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1 4
1.INTRODUCTION
Heterogeneous catalysts such as UV light/ TiO2/ZnO are usedforPhotocatalyticdegradationhasattractedincreasing attentionascleanerandgreenertechnologyforremovalof toxic organic and inorganic pollutants in water and wastewater.[5,6] Figure 1.1 : SchematicdiagramofanirradiatedTiO2 particle.
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Author’s: T.Ajitkumar1 D.Udaya laxmi Sai Durga2 T.Jyothi3 Ch.Sailu..V.V.Basava Rao4 Department of Chemical Engineering University College of Technology (A), Osmania University Hyderabad Telangana 500007 *** Advanced oxidation processes (AOPs) are widely used for the removal of recalcitrant organic constituents from industrial and municipal wastewater. This study mainly focused the use of TiO2 and ZnO catalysts for removal of textile dyes. Synthesis of TiO2 and ZnO photo catalysts was done by sol gel method. These catalysts were used to obtain enhanced photo catalytic action and were coated on glass beads to improve the photo catalytic activity. The synthesized beads were examined using SEM, FTIR and XRD.Synthesizedphotocatalysts were examinedextensively for their photocatalytic activities with Crystal Violet (CV), Direct Red Dye (DR), Textile industry Effluent (TIE) and mixture of dyes (CV+DR, CV+DR+TIE) at various concentrations (50ppm, 100ppm). The photocatalytic degradation of CV, DR, TIE, CV+DR and CV+DR+TIE dyes solution (100mg/Land50mg/L) using TiO2 and ZnO were investigated under UV light irradiation (λ=254nm). Photocatalytic studies revealed that the TiO2 has shown much higher photocatalytic activity than the ZnO catalyst. The photocatalytic activity of the TiO2 catalyst follows the order: Crystal Violet of 50 ppm(82.84%)> Textile Industry Effluent (78.72%) >Direct Red Dye of 50 ppm (78.69%)>Direct Red Dye of 100 ppm(75.12)>CrystalViolet of 100 ppm (73.38). The photocatalytic activity of the ZnO catalyst follows the order: Crystal Violet of 50 ppm (78.1%) > Textile Industry Effluent (75.3%) > Direct Red Dye of 50 ppm (73.98%)>Direct Red Dye of 100 ppm(71.24)>CrystalViolet of 100 ppm (70.29). Key Words: Crystal Violet (CV), Direct Red Dye (DR), Textile Industry Effluent (TIE), Photocatalytic studies, TiO2, ZnO, Textile Dyes
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Abstract
TextileEffluentsneedtobetreatedbeforedischargingthem into water bodies because of Toxicity polluting the environment. In past years, conventional biological and physical treatment methods (adsorption, ultrafiltration, coagulation etc.) have been used to remove organic pollutants.Thesemethodsarenotefficientandcosteffective for wastewaters containing high concentrations of more toxic pollutants. This requires some novel techniques to transferthehighlytoxicpollutantschemicallyinto benign species.[1,2]
Advanced oxidation processes (AOP) became a promising technologyintherecentyears,sincetheyaremostefficient, cheap, and eco friendly in the degradation of any kind of toxic pollutants. AOPs generate hydroxyl radical, a strong oxidant, which can completely degrade or mineralize the pollutants nonselective into harmless products. In this processnoby productsandsludgeareformed[3,4,7]
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0cfor1hrandcalcinatedfor2hrsat450o C.This procedurecontinuedforfurthertimesofcoatings[10,11,12]
Fig: 1.3 ChemicalstructureofCrystalViolet Direct Red in water: Directred,a toxic sulphonatedazo based dye, known for its carcinogenic nature and toxicity towardsanimalandhumansisselectedasasyntheticmodel dye solution for experimentation which is widely used in many industries. It has double azo linkage along with sulphonicacidgroup,makesthedyeeasilysolubleinwater.
