臺灣博碩士論文加值系統

隨著環保意識高漲，染整廢水帶來的污染及色度問題受到政府、產業界及社會大眾的關注，而染整廢水成份複雜，具有高色度、高化學需氧量(COD) 及生物難分解等特性，以傳統二級處理技術無法有效處理，亟需有效提升廢水處理技術。
本研究利用高級氧化程序中之光催化程序，能產生氫氧自由基(•OH) ，迅速將染整廢水脫色，也較無污泥產生問題。而光催化反應主要利用光能來驅動或誘導催化劑表面進行反應，若能充分利用太陽的光來降解環境中的污染物，將更能達到節能的目標。泥漿式反應器大都直接將催化劑加入，因其顆粒微小，使催化劑不易分散及回收再利用，且奈米顆粒釋放於環境中可能會對人體及生物體造成無法預期的健康衝擊。為了避免奈米顆粒不受控制地進入到環境中，本研究(1)以不鏽鋼網作為基材，利用浸鍍(dip coating)方式，將ZnO 披覆於載體(不鏽鋼網)上，以改善粉末不易操作及回收困難問題；(2)探討ZnO 披覆於載體後，結合紫外光或可見光降解Orange G(OG)偶氮染料之可行性。
由FE-SEM、EDS及BET 等基本性質分析後可知，觸媒經浸鍍後能均勻披覆於載體上。藉由批次實驗，探討ZnO 覆膜劑量、染料初濃度、染料溶液pH、光強度、載體反應面積及染料溶液體積等條件，對偶氮染料Orange G降解之影響。ZnO 劑量以60 g/m2 為最佳操作劑量，當劑量超過60 g/m2，降解效率因增加劑量之提升會趨於平緩。染料初濃度測試，則發現隨著染料初濃度的提高，其染料去除率隨之降低，染料溶液pH 則是在鹼性(pH=11)溶液下有最佳脫色效率。紫外光強度愈大、載體反應面積越大、染料溶液體積愈小而有較佳脫色效果。以FTIR 及IC 觀察反應產物變化，結果指出可有效破壞染料中之N=N 鍵結，進而達到脫色的效果。搭配IC 看出反應後有SO42-、NO2-、NO3-等離子生成，並產生HCOOH 及CH3COOH 等產物。

Dyeing industrial wastewater with complicated compositions such as high color intensity, high chemical oxygen demand, and low biodegradation has attracted much attention by government, industry and public. The effluents often are treated insignificantly by the traditional secondary biological treatment processes, that new and effective technologies are urgently needed. In this work, the UV and visible lights were employed to
irradiate the photocatalyst, ZnO, to successfully decolorize the target dye molecules with no sludge production. Instead of solar light or lower energy visible light from UV/ZnO process, the photocatalytic for wastewater treatment saved energy consumption. Wide used slurry type photocatalytic reactors need further separation to recover the spend catalyst, as well as uncontrolled releasing of nano catalyst may cause human health and environmental impacts, that the stainless mesh were used for dip coating ZnO nano particles. UV 365 nm or visible light irradiation utilized ZnO catalyst to test decolorization of Orange G azodye. From FE-SEM and EDS results, stainless steel mesh immobilized ZnO catalyst was shown to be distributed homogenously on the carrier. Experimental conditions such as ZnO dosage, initial dye concentration, pH, light intensity, catalyst area, and solution volume were investigated for Orange G degradation. From the results, the best ZnO dosage was 60 g/m2, that higher than 60 g/m2 could not further improve any color removal efficiency. Under pH 11, the system showed best decolorization efficiency. Higher light intensity, more catalyst area, less solution volume and lower initial dye concentration resulted higher color removal efficiency. From FTIR and IC analysis, dye molecule of Orange G was proved to be destructed to cause color removal. Azo link of -N=N- disappeared during the photocatlytic reaction under FTIR measurement with production of SO42-, NO2-, NO3-, HCOOH and CH3COOH by IC analysis.

致謝 I
摘要 II
Abstract IV
目錄 V
表目錄 X
圖目錄 XII
第一章 緒論 1
1-1 前言 1
1-2 研究目的 3
1-3 研究架構 4
第二章 文獻回顧 6
2-1 染整廢水簡介 6
2-1-1 紡織及染整產業概況 6
2-1-2 染整廢水污染源及其特性 8
2-1-3 染料之分類 12
2-1-4 染整廢水處理現況與法規標準 16
2-1-5 染料廢水處理相關技術 20
2-2 紫外光特性及半導體性質介紹 23
2-2-1紫外線之特性與應用 23
2-2-2 半導體之基本特性 27
2-2-3 半導體之分類 31
2-2-4 覆膜技術 32
2-2-5 半導體光催化之理論 35
2-3 ZnO 40
2-3-1 ZnO的結構及特性 40
2-3-2 光催化反應機制 42
2-3-3 光催化反應動力模式 45
第三章實驗材料設備與方法 48
3-1 ZnO 覆膜之製備 48
3-1-1 光觸媒披覆程序 48
3-1-2 光觸媒基本性質分析 50
3-2 CCFL/ZnO 覆膜光催化程序 51
3-3 實驗藥品與材料 53
3-4 實驗設備 55
3-5 分析儀器 57
3-5-1 分光光度計(UV spectrophotometer) 57
3-5-2 濕式氧化法總有機碳分析儀(Wet Oxidation TOC Analyzer) 58


3-5-3 場發射掃描式電子顯微鏡(Field Emission Scanning Electron Microscope，FE-SEM) 58
3-5-4 BET 比表面積分析儀(Surface Area Analyzer) 59
3-5-5 傅立葉紅外光譜儀(Fourier Transform Infrared Spectroscopy，FT-IR) 59
3-5-6 離子層析儀(Ion Chromatography analyzer，IC) 60
3-5-7雷射粒徑分析儀(Laser Particle Size Analyzer) 61
第四章 結果與討論 62
4-1 ZnO光觸媒披覆特性分析 62
4-2比較懸浮式光觸媒程序與固定式ZnO覆膜程序 67
4-3 比較ZnO與TiO2結合光催化反應 68
4-4 ZnO/UV 覆膜光催化程序 71
4-4-1 背景實驗 71
4-4-2 反應時間之影響 73
4-4-3 載體乾燥溫度之影響 76
4-4-4 攪拌速率之影響 79
4-4-5 載體反應面積之影響 83
4-4-6 ZnO 披覆劑量之影響 86
4-4-7 染料初濃度之影響 88
4-4-8 染料初始pH 值之影響 94
4-4-9 紫外光強度之影響 98
4-4-10 染料溶液體積之影響 102
4-4-11 披覆材料耐久性之影響 106
4-5 比較ZnO/UV及ZnO/Vis兩種程序 110
4-6 比較不同之光源 113
4-7中間產物分析 115
4-7-1 FT-IR 染料結構官能基分析 115
4-7-2 染料溶液陰離子濃度測定 118
第五章 結論與建議 121
5-1 結論 124
5-2 未來方向與建議 125
參考文獻 127
附錄 136
附錄一 ZnO/Vis 覆膜光催化程序 137
附錄1-1 背景實驗 137
附錄1-2反應時間之影響 138
附錄1-3 載體乾燥溫度之影響 140
附錄1-4 攪拌速率之影響 141
附錄1-5 載體反應面積之影響 142
附錄1-6 ZnO 披覆劑量之影響 143
附錄1-7 染料初濃度之影響 144
附錄1-8 染料初始pH 值之影響 145
附錄1-9 光強度之影響 146
附錄1-10 染料溶液體積之影響 147

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