Effect of SSIE structure of Cu-exchanged β and Y on the selectivity for synthesis of diethyl carbonate by oxidative carbonylation of ethanol: A comparative investigation

Cu-exchanged β and Y catalysts were investigated by oxidative carbonylation of ethanol in the gas-phase reaction. Cuβ catalyst has shown better catalytic selectivity for oxidative carbonylation of ethanol to diethyl carbonate (DEC), without the principal by-product 1,1-diethoxyethane (DEE) for CuY catalysts. In order to investigate the effect of zeolite structure on the selectivity for products, computational analysis of molecular dimensions and diffusion parameters of DEC and DEE within Cuβ and CuY catalysts zeolite framework has been performed using molecular mechanics and quantum mechanics methods. The computational analysis results are in good agreement with the experimental results to some extent. DEC having a kinetic diameter of 3.663 Å and the lowest energy barrier was formed preferentially over both zeolites. However, the DEE molecule was not detected among the products over Cuβ because of its greater kinetic diameter 6.059 Å and higher energy barrier. The special architecture of β zeolite did not allow the diffusion of DEE molecules through its pores. The formation of the higher sterically hindered DEE over CuY catalyst could be explained by involvement of the outer surface.