臺灣博碩士論文加值系統

反應蒸餾法為一個有效的粗乳酸純化分離方法，可藉由加入正丁醇進行酯化反應，所生成的乳酸正丁酯再進行水解反應，可得到高純度乳酸。欲開發設計此製程，量測與迴歸該製程相關之相平衡數據乃屬必需，亦為本研究之目標。
本研究採用頂空層析方法來量測水-正丁醇及正丁醇-乳酸正丁酯於恆溫下(348.15K)二元成份系統之汽液相平衡數據，實驗結果通過了熱力學一致性檢驗，此外並量測了水-正丁醇-乳酸正丁酯三元成份系統之液液相平衡數據，再以動態再循環式裝置量測定壓下(45kPa)乳酸-正丁醇-水-乳酸正丁酯四元成份系統之汽液相平衡數據，以及定壓下(101.3 kPa)水-正丁醇系統之汽液液相平衡數據。
本研究依照最大概似原理(Maximum-Likelihood Principle)，分別嘗試以NRTL與UNIQUAC模式進行相平衡數據迴歸，並提出四個迴歸方式，詳加分析與比較各模式之預測能力，尋找出最能代表所有相平衡數據的熱力學模式，最後使用六組NRTL二元交互作用參數(含非隨機參數)，可獲致不錯的結果，將可供製程模擬及設計之用。

Reactive distillation can be an effective means for purification of crude lactic acid. It can be achieved by esterification of crude lactic acid with n-butanol, followed by hydrolysis of butyl lactate. In order to develop this reactive distillation process, measurement of phase equilibrium data and their regression are necessary and are the focus of this study.
In this study, headspace chromatography method was employed to measure binary vapor-liquild equilibrium data of n-butanol/n-butyl lactate and water/n-butanol systems at 348.15K, and the experimental results passed the thermodynamic consistency test. Liquid-liquild equilibrium data were also taken for the ternary water/n-butanol/n-butyl lactate system. In addition, a dynamic recirculating cell was used to measure isobaric quaternary vapor-liquild equilibrium data of lactic acid/n-butanol/water/n-butyl lactate system, together with vapor- liquild-liquid equilibrium data for the water/n-butanol system.
Based on the Maximum Likelihood Principle, data reduction was done using NRTL and UNIQUAC models. Four regression schemes were presented and compared in terms of model predictive accuracy. Six sets of binary interaction parameters, including non-randomness parameters, that best represent the measured data were found and can be used for process simulation and design purposes.

摘要 III
Abstract IV
誌謝 V
目錄 VI
圖目錄 X
表目錄 XIII
第一章 緒論 1
1.1前言 1
1.2研究動機 1
1.3論文組織與架構 4
第二章 文獻回顧 5
2.1汽液相平衡 5
2.1.1汽液相平衡理論 5
2.1.2汽液相平衡實驗量測方法 8
2.2液液相平衡 13
2.2.1液液相平衡理論 13
2.2.2液液相平衡實驗量測方法 14
2.3汽液液相平衡 15
2.3.1汽液液相平衡理論 15
2.3.2汽液液相平衡實驗量測方法 16
第三章 實驗方法與步驟 19
3.1實驗藥品 19
3.2樣品分析方式 20
3.2.1氣相層析儀分析 20
3.2.1.1定性分析 21
3.2.1.2定量分析 21
3.2.2酸鹼滴定分析 22
3.3靜態式汽液相平衡實驗 23
3.3.1實驗裝置與原理 23
3.3.2實驗方法 25
3.3.3實驗步驟 27
3.4動態再循環式汽液相平衡實驗 29
3.4.1實驗裝置 29
3.4.2實驗步驟 29
3.4.2.1酯化反應平衡實驗步驟 30
3.4.2.2汽液相平衡實驗步驟 31
3.5液液相平衡實驗 32
3.5.1實驗裝置 32
3.5.2實驗步驟 33
3.6汽液液相平衡實驗 34
3.6.1實驗裝置 34
3.6.2實驗步驟 34
第四章 實驗分析與數據 36
4.1檢量曲線 36
4.2相平衡實驗 41
4.2.1汽液相平衡實驗數據 41
4.2.2液液相平衡實驗 49
4.2.3汽液液相平衡實驗 51
第五章 數據迴歸分析與討論 53
5.1數據迴歸與檢驗 53
5.1.1熱力學一致性檢驗 53
5.1.2迴歸模式 56
5.2迴歸方式 60
5.3相平衡數據迴歸 64
5.3.1汽液液相平衡 64
5.3.2液液相平衡 68
5.3.3汽液相平衡 74
5.3.4反應性汽液相平衡 77
5.4結果與討論 139
第六章 結論與建議 160
符號說明 164
參考文獻 168
附錄A 汽相非理想氣體之計算 173
附錄B Components´ Antoine Parameter 179
附錄C Objective functions 180
簡歷 181









