探討COSMO-SAC-dsp模型中分散項和組合項之效應

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趙于皞(Yu-Hao Chao) 查詢紙本館藏

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化學工程與材料工程學系

論文名稱

探討COSMO-SAC-dsp模型中分散項和組合項之效應

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至系統瀏覽論文 (2025-6-30以後開放)

摘要(中)

熱力學性質與流體相平衡對化工產業而言是相當重要的資訊，一般而言可以透過實驗量測或是熱力學模型估算來提供所需的熱力學數據。在過去的研究中，COSMO-SAC-dsp模型已被證明可以用來估算相平衡數據，如氣液相平衡、液液相平衡、無限稀釋活性係數等。COSMO-SAC-dsp模型中，分子間的作用力是利用量子化學計算所得到的分子表面電荷估算，因此不存在著參數缺失的問題。COSMO-SAC-dsp模型中活性係數的計算可分為下面三項貢獻：剩餘項(residual term)、分散項(dispersion term)和組合項(combinatorial term)。本研究目標系統性的探討COSMO-SAC-dsp使用不同分散項和組合項之效應，因此將剩餘項固定不動，比較四種組合項模型與三種分散項模型，其中分散項模型中更進一步探討不同溫度函數的作用力參數對模型精確度的效應。
本研究利用440個雙成份氣液相平衡系統與2291個雙成份無限稀釋活性係數之實驗點探討活性係數模型的準確度，結果發現組合項選用COSMO-SAC-dsp模型中所使用的Staverman-Guggenheim模型，並利用不考慮溫度影響的TCLAC模型(theoretically correct liquid activity coefficient model，一滿足配位數守恆之活性係數模型)來考慮分散項，可以在預設雙成份系統氣液相平衡與無限稀釋活性係數中獲得類似於COSMO-SAC-dsp模型的精確度。

摘要(英)

Thermodynamic properties and fluid phase equilibria are important information for the design of chemical engineering processes. Such information can generally be obtained from experiment or estimated from thermodynamic models. In pervious study, COSMO-SAC-dsp has been proved to be reliable in predicting phase equilibria data, such as vapor-liquid equilibria (VLE), liquid-liquid equilibria (LLE), and infinite dilution activity coefficients (IDAC). In the COSMO-SAC-dsp model, the molecular interactions are determined from molecular surface charges obtaining from quantum mechanical calculations, and therefore the issue of missing parameter would not happen. The activity coefficient calculation in the COSMO-SAC-dsp model was obtained from the sum of three contributions: residual term, dispersion term, and combinatorial term. In this study, the effect of using different dispersion models and combinatorial models was investigated, with the residual term remains the same. We investigated the accuracy of the COSMO-SAC-dsp model with four combinatorial models and three dispersion models, including three temperature-dependence functions of interaction parameter in dispersion models.
In this study, 440 binary VLE systems and 2291 binary IDAC experimental data points were used to examine the accuracy of the COSMO-SAC-dsp model with different combinations of combinatorial and dispersion terms. We found that using the Staverman-Guggenheim model as combinatorial term (the combinatorial model of the original COSMO-SAC-dsp model) together with the temperature-independent TCLAC model (theoretically correct liquid activity coefficient model, which satisfied the pair conservation) as dispersion term provides similar accuracy as the original COSMO-SAC-dsp model in both VLE and IDAC predictions.

關鍵字(中)

★ 相平衡
★ 無限稀釋活性係數
★ 預測
★ 分散項貢獻
★ 組合項貢獻
★ COSMO-SAC

關鍵字(英)

★ phase equilibria
★ infinite dilution activity coefficient
★ prediction
★ dispersion contribution
★ combinatorial contribution
★ COSMO-SAC

論文目次

摘要 i
Abstract ii
誌謝 iii
目錄 iv
圖目錄 vi
表目錄 vii
第一章緒論 1
1-1 相平衡數據於工業應用上的重要性 1
1-2 活性係數模型的發展 3
1-3 COSMO-SAC的發展 4
1-4 研究動機 6
第二章 COSMO-SAC-dsp 模型 7
2-1 剩餘項活性係數 8
2-2 分散項活性係數 10
2-3 組合項活性係數 12
2-4 分散項參數優化 14
第三章利用分子模擬探討分散作用力 17
3-1 分子模擬 17
3-2 fdsp的估算 20
第四章結果與討論 32
4-1 非氫鍵氣液相平衡系統和氫鍵氣液相平衡系統(不含水或有機酸)計算 33
4-2 氫鍵氣液相平衡系統(含水或有機酸)計算 38
4-3 探討無限稀釋活性係數之計算結果 41
4-4 針對溫度影響進行結果討論 44
第五章結論 46
參考文獻 47
附錄(一) 組合項模型的預測結果 56
附錄(二) ms2 參數檔(par檔、pm檔) 57
附錄(三) 各模型分散項參數整理 59

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指導教授

謝介銘(Chieh-Ming Hsieh)

審核日期

2020-7-28

推文