Research Article Degradation of Anthraquinone Dye Reactive...

Research ArticleDegradation of Anthraquinone Dye Reactive Blue 4 inPyrite Ash Catalyzed Fenton Reaction

Milena Becelic-Tomin1 Bozo Dalmacija1 Ljiljana Rajic1 Dragana Tomasevic1

Djurdja Kerkez1 Malcolm Watson1 and Miljana Prica2

1 Department of Chemistry Biochemistry and Environmental Protection Faculty of Sciences University of Novi SadTrg Dositeja Obradovica 3 21000 Novi Sad Serbia

2 Faculty of Technical Sciences University of Novi Sad Trg Dositeja Obradovica 6 21000 Novi Sad Serbia

Correspondence should be addressed to Milena Becelic-Tomin milenabecelic-tomindhunsacrs

Received 17 September 2013 Accepted 10 December 2013 Published 9 January 2014

Academic Editors F Marquez-Linares A F Mohedano and F Oktar

Copyright copy 2014 Milena Becelic-Tomin et al This is an open access article distributed under the Creative Commons AttributionLicense which permits unrestricted use distribution and reproduction in any medium provided the original work is properlycited

Pyrite ash (PA) is created by burning pyrite in the chemical production of sulphuric acid The high concentration of iron oxidemostly hematite present in pyrite ash gives the basis for its application as a source of catalytic iron in a modified Fenton processfor anthraquinone dye reactive blue 4 (RB4) degradation The effect of various operating variables such as catalyst and oxidantconcentration initial pH and RB4 concentration on the abatement of total organic carbon and dye has been assessed in this studyHere we show that degradation of RB4 in the modified Fenton reaction was efficient under the following conditions pH = 25[PA]0= 02 g Lminus1 [H

2O2]0= 5mM and initial RB4 concentration up to 100mg Lminus1 The pyrite ash Fenton reaction can overcome

limitations observed from the classic Fenton reaction such as the early termination of the Fenton reaction Metal (Pb Zn and Cu)content of the solution after the process suggests that an additional treatment step is necessary to remove the remaining metalsfrom the water These results provide basic knowledge to better understand the modified heterogeneous Fenton process and applythe PA Fenton reaction for the treatment of wastewaters which contains anthraquinone dyes

1 Introduction

Pyrite is one of the most abundant sulphide minerals on theEarth containing high content of iron [1] and has been widelyused in modern industry for the production of sulphuricacid The hematite-rich waste known as roasted pyrite ashor pyrite ash is left as residue after the following processes inthe production of sulphuric acid roasting for the pyrite con-centrate cooling of the gases in the pot and purifying withdry electronic purifiers and cyclones [2] This waste could beused in the environmentally safe manner as an iron ore inthe steel brick paint and cement industries [3] However theiron oxide-rich residue contains significant concentrations ofpotentially polluting elements (eg Cu S Zn Pb and As)which can be very mobile under environmental conditionsreducing its applicability [2 4] In Serbia sulphuric acid isdominantly made by pyrite processing In the last couple ofyears Serbia has disposed of 300ndash500000 tons of pyrite ash

in neglected landfills (httpwwwekoplangovrs) Howeverthe landfillrsquos capacity is limited and were the waste contam-inated it could represent a serious threat to groundwaterssoils and settlements

Textile manufacturing is one of the largest industrialproducers of wastewaters which are characterized by strongcolour highly fluctuating pH high chemical oxygen demand(COD) and biotoxicity Reactive dyes are frequently usedfor dyeing cotton wool and polyamide fibres Under typicalreactive dyeing conditions not all dyes bind to the fabricdepending on the class of dye up to 50 of the initial dyeremains in the spent dye bath in its hydrolyzed form whichhas no affinity for the fabric and results in a coloured effluentReactive dyes are known to be nondegradable under the typi-cal aerobic conditions found in conventional biological treat-ment systems and adsorb very poorly biological solids result-ing in residual colour in discharged effluents [5] Althoughazo dyes represent about 60 of all reactive dyes used by

Hindawi Publishing Corporatione Scientific World JournalVolume 2014 Article ID 234654 8 pageshttpdxdoiorg1011552014234654

2 The Scientific World Journal

the textile industry other classes of reactive dyes namelyanthraquinone and phthalocyanine dyes are also extensivelyused either as primary or secondary dyes in commercialtrichromatic dyeing formulations [6 7] However in sharpcontrast to the considerable research that has been conductedon the biotransformation and decolourization of azo dyeslimited information exists on the reductive transformationof both anthraquinone and phthalocyanine reactive dyesIn particular detailed information is lacking with regard tothe behaviour of aqueous reactive anthraquinone dyes aswell as the application of advanced analyticalinstrumentaltechniques for the identification and quantification ofthe parent compounds as well as the dye transformationproducts

To eliminate dyes from aqueous coloured effluents andreduce their ecological consequences several biological andchemical techniques have been proposed (adsorption coag-ulation and biological treatments) Traditional processesfor treatment of these effluents prove to be insufficientto clean up the important quantity of wastewaters afterdifferent operations of textile dyeing and washing [8] Inrecent years promising results have been achieved in thetreatment of textile wastewaters using advanced oxidationprocesses (AOPs) [5 9ndash12] A variety of AOPs are based onozonolysis UVVis photocatalysis and the Fenton reaction [1]and include the formation and reactions of ∙OH radicals thatare much more reactive than all the other oxidizing speciesused in oxidative pollution abatement in drinking water andin wastewater [5 13] These highly reactive radicals promotethe destruction of the target pollutant until mineralization[14 15] The advantage of classic Fenton processes besideshaving a powerful oxidative capacity is that they neithertransfer pollutants from one phase to the other nor producemassive amounts of hazardous sludge [16] However theclassic Fenton reaction has a fatal limitation for remedialapplication due to the early termination of the degradationreaction by the rapid precipitation of iron hydroxide incircumneutral pH environments [16] The disposal of ferrichydroxide sludge requires additional unit operations [17 18]

Efforts to overcome the limitations of the classic Fen-ton reaction have been made by modifying the systemandor introducing novel alternative iron sources Numer-ous researchers [19ndash22] have shown that H

