Hydrolytic and catalytic activity of copper catalyst and several additives (water absorbents and solvents) were investigated in the oxidative carbonylation of methanol to synthesis of dimethyl carbonate (DMC). The results showed that synthesis of dimethyl carbonate from methanol can be promoted a little by the introduction of the alkalescence water absorbent K2CO3 and the high boiling polar aprotic solvent N,N-dimethylacetamide. Under the reaction conditions of 100-110 ℃ of temperature, pressure of 3.5 MPa, reaction time of 4 h, CuxBrn Lm catalyst concentration of 0.15 g/mL and CuBr2 concentration of 0.075 g/mL, the methanol conversion could exceed 48.5％ and the DMC selectivity was about 92.5％ when the concentraion of alkalescence water absorbent K2CO3 was 0.001 g/mL and solvent N, N-dimethylacetamide was 0.3 volume ratio to methanol, which may be useful to practical production.%针对甲醇液相氧化羰基合成碳酸二甲酯工艺,探讨了几种铜催化剂水解活性和催化活性之间的关系,考察了各种添加剂(吸水剂和溶剂)对该催化体系的影响.结果表明,具有一定碱性环境的吸水剂K2CO3和高沸点强极性非质子溶剂N,N-二甲基乙酰胺对羰化反应具有一定的促进作用.在温度100～110℃、压力3.5 MPa、反应时间4 h、催化剂浓度0.15 g/mL、助催化剂浓度CuBr2为0.075 g/mL的工艺条件下,碱性吸水剂 K2CO3浓度为0.001 g/mL、溶剂N,N-二甲基乙酸胺浓度为0.3 mL/mL时,甲醇的转化率为48.5%,碳酸二甲酯的选择性可达92.5%,这对于工业应用具有一定的指导意义.
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