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Chemosphere 58 (2005) 14091414 www.elsevier.

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Degradation of azo dyes using low iron concentration of Fenton and Fenton-like system
C.L. Hsueh a, Y.H. Huang a, C.C. Wang b, C.Y. Chen
b

a,*

a Department of Chemical Engineering, National Cheng Kung University, Tainan City 701, Taiwan Department of Chemical Engineering, Southern Taiwan University of Technology, Tainan City 710, Taiwan

Received 10 December 2003; received in revised form 10 September 2004; accepted 29 September 2004

Abstract This study investigated Fenton and Fenton-like reactions at low iron concentration (510 mg l1) to oxidize three commercial azo dyes, namely Red MX-5B, Reactive Black 5 and Orange G. In some local cases in Taiwan, wastewater color was found to be the only problem in meeting local euent standards. This investigation reveals that both of these methods can remove the color of these dyes completely. Moreover they only produce little sludge in wastewater that meet local euent standards and do not need to further treat. The eects of Fe2+, Fe3+, H2O2 and solution pH on dye decolorization are demonstrated in detail. The optimum pH for both Fenton and Fenton-like reactions in this study are about pH 2.53.0. Increasing the dose of ferric nitrate enhances the dye decolorization. The optimal levels of H2O2 required for the process are also examined. High levels of H2O2 appear to reduce dye decolorization. In addition, it is also found that decolorization of azo dyes undergoes a faster reaction rate than mineralization of azo dyes. 2004 Elsevier Ltd. All rights reserved.
Keywords: Azo dye; Dye decolorization; Fenton; Fenton-like; Mineralization

1. Introduction Azo dyes are a major class of synthetic, colored organic compounds and account for about half of the textile dyestus used today (Zollinger, 1987). Until recently, no eective methods have existed for removing color produced by residual dye in wastewater. Approximately 15% of total world production of wastewater, or

* Corresponding author. Tel.: +886 6 275 7575 62643; fax: +886 6 236 0464. E-mail address: ccy7@ccmail.ncku.edu.tw (C.Y. Chen).

150 tons per day, is estimated to be released into the environment without proper treatment (Maynard, 1983). Dye decolorization is a required part of euent treatment and currently is an important issue in Taiwan. Several methods are being used to decolorize dye wastewater, but individually these methods are ineective for dealing with treating wastewater containing soluble and insoluble dyes. For example, the ozonation oxidation process can eectively decolorize wastewater containing soluble dyes, such as reactive dyes (Perkins et al., 1980). However, ozonation oxidation cannot decolorize insoluble dyes, such as disperse dyes. Insoluble dyes can be eectively decolorized by coagulation, but coagulation is ineective for soluble dyes (Thiravetyan et al., 2003). Finally, Fentons reagent (Fenton, 1894)

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that has been demonstrable eectively in decolorizing both soluble and insoluble dyes (Kuo, 1992). The Fenton reaction reacts ferrous salts with H2O2 to produce OH as shown in Eqs. (1)(3) (Walling, 1975). Fe2 H2 O2 H ! Fe3 OH H2 O Fe3 H2 O2 ! Fe2 OOH H Fe3 OOH ! Fe2 O2 H 1 2 3

2. Materials and methods 2.1. Reagent Ferric nitrate [(Fe(NO3)3 9H2O)], Ferrous sulfate (FeSO4 7H2O) and 35% hydrogen peroxide (H2O2) were purchased from Sigma (St. Louis, MO). Other chemicals used in the experiment were all of analytical grade. Reactive Black 5 and Red MX-5B were purchased from Aldrich (Milwaukee, WI). Orange G was obtained from Sigma. All azo dyes were used without further purication. A known dye concentration was prepared in deionized water and used as the stock solution for all studies. The structures of all azo dyes used in the study are shown in Fig. 1. 2.2. Experimental procedures All experiments were carried out in a 3000 ml reactor at room temperature, 28 2 C. Solution pH was adNaO3S SO3Na

