湖南省土木建筑学会给排水专业委员会第三十二次学术会马军教授ppt

饮用水厂升级改造与深度处理技术进展

马军哈尔滨工业大学市政环境工程学院majunhit@126.com

内容水质问题预氧化技术常规工艺强化技术臭氧催化氧化技术过硫酸盐催化氧化技术膜技术饮用水水质问题WaterqualityprobleminurbanareaMicropollutantNandPNOMsOrganicmicropollutantsPOPs,EDCsheavymetalsAlgaeandtasteOdourtoxinsNitriteandMnStabilizationofcolloidsDisinfectionBy-productsIndustrialwastewaterMunicipalwastewaterRainwaterAgriculturesurfacerunoffWastewaterfrom

LivestockEartherosion预氧化技术氧化剂臭氧高锰酸盐高铁酸盐二氧化氯过硫酸盐氯高级氧化(AOPs)—高锰酸盐预氧化预氧化技术

EDCs/PPCPsPseudo-PersistentContainingSomeElectron-RichMoieties氧化有机污染物高锰酸钾氧化内分泌干扰物和药物Jiang,Pang,Ma.Environ.Sci&Technol.,2009ShaoandMa,JWaterST-Aqua,2010ShaoandMa,JWaterST-Aqua,2010ShaoandMa,JWaterST-Aqua,2010ImpactofbackgroundconstituentsHe,Guan,Ma,Environ.Sci.&Technol.,2009,43,8332-8337●MnO2/KMnO4●MnO2/KMnO4PermanganateoxidationofvariousorganicsIdentificationofmanganeseintermediatesLigandssignificantlyinhibitthedisproportionationofMn(III)intoMnO2(i.e.,enhancethestabilityofMn(III))Jiang,Pang,Ma.Environ.Sci.Technol.2010,44,4270-4275Application:Enhancedremovalofalgaebypermanganatepreoxidation

藻含量：2.5×106个/L，pH7.2-7.5,水温27oCWithpreoxidationPACdose(mg/L)PAC(mg/L)PAC(mg/l)Removalofalgae(%）

EnhancedremovalofalgaebypermanganatepreoxidationPermanganateCompositepermanganateconcenmtration(μg/L)AlgaeWavelength(nm)RemovaloftasteandodorbypermanganatepreoxidationIntensityofodour

Fullscaleapplicationofpermananatepreoxidationforalgaeremoval(200000m3/d)WithoutPPCpreoxidationWithPPCpreoxidationAlgaeaftersedimentation(Cell/L)Withpermanganaste

preoxidationPACcoagualtiononlyFullscaleapplicationofpermanganatepreoxidationfortasteandodorremoval(1500000m3/d)OdorIntensity—高铁酸盐预氧化预氧化技术高铁酸盐预氧化除藻

湖泊水

浊度

10-30NTU；含藻量

8×106-2×107个/升；pH7.5-7.7.MaandLiu,WaterResearch,2002Effectofferrateoxidationoncell’structuresEnhancedremovalofturbiditybypreoxidationwithferratepreoxidation

a)Al2(SO4)318H2OMaandLiu,WaterResearch,2002Turbidityinsettledwater(NTU)Turbidityinfilteredwater(NTU)EnhancedremovalofFeandMnfromsurfacewaters

MaandLiu,WaterResearch,2002FerrateDosage(K2FeO4,mg/L)FerrateDosage(K2FeO4,mg/L)EnhancedcolorandturbityreductionbyferrateproxidationFerrateDosage(K2FeO4,mg/L)FerrateDosage(K2FeO4,mg/L)Enhancedremovalofheavymetals

FerrateDosage(K2FeO4,mg/L)FerrateDosage(K2FeO4,mg/L)CdRemoval(%)PbRemoval(%)—各种预氧化技术效能比较预氧化技术各种预氧化技术氧化动力学Jiang,Pang,Ma.Environ.Sci.Technol.2010,44,4270-4275OxidationofE2insurfacewater(a)andwastewater(b)backgroundLogarithmoftherelativeresidualconcentrationofE2duringoxidativetreatmentasafunctionofoxidantdoseinsurfacewater(a)andwastewatereffluent(b)atpH8,andtheconsumptionkineticsoftheselectiveoxidants(~12μM)inthesetwowaters(cforsurfacewateranddforwastewatereffluent).Effectofpermanganateoxidationonalgaecells

