BS EN 13723-2002 Methods of test for petroleum and its products - Petroleum products - Determination of low lead contents in gasolines - Wavelength-dispersive X-ray fluorescence sp.pdf

1、Licensed Copy: Wang Bin, ISO/Exchange China Standards Information Centre, 11 November 2002, Uncontrolled Copy, (c) BSIBRITISH STANDARD BS EN 13723:2002 BS 2000-489:2002 Methods of test for petroleum and its products BS 2000-489: Petroleum products Determination of low lead contents in gasolines Wave

2、length-dispersive X-ray fluorescence spectrometry (XRF) (Identical with IP 489:2003) The European Standard EN 13723:2002 has the status of a British Standard ICS 75.160.20 Licensed Copy: Wang Bin, ISO/Exchange China Standards Information Centre, 11 November 2002, Uncontrolled Copy, (c) BSIBS EN 1372

3、3:2002 This British Standard, having been prepared under the direction of the Materials and Chemicals Sector Policy and Strategy Committee, was published under the authority of the Standards Policy and Strategy Committee on 12 August 2002 Institute of Petroleum present to the responsible internation

4、al/European committee any enquiries on the interpretation, or proposals for change, and keep the UK interests informed; monitor related international and European developments and promulgate them in the UK. Summary of pages This document comprises a front cover, an inside front cover, the EN title p

5、age, pages 2 to 9 and a back cover. The BSI copyright date displayed in this document indicates when the document was last issued. Amendments issued since publication Amd. No. Date Comments Licensed Copy: Wang Bin, ISO/Exchange China Standards Information Centre, 11 November 2002, Uncontrolled Copy,

6、 (c) BSIEUROPEANSTANDARD NORMEEUROPENNE EUROPISCHENORM EN13723 July2002 ICS75.160.20 Englishversion PetroleumproductsDeterminationoflowleadcontentsin gasolinesWavelengthdispersiveXrayfluorescence spectrometry(XRF) ProduitsptroliersDterminationdesfaiblesteneursen plombdanslesessencespourmoteursSpectr

7、omtriede fluorescencederayonsxdispersiveenlongueurdonde (FRX) MinerallerzeugnisseBestimmungniedrigerBleigehaltein KraftstoffenWellenlngendispersiveRntgenfluoreszenz Analyse(RFA) ThisEuropeanStandardwasapprovedbyCENon5April2002. CENmembersareboundtocomplywiththeCEN/CENELECInternalRegulationswhichstip

8、ulatetheconditionsforgivingthisEurope an Standardthestatusofanationalstandardwithoutanyalteration.Uptodatelistsandbibliographicalreferencesconcernings uchnational standardsmaybeobtainedonapplicationtotheManagementCentreortoanyCENmember. ThisEuropeanStandardexistsinthreeofficialversions(English,Frenc

9、h,German).Aversioninanyotherlanguagemadebytra nslation undertheresponsibilityofaCENmemberintoitsownlanguageandnotifiedtotheManagementCentrehasthesamestatusasthe official versions. CENmembersarethenationalstandardsbodiesofAustria,Belgium,CzechRepublic,Denmark,Finland,France,Germany,Greece, Iceland,Ir

10、eland,Italy,Luxembourg,Malta,Netherlands,Norway,Portugal,Spain,Sweden,SwitzerlandandUnitedKingdom. EUROPEANCOMMITTEEFORSTANDARDIZATION COMITEUROPENDENORMALISATION EUROPISCHESKOMITEEFRNORMUNG ManagementCentre:ruedeStassart,36B1050Brussels 2002CEN Allrightsofexploitationinanyformandbyanymeansreserved

11、worldwideforCENnationalMembers. Ref.No.EN13723:2002E Licensed Copy: Wang Bin, ISO/Exchange China Standards Information Centre, 11 November 2002, Uncontrolled Copy, (c) BSIEN13723:2002(E) 2 Contents page Foreword3 1 Scope 4 2 Normativereferences 4 3 Principle4 4 Chemicalsandsolvents 5 4.1 2,2,4trimet

