Photo-Fenton程序兼具OH‧氧化及鐵鹽混凝雙重功能去除有機物，本研究評估Photo-Fenton相關程序氧化與混凝去除有機物之比較，Photo-Fenton相關程序包含Photo-Fenton-like、H2O2/UV、Fenton。以反應性偶氮染料Evercion Red H-E3B與聚乙烯醇(Poly(vinyl alcohol), PVA)分別模擬染整廢水中色度與DOC，人工染整廢水色度與DOC濃度分別為1300 單位與31 mg/L。以pH、氧化時間、鐵鹽種類與加藥量及H2O2加藥量為操作變數，分析H2O2、色度及DOC殘留，以比較Photo-Fenton相關程序去除DOC效率、反應動力學及機制。所有實驗採批次式H2O2/UV光反應槽。
研究結果顯示Photo-Fenton程序去除DOC與色度最佳pH為3，於氧化時間5分鐘時色度與DOC去除率分別為98%與45%。當氧化時間120分鐘時，Photo-Fenton及H2O2/UV程序之DOC去除率皆可達90 %以上，但Fenton程序僅有50%，DOC去除效率依序為Photo-Fenton = H2O2/UV > Fenton程序。去除DOC為擬一階反應動力學，Photo-Fenton程序反應動力常數為H2O2/UV程序之3.2倍，顯示H2O2/UV程序添加Fe2+加藥量，可提高反應速率縮短反應時間，但無法提高DOC去除率。Fenton程序去除DOC機制主要為混凝去除；Photo-Fenton程序於反應初期(5分鐘)，DOC去除率為49.7%，混凝與氧化去除DOC分別為41.6%與8.1%，故主要以混凝機制去除DOC。相對地，於反應後期(30分鐘) DOC去除率為81.4%，混凝與氧化去除DOC分別為26.3%與55.1%，主要以氧化機制去除DOC。此乃因於反應後期，H2O2/UV可持續催化產生OH‧氧化有機物及膠羽，此外，Photo-Fenton-like程序去除DOC機制與相似。

The Photo-Fenton process is one of the advanced oxidation processes (AOPs) which eliminates organic matter by both hydroxyl radical (OH‧) oxidation and iron salts coagulation. The research evaluates the extent of oxidation and coagulation in Photo-Fenton-related processes. The Photo-Fenton-related processes include Photo-Fenton-like, H2O2/UV and Fenton processes. A reactive azo dyestuff (Evecion Red H-E3B) and polyvinyl alcohol (PVA) were used to simulate color and dissolved organic carbon (DOC) in the industrial textile wastewater, which contains color of 1300 ADMI unit and DOC of 31 mg/L. The experimental variables include pH, oxidation time, dosages of iron salt (ferric or ferrous) and hydrogen peroxide (H2O2). The content of H2O2, color unit and residual of DOC were measured for comparing the efficiency of DOC removal and reaction kinetics. All the experiments were batch conducted in H2O2/UV reactor.
The results show that the optimal pH to remove DOC and color is 3 within 5 minutes of oxidation time and the color and DOC removal efficiency is 98% and 45% respectively.  The DOC removal efficiency could go more than 90% in both Photo-Fenton and H2O2/UV processes while only of 50% in Fenton process. The efficiency of DOC removal was in the order of Photo-Fenton = H2O2/UV > Fenton. The pseudo-first-order reaction kinetics were fitted in DOC removal and found the rate constant in Photo-Fenton process is 3.2 times higher than H2O2/UV processes which indicated that dosing more Fe2+ in the process could only promote the reaction rate not DOC removal efficiency instead. The major mechanism to remove DOC is coagulation in Fenton process. In Photo-Fenton process, the major mechanism to remove DOC is coagulation at the first 5 minutes of the experiment with 49.7% COD removal efficiency, within which 41.6% was contributed by coagulation and the other 8.1% was by oxidation. Contrarily, in Photo-Fenton process, the major mechanism to remove DOC is oxidation at 30 minutes of the experiment with 81.4% COD removal efficiency, within which 26.3% was contributed by coagulation and the other 55.1% was by oxidation. This is due to the OH‧ was constantly generated at the final stage in the H2O2/UV process for oxidizing organic matter and floc. Meanwhile, the DOC removal mechanism by Photo-Fenton-like process was alike to Photo-Fenton process.