圖目錄
圖1-1 反應蒸餾製程示意圖 3
圖2-1 汽相締合現象 7
圖2-2 靜態式汽液相平衡裝置示意圖 10
圖2-3 流動式汽液相平衡裝置示意圖 11
圖2-4 動態再循環式汽液相平衡裝置示意圖 12
圖2-1 Font et al.(2003)之設備示意圖 17
圖2-2 Font et al.(2003)之設備局部放大圖 18
圖2-3 Iwakabe and Kosuge(2001)之設備示意圖 18
圖3-1 平衡壓力頂空取樣實驗裝置示意圖 24
圖3-2 平衡壓力轉移系統 25
圖3-3 Progressive模式操作示意圖 28
圖3-4 動態再循環式相平衡裝置 30
圖3-5 液液相平衡裝置示意圖 32
圖4-1 氣相層析儀滯留時間分析圖譜 39
圖4-2 水-甲醇之檢量線 39
圖4-3 丁醇-甲醇之檢量線 40
圖4-4 乳酸正丁酯-甲醇之檢量線 40
圖4-5 酯化反應平衡濃度與時間關係圖 49
圖4-6 水(1)-正丁醇(2)-乳酸正丁酯(3)之液液相平衡圖 51
圖5-1 熱力學模式選擇流程圖(Carlson, 1996) 59
圖5-2 水(1)–正丁醇(2)汽液相平衡系統ㄧ致性檢驗圖(348.15K) 68
圖5-3 水(1)-正丁醇(2)-乳酸正丁酯(3)液液相平衡圖(298.15K) 73
圖5-4 水(1)-正丁醇(2)-乳酸正丁酯(3)液液相平衡Othmer and Tobias關聯圖 73
圖5-5 正丁醇(1)–乳酸正丁酯(2)汽液相平衡系統ㄧ致性檢驗圖(348.15K) 76
圖5-6 正丁醇(1)–乳酸正丁酯(2)二元系統汽液相平衡 圖(348.15K) 76
圖5-7 正丁醇(1)–乳酸正丁酯(2)二元系統汽液相平衡 圖(348.15K) 77
圖5-8 水(1)–正丁醇(2)汽液相平衡 預測圖(348.15K) 155
圖5-9 水(1)–正丁醇(2)汽液相平衡 預測圖(348.15K) 155
圖5-10正丁醇(1)–乳酸正丁酯(2)汽液相平衡 預測圖 (348.15K) 156
圖5-11正丁醇(1)–乳酸正丁酯(2)汽液相平衡 預測圖 (348.15K) 156
圖5-12液液相平衡 探討並預測水(1)–正丁酯(2)汽液相平衡 圖(348.15K) 157
圖5-13液液相平衡 探討並預測水(1)–正丁酯(2)汽液相平衡 圖(348.15K) 157
圖5-14液液相平衡 探討並預測正丁醇(1)–乳酸正丁酯(2)汽液相平衡 圖(348.15K) 158
圖5-15液液相平衡 探討並預測正丁醇(1)–乳酸正丁酯(2)汽液相平衡 圖(348.15K) 158
圖6-1 反應蒸餾純化粗乳酸之流程示意圖 163











