臺灣博碩士論文加值系統

染整工業廢水主要特性為高色度及高COD，經傳統二級處理程序後，仍普遍無法符合台灣放流水標準。因此，為提高處理效率及節省處理時間，開發具高效率及低成本的處理技術已刻不容緩。本研究利用奈米零價鐵金屬 (NZVI)及奈米鐵複合雙金屬 (Fe/Ni及Fe/Zn)進行個別基礎實驗，探討各項操作參數對偶氮染料Acid Blue 113廢水處理效率的影響及評估最適化條件，操作參數包括反應時間、金屬劑量、染料初濃度、奈米複合雙金屬配比及耐久性測試等。之後再以奈米零價鐵結合UV/H2O2程序期望提高處理效率，並減少操作時間及成本之目標。由研究結果顯示奈米零價鐵確實具高效率脫色能力，但因奈米零價鐵容易受到氧化而失效，因此本研究以奈米鐵複合雙金屬(Fe/Ni及Fe/Zn)對染料進行試驗，藉由耐久性測試結果發現，奈米鐵複合雙金屬抗氧化性確實優於單一奈米零價鐵。此外，雖然奈米零價鐵具良好脫色能力，但對於染料溶液之總有機碳卻無顯著效果。因此，本研究嘗試先以奈米零價鐵反應30分鐘後，再導入UV/H2O2系統進行處理。由結果發現，以奈米零價鐵反應30分鐘，色度及總有機碳去除率分別為96.24及11.81%；而再串聯UV/H2O2程序120分鐘後，色度及總有機碳去除率分別為99.63及92.68%，顯示奈米零價鐵串聯UV/H2O2程序是一種可行的處理技術，可同時有效去除色度及TOC。

In general, effluents discharged from dye manufacturing and industries with strong color and high level of chemical oxygen demand (COD) which can not meet the stricter Taiwan’s Nation Effluent Standard by convention wasterwater treatment system. Thus, it demands urgently to develop an economic and effective technique for increase of color removal of wastewater treatment efficiency and time-saving operation. This study proposed decoloration of azo dye Acid Blue 113 wastewater using nanoscale zero-valent iron (NZVI) and bimetal Fe/Ni, Fe/Zn by considering the operating conditions such as reaction time, metal dosage, initial dye concentration, bimetal ratio and nanomaterials durable test. Moreover, NZVI was conneted with UV/H2O2 process for enhancement of TOC mineralization as well as the operating time and cost effectiveness. The experimental results demonstrated efficient decolorization by NZVI, however, gradual oxidized of NZVI reduce the color removal. Thus, bimetal Fe/Ni and Fe/Zn were employed to avoid easy oxidation of iron. From the duration test results, they were better than that of NZVI. Besides, NZVI was capable to decolorize the dye wastewater but insignificant for TOC removal so that initial NZVI addition 30 minutes for color removal in connection with UV/H2O2 process for TOC removal were conducted. The results showed color and TOC removal efficiency were 96.24 and 11.81% by NZVI addition during initial 30 minutes, respectively, while 99.63 and 92.68%, respectively by the following UV/H2O2 process till 120 minutes. Therefore, the connection of NZVI and UV/H2O2 process was proved to be a high feasible technology to obtain color removal as well as TOC removal.

目錄
中文摘要 I
英文摘要 Ⅱ
中英文縮寫對照表 Ⅲ
目錄 IV
圖目錄 ⅥI
表目錄 Ⅸ
第一章 前言 1
1-1研究背景 1
1-2研究目的 3
第二章 文獻回顧 4
2-1染整業發展及回顧 4
2-1-1染料分類 7
2-1-2染料廢水特性 9
2-1-3現行法規及管制標準 10
2-1-4染料廢水處理方法 12
2-2 奈米零價鐵處理技術及發展 15
2-2-1奈米科技概述 15
2-2-2奈米金屬製備 18
2-2-3奈米鐵技術發展及反應機制原理 19
2-2-4可能影響零價鐵還原反應之因素 24
2-2-5奈米零價鐵應用相關文獻 26
2-3雙金屬處理技術及發展 29
2-3-1雙金屬反應原理機制 29
2-3-2 雙金屬相關應用文獻 32
2-4 UV/H2O2氧化程序 24
第三章 實驗材料與方法 35
3-1研究架構 35
3-2實驗藥品與材料 36
3-3實驗設備與分析儀器 38
3-4研究方法 44
3-4-1實驗流程 44
3-4-2實驗方法 46
第四章 結果與討論 52
4-1奈米零價鐵及複合雙金屬特性分析 52
4-1-1奈米零價鐵及複合雙金屬表面型態構造 52
4-1-2奈米零價鐵及複合雙金屬表面特性分析 56
4-2奈米零價鐵金屬及複合雙金屬還原反應 64
4-2-1反應時間之影響 64
4-2-2染料溶液初濃度之影響 69
4-2-3金屬劑量之影響 72
4-2-4複合雙金屬之金屬配比影響 76
4-2-5奈米零價鐵及複合雙金屬材料耐久性之影響 80
4-2-6染料反應前、後之FTIR圖譜比較 82
4-3奈米零價鐵還原反應結合UV-H2O2氧化程序 84
第五章 結論與建議 86
5-1結論 86
5-2未來方向與建議 87
參考文獻 88

