The effects of promoters on catalytic properties and deactivation–regeneration of the catalyst in the synthesis of dimethyl carbonate Original Research Article

The effects of different alkali metal promoters in PdCl2-CuCl2/activated carbon (a.c.) catalyst on the reaction performance for synthesizing dimethyl carbonate (DMC) by gas-phase oxidative carbonylation of methanol were studied. The bulk and surface properties of catalyst PdCl2-CuCl2-CH3COOK/a.c. were characterized by XRD, XPS, and AAS techniques. On the basis of catalyst characterization and activity evaluation, the functions of promoters were further investigated, and the deactivation–regeneration of catalyst PdCl2-CuCl2-CH3COOK/a.c. was also discussed. The results show that the space time yield (STY) of DMC on catalysts with different alkali metal promoters ranks in the following order: K>Na>Li. The main reason for catalyst deactivation is the loss of chlorine. Fortunately, during the preparation of the catalyst, the interaction between CH3COOK and PdCl2 or CuCl2 that results in the formation of KCl limits the loss of chlorine. An obvious increase of the catalyst lifetime and catalytic activity is observed by treating fresh catalyst with a methanol solution of methyl chloroacetate. If deactivated catalyst is treated with a methanol solution of methyl chloroacetate in N2 stream at 200 °C for 4 h and then treated in N2 stream at 200 °C for 2 h, the catalytic activity can be restored effectively and the regeneration induction period can be shortened. The catalytic activity after two times of regeneration can still be restored to 93% of the fresh catalyst. The run time of this catalyst is up to 300 h.