The hydroxyl free radical thus generated attacks the unsaturated dye molecules and the azo bond (N@N) in the chromogen, thus decolorizing the wastewater. Application of the Fentons reagent in the destruction of organic compounds is limited by the slurry system because it produces a signicant amount of Fe(III)-iron sludge, which requires further separation and disposal. Our previous studies used the electro-Fenton (Huang et al., 1999, 2000a; Chou et al., 1999a) and FBR-Fenton methods (Chou et al., 1999b, 2001; Huang et al., 2000b) to solve these problems. However, in some local cases wastewater color was found to be the only problem in meeting local euent standards. Consequently, this study used low iron concentration in the Fenton or Fenton-like systems to meet local euent standards. Both Fe2+ and hydrogen peroxide are common constituents of oxygenated natural waters. In sunlit surface waters containing natural organic matter, photo-chemical reactions can cause rapid formation of both Fe, through ligand-to-metal charge transfer reactions of Fe3+-organo complexes, and hydrogen peroxide, mainly through photo-excited organic substances reducing oxygen. Recent investigations have shown that UV/visible irradiation accelerates both Fenton (H2O2/Fe2+) and Fenton-like (H2O2/Fe3+) reactions, improving the degradation rates of various azo dyes (Liao et al., 1999; Herrera et al., 1999; Aplin and Waite, 2000; Arslan et al., 2000; Xu, 2001; Scheeren et al., 2002; Lee et al., 2003). Although photo-excitation can accelerate the degradation, Fe(III)-iron sludge also must be removed after treatment. This work attempts to treat wastewater of three synthetic azo dyes by using low concentration of iron ions (510 mg l1) to decolorize the wastewaters, and also to conform to the water euent standards for iron levels in Taiwan (the maximum limit for total iron in euent is 10 mg l1). Such treatment can avoid creating a large volume of sludge. Experiments were conducted to examine the inuences of various operating conditions on treatment system performance. The experimental results can help understand the Fenton and Fenton-like treatment processes, as well as the various practical aspects of their potential application.

N NH N N N OH

Cl

Cl

Red MX-5B
O NaO3SOCH2CH2 S O HO N N SO3Na

H2N O NaO3SOCH2CH2 S O N N SO3Na

Reactive Black 5
HO N N

NaO3S SO3Na

Orange G

Fig. 1. Structures of the azo dyes in the study.

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Red MX-5B Concentration (mM)

justed by using sulfuric acid or sodium hydroxide using a pH meter (Action, A211). A predetermined quantity of ferric nitrate and H2O2 was dripped into the reactor and stirred with a recycle pump. The reaction time was recorded as the H2O2 solution was added. Samples were taken from the reactor periodically using a pipette, and were immediately analyzed after ltration by a 0.25 lm syringe lter made of poly-(vinylidene uoride). 2.3. Analytical methods The UVVIS spectra of the dyes were recorded from 200 to 800 nm using a UVVIS spectrophotometer (Jasco Model 7850). The maximum absorbance wavelength (kmax) of Red MX-5B, Reactive Black 5 and Orange G are 533, 591 and 475 nm from the spectra. Therefore, the concentration of azo dyes in water was determined by the absorption intensity at kmax. The dye decolorization was used in the study, which is dened as follows: dye decolorization 1 C dye;t =C dye;0 100% 4

0.12
Fenton system 2+ [Fe ] = 1 mg/l [H2O2] = 100 mg/l Ionic strength : 5.0 mM NaClO4

0.10

0.08

0.06

0.04

0.02

0.00

100

200

300

400

500

(a)
0.12

Time (min)

Red MX-5B Concentration (mM)

Fenton-like system 3+ [Fe ] = 1 mg/l [H2O2] = 100 mg/l Ionic strength : 5.0 mM NaClO4

0.10

0.08

where Cdye,t and Cdye,0 are the concentration of dye at kmax at reaction time t and 0, respectively. Total organic carbons (TOC) was analyzed with a Shimadzu 500 instrument. The characteristics of all azo dyes used in the study are detailed in Table 1.

0.06

0.04

0.02

3. Results and discussion 3.1. Eect of pH on Fenton and Fenton-like system Fig. 2a and b illustrate the concentration of Red MX5B for Fe2+/H2O2 and Fe3+/H2O2 system as a function of time at which solution pH is systematically varied. Concentration of 0.1 mM Red MX-5B was used because it corresponded to the level of pollution found in strongly colored polluted waters located close to textile manufacturing sites. H2O2 is unstable in alkaline solutions, and loses its oxidizing potential. Therefore, the pH of this study focuses on the range of 1.56.5. Clearly, the change of Red MX-5B concentration is signicantly inuenced by the solution pH, which is similar to the results observed in both Fenton and Fenton-like reactions. The optimum solution pH was observed at a pH of about 2.53.0 for both reactions. The results were
(b)

0.00

100

200

300

400

500

Time (min)

Fig. 2. Eect of pH on the change of Red MX-5B concentration: (a) Fenton and (b) Fenton-like systems. (d) 1.5; (r) 2.5; ( ) 3.0; (m) 3.5; (}) 4.5; (j) 6.5.

