AOO生物流化床处理焦化废水中酚类组成及降解特性分析张伟1

4　2环境工程学报Vol.4,No.220102ChineseJournalofEnvironmentalEngineeringFeb.2010A/O/O张　伟1　韦朝海1,2＊　彭平安1　任　曼1(1.,510640;2.,510006)　　,HLB,GC-MS15,72.6%,1487.6%～102.3%,7.62%,。,、,。A/O/O,(、)、29.3%31.6%;99%92.4%;89%6%;0.045mg/L,。　　　　X703.1　　　A　　　1673-9108(2010)02-0253-06ComponentsanddegradationcharacteristicsanalysisofphenolsincokingwastewaterinbiologicalfluidizedbedA/O/OprocessZhangWei1　WeiChaohai1,2　PengPing'an1　RenMan1(1.PearlRiverDeltaResearchCenterofEnvironmentalPollutionandControl,GuangzhouInstituteofGeochemistry,ChineseAcademyofSciences,Guangzhou510640,China;2.CollegeofEnvironmentalScienceandEngineering,SouthChinaUniversityofTechnology,Guangzhou510006,China)Abstract　Forstudyingonthecompositionanddegradationcharacteristicofphenolsinprocessofcokingwastewatertreatment,phenolswereextractedthroughHLBsolidphaseextraction(SPE)cartridgeand15kindsofphenolswereanalyzedbyGC-MSselectiveionscanningmethodinthisresearch.Theresultsshowedthataveragerecoveryrateof14kindsofphenolsrangedfrom87.6%to102.3%whiletherecoveryrateofphenolwas72.6%,andtherelativestandarddeviationswerelessthan7.62%,whichcouldmeetthestandarforphenolsdetectionintheenvironment.Theresultsindicatedthatphenol,methylphenolsandnaphthols,withhighconcen-tration,exsistedincokingwastewater,andasmallquantityofchorophenolsandnitrophenolswasalsoinsideit.IntheprocessofcokingwastewatertreatmentbybiologicalfluidizedbedA/O/O,theremovalrateofhighcon-centrationphenols(phenol,methylphenolsandnaphthols),chorophenolswas29.3%and31.6%respectivelyduringanaerobicstage;99%and92.4%respectivelyinfirstaerobicstage,89%and6%respectivelyinsecondaerobicstage.Theconcertrationofthefinaleffluentwas0.045mg/L,whichmetthenationaldischargestandardforironsteelindustry.Keywords　cokingwastewater;phenoliccompounds;biodegradation:(50278036);(2008BAC32B06-2):2009-02-23;:2009-03-17:(1984～),,,。E-mail:[e-mail]＊,E-mail:[e-mail]　　、、,、、;、、、,、、、、、、(PAHs),,COD3000～5000mg/L,200～500mg/L[1]。450%,PHs(phenols),,,,,。,。EPA12911,686(、、2,4-、2,4,6-、、)[2]。,4-(0.1mg/L),4-,()(、),,。,,GC-MS,HPLC-MS[3～5]。2004,//(A/O/O),、、、,64h,,、、24、99h,180、3045d,《》(GB13456-1992)[6]。,,,,GC-MSA/O/O,,,。1　　1.1　,,1。1　Table1　QualitiesofcokingwastewaterCOD(mg/L)TOC(mg/L)NH+4-N(mg/L)S2-(mg/L)SS(mg/L)(mg/L)(mg/L)()pH3500±6001050±150281±10047±2565±4026±10270±100120±409±210020150.5600.50.5507±1　　61L。,、、。3,,,,、、、、。,(4℃)。,,。7d,1。1.2　:EPA82702000μg/mL(、、、、2-、2,4、4-3-、2,6-、2,4-、2,4,6-、2,4,5-、2-、4-、2,3,4,6-、);EPA80402000μg/mL(1-、2,4,6-),2000μg/mL;BSTFA,;、、、,,;MTBE(HPLC)。,72h;,450℃4h。