臺灣博碩士論文加值系統

本研究主要為探討新混合溶劑除濕液(醇類 + 水 + 鹽類)系統之氣液平衡量測，所選擇溶劑為醇類diethylene glycol (DEG)、triethylene glycol (TEG)、propylene glycol (PG)、tetraethylene gloycol (T4EG)、dipropylene glycol (DPG)、tripropylene glycol (TPG)這六種，鹽類則選擇氯化鎂(Magnesium chloride)以(4.0, 9.0 and 16.0wt%)與固定濃度(40wt%)的醇類水溶液做配製。由於本系統中含有電解質，故採用(Söhnel and Novotný, 1985; Söhnel and Novotný, 1988)提出之經驗式加以改良來表示本研究系統之密度與黏度。蒸氣壓部分則是利用Antoine equation熱力學模式，描述系統蒸氣壓與溫度之間的關係；並以平均圓球近似法理論(Söhnel and Novotný, 1985; Söhnel and Novotný, 1988; Shiah and Tseng, 1994)來描述系統蒸氣壓、濃度與溫度的關係。實驗所得結果，可應用於設計設備之基本數據。

In this work, new experimental data for vapor pressure, density, and viscosity of the mixed-solvent desiccant systems containing 40.0 wt% glycol (1) + salt (2) + water (3) were reported for temperatures up to 343.15 K (normal atmospheric condition). The considered glycols were diethylene glycol, triethylene glycol, propylene glycol, tetraethylene gloycol, dipropylene glycol and tripropylene glycol; and the salt is magnesium chloride (wt% = 4.0, 9.0, and 16.0). The vapor pressure, density, and viscosity were presented as functions of temperature and compositions. An empirical equation was used to correlate the temperature and compositional dependence of the density and viscosity data and a model based on the mean spherical approximation for aqueous electrolyte solutions incorporating the pseudo-solvent approach was used to represent the measured vapor pressure as functions of temperature and composition. Satisfactory results were obtained for both density and vapor pressure calculations.

目錄

摘要 I
ABSTRACT II
誌謝 III
目錄 IV
圖目錄 VIII
第1章 緒論 1
1-1 研究背景與目的 1
1-2 研究動機與方向 2
1-2-1 混合除濕溶劑選取 3
1-2-2 蒸氣壓、密度與黏度的量測 4
1-2-3 計算部份 4
第2章 文獻回顧 7
2-1 蒸氣壓測量方法 7
2-2 文獻數據收集 9
2-3 除濕效率 12
2-4 電解質水溶液之蒸氣壓關聯模式 15
2-4-1 安東尼方程式蒸氣壓關聯式 15
2-4-2 平均圓球近似法(Mean spherical Approximation, MSA) 16
2-4-3 混合溶液介電常數 21
2-4-4 水的活性係數 22
2-5 混合溶劑除濕劑熱物性質關聯模式 22
2-5-1 醇類水溶劑密度關聯式 22
2-5-2 混合溶劑除濕劑密度關聯模式 23
2-5-3 醇類水溶液動黏度關聯模式 24
2-5-4 混合溶劑除濕劑動黏度關聯模式 25
第3章 實驗 26
3-1 實驗藥品 26
3-2 蒸氣壓之量測 26
3-2-1 蒸氣壓實驗裝置 26
3-2-2 蒸氣壓實驗步驟 29
3-3 密度之量測 30
3-3-1 密度實驗裝置 30
3-3-2 密度實驗步驟 31
3-4 黏度之量測 32
3-4-1 黏度實驗裝置 32
3-4-2 黏度實驗步驟 33
3-4-3 AMVn 黏度實驗步驟 34
3-4-4 黏度數據處理 35
3-4-5 AMVn 黏度數據處理 35
第4章 結果與討論 40
4-1 密度量測結果與計算 40
4-2 蒸氣壓之量測與計算 65
4-3 MSA蒸氣壓計算模式 90
4-4 黏度量測結果與計算 108
第5章 結論 120