12、hylpentane(isooctane) 5 4.2 Toluene .5 4.3 Kerosene.5 4.4 Lead2ethylhexanoate . .5 4.5 Triphenylbismuthorbismuth2ethylhexanoate 5 4.6 Ethylhexanoicacid 5 4.7 Blanksolution 5 4.8 Leadstocksolution . 5 4.9 Bismuthinternalstandardsolution .5 5 Apparatus .5 5.1 WavelengthdispersiveXrayfluorescencespectr

13、ometer . .5 5.2 Onemarkpipettes. 6 5.3 Volumetricflasks . 6 5.4 Conicalflasks .6 5.5 Frittedglassfilter .6 5.6 Analyticalbalance 6 6 Samplesandsampling 6 7 Calibrationsolutions . 6 7.1 Preparationofleadcalibrationsolutions . .6 7.2 Preparationofcalibrationsolutionsbyadditionoftheinternalstandard.7 8

14、 Calibration 7 8.1 General7 8.2 Calibrationgraph . 7 8.3 Checking.8 9 Procedure .8 10 Calculation8 11 Expressionofresults 8 12 Precision.8 12.1 Repeatability.8 12.2 Reproducibility.8 13 Testreport 9 Licensed Copy: Wang Bin, ISO/Exchange China Standards Information Centre, 11 November 2002, Uncontrol

15、led Copy, (c) BSIEN13723:2002(E) 3 Foreword ThisdocumentEN13723:2002hasbeenpreparedbyTechnicalCommitteeCEN/TC19“Petroleumproducts, lubricantsandrelatedproducts“,thesecretariatofwhichisheldbyNEN. ThisEuropeanStandardshallbegiventhestatusofanationalstandard,eitherbypublicationofanidenticaltextor byend

16、orsement,atthelatestbyJanuary2003,andconflictingnationalstandardsshallbewithdrawnatthelatest byJanuary2003. AccordingtotheCEN/CENELECInternalRegulations,thenationalstandardsorganizationsofthefollowing countriesareboundtoimplementthisEuropeanStandard:Austria,Belgium,CzechRepublic,Denmark,Finland, Fra

17、nce,Germany,Greece,Iceland,Ireland,Italy,Luxembourg,Malta,Netherlands,Norway,Portugal,Spain, Sweden,SwitzerlandandtheUnitedKingdom. Licensed Copy: Wang Bin, ISO/Exchange China Standards Information Centre, 11 November 2002, Uncontrolled Copy, (c) BSIEN13723:2002(E) 4 1Scope ThisEuropeanStandardspeci

18、fiesamethodforthedeterminationoftheleadcontentofgasolineswithalead concentrationfrom4mg/lto25mg/l. NOTE ForthepurposeofthisEuropeanStandard,theterm“%( V/V)”isusedtorepresentthevolumefraction. WARNING: TheuseofthisEuropeanStandardcaninvolvehazardousmaterials,operationsandequipment.This standarddoesno

19、tpurporttoaddressallofthesafetyproblemsassociatedwithitsuse.Itistheresponsibilityofthe userofthisstandardtoestablishappropriatesafetyandhealthpracticesanddeterminetheapplicabilityof regulatorylimitationspriortouse. 2 Normativereferences ThisEuropeanStandardincorporatesbydatedorundatedreference,provi

20、sionsfromotherpublications.These normativereferencesarecitedattheappropriateplacesinthetext,andthepublicationsarelistedhereafter.For datedreferences,subsequentamendmentstoorrevisionsofanyofthesepublicationsapplytothisEuropean Standardonlywhenincorporatedinitbyamendmentorrevision.Forundatedreferences

21、thelatesteditionofthe publicationreferredtoapplies(includingamendments). ENISO3170, PetroleumliquidsManualsampling(ISO3170:1988,includingAmendment1:1998). ENISO3171, PetroleumliquidsAutomaticpipelinesampling(ISO3171:1988). 3Principle Thetestportionandabismuthsolutionasinternalstandardaremixedinagive

22、nvolumeratioandexposed,ina samplecell,totheprimaryradiationofanXraytube. Amixtureof2,2,4trimethylpentane(isooctane)andtoluenewithbismuthasinternalstandardismeasuredasblank solutionunderthesameconditions. TheratioofthePbL a 1 netcountratestotheBiL a 1 grosscountratesiscalculatedbysubtractingthecorres