Table 1 Main characteristics of azo dyes Dye sample Red MX-5B Reactive Black 5 Orange G Molecular weight 615.34 991.82 452.4 kmax (nm) 533 591 475 TOC/mM dye (mg l1) 125.0 178.2 141.1

closely agree with the literatures (Kuo, 1992; Sheng and Cho, 1997; Kang and Hwang, 2000; Sevimli and Kinacl, 2002). At pH 1.5, the dye decolorization rate dramatically decreased as shown in Fig. 2a and b, revealing that the scavenging eect of the OH by H+ is severe at low pH. When at a pH higher than 3, it also showed low dye decolorization eciency. It may be explained by the hydrolysis of Fe3+ in the solution to reduce OH producing rate. Table 2 shows the degradation of Fenton and Fenton-like reaction systems of Red MX-5B at pH 2.5. An important and interesting phenomenon observed in this table is the dierence of dye decolorization eciency between Fenton and Fenton-like reaction. In the initial stage of reaction (530 min), the dye decolorization rate of Fenton reaction exceeds than that of Fenton-like one. However, when the reactions time over 60 min, there shows almost no dierence of the dye decolorization eciencies between Fenton and Fenton-like reaction. The reason is that almost all of Fe2+ was

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Table 2 Degradation of Red MX-5B by Fenton ([Fe2+] = 1 mg l1, [H2O2] = 100 mg l1) and Fenton-like ([Fe3+] = 1 mg l1, [H2O2] = 100 mg l1) systems at pH 2.5 Substituent kmax (nm) 533 System Reaction time (min) 10 20 30 60 480 10 20 30 60 480 Absorbance decrease at kmax (%) 59.9 83.3 90.7 96.0 99.8 22.3 53.7 78.2 95.1 99.5

Red MX-5B

Fenton

10 mg l1 ferric nitrate dosage, respectively. However, after 1 h of the reaction, it increased to about 13%, 95%, 96% and 97% with 0.1, 1, 5 and 10 mg l1 ferric nitrate dosages, respectively. The results show that there is almost no dierence between 1 and 10 mg l1 of Fe3+ for the dye decolorization during a 1 h reaction time. Although dye decolorization increases with increasing Fe3+ concentration at the initial stage of reaction, in order to reduce the volume of sludge, we choose 1 mg l1 of Fe3+ for the rest of the experiments. 3.3. Eect of H2O2 dose Fig. 4 shows the concentration of Red MX-5B as a function of reaction time when dierent concentration of H2O2 was used. Apparently, as the H2O2 concentration increases from 20 to 200 mg l1, the decolorization of Red MX-5B is enhanced because more Fe2+ and OH are formed at higher H2O2 concentrations in solution. However, when the H2O2 concentration is larger than 200 mg l1, the degradation rate of Red MX-5B slightly slows down. This can be explained by the socalled scavenging eect when using a higher H2O2 concentration. Addition of H2O2 is known to inuence the decomposition of organic compounds through Fentonlike reaction. Generally, the degradation rate of organic compounds increases as the H2O2 concentration increases until a critical H2O2 concentration is achieved. However, when a concentration higher than the critical concentration is used, the degradation rate of organic compounds will decrease as a result of the so-called scavenging eect (Fernandez et al., 1999; Dhananjeyan et al., 2001). The reaction of H2O2 and OH in aqueous solution can be expressed by the following equation (Walling and Kato, 1971): H O OH ! HO H O 5
2 2 2 2

Fenton-like

converted to Fe3+ at this time. Additionally, the results demonstrate that dye decolorization can occur at low iron concentrations for both Fenton and Fenton-like reaction reaction. The following experiments thus performed using Fenton-like system. 3.2. Eect of Fe3+ dose Fig. 3 displays the eect of iron dose on the concentration of dye under the following experiment conditions: pH xed at 2.5, H2O2 dose of 100 mg l1, ferric nitrate dose in the form of Fe3+, varied from 0 to 10 mg l1. The gure reveals the concentration of Red MX-5B as a function of time for dierent concentrations of Fe3+ in the solution. The gure shows that the decolorization of Red MX-5B increases with increasing Fe3+ concentration. At the rst 10 min, dye decolorization was about 5%, 22%, 52% and 67% for 0.1, 1, 5 and

