Fenton氧化深度处理石化废水厂二级出水研究

36720157ENVIＲONMENTALSCIENCEVol．36No．7Jul．2015Fenton1222*12111．7300702．100012FentonCOD．COD64.8mg·L－1PO3－4-P0.79mg·L－1H2O230%0.4mL·L－1FeSO4·7H2O0.8g·L－1PAM0.9mg·L－130minCOD24.3%COD50mg·L－1PO3－4-P95.5%1×10380.4%Fenton95.6%．Fenton、．GC-MS11727．Fenton．FentonX703.1X742A0250-3301201507-2597-07DOI10．13227/j．hjkx．2015．07．0362014-08-242015-02-092012ZX07201-005512084841989～[e-mail]*[e-mail]calTreatmentPlantSecondaryEffluentbyFentonOxidationWANGYi12WUChang-yong2ZHOUYue-xi2*ZHANGXue12DONGBo1CHENXue-min11．SchoolofEnvironmentalandMunicipalEngineeringLanzhouJiaotongUniversityLanzhou730070China2．ＲesearchCenterofWaterPollutionControlTechnologyChineseＲesearchAcademyofEnvironmentalSciencesBeijing100012ChinaAbstractFentonoxidationwasappliedtotreatthepetrochemicaltreatmentplantsecondaryeffluentbythecontinuousflowconfiguration．TheeffectofFentonagentdosageontheCODandphosphorusremovalandthevariationofthedissolvedorganicmattercharacteristicsduringthetreatmentprocesswereinvestigated．TheresultsshowedtheaverageCODandPO3－4-Pconcentrationswere64.8mg·L－1and0.79mg·L－1respectively．WhenthedosageofH2O230%FeSO4·7H2OandPAMwere0.4mL·L－10.8g·L－1and0.9mg·L－1andtheresidencetimewas30mintheaverageremovalrateofCODandPO3－4-Pwere24.3%and95.5%respectively．TheeffluentCODwaslowerthan50mg·L－1．Thepercentageofdissolvedorganicmatterswithmolecularweightlessthan1×103was80.4%intherawwastewaterhoweverthepercentageincreasedto95.6%whentreatedbyFentonoxidation．Three-dimensionalfluorescenceanalysisshowedthattheFentonoxidationcaneffectivelyremoveproteinandphenols．GC-MSresultsshowedthattherewereabout117kindsoforganicmattersdetectedinthesecondaryeffluentwhilethenumberreducedto27afteroxidationbyFenton．Theorganicscontainingunsaturatedbondhadabetterremovalthanthoseofothertypesoforganics．Fentonoxidationcanbeusedintheadvancedtreatmentofpetrochemicalsecondaryeffluent．KeywordssecondaryeffluentofpetrochemicalwastewateradvancedtreatmentFentonoxidationmolecularweightdistributionorganicmatter．2.1×1010t3%～5%．40%1．．．19981《》GB8978-1996COD＜100mg·L－1．CODBOD55.0mg·L－1234．COD36．Fenton、、、、CO2H2O．FentonFe2+、Fe3+．Fenton、、．FentonFenton、5～8．FentonpH9．pHFentonCODFenton．11.11、FentonFeSO4·7H2O．Fenton43.2L41H2O230%4PAM．14.4LFenton．1．1Table1WastewaterqualityusedinthisstudypHCOD/mg·L－1BOD5/mg·L－1PO3－4-P/mg·L－1TP/mg·L－16.9～7.860～1204.38～2.050.60～1.081.04～1.627.5377.323.140.791.321Fig．1Schematicdiagramoftheexperiment10～12CODH2O230%、FeSO4PAMCOD、UV254、PO3－4-P．1.21.2.1GC-MS13-Agilent7890NIST．