高级氧化技术在造纸废水处理中的应用

中　国　造　纸　学　报TransactionsofChinaPulpandPaperVol.25,No.4,2010　　刘　生1　杨德敏2　方　健3　高　澍4,＊　谭　婷5(1.,,132013;2.,,610500;3.,,530000;4.,,541004;5.,,610065)　:,。、、、、,、。:;;;:X793　　　　　:A　　　　:1000-6842(2010)04-0056-07　:2010-09-20()　:　,1964,;;:。　＊:　,E-mail:[e-mail]。　　、、、、,、、、,,,[1]。、、。、、,。,COD()CODCr17%35.2%[2-3]。,、、。(AOPs)[4],、、、(·OH),、、、、,,CO2H2O,。,(HO·)、、、、,,[5-7]。1　[8]Fe2+(UV)、H2O2,(·OH),,,CO2H2O;,Fe(OH)3、,。[9]Fe0-H2O2,45min、pH3.0、Fe/C=2.0、H2O250mg/L0.6L/min,16020,CODCr420mg/L14mg/L,。[10]Fenton-Fenton。,Fen-ton-Fenton,(Fenton10∶1、H2O21678.75mg/L、30℃、Fenton-FentonpH2.83.0),90min,56　25　492%99%,87%95%CODCr。,Fenton,H2O2。,,-Fenton-,CODCr5826mg/L200mg/L,96.6%;8002,99.7%;SS582mg/L3mg/L,99.3%。,,,[11]。-Fenton,H2O2。200mg/L,H2O21500mg/L,pH3.035℃,90min,TOC33213mg/L10960mg/L,67%,[12]。Tam-bosiJL[13]H2O2/Fe3+,400mg/LFe3+、500～1000mg/LH2O2、pH2.5,CODCr75%,98%。2　[14](SCWO)2080Modell。、。,99%。(O2、H2O2)CO2H2O。、HCl、H2SO4H3PO4,N2N2O[15]。,[16-17]:RH+O2※R·+HO2·RH+HO2·※R·+H2O2H2O2+M※2HO·M。(586kJ),。RH+HO·※R·+H2O(R·)。。R·+O2※ROO·ROO·+RH※ROOH+R·,。。[18],250～440℃20～24MPa,,TOC6603.5mg/L13.2mg/L,99.8%。TOC。,TOC100%。,400～650℃25.5MPa,、CO2、H2O。,,99.0%～99.5%,95.0%～99.9%,,[19]。[20],。,450%,CODCr175000mg/L,5mL、560℃、90s,27MPa,CODCr170mg/L,2870001350,99.9%99.5%。[21],,、、COD。,2.0、450℃、24～25MPa,60s,,CODCr175000mg/L170mg/L,99.9%。3　[22](·OH),、,,。,,、、CC、C≡C、NN、CN、—CHO。:(D)(·OH)(R)。D,;R,[23]。5725　4(D):+O3※(R):+HO·※[24]:O3※O+O2,O+H2O※2HO·,O3OH-,:O3+OH-※HO2·+O-2O3+HO2·※HO·+2O22HO2·※O3+H2OHO·O3,[25]:HO·+RH※R·+H2OR·+O2※RO2·RO2·+RH※ROOH+R·ROOH+HO·※CO2+H2O+,,。[26]:,;,CO2H2O,,COD。,,O3/H2O2、O3/BACO3/UV/TiO2,,,。[27]-,CODCr、SS1576mg/L、429mg/L、9524mg/L、1.2mg/L2.24,99%,,,。[28]//,,,CODCr1600mg/L157.6mg/L,BOD5150mg/L55.8mg/L,200020,CODCr、BOD590.2%、62.8%99.6%,。[29](CODCr:350～450mg/L;:400～500),。,、,,13.98mg/min,30min,CODCr62.3%99.5%,。[30]-BAF。,,-BAF(100mg/L,5min,BAF2.0h),CODCr40mg/L,,,-BAF3.7/t。[31]--/--,CODCr9000mg/L80mg/L,BOD53000mg/L18mg/L,SS2500mg/L20mg/L;1,CODCr100mg/L,BOD520mg/L,SS20mg/L,(GB3544—2008),。4　[32]20,,、、,。()n(TiO2、ZnO、WO3、CdS),,(e-),(h+),-(h+-e-)。,,(HO·),,CO2、H2O,。TiO2,[33]:TiO2+hv※e-+h+h++H2O※HO·+H+e-+O2※·O2※HO2·2HO2·※O2+H2O2H2O2+·O2※OH·+OH-+O2+HO·/HOO·(H2O2/O3)※…※58　25　4[34]、pH4、、1.5g/L,NiTiO2。,Ni2%,。Ni2%TiO2,,12h,,CODCr500mg/L83mg/L,100%83.4%。[35]TiO2、、(PCP-Na)。,(TiO2、、40%4∶20∶2,650℃3h),,。CODCr400mg/L,PCP-Na10mg/L,30kW/m22h,CODCr65%,PCP-Na92%。Pintar[36]TiO2Ru/TiO2,。,TiO2,TOC。Ru/TiO2,TOC(99.6%),,。[37]TiO2(Pt/TiO2),。,()0.5%,0.5g/L,,Co(CHCl3)=1mmol/L,pH5,300W120min,98.4%。