Aqueous-phase catalytic oxidation of furfural with H2O2: high yield of maleic acid by using titanium silicalite-1

This investigation explores the selective liquid-phase oxidation of furfural to maleic acid (MA) using hydrogen peroxide as an oxidant and titanium silicalite (TS-1) as a catalyst. The effect of temperature and of the concentration of H2O2, furfural and catalyst on the MA yield was studied. The highest yield, 78 mol%, was obtained under the following reaction conditions: 4.6 wt% of furfural, 4.6 wt% of catalyst, a H2O2/furfural mol ratio of 7.5, corresponding to 12.3 wt% of H2O2, 323 K and 24 hours of reaction. To reduce the amount of H2O2 employed, a two-step sequence of reactions was conducted using TS-1 and Amberlyst 70 consecutively as catalysts in the first and second steps, respectively. In this case, a H2O2/furfural mol ratio = 4.4 was required, which is quite close to the stoichiometric ratio (3.0), and a maleic acid yield close to 80% was obtained under 4.6 wt% of furfural, 4.6 wt% of catalyst and 28 h of reaction at 323 K; after 52 h of reaction, the MA yield reached 92%. Fresh and used catalysts were characterised by X-ray diffraction (XRD), Raman spectroscopy, total reflection X-ray fluorescence (TXRF), X-ray photoelectron spectroscopy (XPS), N-2 adsorption-desorption isotherms and thermogravimetric analysis. Ti was largely incorporated within the silicalite framework, but the presence of some TiO2 anatase was also confirmed. Ti leaching was observed, especially during the first run but became much less important in successive cycles. Leaching affects both anatase and Ti species within the silicalite framework. Notwithstanding the leaching, when using pure furfural, TS-1 could be reused for six runs without noticeable deactivation, whereas when using furfural directly derived from biomass, weak but visible deactivation occurred upon reutilisation; this deterioration must be related to the presence of some organic products other than furfural.