2O2can oxidize

organic pollutants in the presence of solid catalysts whichcontain iron In the literature these processes are knownas ldquomodified heterogeneous Fenton processesrdquo [23 24]Iron oxides have been put forward as potential promisingiron sources for the modified Fenton reaction to treat avariety of environmental contaminants in wastewater andgroundwater systems [25] However to date limited basicknowledge has been produced to characterize the pyrite ashin heterogeneous Fenton reaction for the development ofenhanced remediation technologies to treat environmentalcontaminants such as anthraquinone dyes

If waste materials such as pyrite ash can be used in themodified Fenton process as an alternative source of catalyticmaterial for anthraquinone dye degradation it would be atthe same time a cost-effective method for its disposal andminimise possible negative environmental effects originating

from either the pyrite ash or wastewaters through properengineering control

In view of the above the objectives of this study were(1) to evaluate the effectiveness of the oxidative degradationand mineralization of reactive anthraquinone dye reactiveblue 4 (RB4) in aqueous solutions using pyrite ash asa catalytic material in a modified heterogeneous Fentonprocess (2) to evaluate the influence of operative conditionson dye degradation (3) to evaluate the contribution from ahomogenous Fenton reaction to the overall heterogeneousFenton reaction (4) to determine the residual metal contentin the aqueous solution and (5) to evaluate the possibility ofmetal immobilization after the Fenton reaction

2 Materials and Methods

Commercial RB4 (CAS no 13324-20-4 EC no 236-363-6and pH 478) H

2O2(30wt) H

2SO4 and quicklime (99

CaO) were of obtained from Sigma-Aldrich All chemicalsused were analytical grade and used without further purifi-cation All solutions were prepared with deionised waterAll experiments were conducted at room temperature (25 plusmn05∘C) Figure 1 presents the structure of the dye investigated

The PA used in this work was left after the combustionof pyrite in the production of sulphuric acid in the ChemicalIndustry ldquoZorkardquo Sabac The chemical composition of thePA (wt gt 1) was determined by wavelength dispersive X-ray fluorescence spectrometry (S8 Tiger Bruker Germany)hematite 7974 quartz 909 magnetite 508 calcite and136 plagioclase 121 PAwaswashed three times in doubledistilled water prior to conducting the experiment and wasdried for an hour at 105∘CThe PA digestion for assessing themetals concentrations was conducted in a Milestone Start E(Milestone Germany) microwave oven [26] Mean values ofmetals were used 9138 plusmn 52mg kgminus1 (Zn) 1062 plusmn 58mgkgminus1 (Cr) 5728 plusmn 33mg kgminus1 (As) 2130 plusmn 154mg kgminus1(Pb) 5227 plusmn 345mg kgminus1 (Fe) 1492 plusmn 110mg kgminus1 (Cu) and189 plusmn 08mg kgminus1 (Cd) The relative standard deviations (RSD) obtained (119899 = 3) were below 10

The metals content in the PA was determined by atomicabsorption spectrophotometer (AAS) Perkin Elmer Analyst700 using standard methods [27 28]

The experiments were conducted on a jar test apparatus(FC6S Velp Scientifica Italy) where reactive mixtures with025 L volumes were continuallymixed in 1 L laboratory cupsat 150 rpmThe experiments were performed in the followingmanner firstly the appropriate PA dosage (005ndash05 g Lminus1)was added to the model dye solution (RB4 concentrationfrom 50 to 250mg Lminus1) which was followed by pH adjust-ment to the desired value (25ndash4) and the addition of therequired amount of H

2O2(10ndash25mM) Each experiment

lasted 30min Samples were centrifuged at 12000 rpm for5min to remove solid particles The aliquots were subse-quently filtered through a 045 120583m pore size membrane filterand immediately analyzed thereafter

Decolourization of the synthetic dye solution was mon-itored by absorbance (119860) at 120582max = 59478 nm (UVVISspectrophotometer Shimadzu Japan) Total organic carbon

The Scientific World Journal 3

O

O

O

O

O

O

OH

OH

HN HN

NN

N

Cl

Cl

S

S

NH2

Figure 1 Structure of RB4 dye

(TOC) concentrations were determined by Elementar LiquiTOCII analyzer Germany The pH was measured by pH-meter inoLap pHION 735 (WtW GmbH Germany)

The efficiency of dye decolourization and oxidation wasobtained by the application of the following formulas

100 (

1198600minus 119860

1198600

) = dye removal ()

100 (TOC0minus TOC) = TOC removal ()

(1)

where 119860 and TOC values were received after a certainreaction time and 119860

0and TOC

0are the initial absorbance

and total organic carbon levelsAn additional experiment was carried out to check the

possibility of the contribution from a homogenous Fentonreaction caused by the dissolution of iron from the PA cata-lyst In this procedure the samedye solutionRB4 (100mg Lminus1)used in previous experiments was kept in contact with thesame PA catalyst (02 g Lminus1) at pH 25 for 30 minutes Thesample was filtered through a 045120583m pore size membranefilter and the (5mM H

2O2) solution was added for an

additional 30 minutes of reaction time After the reactiontime the sample was filtered through a 045120583m pore sizemembrane filter and analyzed for absorbance and TOC

3 Results and Discussion

31 Effects of Operational Parameters on Process EfficiencyThe effects of various experimental parameters (solution pHinitial concentration of H

2O2 catalyst (PA) and dye RB4

concentration) are presented in Figure 2The classic Fenton process has a typically sharp preferred

pH region in which it is optimally operated pH affects theactivity of both the oxidant and the substrate the speciationof iron and hydrogen peroxide decomposition [29] In thisstudy the pH effect on the efficiency of solution decolour-ization was analyzed in the pH range of 25ndash4 The initialconcentration of RB4 was 100mg Lminus1 H

2O25mM and PA

02 g Lminus1 The maximum colour (999) and TOC (743)removal were obtained at pH 25 (Figure 2(a)) This suggeststhat the PAFenton reaction also needs the acidic environment(for decolourization efficacy above 90) required for theproper operation of the classic Fenton system [16] to effec-tively form ∙OH and avoid the precipitation of Fe(OH)3

(s)

