16张裕卿南京废气废水会议

用于含油废水和海水净化的超滤膜功能材料的设计和应用案例南京用于含油废水和海水净化的超滤膜功能材料的设计和应用案例张裕卿天津大学化工学院化学工程系Outline1.背景2.用于含油废水和海水净化的超滤膜功能材料的设计和应用案例3.结论MembraneTechnologyBackgroundMembraneTechnologyBackgroundDrawbacksofpolymermembrane(PSF,PVDF)duringapplication聚合物超滤膜存在的缺点PolyvinylideneFluoride,PVDFPolysulfone,PSFPoorhydrophilicityPooranti-foulingPooranti-compactionBackgroundFormationstrategiesofmembrane膜的制备方法BackgroundFunctionalmaterialsblendingFabricationstrategiesStrategyofenhancingpropertiesofpolymermembrane提高聚合物膜性能的途径Design,Dopefunctionalmaterials,Dissolveanddispersesufficiently填充功能材料Pour,Cast,Formhybridmembrane浇铸成膜FlatHollowfiberBackgroundOutline1.背景2.用于含油废水和海水净化的超滤膜功能材料的设计和应用案例3.结论Properties:Smallsize小尺度Abundanthydroxyl(-OHgroups),Lewisacidsites多活性位Highspecificsurfacearea高比表面积OOOSiOOOOOOOOCeFunctionalmaterialsNonstoichiometricfunctionalmateriales非化学计量功能材料FunctionalmaterialsOOOSiOOOOOOOOCeCe-dopednanosilica铈掺杂二氧化硅FunctionalmaterialsCe-DopedNonstoichiometricNanosilicaformodifyingPSFmembranesYZhangetal,ChemicalEngineering&Technology33(2010)676–681铈掺杂二氧化硅改性的聚砜膜BetterhydrophilicityBettertensilestrengthBetteranti-compactionLimitedpropertiesNonstoichiometricinorganicmaterialesChallenge问题Limitedhydrphilicity亲水性有限Limitedproperties性能有限Acidulatednonstoichiometricinorganicmateriales酸促进型非化学计量无机材料Acidulatedinorganicmaterials酸促进型功能材料SulfatedY-dopedzirconia硫酸化钇掺杂二氧化锆PhosphorylatedZr-dopedsilicananotube磷酸化锆掺杂二氧化硅纳米管PhosphorylatedZr-dopedsilica磷酸化锆掺杂二氧化硅AcidulatednonstoichiometricinorganicmaterialesPhosphorylatedZr-dopedhybridsilica（SZP）formodifyingPSFmembranes磷酸化锆掺杂二氧化硅/聚砜膜SEMofSZPandmembraneYZhangetal,JournalofHazardousMaterials186(2011)390-395Particlesize:1-3umAcidulatednonstoichiometricinorganicmaterialesInteractionbetweenpolymerchainsandparticles功能材料和聚合物间的作用PSFPVDFAcidulatednonstoichiometricinorganicmateriales方法和技术路线AcidulatednonstoichiometricinorganicmaterialesAcidulatednonstoichiometricinorganicmaterialesYZhangetal,JournalofHazardousMaterials186(2011)390-395SZP/PSFmembranesfortreatingoilywastewater处理含油废水Higherflux较高的水通量SulfatedY-dopednonstoichiometriczirconia(SZY)formodifyingPSFmembranes硫酸化钇掺杂二氧化锆/聚砜膜YZhangetal,separationandpurificationtechnology70(2009)153-159AcidulatednonstoichiometricinorganicmaterialesPhosphorylatedZr-dopedsilicananotubes（PSNTs）formodifyingPVDFmembranes磷酸化锆掺杂二氧化硅纳米管/聚偏氟乙烯膜YZhangetal,ChemicalEngineeringJournal230(2013)260-271AcidulatednonstoichiometricinorganicmaterialesYZhangetal,ChemicalEngineeringJournal230(2013)260-271AdvantageBetterhydrophilicity亲水Betteranti-fouling抗污染Betteranti-compaction抗压实Betterproperties良好的膜性能AcidulatednonstoichiometricinorganicmaterialesYZhangetal,ChemicalEngineeringJournal230(2013)260-2714060801001201401606080100120140160180200220240260Flux/(L/(m2h))theoilconcentrationofthewastewater/(mg/L)PVDFSiO2/PVDF-15SNTs/PVDF-15PSNTs/PVDF-150246810121416Oilconcentrationinthepermeation/(mg/L)PVDFSiO2/PVDF-15SNTs/PVDF-15PSNTs/PVDF-1512016075Oilconcentrationinthefeedsolution/(mg/L)45Application:Treatingoilywastewater膜处理含油废水的性能PSNTs/PVDFmembrane:Highflux(at0.1MPa)HighseparationAcidulatednonstoichiometricinorganicmaterialesHybridmembraneBetterHydrophilicity较好的亲水Betteranti-fouling较好的抗污染Betteranti-compaction较好的抗压实PerformattractivepropertiesViaphysicalinteractionontheinterfacebetweenaqueoussolutionandmembranes，withoutanychemicalreaction膜改性只是物理作用,没有任何化学反应过程Furtherenhancemembranepropertiesarelimited,Whydo??AcidulatednonstoichiometricinorganicmaterialesEffectofmicroreactionlocations(MRLs)onpropertiesofpolymermembrane具有微反应位的小尺度功能材料StrategyoffurtherenhancingpropertiesofmembraneDopenewfunctionalmaterials掺杂新功能材料Formhybridmembranewithmicroreactionlocations(MRLs)形成微反应位Microreactionlocations(MRLs)Threeclassesofpollutantsinwastewater:1)Organicpollutants(hydrocarbonandsolubleoiletc.)有机污染物2)Microbes微生物3)Inorganicpollutants(metaloxideetc)无机污染物Thesepollutantscanformthegellayeronthesurfaceofmembranes,causingthedeclineofthefluxandpropertiesofmembranes这些污染物在膜上形成凝胶质Microreactionlocations(MRLs)ⅠClassⅡClassSchemeoforganicpollutantsdegradedbyTiO2二氧化钛光催化作用Microreactionlocations(MRLs)YZhangetal,JournalofMembraneScience520(2016)54–65YZhangetal,ChemicalEngineeringJournal301(2016)342-352Microreactionlocations(MRLs)TetragonalZrO2shell四方相Strongacid超强酸:Degradeandrestraininorganicpollutantsviastrongacid(acidity=-16.5)超强酸分解金属氧化物或抑制其形成PorousZrO2solidsuperacidparticles多孔二氧化锆固体超强酸ⅡClassPVDFDopeYZhangetal,ChemicalEngineeringScience135(2015)67–75PorousZrO2solidsuperacidshell/void/TiO2coreparticles(ZVT)多孔ZrO2包覆TiO2固体超强酸/聚偏氟乙烯膜Microreactionlocations(MRLs)Degradeorganicpollutants(hydrocarbonandsolubleoiletc.)andmicrobesviaphotocatalyticreaction光催化降解有机污染物和微生物Degradeandpreventinorganicpollutants(metaloxide)viastrongacid超强酸分解金属氧化物或抑制其形成Microreactionlocations(MRLs)PSFDopeYZhangetal,JournalofMembraneScience493(2015)275–284SulfatedTiO2depositedonSiO2Nanotubes(STSNs)硫酸化TiO2沉积SiO2纳米管/聚砜膜Microreactionlocations(MRLs)YZhangetal,JournalofMembraneScience520(2016)54–65YZhangetal,ChemicalEngineeringJournal301(2016)342-352PorousYxFeyZr1-x-yO2coatedTiO2solidsup