臺灣博碩士論文加值系統

本研究旨針對含重金屬離子廢水，探討應用電泳沉積-薄膜(Electrophoretic deposition - membrane, EPDM)程序，回收水中重金屬離子之可行性研究。EPD係一種藉由外加電動勢的協助，來促進水中離子傳移至特定電極而沉積的程序，此類程序對於水中溶解鹽類或膠體物質，具有促進凝聚沉積的作用，可獲得較高品質(純度)沉積物，有利於資源物質的循環利用；而薄膜程序則具有分離及濃縮作用，可選擇性地分離濃縮陰、陽離子。本研究以人工含重金屬廢液(硫酸銅及硫酸亞鐵)，配合以不銹鋼編織網(陰極)及鈦鈑(陽極)，並以質子交換膜隔離陰陽極兩端，在施加電壓下，促使金屬離子沉積在不鏽鋼編織網上，可藉以回收高品質的金屬離子。
研究結果顯示：金屬氫氧化物的沉積效能，與溶液種類、濃度、操作電壓等操作條件有關，可針對不同金屬離子或鹽類離子，篩選出較佳的鹽類沉積條件，供產業界參考；以不同電壓(2 V~10 V)處理硫酸銅廢液試驗結果發現，陽極端的銅離子下降，但陰極端銅離子濃度上升。外加電壓，搭配陽離子交換膜，可將銅離子誘導至陰極端，可促使陽離子端溶液中的銅離子濃度減少；就反應終了的成果而言，於pH＝13環境下，施加4 V及8 V電壓條件下，對於銅離子去除效率達50%以上；pH＝7時，施加4 V~10 V之電壓對於銅離子去除效率達50%以上，並以8 V之去除效率最高。
本研究進一步針對陽離子交換膜及不銹鋼編織網，進行場發射型掃描式電子顯微鏡(SEM)及能量色散X-射線光譜(EDS)掃描鑑定沉積物的特性，結果發現兩者表面皆有明顯的結晶物產生，呈現方型或不規則結晶型態，其主要是銅、鐵金屬結晶物；此外，在相同濃度下，不同pH值(pH＝2、7、13)環境中，利用循環伏安法所測量到的CV曲線圖，以pH＝ 2的電流密度高於pH＝ 7及13。其原因可能為調配pH值時，氫氧化鈉溶液中之氫離子濃度增加，導致電流密度較高，在相同pH，不同濃度(0.005 M、0.004 M、0.003 M、0.002 M)環境下所量測到的CV曲線圖，以0.005 M之電流密度最高，應與離子含量較高，導致電流密度較高有關。

A feasibility study of applying electrophoretic deposition- membrane (EPDM) processes to recover heavy metals form metal-containing wastewater was investigated. EPD system facilitates the transfer of ions from aqueous phases to specific electrodes by providing an additional electromotive force. The assistance by an additional selective membrane separation process to EPD process, named as EPDM, can selectively separate and concentrate both anions and cations for further producing better quality crystallization products. In this study, an artificial wastewater containing copper sulfate or ferrous sulfate was prepared as the target wastewater. Both cathode, stainless steel woven mesh, and anode, titanium sheet, were separated by a proton exchange membrane. Metal ions are deposited on the stainless steel woven mesh and cathode while an external bias was applied.
Some important results were achieved in the study. The experimental results indicated that both metals, copper and iron, are immobilized on the stainless steel wove mesh and cathode as metal hydroxides, which is confirmed by performing field emission scanning electron microscopy (SEM) and energy dispersive X-ray spectroscopy (EDS) scanning. Higher deposition rates for the metals are observed in higher pH conditions and external biases. Compared in the pH= 7 solution, the removal ratios of both metals from the prepared wastewater were enhanced by 0.5 fold in the pH= 11 solution. Similar results were also observed by the external bias of 8.0 V than by 4.0 V. This study successfully demonstrates the EPDM process can produce metal hydroxides with high purity, which is not only benefit for producing less metal-containing sludge, but also good for metal recycling.

摘要 I
Abstract III
誌謝 IV
目錄 V
表目錄 VII
圖目錄 VIII
第一章 緒論 1
1-1研究緣起 1
1-2研究目的 2
第二章 文獻回顧 4
2-1電化學反應系統特性 4
2-1-1電凝聚(EC)程序 4
2-1-2電透析(ED)程序 6
2-1-3循環伏安法 7
2-1-4隔膜電解 9
2-1-5電泳沉積原理 9
2-1-6懸浮液種類 14
2-1-7粒子電荷來源 15
2-1-8膠體粒子的分散 15
2-1-9影響電泳速度的因素 16
2-2薄膜應用程序 17
2-3離子交換技術 20
2-4結晶程序 23
2-4-1成核現象 23
2-4-2核成長現象 26
第三章 研究方法與材料 27
3-1實驗內容與規劃 27
3-1-1研究概要 27
3-1-2研究流程 27
3-2實驗材料與設備 29
3-2-1實驗藥品 29
3-2-2實驗材料及儀器設備 29
3-2-2-1火焰式原子吸收光譜儀(Atomic Absorption Spectrometer) 31
3-2-2-2掃描式電子顯微鏡(SEM) 33
3-2-2-3 X光繞射儀(X-Ray diffraction, XRD) 34
3-2-2-4電泳沉積-薄膜反應系統(electrophoretic deposition-membrane，EPDM) 35
3-3實驗方法與分析 36
3-3-1循環伏安法分析 36
3-3-2電泳沉積-薄膜反應系統試驗 37
第四章 結果與討論 38
4-1電泳沉積-薄膜反應系統處理硫酸銅廢液之成效 38
4-1-1 pH值 40
4-1-2施加電壓 44
4-1-3 去除及回收成效 49
4-2電泳沉積-薄膜反應系統處理硫酸亞鐵廢液之成效 50
4-2-1 pH值 51
4-2-2施加電壓 55
4-2-3去除及回收成效 60
4-3電泳沉積-薄膜反應系統表面形貌變化分析 60
4-3-1硫酸銅廢液試驗系統之表面形貌變化 61
4-3-2硫酸亞鐵廢液試驗系統之表面形貌變化 67
4-4電泳沉積-薄膜反應系統結晶物之XRD光譜分析 71
4-4-1硫酸銅廢液試驗系統之結晶物XRD晶相分析 71
4-4-2硫酸亞鐵廢液試驗系統之結晶物XRD晶相分析 71
4-5電泳沉積-薄膜反應系統電化學分析 72
4-5-1硫酸銅廢液CV掃描結果 72
4-5-2硫酸亞鐵廢液CV掃描結果 77
4-6電泳沉積-薄膜程序之效益評估 82
4-7電泳沉積-薄膜程序之可行性說明 84
第五章 結論與建議 86
5-1結論 86
5-2建議事項 87
參考文獻 88

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