2羟丙基三甲基氯化铵壳聚糖聚砜复合纳滤膜的制备

　40　620076　　　　　JournalofTianjinUniversityVo.l40　No.6Jun.2007　　　　:2006-07-10;:2007-01-09.　　　:973(2003CB615706).　　　:(1976—　　),,,[e-mail]　　　:,[e-mail].2-/黄瑞华1,2,陈国华1,孙明昆1,高丛堦1(1.,266100;2.,712100)　:以2-羟丙基三甲基氯化铵壳聚糖(HACC)为活性功能层,聚砜超滤膜为支撑层,以六亚甲基二异氰酸酯(HDI)为交联剂,制备了一种荷正电复合纳滤膜.探讨了HACC浓度、HDI浓度、交联温度等制备条件对膜性能的影响.通过电镜扫描对膜的结构进行了表征,显示了该膜的复合结构.复合膜的截留相对分子质量为500左右,膜孔径约为0.71nm.并且,对膜的性能进行了测试,探索了操作压力、料液浓度、料液类型等操作条件对膜性能的影响.其中,在20℃,复合膜的纯水渗透系数为13.6L/(hm2MPa);对不同无机盐的截留顺序为:MgCl2NaClKClMgSO4Na2SO4K2SO4,呈现荷正电纳滤膜的特征.:2-;;;:TQ028　　　:A　　　:0493-2137(2007)06-0688-06Preparationof2-HydroxypropyltrmiethylAmmoniumChlorideChitosan/Poly(Sulfone)CompositeNanofiltrationMembraneHUANGRui-hua1,2,CHENGuo-hua1,SUNMing-kun1,GAOCong-jie1(1.CollegeofChemistryandChemicalEngineering,OceanUniversityofChina,Qingdao266100,China;2.CollegeofScience,NorthwestAFUniversity,Yangling712100,China)Abstract:Anovelpositivelychargedcompositenanofiltration(NF)membranewaspreparedusing2-hydroxypropyltrimethylammoniumchloridechitosan(HACC)asactivefunction-layer,poly(sulfone)(PSF)UFmembraneassupportlayerandhexamethylenediisocyanate(HDI)ascross-linkingreagen.tTheeffectofpreparationconditionsonmembraneperformancewereinvestigatedsuchasHACCconcentration,HDIconcen-tration,etc.ThestructurecharacteristicsoftheresultantNFmembraneisobservedbyscanningelectronmicro-scope,revealingthecompositestructureoftheNFmembrane.Andthecut-offmolecularweightofthecompositemembraneisabout500withaporediameterof0.71nm.Additionally,theeffectofoperationconditionsonmembraneperformancewerestudiedsuchasoperatingpressure,feedconcentration,thetypeoffeed,etc.At20℃,thepermeabilityofpurewateroftheNFmembraneis13.6L/(hm2MPa).TheorderofrejectiontodifferentsaltsolutionsisMgCl2NaClKClMgSO4Na2SO4K2SO4,revealingthecharacteristicsofpositivelychargedNFmembranes.Keywords:HACC;HDI;positivelychargednanofiltrationmembrane;membraneperformance　　,.,,、,[1—3]、[4—5]、[6]、[7—9],、.,,,,,,[10—12]、[13]、[14—15],,[16]..,,、、.,2-(2-hydroxypropyltrimethylammoniumchloridechitosan,HACC),(hexam-ethy-lenediisocyanate,HDI),.HACC,,,HACC/PSF..1　1.1　[17—18].1.1.1　实验流程1.,,19.6cm2.,30min,.,,.1　Fig.1　Membraneevaluationapparatus1.2　HACC,,PSFUF,50℃2h,HDI,,50℃20min,,24h.1.3　FR　F=VAt×600(1)　R=1-cpcm(2):F,L/(hm);V,cm3;A,cm2;t,s;R;cp,mg/L;cm,mg/L.,,.