光催化氧化反应机理及在造纸废水处理中的应用

·光催化氧化·作者简介:李翠翠女士,在读硕士研究生;主要研究方向:全自动造纸污水光催化反应器的研究与开发。李翠翠　沈文浩　陈小泉(,,510640)　:、、、pH、、、、。,,。:;;:X793　　　　:B　　　　:0254-508X(2009)08-0065-08MechanismofPhotocatalyticOxidationReactionandItsApplicationintheTreatmentofWastewaterfromPaperMillsLICui-cui　SHENWen-hao＊　CHENXiao-quan(StateKeyLabofPulpandPaperEngineering,SouthChinaUniversityofTechnology,Guangzhou,GuangdongProvince,510640)(＊E-mail:[e-mail])Abstract:Themechanismofphotocatalyticoxidationreactionandthefactorsinfluencingthereactionsuchaspropertiesofsemiconductors,dosageofcatalyst,pHvalue,lightintensity,reactiontime,oxidants,dopingagentsandsoonwereintroduced.Thestudyprogressandapplicationsofphotocatalyticoxidationreactioninthetreatmentofwastewaterfrompulpandpapermakingprocesswerereviewed.Thepotentialadvantagesandthedevelopmenttrendofphotocatalyticoxidationreactioninthefieldsofeffluenttreatmentwerediscussed.Keywords:photocatalyticoxidationreaction;semiconductor;pulpingandpapermaking;treatmentofwastewater　　　　:2009-03-16()　　　(:2008A090300016)。　　、,,[1-2]。。CODCrBOD560%～74%60%～70%,;,,,、[3-4]。,,、、、、[5]。,,。J.H.Cary1976TiO2[2],。,[5-6],,。,。1　,。(VB)(CB),·65·　《》2009288,,,,-(electron/holepairs,e-/h+)。-,。,,,[7]。,(h+),OH-H2O(·OH),,;,O2(O2·-),O2·-H+HO2·、H2O2、·OH[8-9]。·OH(2.80eV),,,h+e-[10],。,CO2、H2O,NO-3、PO3-4。1。1　,[11-12]:(1),;(2),,、;(3),,。;(4),CO2;(5),;(6),e-/h+,,,,。2　2.1　,TiO2、ZnO、CeO2、CdS、ZnS,TiO2,,pH、、、,,[13]。,,,TiO2,TiO23,、,,TiO2TiO2,,TiO2TiO2,TiO2e-/h+[9]。,,,,,e-/h+-,,[14]。,。,,,,·OH。e-/h+,。,·OH,e-/h+,。,,,[15]。,。2.2　pHpH、,。pHOH-·OH,pHH2O·OH,pH·OH,[16]。·66·ChinaPulpPaper　Vol.28,No.8,2009　　pH,,,。TiO2,TiO2pH。pH,TiO2,,TiO2;pH,TiO2,TiO2,TiO2OH-,h+OH-·OH,[13、15]。pH·OH,pH。A.K.Ray,pH。2.3　、、、、。、。。,,e-/h+,·OH,,,,。Bahneman[17]TiO2,e-/h+,。[18],,,。[19]0、300500W,,COD;,COD,,。2.4　,-。H2O2O2,,H2O2[20],·OH。,。H2O2,·OH,·OH,·OH,·OH,,H2O2,。,H2O2·OH,(HO2·),·OH,。[21]TiO2,H2O2,COD,H2O2,COD。O2,O2O2·-、HO2·、H2O2·OH,,[15]。O3、K2S2O8、H2O2、NaIO4、KBrO4,TiO2e-,,。2.5　。、、。[22],Pt、Pd、Au,Fe3+、Mo5+、Ru3+、Os3+、Re5+Rh3+0.1%～0.5%,Co3+、Al3+。():①(),,,、、,[11];②,,(e-)(h+),e-/h+,,,[23];③Ni2+、Co2+,,(e-)(h+),e-/h+。2001AsahiNTiO2,C、S、F、I、P·67·　《》2009288[24],、。,,。[18]TiO2,Fe3+0.02%(),,TiO2,Fe3+0.02%,,TiO2,TiO2Fe3+0.02%。2.6　,,。Langmuir-Hinshelwood,,,[25],[5]。2.7　、,、、,[26]。,,,,。,、,、、20%～70%。3　()、()、()。,90%,、、、;,;,;、,。、、、、,。3.1　,、。,,。,,,。[27],,,(4--3-)、[1-(4--3-)],(4--3-)、(4--3-)1--3-(4--3-),,。,1-、、2--6--7--2-、、,,,,,CO2。2。,,,。[28],·OH,、、,,;;3。[29]、TiO2,,,25mLTiO20.3g、3%H2O24mL、pH12.5,2h,CODCr60%90%。[30]ZnO,,ZnO0.4g/L,H2O2235.3mmol/L,pH4.0,500W7h,CODCr98.8%,CODCr20mg/L。