臺灣博碩士論文加值系統

本研究完成了二氧化碳在立體障礙醇胺AMP水溶液及混合醇胺AMP + PZ水溶液氣液平衡溶解度量測，氣液平衡數據量測在一控制溫度之平衡槽內進行，所量測的系統濃度包括：2.0 M (kmol•m-3) 和3.0 M (kmol•m-3) AMP水溶液及2.0 M和3.0 M AMP水溶液分別加入0.5、1.0及1.5 M PZ水溶液；溫度分別為40、60、80℃；二氧化碳分壓範圍：1 ~ 150 kPa。
以Kent and Eisenberg (1976)模式，加上Hu and Chakma (1990)與Li and Shen (1993)所提出的熱力學模式來建立適用於本系統CO2/AMP/H2O及CO2/AMP/PZ/H2O的氣液平衡模式。模式所預測的範圍為溫度20 ~ 120℃，酸性氣體分壓0.1 ~ 10000 kPa，PZ濃度範圍由0 M ~ 2.0 M。在本研究中所完成之氣液平衡溶解度數據及氣液平衡模式可作為設計吸收設備時的參考使用，提供一符合經濟效益設計的依據。

In this work, the solubility of carbon dioxide in aqueous mixture containing different concentrations of 2-amino-2-methyl-1-propanol (AMP), a sterically hindered amine, and piperazine (PZ), an activator, were carefully measured in a 1.0-L stainless steel vapor-recirculation equilibrium cell at 40, 60, and 80 oC, and pressures of 1 kPa up to 150 kPa. The AMP concentrations in the binary and ternary mixtures considered were 2.0 M (kmol•m-3) and 3.0 M (kmol•m-3); those of PZ’s were 0.5 M, 1.0 M, and 1.5 M.
The measured equilibrium loading – partial pressure pairs at different temperatures and concentration levels were compared against the corresponding values predicted by modified Kent-Eisenberg model which based on previous works of Hu and Chakma (1990) and Li and Shen (1993). This study is useful for the vapor-liquid equilibrium calculations of acid gas processes design, as the absorption fluid.

目錄
摘要 I
Abstract II
誌謝 III
目錄 IV
表目錄 VII
圖目錄 IX
第1章 緒論 1
1-1 前言 1
1-2 常用氣體捕捉方法 1
1-3 醇胺的使用 2
1-4 掺合醇胺的使用 4
1-5 研究目的 5
第2章 原理 9
2-1 平衡常數概述 9
2-2 熱力學模式文獻回顧 10
2-2-1 Ideal Solution Model 11
2-2-2 Activity Coefficient Model 12
2-3 熱力學模式之推導 14
第3章 實驗 20
3-1 實驗設備 20
3-2 實驗藥品 21
3-3 實驗步驟 25
3-4 液相分析 25
3-5 氣相分析 26
第4章 結果討論 28
4-1 對照實驗 28
4-2 雙成份系統中氣液平衡溶解度之量測 31
4-3 三成份系統中氣液平衡溶解度之量測 50
第5章 結論 79
符號說明 80
參考文獻 82
自述 87


表目錄
Table 1 1 Commonly used alkanolamines 6
Table 1 2 Comparison of alkanolamines 7
Table 1 3 Literature review of thermophysical property data for AMP/PZ/H2O system 8
Table 3 1 Absorbent details in this study 24
Table 4 1 Solubility of CO2 in aqueous 3.0 M AMP solutions at 40oC 29
Table 4 2 Solubility of CO2 in aqueous 2.0 M AMP solutions 32
Table 4 3 Solubility of CO2 in aqueous 3.0 M AMP solutions 33
Table 4 4 Equilibrium constants and Henry's law constant used in this study 39
Table 4 5 Vapor-liquid equilibrium data CO2/AMP/H2O system used in this study 41
Table 4 6 Solubility of CO2 in aqueous 2.0 M AMP + 0.5 M PZ solutions 53
Table 4 7 Solubility of CO2 in aqueous 2.0 M AMP + 1.0 M PZ solutions 54
Table 4 8 Solubility of CO2 in aqueous 2.0 M AMP + 1.5 M PZ solutions 55
Table 4 9 Solubility of CO2 in aqueous 3.0 M AMP + 0.5 M PZ solutions 56
Table 4 10 Solubility of CO2 in aqueous 3.0 M AMP + 1.0 M PZ solutions 57
