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研究生:蕭宜弘
研究生(外文):HSIAO, I-HUNG
論文名稱:以二(2-乙基己基)磷酸萃取分離稀土元素銩(III)和鐿(III)之平衡研究
論文名稱(外文):The Extraction Equilibria and Separation of the Thulium(III) and Ytterbium(III) with Di(2-ethylhexyl) Phosphoric Acids
指導教授:蔡德華
口試委員:張裕祺蘇至善蔡德華洪桂彬郭文正
口試日期:2016-07-04
學位類別:碩士
校院名稱:國立臺北科技大學
系所名稱:技術及職業教育研究所
學門:教育學門
學類:綜合教育學類
論文種類:學術論文
畢業學年度:104
語文別:中文
中文關鍵詞:萃取平衡酸性萃取劑鐿(III)銩(III)二(2-乙基己基)磷酸萃取
外文關鍵詞:Extraction equilibriumAcidic extractionYtterbium (III)Thulium (III)Di(2-ethylhexyl) phosphoric acidExtraction
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本論文是探討在25C下利用酸性萃取劑二(2-乙基己基)磷酸,以煤油為稀釋劑,分別探討萃取銩和鐿單成分系統及銩和鐿雙成分系統之萃取平衡實驗,將所得的萃取平衡數據,探討反萃取時所需硝酸濃度、pH值、萃取劑濃度等因素對萃取反應的影響。
由實驗數據可得,以酸性萃取劑D2EHPA萃取銩和鐿單成分系統以及銩和鐿雙成分系統平衡實驗中,銩和鐿之萃取分配比會隨著萃取劑濃度及pH值增加而增加,並由圖解分析法可得有機錯合物組成。
在銩的單成分系統中,所形成的有機錯合物為TmA3(HA)2和TmA3(HA)3。其萃取平衡常數為KTm32 = 1282.8 (kmol/m3)0.5和KTm33 = 2147.5;在鐿的單成分系統中,所形成的有機錯合物為YbA3(HA)2和YbA3(HA)3。
其萃取平衡常數為KYb32 = 1893.6(kmol/m3)0.5和KYb33 = 12551。


在銩和鐿雙成分系統中,所形成的有機錯合物分別為TmA3(HA)2和TmA3(HA)3;YbA3(HA)2和YbA3(HA)3。其萃取平衡常數為KTm32 = 180.91 (kmol/m3)0.5、KTm33 = 766.66和KYb32 = 1138.2 (kmol/m3)0.5、KYb33 = 1735.6。其分離係數為: 。
另外在雙成分系統中發現,有二種情況下會出現乳化現象”
(1)硝酸銩溶液和硝酸鐿溶液濃度在0~0.0025 M的範圍,與0.01M D2EHPA下進行萃取平衡研究,當平衡結束後,pHeq >0.941,會出現乳化現象。
(2)硝酸銩溶液和硝酸鐿溶液濃度在0.0015~0.003 M的範圍,與0.02M D2EHPA下進行萃取平衡研究時,當平衡結束後,pHeq>0.859,會出現乳化現象。
In this study, the equilibrium of the separation of Thulium(III) and Ytterbium(III) by solvent extraction methods were investigated at 25C;meanwhile, the acidic extractants D2EHPA was used. It began with the extraction equilibrium of Thulium(III) and Ytterbium(III) in extractants-kerosene solution and extractants-aqueous solution, and eventually the mixed Thulium(III) and Ytterbium(III)extractants-aqueous solution was studied.
The experimental results indicated that the extraction distribution ratio of Thulium(III) and Ytterbium(III) increased with either of rising concentrations of extractant in the organic phase or equilibrium pH values in the aqueous phase. Moreover we could realize the composition of the extractants through the graphical and numerical analysis.
The composition of Tm(NO3)3/D2EHPA complex formed in the organic phase were found to beTmA3(HA)2, TmA3(HA)3, and at the same time the respective corresponding equilibrium constants were KTm32 =1282.8323 (kmol/m3)0.5, KTm33 =2147.5163 ; The composition of Yb(NO3)3/D2EHPA complex formed in the organic phase were found to be YbA3(HA)2, YbA3(HA)3, and furthermore the respective corresponding equilibrium constants were KYb32 = 1893.6033(kmol/m3)0.5, KYb33 = 12551.4296.
The composition of Tm(NO3)3, Yb(NO3)3/D2EHPA complex formed in the organic phase were found to be TmA3(HA)2, TmA3(HA)3;YbA3(HA)2, YbA3(HA)3, and simultaneously the respective corresponding equilibrium constants were KTm32 = 180.9103 (kmol/m3)0.5, KTm33 = 766.6627;KYb32 = 1138.2018 (kmol/m3)0.5, KYb33 = 1735.6419。;separation factor:
In addition, there has set the emulsion condition as follows”
(1) Emulsions was formed by D2EHPA (0.01M) and binary solution (0-0.0025 M),
when pHeq> 0.941.
(2) Emulsions was formed by D2EHPA (0.02M) and binary solution (0.0015-0.003 M),
when pHeq> 0.859.
摘要 i
ABSTRACT iii
致謝 v
目錄 vi
表目錄 ix
圖目錄 x
第一章 緒論 1
1.1 前言 1
1.2 研究動機與目的 6
1.3 論文研究架構 9
第二章 文獻回顧 10
2.1 溶劑萃取技術 10
2.1.2 萃取反應式 14
2.1.3 萃取平衡常數 14
2.1.4 萃取分配比 15
2.1.5 萃取百分率 16
2.2 萃取劑的分類及選擇 17
2.2.1 萃取劑的分類 17
2.2.2 萃取劑的選擇 41
2.3 稀釋劑的用途與選擇 42
2.4 酸性萃取劑的萃取原理 44
2.5 酸性萃取劑的反萃取原理 47
2.6 溶劑萃取過程乳化、泡沫的形成及其消除 48
2.6.2 乳狀液的鑑別 49
2.6.4 乳化與泡沫的預防與消除[3, 16, 38, 62-67] 52
2.7 稀土元素銩(III)和鐿(III)簡介 55
2.7.1 銩(III)的性質 55
2.7.2 鐿(III)的性質 56
第三章 實驗部分 58
3.1 實驗設備及藥品 58
3.1.1 實驗藥品 58
3.1.2 實驗設備 63
3.2 實驗方法 66
3.2.1 銩(III)之反萃取率實驗 66
3.2.2 鐿(III)之反萃取率實驗 66
3.2.3 銩(III)單成分系統之萃取平衡實驗 67
3.2.4 鐿(III)單成分系統之萃取平衡實驗 68
3.2.5 鐿(III)和銩(III)雙成分系統之萃取平衡實驗 69
3.3 ICP-OES操作 72
3.4 HORIBA FT-IR操作 74
第四章 結果與討論 77
4.1 反萃取實驗 77
4.1.1 銩(III)和鐿(III)以D2EHPA萃取之反萃取率實驗 77
4.2 萃取平衡實驗 80
4.2.1 銩(III)單成分系統之萃取平衡實驗 80
4.2.2 鐿(III)單成分系統之萃取平衡實驗 92
4.2.3 銩(III)和鐿(III)雙成分系統之萃取平衡實驗 103
4.2.4 銩(III)和鐿(III)之分離係數 123
4.3 乳狀液的類型和分析 131
4.3.1 乳狀液的類型 131
4.3.2 SEM分析 135
4.3.3 FT-TR光譜分析 139
第五章 結論 142
符號說明 146
參考文獻 148
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