臺灣博碩士論文加值系統

本研究使用一套具有視窗平衡釜的靜態式相平衡量測裝置，量取恆溫下之汽液相平衡數據，混合物係由醋酸、丙二醇甲醚、丙二醇甲醚醋酸酯所組成的雙成分系統，溫度分別介於343.15-393.15 K之間，這些新數據是開發以反應性蒸餾法產製丙二醇甲醚醋酸酯的製程所亟需的。雙成份的汽液平衡新數據分別以NRTL與UNIQUAC活性係數模式關聯;對於含醋酸之系統在計算時以Hayden-O’Connell (HOC)模式估算第二維里係數，以便考慮汽相中醋酸分子結合成二元體的效應。NRTL與UNIQUAC模式可準確描述丙二醇甲醚 + 丙二醇甲醚醋酸酯系統的相行為。模式關聯結果顯示，對於醋酸 + 丙二醇甲醚醋酸酯系統NRTL-HOC法較UNIQUAC- HOC法為佳。

A static-type apparatus equipped with a visual cell was utilized in the present study to measure isothermal vapor-liquid equilibrium (VLE) data. The investigated binary mixtures were composed of acetic acid, propylene glycol monomethyl ether (PGME), and propylene glycol methyl ether acetate (PGMEA). The measurements were conducted in a temperature range from 343.15K to 393.15K. These new VLE data are urgently needed in process development of manufacturing propylene glycol methyl ether acetate via reactive distillation. The vapor-liquid equilibrium data were correlated with the NRTL and the UNIQUAC models . For the acetic acid —containing system, the Hayden-O’Connell model was used to estimate the second virial coefficients to account the dimerization of acetic acid in the vapor phase. While the NRTL and the UNIQUAC models represented well the phase behavior of PGME + PGMEA system, the NRTL-HOC method was found to be better than the UNIQUAC-HOC method for acetic acid + PGMEA.

目錄
中文摘要 I
英文摘要 II
致謝 III
目錄 IV
圖表索引 VI
第一章 緒論 1
1-1 前言 1
1-2 汽液相平衡平衡理論基礎 4
1-3 本文各章要點 6
第二章 汽液相平衡之量測 7
2-1 儀器設備 7
2-2 實驗裝置 8
2-2-1 除氣與進料系統 9
2-2-2 平衡系統 9
2-2-3 取樣與組成分析系統 10
2-3 實驗藥品 11
2-4 實驗程序 11
2-4-1 樣品進料操作程序 11
2-4-2 取樣操作程序 12
2-5 GC之校正曲線 14
2-6 純質蒸汽壓 14
2-7 雙成份系統之實驗結果 15
2-8 熱力學一致性測試 16
2-8-1 Gibbs-Duhem方程式 17
2-8-2 熱力學一致性測試法 18
2-8-3 熱力學一致性測試之結果 20
第三章 汽液相平衡計算 47
3-1 雙成份交互作用參數訂定 47
第四章 結論與建議 70
4-1 結論 70
4-2 建議 71
參考文獻 72
符號說明

參考文獻
Abrams, D. S. 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., Vol. 21, pp. 116-128 (1975).
Asensi, J. C., J. Molto, and M. D. M. Olaya, “Isobaric Vapour-Liquid Equilibria Data for the Binary System 1-Propanol + 1-Pentanol and Isobaric Vapour-Liquid-Liquid Equilibria Data for the Ternary System Water + 1-Propanol + 1-Pentanol at 101.3 kPa,” Fluid Phase Equilibria, Vol. 200, pp. 287-293 (2002).
Boublik, T.; V. Fried and E. Hala, “The Vapour Pressures of Pure Substances,” 2nd ed., Elsevier Science: New York, 1984.
Chiavone-Filho, O., P. Patricio, and P. Rasmussen, “Vapor-Liquid Equilibria for Glyol Ether + Water Systems,” J. Chem. Eng. Data, Vol. 38, pp.128-131 (1993).
Cho, T. H., K. Ochi, and K. Kojima , “Isobaric Vapor-Liquid Equilibria for Binary System with Limited Miscibility, Water-n-Amyl Alcohol and Water-Isoamyl Alcohol,” Kagaku Kogaku Ronbunshu, Vol. 10, pp. 181 -183 (1984).