Table 4 11 Solubility of CO2 in aqueous 3.0 M AMP + 1.5 M PZ solutions 58
Table 4 12 Vapor-liquid equilibrium data CO2/AMP/PZ/H2O system in this study 59


圖目錄
Figure 3 1 Experimental setup 23
Figure 4 1 Solubility of CO2 in aqueous 3.0 M AMP solutions at 40oC 30
Figure 4 2 Solubility of CO2 in aqueous 2.0 M AMP solutions at 40, 60 and 80oC 34
Figure 4 3 Solubility of CO2 in aqueous 3.0 M AMP solutions at 40, 60 and 80oC 35
Figure 4 4 Solubility of CO2 in aqueous 2.0 M and 3.0 M AMP solutions at 40oC 36
Figure 4 5 Solubility of CO2 in aqueous 2.0 M and 3.0 M AMP solutions at 60oC 37
Figure 4 6 Solubility of CO2 in aqueous 2.0 M and 3.0 M AMP solutions at 80oC 38
Figure 4 7 Solubility of CO2 in aqueous 2.0 M AMP solutions at 40, 60 and 80oC 42
Figure 4 8 Solubility of CO2 in aqueous 3.0 M AMP solutions at 40, 60 and 80oC 43
Figure 4 9 Correlation of literature solubility data for CO2 in aqueous 2.0 M AMP solutions at 40 and 100oC 44
Figure 4 10 Correlation of literature solubility data for CO2 in aqueous 3.0 M AMP solutions at 40oC 45
Figure 4 11 Correlation of literature solubility data for CO2 in aqueous 3.43 M AMP solutions at 50oC 46
Figure 4 12 Correlation of literature solubility data for CO2 in aqueous 2.0 M AMP solutions at 40 and 70oC 47
Figure 4 13 Comparison of calculated and measured partial pressure for 48
Figure 4 14 Comparison of calculated and measured partial pressure for 49
Figure 4 15 Solubility of CO2 in aqueous 2.0 M AMP + 0.5 M PZ solutions at 40, 60 and 80oC 60
Figure 4 16 Solubility of CO2 in aqueous 2.0 M AMP + 1.0 M PZ solutions at 40, 60 and 80oC 61
Figure 4 17 Solubility of CO2 in aqueous 2.0 M AMP + 1.5 M PZ solutions at 40, 60 and 80oC 62
Figure 4 18 Solubility of CO2 in aqueous 3.0 M AMP + 0.5 M PZ solutions at 40, 60 and 80oC 63
Figure 4 19 Solubility of CO2 in aqueous 3.0 M AMP + 1.0 M PZ solutions at 40, 60 and 80oC 64
Figure 4 20 Solubility of CO2 in aqueous 3.0 M AMP + 1.5 M PZ solutions at 40, 60 and 80oC 65
Figure 4 21 Solubility of CO2 in aqueous 2.0 M AMP + 0.5 M PZ and 3.0 M AMP + 0.5 M PZ solutions at 40, 60 and 80oC 66
Figure 4 22 Solubility of CO2 in aqueous 2.0 M AMP + 1.0 M PZ and 3.0 M AMP + 1.0 M PZ solutions at 40, 60 and 80oC 67
Figure 4 23 Solubility of CO2 in aqueous 2.0 M AMP + 1.5 M PZ and 3.0 M AMP + 1.5 M PZ solutions at 40, 60 and 80oC 68
Figure 4 24 Solubility of CO2 in aqueous 2.0 M AMP and 2.0 M AMP + PZ solutions at 40oC 69
Figure 4 25 Solubility of CO2 in aqueous 2.0 M AMP and 2.0 M AMP + PZ solutions at 60oC 70
Figure 4 26 Solubility of CO2 in aqueous 2.0 M AMP and 2.0 M AMP + PZ solutions at 80oC 71
Figure 4 27 Solubility of CO2 in aqueous 3.0 M AMP and 3.0 M AMP + PZ solutions at 40oC 72
