硅酸铁催化臭氧去除水中的阿特拉津和硝基苯

32220154JOUＲNALOFNATUＲALSCIENCEOFHEILONGJIANGUNIVEＲSITYVol.32No.2April2015DOI10．13482/j．issn1001－7011．2015．03．11012221．1500012．150090。－FT－IＲ、N2/pHPZC、、pH。1.2700mg·L－127.4%34.5%2.1pHFe3+。。X703.1A1001－7011201502－0223－06ＲemovalofatrazineandnitrobenzeneinwaterbyironsilicatecatalizedozonationHOUBingjiang1SHENJimin2LITaiping2XUPeng21．DepartmentofWaterOualityDetectionHydrologyBureauofHeilongjiangProvinceHarbin150001China2．StateKeyLaboratoryofUrbanWaterＲesourcesandEnvironmentSchoolofMunicipal＆EnvironmentalEngineeringHarbinInstituteofTechnologyHarbin150090ChinaAbstractInthisstudyironsilicatewaspreparedandusedasacatalystintheozonationofatrazineandnitrobenzene．ThecatalystdosageozonedosageandpHvalueswereoptimizedintermsoftheremovalefficiencyofatrazineandnitrobenzene．Themechanisminvolvedintheironsilicatecatalyzedozonationwasinvestigated．Theironsilicatewaspreparedbysol-gelmethodandcharacterizedusingFT-IＲN2-physisorptionandpHPZC．Undertheoptimizedcondition700mg·L－1catalystand1.2mg·L－1o-zonecatalyzedozonationincreasedtheremovalefficienciesofatrazineandnitrobenzeneby27.4%and34.5%respectivelycomparedtoozonationalone1.2mg·L－1ozoneonly．Theozonedecompo-sitionrateincreasedby2.1timesunderthecatalysiswithironsilicate．I[e-mail][e-mail]thecatalyticozonationwasmarginalandthei-ronionconcentrationmetNationalDrinkingWaterStandard．Catalyticactivitywassuppressedbyaddingtert-buta-nolTBAandbicarbonatewhichprovedthatcatalysisprocessfollowedthehydroxylradicalHO·mecha-nism．Itisconcludedthatironsilicatepreparedinthisstudypromotedtheozonationdegradationofatrazineandni-trobenzenethermodynamicallyandkineticallyandhydroxylradicaloxidationwasthemajormechanisminvolved．Keywordsironsilicatecatalyzedozonationozonemasstransferefficiencyatrazinenitrobenzene01。、2。AOP·OH3UV/O3、/O3、O3/H2O2/O34－8。、9。FeOOH10－11。。FeFeOOH。FeFeOOH。、。－Na3SiO3Fe3+1。Na2SiO3+H2O+Fe3+→FeOOH－SiOH41。11.16890N、1200Optima5300DV、Spectrum2000PEASAP－2020Zen2600COM－AD－01。、、。1.2－Na3SiO3FeNO33pHpH8±0.5。1h60℃6hpH7.0±0.2。60℃2h。1.31.2L。·422·320～4g·h－1。O3/O21L0.1mol·L－1Na2S2O3。1.4ECDHP530m×530μm×1.0μm120℃ECD300℃260℃99．999%6mL·min－1ECD27mL·min－15∶11μL。HPLCZOＲBXClipsePlusC184.6cm×100mm×5μm/60400.8mL·min－120μL220nm。。ICP。FT－IＲKBr、、0.1g90℃10h。pHPZCpHZeta。22.11FT－IＲ437cm－1Fe－O8001023cm－1Si－O－Si1606cm－1H－O－H3380cm－1－OH。2N2－2～100nm4．1nm0．39cm3·g－1BET384．1322m2·g－1。2IUPAC。ZetapHPZC6.93。