表目錄
表2-1 反應性汽液相平衡所使用之量測方法 9
表4-1 氣相層析儀滯留時間 37
表4-2 檢量線實驗數據 37
表4-3 檢量線擬合結果 38
表4-4 水(1)-正丁醇(2)之汽液相平衡數據(348.15K) 43
表4-5 正丁醇(1)- 乳酸正丁酯(2)之汽液相平衡數據(348.15K) 43
表4-6 乳酸濃度與其寡聚物關係表(Lira and Miller, 2005) 44
表4-7 水(1)-正丁醇(2)-乳酸正丁酯(3)-乳酸(4)之汽液相平衡數據(乳酸濃度≦20wt%) 45
表4-8 水(1)-正丁醇(2)-乳酸正丁酯(3)-乳酸(4)之汽液相平衡數據(乳酸濃度≦90wt%) 47
表4-9 水(1)-正丁醇(2)-乳酸正丁酯(3)之液液相平衡數據 (莫耳分率) 50
表4-10水(1)-正丁醇(2)-乳酸正丁酯(3)之液液相平衡數據 (重量分率) 50
表4-11水(1)-正丁醇(2)汽液液之相平衡數據(101.325kPa) 52
表5-1 目標函數之形式 58
表5-2 文獻迴歸方式之比較 62
表5-3 本研究採用之迴歸方法 63
表5-4 水(1)-正丁醇(2)定溫下汽液相平衡數據迴歸之偏差值(NRTL ) 65
表5-5 水(1)-正丁醇(2) 定溫下汽液相平衡數據迴歸之偏差值(NRTL ) 65
表5-6 水(1)-正丁醇(2)定溫下汽液相平衡數據迴歸之偏差值(UNIQUAC) 66
表5-7 水(1)-正丁醇(2)定壓下汽液液相平衡數據迴歸之偏差值 67
表5-8 水(1)-正丁醇(2)相平衡數據迴歸之參數 67
表5-9 水(1)-正丁醇(2)-乳酸正丁酯(3)液液相平衡數據迴歸之偏差值(NRTL) 70
表5-10水(1)-正丁醇(2)-乳酸正丁酯(3)液液相平衡數據迴歸之偏差值(UNIQUAC) 71
表5-11水(1)-正丁醇(2)-乳酸正丁酯(3)液液相平衡數據迴歸之參數 72
表5-12正丁醇(1)-乳酸正丁酯(2)汽液相平衡數據迴歸之偏差值(NRTL) 74
表5-13正丁醇(1)-乳酸正丁酯(2)汽液相平衡數據迴歸之偏差值(UNIQUAC) 75
表5-14正丁醇(1)-乳酸正丁酯(2) 汽液相平衡數據迴歸之參數 75
表5-15相平衡數據迴歸步驟(Method I) 79
表5-16相平衡數據迴歸步驟(Method II) 80
表5-17相平衡數據迴歸步驟(Method III) 81
表5-18相平衡數據迴歸步驟(Method IV) 82
表5-19水(1)-正丁醇(2)-乳酸正丁酯(3)-乳酸(4)四成份系統之汽液相平衡數據與模式偏差值 (乳酸濃度≦20wt%, Method I, NRTL) 83
表5-20水(1)-正丁醇(2)-乳酸正丁酯(3)-乳酸(4)四成份系統之汽液相平衡數據與模式偏差值(乳酸濃度≦20wt%, Method I, UNIQUAC) 85
表5-21水(1)-正丁醇(2)-乳酸正丁酯(3)-乳酸(4)四成份系統之汽液相平衡數據與模式偏差值(乳酸濃度≦20wt%, Method II, NRTL) 87
表5-22水(1)-正丁醇(2)-乳酸正丁酯(3)-乳酸(4)四成份系統之汽液相平衡數據與模式偏差值(乳酸濃度≦20wt%, Method II, UNIQUAC) 89
表5-23水(1)-正丁醇(2)-乳酸正丁酯(3)-乳酸(4)四成份系統之汽液相平衡數據與模式偏差值(乳酸濃度≦20wt%, Method III,NRTL) 91
表5-24水(1)-正丁醇(2)-乳酸正丁酯(3)-乳酸(4)四成份系統之汽液相平衡數據與模式偏差值(乳酸濃度≦20wt%, Method III, UNIQUAC) 93