Process efficacy dropped with the further increase of thepH values These results are in accordance with some otherstudies [7 30 31] It should be noted that at initial pH valuesas high as 3 to 4 about 60ndash70 RB4 decolourization is stillobtained within the reaction time which is an improvementover conventional Fenton process [7 31] Nevertheless thesolubility of the total iron drops with increasing initial pHThe heterogeneous Fenton process with pyrite ash involvesa complex series of reactions on the surface of the catalystproducing ∙OH and ∙OH

2radicals (reactions 3ndash6) [25 31 32]

Fe3+ +H2O2997888rarr Fe3+ +OHminus +HO

2

∙+H+ (2)

Fe2+ +H2O2997888rarr Fe3+ +OHminus +HO∙ (3)

HO2

∙997888rarr H+ +O

2

∙minus (4)

Fe3+ +HO2

∙997888rarr Fe2+ +H+ +O

2(5)

Pham et al [33] have also suggested similar mechanisms-including adaptations to the heterogeneous Fenton reactioncondition steps based on the original Haber-Weiss mech-anism In those studies the bottom line is aqueous H

2O2

on the surface of hematite decomposes to H2O + O

2 This

may either initiate via a true surface catalytic path thegeneration of intermediate ∙OH or ∙OH

2free radicals or as

we will discuss below a noncatalytic nonradical redox routeby which solid Fe

2O3may actually release Fe ions to the

solution via a reductive step that leads to aqueous Fe2+ (+O2)

The released aqueous Fe2+ together with remaining H2O2

in the solution could then fuel a continuing conventionalhomogeneous Fenton reaction step [25] which can possiblyextend the durability of the Fenton process [1 13 23 25]

After 30min of reaction the concentration of iron atinitial pH values of 25 and pH 4 was 988mg Lminus1 and3mg Lminus1 respectively These results indicate a significanteffect of pH on the leaching of iron which is supposedto greatly affect the efficiency of the applied process [25]The increase in oxidation rate at low pH was attributed tothe enhanced solubility of iron (III) species at acidic pHpromoting the homogeneous Fenton reaction Fe(III) canalso be solubilised by forming complexes with organic acidintermediates produced during pollutant degradation [34ndash36] According to [31] who used the hematite mineral forthe decolourization of a reactive dye the inhibition of irondissolution can be assigned to the presence of dye moleculeswhich interfere with the interface between the materialsurface and the aqueous phase

Colour and TOC removals are enhanced with increasingH2O2dosage until reaching the optimum dosage since it is

the source of ∙OH radicals produced in the Fenton processFigure 2(b) shows the dependency of RB4 degradationefficiency on the initial concentration of H

2O2 A high

decolourization efficiency 995 is already achieved with aninitial concentration of 4mM H

2O2 Further increasing the

oxidant concentration did not result in a significant effect onthe decolourization process The maximum colour removalwas obtained at the initial concentration of 5mM H

2O2

TOC removal was improved from 382 to 743 by increasingH2O2dose from 1 to 5mM With H

2O2concentrations


20 25 30 35 40 4510

20

30

40

50

60

70

80

90

100

110

pH

Rem

oval

()

2

3

4

5

6

7

8

9

10

11

Iron

(mg

L)

(a)

0 2 4 6 8 10 12 14 16 18 20 22 24 26

40

50

60

70

80

90

100

H2O2 (mM)

Rem

oval

()

70

75

80

85

90

95

100

Iron

(mg

L)

(b)

00 01 02 03 04 05 0620

30

40

50

60

70

80

90

100

110

PA (gL)

Rem

oval

()

5

6

7

8

9

10

Iron

(mg

L)

ColorTOCIron total

(c)

50 100 150 200 2500

10

20

30

40

50

60

70

80

90

100

110

RB4 (mgL)

Rem

oval

()

5

6

7

8

9

10

11

Iron

(mg

L)

ColorTOCIron total

(d)

Figure 2 Effects of operational parameters on process efficiency and iron leaching (a) pH (b) H2O2concentration (c) PA concentration

(d) RB4 concentration

higher than 5mM less mineralization was observed Byfollowing the iron concentration in the solution after thereaction a mild increase of this metalrsquos content was notedalong with the increase in the initial concentration of H

2O2

Bearing in mind the almost unchanged iron content in allthe applied concentrations of H

2O2 it can be concluded that

concentrations higher than 5mMH2O2triggered the radical

scavenging effect in the solution Namely at higher dosagesH2O2molecules could trap ∙OH thus forming less reactive

perhydroxyl radicals (ie H2O2+

∙OH rarr ∙OH2+H2O) and

lowering the efficiency of the degradation process [7 37 38]The effect of PA concentration on the efficiency of the pro-

cess was analyzed within the 005ndash05 g Lminus1 range under thefollowing conditions [H

2O2]0= 5mM [RB4]

0= 100mg Lminus1

and pH25 (Figure 2(c))The Increasing themass of PA addedmass from 005 to 01 g brought a significant improvement inthe decolourization efficiency It is assumed that the reason

for this is the increase of iron content in the Fenton processThis is consistent with literature data [1 23] Any furtherPA concentration increase did not affect the percentage ofremoved dye in the solution The maximum decolourizationefficiency was achieved with a PA concentration of 02 g Lminus1In mineralization occurrences adding greater PA amountsthan 02 g Lminus1 into the solution resulted in a decrease in TOCremovals Some authors [39 40] explained this phenomenonby naming it a consequence of iron complex formation andsome unwanted reactions between iron and other types offormed radicals

The effect of the initial concentration of RB4 on thedecolourization and mineralization was investigated at 50100 200 and 250mg Lminus1 RB4 (Figure 2(d)) Generallyincreasing the dye concentration to values above 100mg Lminus1decreased the dye degradation effect Namely the increaseof the dye concentration leads to an increase in the dye


molecules in the solution with the same number of ∙OHwhich has such an effect as a consequence With the ini-tial RB4 concentration of 250mg Lminus1 process has provedcompletely inefficient This is accordance with literature data[8 40] In heterogeneous Fenton process the reaction occursat the catalytic surface between ∙OH radicals generated at theactive sites and RB4molecules adsorbed on the surfaceThuswhen the RB4 concentration is too high the number of activesites available is decreased by the RB4 molecules due to theircompetitive adsorption on the catalytic surface In additionthe intermediates product of RB4 oxidation might alsocompete for the limited adsorption sites with RB4 moleculeswhich blocked their interactions with Fe(II)Fe(III) activesites [8 30]

