高浓度焦化废水湿式氧化铜系催化剂的研制韩利华

韩利华　李国江　芮玉兰　梁英华(,063009)　　,。,;,Cu2+,。　　　　Preparationofcoppercatalystsforwetairoxidationofhighconcentrationcoking-plantwastewaterHanLihua　LiGuojiang　RuiYulan　LiangYinghua(DepartmentofChemicalEngineering,HebeiInstituteofTechnology,Tangshan063009)Abstract　Coppercatalystswerepreparedwiththecodepositionmethod,andappliedtothetreatmentofhighconcentrationcokingplantwastewaterbycatalyticwetoxidation(CWO).Theresultsshowthattheac-tivityofcopperoxidecatalystswasbetterthanthatofothertransitionmetaloxides.Somemeasuresofcon-trollingtheleachingofCu2+,suchaschangingthereactionconditionandoptimizingthedesignandmakeofcatalystswerediscussedinthepaper.Thecatalystswouldhavewideapplicationprospectiftheleachingcouldbecontrolled.Keywords　catalyticwetoxidation;coking-plantwastewater;wastewatertreatment;coppercatalyst:(00547001D-11):2002-8-12;:2002-11-13:(1972～),,,,。　　(CWO)2080,、,、CO2、H2ON2。、、、。、、,[1—3],,[4,5]。,。,、(T240℃,P8.0MPa),CODNH3-N。、,。,,,,。,。,,,Cu2+,,,Cu2+。1　1.1　Cu-Mn、Cu-Cd、Cu-Ce,,,、、、,43Vol.4,No.320033TechniquesandEquipmentforEnvironmentalPollutionControlMar.20031∶1。1.2　2LFYX2a,,,。1L,,N2,,,,。。1.3　,500mL、200℃、1.2MPa、60min。、,COD7340mg/L,pH8.4。1.4　CODCr,CODCr,,。CODCr[6]。Cu2+[7],(180-80)Cu2+。pHpHS-2。2　2.1　,2:M=OM—O—M,MnO2、Co3O4、NiO、CuOM=O。CO2H2O,M=O。,,,,,,,,;,,,。,[8]。2.2　2.2.1　与常压催化氧化、湿式氧化法的比较　　CuO,γ-Al2O3,20g/L,220℃,1.2MPa,1h,,1。1　COD(mg/L)COD(mg/L)COD(%)73404551387340390546.87340177675.8,COD,,,。2.2.2　试验反应工艺参数的选择,160℃、200℃240℃,1。1　COD1,240℃,1.2MPa,,160℃,COD,,,200℃,,COD。60min,COD。,,:200℃,1.2MPa,60min。2.2.3　单组分催化剂的试验γ-Al2O3,CuO/Al2O3、Fe3O4/Al2O3、NiO/Al2O3、MnO2/Al2O3、Co3O4/Al2O3,,,CuO/Al2O3,60minCOD66.3%,2042　COD(mg/L)30min60min90min120minCOD(%)(60min)Cu2+(mg/L)(60min)Cu(NO3)2264617351568143276.4—CuO283924761747163166.373.1Cu-Ce(1∶1)360728962578216060.548.6Cu-Mn(1∶1)369731922718239056.553.5Cu-Cd(1∶1)391233272943273754.750.2,,,。2.2.4　多组分催化剂的试验,,,、,2。2,:,,,。Cu2+,,Cu2+。,Cu-Ce,Cu2+,Ce,Cu2+,。Cu-Ce,γ-Al2O3,,,3。3　CODCrCOD(%)1∶279.31∶183.2Ce-Cu2∶185.43∶188.64∶186.03,Ce-Cu3∶1。2.2.5　负载化对铜系催化剂稳定性的影响,,4。4　pHCOD(%)Cu2+(mg/L)6.0266.373.1CuOγ-Al2O34.3884.748.7Al2O3/TiO25.1477.343.66.7860.548.6Cu-Ceγ-Al2O34.8383.232.4(1∶1)γ-Al2O3/TiO25.8173.527.9,γ-Al2O3,Cu2+,TiO2,,。4,Cu2+,。,。2.2.6　催化剂制备对铜系催化剂溶出的影响、。,,Cu-Ce/Al2O3,5。5　Cu2+(℃)pHCOD(%)Cu2+(mg/L)6004.6877.639.27004.7681.334.78004.8383.232.49004.6372.728.15,800℃,,,Cu2+。(600℃),213:CuO,,,CuO,,,;900℃,CuOAl2O3,CuAl2O4,,,Cu2+,。3　　(1)200℃、1.2MPa、60min,,,Cu2+。(2),,,Cu2+。(3)。(CeMn),,Cu2+。Cu2+,。[1]SafiaH.,etal.Catalyticoxidationofaqueousphenolicso-lutionscatalystdeactivationandkinetics.ChemicalEngi-neeringScience,1999,54:3569—3576[2]HaradaY.,etal.Treatmentofhighconcentrationorganicwastewaterbyacatalyticwetoxidationprocess.IDA&WRPCWorldConferenceonDesalinationandTreatment.Nov.Japan:Yokohama,1993,2[3]PintarA.andLevecJ.Catalyticoxidationoforganicsinagueoussolutions.J.ofCatalysis,1992,135:345—357[4],,..,1996,16(2):70—74[5],,..,1997,23(2):83—87[6]().GB11914-89[7],,.Cu.,2000,21(4):82—85[8]..:,1991(责任编辑:刘　颖)(上接第89页)4　()(t)(t)(t)82554.631936.791.3192,93999.293086.561.296104703.663989.021.179,113524.983178.51.109124437.924002.91.117“”,。,,3。(2),,20%;,。4。(3)“”、,、,,。3—5d15—20d,;,4。4　　,“”,、,,,;,,“”。[1],.CODCr.,2000,(4):28—30[2],,.-.,2001,19(2):17—19(责任编辑:刘　颖)224