高盐度化学制药废水预处理试验研究李再兴

311Vol.31,No.120102JournalofHebeiUniversityofScienceandTechnologyFeb.2010　　:1008-1542(2010)01-0052-05李再兴1,李　萍1,苗志加1,杨景亮1,严　伟2(1.河北科技大学环境科学与工程学院,河北石家庄　050018;2.河北省农业机械化研究所有限公司,河北石家庄　050051)　:采用“蒸馏+铁炭内电解+絮凝”工艺对某制药企业排放的废水进行预处理。经过蒸馏脱盐后,综合废水盐度(质量分数,下同)由7.4%降至0.15%;再采用“铁炭内电解+絮凝”工艺进行处理,内电解试验最佳工艺条件:进水pH值为3.0、铁炭比为4∶1(体积比)、停留时间为6h,COD去除率达到26.5%;絮凝试验最佳pH值为9.0,COD去除率达到1.5%。废水经过预处理后,COD去除率达到28.0%,出水COD质量浓度(下同)降至20988mg/L,ρ(BOD)5/ρ(COD)由0.28提高至0.41。预处理出水厌氧可生化性试验表明,当进水COD质量浓度为9000mg/L左右时,容积负荷(COD)为1.0kg/(m3·d),出水COD质量浓度降低至2100mg/L左右,COD去除率达到75.0%。说明该制药废水经过预处理后可生化性显著提高,为后续的生化处理创造了有利条件。:化学制药废水;高盐度;预处理;脱盐;铁炭内电解;絮凝;可生化性:X703　　　:APretreatmentofchemicalpharmaceuticalwastewaterwithhighsalinityLIZai-xing1,LIPing1,MIAOZhi-jia1,YANGJing-liang1,YANWei2(1.CollegeofEnvironmentalScienceandEngineering,HebeiUniversityofScienceandTechnology,ShijiazhuangHebei050018,China;2.HebeiResearchInstituteofAgriculturalMechanizationCompanyLimited,ShijiazhuangHebei050051,China)Abstract:Thechemicalpharmaceuticalwastewaterwaspretreatedbydistillation+ferric-carbonmicroelectrolysis+floccula-tionprocess.Theresultsindicatethatthesalinityoftheintegratedwastewaterfallsfrom7.4%to0.15%afterdistillation.Thenitwastreatedbyferric-carbonmicroelectrolysis+flocculation,andtheoptimizedconditionsofferric-carbonmicroelec-trolysisarepH=3.0,V(Fe)/V(C)=4∶1andHRT=6h.CODremovalrateis26.5%.TheoptimizedpHvalueoffloccula-tionare9.0andCODremovalrateare1.5%.Afterthesepretreatmentprocesses,CODremovalratereaches28.0%,CODisdecreasedto20988mg/L,andtheratioofBOD5/CODofwastewaterincreasedfrom0.28to0.41.Thentheeffluentofthepretreatmentprocesswastreatedbyanaerobicdigestion.TheresultsshowthatCODdecreasesfrom9000mg/Lto2100mg·L-1andCODremovalrateis75.0%,ThevolumetricCODloadingrateis1.0kg/(m3·d).Thenitcouldbeconcludedthataf-terpretreatment,thebiodegradabilityofthechemicalpharmaceuticalwastewaterisimprovedandsuitableforthefollowingbiotreatment.Keywords:chemicalpharmaceuticalwastewater;highsalinity;pretreatment;desalination;ferric-carbonmicroelectrolysis;flocculation;biodegradability　　:2009-01-09;:2009-04-28;::(1973-),,,,,。　　[1,2],、,,、[3,4]。,[5,6]。“++”[7,8],,。1　1.1　,1。表1　废水水质Tab.1　Wastewaterproperties/(m3·d-1)pHρ(COD)/(mg·L-1)()/%20.4—124678.913.2—637225.97.26.0200860.03218.02.096964.051.611.0304760.0168.07.0374020.04316.0—2770513.751.2　1):。2):。,,10%,5%10min,。,0.5～2mm。1-;2-;3-图1　厌氧消化试验装置Fig.1　Anaerobicdigestiondevice3):,1。500mL,35℃,,(VSS)21.3g/L()。1.3　[9]pH:pHS-2;COD:;:;BOD5:。1.4　1):、、4,。pH、ρ(COD)。2):、、,。,NaOHpH,。pH、ρ(COD)ρ(BOD5)。