改性聚偏氟乙烯微滤膜深度处理城市污水的研究宋来洲

宋来洲1,　张尊举1,　李洪喜2,　李晓博1(1.燕山大学环境与化学工程学院,河北秦皇岛066004;2.秦皇岛市第三污水处理厂,河北秦皇岛066004)　　　:　采用改良的热诱导化学聚合技术,在聚偏氟乙烯(PVDF)微滤膜表面接枝具有离子交换性能的羧酸基团,并借助X衍射光电子能谱(XPS)和环境扫描电镜(ESEM)对改性PVDF微滤膜进行了表征。采用该改性PVDF(PAA/PVDF)膜深度处理城市污水,探讨了pH值、接触时间对处理效果的影响。试验结果表明:热诱导化学聚合技术在PVDF膜表面成功接枝了羧酸基团,PAA/PVDF膜对水溶性金属离子具有交换去除作用,出水水质优良。　　:　聚偏氟乙烯;　微滤膜;　改性;　城市污水;　深度处理:X703.1　　:A　　:1000-4602(2006)13-0038-04ApplicationofModifiedPolyvinylideneFluorideMicrofiltrationMembraneforAdvancedTreatmentofMunicipalWastewaterSONGLai-zhou1,　ZHANGZun-ju1,　LIHong-xi2,　LIXiao-bo1(1.SchoolofEnvironmentalChemicalEngineering,YanshanUniversity,Qinhuangdao066004,China;2.ThirdSewageTreatmentPlant,Qinhuangdao066004,China)　　Abstract:　PolyvinylideneFluoride(PVDF)microfiltrationmembranemodifiedbyacrylicacidgraftpolymerizationwasusedtotreatsecondaryeffluentofamunicipalwastewatertreatmentplan.tUsingX-rayPhotoelectronSpectroscopy(XPS)andEnvironmentalScanningElectronMicroscopy(ESEM),thesurfacemorphologyandsectionmorphologyofthemodifiedPVDFmembranewereinvestigated.TheperformancewasevaluatedbydeterminingtheremovalsofChemicalOxygenDemand(COD),SuspendedSubstance(SS),turbidity,andmetalions.Atthesametime,influenceofpHandcontacttimeonre-movaleffectwasdiscussed.TheresultsshowthatthemodifiedPVDFmembraneisefficientintreatingsolublemetalionswithabettereffluentqualitythanthePVDFmembrane.　　Keywords:　polyvinylidenefluoride;　microfiltrationmembrane;　modification;　municipalwastewater;　advancedtreatment　　(PVDF)、、、,[1～6]。PVDF,,。[7],,,X(XPS)(ESEM)PVDF(PAA/PVDF),PAA/PVDF。1　试验部分1.1　PVDFPVDF[8]。:,15%～20%;(),3%～5%;N,N—(38第22卷　第13期2006年7月　　　　　　　　　　　　中国给水排水CHINAWATERWASTEWATER　　　　　　　　　　　　　Vo.l22No.13Ju.l2006),73%～81.5%;,35～45℃。,:(40.6mL/L)、(6.25g/L)、(1.72g/L)、(1.5g/L),,。PVDF:30～45min;;(100～110℃)30min;PAA/PVDF12h,,。1.2　VGESCA250X,XL30。2100P,[9]。pH0.1mol/L0.1mol/LNaOH。2　结果与讨论2.1　PVDFX1PVDFPAA/PVDFX(XPS)。1　PVDFPAA/PVDFXPSFig.1　XPSspectraofPVDFmembraneandPAA/PVDFmembrane1(a)PVDFC1sXPS,[10、11],CH2CF2285.8、290.43eV。1(b)PAA/PVDFC1sXPS,5,285.8、290.43eVPVDFCH2CF2,288.5eVO-CO,286.2eVCO,284.6eV。XPS,PVDF。2.2　PVDFPVDFPAA/PVDF2。39第13期宋来洲,等:改性聚偏氟乙烯微滤膜深度处理城市污水的研究第22卷2　PVDF、PAA/PVDFFig.2　SEMphotographsofPVDFandPAA/PVDFmembranes　　2,,0.25μm0.2μm,;PVDF、PAA/PVDF,,,。2.3　PVDFPVDFPAA/PVDF:[6],0.05MPa,160μm,19.6cm2。PVDFPAA/PVDF、SS、COD12。1　PVDFTab.1　EffectofcontacttimeonpollutantremovalbyPVDFmembrane　/min306090120COD/%42444344SS/%94939493/%95949694Fe/%46454746Al/%30313132Mg/%1010.710.911Ca/%3.843.83.9　　PVDF,CODSS、,。