Figure 4 28 Solubility of CO2 in aqueous 3.0 M AMP and 3.0 M AMP + PZ solutions at 60oC 73
Figure 4 29 Solubility of CO2 in aqueous 3.0 M AMP and 3.0 M AMP + PZ solutions at 80oC 74
Figure 4 30 Comparison of calculated and measured partial pressure for aqueous 2.0 M AMP + PZ solutions 75
Figure 4 31 Comparison of calculated and measured partial pressure for aqueous 3.0 M AMP + PZ solutions 76
Figure 4 32 Prediction of solubility data for CO2 in aqueous 2.0 M AMP + 0.5 M PZ solutions at various temperatures 77
Figure 4 33 Prediction of solubility data for CO2 in aqueous 3.0 M AMP and 3.0 M AMP + PZ solutions at 60oC 78

Appl, M.; Wagner, U.; Henrici, H. J.; Kuessner, K.; Voldamer, K.; Fuerest, E. Removal of CO2 and/or H2S and/or COS from Gases Containing These Constituents. 1982, U.S. Patent 4,336,233.
Aroua, M. K.; Salleh, R. M. Solubility of CO2 in Aqueous Piperazine and its Modeling using the Kent-Eisenberg Approach. Chem. Eng. Technol. 2004, 27, 65-70.
Austgen, D. M.; Rochelle, G. T.; Peng, X.; Chen, C. C. Model of Vapor-liquid Equilibria for Aqueous Acid Gas-alkanolamine Systems Using the Electrolyte-NRTL Equation. Ind. Eng. Chem. Res. 1989, 28, 1060-1073.
Bishnoi, S.; Rochelle, G. T. Absorption of Carbon Dioxide into Aqueous Piperazine: Reaction Kinetics, Mass Transfer and Solubility. Chem. Eng. Sci. 2000, 55, 5531-5543.
Bishnoi, S.; Rochelle, G. T. Thermodynamics of Piperazine/Methyldiethanolamine/Water/Carbon Dioxide. Ind. Eng. Chem. Res. 2002, 41, 604-612.
Chakravarty, T.; Phukan, U. K.; Weiland, R. H. Reaction of Acid Gases with Mixtures of Amines. Chem. Eng. Prog. 1985, 81, 32-36.
Chen, C.-C.; Evans, L. B. A Local Composition Model for the Excess Gibbs Energy of Aqueous Electrolyte Systems. AIChE J. 1986, 32, 444-454.
Choi, W.-J.; Cho, K.-C.; Lee, S.-S.; Shim, J.-G.; Hwang, H.-R.; Park, S.-W.; Oh, K.-J. Removal of Carbon Dioxide by Absorption into Blended Amines: Kinetics of Absorption into Aqueous AMP/HMDA, AMP/MDEA, and AMP/piperazine Solutions. Green Chem. 2007, 9, 594-598.
Clegg, S. L.; Pitzer, K. S. Thermodynamics of Multicomponent, Miscible, Ionic Solutions: Generalized Equations for Symmetrical Electrolytes. J. Phys. Chem. 1992, 96, 3513-3520.
Crooks, J. E.; Donnellan, J. P. Kinetics and Mechanism of the Reaction Between Carbon Dioxide and Amines in Aqueous Solution. J. Chem. Soc., Perkin Trans. 2 1989, 331-333.
Derks, P. W. J.; Dijkstra, H. B. S.; Hogendoorn, J. A.; Versteeg, G. F. Solubility of cCrbon Dioxide in Aqueous Piperazine Solutions. AIChE J. 2005, 51, 2311-2327.
Deshmukh, R. D.; Mather, A. E. A Mathematical Model for Equilibrium Solubility of Hydrogen Sulfide and Carbon Dioxide in Aqueous Alkanolamine Solutions. Chem. Eng. Sci. 1981, 36, 355-362.