表目錄
Table 1冷凍除濕與物理性除濕之優缺點比較：(Luo et al., 1999) 5
Table 2有機溶劑與無機鹽類水溶液除濕劑優缺點：(Luo et al., 1999) 6
Table 3除濕劑之蒸氣壓數據 11
Table 4無機鹽類與有機醇類藥品名稱 26
Table 5 Density of DEG 42
Table 6 Density of TEG 42
Table 7 Densities of TPG + H2O 43
Table 8 parameters in Eq. (2 48) 44
Table 9 parameters in Eq. (2 47) 44
Table 10 Densities of MgCl2 (1) + DEG (2) + H2O 45
Table 11 Densities of MgCl2 (1) + TEG (2) + H2O 46
Table 12 Densities of MgCl2 (1) + PG (2) + H2O 47
Table 13 Densities of MgCl2 (1) + T4EG (2) + H2O 48
Table 14 Densities of MgCl2 (1) + DPG (2) + H2O 49
Table 15 Densities of MgCl2 (1) + TPG (2) + H2O 50
Table 16 The parameters in Eq. (4 1) 51
Table 17 The parameters in Eq. (4 1) 52
Table 18 The parameters in Eq. (4 1) 53
Table 19 Vapor pressures of H2O 68
Table 20 Vapor pressures of DPG + H2O 69
Table 21 Vapor pressures of TPG + H2O 69
Table 22 Vapor pressures of MgCl2 (1) + DEG (2) + H2O 70
Table 23 Vapor pressures of MgCl2 (1) + TEG (2) + H2O 71
Table 24 Vapor pressures of MgCl2 (1) + PG (2) + H2O 72
Table 25 Vapor pressures of MgCl2 (1) + T4EG (2) + H2O 73
Table 26 Vapor pressures of MgCl2 (1) + DPG (2) + H2O 74
Table 27 Vapor pressures of MgCl2 (1) + TPG (2) + H2O 75
Table 28 The parameters in Eq. (4 3) 76
Table 29 The parameters in Eq. (4 3) 77
Table 30 The parameters in Eq. (4 3) 78
Table 31 The parameters in MSA Eq. (2 16) 92
Table 32 The parameters in MSA Eq. (2 16) 93
Table 33電解質Pauling陽離子以及陰離子粒徑 (Shiah and Tseng 1994) 94
Table 34 Viscosity of TEG 110
Table 35 Viscosity of PG 110
Table 36 Viscosities of MgCl2 (1) + TEG (2) + H2O 111
Table 37 Viscosities of MgCl2 (1) + PG (2) + H2O 112
Table 38 The parameters in equation (4 4) 113



