Impact of Partial Pressure, Conversion, and Temperature on the Oxidation Reaction Kinetics of Cu₂O to CuO in Thermochemical Energy Storage

Abstract

Metal oxides are promising potential candidates for thermochemical energy storage in concentrated solar power plants. In particular, the Cu2O/CuO system is suitable because of its high energy density, applied temperature interval, and reduced cost compared to the CoO/Co3O4 system. In heterogenous gas-solid reactions, the pressure affects the kinetics significantly. To quantify this effect for oxidation of Cu2O to CuO, isothermal runs between 800 °C and 930 °C at different oxygen partial pressures (0.1, 0.2, 0.5, and 1.0 bar) were conducted with thermogravimetric analysis (TGA). Defined fractions of CuO samples (1⁻100 µm) were analyzed with X-ray diffraction (XRD), Brunauer-Emmett-Teller (BET) analysis, and scanning electron microscopy (SEM) analysis. The kinetic analyses were performed with extended non-parametric kinetics (NPK), which is applied for the first time to consider the pressure term in the general kinetic equation in addition to the conversion and the temperature term. The results show how the oxygen partial pressure impacts the kinetics and how reparameterization of the pressure term affects the kinetic analysis of the oxidation reaction of Cu2O to CuO. The best conversion model is a two-dimensional Avrami-Erofeev model with an activation energy of 233 kJ/mol. The kinetic models for conversion, temperature, and pressure presented in this work provide one of the most important requirements for reactor designs.

Keywords

• thermochemical energy storage
• partial pressure
• kinetics
• thermogravimetric analysis
• Cu₂O/CuO