常壓下乙酸酯類之雙成份混合物汽液相平衡

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吳奇鴻(Chi-Hung Wu) 查詢紙本館藏

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化學工程與材料工程學系

論文名稱

常壓下乙酸酯類之雙成份混合物汽液相平衡
(Isobaric Vapor-Liquid Equilibria of Isobutyl Acetate + C4 Alcohols from Experiments & Thermodynamic Models)

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摘要(中)

本研究利用改良式之Othmer循環式汽液相平衡裝置量測等壓下（101.3 kPa）六組雙成份混合物之汽液相平衡數據，研究系統為：乙醇＋碳酸二乙酯、異丁醇＋碳酸二乙酯、正丁醇＋乙酸異丁酯、仲丁醇＋乙酸異丁酯、叔丁醇＋乙酸異丁酯與異丁醇＋乙酸異丁酯等系統。其中兩組系統（乙醇＋碳酸二乙酯與異丁醇＋乙酸異丁酯）用以驗證實驗量測系統與手法之可靠性，並以相同研究裝置及實驗技巧研究四組雙成份混合物之等壓（101.3 kPa）汽液相平衡實驗數據（異丁醇＋碳酸二乙酯、正丁醇＋乙酸異丁酯、仲丁醇＋乙酸異丁酯、叔丁醇＋乙酸異丁酯）。上述六組汽液相平衡實驗數據均須通過熱力學一致性的檢測，其中包含Herington提出的面積法與van Ness的點對點測試。本研究中，液相組成採用常見的活性係數模型（UNIQUAC、NRTL），並搭配汽相組成以計算逸壓係數的兩種方式（理想氣體和Hayden O’Connell（HOC））進行回歸。實驗結果顯示當系統含有碳酸二乙酯成份，以HOC的效果最佳；然而，當系統含有乙酸異丁酯成份，則以理想氣體的回歸表現較好。此外，對於雙成份混合物系統的預測，modified-UNIFAC與COSMO-SAC兩種模型在趨勢的走向上均能有相當不錯的表現。回歸的處理均在Aspen Plus可操作完成。

摘要(英)

In this research, the isobaric vapor-liquid equilibrium (VLE) of six binary mixtures of ethanol + diethyl carbonate (DEC), 2-methyl-1-propanol + DEC, n-butanol + isobutyl acetate (IBAc), 2-butanol + IBAc, 2-methyl-2-propanol + IBAc and 2-methyl-1-propanol + IBAc were all measured at 101.3 kPa by using a recirculating type of modified Othmer equilibrium device. The newly measured isobaric VLE results of ethanol + DEC and 2-methyl-1-propanol + IBAc were compared to the experimental data from the open literatures in order to validate the employed experimental apparatus and measuring procedure. Then, the rest of the isobaric VLE of 2-methyl-1-propanol + DEC, n-butanol + IBAc, 2-butanol + IBAc and 2-methyl-2-propanol + IBAc at 101.3 kPa were investigated with the same apparatus and equal procedure because only very few or no available experimental data were found for each of these two binary mixtures system in open literatures. All measured data were tested by the thermodynamic consistency test methods proposed by Herington and van Ness. Binary interaction parameters for universal quasi-chemical (UNIQUAC) and non-random two liquid (NRTL) activity-coefficient models associating with the fugacity-coefficient method (ideal gas and Hayden O’Connell) were employed to correlate the measured VLE data. Furthermore, accuracy of the modified-UNIFAC model in predicting the six binary VLE of measured systems were do better agreement with our experimental data. All regression processes were do in Aspen Plus only.