圖目錄
圖2-1染料微粒子化示意圖 8
圖2-2表面原子數之比例與粒徑關係 17
圖2-3水中零價鐵與污染物之Eh-pH關係圖 21
圖2-4 零價鐵分解含氯有機物示意 23
圖2-5 含氯有機物由Pd/Fe雙金屬反應降解示意圖 31
圖3-1研究架構 35
圖3-2 BET比表面積分析儀 39
圖3-3 FT-IR傅立葉紅外線光譜儀 40
圖3-4 場發射掃描式電子顯微鏡 41
圖3-5 紫外光可見光分光光度計 42
圖3-6 總有機碳分析儀 43
圖3-7 實驗流程 45
圖3-8 奈米鐵與奈米雙金屬製備步驟 47
圖3-9 批次還原反應實驗流程圖 51
圖4-1 自行合成之奈米零價鐵(NZVI)於反應前後之之電子掃描圖 53
圖4-2 自行合成之奈米鐵鎳雙金屬(Fe/Ni)於反應前後之電子掃描圖 54
圖4-3 自行合成之奈米鐵鋅雙金屬(Fe/Zn)於反應前後之電子掃描圖 55
圖4-4 奈米零價鐵(NZVI)之能量分散光譜儀(EDS)圖譜 58
圖4-5 奈米鐵鎳雙金屬(Fe/Ni)之能量分散光譜儀(EDS)圖譜 59
圖4-6 奈米鐵鋅雙金屬(Fe/Zn)之能量分散光譜儀(EDS)圖譜 60
圖4-7 奈米鐵鎳雙金屬(Fe/Ni)之能量分佈掃描(Mapping)圖像 61
圖4-8 奈米鐵鋅雙金屬(Fe/Zn)之能量分佈掃描(Mapping)圖像 62
圖4-9 NZVI與Acid Blue 113 染料還原脫色反應全波長變化圖 66
圖4-10 NZVI、Fe/Ni及Fe/Zn與染料AB113之時間效應 67
圖4-11 金屬溶出濃度 68
圖4-12染料初濃度效應 70
圖4-13 奈米金屬NZVI, Fe/Ni及Fe/Zn對Acid Blue 113之單位去除量 71
圖4-14 NZVI劑量效應 74
圖4- 15 NZVI劑量對鐵金屬溶出濃度效應 75
圖4-16鹽酸萃取零價鐵表面TOC濃 75
圖4-17 Fe/Ni不同重量比對染料溶液之效應 77
圖4- 18 Fe/Zn不同重量比對染料溶液之效應 78
圖4-19 不同重量比之雙金屬對處理染料溶液之個別金屬溶出結果 79
圖4-20自製奈米金屬材料耐久性測試結果 81
圖4-21 AB113溶液與鐵鋅雙金屬反應前後之FTIR圖譜比較 83
圖4- 22 NZVI串聯UV-H2O2處理染料之(a)色度去除率(b) TOC去除率 85

表目錄
表2-1 1999～2008年各類產業出口比較表 5
表2-2紡織工業對貿易貢獻度 6
表2-3紡織業各類出口量比較(1999～2003與2004～2008比較) 6
表2-4 酸性染料分類表 8
表2-5行政院環保署放流水標準(2000年) 11
表2-6廢水織物理及化學處理方法優缺點比較表 14
表2-7奈米晶表面原子數與表面能量估計 17
表2-8零價鐵分解污染物模式 25
表3-1 染料基本特性 36
表3-2 批次實驗參數表 51
表4-1 奈米零價鐵與複合雙金屬之比表面積、孔隙度及孔隙體積 63
表4-2 奈米零價鐵與複合雙金屬加酸消化後理論值與實際測值比較 63

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