Edwards, T. J.; Newman, J.; Prausnitz, J. M. Thermodynamics of Aqueous Solutions Containing Volatile Weak Electrolytes. AIChE J. 1975, 21, 248-259.
Guggenheim, E. A. The Specific Thermodynamic Properties of Aqueous Solutions of Strong Electrolytes. Philos. Mag. 1935, 19, 588-643.
Hosseini Jenab, M.; Abedinzadegan Abdi, M.; Najibi, S. H.; Vahidi, M.; Matin, N. S. Solubility of Carbon Dioxide in Aqueous Mixtures of N-Methyldiethanolamine + Piperazine + Sulfolane. J. Chem. Eng. Data 2005, 50, 583-586.
Hu, W.; Chakma, A. Modelling of Equilibrium Solubility of CO2 and H2S in Aqueous Amino Methyl Propanol (AMP) Solutions. Chem. Eng. Commun. 1990, 94, 53-61.
Kent, R. L.; Eisenberg, B. Better Data for Amine Treating. Hydrocarbon Processing 1976, 55, 87-90.
Kohl, A. L.; Nielsen, R. B. Gas Purification, Gulf Pub. Co., Houston, 1997.
Kundu, M.; Chitturi, A.; Bandyopadhyay, S. S. Prediction of Equilibrium Solubility of CO2 in Aqueous Alkanolamines Using Differential Evolution Algorithm. Can. J. Chem. Eng. 2008, 86, 117-126.
Li, M.-H.; Chang, B.-C. Solubilities of Carbon Dioxide in Water + Monoethanolamine + 2-Amino-2-methyl-1-propanol. J. Chem. Eng. Data 1994, 39, 448-452.
Li, M.-H.; Chang, B.-C. Solubility of Mixtures of Carbon Dioxide and Hydrogen Sulfide in Water + Monoethanolamine + 2-Amino-2-methyl-1-propanol. J. Chem. Eng. Data 1995, 40, 328-331.
Li, M.-H.; Shen, K.-P. Calculation of Equilibrium Solubility of Carbon Dioxide in Aqueous Mixtures of Monoethanolamine with Methyldiethanolamine. Fluid Phase Equilibria 1993, 85, 129-140.
Li, M. H.; Shen, K. P. Solubility of Hydrogen Sulfide in Aqueous Mixtures of Monoethanolamine with N-methyldiethanolamine. J. Chem. Eng. Data 1993, 38, 105-108.
Li, Y.-G.; Mather, A. E. Correlation and Prediction of the Solubility of Carbon Dioxide in a Mixed Alkanolamine Solution. Ind. Eng. Chem. Res. 1994, 33, 2006-2015.
Lin, S.-H.; Chiang, P.-C.; Hsieh, C.-F.; Li, M.-H.; Tung, K.-L. Absorption of Carbon Dioxide by the Absorbent Composed of Piperazine and 2-amino-2-methyl-1-propanol in PVDF Membrane Contactor. J. Chin. Inst. Chem. Engrs. 2008, 39, 13-21.
Liu, H.-B.; Zhang, C.-F.; Xu, G.-W. A Study on Equilibrium Solubility for Carbon Dioxide in Methyldiethanolamine-Piperazine-Water Solution. Ind. Eng. Chem. Res. 1999, 38, 4032-4036.
Paul, S.; Mandal, B. Density and Viscosity of Aqueous Solutions of (2-Piperidineethanol + Piperazine) from (288 to 333) K and Surface Tension of Aqueous Solutions of (N-Methyldiethanolamine + Piperazine), (2-Amino-2-methyl-1-propanol + Piperazine), and (2-Piperidineethanol + Piperazine) from (293 to 323) K. J. Chem. Eng. Data 2006, 51, 2242-2245.
Paul, S.; Mandal, B. Density and Viscosity of Aqueous Solutions of (N-Methyldiethanolamine + Piperazine) and (2-Amino-2-methyl-1-propanol + Piperazine) from (288 to 333) K. J. Chem. Eng. Data 2006, 51, 1808-1810.
Peng, D.-Y.; Robinson, D. B. A New Two-Constant Equation of State. Ind. Eng. Chem. Fundam. 1976, 15, 59-64.
