預測有機物與二氧化碳雙成份系統之固液氣三相平衡

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姓名

陳崇毅(Chong-Yi Chen) 查詢紙本館藏

畢業系所

化學工程與材料工程學系

論文名稱

預測有機物與二氧化碳雙成份系統之固液氣三相平衡
(Prediction of solid-liquid-gas equilibrium for binary mixtures of carbon dioxide + organic compounds)

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摘要(中)

固液氣三相平衡數據為優化或決定超臨界製程中最佳操作條件的關鍵因素之一，在此研究中蒐集了近四十年來的文獻，總共21 種有機物在二氧化碳的雙成分系統，此研究的主軸以Peng-Robinson 狀態方程式為主，接著選擇了兩種過剩自由能為基礎的混合律分別為MHV1 及Wong-Sandler (WS)混合律，搭配兩種活性係數模型分別為COSMO-SAC(2002) 及COSMO-SAC(2010) ，最後部分為PR+COSMOSAC 狀態方程式兩種版本，總共探討六種方法的結果。在這六種方法中以PR+COSMOSAC 狀態方程式(2015)及PR+MHV1+COSMOSAC(2010)所得到
固液氣三相平衡溫度的誤差為最小分別為6.25 K 及6.53 K，同時在固液氣三相平衡的液相莫爾分率之分析上也是這兩種方法表現最佳，PR+COSMOSAC 狀態方程式(2015)及PR+MHV1+COSMOSAC(2010)的誤差分別為0.07 及0.10。雖然兩者的誤差非常的接近，但此兩種分法對於每一種類的有機物的結果卻大不相同，將其利用其主官能基細分成每一種類並深入探討，會發現每一種方法對特定種類的有機物各有千秋。最後並探討有機物質之固相體積對預測精確度的影響。

摘要(英)

The knowledge of the solid–liquid–gas equilibrium (SLGE) for binary mixtures of organic compounds in CO2 is one of the key information determine the best operation condition for many supercritical fluid processes. In this work, the SLGE of 21 organic compounds in carbon dioxide is calculated from six approaches based on Peng-Robinson equation of state (PR EOS) and the COSMO-SAC models. These methods include two versions of PR+COSMOSAC EOS and combining PR EOS with MHV1 or Wong-Sandler (WS) mixing rules and two versions of COSMO-SAC models. The PR+COSMOSAC(2015) and PR+MHV1+COSMOSAC(2010) provide the lowest overall absolute average deviation in temperature (AAD-T), which are 6.23 K and 6.37 K, respectively, and the overall absolute average deviation in SLGE liquid phase composition prediction from the PR+COSMOSAC EOS(2015) and PR EOS+MHV1+COSMO-SAC(2010), which are 0.07 and 0.10 respectively. Although the overall deviations are similar, their prediction results can be very different for substances in different families of chemicals, and it can be found clearly each method is good at specific families of chemicals. In the last part, the effect of experimental solid volumes of organic compounds in SLGE prediction accuracy is investigated.

關鍵字(中)

★ 固液氣三相平衡
★ 二氧化碳

關鍵字(英)

★ solid-liquid-gas equilibrium
★ MHV1 mixing rule
★ PR+COSMOSAC EOS

論文目次

中文摘要 i
英文摘要 ii
致謝 iii
目錄 iv
圖目錄 vi
表目錄 viii
第一章緒論 1
1-1超臨界流體的特性與應用 1
1-2 相平衡於超臨界流體製程之重要性 2
1-3 固液氣三相平衡實驗 2
1-4熱力學模型 3
1-5 研究背景及動機 8
第二章理論 9
2-1 固液氣三相平衡之理論模式 9
2-2 熱力學模型 10
2-3 立方狀態方程式搭配過剩吉布斯自由能模型 10
2-4 Peng–Robinson + COSMOSAC EOS 13
2-5 計算細節 16
第三章結果與討論 20
3-1不同的活性係數模型的影響 20
3-2 PR 狀態方程式不同的混合律與 PR+COSMOSAC EOS之比較 21
3-3 固相體積對固液氣三相平衡預測之效應 23
第四章結論 45
參考文獻 46
附錄A 21種有機物的固液氣三相平衡的P-T計算結果圖 51
附錄B WS 混合律結合不同結合律之結果 56
附錄C 利用固相體積修正公式之結果 57
附錄D COSMO-SAC模型 62
附錄E PR+CSOMOSAC EOS 66

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指導教授

謝介銘(Chieh-Ming Hsieh)

審核日期

2017-6-29

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