目錄	I
圖目錄	III
表目錄	IV
第一章	前言	1
1-1	研究緣起	1
1-2	研究目的	2
第二章	文獻回顧	3
2-1	染整廢水特性	3
2-1-1	染整廢水特性	3
2-1-2	染整廢水處理技術	3
2-2	H2O2/UV程序原理及去除有機物之影響因子	5
2-2-1	H2O2/UV 程序原理	5
2-2-2	H2O2/UV程序影響因子	6
2-3	Fenton程序原理及去除有機物之影響因子	9
2-3-1	Fenton 程序原理	9
2-3-2	Fenton程序影響因子	9
2-4	Photo-Fenton程序原理及去除有機物之影響因子	12
2-4-1	Photo-Fenton 程序原理	12
2-4-2	Photo-Fenton程序影響因子	13
第三章	實驗材料與方法	15
3-1	實驗材料	15
3-1-1	人工染整廢水	15
3-1-2	實驗設備	18
3-1-3	實驗藥品	20
3-2	實驗方法	21
3-2-1	Photo-Fenton相關程序實驗方法	21
3-2-2	DOC溶出	22
3-3	水質分析	23
3-3-1	色度分析方法	23
3-3-2	DOC分析方法	23
3-3-3	H2O2殘留分析方法	23
第四章	結果與討論	25
4-1	pH對Photo-Fenton程序脫色與DOC去除之影響	25
4-1-1	pH對H2O2分解之影響	25
4-1-2	pH對脫色與DOC去除之影響	27
4-2	Photo-Fenton相關程序脫色與DOC去除之比較	30
4-2-1	Photo-Fenton相關程序H2O2分解之比較	30
4-2-2	Photo-Fenton相關程序脫色與DOC去除之比較	32
4-2-3	Photo-Fenton相關程序DOC去除機制之探討	36
4-3	鐵鹽加藥量對Photo-Fenton程序脫色與DOC去除之影響	38
4-3-1	鐵鹽加藥量對H2O2分解之影響	38
4-3-2	鐵鹽加藥量對脫色與DOC去除之影響	40
4-3-3	鐵鹽種類對H2O2分解、脫色及DOC去除之影響	43
4-4	H2O2加藥量對Photo-Fenton程序脫色與DOC去除之影響	46
4-4-1	H2O2加藥量對分解H2O2之影響	46
4-4-2	H2O2加藥量對脫色與DOC去除之影響	48
4-5	Photo-Fenton程序初期去除DOC之機制	51
4-5-1	Photo-Fenton程序去除DOC之機制	51
4-5-2	Photo-Fenton-like去除DOC之機制	54
第五章	結論	56
參考文獻	57

圖3- 1 Evercion Red H-E3B染料之UV-VIS光譜 (Dye=20 mg/L)	16
圖3  1 UV反應槽設備	19
圖3- 3 H2O2標準檢量線	24
圖4- 1 pH對Photo-Fenton程序分解H2O2之影響	26
圖4- 2 pH對Photo-Fenton程序分解H2O2反應動力學	26
圖4- 3 pH對Photo-Fenton程序脫色、DOC去除之影響	28
圖4- 4 pH對Photo-Fenton程序DOC殘留率擬一階動力比較	29
圖4- 5 H2O2/UV、Fenton及Photo-Fenton程序之 H2O2殘留之比較	31
圖4- 6 H2O2/UV及Photo-Fenton之 H2O2殘留反應動力比較	31
圖4- 7 H2O2/UV、Fenton、Photo-Fenton 脫色之比較	33
圖4- 8 H2O2/UV、Fenton、Photo-Fenton去除DOC比較	34
圖4- 9 H2O2/UV、Fenton、Photo-Fenton殘留DOC擬一階反應動力比較	34
圖4- 10 Fenton及Photo-Fenton程序溶出前後之DOC殘留	37
圖4- 11鐵鹽加藥量對Photo-Fenton程序分解H2O2之影響	39
圖4- 12鐵鹽加藥量對Photo-Fenton程序分解H2O2之反應動力學	39
圖4- 13鐵鹽加藥量對Photo-Fenton程序脫色之影響	41
圖4- 14鐵鹽加藥量對Photo-Fenton程序DOC去除之影響	41
圖4- 15鐵鹽加藥量對Photo-Fenton程序DOC殘留擬一階反應動力比較	42
圖4- 16 Photo-Fenton及Photo-Fenton-like程序之H2O2分解比較	44
圖4- 17 Photo-Fenton及Photo-Fenton-like程序之脫色及DOC去除之比較	44
圖4- 18 Photo-Fenton及Photo-Fenton-like程序之H2O2、DOC殘留反應動力	45
圖4- 19 H2O2加藥量對Photo-Fenton程序分解H2O2之影響	47
圖4- 20 H2O2加藥量對Photo-Fenton程序H2O2殘留反應動力比較	47
圖4- 21 H2O2加藥量對Photo-Fenton程序脫色之影響	49
圖4- 22 H2O2加藥量對Photo-Fenton程序DOC去除之影響	49
圖4- 23 H2O2加藥量對Photo-Fenton程序DOC殘留反應動力比較	50
圖4- 24不同鐵鹽加藥量於Photo-Fenton程序溶出前後之DOC殘留率	53
圖4- 25不同鐵鹽加藥量於Photo-Fenton程序溶出前後之DOC殘留率	53
圖4- 26不同Fe3+加藥量於Photo-Fenton-like程序之溶出前後DOC殘留率	55

表2- 1典型染整廢水水質特性	3
表2- 2我國目前印染整業規範之放流水標準	4
表3- 1 反應性偶氮染料Evercion Red H-E3B 基本資料	16
表3- 2 聚乙烯醇(PVA)基本資料	17
表3- 3 實驗條件表	22
表4- 1 不同pH分解H2O2及DOC殘留之反應動力常數……………………….29
表4- 2 Photo-Fenton相關程序H2O2及DOC殘留之反應動力常數……………..35
表4- 3 Fe2+加藥量對Photo-Fenton程序H2O2及DOC殘留反應動力常數……..42
表4- 4 Photo-Fenton及Photo-Fenton-like程序H2O2、DOC殘留反應動力常數.	45
表4- 5 H2O2加藥量對Photo-Fenton程序H2O2及DOC殘留反應動力常數……50

