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目前生产碳酸二甲酯(DMC)的工艺大多采用非光气法清洁路线,而光气法路线因存在对环境不利等因素现已少有人研究.为了解决氯碱厂氯气产能过剩且难以利用的现状,提出了利用氯气与甲醇增产DMC新工艺思路.将DMC深度氯代生成氯代物,将生成的氯代物与甲醇进行反应精馏,同时考察了氯代液与甲醇反应生成DMC的条件.结果表明,氯代液密度为1.539 8g/mL时,反应精馏塔顶采出液中DMC质量分数为83.33％,DMC单程增产30.43％.“,”At present,most of dimethyl carbonate (DMC) production plants use clean non-phosgene route.Few people research the phosgene route because it is unfriendly to the environment.In order to solve the chlorine overcapacity problem in chlor-alkali plants,this paper proposes a new process idea to increase production of dimethyl carbonate by means of chlorine gas and methanol.DMC is deeply chlorinated to manufacture chlorinated hydrocarbons that experience reactive distillation with methanol together in experimental device.The conditions for production of DMC by reaction between chlorinated hydrocarbons and methanol are investigated.The experiment shows that the mass content of DMC in the produced fluid on the top of reactive distillation column can reach 83.33％ and the one-pass production of DMC can increase 30.43％ when the specific gravity of chlorinated hydrocarbons is around 1.539 8 g·mL-1.