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  • 學位論文

以液膜萃取分離錳(II)和鎳(II)之研究

Studies on the Separation of Manganese(II) and Nickel(II) by Liquid Membrane Extraction

指導教授 : 蔡德華
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摘要


本論文分別以酸性和鹼性萃取劑,在25℃下以煤油為稀釋劑,分別探討錳(II)和鎳(II)之萃取平衡與萃取動力行為,並將所得的萃取平衡數據,應用於支撐式液膜分離之理論分析上,解析出錳(II)和鎳(II)在支撐式液膜分離程序中之傳送行為。最後結合酸性和鹼性萃取劑作為支撐式液膜之載劑操作,以從事複合支撐式液膜分離錳(II)和鎳(II)之分離程序。 首先由實驗分別探討以酸性萃取劑D2EHPA、PC-88A及Cyanex 272從硫酸水溶液中萃取錳(II)之萃取平衡,實驗結果顯示錳(II)在有機相和水相間的萃取分配比隨酸性萃取劑D2EHPA、PC-88A及Cyanex 272濃度和pH值之增加而遞增。且經由圖解和數值分析,有機相Mn-D2EHPA錯合物的組成為和,其萃取平衡常數分別為和;有機相Mn-PC88A錯合物的組成為和,其萃取平衡常數分別為和;有機相Mn-Cyanex 272錯合物的組成為和,其萃取平衡常數分別為和。此外並探討D2EHPA在不同溫度下萃取錳(II)之平衡研究,進而估算 出萃取反應中其各種熱力學參數。 以D2EHPA、PC-88A及Cyanex 272分別從含鎳(II)之硫酸水溶液中萃取錳(II)和鎳(II)之研究上,錳(II)和鎳(II)的萃取分配比皆隨萃取劑濃度和pH值之增加而遞增。對錳(II)而言,經由圖解和數值分析有機相錳-D2EHPA錯合物的組成為和,其萃取平衡常數分別為和;有機相錳-PC88A錯合物的組成為和,其萃取平衡常數分別為和;有機相錳-Cyanex 272錯合物的組成為和,其萃取平衡常數分別為和。對鎳(II)而言,經由圖解分析有機相鎳-D2EHPA錯合物的組成為和,其萃取平衡常數分別為和;有機相鎳-PC88A錯合物的組成為和,其萃取平衡常數分別為和;有機相鎳-Cyanex 272錯合物的組成為,其萃取平衡常數為。另外,錳(II)和鎳(II)之萃取百分比皆隨酸性萃取劑D2EHPA、PC-88A及Cyanex 272濃度、平衡pH值之增加而增大;而經過皂化後的鈉型萃取劑(Na-D2EHPA、Na-PC-88A及Na-Cyanex 272),雖萃取效果有明顯提昇,但錳(II)和鎳(II)會同時被萃取至有機相中,無法達到完全分離之效果。 本論文利用固定界面積攪拌槽分別以D2EHPA測定錳(II)和鎳(II)在硫酸水溶液中之萃取與反萃取的初速率,實驗時二相的攪拌速率皆選定在120 rpm,在此情況下界面附近二相擴散層的厚度已減至最小,屬於動力區,且擴散阻力因素對萃取及反萃取速率的影響皆可忽略,且由實驗得知,化學反應是在界面上發生。此外,錳(II)和鎳(II)之萃取與反萃取速率之測定,結果發現水溶液中錳離子、鎳離子、氫離子及有機相中游離之D2EHPA濃度皆會影響萃取速率,其錳(II)和鎳(II)之萃取速率式分別為和。而反萃取速率只受有機相中錯合物濃度的影響,而與反萃取液中硝酸濃度及有機相中遊離之D2EHPA濃度皆無關,其錳(II)和鎳(II)之反萃取速率式分別為和。 本論文利用PVDF作為支撐膜,進行支撐式液膜分離錳(II)和鎳(II)之研究。於穩定狀態下以D2EHPA為載劑,錳(II)的理論傳送速率式可推導為。上式分母三項依序表示為水溶液中水相擴散層、界面化學反應及液膜擴散的傳送阻力。在實驗方面分別以D2EHPA及PC-88A為載劑,當兩相的體積流率為400 rpm時,其水相邊界層的厚度已減至最小;錳(II)和鎳(II)的透過係數隨進料液pH值與載劑濃度之增加而增大,但隨進料液錳(II)和鎳(II)濃度的增加而降低。 以Aliquat 336及Alamine 336為萃取劑,煤油為稀釋劑,在25℃下,從鹽酸水溶液中萃取氯化錳之研究顯示,錳(II)在有機相和水相間的萃取分配比隨水相鹽酸濃度與萃取劑濃度之增加而增加。且當水溶液中鹽酸、有機相Aliquat 336或Alamine 336之濃度愈高,錳(II)之萃取百分比愈大。其平衡常數關係式可分別表示為。 利用Alamine 336為載劑之支撐式液膜分離錳(II)和鎳(II)之探討上,液膜擴散層厚度不受體積流率影響;Alamine 336載劑濃度愈高,透過係數愈大。進料液錳(II)離子濃度增加,透過係數沒有明顯的變化趨勢,但質量傳送通量則隨著進料金屬離子濃度上升均上升。 最後,在複合支撐式液膜傳送分離方面,第I室和第II室金屬離子之分離效果,隨著SLM(A)載劑濃度的增加而增加;同樣地,第II室和第III室金屬離子之分離效果,亦隨SLM(B)載劑濃度的增加而增加。另外,因第II室的體積較小,將有助於金屬之質量傳送,且可避免金屬溶質囤積在第II分隔室中。