圖目錄
Figure 1 Schematic diagram of the vapor pressure measurement apparatus 36
Figure 2 Anton Paar SVM3000 37
Figure 3 Cannon-Fenske Routine Viscometer 38
Figure 4 Anton Paar AMVn 39
Figure 5 Densities of pure DEG 54
Figure 6 Densities of pure TEG 55
Figure 7 Densities of TPG + H2O 56
Figure 8 Densities of MgCl2 (1) + DEG (2) + H2O 57
Figure 9 Densities of MgCl2 (1) + TEG (2) + H2O 58
Figure 10 Densities of MgCl2 (1) + PG (2) + H2O 59
Figure 11 Densities of MgCl2 (1) + T4EG (2) + H2O 60
Figure 12 Densities of MgCl2 (1) + DPG (2) + H2O 61
Figure 13 Densities of MgCl2 (1) + TPG (2) + H2O 62
Figure 14 Plot of (ρ - ρa) as function of temperature for MgCl2 (1) + TPG (2) + H2O 63
Figure 15 Plot of (ρ - ρa ) as function of temperature for MgCl2 (1) + DEG 64
Figure 16 Vapor pressures of H2O 79
Figure 17 Vapor pressures of DPG + H2O (Solid lines, calculated using the Antoine equation). 80
Figure 18 Vapor pressures of TPG + H2O (Solid lines, calculated using the Antoine equation). 81
Figure 19 Vapor pressures of MgCl2 (1) + DEG (2) + H2O (Solid lines, 82
Figure 20 Vapor pressures of MgCl2 (1) + TEG (2) + H2O (Solid lines, 83
Figure 21 Vapor pressures of MgCl2 (1) + PG (2) + H2O (Solid lines, 84
Figure 22 Vapor pressures of MgCl2 (1) + T4EG (2) + H2O (Solid lines, 85
Figure 23 Vapor pressures of MgCl2 (1) + DPG (2) + H2O (Solid lines, 86
Figure 24 Vapor pressures of MgCl2 (1) + TPG (2) + H2O (Solid lines, 87
Figure 25 Vapor pressure against reciprocal temperature to compare the commonly used liquid desiccant counterparts and a system used in this study: □ (40 wt% T4EG + 16 wt% MgCl2 + H2O), this work; ● (16wt% MgCl2+ H2O), Patil et al., 1990; ▲ (50 wt% T4EG + H2O), The Dow Chemical Co.; ▼ water, Perry et al., 1997. 88
Figure 26 Vapor pressures of MgCl2 + DPG + H2O, MgCl2 + DEG + H2O, MgCl2 + TPG + H2O. 89
Figure 27 Vapor pressures of MgCl2 (1) + DEG (2) + H2O (Solid lines, 95
Figure 28 Vapor pressures of MgCl2 (1) + TEG (2) + H2O (Solid lines, 96
Figure 29 Vapor pressures of MgCl2 (1) + PG (2) + H2O (Solid lines, 97
Figure 30 Vapor pressures of MgCl2 (1) + T4EG (2) + H2O (Solid lines, 98
Figure 31 Vapor pressures of MgCl2 (1) + DPG (2) + H2O (Solid lines, 99
Figure 32 Vapor pressures of MgCl2 (1) + TPG (2) + H2O (Solid lines, 100
Figure 33 Vapor pressures of MgCl2 (1) + DEG (2) + H2O (Solid lines, 101
Figure 34 Vapor pressures of MgCl2 (1) + TEG (2) + H2O (Solid lines, 102
Figure 35 Vapor pressures of MgCl2 (1) + TPG (2) + H2O (Solid lines, 103
Figure 36 Dielectric constants of H2O and glycols ( data of Lide, 2001-2002 ) 104
Figure 37 Vapor pressures of MgCl2 (1) + TEG (2) + H2O (Solid lines, 105
Figure 38 Vapor pressures of MgCl2 (1) + DPG (2) + H2O (Solid lines, 106
Figure 39 Comparison of Vapor Pressures MgCl2 (1) +Glycols (2) + H2O 107
Figure 40 Viscosities of pure TEG 114
Figure 41 Viscosities of pure PG 115
Figure 42 Viscosities of MgCl2 (1) + TEG (2) + H2O 116
Figure 43 Viscosities of MgCl2 (1) + PG (2) + H2O 117
Figure 44 Comparison of Viscosities MgCl2 (1) + ( 40wt% ) Glycols (2) + 118
Figure 45 Plot of (η - ηa) versus molality of salt at 343.15K: ■, MgCl2 + 119

