Abstract
In this study, we investigated urea glycerolysis over ZnAl2O4 catalysts that were prepared by using a citrate complex method and the influence of calcination temperatures on the surface properties of the prepared catalysts by varying the calcination temperature from 550 °C to 850 °C. As the reciprocal substitution between Al3+ and Zn2+ cations led to the formation of a disordered bulk ZnAl2O4 phase, different calcination temperatures strongly influenced the surface properties of the ZnAl2O4 catalysts, including oxygen vacancy. The increase in the calcination temperature from 550 °C to 650 °C decreased the inversion parameter of the ZnAl2O4 structure (from 0.365 to 0.222 for AlO4 and 0.409 to 0.358 for ZnO6). The disordered ZnAl2O4 structure led to a decrease in the surface acidity. The ZnAl2O4-550 catalyst had a large specific surface area, along with highly disordered surface sites, which increased surface acidity, resulting in a stronger interaction of the Zn NCO complex on its surface and an improvement in catalytic performance. Fourier transform infrared and thermogravimetric analysis results of the spent catalysts demonstrated the formation of a greater amount of a solid Zn NCO complex over ZnAl2O4-550 than ZnAl2O4-650. Consequently, the ZnAl2O4-550 catalyst outperformed the ZnAl2O4-650 catalyst in terms of glycerol conversion (72%), glycerol carbonate yield (33%), and byproduct formation.