臺灣博碩士論文加值系統

由於醋酸和正丁醇會起酯化反應，產生水和醋酸正丁酯，若僅以兩成份系統之汽液相平衡數據來考慮此混合物的相平衡，與實際的情形有所出入。本研究將直接考慮醋酸-正丁醇-水-醋酸正丁酯四成份系統的汽液相平衡行為，讓反應平衡和汽液相平衡均達到之後，再進行濃度分析。
實驗係以改良Othmer的汽液平衡裝置進行相平衡數據的量測，並在系統中加入觸媒(對甲苯磺酸)以縮短化學反應平衡所需的時間，並收集了41點的實驗數據。
在結果與討論中分別以實驗數據來迴歸UNIQUAC及NRTL兩種液相活性係數模式的參數，汽相考慮有強結合效應，並且比較關聯結果和實驗數據的差異。由結果顯示，UNIQUAC和NRTL二種液相模式所得之關聯結果都不錯，但又以UNIQUAC較好一點。最後以UNIQUAC模式來計算液相活性係數，繪出此四成份系統的反應相圖，並由相圖中判斷此四成份系統在伴隨反應的情形下，不會出現共沸點。

The aim of this study will probe into the thermodynamic behavior of acetic acid, n-butanol, water and n-butyl acetate mixture. Because the influence of chemical reaction on the distillation process can''t be neglected, both the phase equilibrium and the chemical reaction equilibrium must be concerned.
The experiments of chemical equilibrium and phase equilibrium were conducted in a modified Othmer type equilibrium cell. The catalyst(p-toluenesulfonic acid) was added to increase chemical reaction rate, and found no effect on the phase equilibrium. 41 experimental data were collected for this study.
The experimental VLE data were correlated by activity coefficient models of UNIQUAC and NRTL, respectively, with consideration of the strongly association of acetic acid moleculars in vapor phase. Our calculated results show that the correlation by UNIQUAC model was in good agreement with the experimental data. It is also found that the reactive azeotrope does not exist in this study by using Barbosa and Doherty’s criterion of a reactive system.

中文摘要 I

英文摘要 II

目錄 III

表目錄 V

圖目錄 VII

符號說明 IX

第一章 緒論 1
1.1 前言 1
1.2 反應蒸餾 2
1.3 酯化反應及汽液相平衡 4
1.4 系統介紹 5

第二章 理論 7
2.1 汽液相平衡理論 7
2.2 化學反應平衡理論 12

第三章 實驗部份 14
3.1 實驗裝置 14
3.1.1 酯化反應 14
3.1.2 汽液相平衡 15
3.2 實驗藥品 17
3.3 實驗設備 18
3.4 樣品分析之儀器配件 19
3.5 濃度分析 19
3.6 實驗步驟 20
3.6.1 酯化反應平衡實驗步驟 20
3.6.2 汽液相平衡實驗步驟 21
3.7 實驗數據處理 21

第四章 結果與討論 23
4.1 檢量曲線的擬合 23
4.2 可靠性實驗 23
4.3 酯化反應平衡的決定 24
4.4 伴隨反應的汽液相平衡實驗數據 25
4.5 數據迴歸 26
4.6 反應相圖 27

第五章 結論 30

參考文獻 31
表、圖 34
附錄 A 58
附錄 B 64
附錄 C 66

1Abrams, D. E. and J. M. Prausnitz, "Statistical Thermodynamics of Liquid Mixtures : A New Expression for the Excess Gibbs Energy of Partly or Completely Miscible Systems," AIChE J., 21(1), 116-128(1975)
2Renon, H. and J. M. Prausnitz, "Local Compositions in Thermodynamic Excess Functions for Liquid Mixtures," AIChE J., 14(1), 135-144(1968)
3Wilson, G. M., "Vapor-Liquid Equilibrium. XI. A New Expression for the Excess Fress Energy of Mixing," J. Am. Chem. Soc., 86, 127-130(1964)
4Barbosa, D. and M. F. Doherty, "The Influence of Equilibrium Chemical Reactions on Vapor-Liquid Phase Diagrams, " Chem. Engng Sci., 43, 529-540(1988)
5Kang, Y. W., Y. Y. Lee, and W. K. Lee "Vapor-Liquid Equilibria with Chemical Reaction Equilibrium-Systems Containing Acetic Acid, Ethyl Alcohol, Water, and Ethyl Acetate-," J. Chem. Engng Japan, 25(6), 649-655(1992)
6Lee, L. S. and M. Z. Kuo, "Phase and Reaction Equilibria of the Acetic Acid-Isopropanol-Isopropyl Acetate-Water System at 760mmHg," Fluid Phase Equilibria, 123, 147-165(1996)
7Saito, S., T. Michishita, and S. Maeda, "Separation of meta- and para- Xylene Mixture by Distillation Accompanied by Chemical Reactions," J. Chem. Engng Japan, 4, 37-43(1971)
8Terrill, D. L., L. F. Sylvestre, and M. F. Doherty, "Separation of Closely Boiling Mixtures by Reactive Distillation. 1. Theory," Ind. Engng Chem. Process Des. Dev., 24, 1062-1071(1985)
9Mommessin, P. E. and C. D. Holland, "Solve More Distillation Problems. Part 13-Multiple Columns with Reactions," Hydrocarb. Process. Int. Edn, 62(11), 195-200(1983)
10Grosser, J. H., H. F. Doherty, and M. F. Malone, "Modeling of Reactive Distillation Systems," Ind. Engng Chem. Res., 26, 983-989(1987)

