Oxidation of xylose – methanol mixture into methyl lactate and methyl glycolate on CeO2-SnO2/Al2O3 catalyst

The development of catalytic methods for xylose transformation as renewable raw material into value-added chemicals such as lactic and glycolic acid esters has been the subject of intensive research in recent years. Thus, methyl lactate and methyl glycolate are used as a starting material for the production of lactide and glycolide – an important monomers for the production of biodegradable polymers. The aim of this work was to search of simple effective catalyst for transformation of xylose into methyl esters of lactic and glycolic acids. For this purpose, tin-containing alumina doped with СeO2, MoO3 and CuO oxides were synthesized by impregnation method. Textural and structural parameters of obtained МeO‑SnO2/Al2O3 mixed oxides were estimated from the results of low-temperature adsorption-desorption of nitrogen and X-ray diffraction. The formation of morphology ceria close to octahedra for CeО2‑SnO2/Al2O3 sample is confirmed by the X-ray phase analysis data and SEM microphotographs. The UV spectroscopy data indicates the nanosize of tin dioxide particles on the γ‑Al2O3 surface. According to the titration results, CeО2‑SnO2/Al2O3 is acid mixed oxide with H0 ≤ –3.0. The catalytic conversion of xylose solution in methanol was carried out in rotated autoclaves and in a flow stainless steel reactor with a fixed bed of catalyst. The products of the target reaction C5H10O5+2CH3OH+1/2O2 = C4H8O3+C3H6O3+2H2O were analyzed by 13C NMR. It was found that a complete conversion of 4 % xylose solution in a 70 % aqueous methanol solution occurs with the formation of methyl lactate (42 %) and methyl glycolate (24 %) on the developed CeO2-SnO2/Al2O3 catalyst loading of 3.5 mmol C5H10O5/gcat/h at 190 °C/3.0 MPa in air flow. The path of the reaction is proposed, namely: the IVSn4+ ions in CeO2-SnO2/Al2O3 catalyst as Lewis acid sites promote retro-aldol xylose condensation and further Cannizzaro rearrangement of intermediate methyl pyruval hemiacetal into methyl lactate. And CeO2 provides selective oxidation of glycol aldehyde formed as a result of aldol decondensation of xylose to methyl glycolate.