臺灣博碩士論文加值系統

本研究是在利用丁氧基乙醇(ethylene glycol monobutyl ether, EGMBE)為修飾劑，二氯甲烷為稀釋劑，二(2-乙基己基)磷酸(D2EHPA)為萃取劑，大孔性樹脂Amberlite XAD-4爲載體，製備成的萃取劑含浸樹脂 (extractant-impregnated resin, EIR)，藉由改變其鎘離子初濃度、EIR量及溫度之操作條件，與硝酸鎘水溶液達吸附平衡後，探討金屬離子之吸附情形及吸附模式。
由實驗數據可知，最佳修飾劑(EGMBE)為5mL。吸附平衡時間大約為600分鐘。在不同濃度的硝酸鎘水溶液下，其鎘離子被吸附量隨著萃取劑D2EHPA含量的增加而增加，而pH值隨EIR吸附量的增加而降低。
由結果顯示樹脂萃取鎘離子的吸附模式適用Freundlich吸附等溫線來描述之。另外，實驗結果經由實驗圖表分析，在25℃時，有機相鎘錯合物的組成分別為 和 ，而萃取平衡常數分別為Kex26 = 2.6384*10-5及Kex27 = 3.5562*10-5 (mol/L)-0.5。在此系統鎘之ΔH°為14.32～46.52 (kJ/mol)，而ΔG°為-8.6758～-3.417 (kJ/mol)，ΔS°為0.0691～0.1767 (kJ/mol．K)。

In this study, we used the ethylene glycol monobutyl ether, EGMBE as the modifier, dichloromethane as the diluents, D2EHPA as the extractant and Amberlite XAD-4 as a support. All of them were rendered into the extractant-impregnated resin, EIR, we examined the effects of various parameters, such as the initial metal concentrations, EIR mass and the operating temperature. We examined the adsorption of metal ions and adsorption models after balance.
The data showed the best modifier (EGMBE) was 5ml. The lengths of time to achieve adsorption balance for this system was 600 minutes. In different metal concentrations of solution, A adsorpted mass of Cadmium ion was increasing with D2EHPA mass. The pH value of solution was decreasing while EIR adsorpted mass was increasing.
The results also reveal the adsorption mode of extract Cadmium ions can be described by the Freundlich isotherm. Graphical analysis of the results from extraction equilibrium indicates that Cadmium -D2EHPA complex, in the organic phase are and with the extraction equilibrium constants of 2.6384*10-5 and 3.5562*10-5 ( mol/L)-0.5, respectively.In this system ΔH° is 14.32～46.52 (kJ/mol). ΔG° is -8.6758～-3.417 (kJ/mol). ΔS° is 0.0691～0.1767 (kJ/mol．K).

摘　要 i
Abstract ii
誌　謝 iv
目　錄 v
表目錄 viii
圖目錄 ix
第一章 緒論 1
1.1 前言 1
1.2 研究動機及目的 1
1.3 鎘金屬及化合物簡介 2
第二章 文獻回顧 4
2.1吸附現象 4
2.1.1 物理吸附 5
2.1.2 化學吸附 5
2.2離子交換技術簡介 6
2.2.1 離子交換技術之原理 7
2.2.2 離子交換樹脂種類 8
2.2.2.1 陽離子交換樹脂 10
2.2.2.2 陰離子交換樹脂 12
2.2.2.3 螯合樹脂 13
2.2.2.4 多孔型樹脂 13
2.3 萃取技術的簡介 14
2.3.1 分佈係數(Distribution coefficient) 15
2.3.2 分配比(Distribution ratio) 16
2.3.3 萃取百分率(Percentage extraction) 16
2.4 稀釋劑與修飾劑的用途及選擇 17
2.4.1 稀釋劑之用途及選擇 17
2.4.2 丁氧基乙醇(Ethylene glycol monobutyl ether, EGMBE) 18
2.5 萃取劑的用途及選擇 19
2.5.1 酸性萃取劑(Acidic extractants) 19
2.5.2 螯合萃取劑(Chelating extractants) 20
2.5.3 鹼性萃取劑(Basic extractants) 20
2.5.4 中性萃取劑(Neutral extractants) 21
2.5.5 溶合萃取劑(Solvation extractants) 21
2.5.6 萃取劑的選擇 22
2.6 萃取劑含浸樹脂的簡介 24
2.6.1 Amberlite XAD-4簡介 24
2.6.2 Di(2-ethylhexyl)phosphoric acid 之簡介 27
2.7 等溫吸附方程式 29
2.7.1 Freundlich吸附等溫線(Freundlich isotherm) 29
2.7.2 Langmuir吸附等溫線(Langmuir isotherm) 30
2.7.3 B.E.T吸附等溫線(Brunauer-Emmett-Teller isotherm) 31
第三章 研究設備及方法 33
3.1 實驗藥品及設備 33
3.1.1 實驗藥品 33
3.1.2 實驗設備及器材 34
3.2 實驗方法及步驟 35
3.2.1 樹脂前處理 35
3.2.2 空白實驗 35
3.2.3 含浸樹脂的製備 35
3.2.4 改變EIR中修飾劑之含量 36
3.2.5 平衡時間之測定 37
3.2.6 改變金屬離子初濃度之吸附平衡 37
3.2.7 改變溫度對吸附平衡的影響 37
3.2.8改變EIR用量對吸附平衡的影響 37
第四章 結果與討論 39
4.1 空白實驗 39
4.2 含浸樹脂的製備 40
4.3 最佳修飾劑的用量 40
4.4 平衡時間之測定 42
4.5 金屬離子吸附平衡實驗 47
4.6 萃取平衡常數 50
4.7 吸附等溫線的計算 57
4.8 改變溫度對吸附平衡的影響 83
4.9 改變EIR用量對吸附平衡的影響 115
第五章 結論 116
符號表 118
參考文獻 120

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