BS EN 14077-2003 Petroleum products - Determination of organic halogen content - Oxidative microcoulometric method《石油制品 有机卤素含量的测定 氧化微库仑法》.pdf

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1、Licensed Copy: Wang Bin, ISO/Exchange China Standards Information Centre, 27 July 2004, Uncontrolled Copy, (c) BSIBRITISH STANDARD BS EN 14077:2003 BS 2000-510:2004 BS 2000-510: Petroleum products Determination of organic halogen content Oxidative microcoulometric method (Identical with IP 510-2004)

2、 The European Standard EN 14077:2003 has the status of a British Standard ICS 75.080 Licensed Copy: Wang Bin, ISO/Exchange China Standards Information Centre, 27 July 2004, Uncontrolled Copy, (c) BSIBS EN 14077:2003 This British Standard, was published under the authority of the Standards Policy and

3、 Strategy Committee on 19 December 2003 BSI 19 December 2003 ISBN 0 580 43140 1 National foreword This British Standard is the official English language version of EN 14077:2003. The UK participation in its preparation was entrusted to Technical Committee PTI/13, Petroleum testing and terminology, w

4、hich has the responsibility to: A list of organizations represented on this committee can be obtained on request to its secretary. The Institute of Petroleum publishes and sells all Parts of BS 2000, and all BS EN petroleum test methods that would be Part of BS 2000, both in its annual publication “

5、Standard methods for analysis and testing of petroleum and related products and British Standard 2000 Parts” and individually. For further information is available from: Energy Institute, 61 New Cavendish Street, London W1G 7AR. Tel: 020 7467 7100. Fax: 020 7255 1472. Cross-references The British St

6、andards which implement international or European publications referred to in this document may be found in the BSI Catalogue under the section entitled “International Standards Correspondence Index”, or by using the “Search” facility of the BSI Electronic Catalogue or of British Standards Online. T

7、his publication does not purport to include all the necessary provisions of a contract. Users are responsible for its correct application. Compliance with a British Standard does not of itself confer immunity from legal obligations. aid enquirers to understand the text; present to the responsible in

8、ternational/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 E

9、N title page, pages 2 to 17 and a back cover. The BSI copyright notice 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, 27 July 2004, Uncontroll

10、ed Copy, (c) BSIEUROPEANSTANDARD NORMEEUROPENNE EUROPISCHENORM EN14077 December2003 ICS75.080 Englishversion PetroleumproductsDeterminationoforganichalogencontent Oxidativemicrocoulometricmethod ProduitsptroliersDterminationdelateneuren halognesorganiquesMthodeparmicrocoulomtrie oxydante Minerallerz

11、eugnisseBestimmungdesGehaltesan organischgebundenemHalogenVerfahrenderoxidativen Mikrocoulometrie ThisEuropeanStandardwasapprovedbyCENon1October2003. CENmembersareboundtocomplywiththeCEN/CENELECInternalRegulationswhichstipulatetheconditionsforgivingthisEurope an Standardthestatusofanationalstandardw

12、ithoutanyalteration.Uptodatelistsandbibliographicalreferencesconcernings uchnational standardsmaybeobtainedonapplicationtotheManagementCentreortoanyCENmember. ThisEuropeanStandardexistsinthreeofficialversions(English,French,German).Aversioninanyotherlanguagemadebytra nslation undertheresponsibilityo

13、faCENmemberintoitsownlanguageandnotifiedtotheManagementCentrehasthesamestatusasthe official versions. CENmembersarethenationalstandardsbodiesofAustria,Belgium,CzechRepublic,Denmark,Finland,France,Germany,Greece, Hungary,Iceland,Ireland,Italy,Luxembourg,Malta,Netherlands,Norway,Portugal,Slovakia,Spai

14、n,Sweden,SwitzerlandandUn ited Kingdom. EUROPEANCOMMITTEEFORSTANDARDIZATION COMITEUROPENDENORMALISATION EUROPISCHESKOMITEEFRNORMUNG ManagementCentre:ruedeStassart,36B1050Brussels 2003CEN Allrightsofexploitationinanyformandbyanymeansreserved worldwideforCENnationalMembers. Ref.No.EN14077:2003E Licens

