臺灣博碩士論文加值系統

EDTA-Fe及雙氧水，在中性pH下，可產生強效催化氧化反應，且在相同劑量與條件下，氧化效果優於傳統芬頓法，也已有相關專利發表。綜此，本研究希望能從實用角度，進一步深化此技術，並將研究成果，以論文方式呈現。本研究利用EDTA-Fe及雙氧水氧化效力，試圖解決二項實際問題：其一是染整廢水COD處理問題; 其二是抑菌性問題。在染整廢水處理問題上，由於目前染整客戶需求多樣，加上染色技術進步，染整產業發展比以往都要快速。而台灣原始設備製造（OEM）和原始設計製造（ODM）在關鍵染色能力、在跨國紡織企業等，都有著至關重要的角色。惟客製染色需求與環保節水思維，使得染整廢水處理困難度增加，新技術的導入有其需要性。在抑菌應用上，雙氧水一直是殺菌常用化學品，在催化劑使用下，是否能有效降低雙氧水劑量，而能達到同樣抑菌目標，亦是需要更多的測試與評估。

針對染整廢水處理，本研究將EDTA-Fe與雙氧水和二氧化鈦分別用於常用各式染劑氧化降解上，並在瞭解其高降解效力後，將此一氧化效力，用在高濃度染整廢水處理上。另，在抑菌研究上，不同EDTA-Fe與雙氧水劑量所產生的抑菌效力及其抑菌反應機制等，皆有所探討。這些研究成果總結於三篇研究論文中：“水中染料的光催化和化學催化氧化反應”、“以活性碳吸附直接從染料廢水中去除化學需氧量“，及“螯合鐵（EDTA-Fe）和過氧化氫（H2O2）藉由產生氧化壓力而成的殺菌效能”等。這些文章的主要結論如下：（1）過氧化氫和EDTA-Fe螯合鐵可降解超過8成酸性及反應性染劑，且如加入二氧化鈦（TiO2），降解可再增加，具加成性的效果。(2)過氧化氫和EDTA-Fe螯合鐵可再活化吸附高濃度染整廢水COD的活性碳，從源頭降解染整廢水COD。(3)螯合鐵可在中性pH下，用於增加氧化效力和殺菌效果。更詳細的結論，如劑量、操作條件等，亦可一併參考內文中上述三篇已發表文章。

Under neutral pH, the combination of EDTA-Fe and peroxide effectively promotes catalytically oxidative reactions. Under the same dosage and operational conditions, the oxidative effect of EDTA-Fe and peroxide is also superior to the conventional Fenton’s reagents. In addition, this oxidative technique has been patented by Intellectual Property Office of Taiwan. However, two major problems were aimed to be further investigated: the treatment of dyeing wastewater COD and bacterial inhibition. Due to diverse demands and advanced technologies in dyeing industry as well as the global water-saving trend, new techniques for dyeing wastewater treatment are gaining interest. Moreover, considering the growing need of peroxide in bacterial disinfection, the use of a catalyst might be able to reduce the use of peroxide. Because of these reasons, the combination of EDTA-Fe and peroxide must be investigated in detail.

In order to remove the COD of the dyeing wastewater, the EDTA-Fe and peroxide as well as titanium dioxide were separately tested. The enhanced oxidative effect of EDTA-Fe and peroxide was confirmed and further applied in the treatment of the highly contaminated dyeing wastewater from the dyeing bath. On the other hand, various dosages of EDTA-Fe and peroxide were employed to inhibit the growth of bacteria. All the results were summarized into three research manuscripts, namely, “Photo- and chemo-catalytic oxidation of dyes in water”, “Removal of chemical oxygen demand directly from dyeing bath effluent by activated carbon adsorption”, and “Bactericidal effects of oxidative stress generated by EDTA-Fe and hydrogen peroxide”. The main conclusions of these studies include: (1) More than 80% of the acid and reactive dyes were easily oxidized. In case where titanium dioxide was added with UV light, the percent removal of dye increased which indicated the additive nature of these oxidizing reactions. (2) Activated carbon that saturated with COD of the dyeing wastewater could be regenerated by EDTA-Fe and peroxide, which allowed the treatment of the dyeing wastewater COD from the beginning of the contamination. (3) The EDTA-Fe enhanced oxidative effectiveness at neutral pH; therefore, the use of peroxide dosage could be reduced if the same oxidative effectiveness was desired. For more detailed conclusions including dosages, operational conditions, and other parameters, please refer to the three written articles in the text.

中文摘要 i
Abstract ii
誌謝 iv
Acknowledgements v
Table of Contents vi
List of Tables ix
List of Charts x
Introduction 1
Literature Review 3
1. Introduction to the chemical fiber industry 3
2. Introduction to wastewater 6
3. Hazards of wastewater 16
4. Wastewater-related disasters 17
Disasters in Japan 17
Disasters in US 24
Disasters in Taiwan 27
5. Technologies in treating wastewater 34
5.1 General treatment of wastewater 34
5.2 Textile effluent and treatment 35
(A) Physical removal processes 37
1. Precipitation: 37
2. Filtration: 37
3. Electrosorption: 37
4. Membrane filtration: 37
(B) Chemical removal processes 38
1. Neutralization 38
2. Chemical precipitation 38
3. Oxidation-reduction reactions 38
3.1 Chemical oxidation 39
3.1.1 Ozone 40
3.1.2 Chlorine dioxide 42
3.1.3 Hydrogen peroxide 44
3.1.4 Fenton reagent 48
3.2 Advanced oxidation processes 49
AOP principles 51
Photocatalytic oxidation 51
Fenton reaction 51
3.2.1 UV/H2O2 52
3.2.2 UV/O3/H2O2 52
3.2.3 TiO2/UV/H2O2 53
4. Oxidative decolorization of dyes 54
4.1 Photo-oxidative decolorization process 56
4.2 Chlorine-oxidative decolorization process 57
4.3 Peroxide-oxidative decolorization process 57
4.4 Ozone-oxidative decolorization process. 58
4.5 Reductive decolorization process. 59
(C) Physical-chemical Treatment 61
1. Adsorption: 61
2. Air flotation: 61
3. Blow-off method: 62
4. Coagulation-flocculation: 62
5. Crystallization: 62
6. Electrodeionization (EDI): 63
7. Evaporation: 63
8. Electrolysis: 63
9. Filtration 64
10. Gas-filled membrane absorption 65
11. Liquid–liquid extraction 66
12. High Gradient Magnetic Separation (HGMS) 67
13. Supercritical fluid extraction 68
(D) Biological removal processes 69
1. Biological membrane process 69
2. Activated sludge process 70
3. Anaerobic process 71
Materials and Methods 72
1. Properties of studied dyes 72
2. Studied oxidants 73
3. Properties of other added materials 73
4. Fractional and full factorial designs 74
5. Grid experiment design 74
6. Cell culture and measurement 74
7. OD interference minimization 76
8. Measurement of wastewater parameters 76
9. Data quality control 77
Research and Manuscripts 79
Photo- and Chemocatalytic Oxidation of Dyes in Water 80
Bactericidal Effects of Oxidative Stress Generated by EDTA-Fe and Hydrogen Peroxide 109
Removal of Chemical Oxygen Demand directly from Dyeing Bath Effluent by Activated Carbon Adsorption 126
Conclusions 150
Questions and responses 153
Bibliography 156
Appendix 175

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