Catalytic Activity of Titanium Silicates Synthesized in the Presence of Alkali-Metal and Alkaline-Earth Ions

Abstract

Titanium containing aluminum-free ZSM-5 (TS-1) synthesized in the presence and absence of alkali metal and alkaline earth ions are investigated as catalysts for the selective oxidation of alkanes and alkenes using aqueous H2O2 as oxidant at temperatures below 100°C. Sodium-exchanged TS-1 is not active for alkane oxidations. Similarly, no catalytic activity is observed for TS-1 synthesized in the presence of high concentrations of alkali metal ions (Si/Na <20). For both cases, the catalytic activity can be restored by washing the solid with acid solution prior to catalytic evaluation. Similar results are obtained for TS-1 synthesized in the presence of other alkali metal ions, e.g., Li, K. However, the presence of alkaline earth ions, e.g., Mg, in the synthesis gel does not have a significant effect on the catalytic activity of TS-1. Based on the catalytic data and the physicochemical properties of the samples, a plausible explanation for the above results is described. The acid treatment may be useful in overcoming the problems of synthesizing TS-1 from reagents that contain alkali metal ions, e.g., TPAOH solutions. More importantly, this treatment opens the possibility of synthesizing other titanium-containing silicate structures that require the presence of alkali metal ions in the synthesis gel for their formation.