CuOAl2O3催化双氧水处理聚乙烯醇废水的研究

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:,,1994,,。#。*(No.JUSRP51723B)。/γ-*11,211,2#(1.,214122;2.(),214122)—CuO/γ-Al2O3,(PVA),CuO/γ-Al2O3、、PVAPVA。,450℃CuO/γ-Al2O3,CuO/γ-Al2O3PVA,PVA,PVA。PVA1.0%,60mL/L,CuO/γ-Al2O31.0g/L,60℃,pH=3,2hPVA90%,PVA1007733194,97%,CuO/γ-Al2O3。CuO/γ-Al2O3:10.15985/j.cnki.1001-3865.2017.12.004/γ-1,1,2,1,1,2.(1.,,214122;2.-(),,214122):CuO/γ-Al2O3nanoparticleswerepreparedbywetimpregnation-calcinationmethod,theobtainedcat-alystwasusedtocatalyzehydrogenperoxideforthetreatmentofpolyvinylalcoholsolution.TheeffectofcalcinationtemperatureonCuO/γ-Al2O3propertyandCuO/γ-Al2O3dosage,hydrogenperoxidedosage,initialPVAconcentra-tionontheremovalefficiencyofPVAwereinvestigated.ResultsrevealedthattheCuO/γ-Al2O3nanoparticlescalci-natedat450℃exhibitedthebestcatalyticcapability.Besides,thedegradationofPVAwaspromotedbyincreasinghy-drogenperoxideaswellasCuO/γ-Al2O3dosage,whilehigherinitialPVAconcentrationgoingagainsttheeffectivedegradation,leadingtoahigherviscosity-averagemolecularweightofdegradationproducts.Inthispaper,morethan90%ofPVAwasremovedafter2hoftreatmentunderconditionsofinitialPVAconcentrationof1.0%,temperatureof60℃,pH=3,hydrogenperoxidedosageof60mL/LandCuO/γ-Al2O3dosageof1.0g/L,averagemolecularweightofPVAdegradationproductswasdecreasedby97%,from100773to3194.Thenanocatalystcouldberecy-cledbyfiltrationandcalcination,butthecatalyticabilitywasslightlydecreasedinfour-timesutilization.:CuO/γ-Al2O3;catalyticoxidation;degradation;polyvinylalcohol;recyclingability(PVA)、,(、)()、、[1-2]。,PVA[3]。PVA3[4-6]:1PVA,PVA、、;2PVA,PVA,,;3PVA,、,,。3PVAPVA,PVA,,,,,,[7-8]。,Cu+·OH4.1×103mol/(L·s),Fe2+·OH76mol/(L·s),Cu2+Cu+·9921·/γ-H2O2/Fe2+/Fe3+。,、,[9-11]。Al2O3、,,,,。、[12-14]、[15]、[16],Fenton[17-18]。—CuO(γ-Al2O3)CuO/γ-Al2O3,γ-Al2O3、CuO/γ-Al2O3、。PVA、、PVACuO/γ-Al2O3PVA。1.1PVA,1750,99%,PVA95℃,,PVA,;γ-Al2O320nm;CuSO4·5H2O、、、、;30%。QuantaF250(SEM,FEI);GenesisXMX(EDS)(EDAX);UV-2600();D8AdvanceX(XRD)();NicoletiS10(FT-IR)();Waters2545(HPGPC)()。1.2CuO/γ-Al2O35gγ-Al2O3,250mL0.25mol/LCuSO4,24h,,,110℃4h,,10℃/min,3h,350~600℃,,CuO/γ-Al2O3。1.3XRD:40kV,40MA,0.02°,10°~90°。FT-IR:KBr,4000~5000cm-1,64。SEM:γ-Al2O3、CuO/γ-Al2O3,5.00kV,40000,γ-Al2O3、CuO/γ-Al2O3,EDS。1.4PVAPVA670nm[19],0~1mL0.1%PVA10mL,0.20mL-1.00mL,5mL,5~10min,1cm670nmPVA,PVAPVA。2.1CuO/γ-Al2O32.1.1XRD1γ-Al2O3CuO/γ-Al2O3XRD。γ-/γ-Fig.1XRDpatternsofγ-Al2O3andCuO/γ-Al2O3obtainedatdifferenttemperature1,γ-Al2O3CuO/γ-Al2O32θ=33.0°、37.0°、46.0°、67.0°γ-Al2O3,,CuOγ-Al2O3。CuO,CuO/γ-Al2O32θ=37.9°、35.5°CuO,CuO,,γ-Al2O337.0°·0031·[20],γ-Al2O3CuO,CuOγ-Al2O3[21],γ-Al2O3。