表5-25水(1)-正丁醇(2)-乳酸正丁酯(3)-乳酸(4)四成份系統之汽液相平衡數據與模式偏差值(乳酸濃度≦20wt%, Method IV,NRTL) 95
表5-26水(1)-正丁醇(2)-乳酸正丁酯(3)-乳酸(4)四成份系統之汽液相平衡數據與模式偏差值(乳酸濃度≦20wt%, Method IV, UNIQUAC) 97
表5-27水(1)-正丁醇(2)-乳酸正丁酯(3)-乳酸(4)汽液相平衡數據迴歸之參數(乳酸濃度≦20wt%, Method I, NRTL) 99
表5-28水(1)-正丁醇(2)-乳酸正丁酯(3)-乳酸(4)汽液相平衡數據迴歸之參數(乳酸濃度≦20wt%, Method I, UNIQUAC) 99
表5-29水(1)-正丁醇(2)-乳酸正丁酯(3)-乳酸(4)汽液相平衡數據迴歸之參數(乳酸濃度≦20wt%, Method II, NRTL) 100
表5-30水(1)-正丁醇(2)-乳酸正丁酯(3)-乳酸(4)汽液相平衡數據迴歸之參數(乳酸濃度≦20wt%, Method II, UNIQUAC) 100
表5-31水(1)-正丁醇(2)-乳酸正丁酯(3)-乳酸(4)汽液相平衡數據迴歸之參數(乳酸濃度≦20wt%, Method III, NRTL) 101
表5-32水(1)-正丁醇(2)-乳酸正丁酯(3)-乳酸(4)汽液相平衡數據迴歸之參數(乳酸濃度≦20wt%, Method III, UNIQUAC) 101
表5-33水(1)-正丁醇(2)-乳酸正丁酯(3)-乳酸(4)汽液相平衡數據迴歸之參數(乳酸濃度≦20wt%, Method IV, NRTL) 102
表5-34水(1)-正丁醇(2)-乳酸正丁酯(3)-乳酸(4)汽液相平衡數據迴歸之參數(乳酸濃度≦20wt%, Method IV, UNIQUAC) 102
表5-35水(1)-正丁醇(2)-乳酸正丁酯(3)-乳酸(4)汽液相平衡數據迴歸之偏差值(乳酸濃度≦90wt%, Method I NRTL模式) 103
表5-36水(1)-正丁醇(2)-乳酸正丁酯(3)-乳酸(4)汽液相平衡數據迴歸之偏差值(乳酸濃度≦90wt%, Method I UNIQUAC模式) 107
表5-37水(1)-正丁醇(2)-乳酸正丁酯(3)-乳酸(4)汽液相平衡數據迴歸之偏差值(乳酸濃度≦90wt%, Method II NRTL模式) 111
表5-38水(1)-正丁醇(2)-乳酸正丁酯(3)-乳酸(4)汽液相平衡數據迴歸之偏差值(乳酸濃度≦90wt%, Method II UNIQUAC模式) 115
表5-39水(1)-正丁醇(2)-乳酸正丁酯(3)-乳酸(4)汽液相平衡數據迴歸之偏差值(乳酸濃度≦90wt%, Method III NRTL模式) 119
表5-40水(1)-正丁醇(2)-乳酸正丁酯(3)-乳酸(4)汽液相平衡數據迴歸之偏差值(乳酸濃度≦90wt%, Method III UNIQUAC模式) 123
表5-41水(1)-正丁醇(2)-乳酸正丁酯(3)-乳酸(4)汽液相平衡數據迴歸之偏差值(乳酸濃度≦90wt%, Method IV NRTL模式) 127
表5-42水(1)-正丁醇(2)-乳酸正丁酯(3)-乳酸(4)汽液相平衡數據迴歸之偏差值(乳酸濃度≦90wt%, Method IV UNIQUAC模式) 131
表5-43水(1)-正丁醇(2)-乳酸正丁酯(3)-乳酸(4)汽液相平衡數據迴歸之參數(乳酸濃度≦90wt%, Method I, NRTL) 135
