方振炜,李光明,赵建夫(同济大学污染控制与资源化研究国家重点实验室,上海 200092) []、、,。,。。 [];; []X703.1 []A []1005-829X(2003)01-0012-04AnalysisonthetreatmentofcokewastewaterforthecatalyticwetoxidationprocessFangZhenwei,LiGuangming,ZhaoJianfu(StateKeyLab.ofPollutionControlandResourceReuse,TongjiUniv.,Shanghai200092,China)Abstract:Thecharacteristicsofthecokewastewatersuchasgreatvolume,complexityoncontaminations'com-positionandhighconcentrationofcontaminationsareintroduced,sodothetraditionaltreatmentsofthecokewastewaterandtheirshortcomings.Then,anewtechnology,thecatalyticwetoxidationprocess(CWO),isputforward.ThetreatmentofcokewastewaterfortheCWOisanalyzedbythestudyofeconomicandtechno-logicalpracticability,whichsuggeststhisprocessisfeasibletechnologicallyandhasgoodcost-effect.Further-more,someproblemsaboutindustrializationofCWOarebroughtforward.Keywords:cokewastewater;catalyticwetoxidationprocess(CWO);activatedsludge m3、。2080,。、,,,。,。。1 、、。,CODCr5000~6000mg/L,NH3-N3000~4000mg/L。,,、、、、、,。 ,。1〔1〕。表1 上海焦化总厂的废水来源及水质/(m3·h-1)/(mg·L-1)CODCrCNS15080030541000.1452000503-8000.220300010010-8000.08618660.021.762.551960.1,55218281180160-603000.50.5-1227.193017308832.874.70.1421121822.53.639.32311.27—12—2003年1月第23卷第1期 IndustrialWaterTreatment Jan.,2003Vol.23No.1 ,,,。2 ,。,,。1〔2〕。,,COD,。NH3-N200mg/L、CODCr300mg/L,《》(GB8978—1996)CODCr150mg/L、NH3-N15mg/L。2〔3〕。图1 焦化废水生物处理工艺流程表2 国内外几个焦化厂的数据COD/(kg·m-3·d-1)/(mg·L-1)COD/(mg·L-1)/(mg·L-1)1.8~3.362~4887~1553492~231200~2500.50.8587520040~500.5CW1.321-19606475041.271200150-0.1:1)COD;2)。 ,。,、、、、。、〔4,5〕,COD1300mg/L,72h,COD246mg/L;CODMn1200mg/L,3h150mg/L。,。 ,CODCr,CODCr100mg/L,,。COD,,。COD,,10%;,,,,。,0.5/t〔6〕。3 3.1 技术分析 ,,,N2CO2。,,,。,。 2070,Zimpro,。LevecCu/ZnO/Al2O3(424710)〔7〕。130℃、0.3MPa,100min100%。KulkarniDixit〔8〕。Cu2+,SO32--O2,110℃、0.45MPa,20min100%。2080〔10〕,,200~300℃,1.5~9.0MPa,0.12~3.0h,COD(10000~30000mg/L)、CO2,N2H2O,60m3/d,。,Ti-Zr,Ti-Si,Ti-Zn,Mn,Fe,Co,Ni,Ce,W,Cu,Ag,Au,Pt,Pd,Rh,Ru,Ir,COD40g/L、2.5g/L、SS10g/L,240℃,5MPa,COD、NNH3-N99.9%,99.2%99.9%〔10〕。1989—13—2003-01,23(1) 催化湿式氧化法处理焦化废水的分析50m3/d,COD25000mg/L,250℃,7.0MPa,O2/COD1.05,2h-1,99.9%。〔11〕,1L,150~250℃、0.7~5.0MPa,30min,COD52.9%~90%,86%~99%,。,、,CODNH3-N99.5%99.9%〔12〕。,、,〔13〕。 、A/O,3〔14〕。3,。表3 几种焦化废水处理技术的出水水质的比较CODCr/(mg·L-1)NH3-N/(mg·L-1)BaP/(μg·L-1)20018025A/O100102050102 ,,、、、、。,。,,。3.2 经济分析 ,A/O(A2/O)。、A/O(4):A/O,20%〔14〕。、,,A/O。A/O,。,A/O,COD,,;,。,、〔12〕。,,,、、,。 表4 三种处理技术的运行费用比较元A/ONaOH(30%)376000374000350400Na2CO3588000(PFS)5600047250(85%)6450053750210000140000252000180000141608012771001252350112635013140013140059130264000264000120000600000350000375000116500350000375000116500333100037807503904960(m3)25.3528.7729.724 4.1 氧化剂的溶出问题 、,,、。,。,Cu、。。,、、〔15〕;,〔15〕;,Cu(NO3)2,;,。Cu,Cu2+。、,Cu,pHKSP;—14—专论与综述 2003-01,23(1)。Cu2+,,〔16〕。〔10〕,CuZn、CeCu/Zn/Ce/Al2O3,。4.2 反应设备材质要求高 (150~350℃)(0.5~20MPa),,,,、、()。,。,。,:;。,,(:0.1~0.6MPa,:104~165℃);,H2O2。5 (1),、,,。 (2),,,。 (3)(),。 ,,。,,。[][1].()[D].,1999[2],.[J].,2000,26(6):35-37[3],.[M].:,1984.442[4],.[J].,1994,(8):7-10[5],.[J].,1996,22(10):28-30[6].[M].:,1992.166-169[7]LevecJ.CatalyticOxidationofToxicOrganicsinAqueousSolution[J].AppliedCatalysis,1990,63:1[8]KulkarniU,DixitSG.DestructionofPhenolfromWastewaterbyOxidationwithSO32--O2[J].Ind.Eng.Chen.Res.,1991,30:1916[9].[J].,1996,(4):53-57[10],.(:)[M].:,2000.109-114[11],.[J].,1995,8(6):37-41[12],.[J].,1996,16(6):11-13[13],.[J].,1998,11(4):253-256[14],.[J].,2000,26(10):43-45[15],.[J].,1998,(3):7-10[16],.Cu[J].,2000,21(4):82-85[](1980— ),。:021-65901132,E-mail:fangzhw@eyou.com。[]2002-06-29 ———THOMASH.PIKE,.IWC-2001-08 ,(MEKO),。,MEKO,,ORP。(纪永亮供稿)—15—2003-01,23(1) 催化湿式氧化法处理焦化废水的分析