以鹼性萃取劑及支撐式液膜萃取分離鈀(II)與鉑(II)並以生命週期評估法探討環境影響係數之研究

The Extraction and Separation of Platinum(II) and Palladium(II) Using Basic Extractants and Supported Liquid Membranes and to Explore the Life Cycle Assessment Study of the Environmental Impact Factor

彭振育(Chen-Yu Peng)

指導教授 ： 蔡德華

國立臺北科技大學/工程學院/工程科技研究所/博士(2014年)

https://doi.org/10.6841/NTUT.2014.00591

摘要

本論文以鹼性萃取劑，在25℃下以煤油為稀釋劑，各別探討鉑(II)和鈀(II)之萃取平衡及萃取動力行為，並將所得相關萃取平衡數據，應用於支撐式液膜分離之理論分析上，解析出鈀(II)和鉑(II)在支撐式液膜分離程序中之傳送行為。 首先以實驗方式探討以鹼性萃取劑Alamine 336從氫氯酸水溶中萃取鈀(II)之萃取平衡，實驗結果發現，隨著鹼性萃取劑Alamine 336濃度的增加，鈀(II)在有機相和水相間的萃取分配比(D)為遞增；隨著氯離子濃度的增加，鈀(II)的萃取分配比(D)為遞減。經由圖解法與數值分析法得知，有機相Pd-Alamine 336錯合物的分子式為 及 ，其萃取平衡常數K20 = 2.61×103 及K21 = 2.47×104 (kmol/m3)?1。 以鹼性萃取劑Alamine 336從氫氯酸水溶中萃取鉑(II)之萃取平衡，實驗結果發現，隨著鹼性萃取劑Alamine 336濃度的增加，鉑(II)在有機相和水相間的萃取分配比(D)為遞增；隨著氯離子濃度的增加，鉑(II)的萃取分配比(D)為遞減。經由圖解法與數值分析法得知，有機相Pt-Alamine 336錯合物的分子式為 及 ，其萃取平衡常數 = 7.76×103及 = 5.38×103(kmol/m3)?1。 以鹼性萃取劑Aliquat 336從氫氯酸水溶中萃取鈀(II)之萃取平衡，實驗結果發現，隨著鹼性萃取劑Aliquat 336濃度的增加，鈀(II)在有機相和水相間的萃取分配比(D)為遞增；隨著氯離子濃度的增加，鈀(II)的萃取分配比(D)為遞減。經由圖解法與數值分析法得知，有機相Pd-Aliquat 336錯合物的分子式為 ，其萃取平衡常數K20 = 4.68×103。 以鹼性萃取劑Aliquat 336從氫氯酸水溶中萃取鉑(II)之萃取平衡，實驗結果發現，隨著鹼性萃取劑Aliquat 336濃度的增加，鉑(II)在有機相和水相間的萃取分配比(D)為遞增；隨著氯離子濃度的增加，鉑(II)的萃取分配比(D)為遞減。經由圖解法與數值分析法得知，有機相Pt-Aliquat 336錯合物的分子式為 ，其萃取平衡常數K20 = 3.11×104。 以Alamine 336從含鈀(II)及鉑(II)之氫氯酸水溶液中萃取鈀(II)和鉑(II)，實驗結果顯示，鈀(II)和鉑(II)的萃取分配比(D)隨萃取劑濃度之增加而遞增，鈀(II)和鉑(II)的萃取分配比(D)隨氯離子濃度之增加而遞減。對鈀(II)而言，經由圖解和數值分析有機相鈀-Alamine 336 錯合物的組成為 及 ，其萃取平衡常數分別為 = 2.91×103，截距為 = 2.48×104 (kmol/m3)?1；對鉑(II)而言，有機相鉑-Alamine 336 錯合物的組成為 及 ，其萃取平衡常數分別為 = 7.76×103及 = 5.38×103 (kmol/m3)?1。 以Aliquat 336從含鈀(II)及鉑(II)之氫氯酸水溶液中萃取鈀(II)和鉑(II)，實驗結果顯示，鈀(II)和鉑(II)的萃取分配比(D)隨萃取劑濃度之增加而遞增，鈀(II)和鉑(II)的萃取分配比(D)隨氯離子濃度之增加而遞減。對鈀(II)而言，經由圖解分析有機相鈀-Aliquat 336 錯合物的組成為 ， 其萃取平衡常數分別為 = 5.41×103；對鉑(II)而言，有機相鉑-Aliquat 336 錯合物的組成為 ，其萃取平衡常數分別為 = 6.41×104。 將萃取過程中所消耗之化學藥品使用量統計歸納，並以生命週期評估法進行模擬，再將所得數據以交叉比對的方式進行探討，可分析出不同模擬情況下對環境危害之程度。