15、ed Copy: Wang Bin, ISO/Exchange China Standards Information Centre, 27 July 2004, Uncontrolled Copy, (c) BSIEN14077:2003(E) 2 Contents page Foreword3 1 Scope 4 2 Normativereferences 4 3 Termsanddefinitions. .4 4 Principle5 5 Reagentsandmaterials .5 6 Apparatus .7 7 Samplingandsamplepreparation . 8 7

16、.1 Sampling.8 7.2 Samplepreparation .8 7.2.1 Distillatefuels .8 7.2.2 Residualfuels .8 8 Preparationofapparatus 9 9 Procedure .12 9.1 Checkofapparatusstability .12 9.2 Sampleanalysis . 13 10 Calculation13 11 Expressionofresults 14 12 Precision.14 12.1 General14 12.2 Repeatability, r .14 12.3 Reprodu

17、cibility, R.14 12.4 Bias14 13 Testreport 14 AnnexA(normative)Calculationofconversionfactor 16 Bibliography 17 Licensed Copy: Wang Bin, ISO/Exchange China Standards Information Centre, 27 July 2004, Uncontrolled Copy, (c) BSIEN14077:2003(E) 3 Foreword ThisdocumentEN14077:2003hasbeenpreparedbyCEN/TC19

18、,“Petroleumproducts,lubricantsandrelated products“,thesecretariatofwhichisheldbyNEN. ThisEuropeanStandardshallbegiventhestatusofanationalstandard,eitherbypublicationofanidenticaltextor byendorsement,atthelatestbyJune 2004,andconflictingnationalstandardsshallbewithdrawnatthelatestby June2004. Inthiss

19、tandardannexAisnormative. ThisdocumentincludesaBibliography. AccordingtotheCEN/CENELECInternalRegulations,thenationalstandardsorganizationsofthefollowing countriesareboundtoimplementthisEuropeanStandard:Austria,Belgium,CzechRepublic,Denmark,Finland, France,Germany,Greece,Hungary,Iceland,Ireland,Ital

20、y,Luxembourg,Malta,Netherlands,Norway,Portugal, Slovakia,Spain,Sweden,SwitzerlandandtheUnitedKingdom. Licensed Copy: Wang Bin, ISO/Exchange China Standards Information Centre, 27 July 2004, Uncontrolled Copy, (c) BSIEN14077:2003(E) 4 1Scope Themethodisdirectlyapplicabletothedeterminationoflowcontent

21、s(2mg/kgto100mg/kg)oforganichalogenin petroleumproductssuchasgasolines,middledistillatesandresidualfuels.Themethodcanalsobeappliedto crudeoils;however,noprecisiondatahavebeenestablishedforthisadditionalproducttype.Exceptforfluorine (F),theorganichalogenschlorine(Cl),bromine(Br)andiodine(I)thatmaybep

22、resentinthesampleare determinedquantitatively.Thehalogenisreportedastheequivalentnumberofchlorideions.Asamplepreparation isdescribedfortheremovalofinorganichalidesfromresidualfuels,beforethedeterminationoftheorganic halogencontent.Thisprocedureisessentialtoobtainaresultoforganichalogenonly. NOTE The

23、totalhalogencontentcanbemeasuredbyISO15597PetroleumandrelatedproductsDeterminationof chlorineandbrominecontentWavelengthdispersiveXrayfluorescencespectrometrymethod.Thismethoddoesnotusea combustionstep,butitrequiresasamplepreparationaccordingtoclause7ofthisstandardtodeterminetheorganichalogen conten

24、t. WARNINGTheuseofthisstandardmayinvolvehazardousmaterials,operationsandequipment.This standarddoesnotpurporttoaddressallofthesafetyproblemsassociatedwithitsuse.Itisthe responsibilityoftheuserofthisstandardtoestablishappropriatesafetyandhealthpracticesand determinetheapplicabilityofregulatorylimitat