The analysis of leached iron dependency on the RB4 dyesolution concentration at the end of contact time showed thatthe iron content in the solution with initial RB4 200 and250mg Lminus1 was about 55mg Lminus1 and at the same time waslower than the iron content in the dye solution with initialconcentration 100mg Lminus1 The assumption is that the smalleriron content in the solution contributed to the decreasedefficiency of the process in solutions of concentrations higherthan 100mg Lminus1 [1 16 23]

It can be concluded that the following reaction conditionsgive satisfying colour andTOC removal efficiencies in the dyesolution with initial concentration up to 100mgL pH = 25[PA]0= 02 gLminus1 [H

2O2]0= 5mM

In order to evaluate the contribution of the homogenousreaction during the overall heterogeneous Fenton reaction afurther experiment was carried out using only the aqueousiron ions produced by PA dissolution at pH 25 as the catalystThis experiment showed that the homogenous Fenton reac-tion resulted in 85 colour removal and 72 TOC removalrespectively This indicates that most RB4 was degraded by∙OH produced from dissolved Fe(II) and not by the surfacecatalyzed process [23] This leads to the conclusion thatthe role of soluble leached iron from PA is significant indecolourization of RB4

Thus at this point of the discussion it may be consideredthat the heterogeneous Fenton process is likely to start on thehematite surface by either [25 31 32] (a) catalytic decompo-sition of adsorbed H

2O2leading to adsorbed ∙HO and ∙HO

2

which either still on the surface or just after desorption willattack nearby (adsorbed or not) dye molecules as proposedby reactions (2) to (5) or (b) as proposed in the presentwork with the reduction and release of surface Fe3+ as Fe2+into the solution in which H

2O2plays the role of reductant

Once in solution Fe2+ will react with the remaining H2O2 as

in the conventional homogeneous Fenton reaction inducingdegradation of the dye molecules Although not specificallydemonstrated in previous works this hypothesis supportsthe findings of previous authors [25 41 42] who suggestedthat the heterogeneous Fenton reaction mechanism merelystarts on the surface and continues mainly in the bulk of theaqueous solution as a homogeneous Fenton reaction In thosecases where leaching takes place overall catalytic activity isa combination of the two types of activities activity of solidcatalysts and activity of dissolved leached iron and in further

studies it will be necessary to determine the contribution ofthese two parameters in the experimental activities

32 Solubilisation Rates of Other Metals during the FentonReaction Figure 3 shows solubilisation rates ofmetals duringthe reaction time

The greatest initial metals leaching rates were determinedfor Pb Cu and Zn This phenomenon can have a positiveeffect as transition metals (Cu and Zn) being heterogeneouscatalysts can contribute to the efficiency of the Fentonprocess [43] Regardless applying the PA under optimalconditions for RB4 degradation was satisfactory but themetals content of the solution namely iron after the processsuggests that an additional treatment step is necessary inorder to remove the residual metals from the water Amongthe principal technologies used and proposed for the removalof potential toxic matters from effluents precipitation is themost widely used approach for the removal of metals fromindustrial effluents [44 45] Heavy metals like Cr Cu PbMn and Zn do not precipitate below pH 70 allowing theirseparation from ferric and aluminium ions which precipitateat pH below 65 [46 47]

Lime was added to the aqueous solution after the Fentonprocess until pH 9 was reached This pH value representsthe limit pH value for wastewaters from factories and instal-lations for processing and manufacturing textile defined bynational law [48] At the same time this value is close to thepH range 95ndash100 which according to [49] presents the pHrange of minimal solubility of the hydroxides for themajorityof metals The metal concentrations in the aquatic solutionsafter the Fenton process and lime addition are presented inFigure 4 The addition of lime in the water solution afterthe Fenton process contributed to significant reduction inthe metals content The percentage of metal removal fromsolution ranged from 78 to 995 while Pb and Ni were notdetected

4 Conclusion

PA has been proved to be a superior catalyst for decolour-ization of RB4 in a modified Fenton process The bestoperation parameters for the modified Fenton oxidation are02 g Lminus1 of catalyst (PA) and 5mM of H

2O2 for an initial

RB4 concentration of 100mg Lminus1 at pH 25 Under theseconditions 999 decolourization and 743 mineralizationof RB4 in aqueous solution were achieved within a 30minreaction time

RB4 dye degradation was satisfactory but the metalcontent of the solution after the process suggests that an addi-tional treatment step is necessary to remove the remainingmetals from thewater One possible solution is the addition oflime up to pH 9 leading to metal immobilization by forminglow solubility hydroxides On the other hand lime could alsobe used as a potential stabilizing agent for the PA remainingafter application of the Fenton process

Due to the large volumes of PA generated it is necessaryto continue rising environmental awareness of differentapplications for this waste while taking into account the


0 5 10 15 20 25 30

000102030405060708091011121314

Zn

NiPbCrCu

As

Time (min)

Met

al co

ncen

trat

ion

(mg

L)

Figure 3 Leaching metals from PA during the reaction (pH = 25[PA]0= 02 gLminus1 [H

2O2]0= 5mM [RB4] = 100mgL)

Cr Fe Cu Zn Cd As000

002

004

006

008

010

Con

cent

ratio

n (m

gL)

Metals

Figure 4 Metal concentrations after lime addition

environmental and economic factors of these waste treat-ments Conventional waste management methods whichmight have been acceptable in the past might not be optimalto meet present and future requirements PA utilisation toldquocatalyserdquo a modified Fenton process could be an interestingapproach while taking into account a final treatment formetals in the Fenton process solution and solid residue

These results provide basic knowledge to better under-stand the modified heterogeneous Fenton process and applythe PA Fenton reaction for the treatment of wastewaterscharacterized by high levels of anthraquinone dyes

Conflict of Interests

The authors declare that there is no conflict of interestsregarding the publication of this paper

Acknowledgment

This research was financed by the Ministry of Science andTechnological Development of Republic of Serbia (ProjectIII43005 and TR37004)

References

[1] H Che S Bae and W Lee ldquoDegradation of trichloroethyleneby Fenton reaction in pyrite suspensionrdquo Journal of HazardousMaterials vol 185 no 2-3 pp 1355ndash1361 2011

