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Decolorization of Rhodamine B by a Photo-Fenton Process: Effect of System Parameters and Kinetic Study

Decolorization of Rhodamine B by a Photo-Fenton Process: Effect of System Parameters and Kinetic Study

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A low-energy photo-Fenton process is carried out in this study to investigate the effect of pH, temperature, Fe2+ and H2O2 dosages on the decolorization of Rhodamine B dyeing wastewater. Experimental results indicate that the decolorization efficiency of Rhodamine B by UV light illumination only and UV/H2O2 (H2O2 of 30 to 90 mg/L) are insufficient. Decolorization efficiency is remarkably enhanced to more than 83% by the photo-Fenton process at pH 5.5 and the pseudo first-order kinetic rate constants are in the range of 13.6-14.7×10-3 min-1. The optimal reaction condition is found at pH 3, H2O2 30 mg/L; Fe2+ 8 mg/L and 30oC followed by 98.3% decolorized efficiency of Rhodamine B. In conclusion, the photo-Fenton process can effectively decolorize the Rhodamine B in short reaction time under proper condition. Additional H2O2 and Fe2+ dosages and the reaction temperature up to 30oC are worthless to enhance the decolorization of Rhodamine B.
A low-energy photo-Fenton process is carried out in this study to investigate the effect of pH, temperature, Fe2+ and H2O2 dosages on the decolorization of Rhodamine B dyeing wastewater. Experimental results indicate that the decolorization efficiency of Rhodamine B by UV light illumination only and UV/H2O2 (H2O2 of 30 to 90 mg/L) are insufficient. Decolorization efficiency is remarkably enhanced to more than 83% by the photo-Fenton process at pH 5.5 and the pseudo first-order kinetic rate constants are in the range of 13.6-14.7×10-3 min-1. The optimal reaction condition is found at pH 3, H2O2 30 mg/L; Fe2+ 8 mg/L and 30oC followed by 98.3% decolorized efficiency of Rhodamine B. In conclusion, the photo-Fenton process can effectively decolorize the Rhodamine B in short reaction time under proper condition. Additional H2O2 and Fe2+ dosages and the reaction temperature up to 30oC are worthless to enhance the decolorization of Rhodamine B.

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International Journal of Environment and ResourceVol. 1 Iss. 2, November 2012
 
73
 
Decolorization of Rhodamine B by aPhoto-Fenton Process: Effect of SystemParameters and Kinetic Study
Y. S. Ma
1
 , C. N. Chang
2
 , C. R. Chao
2
 
1
Department of Environmental Engineering and Health, Yuanpei University, Hsinchu, Taiwan
2
Department of Environmental Science and Engineering, Tunghai University, Taichung, TaiwanEmail: ysma0728@mail.ypu.edu.tw
 Abstract 
A low-energy photo-Fenton process is carried out in this studyto investigate the effect of pH, temperature, Fe2
+
and H
2
O
2
 dosages on the decolorization of Rhodamine B dyeingwastewater. Experimental results indicate that thedecolorization efficiency of Rhodamine B by UV lightillumination only and UV/H
2
O
2
(H
2
O
2
of 30 to 90 mg/L) areinsufficient. Decolorization efficiency is remarkably enhancedto more than 83% by the photo-Fenton process at pH 5.5 andthe pseudo first-order kinetic rate constants are in the range of13.6-14.7
×
10
-3
min
-1
. The optimal reaction condition is found atpH 3, H
2
O
2
30 mg/L; Fe
2+
8 mg/L and 30
o
C followed by 98.3%decolorized efficiency of Rhodamine B. In conclusion, thephoto-Fenton process can effectively decolorize the RhodamineB in short reaction time under proper condition. AdditionalH
2
O
2
and Fe
2+
dosages and the reaction temperature up to 30
o
Care worthless to enhance the decolorization of Rhodamine B.
 
Keywords
Decolorization; Photo-Fenton Process; Pseudo First-order Kinetic;Rate Constants; Rhodamine B
Introduction
Advanced oxidation processes (AOPs) have beengenerally employed as an attractive alternative methodfor the removal of hazardous, bio-refractory and toxicmaterials from waters and wastewaters. In principle,AOPs are known to generate highly reactive andnon-selective hydroxyl radicals (
OH), which is able tooxidize almost all toxic and non-biodegradable organiccompounds to simple ones.
 
