甲醇氧化羰化合成DMC铜系催化剂的研究

Study of the copperbased catalysts for oxidative carbonylation of methanol to dimethyl carbonate

用ＣｕＣｌ２或ＣｕＣｌ作催化剂，ＣＨ３ＯＨ、Ｏ２、ＣＯ为原料，合成碳酸二甲酯（ＤＭＣ）。研究了催化剂及其用量、氧气浓度、反应压力以及含氮助剂对反应的影响。结果表明，当ＣｕＣｌ２量达到０．１ｇ／ｍｌ甲醇，ＣｕＣｌ量达到０．０４ｇ／ｍｌ甲醇后，增加催化剂对ＤＭＣ的生成速度影响不大；一次性加入氧气浓度超过１０％的原料气，ＤＭＣ的生成速率下降；ＤＭＣ的生成速度随系统总压力升高而加快；加入有机含氮助剂可使反应速度加快，同时可提高ＤＭＣ的选择性。

Dimethyl carbonate(DMC) is synthesized from methanol with carbon monoxide and oxygen over a cupric chloride or cuprous chloride catalyst. A study is performed on effects of the amount of catalyst, oxygen concentration, reaction pressure, and nitrogen donor ligands on carbonylation.The results show that the catalytic activity and selectivity of cuprous chloride to DMC are higher than those of cupric chloride. When the quantities of cupric and cuprous chlorides are lifted to 1.0 × 10^-1 g/ml CH_3OH and 4.0 × 10^-2 g/ml CH_3OH respectively, further increment has little influence on the formation rate of DMC. When a mixed gas with an oxygen content over 10% is fed at one time, the formation rate of DMC will decrease. Put nitrogen donor ligands can accelerate the formation of DMC and increase the selectivity to DMC.