2种孔径沸石分子筛对水中土霉素的去除研究

31420104ENVIRONMENTALSCIENCEVol.31No.4Apr.20102*20009225A13XOTCpH、.2OTC298K、pH=7.05A13X667mg/g1429mg/g13X5A2OTC5A13X91%95%OTCpHOTC2OTC.X131.2A0250-3301201004-0990-062009-05-182009-07-012008ZX07425-0071987～[e-mail]*[e-mail]linAqueousbyTwoKindsofZeoliteswithDifferentBoreDiameterLIYuanZHAOChunDENGHui-pingKeyLaboratoryofYangtzeRiverWaterEnvironmentMinistryofEducationCollegeofEnvironmentalScienceandEngineeringTongjiUniversityShanghai200092ChinaAbstract5Aand13XastwokindsofhydrophiliczeoliteswithdifferentborediameterswerechosenasadsorptionmaterialsforoxytetracyclineOTCadsorptionanddesorptioninaqueous.TheeffectsofpHvalueandtemperatureonOTCadsorptionwereinvestigatedrespectivelyandthentheadsorptionkineticsaswellasthermodynamicwerecalculatedtoanalyzethecorrespondingadsorptionmechanism.TheresultsshowedthattwozeoliteshadsatisfactoryadsorptioncapacitiesonOTCandtheadsorptionprocesseswerewellfittedbythesingle-layeradsorptionmodel.Thesaturatedadsorptionwere667mg/gand1429mg/gon5Aand13Xrespectively298KpH=7.0.TheadsorptionpropertyofOTCon13Xwasmuchbetterthanthatof5Aatthesametemperature.TheadsorptionkineticswerewelldescribedbythesecondarykineticequationsandtheOTCdesorptionratesby5Aand13Xwere91%and95%individuallyinthedesorptionprocesses.Themaximumadsorptioncapacitiesoftwozeoliteswereinneutralsolutions.AndthethermodynamiccalculationsshowedthattheadsorptionofOTContwozeoliteswasspontaneousendothermicreactionwiththechemicalhydrogenbondasdominant.KeywordsoxytetracyclineOTCzeolitesadsorptiondesorptionkineticsthermodynamicsOTC.1～34～678.、910、、.500.460.44496.60111.OTC12、、13/14、15.、.、、、、、421Fig.1MolecularstructureofOTC16.5A5A13X13X17.2OTCpH.11.1、CASno.2058-46-0NaOH、HCl、.5A2000.5nm13X2001nm.LC-2010AHTHYG-A105mm40mm300mL.1.21.2.1200mLOTC1mol/LNaOHHClpH7.00.1g5A13XpH11.530min.1.2.2、pH2A、BOTC50、75、100、150、200、300、400、500mg/L100mL250mLA0.02g5AB0.02g13X1mol/LNaOHHClpH200r/min、±0.5K24h.OTC50、500mg/L1.5%2.1%.1.30.45μmLC-2010AHTOTC.HPLCshim-packVP-ODS250mm×4.6mmi.d.A0.01mol/LB∶=2∶1308K0.8mL/min355nm20μL.1.4、1819lgqe－qt=lgqe－k1t/2.30311/qt=1/k2tq2e+1/qe2qt=kdt1/23qt、qetmg·g－1k1min－1tmink2g·mg·min－1kdmg·g·min1/2－1.LangmuirFreundlich1/qe=1/ceqmb+1/qm4lgqe=1/nlgce+lgKf5cemg·L－1qmmg·g－1bg·mg－1nKfmg·g－1.Van’tHoffΔG=－RTlnKd6lnKd=ΔH/－RT+ΔS/R7ΔGkJ·mol－1RTKΔHkJ·mol－1ΔSJ·mol·K－1KdKd=qe/ce20.22.1199312.1.10.1g、pH=7.0、293K2OTC2.13X5AOTC70min90min150min90%.2OTCFig.2AdsorptionkineticcurvesofOTCremovalonzeolites31kd.13Xk1、k25A21821.13Xd=M1/322OTC496.600.79nm1nm13XOTC.OTC13XOTC.2.1.21Table1Kineticmodelconstantsk1/min－1R2qe/mg·g－1k2×10－3g·mg·min－1R2kd/mg·g·min1/2－1R25A0.0350.9672630.170.99221.210.80813X0.0420.9222500.340.96815.710.941210minpH11.55A13X91%95%OTC.