、;BaCl2.2　、、,:1000mg/LMgCl2;30L/h;20℃(,).2.1　HDIHACC,HACC,,,HDI,2.:2.00/0HACC,50℃2h,HDI(0.2～0.6)∶50,50℃22h,50℃20min.,,.,,,,.,,,.HDI,.,,,,.,HDI(0.3～0.4)∶50.2.2　3.:2.00/0HACC,50℃2h,689　20076　　　　　　　　:2-/2　HDIFig.2　EffectsofHDIconcentrationoncompositemembraneperformanceHDI0.3∶50,50℃17～30h,50℃20min.3,;.,,,,.,,,,,.,26h.3　Fig.3　Effectsofcross-linkingtimeoncompositemembraneperformance2.3　,,20～60℃,4.:2.00/0HACC,50℃2h,HDI0.3∶50,20～60℃26h,50℃20min,,,,50℃,,.,,,,,.,,HDI、HDI,,,.50℃.4　Fig.4　Effectsofcross-linkingtemperatureoncompositemembraneperformance2.4　(HACC),.,,(1.0～3.0)0/0.5,:(1.0～3.0)0/0HACC,50℃2h,HDI0.3∶50,50℃26h,50℃20min,,;,2.00/0,.,,,,,,;,,,,,,.[3].,2.00/0.5　HACCFig.5　EffectsofHACCconcentrationoncompositemembraneperformance690　　　　　　　　　　　　　　　　　　　　　　40　6　3　3.1　,,JMS-840.650002500.,、,.(a)(b)6　Fig.6　Surfaceandcross-sectionimagesofcompositemembrane3.2　7,:(M=198)、(M=342),(M=600～1000).1000mg/L,1.0MPa、30L/h,,.(1),900/0,500,0.71nm[19].3.4　:2.00/0,50℃2h,HDI0.3∶50,50℃26h,50℃20min.7　Fig.7　Curveofthecut-offmolecularweightofcompositemembrane20℃.3.4.1　膜的纯水渗透系数8,,.0.5～1.4MPa、7.1～19.4L/(hm2),Spiegler-Kedem[20]　Jv=Lp(Δp-σΔπ)(3):Jv;Lp;Δp,;Δπ;σ.,,Jv,.,σΔπ.,Lp13.6L/(hm2MPa).8　Fig.8　Curveofthefluxforpurewateragainstoperatingpressure3.4.2　操作压力对复合膜性能的影响9.1000mg/LMgCl2.,;,,1.0MPa,,[21].691　20076　　　　　　　　:2-/9　Fig.9　Effectsofoperatingpressureoncompositemembraneperformance3.4.3　料液浓度对复合膜性能的影响1MgCl2NaCl,1,,.[22—25],Donnan,,,Donnan,.,,,.1　Tab.1　EffectsoffeedconcentrationsoncompositemembraneperformanceMgCl2NaCl/(mgL-1)RF/(Lh-1m-2)/(mgL-1)RF/(Lh-1m-2)10000.96912.9010000.80913.920000.96111.5020000.63813.630000.9468.7930000.60712.8　　:1.0MPa,30L/h.3.4.5　料液类型对复合膜性能的影响2,.:MgCl2NaClKClMgSO4Na2SO4K2SO4,[26],.,MgCl2NaClKClMgSO4Na2SO4K2SO4,,Ca2+Mg2+K+Na+;MgCl2MgSO4,NaClNa2SO4KClK2SO4,SO42-Cl-.,KClMgSO4,(),(SO42-)(Cl-);,NaClKClNa2SO4K2SO4,Na+K+,.2　Tab.2　EffectsofthevarietyofsaltsolutiononcompositemembraneperformanceRF/(Lh-1m-2)MgCl20.96912.9MgSO40.58511.9Na2SO40.36511.6K2SO40.33111.6KCl0.76013.8NaCl0.80913.9　　:1.0MPa;30L/h;1000mg/L.4　　(1)HACC,PSFUF,.、、,、.(2),、、.,20℃,13.6L/(hm2MPa);MgCl2NaClKClMgSO4Na2SO4K2SO4,.1.0MPa、30L/h,1000mg/LMgCl2、MgSO4、Na2SO4、K2SO4、KCl、NaCl0.969、0.585、0.365、0.331、0.760、0.809,12.9、11.9、11.6、11.6、13.8、13.9L/(hm2).,.:[1]　MusaleDA,KumarA.Effectsofsurfacecrosslinkingonsievingcharacterisationofchitosan/poly(acrylonitrile)com-positenanofiltrationmembrane[J].SeparationPurificationTechnology,2000,21:27-38.692　　　　　　　　　　　　　　　　　　　　　　40　6　[2]　,,.[J].,2002,17(2):63-66.TanShaozao,ChenZhonghao,ChenZhenhua.Preparationof/poly(acrylonitrile)nanofiltrationmembraneanditsre-jectionperformanceinpulpandpaperwaste-water[J].TransactionofChinaPulpandPaper,2002,17(2):63-66(inChinese).[3]　MiaoJing,ChenGuohu