23、ponding ratiofoundfortheblank. Theleadconcentrationisdeterminedfromacalibrationgraphpreviouslypreparedbymeansofleadstandard solutionsandablanksolution. Thisprocedureisindependentofthetypeofleadcompoundsandofthecompositionofthesample. Licensed Copy: Wang Bin, ISO/Exchange China Standards Information

24、Centre, 11 November 2002, Uncontrolled Copy, (c) BSIEN13723:2002(E) 5 4 Chemicalsandsolvents Useonlyreagentsofrecognizedanalyticalgrade,unlessotherwisespecified. 4.1 2,2,4trimethylpentane(isooctane). 4.2Toluene. 4.3Kerosene, regulargrade . Keroseneisusedassolventwhereconvenientlyavailable.Alternativ

25、ely,ablanksolution(4.7)canalsobeused. 4.4Lead2ethylhexanoate, oracertifiedleadreferencestandard . 4.5 Triphenylbismuthorbismuth2ethylhexanoate, pure,oracertified,commerciallyavailablesolution . 4.6 Ethylhexanoicacid, minimumpurity98% . 4.7 Blanksolution. Mix50%( V/V)of2,2,4trimethylpentaneand50%( V/

26、V)oftoluene. 4.8 Leadstocksolution, c(Pb)=approx.100mg/l . Commerciallyavailableleadstocksolutionscanbeusedorbepreparedasfollows: Dissolvetheappropriatequantityofleadcompound(4.4)inkerosene(4.3)orintheblanksolution(4.7).Storethe solutioninatightlystopperedbrownglassbottleprotectedfromlightandattempe

27、raturesbetween18Cand 28C.Thesolutionshallbecheckedbeforeuseforabsenceofcloudiness.Incaseofdoubt,anewsolutionshall beprepared. 4.9 Bismuthinternalstandardsolution, c(Bi)=approx.0,8g/l. Commericallyavailablebismuthstandardscanbeusedorbepreparedasfollows: Dissolvetheappropriatequantityofbismuthcompound

28、4.5)inkerosene(4.3)orinblanksolution(4.7).Inorderto stabilizethesolution,add5%( V/V)of2ethylhexanoicacid(4.6).Ifcloudinessoccurs,filterthesolutionsthrougha frittedglassfilter(5.5). Thebismuthsolutionhastobeprotectedagainsthumidity.Storethesolutioninatightlystopperedbrownglass bottleprotectedfromlig

29、htandattemperaturesbetween18Cand28C.Thesolutionshallbecheckedbeforeuse forabsenceofcloudiness.Incaseofdoubt,anewsolutionshallbeprepared. 5Apparatus Usuallaboratoryapparatusandglassware,togetherwiththefollowing. 5.1 WavelengthdispersiveXrayfluorescencespectrometer, capableofbeingoperatedconformingto

30、thegeneralrequirementsgiveninTable1.Itshallbesetupaccordingtothemanufacturersinstructions. Licensed Copy: Wang Bin, ISO/Exchange China Standards Information Centre, 11 November 2002, Uncontrolled Copy, (c) BSIEN13723:2002(E) 6 Table1Generalrequirementsforthespectrometer Anode Voltage current power c

31、ollimator analyzingcrystal opticalpath cellwindow detector rhodium,molybdenum,tungstenorgoldtarget 50kVto75kV 40mAto60mA 2,0kW fine lithiumfluoride(2d=4,028nm) helium Polyesterorpolypropylenefilm,thicknessapprox. 4 m mto6 m m,leadfree scintillationdetectorwithpulseheightanalyser NOTE Othersystems,li

32、kesystemswithlowerpower,canalsobeused,providedthattheyhavebeenvalidatedtofully meettheotherrequirementsin5.1,8.2and12. 5.2 Onemarkpipettes, conformingtoISO648,capacity2mland20ml,orsuitabledispenser. 5.3Volumetric flasks, withgroundglassstopper. 5.4Conical flasks, withconicalgroundglassstopper. 5.5Fr

33、itted glass filter, 10 m mto16 m mporesize. 5.6 Analyticalbalance, capableofweighingtothenearest0,1mg. 6 Samplesandsampling Unlessotherwisespecifiedinthecommodityspecification,samplesshallbetakenasdescribedinENISO3170or ENISO3171,and/orinaccordancewiththerequirementsofnationalstandardsorregulationsf

