Hydrogenous environments put forward new requirements to refractories for the hydrogen metallurgy field. The temperature and impurities in refractories played an important role in stability. A commercial brown corundum with many impurities was adopted as a raw material, thermodynamic calculations and reduction experiments of the brown corundum by high-purity hydrogen (99.99%) were accepted to investigate the stability of the oxides. The weight loss and mass fraction were tested to estimate the stability of the oxides in the brown corundum. XRD and SEM were used to analyze the mineral compositions and microstructures. The results showed that: the thermodynamic stability of the oxides in the brown corundum under high-purity hydrogen was in the order of Al2O3 > CaO > MgO > SiO2 > TiO2 > Fe2O3 at temperatures lower than 1400 °C. Obvious weight loss appeared after heating at 1400 °C for 8 h. The content of CaO did not decline after reduction even at 1800 °C, owing to the formation of hibonite (CaAl12O19), high-purity Al2O3 and CaAl12O19 -based refractories had the prospect for lining materials in the hydrogen metallurgy field, owing to their excellent chemical stability under hydrogenous environments.
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