On the Kinetic Mechanisms of the Reduction and Oxidation Reactions of Iron Oxide/Iron Pellets for a Hydrogen Storage Process

Abstract

This work aims at investigating the kinetic mechanisms of the reduction/oxidation (redox) reactions of iron oxide/iron pellets under different operating conditions. The reaction principle is the basis of a thermochemical hydrogen storage system. To simulate the charging phase, a single pellet consisting of iron oxide (90% Fe2O3, 10% stabilising cement) is reduced with different hydrogen (H2) concentrations at temperatures between 600 and 800 °C. The discharge phase is initiated by the oxidation of the previously reduced pellet by water vapour (H2O) at different concentrations in the same temperature range. In both reactions, nitrogen (N2) is used as a carrier gas. The redox reactions have been experimentally measured in a thermogravimetric analyser (TGA) at a flow rate of 250 mL/min. An extensive literature review has been conducted on the existing reactions’ kinetic mechanisms along with their applicability to describe the obtained results. It turned out that the measured kinetic results can be excellently described with the so-called shrinking core model. Using the geometrical contracting sphere reaction mechanism model, the concentration- and temperature-dependent reduction and oxidation rates can be reproduced with a maximum deviation of less than 5%. In contrast to the reduction process, the temperature has a smaller effect on the oxidation reaction kinetics, which is attributed to 71% less activation energy (Ea,Re=56.9 kJ/mol versus Ea,Ox=16.0 kJ/mol). The concentration of the reacting gas showed, however, an opposite trend: namely, to have an almost twofold impact on the oxidation reaction rate constant compared to the reduction rate constant.