1.	Aleboyeh, A., Moussa Y. and Aleboyeh H., 2005. The effect of operational parameters on UV/H2O2 decolourisation of Acid Blue 74, Dyes and Pigments, 66(2), 129-134.
2.	Aleboyeh, A., Olya M.E. and Aleboyeh H., 2008. Electrical energy determination for an azo dye decolorization and mineralization by UV/H2O2 advanced oxidation process, Chemical Engineering Journal, 137(3), 518-524.
3.	AlHamedi, F.H., Rauf M.A. and Ashraf S.S., 2009. Degradation studies of Rhodamine B in the presence of UV/H2O2, Desalination, 238(1-3), 159-166.
4.	Azbar, N., Yonar T. and Kestioglu K., 2004. Comparison of various advanced oxidation processes and chemical treatment methods for COD and color removal from a polyester and acetate fiber dyeing effluent, Chemosphere, 55(1), 35-43.
5.	Chelme-Ayala, P., El-Din M.G. and Smith D.W., Degradation of bromoxynil and trifluralin in natural water by direct photolysis and UV plus H2O2 advanced oxidation process, Water Research, 44(7), 2221-2228.
6.	Daneshvar, N., Behnajady M.A., Mohammadi M.K.A. and Dorraji M.S.S., 2008. UV/H2O2 treatment of Rhodamine B in aqueous solution: Influence of operational parameters and kinetic modeling, Desalination, 230(1-3), 16-26.
7.	Duesterberg, C.K., Mylon S.E. and Waite T.D., 2008. pH effects on iron-catalyzed oxidation using Fenton's reagent, Environmental Science and Technology, 42(22), 8522-8527.
8.	Elmolla, E.S. and Chaudhuri M., Comparison of different advanced oxidation processes for treatment of antibiotic aqueous solution, Desalination, 256(1-3), 43-47.
9.	Elmorsi, T.M., Riyad Y.M., Mohamed Z.H. and Abd El Bary H.M.H., Decolorization of Mordant red 73 azo dye in water using H2O2/UV and photo-Fenton treatment, Journal of Hazardous Materials, 174(1-3), 352-358.
10.	Ghodbane, H. and Hamdaoui O., Decolorization of antraquinonic dye, C.I. Acid Blue 25, in aqueous solution by direct UV irradiation, UV/H2O2 and UV/Fe(II) processes, Chemical Engineering Journal, 160(1), 226-231.
11.	Giroto, J.A., Teixeira A.C.S.C., Nascimento C.A.O. and Guardani R., Degradation of Poly(ethylene glycol) in aqueous solution by photo-fenton and H2O2/UV processes, Industrial and Engineering Chemistry Research, 49(7), 3200-3206.
12.	Gryglik, D., Olak M. and Miller J.S., Photodegradation kinetics of androgenic steroids boldenone and trenbolone in aqueous solutions, Journal of Photochemistry and Photobiology A: Chemistry, 212(1), 14-19.
13.	Hermosilla, D., Cortijo M. and Huang C.P., 2009. Optimizing the treatment of landfill leachate by conventional Fenton and photo-Fenton processes, Science of the Total Environment, 407(11), 3473-3481.
14.	Hermosilla, D., Cortijo M. and Huang C.P., 2009. The role of iron on the degradation and mineralization of organic compounds using conventional Fenton and photo-Fenton processes, Chemical Engineering Journal, 155(3), 637-646.
