臺灣博碩士論文加值系統

本研究量測333.15 K、343.15 K、及353.15 K的雙成分混合物的汽液相平衡。七組系統為苯(1)＋壬烷(2)、甲苯(1)＋鄰二甲苯(2)、間二甲苯(1)＋環丁&;#30904;(2)、鄰二甲苯(1)＋環丁&;#30904;(2)、鄰二甲苯(1)＋N-甲基甲醯胺(2)、間二甲苯(1)＋N-甲基甲醯胺(2)、及對二甲苯(1)＋N-甲基甲醯胺(2)。量測壓力範圍從0.01到101.3 kPa之間。分別以Wilson、NRTL、UNIQUAC三種活性係數模式，進行壓力與液相莫爾分率的實驗值間彼此，相關性之研究。以泡點壓力方法來計算汽相莫爾分率，並以Peng-Robinson狀態方程式關聯汽相數據。同時，量測汽相與液相的密度，得汽液相的過剩莫爾體積值。實驗結果發現甲苯(1)＋鄰二甲苯(2)、鄰二甲苯(1)＋N-甲基甲醯胺(2)、間二甲苯(1)＋N-甲基甲醯胺(2)、及對二甲苯(1)＋N-甲基甲醯胺(2)的四組混合物，呈現近似理想溶液。苯(1)＋壬烷(2)、間二甲苯(1)＋環丁&;#30904;(2)以及鄰二甲苯(1)＋環丁&;#30904;(2)三組混合物，呈現偏離理想溶液。過剩吉布士自由能的計算值顯示，僅有甲苯(1)＋鄰二甲苯(2)雙成分系統呈現負值，其餘六組雙成分系統的自由能皆為正值。

Vapor-liquid equilibria at 333.15 K 343.15K and 353.15 K for seven binary mixtures of benzene + nonane, toluene + o-xylene, m-xylene + sulfolane, o-xylene + sulfolane, o-xylene + NMF, m-xylene + NMF and p-xylene + NMF have been obtained at pressures ranged from 0.01 to 101.3 kPa. The Wilson, NRTL and UNIQUAC activity coefficient models have been employed to correlate experimental data to find intermolecular parameters. The non-ideal behavior of the vapor phase has been considered by using the Peng-Robinson equation of state in calculating the vapor mole fraction. Liquid and vapor densities were measured by using two vibrating tube densitometers to determine liquid excess molar volumes. Six systems of benzene + nonane , m-xylene + sulfolane , o-xylene + sulfolane , o-xylene + NMF, m-xylene + NMF and p-xylene + NMF mixtures present large positive deviations from the ideal solution and belong to endothermic mixings because their excess Gibbs energies are positive. Temperature dependent intermolecular parameters in the three models were obtained in this study.

中文摘要 i
Abstract ii
表目錄 v
圖目錄 ix
符號說明 xv
第一章 緒論 1
第二章 文獻回顧 2
2-1 石油簡介 2
2-2 相平衡量測方法簡介 3
2-2-1 靜態式的相平衡實驗 3
2-2-2 循環式的相平衡實驗 4
2-2-3 動態式的相平衡實驗 5
2-2-4 觀測霧泡現象之相平衡實驗 6
2-2-5 綜合式之相平衡實驗 6
2-2-6 改良靜態式之相平衡實驗 7
2-2-7 密度儀分析之相平衡實驗 7
2-3 相關文獻蒐尋 8
第三章 實驗部分 10
3-1 藥品 10
3-2 汽液相平衡儀器 12
3-3 兩相汽液相平衡實驗 15
3-3-1 空白實驗及穩壓測試 15
3-3-2 壓力檢量常數的實驗 15
3-3-3 汽液相密度的平衡實驗 16
3-3-4 相平衡系統總體積之量測 17
3-3-5汽液相莫爾分率計算 18
3-3-6汽液相平衡實驗步驟 18
第四章 理論部分 21
4-1 汽液相平衡理論模式 21
4-2 狀態方程式 23
4-2-1 對應狀態方程式 26
4-2-2 維理狀態方程式 27
4-2-3 立方狀態方程式 28
4-2-4 複雜狀態方程式 29
4-3 混合律 30
4-4 活性係數方法 32
4-4-1 NRTL模式 33
4-4-2 UNIQUAC模式 35
4-4-3 Wilson模式 38
4-5 密度的測量原理 41
4-6 高壓流體密度之壓力檢量常數 42
4-7 目標函數之訂定 43
4-8 純成分臨界參數之計算 44
4-9 MATLAB擬合程式計算 45
第五章 結果與討論 47
5-1 汽液相平衡實驗結果 48
5-1-1汽相及液相溶液的密度 48
5-1-2七組雙成分系統之汽液相平衡 49
5-2雙成分系統活性係數及過剩吉布士自由能計算 52
5-3理論模式參數計算迴歸結果 54
第六章 結論 57
參考文獻 60

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