FeZSM5催化降解高浓度焦化废水的研究许俊强

Fe/ZSM-5许俊强,全学军,赵清华,高焕方,黄国文,李　军(重庆理工大学化学与生物工程学院,重庆400050):Fe/ZSM-5,H2O2,。:2h,75℃,H2O2,H2O2Fe/ZSM-590mL/L:20g/L,pH4,CODCr5080mg/L300mg/L,CODCr94%。,Fe。:ZSM-5;;;:O661.1　:A　:0253-4320(2009)S1-0174-03ResearchoncatalyticdegradationofhighconcentrationcokingwastewaterbymicroporousFe/ZSM-5zeoliteXUJun-qiang,QUANXue-jun,ZHAOQing-hua,GAOHuan-fang,HUANGGuo-wen,LIJun(DepartmentofChemicalandBiologicalEngineering,ChongqingUniversityofTechnology,Chongqing400050,China)Abstract:TheheterogeneousFe/ZSM-5catalystispreparedbywetimpregnation.Catalyticoxdiationisappliedinthedegradationofthehighconcentrationcokingwastewater,usingH2O2asaoxidantandFe/ZSM-5asacatalyst.Aseriesofreactionprocessparametersareoptimizedasfollows:thereactiontimeandtemperatureare2hand75℃,theaddingmodeofH2O2isdropwisewith3times,thequantityratioofH2O2/Fe/ZSM-5is90mL/L:20g/L,thepHvalueis4.Undertheoptimalconditions,CODCrvalueofcokingwaterisdegradedfrom5080mg/Ltoaround300mg/L,theremovalratecanreach94%.TheFe/ZSM-5catalystshowsobviouslymicroporouscharacteristicsbythelowtemperatureliquidnitrogenadsorption/desorptionanalysis.Keywords:ZSM-5zeolite;heterogeneous;catalyticdegradation;cokingwastewater　:2009-07-20　:(CSTC2008BB7334);(KJ080617);(0826073);(2007ZD14)　:(1979-),,,,、,[e-mail];(1963-),,,,,023-68667184,[e-mail]。　　、,。,、、,、、、、、。,[1-2]。,、,、、[3-5]。Fenton,、、[6-7]。ZSM-5Fe,,。1　1.1　。ZSM-5,,110℃,3.5h。,Beck-manCoulterSA3100。1.2　100mL,pH250mL,H2O2,,,·174·Sep.2009现代化工29(1)ModernChemicalIndustry20099DOI:10.16606/j.cnki.issn0253-4320.2009.s1.092,(CODCr)。2　2.1　1(,15%Fe/ZSM-5)。1,,CODCr,。2h,CODCr,;2h,CODCr,,,2h。1—CODCr;2—:T=75℃,pH=3,FeH2O220g/L:30mL/L图1　反应时间对焦化废水降解的影响2.2　H2O22。270minCODCr,,150minCODCr,,CODCr430mg/L,H2O2。,H2O2,,,,1—H2O2;2—H2O23:T=75℃,pH=3,FeH2O220g/L:30mL/L图2　双氧水的滴加方式对焦化废水降解的影响H2O2,,H2O2,H2O2,,H2O2,,H2O2。2.3　3。2,H2O2,H2O2。3,H2O2,,,;,H2O2,,H2O2,CODCr,,H2O290mL/L。1—CODCr;2—:T=75℃,pH=3,t=120min图3　双氧水的加入量对焦化废水降解的影响2.4　4。4,CODCr:,,;,,;,,,1—CODCr;2—:T=75℃,pH=3,t=120min图4　催化剂的加入量对焦化废水降解的影响·175·20099:Fe/ZSM-5。,20g/L。2.5　pHpH5。5,pHCODCr。,pH,,,,pH,,,pH,。,pH4。1—CODCr;2—:T=75℃,FeH2O220g/L:90mL/L,t=120min图5　反应的pH对焦化废水降解的影响2.6　6。6,CODCr,,CODCr,75℃CODCr,75℃CODCr。,;,,,,,,,75℃。1—CODCr;2—:pH=4,FeH2O220g/L:90mL/L,t=120min图6　反应温度对焦化废水降解的影响2.7　Fe/ZSM-5,,0.6nm。ZSM-5,,,Fe5%15%,,Fe,,Fe,。,10%()Fe,,Fe10%。Fe3+Fenton,H2O2,·OOH·OH。:H2O2+Fe3+Fe2++H++HOO·(1)RH+Fe3+R+H++Fe2+(2)R+O2ROO·(3)R+H2O2+·OH(4)ROO+RHROOH+R(5)ROOHRO·+·OH(6)RH+·OH+H2O(7)3　ZSM-5Fe/ZSM-5,H2O2,,,:2h,75℃,H2O2,H2O2/Fe/ZSM-590mL/L:20g/L,pH4,CODCr5080mg/L300mg/L,CODCr94%。[1]WooSH,JeonCO,YunYS,etal.On-lineestimationofkeyprocessvariablesbasedonkernelpartialleastsquaresinanindustrialcokeswastewatertreatmentplant[J].JHazardMater,2009,161(1):538-544.[2]QiR,YangK,YuZX.TreatmentofcokeplantwastewaterbySNDfixedbiofilmhybridsystem[J].JEnvironSci,2007,19(2):153-159.[3]BuscaG,BerardinelliS,ResiniC,etal.Technologiesfortheremovalofphenolfromfluidstreams:Ashortreviewofrecentdevelopments[J].JHazardMater,2008,160(2/3):265-288.　　(下转第178页)·176·现代化工29(1)。1.3　[6-7]。0.100g,NaOH,,NaOH,。,NaCO3,NaHCO3。、、。JSM-6700F(FESEM);(FT-IR)MODEL-8400S,KBr。2　2.1　FT-IR1CVD,。图1　原始碳球的扫描电镜照片,。28h。,1mol/L8h,1240cm-1C—O,4mol/L,1240cm-1C—O,1730cm-1CO,3200～3500cm-1O—H,8mol/L,1240、1725、3410cm-1,1612cm-1O—H,。FT-IR,,—COOH、—OH、CO,,。3,2～8h,3411、1726、1612、1240cm-1,2～8h。1—;2—1mol/LHNO;3—4mol/LHNO3;4—8mol/LHNO3;5—HNO3图2　碳球经不同浓度的HNO3处理8h后的FT-IR图1—;2—2h;3—4h;4—8h图3　碳球经浓HNO3处理不同时间的FT-IR图2.2　　　(上接第176页)[4]El-GoharyFA,BadawyMI,El-KhateebMA,etal.Integratedtreat-mentofolivemillwastewater(OMW)bythecombinationofFenton'sre-actionandanaerobictreatment[J].JHazardMater,2009,162(2/3):1536-1541.[5]NingP,BartHJ,JiangYJ,etal.Treatmentoforganicpollutantsincokeplantwastewaterbythemethodofultrasonicirradiation,catalyticoxida-tionandactivatedsludge[J].SepPurifTechnol,2005,41(2):133-139.[6]KasiriMB,AleboyehH,AleboyehA.DegradationofAcidBlue74usingFe-ZSM5zeoliteasaheterogeneousphoto-Fentoncatalyst[J].ApplCatalB:Environ,2008,84(1/2):9-15.[7]HuangYH,TsaiST,HuangYF,etal.DegradationofcommercialazodyereactiveBlackBinphoto/ferrioxalatesystem[J].JHazardMater,2007,140(1):382-388.□·178·现代化工29(1)