Darwish, N. A., and W. A. Abdalah, “Experimental and Theoretical Investigation of the Vapor-liquid Equilibria of Ethyl Acetate + n-Propyl Acetate and Tetrahydrofuran + Acetonitrile Binary at 93.8 kPa,” Chemical Engineering and Processing, Vol. 39, pp. 107-111 (2000).
Doubert, T. E., and R. P. Danner, “Data Compilation Tables of Property Pure Compounds,” Design Institute for Physical Property Data, AIChE, NY, 1989.
Gmehling, J., U. Onken, and P. Grenzheuser, “Vapor-Liquid Equilibrium Data Collection — Carboxylic Acid, Anhydrides, Esters, Chemistry Data Series,” Vol. 1, Part 5, DECHEMA, Frankfurt, Germany, 1982a.
Gmehling, J., U. Onken, and P. Grenzheuser, “Vapor-Liquid Equilibrium Data Collection — Aqueous-Organic Systems,” Chemistry Data Series, Vol. 1, pp. 41, DECHEMA, Frankfurt, Germany, 1982b.
Gomis, V., F. Ruiz, and J. C. Asensi, “The Application of Ultrasound in the Determination of Isobaric Vapour-Liquid-Liquid Equilibria Data,” Fluid Phase Equilibria, Vol. 172, pp. 245-259 (2002).
Hayden, J. G. and J. P. O''Connell, “A Generalized Method for Predicting Second Virial Coefficients,” Ind. Eng. Chem. Process Des. Dev., Vol. 14,
pp. 209-216 (1975).
Hiaki, T., K. Tochigi, and K. Kojima, “Measurement of Vapor-Liquid Equilibrium and Determination of Azeotropic Point,” Fluid Phase Equilibria, Vol. 26, pp. 83-102 (1986).
Hong, G. B., M. J. Lee, and H. M. Lin, “Multiphase Coexistence for Mixtures Containing Water, 2-Prooanol, and Ethyl Acetate,” Fluid Phase Equilibria, Vol. 203, pp. 227-245 (2002).
Iwai. Y., M. R. Margerum, and B. C.-Y. Lu, “A New Three-parameter Cubic Equation of State for Polar Fluids and Fluid Mixtures,” Fluid Phase Equilibria, Vol. 42, pp. 21-41 (1988).
Jan, D. S. and F. N. Tsai, “A New Four-Parameter Cubic Equation of State for Mixtures. Vapor-Liquid Equilibrium Calculations,” Can. J. Chem., Vol. 70, pp. 320-328 (1992).
Kaul, B. K. and J. M. Prausnitz, “Second Virial Coefficients of Gas
Mixtures Containing Sample Fluids and Heavy Hydrocarbons,” Ind.
Eng. Chem. Fundam., Vol. 16, pp. 335-340 (1977).
Kojima, K., H. M. Moon, and K. Ochi, “ Thermodynamic Consistency Test of Vapor-Liquid Equilibrium Data Methanol-Water, Benzene- Cyclohexane and Ethyl Methyl Ketone-Water,” Fluid Phase Equilibria, Vol. 56, pp. 269-284 (1990).
Laursen, T., P. Rasmussen, and S. I. Andersen, “VLE and VLLE Measurement of Dimethyl Ether Containing System,” J. Chem. Eng. Data, Vol. 47, pp. 198-202 (2002).
Lee, M. J., S. L. Chen, C. H. Kang, and H. M. Lin, “Phase Equilibria for Mixtures of Acetate acid, Amyl Alcohol, Amyl Acetate, and Water,” Ind. Eng. Chem. Res., Vol. 39, pp. 4383-4391 (2000).
Lee, L. S. and S. J. Liang, “Phase and Reaction Equilibria of Acetic Acid-1-Pentanol-Water-n-Amyl Acetate System at 760 mm Hg,” Fluid Phase Equilibria, Vol. 149, pp. 57-74 (1998).
Lewell, P. A. and D. D. Kristmanson, “Vapor-Liquid Equilibria in Mixtures of n-Alcohols and Their Esters,” AIChE J., Vol. 13, pp. 814 (1967).
Marshall, A. J., “The Vapor Pressures of Binary Mixtures. Part 1. The Possible Types of Vapor Pressure Curves,” Chem. Soc., Vol. 89, pp. 1350-1386 (1906).