XieandMa,Environm

Sci&Technol.,2013Effectofozoneoxidationonalgaecells

XieandMa,EnvironmentalScience&Technology,201332ComparisonofpermanganateandozonepreoxidationofalgaeonitsBDPsformationNoinfluenceMuchIncrease臭氧预氧化和高锰酸钾预氧化对藻代谢有机物预处理后续消毒副产物比较ComparisonofpermanganateandozonepreoxidationofAOMofalgaeonitsBDPsformationNoInfluenceMuchincreaseComparisonofpermanganateandozonepreoxidationofAOMofalgaeonfluorescenceabsorption

KMnO4

O3

XieandMa,EnvironmentalScience&Technology,2013ComparisonofpermanganateandozonepreoxidationofAOMfromalgaeonformationofhighmolecularweightorganicmatters

XieandMa,EnvironmentalScience&Technology,2013

XieandMa,EnvironmentalScience&Technology,2013ComparisonofpermanganateandozonepreoxidationofalgaeonitsDBPsformation

常规工艺强化技术--强化混凝技术混凝工艺问题DifficultyintreatingthewaterwithlowtemperatureandlowturibidityDifficultyintreatingthewaterwithhighorganiccontent,particularhumicbearingwaters39强化混凝EnhancedcoagulationConventinalcoagulationRFlocSizeXiaoandMaWaterResearch,

2008剩余铝浓度降低EnhancedcogalutionConventionalcoagulationXiaoandMaWaterResearch,

200841

强化除色除浊效果EnhancedcoagulationConventionalccoagulationXiaoandMaWaterResearch,

200842PACEnhancedcoagulationRawwater43强化混凝处理高色度地表水Dose(mgAl2O3/L)05101520PermanganateindexCODMn(mg/L)2.71.9CODMnReduction(%)065.4475.781.686.1PAC强化混凝原水

PAC强化混凝原水

生产性应用结果Temperature3-5

℃CODReduction68%

LocationsParametersRawwaterSedimentationBeforefiltrationAfterfiltrationDisinfectionwaterStartpointEndpointTurbidity（NTU）8.750.3440.2930.3890.1800.272Color(Unit)3066665pH7.587.357.377.287.347.34CODMn（mg

/L）5.062.101.62生产性应用结果

LocationsParametersRawwaterSedimentationBeforefiltrationAfterfiltrationDisinfectionwaterStartpointEndpointTurbidity（NTU）3.370.1840.2200.2810.1850.230Color(Unit)3866655pH7.366.666.666.686.726.68CODMn（mg

/L）8.802.242.082.122.042.00CODReduction：77.3%AftersedimentationBeforefiltration--强化沉淀

强化常规处理工艺现行沉淀技术存在问题HorizontalflowtankLowefficiency,highlength(100-120m)InclinedtubesettlingtankHighefficiency,lessspacerequired,inferiorflowcondition,inferiorfinishedwaterquality54新型沉淀池双向流平流斜板沉淀池沉淀效率高、适应能力强、抗冲击负荷能力强克服了平流沉淀池的异重流问题5758气浮除有机物效能MaandJiang,Environ.Sci.Technol,200759沉淀与气浮联用技术60生产性应用效果利用沉淀与气浮技术进行平流沉淀池升级改造浊度去除效果TurbidityOperationdays63Reductionoforganics（CODMn)64ReductionofalgaeAlgae65臭氧催化氧化深度处理技术66HydrousMnO2CatalystsdevelopedinourgroupCeramichoneycomb(CH)FeOOH

