催化臭氧氧化深度处理工业废水的研究及应用

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,(,,200092)[],,,。、,、。,、、,,。[];;;[]X703[]A[]1005-829X(2019)01-0001-07ResearchoncatalyticozonationanditsapplicationtotheadvancedtreatmentofindustrialwastewaterPengShuhan,WuDeli(StateKeyLaboratoryofPollutionControlandResourcesReuse,ShanghaiInstituteofPollutionControlandEcologicalSecurity,TongjiUniversity,Shanghai200092,China)Abstract:Sincecatalyticozonationtechnologycanaccelerateozonedecomposition,producingthenon-selectivehyd-roxylradicals,itcaneffectivelypromotethedegradationofrefractoryorganicpollutants,meanwhileimprovingthemineralizationofwastewaterandtheutilizationofozone.Asaresult,catalyticozonationhasattractedagreatatten-tioninthefieldofindustrialwastewatertreatment.Inviewofthecomplexcomponentsofindustrialwastewaterandvarietiesofreportedcatalysts,theperformance,controlparameterandmechanismofthistechniquearedifferent.Bymeansofanalyzingtherelevantapplicationresearchonthecatalyticozonationadvancedtreatmentofindustrialwaste-water,theinfluencingfactors,processtypesandmechanismprocessareintroducedinthispaper,theapplicationlimi-tsofthistechnologysummarized,andthedevelopingtrendspredicted.Keywords:catalyticozonation;industrialwastewater;advancedtreatment;catalyst,2015199.5t293.5t。,,。,。,。,,,〔1〕。,2.80V,。,。1〔2〕。[](21776223)39120191IndustrialWaterTreatmentVol.39No.1Jan.,20191,。,,、、。1.1,,13.1%,UV,、、、、〔3〕,。。、,。4:(1);(2);(3);(4)。,、、3,44.7%、23.4%、14.9%。,、、、。,,2%。:;,,,TOC,,〔4-6〕。,。。,Mn、Fe、Cu,d,,,。。,pH。pH=8,COD30%~65%,:CoZnCuNiCrFeMn〔7〕。〔8〕3pH=7,:Fe2O3TiO2MnO2。M.Trapido〔9〕pH=3,:Fe2O3CoOMoO3CuONi2O3Al2O3TiO2Cr2O3≈MnO2≈。,,:Ni、Cr、Ag,,;Co,Fe、Zn,Fe、Mn。1.21.2.1:。,O2·-、O3·-。,Fe()〔10〕、Mn()〔11〕、NaOH〔12〕、EDTA〔13〕、H2O2〔14〕。,Co2+〔15〕。,。,。,,O2、O3·OH。,(UV):UV,H2O2,H2O2UV〔16-18〕。、,2019-01,39(1)2〔19〕。1.2.2,。,Lewis,,(1)~(4)〔20〕。≡Me—OH+O3→≡Me+O2·-+HO2·(1)O2·-+O3→O3·-+O2(2)O3·-+H+→HO3·(3)HO3·→·OH+O2(4)Bronsted,,〔21〕。FeOOH〔22〕、Al2O3〔23〕、MnO2〔24〕,NiO/Al2O3〔25〕、Ce-AC〔26〕。,,〔19,27〕。,,〔28-29〕。22.1,1。1Mn3O4-Fe3O4/COD72.6%,1.23gCOD/1gO3O387.5mg/L,HRT60min,pH6.5~7.5〔30〕COD62.4%,1.51gCOD/1gO3O330~40mg/L,HRT60min,pH8.1~8.4〔31〕Al2O3COD46%HRT90min,pH6~9〔32〕COD47.9%,1.02gCOD/1gO3O355mg/L,HRT100min,pH6~9〔33〕Fe-Mn/Al2O3、Fe-Mn/ACCOD37.6%,0.78~1.18gCOD/1gO3O380~120mg/L,HRT60min,pH7.69,60%〔34〕++COD36.4%,1.23gCOD/1gO30.5gCOD/1gO3COD40%,0.65gCOD/1gO3O320mg/L,HRT60min〔35〕O340mg/L,HRT31min〔36〕O312~14mg/L,HRT20min〔37〕:,/;+〔38〕,。,。,,,,。,/〔39〕,。COBR,,1〔40〕。,,、,,1COBRCOD。,。COD,COD〔41〕:B/C、,BAF。,,,。2019-01,39(1),:3。2.22.2.1pH,pH。,pH,,。pH,。,pH,。,pH(pHpzc),。,SO42-、NO3-〔23〕。J.Nawrocki〔42〕pH,。,CODpH,,pH。