25、ionspriortouse. 2 Normativereferences ThisEuropeanStandardincorporatesbydatedorundatedreference,provisionsfromotherpublications.These normativereferencesarecitedattheappropriateplacesinthetext,andthepublicationsarelistedhereafter.Fordated references,subsequentamendmentstoorrevisionsofanyofthesepubli

26、cationsapplytothisEuropeanStandardonly whenincorporatedinitbyamendmentorrevision.Forundatedreferencesthelatesteditionofthepublicationreferred toapplies(includingamendments). ENISO5952, ReusableallglassormetalandglasssyringesformedicalusePart2:Design,performance requirementsandtests(ISO5952:1987). EN

27、ISO3170, PetroleumliquidsManualsampling(ISO3170:1988,includingAmendment1:1998). ENISO3171, PetroleumliquidsAutomaticpipelinesampling(ISO3171:1988). ENISO3696, WaterforanalyticallaboratoryuseSpecificationandtestmethods(ISO3696:1987) . ISO5951, ReusableallglassormetalandglasssyringesformedicalusePart1

28、:Dimensions. 3 Termsanddefinitions ForthepurposesofthisEuropeanStandard,thefollowingtermsanddefinitionsapply. 3.1 organichalogen allorganicallyboundhalogen,whichareconvertedtothehalideionundertheconditionsofthetest,titratedwith electrolyticallygeneratedsilverionsandexpressedastheequivalentnumberofch

29、lorideions NOTE Undertheconditionsofthistest,organichalogencompoundsincludeorganiccompoundsofchlorine(Cl),bromine (Br)andiodine(I).Itdoesnotincludeorganiccompoundsoffluorine(F).Someinorganichalidecompounds,ifnotquantitativ ely removed,arealsodeterminedasorganichalogen. 3.2 residualfuel residueofanyd

30、istillationprocess,appliedtohydrocarbonmixturesderivedfromcrudepetroleumandobtained eitherdirectlyorthroughaspecificprocess,whichisintendedtobeusedasafueloilorafueloilcomponent Licensed Copy: Wang Bin, ISO/Exchange China Standards Information Centre, 27 July 2004, Uncontrolled Copy, (c) BSIEN14077:2

31、003(E) 5 NOTE Residualfuelisimpliedtobeanyhydrocarbonmixture,whichcannotbefullyvaporizedunderconditionsnormally appliedinphysicaldistillationprocesses.Forthepurposeofthisstandardthisalsoincludesfueloils,otherthenthoseobt ained asoverheadproductofaphysicaldistillationprocess,derivedfromwastematerials

32、 3.3 distillatefuel distillateproductofanydistillationprocess,appliedtohydrocarbonmixturesderivedfromcrudepetroleumand obtainedeitherdirectlyorthroughaspecificprocess,whichisintendedtobeusedasafueloilorafueloil component NOTE Distillatefuelisimpliedtobeanyhydrocarbonmixture,whichcanbefullyvaporizedu

33、nderconditionsnormally appliedinphysicaldistillationprocesses.Forthepurposeofthisstandardthisalsoincludesdistillatefueloils,containin gnon distillableadditivessuchasignitionandflowimprovers.Itdoesnotincludedistillatefuels,containingadditivesorother non distillablesubstancesoriginatingfromotherproduc

34、tsnotprimarilyintendedasfueloilse.g.thoseoriginatingfromwaste materials. 4Principle Amicrocoulometerissetupanditsperformancecheckedwiththeaidoforganicliquidstandards.Where appropriate,thesampleisdilutedwithasuitablesolvent.Inorganichalidecompounds,ifpresent,areremovedby extractionwithwater.The(dilut

35、ed)sampleisinjectedintoaheatedzoneofthepyrolysistubewhereitevaporates. Thegaseousproductsareentrainedbyaflowofargontothecombustiontubewhereoxygenismixedwithargon andcombustiontakesplace.Thecombustionproducts,includingthehydrogenhalide,arespargedthrougha sulfuricaciddryerintoacoulometriccellandtitrat

