零價鐵（zero valent iron，ZVI）可以有效去除偶氮染料之色度，而Fenton對於TOC有不錯的處理成效，倘若零價鐵一直存在系統中，就會有源源不絕的亞鐵提供Fenton反應，而且染料被零價鐵分解成較小的分子後，也將有利於Fenton氧化降解TOC。因此本研究將結合零價鐵與Fenton法來處理偶氮染料orange II的色度及TOC，一開始先以零價鐵處理染料，探討於不同pH值、零價鐵加入量和初始染料濃度下，色度和TOC之去除、產生亞鐵與用酸量之關係，接著比較ZVI-Fenton、Fenton、ZVI-H2O2三種不同系統對染料去除之影響。
在pH 3.0、加入愈多的零價鐵色度去除速率愈快，而擬一階反應速率常數也愈大，但是不同的初始染料濃度並不會影響反應速率常數；零價鐵處理染料60分鐘後，其TOC去除效果並不明顯；由加酸量和亞鐵產生量的比值觀察主要與零價鐵反應的物質，發現零價鐵在pH 3.0與染料作用的比例高於pH 4.0且加入的零價鐵量越多、染料初始濃度越低會不利於零價鐵的使用率，而色度去除率達90%後，系統會開始出現浮鐵現象，將不利零價鐵連續處理染料。另外，以色度和TOC去除效果來看，ZVI-Fenton的確優於Fenton系統，且零價鐵與Fenton程序最好分開於不同槽體下反應。
最後，以批次式所得之結果，規劃出連續式操作流程與條件，發現染料色度及TOC去除率分別可達95%和40%。

Azo dye can be decolorized easily by zero valent iron (ZVI), and Fenton process is effective for TOC removal. With ZVI presented in the system, supply of ferrous ions for Fenton reaction will be unlimited. After the dye is reduced into small molecules by ZVI, TOC removal of these small molecules by Fenton oxidation will be more favorable. In this study, decolorization and TOC removal of azo dye orange II by ZVI and Fenton were studied. 
First, we observe decolorization, TOC removal and acid added versus ferrous generated under different pH value, ZVI dosage and initial dye concentration. And then, we observe treatment effectiveness of dye removal using different systems, namely ZVI-Fenton, Fenton and ZVI-H2O2.
Decolorization of dye was accelerated by ZVI under pH 3.0 and increasing ZVI dosage. Initial dye concentration did not affect the first-order reaction rate constant. TOC removal by ZVI was negligible for reaction time up to sixty minute. The ratio of acid added versus ferrous generated was used to explore the major reaction substance with ZVI. More ZVI react with dye at pH 3.0 than at pH 4.0. It is unfavorable for utilization of ZVI under higher ZVI dosage and lower initial dye concentration. Floatation of ZVI was observed when more than 90% of color was removed due to the generation of hydrogen gas. Decolorization and TOC removal by ZVI-Fenton is better than Fenton system. Meanwhile, ZVI reduction and Fenton oxidation should be employed under different reactors.  
Finally, based on the results of the batch reaction, we operated ZVI-Fenton process under completely mixed reactor, obtaining more than 95% and 40% of decolorization and TOC removal, respectively.

目錄
第一章、前言	1
1-1  研究緣起	1
1-2  研究目的	3
第二章、文獻回顧	4
2-1  結合Fenton處理染料廢水之相關方法	4
2-1-1  Fenton法	4
2-1-2  Fenton-like法	5
2-1-3	Electro-Fenton法	6
2-1-4  Photo-Fenton法	7
2-2  影響Fenton反應之因數	8
2-2-1  Fe2+ and H2O2 加入量	8
2-2-2  pH值	9
2-2-3	溫度	9
2-3  零價鐵的應用及影響零價鐵反應之因數	10
2-3-1  鐵的表面積	10
2-3-2  pH值	11
2-3-3  攪拌強度	12
2-4  結合零價鐵及Fenton（ZVI/Fenton）處理程序	13
第三章、材料與方法	15
3-1  實驗材料與設備	15
3-1-1  實驗材料	15
3-1-2  實驗設備	16
3-2  實驗步驟	21
3-2-1  批次式零價鐵	21
3-2-2  連續式	21
3-3  分析方法與干擾去除	23
第四章、結果與討論	29
4-1  零價鐵在染料廢水中之處理成效	29
4-1-1  零價鐵對於染料廢水中的真色度及TOC去除情形	29
4-1-2  零價鐵在染料廢水中產生亞鐵情形	37
4-2  ZVI-Fenton在染料廢水中處理成效	47
第五章、結論與建議	52
5-1  結論	52
5-2  建議	54
參考文獻	55