34、orthesamplingof theproductundertest. 7 Calibrationsolutions 7.1 Preparationofleadcalibrationsolutions Diluteinvolumetricflasks(5.3)theleadstocksolution(4.8)usingtheblanksolution(4.7)toobtaincalibration solutionswithapproximate,butpreciselyknownleadconcentrationsof30mg/l,20mg/l,10mg/l,5mg/l,1mg/l. Li

35、censed Copy: Wang Bin, ISO/Exchange China Standards Information Centre, 11 November 2002, Uncontrolled Copy, (c) BSIEN13723:2002(E) 7 Storethecalibrationsolutionsindarkbottles. 7.2 Preparationofcalibrationsolutionsbyadditionoftheinternalstandard Usingthepipettesorsuitabledispenser(5.2),mixthoroughly

36、tenpartsbyvolume,e.g.20ml,ofeachofthelead calibrationsolutionsandtheblanksolutionwithonepartbyvolume,e.g.2ml,ofthebismuthinternalstandard solution(4.9)inconicalflasks(5.4)andsealwiththegroundglassstopperstoavoidevaporationlosses. 8Calibration 8.1General Setupandcheckthespectrometer(5.1),andthenpurge

37、theopticalpaththoroughlywithhelium(seeNOTE1in 8.2). 8.2 Calibrationgraph Transferasuitableamountofeachofthepreparedcalibrationsolutionsandblanksolution(7.2)intosamplecells andplacethemintothespectrometer.Theuseofaloosecoverforthesamplecellsisrecommendedinorderto avoidexcessivepressureanddeformationo

38、fthefilm.Flushtheopticalpathwithhelium(seeNOTE1)andexpose thecellssuccessivelytotheradiationoftheXraytube. NOTE1 Whilepurgingwithheliumisnotabsolutelynecessaryforthisspecificanalysis,itcanbenecessaryforother followingtestseriesmeasuringotherconstituentsinthesameapparatus.Sinceitisessential,however,t

39、ohaveconstant equilibriumgaseousconditionsintheopticalpath,purgingwithheliumisrecommendedinthistestmethod. Measureforeachsolutionthecountrates, I,ofthePbL a 1 lineat0,1175nm,oftheBiL a 1 lineat0,1144nmand ofthebackgroundradiationat0,1194nm. ThesettingsoftheXrayspectrometershallbesuchthatovertheentir

40、emeasurementperiod,theBiL a 1 linewill giveatleast100000counts. Calculateforeachsolutiontheratio, R,ofthePbL a 1 netcountratetotheBiL a 1 grosscountrateusingthe followingequation: I I I = R 0,1144 0,1194 0,1175 where I 0,1175nm isthegrosscountrateofthePbL a 1 line; I 0,1194nm isthecountrateoftheback

41、groundradiation; I 0,1144nm isthegrosscountrateoftheBiL a 1 line. Calculateforeachcalibrationsolutionthecorrectedcountrateratio, R c ,usingthefollowingequation: R R = R b c Licensed Copy: Wang Bin, ISO/Exchange China Standards Information Centre, 11 November 2002, Uncontrolled Copy, (c) BSIEN13723:2

42、002(E) 8 where R b isthecountrateratiofortheblanksolution. Plotacalibrationgraphgivingthecorrectedcountrateratios R C asabsissaeandthecorrespondinglead concentrations,inmilligramsperlitre,asordinates. NOTE2 Manymoderninstrumentsareequippedwithamicroprocessorthatproducesthecalibrationgraphautomatical

43、ly, givingadigitalreadout. 8.3Checking Checkthecalibrationgraphsregularly.Inroutineuse,checkatleasttwopointsoneachcalibrationgraphatleast everysixmonths.Ifthecheckresultdiffersfromthegraphbymorethantherepeatability(see12.1),establisha newcalibrationgraph. 9Procedure Usingthepipettesorsuitabledispenser(5.2),mixthoroughlytenpartsbyvolume,e.g.20ml,ofthesample(see clause6),withonepartbyvolume,e.g.2ml,ofthebismuthinternalstandardsolution(4.9)inconicalflasks(5.4) andsealwiththegroundglassstopperstoavoidevaporationlosses. Followingtheprocedureasgivenin8.2,determinethecountraterati