並列摘要


In this study, the equilibrium and kinetic behavior of the separation of manganese(II) and nickel(II) by solvent extraction and supported liquid membranes methods were investigated at 25°C. The acidic extractants D2EHPA, PC-88A, and Cyanex 272 and the basic extractants Aliquat 336, Alamine 336 were used. The extraction equilibria and kinetics of manganese(II) and nickel(II) in extractants-kerosene solution and extractants-aqueous solution were studied, respectively. The permeation rate of manganese(II) and nickel(II) across a supported liquid membrane(SLM) were determined. Finally, the transport of manganese(II) and nickel(II) through composite supported liquid membranes was discussed. The extraction equilibria of manganese(II) from an aqueous sulfate medium with D2EHPA, PC-88A and Cyanex 272 as an acid extractant were studied. The experimental results indicated that the distribution coefficients for the extraction of manganese(II) increased with increasing either concentrations of extractant in the organic phase or equilibrium pH values in the aqueous phase. Based on graphical and numerical analysis, the compositions of Mn-D2EHPA complex formed in the organic phase were found to be, and the respective corresponding equilibrium constants were and.The compositions of Mn-PC-88A complex in the organic phase were and , and their corresponding equilibrium constants were and , respectively. The compositions of Mn-Cyanex 272 complex in the organic phase were and , and their corresponding equilibrium constants were and ,respectively. The apparent thermodynamic functions for the extraction of Mn(II) using D2EHPA is determined by the temperature variation method. Then, the extraction equilibria of manganese from an aqueous sulfate medium containing nickel(II) ions with D2EHPA、PC-88A or Cyanex 272 as an acid extractant were investigated, respectively. The distribution coefficients for the extraction of manganese(II) increased with increasing either concentrations of extractant in the organic phase or equilibrium pH value in the aqueous phase. Based on graphical and numerical analysis, the compositions of Mn-D2EHPA complex formed in the organic phase were found to be and , and their corresponding equilibrium constants were and , respectively. The compositions of Mn-PC-88A complex in the organic phase were and , and their corresponding equilibrium constants were and, respectively. The compositions of Mn-Cyanex 272 complex in the organic phase were and , and their corresponding equilibrium constants were and , respectively. Based on graphical analysis, the compositions of Ni-D2EHPA complex formed in the organic phase were found to be and , and their corresponding equilibrium constants were and respectively. The compositions of Ni-PC-88A complex in the organic phase were and, and their corresponding equilibrium constants were and, respectively. The compositions of Ni-Cyanex 272 complex in the organic phase was , and their corresponding equilibrium constants was . The experimental results indicated that the extraction percentage of manganese(II) and nickel(II) were low when the acidic extractants D2EHPA、PC-88A and Cyanex 227 were used, but it increased apparently using the modified acidic extractants Na-D2EHPA、Na-PC-88A and Na-Cyanex 272. The kinetic behavior of manganese(II) and nickel(II) extraction from an aqueous sulfate medium with D2EHPA in kerosene was investigated using a constant interfacial area cell. In all experiments, the stirring speed of extraction operation was selected as 120rpm. This speed corresponds to kinetic regime, in which the thickness of diffusion films was reduced to a minimum. The contribution of diffusional resistance to the extraction and stripping was negligible. The experimental results indicate that chemical reaction occurred at the aqueous-organic interfacial. The initial extraction rate and initial stripping rate were independently measured in this study. The initial extraction rate were affected by such factors as the concentration of manganese(II) and nickel(II), the hydrogen ions in the aqueous phase, and the concentration of free dimeric D2EHPA in the organic phase. However, the initial stripping rates were a function of the concentration of Mn-D2EHPA or Ni-D2EHPA complex in the organic phase only. And they were unaffected by the concentration of nitric acid and free dimeric D2EHPA in the organic phase. At 25°C, the rate equations could be expressed as follows: (i)Initial extraction rate (ii)Initial stripping rate A microporous PVDF membrane was used as a solid supported to investigate the permeation rates of manganese(II) and nickel(II) through supported liquid membrane by D2EHPA and PC-88A. When using D2EHPA as carrier and at steady state, the permeation rate equation was derived as where the denominator of the above equation indicates the transport resistance of the aqueous film diffusion, interfacial chemical reaction and membrane diffusion, successively. From the experimental data, the results indicated that the thickness of the aqueous boundary diffusion layers reaches its minimum value at the rotation rate of 400. The experimental data also show that the permeability of manganese(II) and nickel(II) depended on the pH value of the feed solutions, the metal ion concentrations in the feed solutions and the carrier concentration in the supported liquid membrane. A study concern the extraction equilibrium of manganese(II) from hydrochloride solutions with Aliquat 336 and Alamine 336 dissolved in kerosene as an extractant was performed at 25°C. The experimental results indicated that the distribution coefficient and the extraction efficiency for manganese increased with increasing concentration of Aliquat 336 or Alamine 336 and hydrochloride concentration. The equilibrium constants of Aliquat 336 and Alamine 336 system were expressed as follows The mass transport of manganese(II) and nickel(II) through the supported liquid membranes is investigated at 25°C. The experimental results show that the flow rate did not affect the permeability. The permeability of manganese(II) and nickel(II) was found to be dependent on the metal ion concentrations in the feed solutions and the carrier concentration in the supported liquid membrane. Finally, the mass transport of manganese(II) and nickel(II) through composite supported liquid membranes was studied. For SLM(A) and SLM(B), when the concentration of carrier increased, the permeation rate was increased. Furthermore, the compartment II has smaller volume and can progress the transfer rate of metal species and avoid the accumulation of metal species.

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