气相法亚硝酸乙酯再生反应的研究

Study on Ethyl Nitrite Regeneration in a Gaseous Phase Reactor

一氧化气相碳偶联合成草酸二乙酯(DEO)在过去几十年来已引起了广泛兴趣。该过程涉及两个反应:一氧化碳偶联生成DEO的反应和亚硝酸乙酯(EN)的再生反应。这两个反应同时发生,因此只要再生反应速度与偶联反应速度彼此匹配,该系统可构成一个闭路的稳定循环系统。本文研究了一种EN再生气相反应器,以替代以往的副反应严重、乙醇循环能耗高的鼓泡反应器。研究发现气相法EN再生反应的最佳工艺条件为:反应温度80℃,n(乙醇)/n(NO)为1.5～2,n(NO)/n(O2)为6～8,(φN2)为15%～30%,停留时间为24s～29s。

The synthesis of diethyl oxalate （DEO） via carbon monoxide gaseous phase coupling reaction has attracted a lot of interests in past decades. The process involves two chemical reactions, CO coupling to produce DEO and regeneration of ethyl nitrite （EN）. The two reactions take place simultaneously, so the system could be a closed steady recycle system if only the reaction rates of regeneration and coupling match each other. A gaseous phase reactor was studied for EN regeneration to substitute the conventional bubbled reactor which resulted in the problems like side reactions and high energy consumption for ethanol recycle. It was found that the gaseous phase reactor is suitable for EN regeneration and the optimum process conditions were determined to be reaction temperature 80℃, NO to O2 molar ratio 6-8, ethanol to NO molar ratio 1.5-2, N2 volume content 15%-30% and residence time 24s-29s.