and exergy efficiency was evaluated. It was found that the exergy efficiency increased from about 14% for the classical zinc/zinc oxide cycle to almost 40% in the most efficient scenario considered here. The variation of hydrogen conversion in the fuel cell led to a decrease in generated power, from 16.41 MW at hydrogen conversion of 1 down to 11.48 MW at hydrogen conversion of 0.7.

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