36、edwithelectrolyticallygeneratedsilverionsaccordingto: + + - AgCl AG Cl Thesilverionsconsumedarecoulometricallyreplacedatthegeneratoranode: - + + e Ag Ag 0 Thecurrentrequiredtorestorethesilverioncontentisameasureofthehalidetitrated.Thecurrentflowinmicro coulomb/secisrecordedasapeakonastripchart,andth

37、epeakareaintegratedeithermechanicallyor electronically.Thehalideisreportedastheequivalentnumberofchlorideions.Thecontentofhalogeninthe sampleisthencalculatedintheappropriateunitsselected. 5 Reagentsandmaterials Useonlyreagentsofrecognisedanalyticalgradeandwaterconformingtograde3ofENISO3696. 5.1 Gase

38、s Molecularsievescrubbersmaybeusedtoensureadequatepurityofthegases. 5.1.1 Oxygen,99,98%minimumpurity. 5.1.2 Argon,99,99%minimumpurity.Heliumofequalpurityisanacceptablealternative. 5.2 Diluent,xylene. Determinetheorganichalogencontentaccordingto9.2ofthismethod.Theresultshallbe preferablybelow1mg/kgan

39、dinanycasebelow2mg/kg. 5.3 Nitricacidw ,5mol/l,aqueous.Cautiouslydilute325mlofanalyticalgradeconcentratednitricacid(density 1,42g/ml)to1lwithwater,whilststirring. 5.4 Sulfuricacid ,concentrated. 5.5 Aceticacid ,glacial. Licensed Copy: Wang Bin, ISO/Exchange China Standards Information Centre, 27 Jul

40、y 2004, Uncontrolled Copy, (c) BSIEN14077:2003(E) 6 5.6 Hydrazinesulfate 5.7 Qualitycontrolcompounds 5.7.1 Chlorotetradecane,98,0%minimumpurity 5.7.2 Chlorobenzene,98,0%minimumpurity 5.8 ControlSolutions 5.8.1 Stocksolution Preparea10000mg/kgstocksolutionasfollows:weighapproximately2,5g( m 1 )ofchlo

41、rotetradecaneor1,2g( m 1 ) chlorobenzenetothenearest0,1mgintoaclean50mlglassbottle.Addapproximately35g( m 2 )ofxylene weighedtothenearest0,1mgandmixwell.Thestocksolutionisstoredinawellclosedbottle.Donotusescrew capswithPVCinlays.Calculatetheexactcontentbymeansofthefollowingequation: ) ( 10 453 , 35

42、2 1 6 1 m m M m C s + = (1) where: C s isthechlorine(Cl)contentofstocksolution,inmg/kg; m 1 isthemassofqualitycontrolcompound,ing; m 2 isthemassofxylene,ing; M isthemolecularmass ofqualitycontrolcompound. NOTE Forchlorotetradecane M=232,84;forchlorobenzene M=112,56. Afreshsolutionshouldbepreparedwee

43、kly. 5.8.2 Workingcontrolsolutions Prepareworkingcontrolsolutionscontainingapproximately100mg/kg,50mg/kgand10mg/kgchlorine(Cl)daily byappropriatedilutionofthestocksolutionwithxyleneincleanglassbottles.Calculatetheexactcontentofeach workingstandardtothenearest0,1mg/kgbymeansofthefollowingequation: s

44、x s s w C m m m C + = (2) where: C w isthechlorine(Cl)contentofworkingcontrolsolution,inmg/kg; C s isthechlorine(Cl)contentofstocksolution,inmg/kg; m s isthemassofstocksolutiontaken,ing; m x isthemassofxyleneadded,ing. 5.9 Electrolyte Electrolytesolution.75partsbyvolumeofglacialaceticacidwith25partsofwater.Addapproximately0,1%(m/m) hydrazinesulfate. NOTE Whenusingacoulometricsystemincludingasaltbridge(insteadofacapillary),itisadvantageou