非均相催化臭氧处理高浓度制药废水的研究蔡少卿

31720117ActaScientiaeCircumstantiaeVol．31No．7Jul．2011No．2011R09048-04No．Y5090272No．2008C13014-6SupportedbytheKeyScientificInnovationGroupofZhejiangProvinceNo．2011R09048-04theNaturalScienceFoundationofZhejiangProvinceNo．Y5090272andtheProjectofScienceandTechnologyOfficeofZhejiangProvinceNo．2008C13014-61985—[e-mail]*[e-mail]1985—[e-mail]*[e-mail]oneoxidationforpharmaceuticalwastewatertreatmentJ．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