PAA/PVDFSS、CODPVDF,,,,。PVDF30min,FeAl70%44%;90min,FeAl89%63%。2　PAA/PVDFTab.2　EffectofcontacttimeonpollutantremovalbyPAA/PVDFmembrane　/min306090120COD/%48495251SS/%95949396/%96959694Fe/%70838992Al/%44516366Mg/%26344346Ca/%18263032　　pHPVDF3(90min)。3　pHPAA/PVDFTab.3　EffectofwastewaterpHonpollutantremovalbyPAA/PVDFmembrane　pH34579COD/%4851504952SS/%9495949695/%9594969596Fe/%7496949067Al/%3476746737Mg/%3344534631Ca/%2941403224　　3,pHCOD、SS、Ca、Mg,、,pH4～5。,、,pH,PVDF。90min,4。4,PVDFPAA/PVDFSS,COD40第13期　　　　　　　　　　　　　　　　　　　中国给水排水　　　　　　　　　　　　　　　　　　第22卷。PVDF,Fe、Al、Mg、CaPAA/PVDF。PVDF,PAA/PVDF,,。4　Tab.4　Effluentqualityofmicrofiltrationmembrane　PVDFPAA/PVDFCOD/(mgL-1)834839SS/(mgL-1)2822/NTU6.420.540.22Fe/(mgL-1)1.440.780.24Al/(mgL-1)0.760.520.26Mg/(mgL-1)11610463Ca/(mgL-1)312303217　:　、PVDF、PAA/PVDFpH7.52、7.43、6.44;PVDFPAA/PVDF52、48L/(m2h)。3　结论,。,PVDFPVDF,PVDF。PVDF,PVDF。:[1]　HolmbergS,HolmlundP,WilenCE,etal.Synthesisofproton-conductingmembranesbytheutilizationofpreir-radiationgraftingandatomtransferradicalpolymeriza-tiontechniques[J].JPolymSciPartA:PolymChem,2002,40(4):591-600.[2]　HesterJF,MayesAM.Designandperformanceoffoul-resistantpoly(vinylidenefluoride)membranespreparedinasingle-stepbysurfacesegregation[J].JMembrSci,2002,202(1):119-135.[3]MaHuimin,ChristopherNBowman,RobertHDavis.Membranefoulingbybackwashingandsurfacemodifica-tion[J].JMembrSci,2000,173:191-200.[4]　MartínezF,MartínA,PrádanosP,etal.Proteinadsorp-tionanddepositionontomicrofiltrationmembranes:Theroleofsolute-solidinteractions[J].JColloidInterfaceSci,2000,221(2):254-261.[5]　,.[J].,2005,31(4):74-76.[6]VieiraM,TavaresCR,BergamascoR,etal.Applicationofultrafiltrationcomplexationprocessformetalremovalfrompulpandpaperindustrywastewater[J].JMembrSci,2001,194(22):273-276.[7]　ChenJ,ZhaoY.Relationbetweenwaterabsorbencyandreactionconditionsinaqueoussolutionpolymerizationofpolyacrylatesuperabsorbents[J].JApplPolymSci,2000,75(6):808-814.[8],.-[J].,2005,25(2):34-37.[9]　.:[M].:,2001.[10]FlintSD,SladeRCT.Investigationofradiation-graftedPVDF-g-polystyrene-sulfonic-acidionexchangemem-branesforuseinhydrogenoxygenfuelcells[J].SolidStateIonics,1997,97(1):299-307.[11]HolmbergS,NäsmanJH,SundholmF.Synthesisandpropertiesofsulfonatedandcrosslinkedpoly[(vinylidenefluoride)-graft-styrene]membranes[J].PolymAdvTechnol,1998,9(2):121-127.:(1972-　),　,　,　、,　。:(0)13784068167E-mail:[e-mail]:2006-03-1541第13期宋来洲,等:改性聚偏氟乙烯微滤膜深度处理城市污水的研究第22卷