100806040透光率（%）4%0003%5003%0002%5002%0001%5001%0005000波数（cm-1）30025020015010050吸附容量（cm3·g-1）0.00.20.40.60.81.0相对压强（P/P0）图1硅酸铁的FT-IR光谱图Fig.1FT鄄IRspectrumofironsilicate图2硅酸铁的氮气吸附-脱附曲线Fig.2N2adsorption鄄desorptionisothermsofironsilicate3%3801%606800437吸附曲线脱附曲线1.21.00.80.60.40.20.0020406080100孔径（mm）dV/dlogD（cm3·g-1）1%0232.23ATＲANB20min19.8%29.3%20minATＲANB3.2%6.1%ATＲANB52.9%54.3%。·522·21.00.80.60.40.2C/C0O3+ATRA；O3%/硅酸铁+ATRAO3+NB；O3%/硅酸铁+NB硅酸铁+ATRA；硅酸铁+NB05101520反应时间（min）3ATＲANBATＲA0=500μg·L－1NB0=100μg·L－1ATＲA=500mg·L－1NB=700mg·L－1O30=1.2mg·L－1pH=7.0±0.1T=20℃Fig．3TheefficiencyofcatalyticozonationofATＲAandNBbyironsilicate。2.32.2ATＲANBAT-ＲANB4。4O3O30．0271mol－1·L·s－1O30．0543mol－1·L·s－1O3O3·OH。O3pHO35。pHpHPZCO3pHPZC。1.00.80.60.4臭氧浓度（mg·L-1）臭氧自分解硅酸铁催化臭氧分解0246810121416反应时间（min）ko3（mol-1·L·s-1）0.060.040.020.002345678910初始pH值图4不同条件臭氧的分解：［O3］0=10mg·L-1,［硅酸铁］=500mg·L-1,pH=7.0±0.1,T=20℃Fig.4Ozonedecompositionunderdifferentconditions图5不同pH值下的臭氧分解速率常数：［O3］0=10mg·L-1,［硅酸铁］=500mg·L-1,T=20℃Fig.5OzonedecompositionrateconstantsunderdifferentpHvalues2.4、12－14。ATＲANBATＲANBO3。ATＲANBO3。·OHt－BuOHHCO3－6。t－BuOH·OH4.7×108mol－1·L·s－115。·OH16·OH。·OH·OH。6t－BuOHO3O3·OH。t－BuOHATＲANB·622·32·OH。1.00.80.60.40.20.0C/C0单独O3O3%/t-BuOHO3%/硅酸铁O3%/硅酸铁/t-BuOHO3%/硅酸铁/HCO-3（a）05101520反应时间（min）1.00.80.60.40.20.0C/C0单独O3O3%/t-BuOHO3%/硅酸铁O3%/硅酸铁/t-BuOHO3%/硅酸铁/HCO-3（b）05101520反应时间（min）图6自由基抑制剂对催化臭氧氧化降解阿特拉津（a）和硝基苯（b）效率的影响：［ATRA］0=500μg·L-1,［NB］0=100μg·L-1,［催化剂］ATRA=500mg·L-1,［催化剂］NB=700mg·L-1，［O3］0=12mg·L-1,［HCO3-］=200mg·L-1,［t-BuOH］0=50mg·L-1,pH=7.0±01,T=20℃Fig.6TheinfluenceoffreeradicalinhibitorontheefficiencyofcatalyticozonationATRAandNB。O3·OH·OHATＲANB。2.50.200.150.100.050.00总铁离子浓度（mg·L-1）357912初始pH值7pH=1000mg·L－1T=20℃24h。Fig．7Thetotalironiondissolutionofironsili-cateunderdifferentpHconditions。0．3mg·L－1。/O3ATＲANB20min0．140．21mg·L－10．3mg·L－1。。pH。pH7。7pH≈70．09mg·L－1pH≈30．17mg·L－1。31－。30%2、pH·722·234pH。．1HUBNEＲUGUNTENUVJEKELM．Evaluationofthepersistenceoftransformationproductsfromozonationoftraceorganiccompounds-acriti-calreviewJ．WaterＲes201568150－170．2IKHLAQABＲOWNDＲKASPＲZYK-HOＲDEＲNB．CatalyticozonationfortheremovaloforganiccontaminantsinwateronZSM-5zeolitesJ．ApplCatalBEnviron2014154－155110－122．3QIANGZLINGWTIANF．KineticsandmechanismforomethoatedegradationbycatalyticozonationwithFeIII-loadedactivatedcarboninwaterJ．Chemosphere20139061966－1972．4FＲEESESDNOZAICDPＲYOＲMJetal．Comparisonofozoneandhydrogenperoxide/ozoneforthetreatmentofeutrophicwaterJ．WaterSciTechnol19993910－11325－328．5EＲNSTMLUＲOTFSCHＲOTTEＲJC．Catalyticozonationofr