Perry, R. H.; Chilton, C. H. Chemical Engineerings Handbook, McGraw-Hill Inc. , N.Y., 1973.
Pitzer, K. S. Electrolytes. From Dilute Solutions to Fused Salts. J. Am. Chem. Soc. 1980, 102, 2902-2906.
Pitzer, K. S.; Simonson, J. M. Thermodynamics of Multicomponent, Miscible, Ionic Systems: Theory and Equations. J. Phys. Chem. 1986, 90, 3005-3009.
Renon, H.; Prausnitz, J. M. Local Compositions in Thermodynamic Excess Functions for Liquid Mixtures. AIChE J. 1968, 14, 135-144.
Roberts, B. E.; Mather, A. E. Solubility of CO2 and H2S in a Hindered Amine Solution. Chem. Eng. Commun. 1988, 64, 105-111.
Robinson, R. A.; Stokes, R. H. Electrolyte Solutions, 2nd ed, Butterworth and Co., London, 1970.
Sada, E.; Kumazawa, H.; Butt, M. A. Solubility and Diffusivity of Gases in Aqueous Solutions of Amines. J. Chem. Eng. Data 1978, 23, 161-163.
Samanta, A.; Bandyopadhyay, S. S. Absorption of Carbon Dioxide into Aqueous Solutions of Piperazine Activated 2-amino-2-methyl-1-propanol. Chem. Eng. Sci. 2009, 64, 1185-1194.
Samanta, A.; Bandyopadhyay, S. S. Density and Viscosity of Aqueous Solutions of Piperazine and (2-Amino-2-methyl-1-propanol + Piperazine) from 298 to 333 K. J. Chem. Eng. Data 2006, 51, 467-470.
Sartori, G.; Savage, D. W. Sterically hindered amines for carbon dioxide removal from gases. Ind. Eng. Chem. Fundam. 1983, 22, 239-249.
Seo, D. J.; Hong, W. H. Effect of Piperazine on the Kinetics of Carbon Dioxide with Aqueous Solutions of 2-Amino-2-methyl-1-propanol. Ind. Eng. Chem. Res. 2000, 39, 2062-2067.
Shen, K. P.; Li, M. H. Solubility of Carbon Dioxide in Aqueous Mixtures of Monoethanolamine with Methyldiethanolamine. J. Chem. Eng. Data 1992, 37, 96-100.
Soave, G. Equilibrium Constants from a Modified Redlich-Kwong Equation of State. Chem. Eng. Sci. 1972, 27, 1197-1203.
Sun, W.-C.; Yong, C.-B.; Li, M.-H. Kinetics of the Absorption of Carbon Dioxide into Mixed Aqueous Solutions of 2-Amino-2-methyl-l-propanol and Piperazine. Chem. Eng. Sci. 2005, 60, 503-516.
Teng, T. T.; Mather, A. E. Solubility of Carbon Dioxide in an AMP Solution. J. Chem. Eng. Data 1990, 35, 410-411.
Teng, T. T.; Mather, A. E. Solubility of H2S, CO2 and Their Mixtures in an AMP Solution. Can. J. Chem. Eng. 1989, 67, 846-850.
Tontiwachwuthikul, P.; Meisen, A.; Lim, C. J. Solubility of Carbon Dioxide in 2-Amino-2-methyl-1-propanol Solutions. J. Chem. Eng. Data 1991, 36, 130-133.
李夢輝，氣體吸收處裡，化工技術，1999, 8, 180-196.
王成維，二氧化碳在醇胺(AMP)與有機溶劑(sulfolane)摻合物水溶液中之氣液平衡量測研究，中原大學化工所，2001年。
林俊廷，PZ+AMP混合醇胺水溶液吸收二氧化碳之反應動力學數據量測研究，中原大學化工所，2007年。
陳明德，二氧化碳在混合醇胺(MEA/TEA)水溶液中之氣液平衡溶解度量測，中原大學化工所，2000年。
蔡順添，二氧化碳與AMP之氣液平衡測量研究，中原大學化工所，1999年。