Nagata, I., “Vapor-Liquid Equilibria for the Ternary System Methyl Acetate-Benzene-Cyclohexane,” J. Chem. Eng. Data, Vol. 7, pp. 461-466 (1962).
Nataraj, V. and M. R. Rao, “Isobaric Vapor-Liquid Equilibrium Data for the Binary Systme Benzene-Cyclohexane, Benzene-Isobutanol and Cyclohexane-Isobutanol,” Indian J. Technol., Vol. 5, pp. 212-215 (1967).
Osvaldo, C. F., P. Patricio and P. Rasmussen, “Vapor-Liquid Equilibria for Glycol Ether + Water systems,” J. Chem. Eng. Data, Vol. 38, pp. 128-131 (1993)
Patel, N. C. and A. S. Teja, “A New Cubic Equation of State for Fluid and Fluid Mixtures,” Chem. Eng. Sci., Vol. 37, pp. 463-473 (1982).
Peng, D. Y. and D. B. Robinson, “A New Two-Constant Equation of State,“ Ind. Eng. Chem. Fundam., Vol. 15, pp. 59-63 (1976).
Pitzer, K. S. and R. F. Curl, “Empirical Equation for the Second Virial Coefficients,” J. Am. Chem. Soc., Vol. 79, pp. 2369-2370 (1975).
Prausnitz, J. M., T. F. Anderson, E. A. Grens, C. A. Eckert, R. Shieh, and J. P. O''Connell, “Computer Calculations for Multi-Component Vapor- Liquid and Liquid-Liquid Equilibria,” Prentice-Hall, NY, 1980.
Rackett, H. G., “Equation of State for Saturated Lquids,” J. Chem. Eng. Data, Vol. 15, pp. 514-517 (1970).
Redlich, O. and A. T. Kister, “Algebraic Representation of Thermodynamic Properties and Classification of Solutions,” Ind. Eng. Chem., Vol. 40, pp. 345-348 (1948).
Reid, R. C., J. M. Prausrnitz, and B. E. Poling, “The Properties of Gases and Liquids”, 5th Edition, McGraw-Hill, New York, 2001.
Renon, H. and J. M. Prausnitz, “Local Composition in Thermodynamic Excess Functions for Liquid Mixtures,” AIChE J., Vol. 14, pp.135-144 (1968).
Sebastiani, E. and L. Lacquaniti, “Acetic Acid－Water System Thermodynamical Correlation of Vapor-Liquid Equilibrium Data,” Chem. Eng. Sci., Vol. 22, pp. 1155- (1967).
Skrzece, A. and Z. Maczynska, “Saturated Vapor Pressure of Water－Alkyl Acetate Two-Liquid Mixtures,” Pol. J. Chem., Vol. 54, pp. 2383 (1980).
Soave, G., “Equilibrium Constants from a Modified Redlich-Kwong Equation of State,” Chem. Eng. Sci., Vol. 27, pp. 1197-1203 (1972).
Spencer, C. F. and R. P. Danner, “Improved Equation for Predication of Saturated Liquid Density,” J. Chem. Eng. Data, Vol. 17, pp. 236-241 (1972).
Spencer, C. F. and S. B. Alder, “A Critical Review of Equations for Predicting Saturated Liquid Density,” J. Chem. Data, Vol. 23, pp. 82-89 (1978).
TRC Thermodynamics Tables, Non-Hydrocarbons, Thermodynamics Research Center, The Texas A & M University System, College Station, TX, 1993.
Tsonopoulos, C., “An Empirical Correlation of Second Virial Coefficients,” AIChE J., Vol. 20, pp. 263-272 (1974).
Veranna, D. and D. N. Rihani, “Review of Density Estimation of Saturated Liquid Mixtures,” J. Chem. Eng. Data, Vol. 25, pp. 263-271 (1980).
Wilson, G. M., “Vapor-Liquid Equilibrium. XI : A New Expression for the Excess Free Energy of Mixing,” J. Chem. Soc., Vol. 86, pp. 127-130 (1964).
Yamada, T. and R. D. Gunn, “Saturated Liquid Molar Volumes. The Rackett Equation,” J. Chem. Eng. Data, Vol. 18, pp. 234-236 (1973).