31720117ActaScientiaeCircumstantiaeVol.31No.7Jul.2011No.2011R09048-04No.Y5090272No.2008C13014-6SupportedbytheKeyScientificInnovationGroupofZhejiangProvinceNo.2011R09048-04theNaturalScienceFoundationofZhejiangProvinceNo.Y5090272andtheProjectofScienceandTechnologyOfficeofZhejiangProvinceNo.2008C13014-61985—E-mailcnahcsq@163.com*E-mailqzdai@zjut.edu.cnBiographyCAIShaoqing1985—maleE-mailcnahcsq@163.com*CorrespondingauthorE-mailqzdai@zjut.edu.cn.2011.J.3171440-1449CaiSQDaiQZWangJYetal.2011.HeterogeneouscatalyticozoneoxidationforpharmaceuticalwastewatertreatmentJ.ActaScientiaeCircumstantiae3171440-1449*3100322010-11-082010-12-252010-12-31.、/3./COD、TOCBOD5/COD.pH=12、20g·L-1、64mg·min-1COD72.6%TOC57.7%BOD5/COD0.345.pHpH/COD..pHpzc、SEM、BET、.0253-2468201107-1440-10X703.1AHeterogeneouscatalyticozoneoxidationforpharmaceuticalwastewatertreatmentCAIShaoqingDAIQizhou*WANGJiayuCHENJianmengCollegeofBiologicalandEnvironmentalEngineeringZhejiangUniversityofTechnologyHangzhou310032Received8November2010receivedinrevisedform25December2010accepted31December2010AbstractHeterogeneouscatalyticozoneoxidationwasappliedasanefficientwayofpretreatmentofhighlyconcentratedpharmaceuticalwastewater.Thepretreatmentofrealpharmaceuticalwastewaterwascomparedinsystemsofozonationaloneandozone/activatedcarbon.ComparedwithozonationalonetheintegratedprocesscouldgreatlyimprovetheremovalefficiencyofCODwithanobvioussynergisticeffect.IntheintegratedprocessCODremovalcouldreach72.6%undertheconditionsofpH1220g·L-1activatedcarbonand64mg·min-1ozone.ThefinalTOCremovalwas57.7%andBOD5/COD0.345achievingeffectivebiodegradationofpharmaceuticalwastewater.ThepHhasanobviousinfluenceontheremovalofCOD.TheincreaseofpHinhibitsadsorptionbyactivecarbon.Comparedwithacidconditionsahigherremovalratecouldbegainedunderalkalineconditions.ThedosagesofozoneandactivatedcarbonalsohavemarkedeffectonCODremoval.IncreasingtheirdosageobviouslyenhancedtheremovalefficiencyofCOD.Alumpedkineticmodelcouldbesuccessfullyappliedtothepharmaceuticalwastewatertreatment.ThroughtheanalysisofpHpzcSEMBETandinfraredspectrathereactionmechanismwasdifferentunderdifferentpHconditions.Throughanalysisofkineticmodelfitsweconcludethatundertheacidconditionsthemajorfunctionofactivatedcarbonisadsorptionwhileunderbasicconditionsthemajorfunctionistocatalyzetheozonation.Keywordspharmaceuticalwastewatercatalyticoxidationsynergeticeffectkineticmodel1IntroductionChelliapanetal.2006Lietal.2009.、Bortetal.1999Jossetal.2005Jossetal.2006Tolls2001Kummerer2001DOI:10.13671/j.hjkxxb.2011.07.0187Ellis2006.