Surfacebound-OH-ionsplayakeyroleTiO2Mn-TiO2Co-TiO2BimetalliccatalysisFormedinsitudifficulttorecycleMnOx/GACNano-sizecatalystCarbonnanotubeNobelmetalcatalystReducedby-productsImprovedstabilityofsupportPt/CarbonnanotubeSupportedTiO2Nano-sizeparticlesdifficulttoseparateMn-Fe-K/CHMn-Cu-K/CHMultiplemetaloxidessupportedZnO/CH

NiO/CH

Fe2O3/CH

MnO2/CHCuO/CH

metaloxidesupportedAmorphousMnOxeasytoleachCeO2MinimizingbromateformationduringcatalyzedozonationMncatalysts----MnOxformedinsituT=294K,pH=7.0(1mMPO43-buffered),[O3]=2.28mg/L,Mndosage=1mg/L,[Atrazine]0=3uM1)AhighcatalyticactivityofMnOx2)Surfacebound-OH-ionsplayakeyroleMa,OzoneSci.Eng.(1997)227Ma,WaterRes.(1999)785Ma,WaterRes.(2000)3822Heterogeneouscatalyticozonationofrefractoryorganics:1.conceptSurfacehydroxylgroupsinitiatingozonedecompositionintohighlyactivehydroxylradicalsMaJandGrahamN.,WaterResearch,1999；2000HydroxylonsurfaceMncatalysts----MnOx/GACBatchtestContinuoustest(MnOxformedinsitudifficulttorecycle)OzoneSci.Eng.(2004)3WaterRes.(2005)779Mncatalysts----MnO2/CeramichoneycombT=293K,pH=6.92,[NB]0=50ug/L,[totalappliedozone]=1.00mg/L;CHdose=58.3mg/L,2%MnO2/CHdose=60.3g/LO3CH/O3MnO2-CH/O3(AmorphousMnOxonGACeasytoleach)Appl.Catal.B:Environ.(2008)256Fecatalysts----FeOOHAhighlyhydroxylatedsurface

J.Mol.Catal.A:Chem.

(2008)82Appl.Catal.B:Environ.(2008)131Nano-sizedcatalyst----

TiO2andsupportedCatalyzedozonationofnitrobenzenewithdifferentcatalystmass([O3]0=0.367mg/L,[NB]0=60ug/L,T=293K)J.Mol.Catal.A:Chem.

(2007)41OzoneSci.Eng.

(2009)45TiO2/Silica-Gel[O3]0=0.9mg/minCeramichoneycombsupportedcatalystT=293K,pH=6.92,[NB]0=50ug/L,[totalappliedozone]=1.00mg/LEnviron.Sci.Technol.

(2009)2047Environ.Sci.Technol.

(2009)4157ZnONiOFe2O3CuOInitiationof•OHprofoundlydependsonthedensityofsurface-OH2+ofceramichoneycombsupportedcatalyst

Catalyticozone:

Fe＞Ni

＞

Zn

HO•initiationisrelatedtosurfacehydroxyldensityEnviron.Sci.Technol.,2008;2009Ceramichoneycombsupportedcatalyst

------Multipleelementsmetaloxides

T=293K,pH=6.92,[NB]0=50ug/L,[totalappliedozone]=1.00mg/LJ.Environ.Sci:China.(2006)1065Mn-CuMn-Fe-KAppl.Catal.B:Environ.(2009)326能够彻底分解破坏DegradationofNitrobenzenebyCata-ozonationDegradationoforganicsbyultrasonicwavesZhao,Sun&Ma,etal.

Environ.Sci.Technol.

(2009)InitiationofOH.byUSZhao,Sun&Ma,etal.

Environ.Sci.Technol.

(2009)MineralizationbyUS-EffectoftypesofUSfields

Zhao,Sun&Ma,etal.

Environ.Sci.Technol.

