Oxidative coupling of methane-comparisons of MnTiO₃-Na₂WO₄ and MnOₓ-TiO₂-Na₂WO₄ catalysts on different silica supports

Abstract

The oxidative coupling of methane (OCM) converts CH₄ to value-added chemicals (C₂₊), such as olefins and paraffin. For a series of MnTiO₃-Na₂WO₄ (MnTiO₃-NW) and MnOₓ-TiO₂-Na₂WO₄ (Mn-Ti-NW), the effect of loading of MnTiO₃ or MnOₓ-TiO₂, respectively, on two different supports (sol–gel SiO₂ (SG) and commercial fumed SiO₂ (CS)) was examined. The catalyst with the highest C₂₊ yield (21.6% with 60.8% C₂₊ selectivity and 35.6% CH₄ conversion) was 10 wt% MnTiO₃-NW/SG with an olefins/paraffin ratio of 2.2. The catalyst surfaces with low oxygen-binding energies were associated with high CH₄ conversion. Stability tests conducted for over 24 h revealed that SG-supported catalysts were more durable than those on CS because the active phase (especially Na₂WO₄) was more stable in SG than in CS. With the use of SG, the activity of MnTiO₃-NW was not substantially different from that of Mn-Ti-NW, especially at high metal loading.