 

Figure 1. The chemical structue of Orange II...........................................16
Figure 2. (a) The experimental setup for the batch reaction, (b) The size
of glass column. ........................................................................................18
Figure 3. The experimental setup for the completely mixed reaction......20
Figure 4. Color developed versus time for samples been reacted with ZVI
for various reaction time. ..........................................................................24
Figure 5. The calibration curve for analysis of ferrous concentration
(mM). ........................................................................................................25
Figure 6. Color removal as a function of reaction time for various initial
Dye concentration. ZVI=10 g L-1, pH=3.0. ..............................................31
Figure 7. First order decrease as a function of reaction time for various
initial Dye concentration. ZVI=10 g L-1, pH=3.0.....................................31
Figure 8. Color removal as a function of reaction time for various pHs.
ZVI=10 g L-1, Dye concentration=300 mg L-1. ........................................33
Figure 9. First order decrease as a function of reaction time for various
pHs. ZVI=10 g L-1, Dye concentration = 300 mg L-1...............................33
Figure 10. Color removal as a function of reaction time for various ZVI
added. pH=3.0, Dye concentration=300 mg L-1. ......................................34
Figure 11. First order decrease constant k as a function of reaction time
for various ZVI added. pH=3.0, Dye concentration=300 mg L-1.............35
Figure 12. TOC removal as a function of reaction time for various pHs.
ZVI=10 g L-1, Dye concentration=300 mg L-1. ........................................36
Figure 13. TOC removal as a function of reaction time for various ZVI
added. pH=3.0, Dye concentration=300 mg L-1. ......................................37
Figure 14. TOC removal as a function of reaction time for various initial
Dye concentration. ZVI=10 g L-1, pH=3.0. ..............................................37
Figure 15. Ferrous generated as a function of time for various pHs.
ZVI=20 g L-1, Dye concentration=300 mg L-1. ........................................39
Figure 16. Ferrous generated as a function of time for various ZVI added.
pH=3.0, Dye concentration=300 mg L-1...................................................40
Figure 17. Ferrous generated as a function of time for various initial Dye
concentration. pH=3.0, ZVI=20 g L-1.......................................................41
Figure 18. Reaction process of ZVI treated azo dye orange II(Cao et al.,
1999; Nam and Tratnyek, 2000; Bigg and Judd, 2001; Roy et al., 2003;
Mielczarski et al., 2005; Zhang et al., 2005). ...........................................42
Figure 19. The amount of acid added versus ferrous generated for ZVI in
DI water. pH=3.0, ZVI=20 g L-1...............................................................42
Figure 20. The amount of acid added versus ferrous generated for ZVI in
orange II solution (concentration of 300 mgL-1) with pH fixed at 3.0 and
4.0. ZVI=10 g L-1.The time interval picked corresponded to the system
reaction followed not yet the 90% of ADMI removal . ............................43
Figure 21. The amount of acid added versus ferrous generated for
different ZVI in orange II solution with pH 3.0, Dye concentration=300
mg L-1.The time interval picked corresponded to the system reaction
followed not yet the 90% of ADMI removal . ..........................................44
Figure 22. The amount of acid added versus ferrous generated for ZVI in
orange II solution (concentration of 300,150 and 50 mgL-1) with pH 3.0,
ZVI=10 g L-1.The time interval picked corresponded to the system
reaction followed not yet the 90% of ADMI removal . ............................45
Figure 23. The amount of acid added versus ferrous generated.The time
interval picked corresponded to the system reaction followed the 90% of
ADMI removal..........................................................................................46
Figure 24. The react processes of three different system ZVI-Fenton
FentonZVI-H2O2. ..................................................................................47
Figure 25. The color and TOC removal as a function of various ferrous
concentration for ZVI-Fenton and Fenton reaction. pH=3.0, H2O2/Fe2+=2,
Dye concentration=300 mg L-1. ................................................................49
Figure 26. The color and TOC removal as a function of various ferrous
concentration for ZVI-Fenton and ZVI-H2O2 reaction. pH=3.0,
H2O2/Fe2+=2, Dye concentration=300 mg L-1. .........................................50
Figure 27. Color and TOC removal as a function of reaction time for
ZVI=200 g L-1, pH=3.0, Dye concentration=300 mg L-1, H2O2=8 mM...51

 

Table 1. The effect of dye color on ferrous measurement. .......................26
Table 2. The effect of dye color on hydrogen peroxide measurement. ....27
Table 3. Acid added versus ferrous generated at different pHs, ZVI added
and initial Dye concentration. The time interval picked corresponded to
the system reaction followed not yet the 90% of ADMI removal ...........46

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