[2] C Yang Y Chen P Peng C Li X Chang and Y Wu ldquoTraceelement transformations and partitioning during the roasting ofpyrite ores in the sulfuric acid industryrdquo Journal of HazardousMaterials vol 167 no 1ndash3 pp 835ndash845 2009

[3] R Perez-Lopez R Saez A M Alvarez-Valero J M Nieto andG Pace ldquoCombination of sequential chemical extraction andmodelling of dam-break wave propagation to aid assessment ofrisk related to the possible collapse of a roasted sulphide tailingsdamrdquo Science of the Total Environment vol 407 no 21 pp 5761ndash5771 2009

[4] M L S Oliveiraa C R Ward M Izquierdo et al ldquoChemicalcomposition and minerals in pyrite ash of an abandoned sul-phuric acid production plantrdquo Science ofThe Total Environmentvol 430 pp 34ndash47 2012

[5] B Gozmen B Kayan A M Gizir and A Hesenov ldquoOxidativedegradations of reactive blue 4 dye by different advancedoxidation methodsrdquo Journal of Hazardous Materials vol 168no 1 pp 129ndash136 2009

[6] W J Epolito Y H Lee L A Bottomley and S G PavlostathisldquoCharacterization of the textile anthraquinone dye ReactiveBlue 4rdquo Dyes and Pigments vol 67 no 1 pp 35ndash46 2005

[7] H Hassan and B H Hameed ldquoFe-clay as effective heteroge-neous Fenton catalyst for the decolorization of Reactive Blue 4rdquoChemical Engineering Journal vol 171 no 3 pp 912ndash918 2011

[8] A Lahkimi M A Oturan N Oturan and M ChaouchldquoRemoval of textile dyes from water by the electro-Fentonprocessrdquo Environmental Chemistry Letters vol 5 no 1 pp 35ndash39 2007

[9] I Arslan-Alaton B H Gursoy and J-E Schmidt ldquoAdvancedoxidation of acid and reactive dyes effect of Fenton treatmenton aerobic anoxic and anaerobic processesrdquoDyes and Pigmentsvol 78 no 2 pp 117ndash130 2008

[10] W A Sadik ldquoEffect of inorganic oxidants in photodecolouriza-tion of an azo dyerdquo Journal of Photochemistry and PhotobiologyA vol 191 no 2-3 pp 132ndash137 2007

[11] SHammamiNOturanN BellakhalMDachraoui andMAOturan ldquoOxidative degradation of direct orange 61 by electro-Fenton process using a carbon felt electrode application of theexperimental design methodologyrdquo Journal of ElectroanalyticalChemistry vol 610 no 1 pp 75ndash84 2007

[12] L Fu S-J You G-Q Zhang F-L Yang and X-H FangldquoDegradation of azo dyes using in-situ Fenton reaction incor-porated into H

2O2-producing microbial fuel cellrdquo Chemical

Engineering Journal vol 160 no 1 pp 164ndash169 2010[13] C Von Sonntag ldquoAdvanced oxidation processes mechanistic

aspectsrdquoWater Science and Technology vol 58 no 5 pp 1015ndash1021 2008

[14] A Karimi M Aghbolaghy A Khataee and S S Bargh ldquoUse ofenzymatic bio-Fenton as a new approach in decolorization ofmalachite greenrdquoThe Scientific World Journal vol 2012 ArticleID 691569 5 pages 2012

[15] MAhmadian S ReshadatN Yousefi et al ldquoMunicipal leachatetreatment by Fenton process effect of some variable andkineticsrdquo Journal of Environmental and Public Health vol 2013Article ID 169682 6 pages 2013


[16] H Che andW Lee ldquoSelective redox degradation of chlorinatedaliphatic compounds by Fenton reaction in pyrite suspensionrdquoChemosphere vol 82 no 8 pp 1103ndash1108 2011

[17] S Chou Y-H Huang S-N Lee G-H Huang and C HuangldquoTreatment of high strength hexamine-containing wastewaterby electro-Fenton methodrdquo Water Research vol 33 no 3 pp751ndash759 1999

[18] G Sekaran S Karthikeyan K Ramani B Ravindran AGnanamani and A B Mandal ldquoHeterogeneous Fenton oxida-tion of dissolved organics in salt-laden wastewater from leatherindustry without sludge productionrdquo Environmental ChemistryLetters vol 9 no 4 pp 499ndash504 2011

[19] H Kusic A Loncaric Bozic N Koprivanac and S PapicldquoFenton type processes for minimization of organic content incoloured wastewaters Part II combination with zeolitesrdquo Dyesand Pigments vol 74 no 2 pp 388ndash395 2007

[20] M B Kasiri H Aleboyeh and A Aleboyeh ldquoDegradation ofAcid Blue 74 using Fe-ZSM5 zeolite as a heterogeneous photo-Fenton catalystrdquo Applied Catalysis B vol 84 no 1-2 pp 9ndash152008

[21] M Dukkancı G Gunduz S Yılmaz Y C Yaman R VPrikhodrsquoko and I V Stolyarova ldquoCharacterization and catalyticactivity of CuFeZSM-5 catalysts for oxidative degradation ofRhodamine 6G in aqueous solutionsrdquo Applied Catalysis B vol95 no 3-4 pp 270ndash278 2010

[22] J Wu G Lin P Li W Yin X Wang and B Yang ldquoHeteroge-neous Fenton-like degradation of an azo dye reactive brilliantorange by the combination of activated carbon-FeOOH catalystandH

2O2rdquoWater Science and Technology vol 67 no 3 pp 572ndash

578 2013[23] S Bae D Kim andW Lee ldquoDegradation of diclofenac by pyrite

catalyzed Fenton oxidationrdquo Applied Catalysis B vol 134- 135pp 93ndash102 2013

[24] A Zhang N Wang J Zhou P Jiang and G Liu ldquoHeteroge-neous Fenton-like catalytic removal of p-nitrophenol in waterusing acid-activated fly ashrdquo Journal of Hazardous Materialsvol 201-202 pp 68ndash73 2012

