臺灣博碩士論文加值系統

本研究採用靜態式液相循環的相平衡裝置，量測溶劑A + 1,2-丁二醇、溶劑A + 乙二醇在393.15 K、423.15 K及453.15 K 溫度下的雙成分混合物之汽液相平衡數據，溶劑B + 1,2-丁二醇在353.15 K、393.15 K、433.15 K及473.15 K溫度下的雙成分混合物之汽液相平衡數據，溶劑B + 乙二醇在393.15 K、433.15 K及473.15 K溫度下的雙成分混合物之汽液相平衡數據，實驗結果顯示每組雙成分系統皆無共沸物產生，且均是正偏差。所量取之雙成分汽液相平衡數據的熱力學一致性均分別以逐點法、面積法與無限稀釋法確認。本實驗所測得之系統分別以Wilson-HOC，NRTL-HOC以及UNIQUAC-HOC模式關聯，每一種模式均能獲得令人滿意的結果。

A static-type apparatus with a liquid-phase circulation loop was used to measure isothermal vapor-liquid equilibrium (VLE) data for the binary systems of solvent A + 1,2-butanediol and solvent A + ethylene glycol at 393.15 K, 423.15 K, and 453.15 K. And also measured the binary systems of solvent B + 1,2-butanediol at 353.15 K, 393.15 K, 433.15 K, and 473.15 K, and solvent B + ethylene glycol at 393.15 K, 433.15 K, and 473.15 K. The experimental results exhibit no azeotropic behavior and positive deviations from Raoult’s law for each binary system. The thermodynamic consistency of the new binary VLE data has been confirmed by the point, area, and infinite dilution tests. The Wilson-HOC, the NRTL-HOC, and the UNIQUAC-HOC models were used to correlate each binary system measured in this work. Each model yielded satisfactory results.

摘要 I
Abstract II
誌謝 III
目錄 V
表目錄 VIII
圖目錄 X
第一章 緒論 1
1-1 前言 1
1-2 研究動機與背景 2
1-3 研究目的 7
1-4 相平衡 8
1-5 汽液相平衡量測 10
1-6 本文各章的重點 12
第二章 汽液相平衡量測 16
2-1 汽液相平衡量測裝置之主要設備 16
2-2 實驗裝置 18
2-2-1 主要裝置之除氣與進料系統 19
2-2-2 主要裝置之平衡系統 20
2-2-3 主要裝置之取樣與組成分析系統 21
2-2-4 簡易裝置之除氣與進料系統 22
2-2-5 簡易裝置之平衡系統 22
2-3 待測系統與藥品 23
2-4 實驗程序 25
2-4-1 主要裝置之樣品及系統前置操作步驟 25
2-4-2 主要裝置之樣品進料操作步驟 25
2-4-3 主要裝置之汽相取樣分析步驟 26
2-4-4 主要裝置之液相取樣分析步驟 27
2-4-5 簡易裝置之操作步驟 28
2-5 量測系統之測試 29
2-6 氣相層析儀之校正曲線 29
2-7 飽和蒸汽壓之量測 30
2-8 雙成分混合物系統之量測結果 30
第三章 相平衡研究之模式關聯 80
3-1 熱力學一致性測試 80
3-1-1 Gibbs-Duhem 方程式 82
3-1-2 熱力學一致性測試法 83
3-1-3 熱力學一致性測試結果 86
3-2 汽液相平衡之計算 86
3-3 實驗數據之關聯 87
第四章 結論與建議 132
4-1 結論 132
4-2 建議 134
參考文獻 136
附錄A 符號說明 140
附錄B 程式之計算示意圖 144

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., 21, 116-128 (1975).
Chao, K. C., Isobaric Vapor-Liquid Equilibria Modified Equations Correlate Isobaric Vapor-Liquid Equilibria When the System Shows a Wide Boiling Range and Considerable Heat of Solution. Ind. Eng. Chem. Res., 51, 93-94 (1959).
Chemistry WebBook, the National Institute of Standards and Technology (NIST), http://webbook.nist.gov/chemistry/, USA.
Fredenslund, A., J. Gmehling, and P. Rasmussen, Vapor-Liquid Equilibria Using UNIFAC, Elsevier, Amsterdam, 68-74 (1977).
Foster, R.D., T. A. Maliszewski, and J. A. Sims, Continuous Process for Producing Alkylene Glycols from Alkylene Carbonates. Union Carbide Corporation, US4117250 A (1978).
Gliński, M., J. Kijeński, and A. Jakubowski, Ketones from Monocarboylic Acids: Catalytic Ketonization over Oxide Systems. Applied Catalysis A: General, 128, 209-217 (1995).
Gmehling, J. and U. Onken, Vapor-Liquid Equilibrium Data Collecion-Aqueous-Organic Systems, Chemistry Data Series,Vol. I, DECHEMA, Frankfurt, Germany (1977).
Hayden, J. G. and J. P. O'Connell, A Generalized Method for Predicting Second Virial Coefficients. Ind. Eng. Chem. Process Des. Dev., 14, 209-216 (1975).
Herington, E. F. G., Tests for the Consistency of Experimental Isobaric Vapour-Liquid Equilibrium Data. J. Inst. Pet., 37, 457-470 (1951).