表5-44水(1)-正丁醇(2)-乳酸正丁酯(3)-乳酸(4)汽液相平衡數據迴歸之參數(乳酸濃度≦90wt%, Method I, UNIQUAC) 135
表5-45水(1)-正丁醇(2)-乳酸正丁酯(3)-乳酸(4)汽液相平衡數據迴歸之參數(乳酸濃度≦90wt%, Method II, NRTL) 136
表5-46水(1)-正丁醇(2)-乳酸正丁酯(3)-乳酸(4)汽液相平衡數據迴歸之參數(乳酸濃度≦90wt%, Method II, UNIQUAC) 136
表5-47水(1)-正丁醇(2)-乳酸正丁酯(3)-乳酸(4)汽液相平衡數據迴歸之參數(乳酸濃度≦90wt%, Method III, NRTL) 137
表5-48水(1)-正丁醇(2)-乳酸正丁酯(3)-乳酸(4)汽液相平衡數據迴歸之參數(乳酸濃度≦90wt%, Method III, UNIQUAC) 137
表5-49水(1)-正丁醇(2)-乳酸正丁酯(3)-乳酸(4)汽液相平衡數據迴歸之參數(乳酸濃度≦90wt%, Method IV, NRTL) 138
表5-50水(1)-正丁醇(2)-乳酸正丁酯(3)-乳酸(4)汽液相平衡數據迴歸之參數(乳酸濃度≦90wt%, Method IV, UNIQUAC) 138
表5-51相平衡數據迴歸各步驟之平均偏差值(乳酸濃度≦20wt%, Method I , NRTL) 141
表5-52相平衡數據迴歸各步驟之平均偏差值(乳酸濃度≦20wt%, Method I , UNIQUAC) 141
表5-53相平衡數據迴歸各步驟之平均偏差值(乳酸濃度≦20wt%, Method II, NRTL) 142
表5-54相平衡數據迴歸各步驟之平均偏差值(乳酸濃度≦20wt%, Method II, UNIQUAC) 143
表5-55相平衡數據迴歸各步驟之平均偏差值(乳酸濃度≦20wt%, Method III, NRTL) 144
表5-56相平衡數據迴歸各步驟之平均偏差值(乳酸濃度≦20wt%, Method III, UNIQUAC) 145
表5-57相平衡數據迴歸各步驟之平均偏差值(乳酸濃度≦20wt%, Method IV, NRTL) 146
表5-58相平衡數據迴歸各步驟之平均偏差值(乳酸濃度≦20wt%, Method IV, UNIQUAC) 146
表5-59相平衡數據迴歸各步驟之平均偏差值(乳酸濃度≦90wt%, Method I , NRTL) 147
表5-60相平衡數據迴歸各步驟之平均偏差值(乳酸濃度≦90wt%, Method I , UNIQUAC) 147
表5-61相平衡數據迴歸各步驟之平均偏差值(乳酸濃度≦90wt%, Method II, NRTL) 148
表5-62相平衡數據迴歸各步驟之平均偏差值(乳酸濃度≦90wt%, Method II, UNIQUAC) 149
表5-63相平衡數據迴歸各步驟之平均偏差值(乳酸濃度≦90wt%, Method III, NRTL) 150
表5-64相平衡數據迴歸各步驟之平均偏差值(乳酸濃度≦90wt%, Method III, UNIQUAC) 151
表5-65相平衡數據迴歸各步驟之平均偏差值(乳酸濃度≦90wt%, Method IV, NRTL) 152
表5-66相平衡數據迴歸各步驟之平均偏差值(乳酸濃度≦90wt%, Method IV, UNIQUAC) 152
表5-67水(1)-正丁醇(2)-乳酸正丁酯(3)-乳酸(4)汽液相平衡數據於各模式及方法之平均偏差值(乳酸濃度≦20wt%) 153
表6-1 最佳參數值下之相平衡預測偏差 162