2.1Methods:Coating of TiO2 photocatalyst on glass beads: Before coating of glass beads, the glass beads were etched in Hydrofluoricacid(40%pure),for24hrsandwashedwith demineralizedwateranddriedintheovenfor2hrsat1050c. Now the catalyst was prepared using the sol gel method
Fig 2.1.TiO2 catalystcoatedonglassbeads
Fig: 1.4 ChemicalstructureofDirectRed
ovenminutes.formed.wise(98%pure)stirred(98%[11,12].SampleAwaspreparedusingTitaniumIsopropoxidepure)andEthanol(99%pure)with1:4ratioandfor30minutes.Use25mlofHydrochloricAcidasSampleB.AddSampleBtoSampleAdropandstirwelluntilalightorangecoloredgelsolutionImmersetheglassbeadsintothepreparedgelfor30Theimmersedglassbeadsweredriedinthehotairat105
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In this project crystal violet and direct red and textile Industrialdyeeffluentareconsider.ForDegradationusing immobilizedTiO2andZnOcatalystonglassbeadsusingUV lightincontinuousreactor.
2.2. Coating of ZnO photocatalyst on glass beads:
2. Materials & Methods: Materials: Hydrofloruric Acid (5 wt%, purchased from SigmaAldrich),Titanium(IV)isopropoxide(97%,purchased from Sigma Aldrich), Ethanol (96%, from Sigma Aldrich), Hydrochloric Acid (98%, from Molychem), Zinc Acetate Dihydrate (98%,purchasedfromAvra),SodiumCarbonate fromAvra,CrystalViolet,DirectRed,(fromAtulindustries) GlassBeads,(Avra)DistilledWater,TextileIndustryEffluent (AreaofSiricilla,Telangana).
The glass beads were etched in Hydrofluoric acid (40% pure),for24hrsbeforecoating.Thebeadswerethenwashed withdemineralizedwateranddriedintheovenfor2hrsat 1050c.Usingsol gelmethodthecatalystwasprepared. Sample A was prepared using 2.2 grams of Zinc Acetate Dihydrate,50mlofDistilledwaterpreparedandstirredfor 30 minutes. Sample B was prepared using 1.06 grams of SodiumCarbonateand50mlofDistilledwaterandstirred for30minutes.SampleBwasaddeddropwisetoSampleA understirringuntilawhitetransparentgelisformed.The glassbeadswereimmersedinthegelfor30minutes.Later thebeadsweredriedinovenat1050cfor2hrandcalcinated for4hrsat450o C.Thisprocedurewasrepeatedforfurther numberofcoatingsonglassbeads.
Figure 1.2:SchematicdiagramofanirradiatedZnO particle. Crystal Violet in water Crystal Violet (CV), a triphenylmethane dye, has been extensively used in human and veterinary medicine as a biological stain, as a textile dye in textile processing industries and also used to provide a deep violet color to paintsandprintingink.
3. Characterization Techniques; Thecoatedglassbeadswerecharacterizedthroughscanning electron microscope (SEM), Fourier Transform Infrared (FTIR)andX RayDiffraction(XRD). Scanning Electron Microscope (SEM) SEM is used to detect the information about the sample's surface morphology, topography and composition. The electronbeamisgenerallyscannedinascanpattern,andthe beam's position is combined with the detected signal to produceanimage.
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Fig 3.1b .SEMimageaftercoatingofcatalystonglass beads Fourier Transform Infrared (FTIR)
Fig 3.1a .SEMimagebeforecoatingofcatalystonglass beads
Fig 3.3a: XRDphotographof(TiO2)catalyst XRD of ZnO: Thepeakspointedoutat2θvaluesofcanbeassociatewith (100),(002), (101), (102), (110),(103) and (112), respectively, correspond to hexagonal zinc item phase of ZnOwhichareingood.TheaverageZnOnanoparticlessize of30nmcanbeestimatedbyScherrer’sformula
The FTIR analysis method uses infrared light to scan test samplesandobservechemicalproperties.Eachmoleculeor chemical structure will produce a unique spectral fingerprint,makingFTIRanalysisagreattoolforchemical identification.