pHOH-·OH,。pH,·OH,,。2.2.2,。〔43〕,COD,10mg/min20mg/min,COD10%,20mg/min30mg/min,COD5%,,COD。,。,30~80mg/L,0.5~1h,1gO30.6~1.5gCOD。2.2.3,。:,CO32-〔k=4.2×108mol/(L·s)〕、HCO3-〔k=1.5×107mol/(L·s)〕;,H2PO4-〔k1×105mol/(L·s)〕、HPO42-〔k1×107mol/(L·s)〕,,Lewis,,〔44〕。Ca2+CO32-HCO3-〔45〕。Lewis,,。,COD;。,,,20℃。,,,〔46〕。2.32.3.1CO2H2O。,,,。〔47〕,3COD11.9%、19.7%、14.9%。〔31〕,1gCOD1.17g1.51g,29%。TiO2/AC,60minCOD9.9%〔48〕。,10%~30%,。2.3.2。2019-01,39(1)4,,,〔49〕。。,,4~610%〔50-51〕,,。、,,。2.3.3。OH-,,。、、,。,,。J.Wu〔52〕,pH7.18~7.52,COD142mg/L70mg/L,2.8mg/L。,。2.3.4,。,。,,。,,。33.1,B/CCOD,,。,,B/C。。〔53〕,,,,B/C,,。〔54〕CODB/C,B/CCOD,COD,B/C,COD。〔55〕B/C0.06,B/C0.43,60%COD。,B/C,,,B/C。3.2,、,、,。、,,。,Fenton,。、,。X.Huang〔56〕,。、〔13,57-60〕。3.3,、,。,。,,2019-01,39(1),:5〔61〕。。,,。4,,,,。,,、。,,B/C,。,。,,。[1]WangJianlong,BaiZhiyong.Fe-basedcatalystsforheterogeneouscatalyticozonationofemergingcontaminantsinwaterandwastewa-ter[J].ChemicalEngineeringJournal,2017,312:79-98.[2],,,.[J].,2014,33(4):1010-1014.[3]Sanchez-PoloM,Rivera-UtrillaJ,vonGuntenU.Metal-dopedcar-bonaerogelsascatalystsduringozonationprocessesinaqueoussolu-tions[J].WaterResearch,2006,40(18):3375-3384.[4]AlvarezPM,Garcia-ArayaJF,BeltranFJ,etal.Theinfluenceofvariousfactorsonaqueousozonedecompositionbygranularactivatedcarbonsandthedevelopmentofamechanisticapproach[J].Carbon,2006,44(14):3102-3112.[5]FariaPCC,OrfaoJJM,PereiraMFR.Ozonedecompositioninwa-tercatalyzedbyactivatedcarbon:Influenceofchemicalandtexturalproperties[J].Industrial&EngineeringChemistryResearch,2006,45(8):2715-2721.[6],,,.[J].,2010,26(4):6-9.[7],,,.[J].,2017,37(1):79-82.[8],,,.[J].,2016,10(3):1081-1086.[9]TrapidoM,VeressininaY,MunterR,etal.Catalyticozonationofm-dinitrobenzene[J].Ozone:Science&Engineering,2005,27(5):359-363.[10]SauledaR,BrillasE.Mineralizationofanilineand4-chlorophenolinacidicsolutionbyozonationcatalyzedwithFe2+andUVAlight[J].AppliedCatalysisBEnvironmental,2001,29(2):135-145.[11]AndreozziR,CaprioV,InsolaA,etal.Theozonationofpyruvicacidinaqueoussolutionscatalyzedbysuspendedanddissolvedmang-anese[J].WaterResearch,1998,32(5):1492-1496.[12]VonGuntenU.Ozonationofdrinkingwater:PartI.oxidationkine-ticsandproductformation[J].WaterResearch,2003,37(7):1443-1467.[13]HuangXianfeng,XieBihuang,LiXuchun,etal.EnhancedHO·productionfromozonationactivatedbyEDTA[J].ChemicalEngi-neeringJournal,2016,288:562-568.[14]StaehelinJ,HoigneJ.Decompositionofozoneinwater:Rateofini-tiationbyhydroxideionsandhydrogenperoxide[J].EnvironmentalScience&Technology,1982,16(10):676-681.[15]PinesDS,ReckhowDA.Effectofdissolvedco

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