臺灣博碩士論文加值系統

本篇論文選用W/O/W乳化液膜進行金屬銅、鋅離子萃取分離之研究，並使用膜過濾分離W/O乳液回收，接續進行過濾膜的表面改質與改善濾速研究。由於萃取分離過程中以乳化液膜的穩定度是關鍵程序，本研究首先以統計學裡的實驗設計法進行初步探討，並以分離係數作為反應值，以決定製作乳液的操作條件( D2EHPA 0.1M、Span 80 3 vol-%、外水相pH 3.0及乳水體積比7)，確保乳化液膜在穩定狀態下進行萃取過濾實驗。
後續過濾實驗，研究選用PVDF薄膜進行恆壓過濾，因其為疏水性薄膜，結垢及吸附現象顯著，故此，本研究使用大氣純氬氣電漿(150 W、150 s、10 mm及10 slm)及添加甲烷氬氣電漿(200 sccm、150 W、150 s、10 mm及10 slm)進行薄膜表面改質，將其薄膜改質為親水性膜材，並以SEM及CLSM觀察表面型態的變化，實驗發現透過電漿改質後其薄膜孔徑改變甚巨，且並將以阻力串聯模式分析其濾速行為，探討薄膜改質前後之各種阻力變化。
因前述之電漿改質會改變薄膜孔徑，後以遙距式氬氣電漿(150 W、150 s、15 mm及10 slm)及遙距式添加甲烷氬氣電漿(200 sccm、150 W、150 s、15 mm及10 slm)進行表面改質，並加以分析。由分析結果得知，本研究之總阻力以吸附阻力為主，隨透膜壓力的增加濾餅阻力也逐漸上升；經電漿改質過濾薄膜後之薄膜本身阻力及吸附阻力皆有明顯下降。

This research used W/O/W emulsion liquid membrane to extract and separate zinc and copper ions, and recover W/O emulsion through filtration. To improve its limiting flux characteristics, microporous poly(vinylidene fluoride) membrane (PVDF) was surface-modified by cyclonic atmospheric-pressure plasma. Owing to the importance of the stability of the emulsion liquid membrane in extraction and separation process, this study determines the D.O.E (design of experiments) to discuss the experimental conditions (D2EHPA 0.1M、Span 80 3vol-%、external phase pH 3.0 and treatment ratio 7) of the emulsion to ensure the emulsion liquid membrane was stable while carrying out filtration and extraction experiments.
The study used PVDF ultrafiltration membrane in Dead-end system due to its feature as a hydrophobic material which could result significantly in the membrane fouling and adsorption phenomenon. Thus, it was modified the membrane surface by atmospheric argon plasma treatment (150 W、150 s、10 mm、10 slm) and argon mixed methane plasma treatment(200 sccm、150 W、150 s、15 mm、10 slm). Next, the resistance-in-series model was used to analyze the variation of the modified and un-modified membrane.
Because the plasma treatment causes the enlarged membrane pore size, so we modified the membrane surface by remoted plasma treatment to avoid the pore size change. In the analysis, the membrane resistance and adsorption resistance decreased after plasma surface modification. On the other hand, in the resistance-in-series model, the Cake resistances were increased depended on the transmembrane pressure.

致謝 I
摘要 II
ABSTRACT III
目錄 IV
圖目錄 VIII
表目錄 XIV
第一章 緒論 1
1.1 前言 1
1.2 乳化式液膜之簡介 3
1.3 界面活性劑之簡介 6
1.4 載體D2EHPA之簡介 9
1.5 實驗設計 12
1.6 表面改質 13
1.7 文獻回顧 15
1.8 研究動機與目的 18
第二章 實驗部分 21
2.1 實驗藥品儀器 21
2.1.1實驗藥品 21
2.1.2 實驗儀器 22
2.2 實驗裝置與步驟 25
2.2.1 實驗裝置 25
2.2.2 製備W/O/W乳化型液膜 27
2.2.3 實驗設計法決定W/O/W乳化型液膜 27
2.2.4 超過濾法處理W/O液膜 28
2.2.5 電漿表面改質 28
2.2.6 串聯阻力分析 30
第三章 結果與討論 31
3.1 各種變因對乳化液膜萃取的影響 31
3.1.1 製乳攪拌轉速與時間 31
3.1.2 萃取攪拌轉速 31
3.1.3 內水相濃度 32
3.1.4 內水相對油相體積比(ψW)的影響 32
3.1.5 萃取時間 33
3.1.6 界面活性劑濃度 34
3.1.7萃取劑濃度 35
3.1.8 外水相之pH值 36
3.1.9 乳水體積比（Vwe / Vw/o） 37
3.2 統計實驗設計 37
3.2.1 部分因子設計 37
3.2.2 反應曲面 48
3.3 乳液粒徑之探討 50
3.4純氬氣電漿表面改質超過濾薄膜 51
3.4.1改變電漿處理時間 51
3.4.2改變電漿功率 56
3.4.3改變氬氣流率 62
3.4.4改變噴頭至基材距離 66
3.4.5 XPS分析 71
3.4.6 孔隙度分析 73
3.4.7 老化實驗 76
3.5氬氣電漿添加甲烷氣體表面改質超過濾薄膜 77
3.5.1改變甲烷流率 77
3.5.2改變電漿處理時間 82
3.5.3改變電漿功率 86
3.5.4改變氬氣流率 90
3.5.5改變噴頭至基材距離 95
3.5.6 XPS分析 99
3.5.7 孔隙度分析 101
3.5.8老化實驗 103
3.6 遙距式電漿表面改質超過濾薄膜 104
3.6.1 遙距式純氬氣電漿表面改質超過濾薄膜 104
3.6.2 遙距式氬氣電漿添加甲烷氣體表面改質超過濾薄膜 107
3.7 恆壓式攪拌系統以超過濾薄膜分離乳化式液膜 112
3.7.1 恆壓過濾PVDF薄膜 113
3.7.2 純氬氣電漿改質PVDF薄膜 116
3.7.3 添加甲烷之氬氣電漿改質PVDF薄膜 117
3.7.4 遙距式純氬氣電漿改質PVDF薄膜 118
3.7.5 遙距式添加甲烷之氬氣電漿改質PVDF薄膜 119
第四章 結垢理論分析 121
第五章 結論 136
參考文獻 137
自述 144

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