化工程序的開發與設計中，理解流體的行為模式是相平衡中不可缺少一部分。一般而言在汽油中加入如醚類與醇類的燃油含氧化物添加劑，能夠提高辛烷值與減少污染。本研究為選取可能做為汽油辛烷值提升劑的燃油含氧化物與汽油中的成份所組成系統的汽液平衡量測研究。汽液平衡數據可供了解在加入一種添加劑後後，如何影響汽油的總共蒸氣壓及組成。燃油含氧化物考慮乙醇與甲乙基酮(2-丁酮)，汽油中的成份為2,2,4-三甲基戊烷(異辛烷)。本研究量測乙醇、2-丁酮及異辛烷在101.3 kPa下之三組雙成分系統及一組三成份系統的汽液相平衡研究。
本研究利用Hunsmann之汽液相平衡裝置來行汽-液平衡數據的量測，及氣體層析儀來分析汽相與液相相平衡組成。並利用Soave-Redlich-Kwong(SRK)的方法來計算其汽相液壓係數，分析汽液平衡的實驗數據，顯示出雙成份系統均有最小沸點，三成份系統則無最小沸點。雙成份系統的汽液平衡數據均符合Kojima的熱力學一致性測試。三成份系統之汽液平衡數據也通過改良McDermott-Ellis的一致性測試。數據處理方面，雙成份系統採用Wilson、NRTL，和UNIQUAC三種gE模式來做關聯，並將各模式中之最適合之參數用來預測三成份汽液平衡。雙成份系統之平衡沸點溫度、gE/RT和汽相組成，也以Redlich-Kister形式之方程式來關聯。三成份系統之平衡沸點溫度和gE/RT則利用Jasinski and Malanowskiz方程式、Cibulka方程式、Sing 方程式、Pintos方程式、Calvo方程式和其他衍生出來的方程式來關聯三成份數據。

Phase equilibrium is an essential element for developing and designing chemical process as well as enhancing our realization in fluid-pahse behaviors. In general, to add the fuel oxygenates such as ethers and alcohols can enhance octane capability and decrease pollutions. In this study, vapor-liquid equilibria were measured by mixing the fuel oxygenates that might be as an octane enhancer with one of the gasoline components. Such data can provide what the effects in the total vapor pressure of the gasoline and its composition when added the additives. The fuel oxygenates considered are ethanol and 2-butanone, and the component in gasoline is 2,2,4-trimethylpentane. In this study, we measured the vapor-liquid equilibrium (VLE) at 101.3 kPa for the ternary system of ethanol + 2-butanone + isooctane and these of their constituent binaries.
In this study, we used Hunsmann’s apparatus to measure VLE, and determined the composition of these systems by gas chromatography method. We also calculated vapor-phase fugacity coefficients by SRK equation. Analysis of the experimental VLE data, all of the binary systems exhibited a minimum boiling temperature. Azeotropic behavior was not found in the ternary system. The experimental data of these binary systems passed the thermodynamic consistency test based on the method of Kojima et al. The data of ternary system also passed the consistency test by a modified McDermott-Ellis method. In the treatment of experimental data, binary systems were correlated with the mole fraction using the Wilson, NRTL, and UNIQUAC models. The models with their best-fitted parameters were used to predict the ternary vapor-liquid equilibrium. The excess molar Gibbs free energy, equilibrium boiling temperature, and vapor-phase composition of all binary systems were correlated with the Redlich-Kister type equation. We used Jasinski and Malanowski equation, Cibulka equation, Sing equation, Pintos equation, Calvo equation, and other extended equations to correlate the equilibrium boiling temperature and excess Gibbs free energy of the ternary system too.

中文摘要.................................................................................................. Ⅰ
英文摘要……………………………...…………...……………….…... Ⅲ
目錄……………………………………………..………………...……...Ⅳ
表目錄………………………………………….……...………………Ⅶ
圖目錄…………………………….………………….....…………...…Ⅹ
符號表…………………………………………………………..……ⅩⅡ
主文
第一章 緒論………………………………………………...………...…..1
壹 前言……………………………………………………..…….1
1-1 汽油…………………………………………………………1
1-2 汽油添加劑…………………………………………………..2
1-3 汽油添加劑變遷……………………………………………3
1-4 MTBE的危害…………………......…………………………4
1-4-1 對環境影響...........................................................................5
1-4-2 對人體影響...........................................................................6
1-5 各國相關法令.......................................................................6
1-6為何要用 乙醇 異辛烷 2–丁酮 當作汽油添加劑................6
貳 研究目的與方法………………………………………………9
参 汽液平衡實驗方法……………………………………………11
一 靜態式相平衡裝置…………………………………......11
二 流動式相平衡裝置…………………………………......13
三 半流動式相平衡裝置………………………………......14
四 循環式相平衡裝置…………………………………......14
第二章 理論……………………………………………........…………16
2-1 平衡……………………………….......…………………….16
2-1 平衡原則……………………………………….....…..……16
2-3 汽液相平衡理論……………………….....………………...19
2-4 熱力學一致性測試回顧…………………...……..………...21
2-5 汽液相平衡數據的處理方法……………...………..……...32
2-6 液相過剩吉布斯自由能模式…………………………….34
第三章 實驗部分…………………….…...……………………………..43
3-1 藥品…………………………………………...…..………43
3.2 實驗設備……………………….…..………………………..44
3-2-1 汽液平衡裝置................................................................44
3-2-2 氣體層析裝置………………………………………….47
3-2-3 其它裝置……………………………………………….48
3-3 實驗步驟………………………………………...…......…...48
第四章 結果與討論…………………………………………...…...……61
4-1 活性係數、吉布斯自由能計算………………..…...……….61
4-2 共沸點決定………...…….…………………………………63
4-3 熱力學一致性測試……………….………..……..………..65
4-4 參數計算……………………………………………………66
4-5 三成份數據關聯………………………………………….70
第五章 結論………………………………………..……………………74
參考文獻…………………………………………...…………...…….117
附錄……………………………………………………………………127

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