M.CristinaYeber[38]TiO2ZnO,,120min,,85%,TOC50%,AOX,。5　,(T320℃,P20MPa)。(WAO)Zimmerann1944,1958WAO,CODCr90%[39]。(125～320℃)(0.5～20MPa),。WAO,,WAO[40]:RH+O2※R·+HOO·2RH+O2※2R·+H2O2H2O2+M※2OH·(M)RH+OH·※R·+H2OR·+O2※ROO·ROO·+RH※ROOH+R·R·+R·※R-RROO·+R·※ROORROO·+ROOH※ROH+RCOR2+O2Moddl[41],O·,O·HO·,RHRCOOH,RCOOHCO2H2O。,,,,、[42]。,RHR·,R·ROO·,RHR·,;、、CO2;-[43]::ROOH+Me(n-1)+※RO·+Men++OH-:ROH+Men+※ROO·+Me(n-1)++H+,,,[44]。[45]170、190、210℃1h。210℃,COD,40%69%;190℃,,65%。190℃,,CODCr59%、74%～88%。,500mg/LCuSO4,(NH4)2SO4,CODCr95%[46]。[47]CuO,CODCr32505925　41　[1][48]、、、、()、、、、、,、、、、、、、、、、、、、、、、、、、、、、、mg/L、400SS600mg/L。,2.5MPa3h,3g,Cu4%,220℃,CODCr90%,89%,pH9.67.8。,。,450℃3h,,CODCr88%,9CODCr85%。6　、、、、。,1。7　　,,,、。20,、,。。,COD,,。,,([22]--/--,),,。　　　[1]　,　.[J].,2010,29(7):69.[2]　,　,　,./[J].,2006,26(11):32.[3]　.2010—2015[EB/OL].2010-01.[4]　Pera-TitusM,Garcia-MolinaV,BanosMA,etal.Degradationofchlorophenolsbymeansofadvancedoxidationprocesses:ageneralre-view[J].Appl.Catal.B:Environ.,2004,47:219.[5]　EsplugasS,Gimenez,Conteras,etal.Comparisonofdifferentadventoxidationprocessesforphenoldegradation[J].WaterRes.,2002,36:1034.[6]　ZhuW,BinY,LiZ,etal.Applicationofcatalyticwetairoxidation60　25　4forthetreatmentofH-acidmanufacturingprocesswastewater[J].WaterRes.,2002,36:1947.[7]　GrahamN,ChuW,LauC.Observationsof2,4,6-trichlorophenoldegradationbyozone[J].Chemosphere,2003,51:237.[8]　ChamarroE,MarcoA,EsplugasS.UseofFentonreagenttoimproveorganicchemicalbiodegradability[J].WaterRes.,2001,35(4):1047.[9]　,,　.Fe0-H2O2[J].,2006,21(3):30.[10]　,,,.Fenton-Fenton[J].,2006,21(4):34.[11]　.-Fenton-[D].:,2006.[12]　,,.-Fenton[J].,2009,41(8):142.[13]　TambosiJL,MicheleDD,SchirmerWN,etal.Treatmentofpa-perandpulpwastewaterandremovalofodorouscompoundsbyaFenton-likeprocessatthepilotscale[J].J.ofChem.Tech.andBiotech.,2006,81(8):1426.[14]　,,　.-[J].,2004,5(4):62.[15]　AymonierC,GratiasA,MercadierJ,etal.Globalreactionheatofaceticacidoxidationinsupercriticalwater[J].Sup.Flu.,2001,21:219.[16]　GopalanS,SavagePE,MizanTI,etal.Reactionatsupercriticalconditions:applicationsandfundamentals[J].AIChEJ.,1995,419:1723.[17]　JuanR,PortelaJ,LopezE,etal.Eliminationofcuttingoilwastesbypromotedhydrothermaloxidation[J].Haza.Mat.,2001,B88:95.[18]　　,,,.[J].,2000,20(8):23.[19]　,　.-21[J].,1996,15(2):10.[20]　　,.[J].,2007,26(2):66.[21]　,　,.[J].,2009,27(5):41.[22]　AndreozziR,CanterinoM,MarottaR,etal.Antibioticremovalfromwastewaters:Theozonationofamoxicillin[J].J.ofHaz.Mat.,2005,122(3):243.[23]　ChurcheleyJH.Ozonefordyewastecolourremoval:Foury