15.	Hsueh, C. L.; Huang, Y. H.; Wang, C. C. and Chen, C. Y., Degradation of azo dyes using low iron concentration of Fenton and Fenton-like system. Chemosphere 2005, 58, 1409-1414.
16.	Kang, S.F., Liao C.H. and Hung H.P., 1999. Peroxidation treatment of dye manufacturing wastewater in the presence of ultraviolet light and ferrous ions, Journal of Hazardous Materials, 65(3), 317-333.
17.	Kang, S.F., Liao C.H. and Po S.T., 2000. Decolorization of textile wastewater by photo-fenton oxidation technology, Chemosphere, 41(8), 1287-1294.
18.	Kang, S.F., Liao C.H. and Chen M.C., 2002. Pre-oxidation and coagulation of textile wastewater by the Fenton process, Chemosphere, 46(6), 923-928.
19.	Kuo, W.G., 1992. Decolorizing dye wastewater with Fenton's reagent, Water Research, 26(7), 881-886.
20.	Kusic, H., Koprivanac N., Bozic A.L. and Selanec I., 2006. Photo-assisted Fenton type processes for the degradation of phenol: A kinetic study, Journal of Hazardous Materials, 136(3), 632-644.
21.	Li, W., Lu S., Qiu Z. and Lin K., Clofibric acid degradation in UV254/H2O2 process: Effect of temperature, Journal of Hazardous Materials, 176(1-3), 1051-1057.
22.	Meric, S., Kaptan D. and lmez T., 2004. Color and COD removal from wastewater containing Reactive Black 5 using Fenton's oxidation process, Chemosphere, 54(3), 435-441.
23.	Papic S., Vujevic D., Koprivanac N. and Sinko D., 2009. Decolourization and ineration of commercial reactive dyes by using homogeneous and heterogeneous Fenton and UV/Fenton process. Journal of Hazardous Materials, 164, 1137-1145.
24.	Perez, M., Torrades F., Domenech X. and Peral J., 2002. Fenton and photo-Fenton oxidation of textile effluents, Water Research, 36(11), 2703-2710.
25.	Perez-Moya, M., Graells M., Castells G., Amige J., Ortega E., Buhigas G., Perez L.M. and Mansilla H.D., Characterization of the degradation performance of the sulfamethazine antibiotic by photo-Fenton process, Water Research, 44(8), 2533-2540.
26.	Schrank, S.G., Santos J.N.R.d., Souza D.S. and Souza E.E.S., 2007. Decolourisation effects of Vat Green 01 textile dye and textile wastewater using H2O2/UV process, Journal of Photochemistry and Photobiology A: Chemistry, 186(2-3), 125-129.
27.	Sellers, R.M., 1980. Spectrophotometric determination of hydrogen peroxide using potassium titanium(IV) oxalate, The Analyst, 105(1255), 950-954.
28.	Sun, J.H., Sun S.P., Wang G.L. and Qiao L.P., 2007. Degradation of azo dye Amido black 10B in aqueous solution by Fenton oxidation process, Dyes and Pigments, 74(3), 647-652.
29.	Sun, S.P., Li C.J., Sun J.H., Shi S.H., Fan M.H. and Zhou Q., 2009. Decolorization of an azo dye Orange G in aqueous solution by Fenton oxidation process: Effect of system parameters and kinetic study, Journal of Hazardous Materials, 161(2-3), 1052-1057.
30.	Vilhunen, S., Vilve M., Vepsinen M. and Sillanp M., Removal of organic matter from a variety of water matrices by UV photolysis and UV/H2O2 method, Journal of Hazardous Materials.
31.	Wu, K., Xie Y., Zhao J. and Hidaka H., 1999. Photo-Fenton degradation of a dye under visible light irradiation, Journal of Molecular Catalysis A: Chemical, 144(1), 77-84.
32.	Xu, B., Gao N.Y., Cheng H., Xia S.J., Rui M. and Zhao D.D., 2009. Oxidative degradation of dimethyl phthalate (DMP) by UV/H2O2 process, Journal of Hazardous Materials, 162(2-3), 954-959.
33.	Xu, X.R., Li X.Y., Li X.Z. and Li H.B., 2009. Degradation of melatonin by UV, UV/H2O2, Fe2+/H2O2 and UV/Fe2+/H2O2 processes, Separation and Purification Technology, 68(2), 261-266.
34.	中華民國行政院環境保護, 2003. 「印染整理業」、「農藥業」、「印刷電路板業」及「晶圓製造及半導體製造業」等四行業之廢水中特定物質前處理及管理制度評估計畫. 第4-1~4-57頁.
35.	中華民國行政院環境保護署,2009. 水汙染防治法規,放流水標準.