(2009)US-assistedcatalyticozonation☆：AdsorptionbyCH；△：US；●：US/CH；□：Ozone；★：Ozone/US；○：Ozone/CH；▲：US/Ozone/CH臭氧催化氧化工程应用PermanganateproxidationpriortoozonationEnhancedcoagulationandpretreatmentbypreoxidationwithpermanganateOzonationandcatalyticozonationafterfiltrationCatalyticozonationcontactorComparativestudyofcata-O3/BACandBACwithO3/BAC

Ozonation/BAC

Catalyticozonation/BACMonitoringpointsⅠ—OzoneⅡ—Ozone/BACⅢ—CatozoneⅣ—Catozone/BACDOCreductionsbycatalyticozonation过硫酸盐高级氧化降解水中有机污染物脱氢电子转移SO4•-

+有机物2.5-3.1VHO•

1.8-2.7V加成SO42-+产物饮用水水质标准限值250mg/L简介选择性稳态浓度高SO4•-有机污染物除草剂酚类水体修复水处理Antoniou,etal.,2010;Lau,etal.,2007;Waldemeretal.,2007;Chanetal.,2007;Hori,etal.2005;Anipsitakis,etal.,2004藻毒素…简介持久性有机物内分泌干扰物卤代有机物消毒工艺93热过渡金属辐射碱醌SO4•-

简介过氧单硫酸盐（PMS）过氧二硫酸盐（PDS）94基于硫酸根自由基新型高级氧化技术与理论紫外催化活化过氧单硫酸盐磁性金属材料活化过氧单硫酸盐羟胺强化亚铁活化过氧单硫酸盐近期研究结果951紫外催化活化PMS提出并验证了紫外催化PMS体系中HO•和SO4•-产生与转化途径。建立了紫外催化PMS体系中HO•、SO4•-以及有机污染物的降解动力学表达式。961

紫外催化活化PMS通过自由基抑制实验和电子顺磁共振(EPR)技术验证了过氧单硫酸盐在λ=254nm紫外辐射下主要发生-O-O-键断裂，产生羟基自由基(HO•)和SO4•-SO4•-HO•1

紫外催化活化PMS

1

紫外催化活化PMS引用32次99HCO3-Cl-NO3-NOM水质参数的影响1紫外催化活化PMS表明各种参数取值为在天然水体存在的浓度时，该工艺仍应该具有较好的除污染效果。100与UV/

H2O2

和UV/PDS对比：H2O2

：固体药剂，

相对于H2O2容易运输和保存PDS：

相对于UV/PDS

，

UV/PMS在pH8-10自由基产率高，除污染效果好更适用于碱性条件1紫外催化活化PMS101基于硫酸根自由基新型高级氧化技术与理论紫外催化活化过氧单硫酸盐磁性金属材料活化过氧单硫酸盐羟胺强化亚铁活化过氧单硫酸盐2磁性金属材料活化PMS合成了一种对过氧单硫酸盐具有高活化特性的磁性金属材料，CuFe2O4。进一步研究其活化过氧单硫酸盐降解有机污染物的活性物种和自由基的形成机理。分析了不同水质参数如pH、碱度、天然有机物、无机盐类以及不同水质背景水体对降解污染物效果的影响。发现SO4•-比HO•具有更强的选择性，受水体背景成份影响更小，因而稳态浓度更高、氧化效率更高。2磁性金属材料活化PMSNOMHCO3-PMSCuFe2O4pH2磁性金属材料活化PMS水质参数和操作条件的影响105TableS1-waterqualityparametersofeffluentsfromdissolvedairflotation(DAF),biologicalactivecarbon(BAC),andsandfilter(SF)

DOC(mg/L)Alkalinity(asCaCO3,mg/L)CODMn(mg/L)pHNO2--N(mg/L)NO3--N(mg/L)NH3--N(mg/L)EffluentofDAF5.73107.063.437.840.243.380.91EffluentofBAC6.6197.95

2.807.830.254.990.51

EffluentofSF5.47100.11

2.367.820.015.100.25

2磁性金属材料活化PMS实际水体背景下的去除效果106对比了不同金属的铁酸盐活化PMS去除污染物的效果：CoFe2O4>CuFe2O4>MnFe2O4>ZnFe2O4.金属的铁酸盐活化PMS机理实质为电子