Fig 3.2 FTIRofTiO2 X Ray Diffraction (XRD) Powder X ray diffraction technique in useful in catalyst characterization and to investigate both qualitative and quantitativephasechanges.Itgivestheinformationabout the crystallinity of the specific components and allows identification of ensemble size of the components in the ThecatalystXRD pattern of nano catalyst (TiO2) showed the presenceofthreemainpeaksat2θ=25.3o(101),26.1o,and 37.0o,which should be an attributive indication of anatase TiO2.Ontheotherhand,minordiffractionpeaksappearedat 2θ=27.5o(110)and31.5o,whichshouldcorrespondtorutile TiO2. The results were in agreement with its mineral compositionBeringananatasetorutileratioof83:17
Fig 2.2. ZnOcatalystcoatedonglassbeads
Thedyeeffluentistreatedinthereactorforthreehoursand samplesweredrawneveryhour.Theconcentrationofdye determined spectrophotometrically to find out concentrationatrespectivetimes.Percentageofdegradation calculated and compared the degradation against time. Industrial textile dye effluent Initial and final samples are alsoanalyzedforchemicaloxygendemandusingopenreflux %Degradationmethod.= ×100
Fig.5.1a. DegradationofCrystalVioletwithout Fig.5.1b. DegradationofCrystalVioletwithCatalystTiO2
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Fig. 4.1. ExperimentalSetup
The Degradation of Crystal Violet Using TiO2:
Fig. 5.2.%DegradationVstimeofCV50ppm
Fig. 5.3a %Degradationofcrystalvioletdye50ppmand 100ppmusingTiO2
5. RESULTS AND DISCUSSION:
Fig 3.3b: XRDphotographof(ZnO)catalyst
Photocatalytic degradation of textile dye effluents was performed in the continuous reactor system as shown in Fig.4.1, which consists of a cylindrical borosilicate glass reactor(withaneffectivevolumeof275Cm3).TheTiO2and ZnOcoatedglassbeadswereplacedinthereactorsetup.The UV Clight(of254nm)isplacedintheprovisionsuchaway that the UV light located in the middle of the reactor. The reactor covered to restrict natural light from entering. Peristaticpumpisusedtotransferthetreatingsolutionor effluentintothereactor.Inletandoutletofthereactorare connectedsuchawaythatthefluidpassingthroughclosed loop continuous reactor. The flow rate of the system adjustedto20lt/hrinclockwisedirection[9,10].
4. Experimental Setup:
Fig 5.2 shows the degradation of dye studied with and without catalyst, it is found that there is a remarkable difference. In case of Crystal Violet of 50ppm, it showed about 82.84% degradation with catalyst in other hand degradationlimitedtoapproximately1.98%intheabsence ofcatalyst.
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The Degradation of Direct Red Using TiO2:
Fig.5.6 DegradationofCrystalVioletwithCatalystZnO
Fig 5.3b.ConcentrationVsTimefor50ppmand100ppm CVwithTiO2
Intermsofconcentration50ppmto10.65ppmand100ppm to24.28ppmafter3hoursofexperimentusingTiO2.
Fig. 5.5 a. Degradationof50ppmand100ppmdirectred dyeusingTiO2
The Degradation of Crystal Violet Using ZnO:
Fig. 5.4 InitialandfinalsamplesofDirectRedDyeusing TiO2
Fig 5.5b.ConcentrationVsTimefor50ppmand10ppm directreddyewithTiO2
Fig 5.3a&b. shows the Difference between two concentrations (50ppm, 100ppm) of Crystal Violet %degradationisat50ppm82.84%andat100ppm73.3%.In termsofconcentration50ppmisreducedto8.58ppmand 100ppmto26.62ppmafter3hoursofexperimentusingTiO2
Fig. 5.7a.%Degradationofcrystalvioletdye50ppmand 100ppmusingZnO
Fig 5.5a&b. shows the difference between two concentrations (50ppm, 100ppm) of Direct Red %degradationisat50ppm78.69%andat100ppm75.12%.
Fig. 5.9 a.Degradationof50ppmand100ppmdirectred dye UsingZnocatalyst Fig 5.9b.ConcentrationVsTimeforDirectreddye50ppm and100ppmwithZnOcatalyst The fig 5.9a&b. Shows it was observed the Difference betweentwoconcentrations(50ppm,100ppm)ofDirectRed %degradationisat50ppm73.98%andat100ppm70.16%.