[25] E G Garrido-Ramırez B K GTheng and M L Mora ldquoClaysand oxideminerals as catalysts and nanocatalysts in Fenton-likereactionsmdasha reviewrdquo Applied Clay Science vol 47 no 3-4 pp182ndash192 2010

[26] ldquoMicrowave assisted acid digestion of sediments sludges soilsand oilsrdquo USEPA Method 3051a Revision 1 2007

[27] ldquoFlame atomic absorption spectrophotometryrdquo USEPAMethod7000B Revision 2 2007

[28] ldquoGraphite Furnace Absorption Spectrophotometryrdquo USEPAMethod 7010 2007

[29] H Zhang H J Choi and C-P Huang ldquoOptimization ofFenton process for the treatment of landfill leachaterdquo Journal ofHazardous Materials vol 125 no 1ndash3 pp 166ndash174 2005

[30] A Chen XMa andH Sun ldquoDecolorization of KN-R catalyzedby Fe-containing Y and ZSM-5 zeolitesrdquo Journal of HazardousMaterials vol 156 no 1ndash3 pp 568ndash575 2008

[31] F V F Araujo L Yokoyama L A C Teixeira and J C CamposldquoHeterogeneous Fenton process using the mineral hematite forthe discolouration of a reactive dye solutionrdquo Brazilian Journalof Chemical Engineering vol 28 no 4 pp 605ndash616 2011

[32] W P Kwan and B M Voelker ldquoRates of hydroxyl radical gen-eration and organic compound oxidation in mineral-catalyzedfenton-like systemsrdquo Environmental Science and Technologyvol 37 no 6 pp 1150ndash1158 2003

[33] A L-T Pham C Lee F M Doyle and D L Sedlak ldquoA silica-supported iron oxide catalyst capable of activating hydrogenperoxide at neutral pH valuesrdquo Environmental Science andTechnology vol 43 no 23 pp 8930ndash8935 2009

[34] J Feng X Hu and P L Yue ldquoEffect of initial solution pH on thedegradation of Orange II using clay-based Fe nanocompositesas heterogeneous photo-Fenton catalystrdquo Water Research vol40 no 4 pp 641ndash646 2006

[35] C E Martınez and M B McBride ldquoAging of coprecipitated Cuin alumina changes in structural location chemical form andsolubilityrdquoGeochimica et Cosmochimica Acta vol 64 no 10 pp1729ndash1736 2000

[36] M Bobu A Yediler I Siminiceanu and S Schulte-HostedeldquoDegradation studies of ciprofloxacin on a pillared iron cata-lystrdquo Applied Catalysis B vol 83 no 1-2 pp 15ndash23 2008

[37] M A Behnajady N Modirshahla and F Ghanbary ldquoA kineticmodel for the decolorization of CI Acid Yellow 23 by Fentonprocessrdquo Journal of Hazardous Materials vol 148 no 1-2 pp98ndash102 2007

[38] J M Joseph H Destaillats H-M Hung and M R HoffmannldquoThe sonochemical degradation of azobenzene and related azodyes rate enhancements via Fentonrsquos reactionsrdquo The Journal ofPhysical Chemistry A vol 104 no 2 pp 301ndash307 2000

[39] J Carriazo E Guelou J Barrault J M Tatibouet R Molinaand S Moreno ldquoSynthesis of pillared clays containing Al AlndashFe or AlndashCendashFe from a bentonite characterization and catalyticactivityrdquo Catalysis Today vol 107-108 pp 126ndash132 2005

[40] J De Laat and T G Le ldquoEffects of chloride ions on theiron(III)-catalyzed decomposition of hydrogen peroxide andon the efficiency of the Fenton-like oxidation processrdquo AppliedCatalysis B vol 66 no 1-2 pp 137ndash146 2006

[41] A L Teel C R Warberg D A Atkinson and R J WattsldquoComparison of mineral and soluble iron Fentonrsquos catalysts forthe treatment of trichloroethylenerdquoWater Research vol 35 no4 pp 977ndash984 2001

[42] M-C Lu J-N Chen and H-H Huang ldquoRole of goethitedissolution in the oxidation of 2-chlorophenol with hydrogenperoxiderdquo Chemosphere vol 46 no 1 pp 131ndash136 2002

[43] K Pirkanniemi and M Sillanpaa ldquoHeterogeneous water phasecatalysis as an environmental application a reviewrdquo Chemo-sphere vol 48 no 10 pp 1047ndash1060 2002

[44] S A Mirbagheri and S N Hosseini ldquoPilot plant investigationon petrochemical wastewater treatment for the removal ofcopper and chromiumwith the objective of reuserdquoDesalinationvol 171 no 1 pp 85ndash93 2005

[45] B Levasseur J-F Blais and G Mercier ldquoStudy of the metalprecipitation from decontamination leachates of municipalwastes fly ash incineratorsrdquo Environmental Technology vol 26no 4 pp 421ndash431 2005

[46] M B McBride and C E Martınez ldquoCopper phytotoxicity in acontaminated soil remediation tests with adsorptive materialsrdquoEnvironmental Science and Technology vol 34 no 20 pp 4386ndash4391 2000

[47] G Lee J M Bigham and G Faure ldquoRemoval of trace metalsby coprecipitation with Fe Al and Mn from natural waterscontaminatedwith acidmine drainage in theDucktownMiningDistrict Tennesseerdquo Applied Geochemistry vol 17 no 5 pp569ndash581 2002

[48] Ministry of Energy Development and Environmental Pro-tection of Republic of Serbia ldquoRegulation on limit values ofpollutants inwater anddeadlines for their achievementrdquoOfficialGazette vol 67 pp 13ndash41 2011


[49] Q Chen Z Luo C Hills G Xue andM Tyrer ldquoPrecipitation ofheavymetals fromwastewater using simulated flue gas sequentadditions of fly ash lime and carbon dioxiderdquo Water Researchvol 43 no 10 pp 2605ndash2614 2009

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VLSI Design



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the textile industry other classes of reactive dyes namelyanthraquinone and phthalocyanine dyes are also extensivelyused either as primary or secondary dyes in commercialtrichromatic dyeing formulations [6 7] However in sharpcontrast to the considerable research that has been conductedon the biotransformation and decolourization of azo dyeslimited information exists on the reductive transformationof both anthraquinone and phthalocyanine reactive dyesIn particular detailed information is lacking with regard tothe behaviour of aqueous reactive anthraquinone dyes aswell as the application of advanced analyticalinstrumentaltechniques for the identification and quantification ofthe parent compounds as well as the dye transformationproducts