AOPs, including ultra-violet(UV) illumination, ultrasound, ozonation, Fentonprocess and combinations thereof can efficiently produce
OH to oxidize the pollutants and reduce the toxicity[1-4].Photo-Fenton (UV light or visible light + Fenton) is anovel method in which water molecules undergomolecular fragmentation and release
OH to oxidize theorganic compounds [5-7]. Generally, the most importantadvantage of photo-Fenton process is easier handlingtechnologies without complex experimental apparatus.The most important reason that the photo-Fentonprocess can be effectively used in wastewater treatmentis the synergistic effect by the coupled Fenton’s reagentand UV illumination. Eq.1 shows the well-known Fentonreaction in solution. In this equation, Fe
2+
is rapidlytransferred to Fe
3+
and produce
OH. Recent reportsindicate that the acceleration for decomposition oforganic compounds is believed to be in order tophotolysis of iron aqua complex, Fe(H
2
O)
5
(OH)
2+
 (represented hereafter by Fe(OH)
2+
), to providing a newimportance source of
OH. Further, the photolysis ofFe(OH)
2+
regenerates Fe
2+
(Eqs.2 and 3), which meansthat the photo-Fenton reaction would need low Fe
2+
 concentration compared with the Fenton process [8].This UV illumination isolated Fe
2+
can react subsequentlywith H
2
O
2
and produce
OH again (Eq. 1), and then acyclic mechanism is established [9-12]. In addition, H
2
O
2
 can be isolated to two OH radicals by UV irradiation [13];therefore, a photo-Fenton process has been proven as aprofitable method for destroying and oxidizing therefractory compounds.Fe
2+
+ H
2
O
2
Fe
3+
+
OH + OH
-
(1)Fe
2+
+ H
2
O
2
Fe (OH)
2+
+
OH (2)Fe (OH)
2+
+
 
Fe
2+
+
OH (3)* Decolorization of Rhodamine B by a photo-Fenton
 
International Journal of Environment and ResourceVol. 1 Iss. 2, November 2012
 
74
 
Rhodamine B is a typical fluorescent dye used as anion-association reagent in solvent extraction photometryof anionic species and frequently used as fluorescencestandard for absolute fluorescence quantum yield. It isalso used extensively in biotechnology applications suchas fluorescence microscopy, flow cytometry andfluorescence correlation spectroscopy. This cationic dyewith an acid side chain, a well-known stable andnon-volatile dye, has comparatively high resistance tophoto and oxidation degradation. It is understood thatthe Rhodamine B will permeate into the human skin andcause the toxicity to human beings. Hence, if highconcentration Rhodamine B presents in wastewater, aprofitable degradation process is necessary to reduce theharmful effect to environment and human beings, basedon the possible carcinogenic and toxicity of dyeingwastewater. Many researchers have tried to investigatethe behaviors of Rhodamine B [14] and removal of thisdye by activated carbon [15], ultrasound [16],visible-light with Nano-sized Bi
2
WO
6
[17], graphitetailing/H
2
O
2
[18], fly ash sorption with Fentonpre-oxidation [19] and Fenton-like oxidation [20].Besides the above methods, the UV illumination coupledwith H
2
O
2
[21], microwave [22], TiO
2
[23,24], ZnO [25],Fe-carbonnanotubes on TiO
2
[26], Fe
0
-based Fenton [27]have also been carried out in these years to remove theRhodamine B from aqueous phase.In this study, a low-energy cost UV light carried out withapplicable additions of chemicals such as Fe
2+
and H
2
O
2
are considered in this study for the treatment ofRhodamine B wastewater. The objectives of this studyare to investigate the effect of reaction parameters suchas Fe
2+
and H
2
O
2
dosages, pH and temperature on thedecolorization of Rhodamine B dyeing wastewater andto investigate the Rhodamine B decolorization reactionkinetics by the pseudo first-order model in photo-Fentonsystem to find out the better reaction conditions.
Materials and Methods
 Materials
Rhodamine B (purity > 89%, molecular weight =1,017.65) was obtained from Sigma–Aldrich and themolecular structure of this dye has been shown [18, 19].The chemical reagents used in this study also includedferrous sulfate (FeSO
4
7H
2
O, purity > 99.5%, Merck)and an aqueous solution of hydrogen peroxide (H
2
O
2
 ,30% w/w in water, FERAK). These chemicals were thepurest grade commercially available and were usedwithout further purification. The stock Rhodamine Bsolution with 1,000 mg/L was prepared by dissolvingthe Rhodamine B powder in distilled and deionizedwater then stored in brown bottle at 4
o
 Maintaining the Integrity of the Specifications
C.A schematic drawing of the reactor is shown in Figure 1.A 1.6 L double-walled Pyrex glass reactor (workingvolume = 1 L) equipped with pH meter and oxidationreduction potential (ORP) meter (Suntex PC-3200,Taiwan) was with made for the experimental work. Atemperature controller was used to maintain thereaction temperature in certain levels. Complete mixingof solution was achieved by a magnetic mixer with 100rpm. Two 8-Watts monochromatic UV lamps of 312 nm(with emission range between 280 nm and 360 nm)were placed axially in the reactor and kept in place witha quartz sleeve; the UV intensity of each 8 Watts UVlamp was 60
W cm
-2
. The value of the initial pH in allexperiments including 3, 4, 5.5 and 7 were attained byadding 1N H
2
SO
4
or NaOH as required without any buffer solution. During the reactions, the pH valuesvaried freely without any hand correction. TheRhodamine B concentration was initiated at 20 mg/L. The UV lamp was warmed up for 30 minutes and thereactor was loaded with 1,000 mL Rhodamine Bsolution and designed dosages of Fe
2+
(0, 4, 8 and 12mg/L) and H
2
O
2
(30, 60 and 90 mg/L) then mixedthoroughly to mark the start point of the experiment.The temperature was maintained at 15, 20, 30, 40 and50
o
 