11
Agreda, V. H., L. R. Partin, and W. H. Heise, "High-Purity Methyl Acetate via Reactive Distillation," Chem. Engng Prog., 41(2), 40-46(1990)
12DeGarmo, J. L., V. N. Parulekar, and V. Pinjala, "Consider Reactive Distillation," Chem. Engng Prog., 43(3), 43-50(1992)
13Schrans, S., S. de Wolf, and R. Baur, "Dynamic Simulation of Reactive Distillation: An MTBE Case Study," Computers Chem. Engng, 20, s1619-s1624(1996)
14Cleary, W. and M. F. Doherty, "Separation of Closely Boiling Mixtures by Reactive Distillation .2. Experiments," Ind. Engng Chem. Process Des. Dev. 24, 1071-1073(1985)
15Suzuki, I., H. Komatsu, H. Yagi, and M. Hirata, "Calculation of Multicomponent Distillation Accompanied by a Chemical Reaction," J. Chem. Engng Japan, 4(1), 26-33(1971)
16Komatsu, H., and C. D. Holland, "A New Method of Convergence for Solving Reacting Distillation Problems," J. Chem. Engng Japan, 10, 292-297(1977)
17Spencer, C. F. and R. P. Danner, "Improved Equation for Prediction of Saturated Liquid Density," J. Chem. Engng Data, 17(2), 236-241(1972)
18Marek, J. "Vapor-Liquid Equilibria in Mixtures Containing an Associating Substance .II. Binary Mixtures of Acetic Acid at Atmospheric Pressure," Colln Czech. Chem. Commun., Engl. Edn., 20, 1490-1502(1955)
19Prausnitz, J. M., T. F. Anderson, E. A. Grens, C. A. Eckert, R. Hsieh, and J. P. O''connell, "Computer Calculations for Multicomponent Vapor-Liquid and Liquid-Liquid Equilibria," Englewood Cliffs, N. J. : Prentic-Hall, Inc.(1980)
20Nothnagel, K. H., D. S. Arams, and J. M. Prausnitz, "Generalized Correlation for Fugacity Coefficients in Mixtures at Moderate Pressures-Application of Chemical Theory of Vapor Imperfections," Ind. Engng Chem. Process Des. Dev., 12, 25-35(1973)

21

Hayden,J. G. and J. P. O''Connell, "A Generalized Method for Predicting Second Virial Coefficients," Ind. Engng Chem. Process Des. Dev., 14(3), 209-216(1975)
22Prausnitz, J. M., R. N. Lichtenthaler, and E. G. de Azevedo, "Molecular Thermodynamics of Fluid-Phase Equilibria," Second Edition, Englewood Cliffs, N. J. : Prentic-Hall, Inc.(1986)
23Nishi, Y., "Vapor-Liquid Equilibrium of the System: Acetic Acid-Isopropanol-Water-Isopropyl Acetate," Kagaku Kogaku, 35, 1257-1262(1971)
24Sawistowski, H. and A. Pilavakis, "Vapor-Liquid Equilibrium with Associaton in Both Phases. Multicomponent Systems Containing Acetic Acid," J. Chem. Engng Data, 27, 64-71(1982)
25Kemeny, S. and J. Manczinger," Reduction of Thermodynamic Data by Means of the Multiresponse Maximum Likelihood Principle," AIChE J., 28(1), 20-30(1982)
26Ohe, S. "Vapor-liquid equilibrium data," Elsevier, Tokyo, 715(1989)
27Poling, B. E., J. M. Prausnitz, and J. P. O''Connell, "The Properties of Gases and Liquids," Fifth Edition, McGraw-Hill ,New York (2001)
28Barbosa, D. and M. F. Doherty, "A New Set of Composition Variables for the Representation of Reactive-Phase Diagrams," Proc. R. Soc. Lond., A413, 459-464(1987)
29Barbosa, D. and M. F. Doherty, "Theory of Phase Diagrams and Azeotropic Conditions for Two-Phase Reactive Systems, " Proc. R. Soc. Lond., A413, 443-458(1987)
30Barbosa, D. and M. F. Doherty, "The Simple Distillation of Homogeneous Reactive Mixtures, " Chem. Engng Sci., 43(3), 541-550(1988)