Mario Gabriele Clerici

Synthesis of propylene oxide from propylene and hydrogen peroxide catalyzed by titanium silicalite

Abstract The epoxidation of propylene with hydrogen peroxide in the liquid phase, in the presence of titanium silicalite catalyst (TS-1), is described. The best solvents are methanol and methanol/ water mixtures. The temperature is normally between room temperature and 60°C. Under these conditions, reaction rates are fast, yields on H2O2 are quantitative, and selectivity to propylene oxide is very high. Propylene glycol and its monomethyl ethers and trace amounts of formaldehyde are the only by-products formed. Selectivity is further improved and the hydrolysis of the epoxide is almost suppressed when the residual acidity of the catalyst is completely neutralized. The activity of spent catalyst is recovered by calcining at 550°C or, more simply, by washing with solvents. Complete activity recovery shows that Ti is not removed from the crystalline framework during the epoxidation reactions.

Reactions of titanium silicalite with protic molecules and hydrogen peroxide

The properties of titanium silicalite (TS-1) in reactions with water, hydrogen peroxide, and alcohol molecules have been studied by means of IR and NMR spectroscopy, and acid activity tests. An IR absorption is shown by TS-1 in the region 900–975 cm−1. Its exact position depends on the amount of adsorbed water, on exchange reactions with 17O- and 18O-labeled water, and on the average size of the crystallites. In 17O MAS NMR spectra a peak is shown at σ 360 ppm from H2 17O (σ = 0). IR and NMR spectra are discussed and interpreted in terms of Ti sites as constituted by tetrahedral [TiO4] units. TiOSi bonds react with water at near room temperature, producing TiOH and SiOH species. Reactions with hydrogen peroxide produce acidic derivatives, which catalyze the hydrolysis of cis and trans 2,3-epoxybutane in methanol, ethanol, and aqueous media. A five-membered ring hydrogen bonded structure, in which a titanium hydroperoxo moiety, TiOOH, and a protic molecule, ROH (R = H, CH3, C2H5), are involved, is proposed for these species. Their possible role in selective oxidations of hydrocarbons is discussed.