C, respectively, during the reaction. Reaction setswere sampled periodically (0, 2, 5, 10, 20, 30, 45 and 60minutes) for analyses.
FIGURE 1
 
SCHEMATIC DIAGRAM OF THE EXPERIMENTALAPPARATUS DESIGNED FOR RHODAMINE B DECOLORIZATION
 
International Journal of Environment and ResourceVol. 1 Iss. 2, November 2012
 
75
 
 Analytic methods
The profiles of pH and ORP values were measured andrecorded by pH and ORP meters. Rhodamine B in thesamples was filtrated (0.45
µ
m) and analyzed by thespectrophotometer (UV-2102, Unico TM, USA)equipped with quartz cell at the wave length of 550 nm,where the absorption at the wavelength of 550 nm wasnamed as A
550
. The American Dye Manufacture Index(ADMI) was determined by measuring thetransmittance at 590, 540 and 438 nm; the transmittancewas converted to Tristimulus Value and Munsell Valuesto obtain the ADMI of the wastewater sample. Thedesigned H
2
O
2
Results and Discussion
concentration was measured by KItitration method.
Decolorization of Rhodamine B
In this study, the profiles of pH and ORP values duringthe decolorization of Rhodamine B were measured in allexperiments. In Figure 2, the experiments were carriedout at Rhodamine B concentration of 20 mg/L, pH 5.5,temperature of 20
o
C, H
2
O
2
of 30 mg/L and Fe
2+
of 0, 4, 8,12 mg/L, respectively. Experimental results indicate thatthe pH values are decreased from 5.5 (before reaction) to3.9 and 3.6 (after 60 mins reaction) at Fe
2+
concentrationsof 4 mg/L and 12 mg/L, respectively, and the differenceof final pH values among different Fe
2+
concentrationsare insignificant (data were not shown). As it is observed,the initial ORP values of those experiments is 210 mVand then apparent increases when the H
2
O
2
and Fe
2+
aredosing and a slight increase with H
2
O
2
dosing only. Ascan be seen, the maximum ORP values around 529.8 –574.8 mV are taking place at the reaction time of 2 minswith Fe
2+
of 4 – 12 mg/L addition and a progressivedecrease is appreciated with reaction time. As theexperiment was carried out without Fe
2+
 , the ORP valuesgenerally increased and kept constant after the reactiontime of 20 mins. The differences of ORP values amongthe experiments with and without Fe
2+
were in the rangeof 161.7 – 187.4 mV (reaction time of 60 mins), where thehigher ORP values could be explained by the reaction between Fe
2+
and H
2
O
2
A synergistic effect of UV irradiation and Fenton’sreagent on the decolorization of Rhodamine B can beobserved in Figure 3. This figure shows the results ofRhodamine B decolorization efficiency, based on the , named as the Fenton reaction.
0100200300400500600700020406080
   O   R   P   (  m   V   )
Time (min)
Fe2+ (0 mg/L)Fe2+ (4 mg/L)Fe2+ (8 mg/L)Fe2+ (12 mg/L)
 
FIGURE 2 ORP PROFILES IN RHODAMINE B DECOLORIZATIONBY PHOTO-FENTON PROCESS (H
2
O
2
analysis of A
30 MG/L)
550
 , by photo-Fenton process. Decolorizationefficiency was less than 5% without Fe
2+
dosage, whichindicated that the Rhodamine B was difficultlydecomposed or decolorized by the UV/H
2
O
2
process. Asthe Fe
2+
dosages increased to 4 mg/L, A
550
wasremarkably decreased from 2.094 to 0.983 with 10 minsreaction and continuously decreased to 0.784 and 0.563within 20 and 60 mins reaction, where the maximumdecolorization efficiency was 73.2%. When the Fe
2+
 increased to 8 and 12 mg/L, decolorization
efficiencieswere as high as 79.3% and 67.4%, respectively. Thisindicates that a synergetic effect between Fenton’sreagent and UV light takes place in thedecolorization system so that the Rhodamine B wassignificantly decolorized. However, it was alsofound in Figure 3 that the decolorization efficiencyat Fe
2+
of 12 mg/L was slightly lower than those of 4and 8 mg/L. This phenomenon indicates thatadditional Fe
2+
dosages can’t provide sufficientoxidation potential in photo-Fenton system. As aresult of iron photo-redox reaction and formation ofhydroxyl radicals proposed by [28], the2,4-dichlorophenol (DCP) elimination increased byincreasing the initial Fe
2+
concentration up to 45mg/L, and, at the concentrations of Fe
2+
higher than45 mg/L, the DCP degradation efficiency decreased.Katsumata [8] found that the percent decrease ofabsorbance for humic acids (HA) in UV light at 254 nmand visible light at 400 nm rapidly increased withincreasing initial Fe
2+
concentration up to 1×10
5
mol/L. Asmall amount of brown condensate of iron and HA was

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