、2324、.pHOTCOTC.2.22.2.10.02g、pH=7.0283、298、313K23.LangmuirFreundlich3OTCFig.3OTCadsorptionisothermsonzeolites299422..R22LangmuirFreundlich2.2LangmuirFreundlichTable2LangmuirequationandFreundlichequationconstantsT/KLangmuirFreundichqm/mg·g－1b/g·mg－1R21/nKf/mg·g－1R22734170.150.9754170.150.9755A2986670.160.9936670.160.99331316670.460.99016670.460.99027310000.0700.97910000.0700.97913X29814290.0860.99314290.0860.99331320000.0790.98220000.0790.9822.2.22qm298K、pH=7.02667mg·g－11429mg·g－1.31/n0.1～0.5Kf、.13XOTC5A.13X5A..2.2.3OTC、、..、.2bKfnOTC.2.3pH0.02g、298K24pH4.pH=11.02OTCpH=7.0.Langmuir23.pH13X.OTCpHpH3.32pH3.3～7.3OTC14pHOTCFig.4OTCadsorptionisothermsofzeolitesatdifferentpH399313pHLangmuirTable3LangmuirequationconstantsatdifferentpHpHqm/mg·g－1R25.04760.9905A7.06670.9939.05260.9875.06250.98613X7.014290.9939.06670.98812pH=10H+1pH=122H+212.pH.13X.OTC.2.42.2.1Niwas252lnqe/ce-qeKd72Van'tHoff54.5Van'tHoffOTCFig.5Van'tHoffplotforOTCadsorptiononzeolites4OTCTable4ThermodynamicparametersofOTCadsorptiononzeolitesatdifferenttemperaturesT/KKdR2ΔG/kJ·mol－1ΔS/J·mol·K－1ΔH/kJ·mol－12730.51－1.205A2981.050.983－2.60116.9832.013131.82－4.732731.27－2.9913X2982.180.987－5.40138.2736.043132.73－7.1142ΔH2.2.2.3ΔGΔG.2ΔG13X5A13X.Von264～10kJ·mol－15kJ·mol－12～40kJ·mol－140kJ·mol－12～29kJ·mol－160kJ·mol－1.5A13XΔH32.01kJ·mol－136.04kJ·mol－12OTC2.2.1.3125A13XOTC213X5A5A.2pHOTC213XpH5A2.32OTCpH91%95%OTC.42OTC.499421JagobsenPBerglindL.PersistenceofoxytetracyclineinsedimentsfromfishfarmsJ.Aquaculture198870365-370.2SarmahAKMeyerMTBoxallABA.AglobalperspectiveontheusesalesexposurepathwaysoccurrencefateandeffectsofveterinaryantibioticsVAsintheenvironmentJ.Chemosphere200665725-759.3MaddenJCEnochSJHewittMetal.PharmaceuticalsintheenvironmentGoodpracticeinpredictingacuteecotoxicologicaleffectsJ.ToxicologyLetters2009185285-101.4StackelbergPEFurlongETMeyerMTetal.Persistenceofpharmaceuticalcompoundsandotherorganicwastewatercontaminantsinaconventionaldrinking-water-treatmentplantJ.SciTotalEnviron200432999-113.5WesterhoffPYoonYSnyderSetal.FateofendocrinedisruptorpharmaceuticalandpersonalcareproductchemicalsduringsimulateddrinkingwatertreatmentprocessesJ.EnvironSciTechnol2005396649-6663.6AndreozziRCanterinoMLoGRetal.LincomycinsolarphotodegradationalgaltoxicityandremovalfromwastewatersbymeansofozonationJ.WaterRes20064