Bernal-Garcia, J., Manuel Guzman-Lopez, A. Cabrales-Torres,V. Rico-Ramirez and G. A. Iglesias-Silva "Supplementary Densities and Viscosities of Aqueous Solutions of Diethylene Glycol from (283.15 to 353.15) K." J. Chem. Eng. Data 2008, 53: 1028-1031.
Blum, L. "Mean Spherical Model for Asymmetric Electrolytes. I. Method of Solution." Mol. Phys. 1975. 30: 1529-1535.
Castro, C. S. and L. Blum "Explicit Approximation for the Unrestricted Mean Spherical Approximation for Ionic Solutions." J. Phy. Chem. 1989, 93: 7478-7482.
Chen, L.-F., A. N. Soriano and M.-H. Li "Vapour Pressures and Densities of the Mixed-solvent Desiccants (Glycols + Water + Salts)." J. Chem. Thermodyn. 2009, 41: 724-730.
Chung, T. W. " Predictions of Moisture Removal Efficiencies for Packed-Bed Dehumidification Systems." Gas Sep. Purif. 1994, 8: 265-268.
Chung, Tsair-Wang; Luo, Chung-Ming. "Vapor Pressures of the Aqueous
Desiccants." J. Chem. Eng. Data 1999, 44: 1024-1027.
Dow, C. C. Properties of Glycols: Midland, MI, 2007.
Gering, K. L., L. L. Lee and L. H. Landis "A Molecular Approach to Electrolytes: Phase Behavior and Activity Coefficients for Mix-Salt and Multisolvent Systems." Fluid Phase Equilib. 1989, 48: 111-139.
Horvath, A. L. Handbook of Aqueous Electrolyte Solution: Physical Properties, Estimation and Correlation Method; Ellis Horwood: New York, 1985.
Hsu, C. H. and M. H. Li "Densities of Aqueous Blended Amines." J. Chem. Eng. Data 1997, 42: 502-507.
Lee, L. S., I.-C. Ho., C.-H. Lin. and C.-L. Lin. "Measurements, Correlations, and Estimations of the Vapor Pressures of CaCl2, MgCl2, and BaCl2 Aqueous Solutions between 298.15 K and 328.15 K." J. Chin. Inst. Chem. Engrs. 2005, 36: 271-280.
Lide, D. R. CRC Handbook of Chemistry and Physics; CRC: New York, 2001-2002.
Luo C. M. and Chung, T. W. "Vapor Pressures of the Aqueous Desiccants." J. Chem. Eng. Data 1999, 44: 1024-1027.
Patil, K. R., A. D. Tripathi,G. Pathak and S. S. Katti " Thermodynamic Properties of Aqueous Electrolyte Solutions. 1. Vapor Pressure of Aqueous Solutions of LiCl, LiBr, and LiI." J. Chem. Eng. Data 1990, 35: 166-168.
Patil, K. R., A. D. Tripathi,G. Pathak and S. S. Katti "Thermodynamic Properties of Aqueous Electrolyte Solutions. 2. Vapor Pressure of Aqueous Solutions of NaBr, NaI, KCl, KBr, KI, RbCl, CsCl, MgCl2, CaCl2, CaBr2, CaI2, CaI2, SrCl2, SrBr2, SrI2, BaCl2, and BaBr2." J. Chem. Eng. Data 1991, 36: 225-230.
Pikkarainen, L. "Densities and Viscosities of Binary Solvent Mixtures of N-Methylacetamide with Aliphatic Alcohols." J. Chem. Eng. Data 1983, 28: 381-383.
Prausnitz, J. M., R. N. Lichtenthaler and E. G. de Azevedo Molecular Thermodynamics of Fluid-Phase Equilibria; Prentice-Hall: Englewood Cliffs: NJ, 1986.
Söhnel, O. and P. Novotný Densities of Aqueous Solutions of Inorganic Substances; Elsevier Science: Amsterdam, Netherlands, 1985.
Söhnel, O. and P. Novotný "Densities of Binary Aqueous Solutions of 306 Inorganic Substances." J. Chem. Eng. Data 1988, 33: 49-55.
Shiah, I. M. and H. C. Tseng "A Vapor Pressure Model for Aqueous Electrolyte Solutions based on Mean Spherical Approximation." Fluid Phase Equilib. 1994, 90: 75-85.
Sun, T. and A. S. Teja "Density, Viscosity, and Thermal Conductivity of Aqueous Ethylene, Diethylene, and Triethylene Glycol Mixtures between 290 K and 420 K." J. Chem. Eng. Data 2003, 48: 198-202.
Takeshl, S., H. Toshlkatsu and Y. Hlroshl "Vapor Pressures of Binary (H2O-HCI, -MgCI2, and -CaC12) and Ternary (H2O-MgC12-CaC12) Aqueous Solutions ." J. Chem. Eng. Data 1985, 30: 224.
Triolo, R., J. R. Grigera and L. Blum "Simple Electrolytes in the Mean Spherical Approximation." J. Phys. Chem. 1976, 80: 1858-1861.
Tsai, C.-Y., A. N. Soriano and M.-H. Li "Vapour Pressures, Densities, and Viscosities of the Aqueous Solutions containing (Triethylene Glycol or Propylene Glycol) and (LiCl or LiBr)." J. Chem. Thermodyn. 2009, 41: 623-631.
Ullah, M. R., C. F. Kerrleborough and P. Gandhidasan " Effectiveness of Moisture Removal for an Adiabatic Counterflow Packed Tower Absorber Operating with CaCl2-Air Contact System. " ASME J. Solar Energy Eng. 1988, 110: 98-101.
Vemulapalli, G. K. Physical Chemistry; Prentice Hall, Englewood Cliffs: New Jersey, 1993.