HP-5MS60m×250μm×0.25μm40℃3min5℃·min－1300℃3min58min1.0mL·min－1＞99.999%5∶189527Fenton260℃．230℃150℃EI70eV29～350m/z0.5min．1.2.2Models8400Millipore400mL4.18×10－3m20.1MPa．0.45μm100×103、30×103、10×103、5×103、3×103、1×103Millipore．TOCTOCTOC．1.2.30.45μmEx200～500nmEm200～500nm5nm0.5s12000nm·min－1700V．1.2.4CODPO3－4-PUV254752TOCTOC-VCPH/CPN．22.12.1.1H2O2COD、UV254、PO3－4-PL6443H2O230%0.2、0.3、0.4、0.5mL·L－1FeSO4·7H2O0.4、0.6、0.80.10g·L－1PAM0.6、0.9、1.21.5mg·L－1．30min．COD、．、、、、UV254．UV254TOC、CODUV2541415．Fenton·OHUV254．2H2O2H2O2·OHCOD、UV254H2O2．H2O2·OH·OH16～18．H2O2Fe2+Fe3+H2O2·OH．FentonH2O2H2O2FentonH2O2COD．H2O20.4mL·L－1UV254COD．COD1.33VFenton2.8VCOD·OH．PO3－4-P85%～90%2H2O2PO3－4-P．2H2O2COD、UV254、PO3－4-PFig．2EffectsofH2O2dosageontheCODUV254andPO3－4-Premoval2.1.2FeSO4COD、UV254、PO3－4-PCOD、PO3－4-PFeSO4·7H2O0.8g·L－13．FentonFe2+、Fe3+．Fe2+、Fe3+．FentonFe2+、Fe3+9952361920．FeSO4·7H2O-Fe2+、Fe3+20．UV254FeSO4·7H2OFeSO4·7H2OFe2+·OH、、、．3FeSO4COD、UV254、PO3－4-PFig．3EffectsofFeSO4dosageontheCODUV254andPO3－4-Premoval2.1.3PAMCOD、UV254、PO3－4-PFentonPAM．Fe2+、Fe3+PAM、Fe．COD、PO3－4-PPAMPAM0.9mg·L－1COD．PAMPAM19．PAMCODPAMCOD．UV25465%～75%PAMUV2544．2.1.4H2O24PAMCOD、UV254、PO3－4-PFig．4EffectsofPAMdosageontheCODUV254andPO3－4-Premoval30%0.4mL·L－1FeSO4·7H2O0.8g·L－1PAM0.9mg·L－130min．COD64.8mg·L－1COD48.7mg·L－1COD24.3%UV2540.534UV2540.171UV25468.0%PO3－4-P0.78mg·L－1PO3－4-P0.04mg·L－1PO3－4-P95.5%3.4%．UV254COD·OH、．《》GB8978-1996A．H2O230%1400·t－1FeSO4·7H2O300·t－1PAM6000·t－11.9·t－1．2.2Fenton51×10321221×103．FentonCC、NN、CO、、CO2H2O．51×10380.4%1×10395.6%00627FentonFenton·OH、．5FentonFenton5FentonTOCFig．5MolecularweightdistributionandTOCvariationofwastewatertreatedbyFentonoxidation．2.3、65Flu1Flu2Flu3、Flu4Flu523～25．/Ex/EmFI2．Flu1Flu2Fenton．Flu3．FentonCC、NN．Fenton．6FentonFig．6ContourmapofwastewaterbeforeandafterthetreatmentbyFentonoxidation2Table2PositionandintensityoffluorescenceinwastewatersamplesFlu1Flu2Flu3Flu4Flu5Ex/Em230/345275/345236/400236/407313/401FI/AU1414.0409.2302.5307.8232.42.4500mLGC-MS．7、Fenton．MS11780%、、．Fenton27．．6.55nm2.51nm．Fenton95%3．1062367FentonGC-MSFig．7GC-MSspectrogramofthewastewaterbeforeandafterFentonoxidation3FentonTable3NumbersandtypesoforganicsinpetrochemicalsecondaryeffluentandtreatedwastewaterbyFentonoxidation//%//%265.1288.215.601010.50413.412.210.525.9、11.9023.013.731H2O230%0.4mL·L－1FeSO4·7H2O0.8g·L－1PAM0.9mg·L－130minFenton．COD24.3%UV25468.0%PO3－4-P95.5%．COD48.7mg·L－1PO3－4-P0.04mg·L－1《》GB8978-1996A．2Fenton1×1031×103Fenton．3、、Fenton、．4GC-MSFentonCC、NN、CO、．1．M．2011．35．2．J．20136493392-3395．3．