關鍵字(中)

★ 汽液相平衡

關鍵字(英)

論文目次

中文摘要 i
Abstract ii
誌謝 iii
目錄 iv
圖目錄 vii
表目錄 ix
第一章　緒論 1
1-1　前言 1
1-2　相平衡裝置回顧 1
1-2-1　靜態式（static type）裝置 2
1-2-2　半流動式（semi-flow type）裝置 2
1-2-3　流動式（flow type）裝置 3
1-2-4　循環式（circulation type）裝置 4
1-2-5　綜合式（synthetic type）裝置 5
1-3　共沸系統回顧 5
1-4　研究動機 7
1-4-1　系統簡介 8
第二章　實驗部分 15
2-1　藥品 15
2-2　實驗裝置 19
2-3　實驗設備 20
2-4　實驗步驟 20
2-5　成份分析 21
2-5-1　GC配件 21
2-5-2　分析時之條件設定 22
2-5-3　檢量線配製 23
2-6　溫度計校正 24
2-7　實驗數據回歸 26
第三章　理論部分 27
3-1　相平衡理論 27
3-1-1　逸壓與逸壓係數 27
3-1-2　汽液相平衡 28
3-2　熱力學一致性 31
3-2-1　點對點測試 32
3-2-2　面積法 32
第四章　結果與討論 34
4-1　檢量線之擬合 34
4-2　可靠性實驗數據 34
4-2-1　乙醇（1）＋碳酸二乙酯（2）雙成份系統 34
4-2-2　異丁醇（1）＋乙酸異丁酯（2）雙成份系統 35
4-3　汽液相平衡新數據 36
4-3-1　異丁醇（1）＋碳酸二乙酯（2）雙成份系統 36
4-3-2　正丁醇（1）＋乙酸異丁酯（2）雙成份系統 37
4-3-3　仲丁醇（1）＋乙酸異丁酯（2）雙成份系統 37
4-3-4　叔丁醇（1）＋乙酸異丁酯（2）雙成份系統 38
第五章　結論 62
參考文獻 63
附錄一 69
附錄二 76