,。·68·ChinaPulpPaper　Vol.28,No.8,2009　　3.2　,,CDDS,DCDD、PeCDDOCDD,,BOD、CODAOX,(1000),COD,AOX30%～50%[31]。。[32]TiO2(OCP)、(PCP)2,4-(DCP),,[28](3)。,TOC、AOX。M.CristinaYeber[33]TiO2ZnO,,2h,,85%,TOC50%,AOX,。[34]TiO21.0g/L,pH4,CEH,4h,CODCr84.8%,。,。3.3　、、,、、;、、。,,。、、SSCOD、、,。,SS、COD。[35]、,,TiO25g/L,60min,92.5%86%;,TiO23g/L,83.5%。TiO2。,TiO2,,。[36]TiO2,,TiO20.75g/L,5h,pH10,,COD。[37]TiO2,,,,;、,·69·　《》2009288;75W,15mm,10L/h,CODCr297mg/L117mg/L,60.4%。3.4　、,,、,CODCr800mg/L,[6];、,,BOD5/CODCr0.4。,,COD,,,4[30]。4　,,,[30]。,-[38-39]。4　()、。,()。,,。,,,,。DegussaTiO2P25(21nm,50m2/g),,[40],CODCr90%,。TiO20.5～1.0g/L,DegussaP25300/kg,1t150,,。。,、、(5)。,,。,:①,;②;③,[41]。,,,,,;,,、,。,,,,。5　TiO2,[47-48],,、,,,,,。,,,,。,COD、,,,。,,,。,·70·ChinaPulpPaper　Vol.28,No.8,2009　　(),、[36,42,49],。5　　,、、,,、。、()、,、。,,:(1),、,,。(2),。、,。(4),,。(5),、、、()、。(6),。　　　[1]　,,　.TiO2[J].,2006,16(1):80.[2]　,,　,.TiO2[J].,2008,31(3):43.[3]　,,　.[J]..2007,26(6):87.[4]　,.[M].:,2000.[5]　AmatAM,ArquesA,LópezF,etal.Solarphoto-catalysistoremovepapermillwastewaterpollutants[J].SolarEnergy,2005,79:393.[6]　AngelaClaudiaRodrigues,MarcelaBoroski,Natalia,etal.Treat-mentofpaperpulpandpapermillwastewaterbycoagulation-floccula-tionfollowedbyheterogeneousphotocatalysis[J].JournalofPhoto-chemistryandPhotobiologyA:Chemistry,2008,194:1.[7]　,.[M].:,2006.[8]　DionysiouDD,KhodadoustAP,KernAM,etal.Continuous-modephotocatalyticdegradationofchlorinatedphenolsandpesticidesinwaterusingabench-scalTiO2roatingdiskreactor[J].AppliedCatal-ysisB:Environmental,2000,24:139.[9]　AgustinaTE,AngHM,VareekVK.Areviewofsynergisticeffectofphotocatalysisandozonationonwastewatertreatment[J].JournalofPhotochemistryandPhotobiologyC:PhotochemistryReviews,2005,6:264.[10]　AzragueK,AimarP,Benoit-MarquieF,etal.Anewcombinationofamembraneandaphotocatalyticreactorforthedepollutionoftur-bidwater[J].AppliedCatalysisB:Enviromental,2007,72:197.[11]　,,.TiO2[J].,2005,36(2):51.[12]　,　,,.TiO2[J].,2007,22(6):551.[13]　MachadoAEH,MirandaJAde,FreitasRFde,etal.DestructionoftheOrganicMatterPresentinEffluentfromaCelluloseandPaperIndustryUsingPhotocatalysis[J].JournalofPhotochemistryandPhotobiologyA:Chemistry,2003,155(1-3):231.[14]　..[J].(),2007,25(4):1.[15]　,,,.[J].,2008,28(6):12.[16]　　,.[J].,2004,23(1):75.[17]　BahnemanDW,etal.MechanisticStudiesofWaterDetoxificationinHuminatedTiO2Susp-ensions[J].SolarEnergyMaterials,1991,24:564.[18]　.[J].,2008(1):9.[19]　　,.TiO2[J].,2004,12(6):36.[20]　,.[J].,2008,31(1):25.[21]　,,,.[J].,2006,24(4):312.[22]　HoffmannMR,MartinST,ChoiW,etal.EnvironmentalApplica-tion