Abrams D. S. and J. M. Prausnitz, "Statistical thermodynamics of liquid mixtures：a new expression for the excess gibbs energ of partly or completely miscible systems," AlChE Journal, 1975, 21, 116-128.

Albert, M., B. C. García, C. Kreiter, and G. Maurer, "Vapor-liquid and chemical equilibria of formaldehyde-water mixtures, " AIChE Journal, 1999, 45, 2024-2033.

Arlt, W., "A new apparatus for phase equilibria in reacting mixtures," Fluid Phase Equilib., 1999, 158-160, 973-977.

Bernatová S., K. Aim, and I. Wichterle, "Isothermal vapour–liquid equilibrium with chemical reaction in the quaternary water + methanol + acetic acid + methyl acetate system, and in five binary subsystems," Fluid Phase Equilib., 2006, 247, 96-101.

Brinkmeier, C. Reder, and W. Marquardt, "A non-recycle flow still for the experimental determination of vapor-liquid equilibria in reactive system, " Fluid Phase Equilib., 1998, 153, 113-134.

Rogers, W. J., J. A. Bullin, R. R. Davison, R. E. Frazier, and K. N. Marsh, "FTIR method for vle measurements of acid-gas-alkanolamine systems," AIChE Journal, 1997, 43, 3223-3231.

Carlson E. C., "Don’t gamble with physical properties for simulations," Chemical Engineering Progress, 1996, 35-46.

Carvoli, G. and P. Delogu, "Phase equilibria of the quaternary system acetic acid-ethylene glycol monoethyl ether acetate-ethylene glycol monoethyl ether-water," Fluid Phase Equilib., 1986, 25, 91-105.

Delgado, P., M. T. Sanz, and S. Beltrán, "Isobaric vapor–liquid equilibria for the quaternary reactive system: ethanol +water + ethyl lactate + lactic acid at 101.33 kPa," Fluid Phase Equilib., 2007, 255, 17-23.

Dragoescu D., A. Barhala, and R. Vilcu, "Isothermal vapour–liquid equilibrium data for the binary propan-2-oneqchloroalkanes mixtures at temperatures from 298.15 K to 313.15 K," Fluid Phase Equilib., 1999, 157, 41-51.

Font A., J. C. Asensi, F. Ruiz, and V. Gomis, "Application of isooctane to the dehydration of ethanol. design of a column sequence to obtain absolute ethanol by heterogeneous azeotropic distillation," Ind. Eng. Chem. Res., 2003, 42, 140-144.

Gomis V., F. Ruiz, and J. C. Asensi, "The application of ultrasound in the determination of isobaric vapour-liquid-liquid equilibrium data," Fluid Phase Equilib., 2000, 172, 245-259.

Hasse, H. and G. Maurer, "Vapor-liquid equilibrium of formaldehyde - containing mixtures at temperatures below 320 K," Fluid Phase Equilib., 1991, 64, 185-199.

Hayden J. G. and J. P. O’Connell, "A generalized method for predicting second virial coefficients," Ind. Eng. Chem. Process Des. Dev., 1975, 14, 209–216.

Heintz, A., J. K. Lehmann, and C. Wertz, "Thermodynamic properties of mixtures containing ionic liquids. 3.liquid-liquid equilibria of binary mixtures of 1-ethyl-3-methylimidazolium bis (trifluoro methyl sulfonyl) imide with propan-1-ol, butan-1-ol, and pentan-1-ol," J. Chem. Eng. Data, 2003, 48,472-474.

Heintz, A. and S.P. Verevkin, "Simultaneous study of chemical and vapour–liquid equilibria in the reacting system of the methyl cumyl ether synthesis from methanol and α-methyl-styrene, " Fluid Phase Equilib., 2001, 179, 85-100.

Hsieh, C. T., M. J. Lee, and H. M. Lin, "Vapor-liquid-liquid equilibria for aqueous systems with methyl acetate, methyl propionate, and methanol ," Ind. Eng. Chem. Res., 2008, 47, 7927-7933.

Krissmann, J., M. M. A. Siddiqi, and K. Lucas, "Komplexe phasen-und reaktions-gleichgewichte bei der nassen rauchgasreinigung – einsatz der UV-spektralphotometrie am beispiel des SO2/H2O-system," Chemie Ingenieur Technik, 1996, 68, 1598-1602.

Lee, L. S. and M. Z. Kuo, "Phase and reaction equilibria of the acetic acid-isopropanol-isopropyl acetate-water system at 760 mmHg," Fluid Phase Equilib., 1996, 123, 147-165.

Lee, L. S. and R. G.. Lin, "Reaction and phase equilibria of esterification of isoamyl alcohol and acetic acid at 760 mmHg," Fluid Phase Equilib., 1999, 165, 261-278.

Lee, L. S. and S. J. Liang, "Phase and reaction equilibria of acetic acid–1-pentanol–water–n-amyl acetate system at 760 mmHg," Fluid Phase Equilib., 1998, 149, 57-74.