參考文獻

[1] A. Valtz, C. Coquelet, A. Baba-Ahmed, D. Richon, “Vapor–liquid equilibrium data for the propane+1,1,1,2,3,3,3-heptafluoropropane (R227ea) system at temperatures from 293.16 to 353.18 K and pressures up to 3.4 mpa ”, Fluid Phase Equilib., Vol 202, 29-47, 2002.
[2] T. Sommer, J. Trejbal, D. Kopecký, “Isobaric and isothermal vapor–liquid equilibria for the binary system of water + formic acid at 99.41 kpa, 388.15 K, and 398.15 K ”, J. Chem. Eng. Data, Vol 61, 3398-3405, 2016.
[3] P. N. Bengesai, W. M. Nelson, P. Naidoo, D. Ramjugernath, “Phase equilibria for perfluoroethane + (n-perfluorohexane or n-perfluorooctane) binary systems: Measurement and modeling ”, J. Chem. Eng. Data, Vol 61, 3363-3370, 2016.
[4] C. S. Su, M. Tang, Y. P. Chen, “Micronization of nabumetone using the rapid expansion of supercritical solution (RESS) process ”, J. Supercrit. Fluids, Vol 50, 69-76, 2009.
[5] K. W. Cheng, S. J. Kuo, M. Tang, Y. P. Chen, “Vapor–liquid equilibria at elevated pressures of binary mixtures of carbon dioxide with methyl salicylate, eugenol, and diethyl phthalate ”, J. Supercrit. Fluids, Vol 18, 87-99, 2000.
[6] M. Kato, H. Tanaka, H. Yoshikawa, “Vapor-liquid equilibria for four binary systems made of alcohol and cyclohexylamine at 100 kpa ”, J. Chem. Eng. Data, Vol 36, 387-390, 1991.
[7] Q. Wang, K. C. Chao, “Vapor—liquid and liquid-liquid equilibria and critical states of water + n-decane mixtures ”, Fluid Phase Equilib., Vol 59, 207-215, 1990.
[8] C. Zhang, H. Wan, L. Xue, G. Guan, “Investigation on isobaric vapor liquid equilibrium for acetic acid + water + (n-propyl acetate or iso-butyl acetate) ”, Fluid Phase Equilib., Vol 305, 68-75, 2011.
[9] J. Ding, W. Guan, P. Wan, L. Wang, H. Wan, G. Guan, “Isobaric vapor–liquid equilibrium for the binary systems of diethyl carbonate with xylene isomers and ethylbenzene at 101.33 kpa ”, J. Chem. Eng. Data, Vol 61, 3724-3729, 2016.
[10] B. S. Gupta, M. J. Lee, “Isobaric vapor–liquid equilibrium for the binary mixtures of nonane with cyclohexane, toluene, m-xylene, or p-xylene at 101.3 kpa ”, Fluid Phase Equilib., Vol 313, 190-195, 2012.
[11] H. Y. Chiu, R. F. Jung, M. J. Lee, H. M. Lin, “Vapor–liquid phase equilibrium behavior of mixtures containing supercritical carbon dioxide near critical region ”, J. Supercrit. Fluids, Vol 44, 273-278, 2008.
[12] C. M. Hsieh, T. Windmann, J. Vrabec, “Vapor–liquid equilibria of CO2 + C1–C5 alcohols from the experiment and the COSMO-SAC model ”, J. Chem. Eng. Data, Vol 58, 3420-3429, 2013.
[13] C. M. Hsieh, J. Vrabec, “Vapor–liquid equilibrium measurements of the binary mixtures CO2 + acetone and CO2 + pentanones ”, J. Supercrit. Fluids, Vol 100, 160-166, 2015.
[14] W. Reinders, C. H. De Minjer, “Vapour‐liquid equilibria in ternary systems: II. The system acetone‐chloroform‐benzene ”, Recl. Trav. Chim. Pays-Bas, Vol 59, 369-391, 1940.
[15] T. Hiak, K. Kurihara, K. Kojima, “Vapor-liquid equilibria for acetone + chloroform + methanol and constituent binary systems at 101.3 kpa ”, J. Chem. Eng. Data, Vol 39, 714-719, 1994.
[16] D. F. Othmer, “Composition of vapors from boiling binary solutions ”, Ind. Eng. Chem., Vol 35, 614-620, 1943.
[17] J. C. Ojeda Toro, I. Dobrosz-Gómez, M. Á. Gómez García, “The study of water + HCl + ethanol vapor-liquid equilibrium at 78 kpa ”, J. Chem. Thermodyn., Vol 107, 201-206, 2017.
[18] H. H. Otsuki, “Effect of pressure on vapor liquid equilibria for the system ethyl alcohol-water ”, 1951.
