VAPOR-PHASE SYNTHESIS OF LACTIDE FROM ETHYL LACTATE OVER TiO2/SiO2 CATALYST

Abstract

The lactide is monomer for production of polylac- tide – biodegradable polymer that use as an ecological packagingmaterial. In an industry the two-stage lactide synthesis is applied. At first, lactic acid condenses into the oligomer using Sn-octanoate catalyst, then oligo- mer depolymerizes to lactide. The drawbacks of this liquid-phase method are a significant amount of by- products — dimers and trimers of lactic acid and low lactide yield.Now a direct vapor-phase condensation of lactic acid and its esters to lactide is considered as alternative to the industrial process. One-stage lactide obtaining and use of solid catalysts are advantages of such method. In this work, the vapor-phase transfor- mation of ethyl lactate over supported TiO2/SiO2 and TiO2/Al2O3 oxides in nitrogen flow at 200–300 °С
 was studied. The oxide samples were obtained by impregnating silica gel and γ -alumina with an approp- riate amount of titanium tetrabutoxide solution in iso- propanol, then dried at 80 oC, and finally calcined at 500 oC in air for 4 h. The catalysts were characterized by BET method, X-ray diffraction and UV-Vis diffuse reflectance spectroscopy. Catalytic experi- ments were carried out in a steel flow reactor at 200
 –270 °С and atmospheric pressure. The load on a ca-talyst was varied in the interval of 8.2–36.4 mmol ethyllactate/(gcat⋅ h) that corresponds gas hourly space velo- city of the mixture of ethyl lactate and nitrogen of 1230–1490 h–1. It was shown that TiO2/SiO2 with5 wt.% content of titanium dioxide provides 48 % conversion of ethyl lactate with selectivity and pro- ductivity towards lactide 74 % and 7.0 mmol/(gcat⋅ h)at 270 °C, respectively. It was found thatTiO2/SiO2 is more efficiently for lactide producing (STY = 6.2 mmol/(gcat⋅ h) compared to TiO2/Al2O3catalyst (STY =1.8 mmol/(gcat⋅ h). It was shown that spent TiO2/ SiO2 catalyst fully restores activity after regenerati- on in air at 500 °С for 2 h. The two-stage scheme of ethyl lactate condensation with the participation of coordina- tion-unsaturated titanium ions is discussed.