、、、“”Kummereretal.2000Bendeskyetal.2002Carballaetal.2004.、Halling-Sorensenetal.1998Daughtonetal.1999Buseretal.1999Heberer2002Jossetal.2006.、Kajitvichyanukuletal.2006Kusicetal.2006..Fontanieretal.2006Legubeetal.1999Thiruvenkatacharietal.2007.·OHSanchez-Poloetal.2003Quinlivanetal.2005Fariaetal.2005.Fariaetal.2005Linetal.2000Linetal.2003/-Sanchez-Poloetal.2003././pH、、、、/.2Materialsandmethods2.1pH9COD8000~9000mg·L-1.、BOD5/COD0.021..K0740~80≥1000m2·g-11089mg·g-1≤10%≤5%.2.2CFY-399.999%.1.5L.、、、.0.22μm.2.3BOD5OxiTopISBODWTWVahaojaetal.2005CODCTL-12pHpHs-3EpHTOCTOC-VCPHDionexICS-2000AgilentGC7890/MS5975Nicolet6700FT-IRBETASAP2020BETMicromeriticsSEMS24700SEMHitachi.3Results3.164mg·min-1、20g·L-1pH=2pH=12COD1.1a144131/COD60.1%10.2%48.5%.1b/COD72.6%21.5%33.0%/.fDaietal.20071.f=η/η+η11CODa.pH=2b.pH=12Fig.1TheremovalefficiencyofCODindifferentprocessesa.pH=2b.pH=12η/、η、ηCOD.1f1.025f1.330/.pH/..2pHCODFig.2TheremovalefficiencyofCODindifferentpHconditions3.23.2.1pH2pHCOD64mg·min-120g·L-1.2pHCODpHpH212COD60.1%72.6%pH.pHOH-2·OHJurgen1995.·OH、OH-Chuetal.200034.4·OHOH-..O3+OH-→HO·-2+O2·2dC/dt=-k0O3+k·OH·OHC3·OH=3kHO·-2O3OH-/k·OHC4Cmg·L-1kOk·OHO324417s-1kHO·-2HO2·-s-1.3.2.23CODpH=1220g·L-1.3COD16mg·min-140.2%64mg·min-172.6%f1.0901.260.4·OH/.3CODa.CODb.Fig.3TheremovalefficiencyofCODandthechangesofcofactorunderdifferentgasflowrateconditionsa.CODb.cofactor3.2.34CODpH=1264mg·min-1.4a5g·L-131.3%25g·L-179.0%f1.0601.330/.4b20g·L-1.4CODa.CODb.Fig.4TheremovalefficiencyofCODandthechangesofcofactoratdifferentconcentrationsofactivatedcarbona.CODb.cofactor3.33.3.1pHOH-.pHChengetal.2005Alvarezetal.2005.5Newcombeetal.1993Ferro-Garciaetal.1998Rivera-Utrillaetal.2001pHpHpzc.5pHpzc8.83344131pH=2pHpzc5.83pH=12pHpzc9.63.GC/MSpH8.83pHLaszloetal.2007..Terzyk2003../.5pHpzcFig.5ThechangeofpHpzcofactivatedcarbonfordifferenttreatments3.3.26pH/.2921cm-1、2852cm-1pH12pH2.2921cm-1、2852cm-1、C—HO—H、CO、C—H..6a.pH=12b.c.pH=2Fig.6ComparisonofFTIRspectraofactivatedcarbonafterdifferenttreatmentsa.pH=12b.originalsamplec.pH=27Fig.7Theconcentrationofpartialintermediatesduringdegradationprocess3.3.37pH=1264mg·min-120g·L-1.744417、、、、.120min100min、..8TOCBOD5/CODFig.8TheTOCandBOD5/CODratioduringtreatmentwithdifferentdosagesofozone8/TOCBOD5/CODpH=1220g·L-164mg·min-1.8a/TOC16mg·min-164mg·min-1TOC2884mg·L-160min1575mg·L-11221mg·L-1.64mg·min-1TOC2884mg·L-160min2324mg·L-11976mg·L-11.13..8bBOD5/CODBOD5/COD16、32、48、64mg·min-1BOD5/COD0.02160min0.213、0.241、0.303、0.345.48mg·min-164mg·min-1BOD5/COD.3.3.49