UVH2O2联合氧化法去除畜禽养殖废水中抗生素李文君

:,,1985,,。#。＊(“863”)(No.2007AA06Z344、No.2009AA062906);(No.2009ZX07104-005、No.2008ZX07208-004)。UV/H2O2联合氧化法去除畜禽养殖废水中抗生素＊李文君1,2　蓝　梅1　彭先佳2#(1.,　056038;2.,,100085)　　　,,,,。,。UV/H2O2(、、、、),pH、H2O2、,。:(1)(HPLC/MS),,,50.998,HPLC/MS5。(2)UV254nm、2.0mg/L、pH5.0、H2O27.0mmol/L、60min,595%。,UV/H2O2。(3)UV/H2O25。　　　UV/H2O2　　　RemovalofantibioticsfromswinewastewaterbyUV/H2O2combinedoxidation　LIWenjun1,2,LANMei1,PENGXianjia2.(1.SchoolofUrbanConstruction,HebeiUniversityofEngineering,HandanHebei056038;2.StateKeyLaboratoryofEnvironmentalAquaticChemistry,ResearchCenterforEco-EnvironmentalSciences,ChineseAcademyofSciences,Beijing100085)Abstract:　TheUV/H2O2advancedoxidationprocesswasemployedforremovalofantibioticsfromswinewastewater.TheeffectofpH,H2O2dosageandreactiontimeontheremovalefficiencywasinvestigated.ResultsshowedthatUV/H2O2processpresentedperfectperformanceforantibioticsremoval.UndertheoptimalconditionsofinitialpH5.0,H2O2dosageof7.0mmol/Landthereactiontimeof60min,morethan95%of5antibiotics(2.0mg/L)wereremovedfromswinewastewater.Thedegradationof5antibioticscouldbewelldescribedbythefirst-or-derreactionratemodel.Keywords:　UV/H2O2;antibiotics;removal;swinewastewater　　,、,[1,2]。,,,,[3]。,、,。,8000t。,,,,。3:(1),;(2),;(3)。　　,。(Fenton[4]、UV/O3、UV/Fenton)、[5]、[6]。,、,。,。UV/O3、UV/Fenton,。UV/H2O2,,,,·25·　UV/H2O2DOI:10.15985/j.cnki.1001-3865.2011.04.005。　　UV/H2O2,pH、H2O2、,。1　1.1　实验药品(SMX,99%)、(STZ,99%)、(SML,98%)、(SMN,99%)、(SDM,99%)5(MS)1。,100mg/L,4℃。1　5MSTable1　MSparametersandmolecularweightof5antibioticses(m/z)m/z/minSMX253.325415625.19STZ255.32561569.66SML270.327115620.60SMN278.327915616.99SDM310.331115628.16　　(SBR),2。1.2　实验装置1。,,22W,254nm,1.025mW/cm2。1　Fig.1　Experimentsetup1—;2—;3—;4—;5—1.3　分析方法(HPLC)MS(HPLC/MS)。HPLCAlli-ance2695(Waters,USA),C18(2.1mm×150mm,5μm),(2.1mm×10mm);MSZQ4000(Waters,USA)。HPLC/MS[7]。　　HPLC:20μL,30℃,0.2mL/min;/(99.8%0.2%)、。:0min/∶∶90∶4∶6(,)10min,11min/∶90∶102min,13min/∶87∶132min,15min/∶78∶2210min,25min/∶55∶451min,26min7min,33min/∶∶90∶4∶612min,。。　　MS:,120℃,300℃,3.5kV,300L/h,50L/h。1.4　实验步骤SBR[7]。,,。　　:(1)100mL200mL,;(2)HClNaOHpH;(3)10min,;(4)H2O2,,;(5),0.45μm。2　2.1　标准曲线的制作HPLC/MS,,2　Table2　CharacteristicsofwastewatersamplespHCOD/(mg·L-1)SS/(mg·L-1)TN/(mg·L-1)NH+4-N/(mg·L-1)TP/(mg·L-1)8.0～8.7150～2306812～140～164.3～13.0·26·　　33　4　20114,2,(R2)3。2　Fig.2　Standardcurveoftheantibiotics3　5R2Table3　Correlationcoefficientofthe5antibioticsesSMXSTZSMLSMNSDMR20.99900.99870.99810.99950.9996　　3,5R20.998。,HPLC/MS5。2.2　初始pH对抗生素去除率的影响UV/H2O2,pH,[8]。UV254nm、2.0mg/L、10min、H2O25.0mmol/L(),pH5,3。