Lee, M. J., S. L. Chen, C. H. Kang, and H. M. Lin, "Simultaneous chemical and phase equilibria for mixtures of acetic acid, amyl alcohol, amyl acetate, and water, " Ind. Eng. Chem. Res., 2000, 39, 4383-4391.

Li, S. M., I. Rashkov, J. L. Espartero, N. Manolova, and M. Vert, "Synthesis, characterization, and hydrolytic degradation of PLA / PEO / PLA triblock copolymers with long Poly(L-lactic acid) blocks, " Macromolecules, 1996, 29, 57-62.

Lo Y. J., H. M. Lin, and M. J. Lee, "Liquid-Liquid Equilibrium for Ternary Mixtures Containing Methanol and Fatty Acid Methyl Esters," The 3rd Symposium on Green Chemical Process Technology, November 28,Taichung, Taiwan (2009).

Nothnagel, K. H., D. S. Abrams, and J. M. Prausnitz, "Generalized correlation for fugacity coefficients in mixtures at moderate pressures,"
Ind. Eng. Chem. Process Des. Develop., 1973, 12, 25-35.

Othmer, D. F. and P. E. Tobias, "Tie line correlation," Industrial and Engineering Chemistry, 1942, 34, 693-696.

Patel, N. C. and M. A. Young, "Measurement and prediction of vapor- liquid equilibria for a reactive system: application to ethylene oxide + nonyl phenol," Fluid Phase Equilib., 1993, 82, 79-92.

Peschke, N. and S. I. Sandler, "Liquid-liquid equilibria of fuel oxygenate + water + hydrocarbon mixtures," J. Chem. Eng. Data, 1995, 40, 315-320.

Prausnitz, J. M., T. F. Anderson, E. A. Grens, C. A. Eckert, R. Hsieh, and J. P. O´Cconnel, "Computer calculations for multicomponent vapor-liquid and liquid-liquid equilibria," Prentice-Hall：USA (1980).

Reddy, G., M. Altaf, B. J. Naveena, M. Venkateshwar, and E. V. Kumar, "Amylolytic bacterial lactic acid fermentation – areview, " Biotechnology Advances, 2008, 26, 22-34

Reichl, A., U. Daiminger, A. Schmidt, M. Davies, U. Hoffmann, and C. Maurer, G., "Vapor-liquid equilibrium of formaldehyde and water-containing multicomponent mixtures, " AIChE Journal, 1986, 32, 932-948.

Renon, H. and J. M. Prausnitz, "Local compositions in thermodynamic excess functions for liquid mixtures," AlChE Journal, 1968, 14, 135-144.

Sawlstowskl, H. and P. A. Pllavakis, "Vapor-liquid equilibrium with association in both phases. mumkomponent systems containing acetic acid, " J. Chem. Eng. Data, 1982, 27, 64-71.

Siddiqi, M.A., J. Krissmann, and K. Lucas, "A new fibre optic-based technique for the spectrophotometric measurement of phase and chemical equilibria in aqueous solutions of volatile weak electrolytes," Fluid Phase Equilib., 1997, 136, 185-195.

Sundmacher K. and A. Kienle, "Reactive distillation," Wiley-VCH：Federal Republic of Germany (2002).

Teodorescu, M.,K. Aim, and I. Wichterle, "Isothermal vapor-liquid equilibrium in the quaternary water + 2-propanol + acetic acid + isopropyl acetate system with chemical reaction," J. Chem. Eng. Data, 2001, 46, 261-266.

Tester, J. W. and M. Modell, "Thermodynamics and its applications." Prentice Hall PTR: Upper Saddle River, N.J. (1997).

Tischmeyer, M. and W. Arlt, "Determination of binary vapor-liquid equilibria (VLE) of three fast reacting esterification systems," Chem. Eng. Process., 2004, 43, 357-367.

Vu, D. T., A. K. Kolah, N. S. Asthana, L. Peereboom, C. T. Lira, and D. J. Miller, "Oligomer distribution in concentrated lactic acid solutions," Fluid Phase Equilib., 2005, 236, 125-135.

Walas, S., "Phase equilibria in chemical engineering," Butterworth: Stoneham, MA (1985).