3):NaOH,pH,30min,pH、ρ(COD)ρ(BOD5)。4):,,,。pHρ(COD)。53　1　　　　　　　　　　　　　　2　2.1　、、4,,2。,85%。。表2　蒸馏试验结果Tab.2　Resultsofdistillationtest/%pH0.10.2—ρ(COD)/(mg·L-1)24935228578.0()/%1801002,COD,。,,。2.2　4,,。:pH0.6,ρ(COD)29150mg/L,0.15%(),ρ(BOD5)/ρ(COD)0.28。,(V(Fe)/V(C))、pH、。2.2.1　pH3.0,、。V(Fe)/V(C)1∶1,4∶1,9∶1,12∶1,2。2,,COD。,,。pH3,V(Fe)/V(C)4∶1,。pH6.0,COD21335mg/L,COD26.5%。2.2.2　pHpH,V(Fe)/V(C)4∶1,pH0.6,2.0,3.0,4.0,3。,,。pH,,。,pH,,Fe2+,pH,Fe(OH)2Fe(OH)3,。,,pH,,。3,pH3.0,,COD21350mg/L,COD26.5%。54　　　　　　　　　　　　　　　　2010　图4　COD去除率随反应时间的变化Fig.4　RelationbetweenHRTandremovalofCOD2.2.3　,2,4,6,8,10h,4。4,,COD,6h,COD26.5%,COD21436mg/L。,COD,10h,COD27.5%,6h1%。:V(Fe)/V(C)4∶1,pH3.0,6h。COD21436mg/L,COD26.5%。2.3　图5　絮凝沉淀pH值对COD去除率的影响Fig.5　InfluenceofflocculationandprecipitationpHonCODremovalFe2+,NaOHFe(OH)2,。pHCOD,pH7.0,8.0,9.0,10.0,11.0,5。5,pH,,COD1.0%,。Fe2+,pH9.0,1.5%,COD20988mg/L。2.4　“++”,3。表3　预处理对废水的综合处理效果Tab.3　TotaleffectofthepretreatmentprocessonwastewaterpHρ(COD)/(mg·L-1)()/%ρ(BOD5)/ρ(COD)0.6291507.40.286.0209880.150.41/%—28.098.0—图6　厌氧可生化性试验结果Fig.6　Resultsofanaerobicdigestiontest3,,,ρ(BOD5)/ρ(COD)0.280.41。,,6。6,60d,ρ(COD)9000mg/L,(COD)1.0kg/(m3·d),ρ(COD)2100mg/L,COD75.0%。55　1　　　　　　　　　　　　　　,,。3　　“++”。。1)4,pH0.6,ρ(COD)29150mg/L,()7.4%0.15%。2)“+”,,:pH3.0、V(Fe)/V(C)4∶1、6h,COD26.5%;pH9.0,COD1.5%。,COD28.0%,ρ(COD)20988mg/L,ρ(BOD5)/ρ(COD)0.280.41。3)。60d,ρ(COD)9000mg/L,(COD)1.0kg/(m3·d),ρ(COD)2100mg/L,COD75.0%。,,。:[1]　.[M].:,1991.[2]　,,,.[J].(ChineseJournalofAntibiotics),1994,19(2):124-127.[3]　,.[J].(EnvironmentalProtectionScience),2008,34(3):44-46.[4]　,,,.[J].(IndustrialWaterTreatment),2008,28(11):1-4.[5]　　,.[J].(IndustrialWaterTreatment),2005,25(2):1-4.[6]　　,,,.[J].(TechniquesandEquipmentforEnvironmentalPollutionControl),2005,6(8):42-45.[7]　,.[J].(HebeiJournalofIndustrialScienceandTechnology),2003,20(1):50-53.[8]　　,,　,.[J].(HebeiJournalofIndustrialScienceandTechnolo-gy),2008,25(5):326-330.[9]　《》.[M].4.:,2002.(47):[1]　.[M].:,2000.[2]　.[J].(AdvancedMaterialsIndustry),2007(6):7-11.[3]　,,,.2,3--N-[J].(FineChemicals),2007,24(7):682-683.[4]　　,,　,.[J].(FineandSpecialtyChemicals),2005,13(6):20-25.[5]　,,　.-(2--1-)[J].(ChemicalWorld),1993,34(9):437-440.[6]　　,,　,.N--2-[J].(JournalofTianjinInstituteofTextileScienceandTechnology),2000,19(4):27-29.[7]　,.[J].(HebeiChemicalEngineeringandIndustry),2005(6):42-43.[8]　RALPHAO,COLERAINTH.ProcessforpreparingpyridineN-oxidecarbanionandderivatives[P].US:3773779,1973-11-20.[9]　LAWRENCEE,KATZO,RIOHARDH,etal.Processforoxidizinghalopyridinestohaloyridine-N-oxides[P].US:4504667,19