2.1.2FT-IR2γ-Al2O3CuO/γ-Al2O3FT-IR。γ-/γ--Fig.2FT-IRpatternsofγ-Al2O3andCuO/γ-Al2O3obtainedatdifferenttemperature2,γ-Al2O33443cm-1—OH,1636cm-1H—O—H,H—O—HKBrγ-Al2O3。CuO/γ-Al2O3FT-IR,—OH、H—O—H3439、1632cm-1,,LAI[22],CuOγ-Al2O3。,CuO/γ-Al2O31115cm-1Cu—O—Al,CuOγ-Al2O3[23],450℃CuO/γ-Al2O3,CuOγ-Al2O3,Cu—O—Al。2.1.3SEM/EDSγ-Al2O3450℃CuO/γ-Al2O33。3(a),γ-Al2O3,,。3(b),CuO/γ-Al2O3,CuOγ-Al2O3,CuO/γ-Al2O3,,。EDSγ-℃/γ-Fig.3SEMimagesofγ-Al2O3andCuO/γ-Al2O3obtainedat450℃(1),CuO/γ-Al2O3Cu6.24%,2.11%,Cuγ-Al2O3。γ-/γ-Table1Thesurfaceatomiccompositionofγ-Al2O3andCuO/γ-Al2O3particlesγ-Al2O3/%/%CuO/γ-Al2O3/%/%O40鲻.3553骀.2141鬃.3955热.93Al59鲻.6546骀.7952鬃.3741热.96Cu6鬃.242热.112.2CuO/γ-Al2O3PVA2.2.1CuO/γ-Al2O31.0%PVA0.05mol/LpH3,CuO/γ-Al2O3,1.0g/L,60mL/L,,60℃2h,0.2mL,,PVA,CuO/γ-Al2O3,4。4,350~550℃CuO/γ-Al2O3,PVA90%。450℃CuO/γ-Al2O3,·1031·/γ-/γ-Fig.4EffectofcalcinationtemperatureonthecatalyticefficiencyofCuO/γ-Al2O3PVA,PVA99%。650℃,CuO/γ-Al2O3,,[24],FentonCuO/γ-Al2O3。CuO/γ-Al2O3450℃CuO/γ-Al2O3。2.2.2CuO/γ-Al2O3PVA1.0%PVA0.05mol/LpH3,60mL/L,60℃,CuO/γ-Al2O30、0.5、1.0、1.5g/L,CuO/γ-Al2O3PVA5。5,CuO/γ-Al2O30g/L0.5g/L,PVA19%40%。CuO/γ-Al2O31.0g/L,80minPVA90%。PVAHPGPC,CuO/γ-Al2O3/γ-Fig.5EffectofCuO/γ-Al2O3dosageonthecatalyticdegradationofPVA0、0.5、1.0、1.5g/L,PVA10077381991、8884、3194、1934,CuO/γ-Al2O3·OH,PVA。CuO/γ-Al2O31.0g/L,PVA,。CuO/γ-Al2O31.5g/L,PVA1934,99%。2.2.3PVA1.0%PVA0.05mol/LpH3,60℃,CuO/γ-Al2O31.0g/L,0、60、120、180、240、300mL/L,PVA6。6,0mL/L,PVA20%,CuO/γ-Al2O3,PVA,PVA。PVA,PVA99%。Fig.6EffectofH2O2dosageonthedegradationofPVA,6,PVA,60mL/LPVA,PVAHPGPC,PVA。,0、60、120、180、240、300mL/L,PVA71909、3194、1598、1193、1054、721,,,PVA。120mL/L,PVA·2031·2000,CuO/γ-Al2O3,·OHPVA。2.2.4PVA1.0%、2.5%、5.0%、7.5%、10.0%、12.5%PVA,0.05mol/LpH3,60℃,CuO/γ-Al2O31.0g/L,60mL/L,PVAPVA7。Fig.7EffectofinitialmassfractionofPVAsolutiononthedegradationofPVA7,,PVA,PVA。PVA2.5%,PVA51%~70%。PVAHPGPC,PVA1.0%,3194,97%;PVA2.5%、5.0%、7.5%,20882、20941、23063;PVA10.0%,PVA50000,50%。PVA,CuO/γ-Al2O3PVA,PVACuO/γ-Al2O3,,·OH。,PVA,,,,PVA2.5%。2.2.5CuO/γ-Al2O3CuO/γ-Al2O3,3h,450℃,CuO/γ-Al2O3PVA60℃,CuO/γ-Al2O31.0g/L,60mL/L,PVA1.0%,CuO/γ-Al2O34PVA8。/γ-Fig.8CapabilityofCuO/γ-Al2O3infourtimes/γ-Table2ThesurfaceatomiccompositionofCuO/γ-Al2O3particlesbeforeandafterfourtimesreutilization/%/%4/%/%O41鲻.3955骀.8839鬃.4152热.48Al51鲻.3741骀.1259鬃.9847热.32Cu6鲻.242骀.110鬃.610热.208,CuO/γ-Al2O3PVA65%。,CuO/γ-Al2O3,PVA30%~40%。4CuO/γ-Al2O3EDS,2。2,4CuO/γ-Al2O3Cu2.11%0.20%,CuOγ-Al2O3,,PVA。(1)—CuO/γ-Al2O3,XRD、FT-IR、SEM/EDSCuOγ-Al2O3,—γ-Al2O3,CuOγ-Al2O3,CuO/γ-Al2O3。(2)CuO/γ-Al2O3450℃,CuOγ-Al2O3Al—O—Cu,·3031·/γ-,CuO/γ-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