本研究在系統化地設計與控制兩種不同酯化類型之反應蒸餾程序。酯化反應使用酸性離子交換樹脂為觸媒。第一種反應類型為一階段酯化反應，包括五種不同的醇類(甲醇至戊醇)，與醋酸反應的酯化系統；第二種反應類型為二階段酯化反應，在此以己二酸與甲醇的酯化反應系統來介紹。程序模擬部分，採用文獻上已有反應動力學的描述，熱力學模式則在進行模擬之前，先行與實驗數據比對確認。最後，以年總操作成本(TAC)為目標函數對程序進行最適化。
對於五種一階段醋酸酯化之反應蒸餾流程，共可歸類於三大類型，其分類可從各系統中混合物的相關之相行為來區分；如沸點排序、非均相區域的大小以及蒸餘曲線圖等。各系統的非線性程度評估，可從塔板溫度增益變號比例與Allogower所提非線性指標得到，而大部分的程序也多具有多重穩態的現象。雙溫度與一溫度一組成兩控制都能適用於各類型的反應蒸餾流程，以簡單的分散型控制(decentralized control)可有效地控制高度非線性的反應蒸餾系統。
對二階段反應的甲醇與己二酸酯化系統，為使在液液分離操作上的分析能夠準確，本工作量測了兩組三成分系統的液液相平衡數據，包括水、甲醇與酯類。液液相平衡數據以NRTL模式迴歸並得到最佳雙成分交互作用參數。二階段酯化系統有兩種反應蒸餾流程設計，同樣地也進行程序非線性估算。控制架構方面，這裡提出三種溫度架構用於此程序上，其皆可提供相當好的控制效果，但是不同的控制架構會使得程序能源需求上的不同。

總結不論是多複雜的反應系統，先行分析系統的特徵然後選擇正確控制策略，是成功且有效地完成反應蒸餾程序關鍵。如同文中所提，對於簡單的單一反應蒸餾塔或是複雜的整廠反應蒸餾流程，都能提供良好的操作性與控制性。

The design and control of various reactive distillation systems were systematically studied for two categories of heterogeneous catalytic esterification over acidic ion-exchange resins. A series of one-stage esterification of acetic acid with five different alcohols, from methanol to amyl alcohol, was selected as model systems for the first category, while two-stage esterification of adipic acid with methanol was chosen as an illustrative example for the second category. In the process simulations, the kinetic models were taken from literature and the thermodynamic models have been verified with experimental phase equilibrium data before use. The total annual cost (TAC) was adopted as the objective function for process optimization.
Three types of flowsheets were developed for those five one-stage esterification systems. The process development was mainly based on the phase behavior of the related mixtures such as boiling point ranking, immiscibility, and residue curve map (RCM). For each system, the degree of process nonlinearity was evaluated with the fraction of “sign reversal” of tray temperatures and the index of Allgower’s nonlinearity. The multiple steady-state phenomena were also found in most of the studied processes. Both dual-temperature control and one-temperature-one- composition control were investigated for each type of flowsheet. It was found that simple decentralized control was effective for those highly nonlinear reactive distillation systems.
For accurately analyzing the operation of liquid-liquid separation unit in the processes of two-stage esterification of adipic acid with methanol, liquid-liquid equilibrium (LLE) data of two ternary systems containing water, methanol and esters were measured in the present study. These LLE data were correlated with the NRTL model to determine the optimal binary interaction parameters. Two types of reactive distillation flowsheets were developed for this two-stage esterification system. Similarly, the process nonlinearity was also evaluated. Three kinds of temperature control structures were tested in this work. Satisfactory control performances have been achieved regardless of the control structures, but using different control structures lead to substantial difference in energy demands.
It is concluded that analysis the system characteristics first and then selection of correct control stratagem are keys to success for development of an efficient reactive distillation process, regardless of complexity of the reaction systems. As demonstrated in this study, good operability and controllability have been achieved for the processes which consist of only one reactive distillation column or plantwide complex reactive distillation systems.

http://www.dechema.de/detherm
詹凱雯，「己二酸與甲醇的非均相酯化反應動力行為研究」，國立台灣大學科技化學工程研究所碩士論文 (2004)

賴政海，「含甲醇、己二酸單甲酯與己二酸雙甲酯混合物的汽液相平衡研究」，國立台灣大學科技化學工程研究所碩士論文(2004)

童士哲，「反應蒸餾塔之概念性設計: 相對揮發度之影響」，國立台灣大學化學工程研究所碩士論文(2006)

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