[19] A. H. Beebe, K. E. Coulter, R. A. Lindsay, E. M. Baker, “Equilibria in ethanol-water system at pressures less than atmospheric ”, Ind. Eng. Chem., Vol 34, 1501-1504, 1942.
[20] W. J. Gaw, F. L. Swinton, “Thermodynamic properties of binary systems containing hexafluorobenzene. Part 4. Excess Gibbs free energies of the three systems hexafluorobenzene + benzene, touene, and p-xylene ”, J. Chem. Soc., Faraday Trans., Vol 64, 2023-2034, 1968.
[21] A. Chinikamala, G. N. Houth, Z. L. Taylor Jr, “Vapor-liquid equilibriums of binary systems containing selected hydrocarbons with perfluorobenzene ”, J. Chem. Eng. Data, Vol 18, 322-325, 1973.
[22] K. Nakanishi, H. Shirai, T. Minamiyama, “Vapor-liquid equilibrium of binary systems containing alcohols (methanol with aliphatic amines) ”, J. Chem. Eng. Data, Vol 12, 591-594, 1967.
[23] A. Rodríguez, J. Canosa, A. Domínguez, J. Tojo, “Isobaric phase equilibria of diethyl carbonate with five alcohols at 101.3 kpa ”, J. Chem. Eng. Data, Vol 48, 86-91, 2003.
[24] H. P. Luo, W. D. Xiao, K. H. Zhu, “Isobaric vapor–liquid equilibria of alkyl carbonates with alcohols ”, Fluid Phase Equilib., Vol 175, 91-105, 2000.
[25] J. B. Montón, R. Muñoz, M. C. Burguet, J. d. l. Torre, “Isobaric vapor–liquid equilibria for the binary systems isobutyl alcohol + isobutyl acetate and tert-butyl alcohol + tert-butyl acetate at 20 and 101.3 kpa ”, Fluid Phase Equilib., Vol 227, 19-25, 2005.
[26] J. Linek, “Vapour-liquid equilibrium in the isobutyl alcohol-isobutyl acetate binary system ”, Collect. Czech. Chem. Commun., Vol 42, 2469-2473, 1977.
[27] Z. Jiang, X. Liu, S. Qin, S. Ma, X. Zou, L. Wang, “Isobaric vapor–liquid equilibrium for the binary systems of sec-butyl acetate + n-butyl alcohol, isobutyl alcohol, or tert-butyl alcohol at 101.3 kpa ”, J. Chem. Eng. Data, Vol 62, 105-110, 2017.
[28] A. Fredenslund, R. L. Jones, J. M. Prausnitz, “Group-contribution estimation of activity coefficients in nonideal liquid mixtures ”, AIChE J., Vol 21, 1086-1099, 1975.
[29] U. Weidlich, J. Gmehling, “A modified UNIFAC model. 1. Prediction of vle, he, and gamma.. Infin ”, Ind. Eng. Chem. Res., Vol 26, 1372-1381, 1987.
[30] J. Gmehling, J. Li, M. Schiller, “A modified UNIFAC model. 2. Present parameter matrix and results for different thermodynamic properties ”, Ind. Eng. Chem. Res., Vol 32, 178-193, 1993.
[31] S. T. Lin, S. I. Sandler, “A priori phase equilibrium prediction from a segment contribution solvation model ”, Ind. Eng. Chem. Res., Vol 41, 899-913, 2002.
[32] E. Mullins, R. Oldland, Y. A. Liu, S. Wang, S. I. Sandler, C. C. Chen, M. Zwolak, K. C. Seavey, “Sigma-profile database for using COSMO-Based thermodynamic methods ”, Ind. Eng. Chem. Res., Vol 45, 4389-4415, 2006.
[33] P. Susial, J. C. Apolinario, J. J. Rodríguez-Henríquez, V. D. Castillo, E. J. Estupiñan, “Isobaric VLE at 0.6 mpa for binary systems isobutyl acetate + ethanol, +1-propanol or +2-propanol ”, Fluid Phase Equilib., Vol 331, 12-17, 2012.
[34] H. Kehlen, E. Fuhrmann, “Excess enthalpies in butylacetate-butanol mixture ”, Vol 259, pp 373-376, 1978.
[35] D. N. Briggs, K. H. Lawrence, A. T. Bell, “An investigation of carbon-supported CuCl2/PdCl2 catalysts for diethyl carbonate synthesis ”, Appl. Catal., A, Vol 366, 71-83, 2009.
[36] M. A. Pacheco, C. L. Marshall, “Review of dimethyl carbonate (DMC) manufacture and its characteristics as a fuel additive ”, Energy Fuels, Vol 11, 2-29, 1997.