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Intermsofconcentration50ppmto13ppmand100ppmto 28.76ppmafter3hoursofexperimentusingZnO. Textile Industrial Effluent using TiO2 /ZnO: Fig 5.10.TextileIndustryEffluentdegradationinitialand finalsample Fig.5.10a DegradationofTextileIndustryEffluent degradationusingTiO2&ZnO
Fig 5.7b. ConcentrationVsTimeforCrystalvioletdye 50ppmand100ppm
The fig 5.7a&b shows the Difference between two concentrations (50ppm, 100ppm) of crystal violet %degradationisat50ppm78.1%andat100ppm70.29%.In termsofconcentration50ppmto10.95ppmand100ppmto 29.71ppmafter3hoursofexperimentusingZnO.
The Degradation of Direct Red Using ZnO
Fig. 5.8 InitialandfinalsamplesofDirectRedDyeusing ZnO
30 40 50
Fig .5.11b DegradationofDyemixtureusingZnO Thefig5.11b.Showsitwasobservedthecombinedmixtures ofdyeswithtextileIndustrialDyeeffluent%degradationis (CV+DR) 72% and (CV+DR +TIE) is 70% after 3hours of experimentusingZnO.Concentrationof(RO+RB)isreduced from100ppmto28ppmandCODremovalof(CV+DR+TIE)is reducedfrom10824ppmto3175ppm 6. Kinetics: The reaction rate for the photo catalytic reactions is independentofhydroxylconcentrationsThereforeapseudo first order kinetic model was used to fit the experimental data.= kC COH*..(1) By the pseudo secondary hypothesis (i.e the COH* can be considered),therateexpression(1)canbesimplifiedtofit anequationfollowingthefirstorderkinetics, = kC Integratingtheaboveequation;from‘C0’to‘C’ontheleft handside,and‘0’to‘t’ontheright; ln(C/C0) = - kτ
Thefig.5.10a.UsingTiO2ItwasobservedtheIndustrialDye effluent%degradationis78%after3hoursofexperiment.In terms of concentration reduced from 10,640ppm to 2264ppm.andusingZnOItwasobservedtheIndustrialDye effluent %degradation is 75% after 3hours of experiment andconcentrationreducedfrom10640ppmto2628ppm. Mixed dyes with Textile Industrial Effluent using TiO2:
Fig.5.11.InitialandfinalsamplesofDyemixturesanalysis 0 10 20 60 70 80 90 100 CV+DR CV+DR+TIE 7874 Fig .5.11.a.DegradationforDyemixturewithTIEusing TiO2
Thefig.5.11a.showsItwasobservedthecombinedmixtures ofdyeswithtextileIndustrialDyeeffluent%degradationis (CV+DR) 78% and (CV+DR+TIE) is 74% after 3hours of experimentusingTiO2.Concentrationof(CV+DR)isreduced from100ppmto22ppmandCODremovalof(CV+DR+TIE) isreducedfrom10824ppmto2790ppm.
Fig .6.1 TimeVsln(C/C0)forCVusingTiO2
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Mixed dyes with Textile Industrial Effluent using ZnO:
The degradation of Crystal Violet dye without catalyst is 1.98%whereaswithcatalyst 82.84%.
Thekineticsofdegradationofthedyesfollowedfirstorder ratetherateconstantkvaluesare S. No Dye Name Rate constant (K)
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InthepresenceofUVlightandcatalysttextiledyescanbe degraded because it produce more hydroxyl radicals to degradethecompounds. DamodarandSwaminathan,2008 foundIncontinuousmicroreactortheDegradationofcrystal violet(10mg/L)and400minofruntimeanddegradation achievedwas93%.
1. S. Rodriguez Couto, A. Dominguez, A.anroman, Photocatalytic degradation of dyes in aqueous solution operating in a fludisied bed reactor, 46 (2002)83 86
Thekineticsofdegradationofthedyesfollowedfirstorder rateandrateconstantsforCV,DRusingTiO2,CV,DRusing ZnOare0.0095,0.0082,0.0082,0.0071respectively.