To eliminate dyes from aqueous coloured effluents andreduce their ecological consequences several biological andchemical techniques have been proposed (adsorption coag-ulation and biological treatments) Traditional processesfor treatment of these effluents prove to be insufficientto clean up the important quantity of wastewaters afterdifferent operations of textile dyeing and washing [8] Inrecent years promising results have been achieved in thetreatment of textile wastewaters using advanced oxidationprocesses (AOPs) [5 9ndash12] A variety of AOPs are based onozonolysis UVVis photocatalysis and the Fenton reaction [1]and include the formation and reactions of ∙OH radicals thatare much more reactive than all the other oxidizing speciesused in oxidative pollution abatement in drinking water andin wastewater [5 13] These highly reactive radicals promotethe destruction of the target pollutant until mineralization[14 15] The advantage of classic Fenton processes besideshaving a powerful oxidative capacity is that they neithertransfer pollutants from one phase to the other nor producemassive amounts of hazardous sludge [16] However theclassic Fenton reaction has a fatal limitation for remedialapplication due to the early termination of the degradationreaction by the rapid precipitation of iron hydroxide incircumneutral pH environments [16] The disposal of ferrichydroxide sludge requires additional unit operations [17 18]

Efforts to overcome the limitations of the classic Fen-ton reaction have been made by modifying the systemandor introducing novel alternative iron sources Numer-ous researchers [19ndash22] have shown that H

2O2can oxidize

organic pollutants in the presence of solid catalysts whichcontain iron In the literature these processes are knownas ldquomodified heterogeneous Fenton processesrdquo [23 24]Iron oxides have been put forward as potential promisingiron sources for the modified Fenton reaction to treat avariety of environmental contaminants in wastewater andgroundwater systems [25] However to date limited basicknowledge has been produced to characterize the pyrite ashin heterogeneous Fenton reaction for the development ofenhanced remediation technologies to treat environmentalcontaminants such as anthraquinone dyes

If waste materials such as pyrite ash can be used in themodified Fenton process as an alternative source of catalyticmaterial for anthraquinone dye degradation it would be atthe same time a cost-effective method for its disposal andminimise possible negative environmental effects originating

from either the pyrite ash or wastewaters through properengineering control

In view of the above the objectives of this study were(1) to evaluate the effectiveness of the oxidative degradationand mineralization of reactive anthraquinone dye reactiveblue 4 (RB4) in aqueous solutions using pyrite ash asa catalytic material in a modified heterogeneous Fentonprocess (2) to evaluate the influence of operative conditionson dye degradation (3) to evaluate the contribution from ahomogenous Fenton reaction to the overall heterogeneousFenton reaction (4) to determine the residual metal contentin the aqueous solution and (5) to evaluate the possibility ofmetal immobilization after the Fenton reaction

2 Materials and Methods

Commercial RB4 (CAS no 13324-20-4 EC no 236-363-6and pH 478) H

2O2(30wt) H

2SO4 and quicklime (99

CaO) were of obtained from Sigma-Aldrich All chemicalsused were analytical grade and used without further purifi-cation All solutions were prepared with deionised waterAll experiments were conducted at room temperature (25 plusmn05∘C) Figure 1 presents the structure of the dye investigated

The PA used in this work was left after the combustionof pyrite in the production of sulphuric acid in the ChemicalIndustry ldquoZorkardquo Sabac The chemical composition of thePA (wt gt 1) was determined by wavelength dispersive X-ray fluorescence spectrometry (S8 Tiger Bruker Germany)hematite 7974 quartz 909 magnetite 508 calcite and136 plagioclase 121 PAwaswashed three times in doubledistilled water prior to conducting the experiment and wasdried for an hour at 105∘CThe PA digestion for assessing themetals concentrations was conducted in a Milestone Start E(Milestone Germany) microwave oven [26] Mean values ofmetals were used 9138 plusmn 52mg kgminus1 (Zn) 1062 plusmn 58mgkgminus1 (Cr) 5728 plusmn 33mg kgminus1 (As) 2130 plusmn 154mg kgminus1(Pb) 5227 plusmn 345mg kgminus1 (Fe) 1492 plusmn 110mg kgminus1 (Cu) and189 plusmn 08mg kgminus1 (Cd) The relative standard deviations (RSD) obtained (119899 = 3) were below 10

The metals content in the PA was determined by atomicabsorption spectrophotometer (AAS) Perkin Elmer Analyst700 using standard methods [27 28]

The experiments were conducted on a jar test apparatus(FC6S Velp Scientifica Italy) where reactive mixtures with025 L volumes were continuallymixed in 1 L laboratory cupsat 150 rpmThe experiments were performed in the followingmanner firstly the appropriate PA dosage (005ndash05 g Lminus1)was added to the model dye solution (RB4 concentrationfrom 50 to 250mg Lminus1) which was followed by pH adjust-ment to the desired value (25ndash4) and the addition of therequired amount of H

2O2(10ndash25mM) Each experiment

lasted 30min Samples were centrifuged at 12000 rpm for5min to remove solid particles The aliquots were subse-quently filtered through a 045 120583m pore size membrane filterand immediately analyzed thereafter

Decolourization of the synthetic dye solution was mon-itored by absorbance (119860) at 120582max = 59478 nm (UVVISspectrophotometer Shimadzu Japan) Total organic carbon


O

O

O

O

O

O

OH

OH

HN HN

NN

N

Cl

Cl

S

S

NH2




100 (

1198600minus 119860

1198600

) = dye removal ()


(1)


0and TOC











2O25mM and PA


(s)




2

∙+H+ (2)


HO2

∙997888rarr H+ +O

2

∙minus (4)

Fe3+ +HO2

∙997888rarr Fe2+ +H+ +O

2(5)


2O2


2 This











2O2 A high




2O2


2O2concentrations


20 25 30 35 40 4510

20

30

40

50

60

70

80

90

100

110

pH

Rem

oval

()

2

3

4

5

6

7

8

9

10

11

Iron

(mg

L)

(a)

