反應與分離程序同時在蒸餾塔內進行的操作方式，稱作反應蒸餾，此操作方式可節省生產以及設備的成本，但由於反應與分離同時進行，也使得分離程序較為複雜，得同時考慮汔液相平衡與反應的發生，所以此反應蒸餾數據為此程序設計上的重要依據。 本研究係探討碳酸二甲酯與乙醇，經由轉酯化反應(transesterification)產生碳酸二乙酯及甲醇，反應過程中產生中間產物碳酸甲乙酯，此轉酯化反應可達成較低的成本消耗以及避免傳統光氣法製造碳酸二乙酯過程中的高毒性物質，降低對環境的破壞。此五成份在化學達到平衡後，進行汽液相平衡數據的量測，以考慮化學反應對汽液相平衡的影響。 實驗係以汽液平衡裝置進行數據的測量，並在過程中加入觸媒(碳酸鉀塗佈聚乙二醇)以縮短化學反應的時間，並收集了45點的實驗數據。數據分別以UNIQUAC及NRTL兩種液相活性係數模式進行迴歸，並比較關聯結果和實驗數據的差異，由結果顯示，UNIQUAC及NRTL兩種液相模式所得的關聯結果都不錯，但以UNIQUAC較好一點。最後以UNIQUAC模式來計算液相活性係數，繪出此五成份的反應相圖，並由相圖中判斷此研究中的五成份系統在伴隨反應的情形下，所獲得的數據沒有出現反應共沸點(reactive azeotrope)。 In this study, the thermodynamic behaviors of chemical and phase equilibria of dimethyl carbonate, ethanol, ethyl methyl carbonate, enthonol, and diethyl carbonate mixture were experimentally investigated. During experiment, the modified Other type equilibrium cell was used and a catalyst, which is a compound of potassium carbonate and would not affect the phase equilibrium, was added to accelerate the chemical reaction rate and shorten the experimental time for equilibrium. 45 experimental data were collected for this study. The experimental vapor-liquid-equilibrium data were correlated with the activity coefficient models of UNIQUAC and NRTL. The correlated results showed that the UNIQUAC model is more suitable than the NRTL model and agree fairly well with the experimental data. It is also found that the reactive azeotrope defined by Doherty does not exist in this studied system.