0.12

Red MX-5B Concentration (mM)

0.10

Fe / H2O2 [H2O2] = 100 mg/l pH = 2.5 Ionic strength : 5.0 mM NaClO4


[Fe ] =
3+ 3+ 3+ 3+ 3+

3+

0 ppm

0.08

[Fe ] = 0.1 ppm [Fe ] = 1.0 ppm [Fe ] = 5.0 ppm

0.06

[Fe ] = 10 ppm

0.04

0.02 0.00 0 100 200 300 400 500

Time (min)

Fig. 3. Eect of Fe3+ concentration on the change of Red MX-5B concentration in a Fenton-like system.

Fig. 4. Eect of H2O2 dosage on the change of Red MX-5B concentration under a Fenton-like system.

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According to the results shown above, the critical H2O2 concentration for the degradation of 0.1 mM Red MX5B is about 200 ppm. 3.4. Mineralization of all three azo dyes It is known that reaction intermediates can form during the oxidation of azo dyes and some of them could be long-lived and even more toxic than the parent compounds. Therefore, it is necessary to realize the mineralization of azo dyes simultaneously although we focus our study on the decolorization. To quantitatively characterize the mineralization of azo dyes in the solution, the TOC removal ratio is used in the study, which is dened as follows: TOC removal ratio 1 TOCt =TOC0 100% 6

reaction rate than the mineralization of azo dyes under the same conditions. 4. Conclusions Low iron concentration (510 mg l1) of Fenton and Fenton-like reactions were studied on the degradation of azo dyes. The processes not only signicantly decolorize azo dyes but also minimize sludge creation. It has been found that the solution pH, H2O2 concentration and iron concentration in solution are the main factors that inuence the degradation of Red MX-5B. The optimum pH of the reaction solution for both Fenton and Fenton-like systems were 2.53.0. Additionally, the results show that dye decolorization can occur at very low iron concentrations (1 mg l1) in both Fenton-like and Fenton reactions. For a Fenton-like system, increasing ferric sulfate dose enhanced the degradation of Red MX-5B. The optimum H2O2 concentration is about 200 ppm for 0.1 Mm Red MX-5B. Although H2O2 is essential to generate OH, very high levels of H2O2 could reduce decolorization because of scavenging eect. It was also found that the decolorization of azo dyes undergoes a fast reaction than the mineralization of azo dyes, and 37%, 28% and 31% TOC of 0.1 mM Red MX-5B, Reactive Black 5 and Orange G can be eliminated after 480 min of reaction in the presence of 1 mg l1 Fe3+, and 100 mg l1 H2O2 at pH 2.5. Acknowledgments The authors thank the Ministry of Economic Aairs of the Republic of China for nancially supporting this research under contract no. TDPA: 91-EC-17-A-05-S10014. References

where TOCt and TOC0 are the TOC values at reaction time t and 0, respectively. Fig. 5 presents the concentration degradation and TOC removal ratio of three azo dyes as a function of time at pH 2.5. As we can see in Fig. 5, dye decolorization signicantly increased with increasing reaction time for all dyes. After 20 min of reaction time, dye decolorization was 54%, 53% and 75% for Red MX-5B, Reactive Black 5 and Orange G, respectively. However, it shows almost no TOC removal eciency for the rst 20 min. It demonstrates that intermediates form by oxidation of azo dyes during the rst 30 min reaction. After then, TOC removal eciency increases slowly even though a complete dye decolorization is achieved. Meanwhile, at 480 min reaction time, all of the TOC removal ratios reach to about 40%. Compared with the results of decolorization and TOC removal ratio, it can be seen that the decolorization of azo dyes undergoes a fast

0.12 Fe / H2O2 3+ [Fe ] = 1 mg/l [H2O2] = 100 mg/l pH=2.5


concentration of Red MX-5B concentration of Reactive Black 5 concentration of Orange G TOC removal ratio of Red MX-5B
3+

100

Dye concentration (mM)

0.10

80

0.08

60

0.06

TOC removal ratio of Reactive Black 5 TOC removal ratio of Orange G

40 0.04 20

0.02

0.00

100

200

300

400

0 500

Time (min)

Fig. 5. The changes of concentration and TOC removal ratio of three azo dyes as a function of reaction time.

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