0 2 4 6 8 10 12 14 16 18 20 22 24 26

40

50

60

70

80

90

100

H2O2 (mM)

Rem

oval

()

70

75

80

85

90

95

100

Iron

(mg

L)

(b)

00 01 02 03 04 05 0620

30

40

50

60

70

80

90

100

110

PA (gL)

Rem

oval

()

5

6

7

8

9

10

Iron

(mg

L)

ColorTOCIron total

(c)

50 100 150 200 2500

10

20

30

40

50

60

70

80

90

100

110

RB4 (mgL)

Rem

oval

()

5

6

7

8

9

10

11

Iron

(mg

L)

ColorTOCIron total

(d)




2O2









2O2]0= 5mM [RB4]

0= 100mg Lminus1








2O2]0= 5mM




2









4 Conclusion


2O2 for an initial





0 5 10 15 20 25 30

000102030405060708091011121314

Zn

NiPbCrCu

As

Time (min)

Met

al co

ncen

trat

ion

(mg

L)


2O2]0= 5mM [RB4] = 100mgL)


002

004

006

008

010

Con

cent

ratio

n (m

gL)

Metals






Acknowledgment


References


























































RoboticsJournal of





Journal of



RotatingMachinery





VLSI Design



Shock and Vibration







Journal of



Volume 2014


SensorsJournal of





Propagation










O

O

O

O

O

O

OH

OH

HN HN

NN

N

Cl

Cl

S

S

NH2




100 (

1198600minus 119860

1198600

) = dye removal ()


(1)


0and TOC











2O25mM and PA


(s)




2

∙+H+ (2)


HO2

∙997888rarr H+ +O

2

∙minus (4)

Fe3+ +HO2

∙997888rarr Fe2+ +H+ +O

2(5)


2O2


2 This











2O2 A high




2O2


2O2concentrations


20 25 30 35 40 4510

20

30

40

50

60

70

80

90

100

110

pH

Rem

oval

()

2

3

4

5

6

7

8

9

10

11

Iron

(mg

L)

(a)

0 2 4 6 8 10 12 14 16 18 20 22 24 26

40

50

60

70

80

90

100

H2O2 (mM)

Rem

oval

()

70

75

80

85

90

95

100

Iron

(mg

L)

(b)

00 01 02 03 04 05 0620

30

40

50

60

70

80

90

100

110

PA (gL)

Rem

oval

()

5

6

7

8

9

10

Iron

(mg

L)

ColorTOCIron total

(c)

50 100 150 200 2500

10

20

30

40

50

60

70

80

90

100

110

RB4 (mgL)

Rem

oval

()

5

6

7

8

9

10

11

Iron

(mg

L)

ColorTOCIron total

(d)




2O2









2O2]0= 5mM [RB4]

0= 100mg Lminus1








2O2]0= 5mM




2









4 Conclusion


2O2 for an initial





0 5 10 15 20 25 30

000102030405060708091011121314

Zn

NiPbCrCu

As

Time (min)

Met

al co

ncen

trat

ion

(mg

L)


2O2]0= 5mM [RB4] = 100mgL)


002

004

006

008

010

Con

cent

ratio

n (m

gL)

Metals






Acknowledgment


References


























































RoboticsJournal of





Journal of



RotatingMachinery





VLSI Design



Shock and Vibration







Journal of



Volume 2014


SensorsJournal of





Propagation










20 25 30 35 40 4510

20

30

40

50

60

70

80

90

100

110

pH

Rem

oval

()

2

3

4

5

6

7

8

9

10

11

Iron

(mg

L)

(a)

0 2 4 6 8 10 12 14 16 18 20 22 24 26

40

50

60

70

80

90

100

H2O2 (mM)

Rem

oval

()

70

75

80

85

90

95

100

Iron

(mg

L)

(b)

00 01 02 03 04 05 0620

30

40

50

60

70

80

90

100

110

PA (gL)

Rem

oval

()

5

6

7

8

9

10

Iron

(mg

L)

ColorTOCIron total

(c)

50 100 150 200 2500

10

20

30

40

50

60

70

80

90

100

110

RB4 (mgL)

Rem

oval

()

5

6

7

8

9

10

11

Iron

(mg

L)

ColorTOCIron total

(d)




2O2









2O2]0= 5mM [RB4]

0= 100mg Lminus1








2O2]0= 5mM




2









4 Conclusion


2O2 for an initial





0 5 10 15 20 25 30

000102030405060708091011121314

Zn

NiPbCrCu

As

Time (min)

Met

al co

ncen

trat

ion

(mg

L)


2O2]0= 5mM [RB4] = 100mgL)


002

004

006

008

010

Con

cent

ratio

n (m

gL)

Metals






Acknowledgment


References


























































RoboticsJournal of





Journal of



RotatingMachinery





VLSI Design



Shock and Vibration







Journal of



Volume 2014


SensorsJournal of





Propagation













2O2]0= 5mM




2









4 Conclusion


2O2 for an initial





0 5 10 15 20 25 30

000102030405060708091011121314

Zn

NiPbCrCu

As

Time (min)

Met

al co

ncen

trat

ion

(mg

L)


2O2]0= 5mM [RB4] = 100mgL)


002

004

006

008

010

Con

cent

ratio

n (m

gL)

Metals






Acknowledgment


References


























































RoboticsJournal of





Journal of



RotatingMachinery





VLSI Design



Shock and Vibration







Journal of



Volume 2014


SensorsJournal of





Propagation










0 5 10 15 20 25 30

000102030405060708091011121314

Zn

NiPbCrCu

As

Time (min)

Met

al co

ncen

trat

ion

(mg

L)


2O2]0= 5mM [RB4] = 100mgL)


002

004

006

008

010

Con

cent

ratio

n (m

gL)

Metals






Acknowledgment


References


























































RoboticsJournal of





Journal of



RotatingMachinery





VLSI Design



Shock and Vibration







Journal of



Volume 2014


SensorsJournal of





Propagation

















































RoboticsJournal of





Journal of



RotatingMachinery





VLSI Design



Shock and Vibration







Journal of



Volume 2014


SensorsJournal of





Propagation









Research Article Degradation of Anthraquinone Dye Reactive...

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Transcript of Research Article Degradation of Anthraquinone Dye Reactive...