Evaluating the chemical stability of metal oxides in SO3 and applications of SiO2-based membranes to O2/SO3 separation

The decomposition of sulfur trioxide to produce sulfur dioxide and oxygen using a catalytic membrane reactor is technology that promises to improve the economic viability of the thermochemical water-splitting Iodine-Sulfur (IS) process for large-scale CO₂-free hydrogen production. The chemical stability of membrane materials under SO₃, however, is a significant challenge for this strategy. In this study, microporous membranes with a layered structure that consisted of a membrane support prepared from α-Al₂O₃, an intermediate layer prepared from silica-zirconia, and a top layer prepared from bis (triethoxysilyl)ethane-derived organosilica sols, were examined for stability under SO₃ and for use in SO₃/O₂ separation. An α-Al₂O₃ support that features SiO₂–ZrO₂ intermediate layers with large pore sizes and a high Si/Zr molar ratio showed excellent resistance to SO₃, which was confirmed by N₂ adsorption, Energy Dispersive X-ray Spectroscopy (EDS), and Scanning Electron Microscopy (SEM). These membranes also demonstrated a negligible change in gas permeance before and after SO₃ exposure. Subsequently, in binary-component gas separation at 550°C, microporous organosilica-derived membranes achieved an O₂/SO₃ selectivity of 10 (much higher than the Knudsen selectivity of 1.6) while maintaining a high O₂ permeance of 2.5 × 10⁻⁸ mol m^–2 s^–1 Pa^–1.