Kamimura, Y., S. Sato, R. Takahashi, T. Sodesawa, and T. Akshi, Sythesis of 3-Pentanone from 1-Propanol over CeO2-Fe2O3 Catalysts. Applied Catalysis A：General, 252, 399-410 (2003).
Kawabe, K., Development of Highly Selective Process for Mono-Ethylene Glycol Production from Ethylene Oxide via Ethylene Carbonate Using Phosphonium Salt Catalyst. Catalysis Surveys from Asia, Issue 3-4, 111-115 (2010).
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 Equilib., 56, 269-284 (1990).
Ochi, K. and B. C.-Y. Lu, Determination and Correlation of Binary Vapor-Liquid Equilibrium Data. Fluid Phase Equilib, 1, 158-200 (1978).
Park, S. D., C. H. Kim, and C. S. Choi, High-Pressure Binary Vapor-Liquid Equilibrium Measurements of Carbon Dioxide with Aromatic Hydrocarbons. J. Chem. Eng. Data, 36, 80-84 (1991).
Peng, D.-Y. and D. B. Robinson, A New Two-Constant Equation of State. Ind. Eng. Chem. Fundam., 15, 59-64 (1976).
Prausnitz, J. M., R. N. Lichtenthaler, and E. G. de Azevedo, Molecular Thermodynamics of Fluid-Phase Equilibria, 3rd edition, Prentice-Hall, Englewood Cliffs, New Jersey (1999).
Redlich, O. and A. T. Kister, Algebraic Representation of Thermodynamic Properties and the Classification of Solutions. Ind. Eng. Chem. Fundam., 40, 345-348 (1948).
Renon, H. and J. M. Prausnitz, Local Compositions in Thermodynamic Excess Functions for Liquid Mixtures. AIChE J., 14, 135-144 (1968).
Robson, J. H. and E. K George. II, Process for the Production of Alkylene Glycols, Union Carbide Corporation, US4551566 A (1985).
Sada, E. and T. Morisue, Isothermal Vapor-Liquid Equilibrium Data of Isopropanol-Water system. J. Chem. Eng. Jpn., 8, 191-195 (1975).
Soave, G., Equilibrium Constants from A Modified Redlich-Kwong Equation of State. Chem. Eng. Sci., 27, 1197-1203 (1972).
Spencer, C. F. and S. B. Alder, A Critical Review of Equations for Predicting Saturated Liquid Density. J. Chem. Eng. Data, 23, 82-89 (1978).
Tsonopoulos, C., An Empirical Correlation of Second Virial Coefficients. AIChE J., 20, 263-272 (1974).
Van Ness, H. C., S. M. Byer, and R. E. Gibbs, Vapor-Liquid Equilibrium: Part I. An Appraisal of Data Reduction Methods. AIChE J., 19, 238-244 (1973).
Van Ness, H. C., S. M. Byer, and R. E. Gibbs, Vapor-Liquid Equilibrium: Part II. Correlations from P-x Data for 15 Systems. AIChE J., 19, 245-251 (1973).
Wagner, W., New Vapour Pressure Measurements for Argon and Nitrogen and a New Method for Establishing Rational Vapour Pressure Equations. Cryogenics, 13, 470-482 (1973).
Wilson, G. M., Vapor-Liquid Equilibrium. XI. A New Expression for the Excess Free Energy of Mixing. J. Am. Chem. Soc., 86, 127-130 (1964).
Zhu, F., K. Huang, S. Wang, L. Shan, and Q. Zhu, Towards Further Internal Heat Integration in Design of Reactive Distillation Columns-Part IV: Application to a High-purity Ethylene Glycol Reactive Distillation Column, Chemical Engineering Science, 64, 3498-3509 (2009).


何坤榮，「EG供應緊張，價格大幅上漲」，精細與專用化學品，第11卷，第10期（2003）。
張育川，「1,2-丁二醇」，精細與專用化學品，第9卷，第23期（2003）。
潭捷，「草酸酯加氫合成乙二醇專利技術研究進展」，精細與專用學品，第23卷，第1期（2015）。
胡家弘，「低壓下丙酮、乙醇與二異丙基醚混合物之汽液平衡」， 碩士論文，國立台灣科技大學，台北（1994）。
徐武軍、張有義，化工程序設計，五南圖書出版股份有限公司， 第13-166頁，台北（2007）。
賀孝芸，「恆溫下含產製碳酸二苯酯主要成分之混合物的汽液相平衡研究」，碩士論文，國立台灣科技大學，台北 （2013）。