:FinniganVoyager-GC8000TOP-2542　:A/O/O;HP-5MS(30m×0.25mm×0.25μm);(ShimadzuTOC-VCPH,Kyoto);12(SPE);WatersOasisHLB(6mL,200mg)。1.3　:1L,0.45μm(1-、2,4,6-),pH2～3。WatersOasisHLB,3～4mL/min,N2,MTBE/(9∶1)4、33mL3,N2,。50μLBSTFA50μL(),1h。,1。,1mL。1　Fig.1　PhenolderivatizedwithBSTFA:HP-5MS(30m×0.25mm×0.25μm);:;lmL/min;250℃,300℃。70eV,230℃,:50℃3min;4℃/min80℃,2min;6℃/min150℃,2min;20℃/min280℃,2min。1μL,,(SIR)。、2,:①2-;②;③;④;⑤;⑥;⑦2-;⑧2,4;⑨4-3-;⑩2,6-;112,4-;122-;132,4,6-;144-;152,4,5-;162,3,4,6-;172,4,6-;18。1.4　、、、、、,,0.45μm,TOC。TOC10mL,10mL,20mL,100mL,200mL,500mL1L,2。,,;。2　、TICFig.2　TICofPHs,surrogatestandards,andinternalstandard2　　2.1　170.05、0.5、1、2、5、10、2050μg/mL,,。。1L1710μg/L6,6,。,。2。,HLB,MT-BE/(9∶1),BSTFA,GC-MS。,[7]。C18,WatersOasisHLB,HLB。,pH,,。pH2,3～4mL/min,MTBE/(9∶1)。25542　、Table2　Linearrange,recoveryandrelativestandarddeviationsofthemethod(μg/mL)(n=6)(%)(n=6)(%)(m/z)0.05～500.99972.66.911660.05～500.99890.77.621800.05～500.99892.56.531800.05～500.99993.55.361802-0.05～500.99995.62.671852,4-0.05～500.99793.53.561944--3-2,6-0.05～500.05～500.9980.99996.795.85.844.562142342,4-0.05～500.99998.75.622342,4,6-0.05～500.997101.64.312532,4,5-0.05～500.998102.34.862532-0.05～500.99887.66.511962,3,4,6-0.05～500.99996.13.122890.05～500.99898.23.583234-0.05～500.99990.35.981962.2　2.2.1　焦化废水原水中酚类污染物的组成GC-MS。,:、、、、2,4-、3,5-、2,5-、2,3-、2,6-、3,4-1-、2-。。,、、、。2-、4-。2.2.2　焦化废水中各种酚类污染物在生物A/O/O工艺中降解特征,、、、2,4-,、,。3,,100mg/L,,88.26mg/L41.73mg/L,46.46mg/L(2,4-31.77mg/L),28.914mg/L。A/O/O,、、10μg/L,2,4-15.61μg/L,3μg/L;21-,2-5.948μg/L。,。,521.2mg/L270.1mg/L,100mg/L,,。,29.3%;,1mg/L,99%;,89%,,0.05mg/L。,,,。,,。,,、,,。,。,10μg/L,2-4-。2562　:A/O/O3　、Table3　Determinationresultsofphenol,methylphenolsandnaphthols(mg/L)(mg/L)(mg/L)(μg/L)(μg/L)(μg/L)169.888.9766.90415.310.405.81288.2645.8535.8922.686.6012.681166.041.7389.5321.6855.8118.2963.2410.2714.705.8834.8602.8312,6-3.8421.0990.52611.383.7561.5952,4-31.7716.509.372184.828.0715.612,5-0.9530.5320.2279.4814.6022.5803,5-1.2810.2080.15112.242.8211.7703,4-2.9791.0560.4165.8880.7500.0292,3-5.6342.5791.89112.532.0260.9291-5.9771.0020.38475.22NDND2-2.9370.9521.04153.336.0965.948∑521.2270.1190.9876.485.7144.65　　:ND4　Table4　Determinationresultsofchorophenolsandnitrophenols(μg/L)2-1.1320.7690.4140.0120.0030.0034--3-0.4980.2540.0820.0340.0280.0032,6-0.0460.0210.0060.0020.0020.0022,4-0.3470.1750.0850.0120.0630.0082,4,6-2.6341.5141.3010.0560.0120.0102,4,5-NDNDND0.0040.0030.0022,3,4,6-0.1770.0880.0410.0260.0260.019NNDDNNDDNNDDNNDDNNDDNNDD∑4.8342.8211.9290.1460.1370.0472-4.7562.3330.7190.635