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1、DeterminationofPCDDsPCDFsPCBsHCBEmissionsfromtheMetallurgicalSectinPolGROCHOWALSKIAdam1LASSENCarsten21.KrakowUniversityofTechnologyKrakwPol.2.COWIASHavneparken1DK7100WejleDenmarkAbstract:Theaimoftheprojectwastomeasurethe

2、actualemissionsofPCDDFPCBsHCBfrom20edmetallurgicalinstallationsinPolindertoupdatethenationalinventyofdioxinemissionfrommetallurgicalindustryfdevelopingastrategyfdioxinsfuransemissionabatementfromthesubjectfacilities(UNEP

3、2005).SamplingmethodologyusedinthiswkwasdevelopedattheKrakowUniversityofTechnologybecauseofthecomplexityofsimultaneouslysamplingdeterminingPCDFsPCDDsPCBHCB.FthedeterminationaGCMSMSsystemwasused.Resultsfromthewkindicateth

4、atthehighestdioxinsPCBconcentrationswererecdedfironesinteringplantsat1.10–1.32ngTEQNm3followedbyaluminiumscrapmeltingat0.03–0.66ngTEQNm3.ThehighestHCBconcentrationsat613–1491ngNm3werealsorecdedfironesinteringplantswherea

5、sataluminiumplantstheHCBconcentrationswereintherangeofonly10.1–22.7ngNm3.Theaboveinvestigationsindicatethatsecondaryaluminiumproductionisthemostsignificantdioxinssourceifcalculatedasemissionfactvalues.Howeverironesinteri

6、ngplantsareoperatingatmuchhigherproductioncapacitycausingthisprocesstobecomethemajsourceofdioxinsPCBHCBpollutiontotheatmosphereinPol.Keywds:MetalindustrydioxinPCBHCBemissionmeasurementsPOPspollution0IntroductionEmissioni

7、nventydatafthemetallurgicalsectinPoluntil2004wasestimatedonthebasisofdefaultemissionfactstakengenerallyfromtheUNEPtoolkit[1].BecausethefmationofdioxinsfuransPCBHCBisprocessspecificinparticularfthermalprocessesinmetalindu

8、stry[23]theuseofdefaultemissionhastobeconsideredashighlyuncertain[45]Theaimofthestudyperfmedin20042005wastomeasuretheactualdioxinsfuransPCBHCBemissionsfromedmetallurgicalinstallationsinPolindertoupdatethenationalinventyo

9、funintentionallyPOPsemissionfromthemetallurgicalindustrymainlydioxinsfurans.Thegoaloftheprojectisalsotodevelopastrategyfdioxinsfuransemissionabatementfromthesubjectfacilities.Fthispurposeinstallationsin20differentfacilit

10、iesofthemetallurgicalsectinPolwereedchosenamongthosewhichrepliedpositivelytotheinvitationtoparticipate.Regardingtheionofplantsinstallationsanefftwasmadetoincludeintoinvestigationseachofthedifferentproductionprocessesconc

11、ernedtoensurethattheemissionstardofthetestedinstallationwastypicalfthegivenindustrialprocess.Atthetimeofmeasurementthetechnicalprocesshadtoberunundertypicalnominalloadaccdingtoproductionstards.Themeasurementswereperfmedb

12、yCracowUniversityofTechnologywithinthePolishDanish“ReductionofDioxinEmissionfromtheMetallurgicalSectinPol”projectfinancedbytheDanishEnvironmentProtectionAgency(fromDANCEEfunds).ProjectMeltingofironsteelscraps.Becauseofth

13、epresenceofplasticscoatingspaintingssealingaswellasnonferrousmaterialsinthegeduringpreliminaryheatinguptheironsteelscrapastrongemissionofpollutantsincludingdioxinsPCBstakesplace.1.2CoppermetallurgyTwobasicprocessesareope

14、ratedinthePolishcoppermetallurgyasdescribedbelow.InbothcasestheemissionconcentrationvaluesfdioxinsPCBsHCBfromtheseprocessesareunknown.RoastingofcoppereleadstoahighconcentrationofSO2useddirectlyfsulphuricacidproduction.Be

15、causeofextremelyhighSO2concentrationsreachingupto250gm3thedioxinsfmationinthisprocessisnegligible.MeovertheprocessofH2SO4productionrequiresmultistepscrubbingofprocessgasesleadingtoaveryeffectiveremovalofdioxinsPCBstraces

16、.Theinvestigationsperfmedconfirmthisthey.Recoveryofcopperfromslagrequiresapplicationofvariousadditivesinahightemperatureprocess.Thecopperoxideisaknowncatalyserfthefmationofdioxinsinthermalprocesses.Reactionsofdioxinsfmat

17、ionhaveneverbeenstudiedundersuchcircumstancesonlymeasurementsmayconfirmtheactualemissionconcentrationvalues.1.3AluminiummetallurgyInallcases(fourinstallations)thethermalprocesswasusingdifferenttechnologiesfmeltingalumini

18、umscrap.Thelatterissmeltedusinganelectricfurnaceagaschamberfurnaceagasoilfiredrotaryfurnaceanelectricfurnacewithpreheatingtoremoveplasticsdecationcoatings(aluminiumbeveragetins).1.4ZincmetallurgyTwoprocessesfromzincmetal

19、lurgyweresubjectofthisexamination:1)roastingzincereleasesahighSO2concentration.Similarlytocopperetheprocessgasesarealsousedfproductionofsulphuricacid.Theprocessofsulphuricacidproductionreducesdioxinsfromprocessgasestotra

20、cevaluesbelow0.1ngITEQm3.Thisisachievedbymultistagescrubbingoperations.2)remeltingzincwasteobtainedfromtheproductionofzincelectrodesusedinelectrolyticprocesses.Inthisprocessanadditiveofammoniumchlide(NH4Cl)isappliedanoth

21、erpotentialsourceofdioxinfmationduetoitschlinecontent.2SamplingAnalysisMethodologyAlthoughthereisanestablishedEUstardfthedeterminationofPCDDPCDFconcentrationinstackgasfromwasteincineration(EuropeanStardEN1948:1996)[6]thi

22、sstardisnotactuallyvalidfthedeterminationofthesecompoundsconsideredhereinfluegasesfrommetalindustry.MeovertheEN1948stardisnotvalidatedyetfthedeterminationofPCBHCB.TherefethesamplingmethodologyusedinthiswkwasdevelopedatCr

23、acowUniversityofTechnologybecauseofthecomplexityofPCDFsPCDDsPCBHCBsimultaneouslysamplingdetermination.SamplesofstackgasweretakenusingtheEMIOTEST9265samplingapparatus(Wroc?awPol).TheapparatusisrepresentedschematicallyinFi

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