間氯酚與對氯酚之固液相平衡研究

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姓名

許世杰(Shih-Chieh Hsu) 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

間氯酚與對氯酚之固液相平衡研究
(Research of Solid-Liquid Equilibrium of 3-chlorophenol and 4-chlorophenol)

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摘要(中)

摘要
工業上常需分離混合物以得到更高純度的產物，可行的方法有很多，本論文乃是研究以締合結晶法來分離沸點相近的間氯酚及對氯酚混合物。在此分別嘗試以苯胺及特丁醇為中和劑，探討中和劑之合適性。經雙成份之固液相圖研究發現，苯胺與對氯酚及間氯酚生成1：1之複合物；特丁醇則與對氯酚及間氯酚生成2：1之複合物，故兩者均為頗合適的中和劑。我們進一步探討對氯酚、間氯酚與苯胺以及對氯酚、間氯酚與特丁醇兩組三成份之固液相行為，並繪製出三成份固液相圖，利用相圖所提供之資料，我們嘗試找出可行的分離流程，並依不同入料成份加以探討。
本研究中相圖之建立乃是利用固體消失法，經由在恒溫槽中，觀察各不同成份組成之樣品的最後固體消失溫度而來。而數據關聯部份，採用了物理化學模式，以計算活性係數；於無合熔點之系統，以共熔點為分界點，以Wilson模式及NRTL模式計算活性係數；對於有合熔點之系統，則以共熔點及合熔點為分界點，採ICM模式以及依槓桿原理修正後的xi、γi來關聯其結果。

摘要(英)

Abstract
It is very common to have to separate mixtures for getting high purity products. An adductive crystallization method was employed in this study to separate closing-boiling point m-chlorophenol + p-chlorophenol mixtures in this study. Neutralizing agents including tert-butanol and aniline have been tested for separating the mixtures and their applicability were discussed. We found that aniline could be a potential neutralizing agent by the fact that it forms complexes with both m-chlorophenol and p-chlorophenol. Consequently, we further investigated the solid-liquid phase behavior for the ternary system of aniline + m-chlorophenol +p-chlorophenol . This ternary phase diagram provided us useful information for finding a feasible separation procedure and favorable operation conditions. The separating process was discussed by different initial composition of m-chlolrpheno+p-chlorophenol mixture.
This diagram is built by observing the final disappearance temperature of the solid phase under accurately controlled bed temperature. For the curve fitting, the Ott & Goates fitting is chosen. As for the correlation, Wilson , NRTL and ICM models have been used to calculate the activity coefficients of the systems with or without congruent points. And the calculating shows the NRTL model gives better results .

關鍵字(中)

★ 締合結晶法
★ 結晶
★ 固液平衡
★ 分離流程

關鍵字(英)

★ adductive agent
★ separation process
★ SLE
★ crystallization
★ adductive crystallization

論文目次

目錄
中文摘要 I
目錄 III
表目錄 V
圖目錄 VIII
符號說明 XI
第一章緒論
前言 1
1-1 結晶簡介 1
1-2 基本固液平衡相圖及分析 3
1-3 締合結晶法之理論基礎 6
1-4 實驗系統 7
1-5 文獻回顧 9
1-6 本文各章重點 13
第二章固液相平衡數據量測
前言 17
2-1 藥品 17
2-2 實驗設備 17
2-3 固液平衡量測步驟 18
2-3-1 配置樣品 18
2-3-2 熔點之量測 19
2-4 實驗設備配置說明及注意事項 20
2-5 雙成份系統之量測結果 21
2-6 三成份系統之量測結果 24
2-6-1 中和劑為苯胺 24
2-6-2 中和劑為特丁醇 26
2-6-3 三成份相圖之分析 27
2-7 分離程序 28
2-7-1 中和劑為苯胺 28
2-7-2 中和劑為特丁純 30
2-8 熔化熱之量測 32
第三章理論計算 90
3-1 固液相平衡法則 91
3-2 含共熔點之固液相平衡理論 95
3-3 含合熔點之固液相平衡理論 95
3-4 活性係數之計算 98
3-5 三成份系統之固液相平衡計算 99
第四章結果與討論 101
第五章結論與建議 103
參考文獻 105

參考文獻

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指導教授

李亮三(Liang-Sun Lee)

審核日期

2002-7-15

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