Sapkal et al., 2012 treated 1000ppm of textile effluent by photoelectrocatalysis and found COD removal of 69% for 200to400nmwavelengthwithin3hatroomtemperature HoweverinourcaseCODremovalwas85%forTiO2catalyst and82%usingZnOcatalyst.Theintegrallineartransform, ln(C/C0)asafunctionofdegradationtimefollowsfirstorder reactionkinetics[13]
Photocatalyticperformanceforcombinationmixeddyesalso studiedandfoundthatcatalystshowedefficientresultsin degradingmultipledyesatatime.
2 DirectRedDyeusingTiO2 0.0082
IndustrialdyeeffluenttreatedComparedtoindividualdyes degradationislesswhenthecombinationofdyesareused. Thecatalystwasreusedfor7times.
4. R.Saravanan,S.Karthikeyan,V.K.Gupta,G.Sekaran, V. Narayanan, A. Stephen, Enhanced photocatalytic activity of ZnO/CuO nanocomposite for the degradation of textile dye on visible light illumination, c33(2013)91 98.
Becauseoflightintensityandavailabilityofactivecatalyst surface for dye adsorption as well as for hydroxyl radical generation(DamodarandSwaminathan,2008).
When compared to ZnO catalyst TiO2 gives more degradation due to band gap energy which is less in TiO2 (3.2ev) whereas in ZnO (3.4ev) Degradation is slightly reducedforhigherconcentrationbecauselightintensityand activesurfaceareamaynotbesufficient.
3. R.T.Sapkal,S.S.Shinde,M.A.Mahadik,V.S.Mohite, T.R.Waghmode,S.P.Govindwar,K.Y.Rajpure,C.H. Bhosale, Photoelectrocatalytic decolorization and degradation of textile effluent using ZnO thin films, 114(2012)102 107.
1
2. SampaChakrabarti,BinayK.Dutta, Photocatalytic usingdegradationofmodeltextiledyesinwastewaterZnOassemiconductorcatalyst, B112 (2004)269 278.
Zuccaetal.,2012foundthatthecatalystimmobilizedlignin peroxidase likemetalloporphineskeepsasignificantpartof itscatalyticactivityduringmulti cycleemployment.Thisis very important for large scale applications to treat textile dye pollutantwhere classical photocatalysis or filtration approachnotabletoresolveitcompletely.[14]
4 DirectRedDyeusingZnO 0.0071
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3 CrystalVioletusingZnO 0.0082
Thekineticsofdegradationofthedyesfollowedfirstorder rateandrateconstantsforMB,BDandTIEare0.0135,0.007, and0.0112respectively.
REFERENCES
CrystalVioletusingTiO2 0.0095
Discussion: For50ppmofcrystalvioletdyewastreatedfor180minand thedegradationfoundwithoutcatalystdegradationisless (1%)whenitiscomparedtowithcatalyst(83%).
The degradation of Crystal Violet of 50 ppm (78.1%) > TextileIndustryEffluent(75.3%)DirectRedDyeof50ppm (73.98%)>DirectRedDyeof100ppm(71.24)>CrystalViolet of100ppm(70.29)usingZnOcatalyst.
7. CONCLUSIONS
The degradation of Crystal Violet of 50 ppm (82.84%) > Direct Red Dye of 50 ppm (78.69%)> Textile Industry Effluent(78%)>DirectRedDyeof100ppm(75.12)>Crystal Violetof100ppm(73.38)usingTiO2catalyst.
CV+DR (75.5%); CV+DR +TIE (78.8%) for TiO2, CV+DR (70.4%);CV+DR+TIE(75.8%)forZnO.
14. Zucca,P.,Rescigno,A.,Pintus,M. et al. Degradation oftextiledyesusingimmobilizedligninperoxidase like metalloporphines under mild experimental conditions. Chemistry Central Journal 6, 161 (2012).https://doi.org/10.1186/1752 153X 6 161
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5. Phuttamon Chantes, Chalor Jarusutthirak, and Supamas Danwittayakul, A comparison study of Photocatalytic activity of TiO2 and ZnO on the degradation of Real Batik http://dx.doi.org/10.15242/IICBE.C0515033Wastewater,
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