[37] M. Winter, P. Novák, “Chloroethylene carbonate, a solvent for lithium‐ion cells, evolving CO2 during reduction ”, J. Electrochem. Soc., Vol 145, L27-L30, 1998.
[38] U. Romano, R. Tesel, M. M. Mauri, P. Rebora, “Synthesis of dimethyl carbonate from methanol, carbon monoxide, and oxygen catalyzed by copper compounds ”, Ind. Eng. Chem. Proc. Res. Dev., Vol 19, 396-403, 1980.
[39] S. Thaiphanit, P. Anprung, “Physicochemical and flavor changes of fragrant banana (musa acuminata aaa group “gross michel”) during ripening ”, J. Food Process. Preserv., Vol 34, 366-382, 2010.
[40] H. N. Solimo, N. G. Barnes de Arreguez, “Liquid-liquid equilibria for water + ethanol + 2-methylpropyl ethanoate and water + ethanol + 1,2-dibromoethane at 298.15 K ”, J. Chem. Eng. Data, Vol 39, 8-11, 1994.
[41] D. F. Othmer, “Azeotropic distillation for dehydrating acetic acid ”, Chem. Metall. Eng, Vol 40, 91-95, 1941.
[42] L. S. Lee, M. Z. Kuo, “Phase and reaction equilibria of the acetic acid-isopropanol-isopropyl acetate-water system at 760 mmhg ”, Fluid Phase Equilib., Vol 123, 147-165, 1996.
[43] L. S. Lee, S. H. Huang, J. F. Huang, “Pressure effect and its application of separation azeotropic mixture of allyl alcohol and water ”, J. Chin. Inst. Chem. Eng., Vol 26, 1-9, 1995.
[44] H. I. Britt, R. H. Luecke, “The estimation of parameters in nonlinear, implicit models ”, Technometrics, Vol 15, 233-247, 1973.
[45] D. S. Abrams, 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, 116-128, 1975.
[46] H. Renon, J. M. Prausnitz, “Local compositions in thermodynamic excess functions for liquid mixtures ”, AIChE J., Vol 14, 135-144, 1968.
[47] J. P. O′Connell, J. M. Prausnitz, “Empirical correlation of second virial coefficients for vapor-liquid equilibrium calculations ”, Ind. Eng. Chem. Proc. Dec. Dev., Vol 6, 245-250, 1967.
[48] J. G. Hayden, J. P. O′Connell, “A generalized method for predicting second virial coefficients ”, Ind. Eng. Chem. Proc. Dec. Dev., Vol 14, 209-216, 1975.
[49] K. H. Nothnagel, D. S. Abrams, J. M. Prausnitz, “Generalized correlation for fugacity coefficients in mixtures at moderate pressures. Application of chemical theory of vapor imperfections ”, Ind. Eng. Chem. Proc. Dec. Dev., Vol 12, 25-35, 1973.
[50] J. M. Prausnitz, W. C. Edmister, K. C. Chao, “Hydrocarbon vapor‐liquid equilibria and solubility parameter ”, AIChE J., Vol 6, 214-219, 1960.
[51] H. C. Van Ness, S. M. Byer, R. E. Gibbs, “Vapor-liquid equilibrium: Part I. An appraisal of data reduction methods ”, AIChE J., Vol 19, 238-244, 1973.
[52] E. F. G. Herington, “Tests for the consistency of experimental isobaric vapor-liquid equilibrium data ”, J. Inst. Petrol, Vol 37, 457-470, 1951.
[53] O. Redlich, A. T. Kister, “Algebraic representation of thermodynamic properties and the classification of solutions ”, Ind. Eng. Chem., Vol 40, 345-348, 1948.
[54] I. C. Arango, A. L. Villa, “Isothermal vapor – liquid and vapor–liquid–liquid equilibrium for the ternary system ethanol + water + diethyl carbonate and constituent binary systems at different temperatures ”, Fluid Phase Equilib., Vol 339, 31-39, 2013.
[55] S. P. Christensen, J. D. Olson, “Phase equilibria and multiple azeotropy of the acetic acid-isobutyl acetate system ”, Fluid Phase Equilib., Vol 79, 187-199, 1992.
[56] F. Comelli, R. Francesconi, C. Castellari, “Excess molar enthalpies of diethyl carbonate + four butanol isomers in the range (288.15−318.15) K ”, J. Chem. Eng. Data, Vol 44, 739-743, 1999.

指導教授

謝介銘

審核日期

2017-6-29

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