Mechanically mixed ZnO‐Al2O3 catalysts in the synthesis of propylene carbonate via alcoholysis of urea

Alcoholysis of urea with 1,2‐propylene glycol (PG) is a potential industrial process for the synthesis of propylene carbonate (PC) with many advantages. However, the preparation of industrial catalysts such as Zn‐Al oxide by the co‐precipitation method will inevitably produce a large amount of salty water and building desalting equipment will increase the investment cost. The present work attempts to use a mechanically mixed catalyst consisting of commercial ZnO and Al2O3 to solve these problems. This type of catalyst was capable of catalyzing the reaction more than 5 times. The PC yield was gradually increased with each use. The best PC yield of 96.7% is comparable to the co‐precipitated Zn‐Al oxide catalysts and was achieved during the third use. In the reaction, ZnO and Al2O3 were dissolved into the reactants to form complexes, which homogenously catalyzed the reaction. It was found that the dissolved Zn and Al complex significantly influenced the PC yield and re‐precipitated in the late stage of the reaction. Furthermore, the partial dissolution of Al assisted the dissolution and precipitation of Zn, which improved the PC yield. After several dissolution‐precipitation cycles, ZnO‐Al2O3 was homogeneously mixed at the atomic scale. Interestingly, there was an adequate linear relationship between the amount of dissolved Zn and Al in each reaction, the linear correlation coefficient improved after each reaction, and the slope of the line (the ratio of dissolved Zn/Al) was 7.26 in the third use.