3　pH5Fig.3　EffectofpHonantibioticsremoval　　3,pH5.0,5;pH1.0～5.0,pH,;pH5.0～11.0,pH,。pHpH。,UV/H2O2H2O2UV·OH,·OH。pHpH·OH,·OH。,UV/H2O2H2O2,(1)[9]。,·OH,UV/H2O2。,H2O2OH-HO-2((2))。HO-2UV(240L/(mol·cm))H2O2UV(18.6L/(mol·cm)),HO-2·OH((3)),H2O2·OH((4)),·OH,[10]。2H2O2UV2H2O+O2(1)H2O2+OH-UVHO-2+H2O(2)·OH+HO-2UVH2O+·O-2(3)·OH+H2O2UVHO2·+H2O(4)2.3　H2O2投加量对抗生素去除率的影响H2O2UV/H2O2。UV254nm、2.0mg/L、pH5.0、10min,H2O25,4。4　H2O25Fig.4　EffectofH2O2doseonantibioticsremoval　　4,H2O27.0mmol/L,;H2O27.0mmol/L,H2O2;H2O27.0mmol/L,H2O2。H2O2:(1)H2O2UV·OH;(2)H2O2·OH((4)),H2O2·OH[11]。·27·　UV/H2O22.4　反应时间对抗生素去除率的影响UV254nm、2.0mg/L、pH5.0、H2O27.0mmol/L,5,5。5　5Fig.5　Removalrateoffiveantibioticsatdifferentreactiontime　　5,0～20min,UV/H2O2,SMX、STZSDM,SMLSMN20min80%;60min,595%。,UV/H2O2。2.5　UV/H2O2氧化降解动力学研究,(5)[12]。(5)(6)。ln(ct/c0)=-kt(5)ct=c0exp(-kt)(6):t,h;ct、c0t、,mg/L;k,h-1。　　UV/H2O25,6,R24。4,UV/H2O25。4　R2Table4　Theparametersoffittingcurvesk/h-1R2SMX0.3540.999STZ0.3740.999SML0.2140.968SMN0.1070.982SDM0.2020.9736　5Fig.6　Thefirst-orderkineticfittingcurvesof5antibioticsdegradation3　　(1)HPLC/MS,,,5R20.998,HPLC/MS5。(2)UV254nm、2.0mg/L、pH5.0、H2O27.0mmol/L、60min,595%。,UV/H2O2。(3)UV/H2O25。:[1]　,,.[J].,2010,56(2):182-183.[2]　,,.[J].,2010,28(2):26-30.[3]　,,,.[J].,2006,24(8):29-33.[4]　BENWeiwei,QIANGZhimin,PANXun,etal.Removalofvet-erinaryantibioticsfromsequencingbatchreactor(SBR)pre-treatedswinewastewaterbyFenton'sreagent[J].WaterRe-search,2009,43(17):4392-4402.[5]　RIVERAUTRILLAJ,PRADOSJOYAG,SNCHEZPOLOM,etal.Removalofnitroimidazoleantibioticsfromaqueoussolutionbyadsorption/bioadsorptiononactivatedcarbon[J].JournalofHazardousMaterials,2009,170(1):298-305.[6]　KOYUNCUI,ARIKANOA,WIESNERMR,etal.Removalofhormonesandantibioticsbynanofiltrationmembranes[J].JournalofMembraneScience,2008,309(1/2):94-101.[7]　BENWeiwei,QIANGZhimin,ADAMSC,etal.Simultaneousdeterminationofsulfonamides,tetracyclinesandtiamulininswinewastewaterbysolid-phaseextractionandliquidchroma-tography-massspectrometry[J].JournalofChromatographyA,2008,1202(2):173-180.(下转第32页)·28·　　33　4　20114,1610～1670cm-1H-O-H,3000～3700cm-1-OH。512、625cm-1Mg-OHFe-OH。PFMS,。2.4　PFMS处理印染废水的絮凝机制分析ZetaCOD,,7。7　ZetaCODFig.7　CorrelationofflocculantdosagetoZetapotentialandCODremoval　　7,,COD,Zeta-25mV-8mV。,PFMS,Zeta,0mV,PFMS。　　,,,,PFMS,Zeta—。,—。　　—,Zeta,,Zeta0mV0mV[4]。,Zeta,COD。pH,PFMS、,Fe(OH)3Mg(OH)2。,Zeta。Fe(OH)3,Mg(OH)2,。PFMS。3　　(1)PFMS,,30min,。(2),PFMS;,COD69%86%。(3),PFMS-;,PFMS。:[1]　SANGYimin,GUQingbao,SUNTichang,etal.Analysisandremovaloforganicpollutantsinbiologicallytreate