關鍵字

鈀 ； 鉑 ； 分離 ； 萃取 ； 反萃取 ； 支撐式液膜 ； Alamine 336 ； Aliquat 336 ； 鹼性萃取劑

並列摘要

This study employed a tri-n-octyl/decyl amine (Alamine 336) as an extractant dissolved in kerosene to extract Platinum (II) and Palladium(II) from HCI solution at 25°C. Both of the extraction equilibrium and kinetic study were evaluated according to the experimental data to describe the transport phenomena of Platinum (II) and Palladium(II) in the separation process of supported liquid membrane(SLM).
The experiments of different stripping reagents such as HCI, NaCl, KCl, BaCl2, AlCl3, and thiourea were compared, respectively; and the optimal status was determined. The results showed that the extraction distribution ratios are proportional to the extractant concentration and disproportional to chloride ion concentration. By graphical analysis, the compositions of palladium complexes in organic phase and equilibrium constant of recovered extraction reaction were examined. Finally, the recovery efficiency of palladium(II) in acidic chloride solution was determined.
The alkaline extractant, i.e., Alamine 336, were selected and used in the extraction process to recover the palladium (II) from HCl solution. The results indicated that the extraction distribution of palladium (II) for organic and water phases increased as the increases of the concentration of Alamine 336 extractant. According to the results from graphical presentation and numerical analysis, the equilibrium constants of organic phases of Pd-Alamine 336 complexes (i.e., and ) were found to be K20 = 2.61×103 and K21 = 2.47×104 (kmol/m3)?1, responsively.
The extraction of platinum (II) from HCl solution was carried out using the alkaline extractant, i.e., Alamine 336. The results indicated that the extraction distribution of platinum (II) for organic and water phases increased as the increases of the concentration of Alamine 336 extractant. However, the extraction distribution of platinum (II) decreased as the increase of chloride concentration. According to the results from graphical presentation and numerical analysis, the equilibrium constants of organic phases of Pt-Alamine 336 complexes (i.e., and ) were found to be = 7.76×103 and = 5.38×103(kmol/m3)?1, responsively.
The extraction of palladium (II) from HCl solution was carried out using the alkaline extractant, i.e., Alamine 336. The results indicated that the extraction distribution of palladium (II) for organic and water phases increased as the increases of the concentration of Alamine 336 extractant. However, the extraction distribution of palladium (II) decreased as the increase of chloride concentration. According to the results from graphical presentation and numerical analysis, the equilibrium constants of organic phases of Pd-Alamine 336 complexes (i.e., ) were found to be K20 = 4.68×103.
In addition, the extraction of platinum (II) from HCl solution was carried out using the alkaline extractant, i.e., Alamine 336. The results indicated that the extraction distribution of platinum (II) for organic and water phases increased as the increases of the concentration of Alamine 336 extractant. However, the extraction distribution of platinum (II) decreased as the increase of chloride concentration. According to the results from graphical presentation and numerical analysis, the equilibrium constants of organic phases of Pd-Alamine 336 complexes (i.e., ) were found to be K20 = 3.11×104.
Furthermore, the extraction of both platinum (II) and palladium (II) were carried out from HCl solution using the alkaline Alamine 336 extractant. The results indicated that the extraction distribution of platinum (II) and palladium (II) for organic and water phases increased as the increases of the concentration of Alamine 336 extractant. However, the extraction distribution of both platinum (II) and palladium (II) decreased as the increase of chloride concentration. According to the results from graphical presentation and numerical analysis, the equilibrium constants of organic phases of Pd-Alamine 336 complexes (i.e., and ) were found to be = 2.91×103, with a slope of = 2.48×104 (kmol/m3)?1. In the case of platinum (II), the equilibrium constants of organic phases of Pt-Alamine 336 complexes (i.e., and ) were found to be = 7.76×103, with a slope of = 5.38×103 (kmol/m3)?1.
According to the results from graphical presentation and numerical analysis, the equilibrium constants of organic phases of Pd-Alamine 336 complexes (i.e., and ) were found to be = 2.91×103, with a slope of = 2.48×104 (kmol/m3)?1. In the case of palladium (II), the equilibrium constants of organic phases of Pt-Alamine 336 complexes (i.e., and ) were found to be = 7.76×103, with a slope of = 5.38×103 (kmol/m3)?1.
The extraction of both platinum (II) and palladium (II) were carried out from HCl solution using the alkaline Aliquat 336 extractant. The results indicated that the extraction distribution of platinum (II) and palladium (II) for organic and water phases increased as the increases of the concentration of Alamine 336 extractant. However, the extraction distribution of both platinum (II) and palladium (II) decreased as the increase of chloride concentration. In the case of palladium (II), according to the results from graphical presentation and numerical analysis, the equilibrium constants of organic phases of Pd-Aliquat 336 complexes (i.e., ) were found to be = 5.41×103. On the other hand, in the case of platinum (II), the equilibrium constants of organic phases of Pt-Aliquat 336 complexes (i.e., ) were found to be = 6.41×104.
Lastly, the environmental impacts of the extraction process was assessed using Umberto software. The inventory data for extraction process including amounts of chemical consumption was gathered in this study to quantify the environmental impacts of the proposed extraction process.

並列關鍵字

Palladium ； Platinum ； Liquid-Liquid Extraction ； Stripping ； Supported Liquid Membrane ； Alamine 336 ； Aliquat 336 ； Basic Extractants

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