26120041 JOURNALOFNANJINGUNIVERSITYOFTECHNOLOGYVol.26No.1Jan.2004周文俊1,钱仁渊1,金鸣林1,史美仁2(1.上海应用技术学院 材料工程系,上海201101;2.南京工业大学 化学化工学院,江苏南京210009) :进行了CuO/Al2O3、CuO-MnO2/Al2O3、CuO-K2O/Al2O3、CuO/CeO2催化剂在160℃和1.6MPa的氧气压力条件下,催化氧化法处理含酚废水的实验,结果表明催化剂CuO/CeO2具有最高的催化活性,COD为3000mg/L左右含酚废水,反应50min后降解97%。并测定了在135~165℃和1.6MPa氧气压力下,加入催化剂CuO/Al2O3氧化含酚废水的COD与时间的的关系,求取了反应的动力学方程。初步探讨了氧分压和溶液的pH对催化氧化反应速率的影响。:催化湿式氧化;COD;含酚废水;反应动力学:X703 :A :1671-7643(2004)01-0063-05 、,,。,,。[1,2]。,、。:(1)Cu、Mn;(2)Pt、Ru;(3)。,、、,,。Mn、CuAl2O3CuO/CeO2,,、、pH,。1 1.1 1。1—;2—;3—;4—;5—;6—;7—1 Fig.1 Catalyticwetoxidationbatchreactor1.2 (COD)3000mg/L。130mL4g,,,O2,。,,。Al2O3。Al2O3,。,450℃6h。CuO/CeO2Cu(NO3)3:2003-01-26:(1978-),,,,:()。Ce(NO3)3,,6h,,700℃6h。20μm。1.3 (COD)。pHpH。2 2.1 160℃1.6MPaO2,Al2O3CuO/Al2O3、CuO-MnO2/Al2O3,,2。1—;2—Al2O3;3—CuO/Al2O3;4—CuO-MnO2/Al2O32 Fig.2 Effectofcatalyticwetoxidationofphenoloveraluminasupporteddysphasia2,,,80min,COD11%(1)。Al2O3,80min,COD27%(2),。Al2O3CuO,80min,COD36%(3),。Cu[3],Cu2+d,,Cu2+,。MnO2CuO,CuO。MnO2CuO,80minCOD46%(4),,。1—CuO/Al2O3;2—CuO-K2O/Al2O33 K2OFig.3 Effectofcatalyticwetoxidationofphenoloveraluminasupporteddysphasiawithcocatalyst、、,。,,[4]。CuO/Al2O3K2O,。3。3,K2O,,COD15%,。K2O,,。4CeO2、CuOCuOCeO23,,160℃1.6MPa。4CeO2,COD,CuO,CuO/CeO2,50min。CuO/CeO2CuO,CeO2CuO。CeO2,CeO2CuO。CuCe,Cu2+,64 26。CeO2[6]CeO2O,Ce4+Ce3+CeO2,CeO2,。,CuOCe4+,CeO2,,。1—CeO2;2—CuO;3—CuO/CeO24 CeO2Fig.4 EffectofcatalyticwetoxidationofphenolCeO2supporteddysphasia,,。1—135℃;2—145℃;3—155℃;4—165℃5 CODFig.5 CODdegradationindifferenttemperature2.2 CuO/Al2O3,O21.6MPa,135℃、145℃、155℃165℃,COD,5。5,。,、,:dcdt=k0exp-EaRT[c]m[O]n(1)O2,O2,,(1):-dcdt=k1exp-EaRTc(2)k1=k0[O]n,t=0,[C]=[C0],(2)lncc0=-kt(3),k=k1exp(-Ea/RT)(4)(3),:C=C0e-kt(5)(COD)。COD,,;()COD,COD,COD(mg/L)(mg/L):COD=K2×C+A(6)(6)(5),COD:COD=A+Be-kt(7)B=K2C0,COD(7),k,1。1 Table1 Reactionofrateconstantatdifferenttemperature/℃k1350.043431450.062411550.093301650.12187(4),k1=126632,Ea=50.42kJ,651:(2),(8):-dcdt=1.266×105exp-50420RTc(8)2.3 ,COD。、O2pH。2.3.1 ((8))。,。,()。2.3.2 O2155℃,O20.8MPa1.6MPa,CuO,,6。,O2,。,O2COD,,COD。,O2,。1—0.8MPa;2—1.6MPa6 Fig.6 Effectofcatalyticwetoxidationatdifferentoxygenpressure2.3.3 pHpH。155℃,1.6MPaO2,pHCOD,7。pH=3,30min,,pH=13,50%,pH=6。pH。pH,。1—pH=13;2—pH=6;3—pH=37 pHFig.7 EffectofcatalyticwetoxidationatdifferentpH3 (1)CuO/Al2O3、CuO-MnO2/Al2O3、CuO-K2O/Al2O3、Cuo/CeO2,CuO/Ce2O3,160℃1.6MPa,50min,COD3000mg/L。(2);。(3)CuO/Al2O3,,O2,,。(4)pH。c ,mol/L;k0;Ea,kJ/mol;O,mol/L;m,n;t,s;T,K;kC,mg/L;C0,mg/LACOD;K2COD;66 26:[1] LaetitiaOliviero,JacquesBarbierJr,DanielDuprezA.CatalyticwetairoxidationofphenolandacrylicacidoverRu/CandRu-CeO2/Ccatalysts[J].AppliedCatalysisB:Environmental,2000,(25):267-275.[2] ,, .Ⅰ、[J].,1997,(2):83-87.[3] ,, .Ⅱ[J].,1997,(6):160-164.[4] .[M].:,1992,95-100.[5] ,,.[M].:,1990,142-143.[6] Leibenburg.Wetoxidationfaceticacidcatalyzedbydopedceria[J].AppliedCatalysisb:Environmental,1996,(11):29-35.[7] ,,.Ti-Ce[J].,2000(4),375-377.[8] ,,,.Cu[J].,2000,(4):82-85.ResearchonphenolwastewaterbycatalyticwetoxidationZHOUWen-jun1,QIANRen-yuan2,JINMing-lin1,SHIMei-ren2(1.DepartmentofMaterialsScienceandEngineering,ShanghaiInstituteofTechnology,Shanghai201101,China;2.CollegeofChemistryandChemicalEngineering,NanjingUniversityofTechmology,Nanjing210009,China)Abstract:Treatmentofphenolwastewaterbycatalyticwetoxidationat160℃and1.6MPaofO2overCuO/Al2O3、CuO-MnO2/Al2O3、CuO-K2O/Al2O2andCuo/CeO2wasinvestigated.TheresultsshowedthatCuO/CeO2hadahighestcatalyt-icactivity.50minlater,phenolwastewater(CODabout3000mg/L)wasalmostcompletelyremoved.Therelationbe-tweenCODandthetimeoverCuO/Al2O3wat135~165℃and1.6MPaofO2wasdetermined,andkineticequationwasobtaind.TheaffectionaboutoxygenpartialpressureandpHtoreactionratewerealsodiscussed.Keywords:catalyticwetoxidation;COD;phenolwastewater;reactionkinetics671: