EN 14331-2004 en Liquid petroleum products - Separation and characterisation of fatty acid methyl esters (FAME) from middle distillates - Liquid chromatography (LC) gas chromatogra.pdf

1、BRITISH STANDARD BS EN 14331:2004 Liquid petroleum products Separation and characterisation of fatty acid methyl esters (FAME) from middle distillates Liquid chromatography (LC)/gas chromatography (GC) method The European Standard EN 14331:2004 has the status of a British Standard ICS 75.080 BS EN 1

2、4331:2004 This British Standard was published under the authority of the Standards Policy and Strategy Committee on 1 April 2004 BSI 1 April 2004 ISBN 0 580 43626 8 National foreword This British Standard is the official English language version of EN 14331:2004. The UK participation in its preparat

3、ion was entrusted to Technical Committee PTI/13, Petroleum testing and terminology, which has the responsibility to: A list of organizations represented on this committee can be obtained on request to its secretary. Energy Institute, under the brand of Institute of Petroleum publishes and sells all

4、parts of BS 2000, and all BS EN petroleum test methods that would be part of BS 2000, both in its annual publication “Standard methods for analysis and testing of petroleum and related products and British Standard 2000 parts” and individually. Further information is available from: Energy Institute

5、, 61 New Cavendish Street, London W1G 7AR. Tel: 020 7467 7100. Fax: 020 7255 1472. Cross-references The British Standards which implement international or European publications referred to in this document may be found in the BSI Catalogue under the section entitled “International Standards Correspo

6、ndence Index”, or by using the “Search” facility of the BSI Electronic Catalogue or of British Standards Online. This 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

7、itself confer immunity from legal obligations. aid enquirers to understand the text; present to the responsible international/European committee any enquiries on the interpretation, or proposals for change, and keep the UK interests informed; monitor related international and European developments a

8、nd promulgate them in the UK. Summary of pages This document comprises a front cover, an inside front cover, the EN title page, pages 2 to 10, an inside back cover and a back cover. The BSI copyright notice displayed in this document indicates when the document was last issued. Amendments issued sin

9、ce publication Amd. No. Date CommentsEUROPEANSTANDARD NORMEEUROPENNE EUROPISCHENORM EN14331 March2004 ICS75.080 Englishversion LiquidpetroleumproductsSeparationandcharacterisationof fattyacidmethylesters(FAME)frommiddledistillatesLiquid chromatography(LC)/gaschromatography(GC)method Produitsptrolier

10、sliquidesSparationetcaractrisation desestersmthyliquesdacidesgras(EMAG)dansles distillatsmoyensMthodeparchromatographieliquide (CL)etchromatographieenphasegazeuse(CPG) FlssigeMinerallerzeugnisseTrennungundBestimmung vonFettsureMethylestern(FAME)ausMitteldestillaten Flssigchromatographie(LC)/Gaschrom

11、atographie(GC) ThisEuropeanStandardwasapprovedbyCENon16January2004. CENmembersareboundtocomplywiththeCEN/CENELECInternalRegulationswhichstipulatetheconditionsforgivingthisEurope an Standardthestatusofanationalstandardwithoutanyalteration.Uptodatelistsandbibliographicalreferencesconcernings uchnation

12、al standardsmaybeobtainedonapplicationtotheCentralSecretariatortoanyCENmember. ThisEuropeanStandardexistsinthreeofficialversions(English,French,German).Aversioninanyotherlanguagemadebytra nslation undertheresponsibilityofaCENmemberintoitsownlanguageandnotifiedtotheCentralSecretariathasthesamestatusa

13、st heofficial versions. CENmembersarethenationalstandardsbodiesofAustria,Belgium,Cyprus,CzechRepublic,Denmark,Estonia,Finland,France, Germany,Greece,Hungary,Iceland,Ireland,Italy,Latvia,Lithuania,Luxembourg,Malta,Netherlands,Norway,Poland,Portugal, Slovakia, Slovenia,Spain,Sweden,SwitzerlandandUnite

14、dKingdom. EUROPEANCOMMITTEEFORSTANDARDIZATION COMITEUROPENDENORMALISATION EUROPISCHESKOMITEEFRNORMUNG ManagementCentre:ruedeStassart,36B1050Brussels 2004CEN Allrightsofexploitationinanyformandbyanymeansreserved worldwideforCENnationalMembers. Ref.No.EN14331:2004:EEN14331:2004(E) 2 Contents page Fore

15、word3 1 Scope 4 2 Normativereferences 4 3 Principle4 4 Reagentsandmaterials .4 5 Apparatus .4 6 Sampling.5 7 Procedure .5 8 Determinationofthecompositionofamixtureofmethylesters .5 9 Expressionofresults . .6 10 Precision.6 11 Interpretationofresults .6 12 Testreport 6 AnnexA (normative) Summaryofthe

16、conditionsforanalysisoffattyacidmethylestersbygas chromatography.7 AnnexB (informative) ExampleofaFAMEchromatogram8 AnnexC (informative) Typicalcompositionaldataforfattyacidsinvegetableoils .9 Bibliography 10EN14331:2004(E) 3 Foreword Thisdocument(EN14331:2004)hasbeenpreparedbyTechnicalCommitteeCEN/

17、TC19“Petroleumproducts, lubricantsandrelatedproducts“,thesecretariatofwhichisheldbyNEN. ThisEuropeanStandardshallbegiventhestatusofanationalstandard,eitherbypublicationofanidenticaltextor byendorsement,atthelatestbySeptember2004,andconflictingnationalstandardsshallbewithdrawnatthe latestbySeptember2

18、004. AnnexAisnormative.AnnexesBandCareinformative. ThisdocumentincludesaBibliography. AccordingtotheCEN/CENELECInternalRegulations,thenationalstandardsorganizationsofthefollowing countriesareboundtoimplementthisEuropeanStandard:Austria,Belgium,Cyprus,CzechRepublic,Denmark, Estonia,Finland,France,Ger

19、many,Greece,Hungary,Iceland,Ireland,Italy,Latvia,Lithuania,Luxembourg,Malta, Netherlands,Norway,Poland,Portugal,Slovakia,Slovenia,Spain,Sweden,SwitzerlandandUnitedKi ngdom.EN14331:2004(E) 4 1Scope ThisEuropeanStandardspecifiesamethodfortheseparationoffattyacidmethylesters(FAME)frommiddle distillates

20、byliquidchromatography(LC)andforquantitativedeterminationoftheindividualestersbygas chromatography(GC). ThismethodisapplicabletoFAMEofvegetableoranimaloriginthatcontainmethylestersbetweenC 14 toC 24 . TheseFAMEaremainlycomposedofC 16 C 18 estersfromfattyacids.Thismethodisapplicablewhateverthe origin

21、ofthemiddledistillate. ThistestmethodhasbeenevaluatedfortheseparationandcharacterisationofFAMEpresentatupto5% (V/V)in middledistillate. NOTE ForthepurposesofthisEuropeanStandard,theterms“%( m/m)”and“%( V/V)”areusedtorepresentrespectively themassfractionandthevolumefraction. 2 Normativereferences Thi

22、sEuropeanStandardincorporatesbydatedorundatedreference,provisionsfromotherpublications.These normativereferencesarecitedattheappropriateplacesinthetext,andthepublicationsarelistedhereafter.For datedreferences,subsequentamendmentstoorrevisionsofanyofthesepublicationsapplytothisEuropean Standardonlywh

23、enincorporatedinitbyamendmentorrevision.Forundatedreferencesthelatesteditionofthe publicationreferredtoapplies(includingamendments). ENISO3170, PetroleumliquidsManualsampling(ISO3170:1988,includingAmendment1:1998) . ENISO3171, PetroleumliquidsAutomaticpipelinesampling(ISO3171:1988) . ENISO5508 ,Anim

24、alandvegetablefatsandoilsAnalysisbygaschromatographyofmethylestersoffattyacids (ISO5508:1990). 3Principle Themethodconsistsoftwostages: separationoftheFAMEfractionfromthemiddledistillatebyliquidadsorptionchromatographyatatmospheric pressureonasilicamicrocolumn; characterizationoftheseparatedFAMEfrac

25、tionbygaschromatography. 4 Reagentsandmaterials 4.1 Hexane, HPLCanalyticalgrade. 4.2 Diethylether, HPLCanalyticalgrade. 5Apparatus 5.1General Generalgaschromatographicandliquidchromatographicequipmentshallbeused.EN14331:2004(E) 5 5.2Microcolumn,containingapproximately700mgsilica(particlesize55 m m10

26、5 m m),withapproximate dimensionsof25mmofheightand10mmofdiameter. 5.3 Testtube ,20ml. 6Sampling Unlessotherwisespecifiedinthecommodityspecification,samplesshallbetakenasdescribedinENISO3170or ENISO3171and/orinaccordancewiththerequirementsofnationalstandardsorregulationsforthesamplingof theproductund

27、ertest. 7Procedure 7.1Separationonsilicacolumn Addtothetopofthesilicamicrocolumn(5.1)0,100mlofthesampleandallowtopercolateintothecolumnfor about2min. Elutethemiddledistillatefractionwith10mlhexane(4.1).Therateofelutionshallbeslow(dropbydrop)atthe rateofabout3ml/min.Thisfractionisdiscarded. Thenelute

28、theFAMEfractionwith10mldiethylether(4.2)intoatesttube(5.2). NOTE IftheFAMEcontentinthemiddledistillateisgreaterthan5% (V/V),itisrecommendedtodilutethesamplewitha FAMEfreefueltoobtainacontentlowerthan5%( V/V). 7.2 Gaschromatographicanalysis RefertoeitherENISO5508orannexA,whichsummarizestheconditionso

29、ftheanalysis. NOTE InannexBachromatogramofasampleoffattyacidmethylestersfromrapeseedoilisgiven. Chromatographicconditionssuchasinjectionsizeand/orsplitratioshallbeadjustedtodetecttheminor componentse.g.theminorpeaksofC 24:0 andC 24.1 estersfromacids. AchromatogramobtainedfromasamplewithknownFAMEcomp

30、ositionunderidenticalconditionstothoseused fortheanalysisoftheunknownsamplemaybeusedtoestablishretentiontimesforpurposesofpeakidentification. 8 Determinationofthecompositionofamixtureofmethylesters Theamountofconstituent X,expressedasamassfractionoftheFAMEfraction,iscalculatedfromtheareaofthe corres

31、pondingpeakdividedbytheareaofallthepeaks,usingtheequation: = A i A X 100 (1) where: A i istheareaofthepeakcorrespondingtocomponent i. S A isthesumoftheareasofallthepeakselutedbetweenC 14 andC 24 esters.EN14331:2004(E) 6 9 Expressionofresults ReporttheamountofeachcomponentoftheFAMEfractionas%( m/m)to

32、thenearest0,1% (m/m) . 10Precision NOTE Theprecisionofthemethodhasbeenobtainedbystatisticalexaminationofinterlaboratorydataforsamples containingFAMEfromrapeseedoil. 10.1Repeatability Thedifferencebetweentworesultsobtainedbythesameoperatorwiththesameapparatusunderconstant operatingconditionsonidentic

33、altestmaterialwouldinthelongrun,inthenormalandcorrectoperationofthetest method,exceedthevaluesgiveninTable1inonlyonecaseintwenty . 10.2Reproducibility Thedifferencebetweentwosingleandindependentresultsobtainedbydifferentoperatorsindifferentlaboratories onidenticaltestmaterialwouldinthelongrun,inthen

34、ormalandcorrectoperationofthetestmethod,exceedthe valuesgiveninTable1inonlyonecaseintwenty. Table1Precisiondata Methylesterof Repeatability %( m/m) Reproducibility %( m/m) Palmiticacid(C16:0) 0,5 0,8 Oleicacid(C18:1) 0,6 2,8 Linolenicacid(C18:3) 0,4 1,8 11 Interpretationofresults TableC.1containsdat

35、aontherangeoffattyacidmethylestercompositionsfoundontypicalsamplesofoils extractedfrompalm,rapeseedandsunflower. AsignificantdifferenceinthecompositionofasamplefromthevaluesgiveninannexCmayindicatethepresence ofestersderivedfromsourcesotherthanthosegiven,ormixturesofFAME. 12 Testreport Thetestreport

36、shallcontainatleastthefollowinginformation: a) referencetothisEuropeanStandard; b) typeandcompleteidentificationoftheproducttested; c) resultofthetest(seeclause9); d) anydeviation,byagreementorotherwise,fromtheprocedurespecified; e) dateofthetest.EN14331:2004(E) 7 Annex A (normative) Summaryofthecon

37、ditionsforanalysisoffattyacidmethylesters bygaschromatography A.1 Column, capillarytype,impregnatedwithastationaryphaseofpolyethyleneglycoltype Carbowax20M,DBwaxorCPwax; length: 30m internaldiameter: 0,32mm filmthickness: 0,25 m m A.2 Sampleinjector, variableflowsplitinjector,programmableflowratetyp

38、e; flowrate: 20ml/minto100ml/min,accordingtotype temperature: 250C A.3 Carriergas ,hydrogenorhelium; pressure: 30kPato80kPa A.4 Oven; isothermaltemperature: 200C A.5 Detector,flameionizationtype; temperature: 250C A.6 Sampleinjection, sizeandsplitratiotobesimultaneouslyadjustedwiththeinjectedvolume.

39、EN14331:2004(E) 8 Annex B (informative) ExampleofaFAMEchromatogram InFigureB.1achromatogramofasampleoffattyacidmethylestersfromrapeseedoilisgiven. FormoreexamplesthatincludeforinstanceC 24:0 andC 24.1 peaksordetailestersfromlinolenicacid(3peaks)EN 141031shouldbestudied. NOTE Estersfromfattyacid Key

40、C16:0 palmiticacid C16:1 palmitoleicacid C18:0 stearicacid C18:1 oleicacid C18:2 linoleicacid C18:3 linolenicacid C20:0 arachidicacid C20:1 gadoleicacid C22:0 behenicacid C22:1 erucicacid C24:0 lignocericacid C24:1 nervonicacid FigureB.1ChromatogramofasampleofFAMEfromrapeseedoilEN14331:2004(E) 9 Ann

41、ex C (informative) Typicalcompositionaldataforfattyacidsinvegetableoils TableC.1Fattyacidscompositiondatain% (m/m)takenfromCodexAlimentarius2 Fattyacid/Oiltype Palmoil Rapeseedoil a Sunfloweroil Palmiticacid C16:0 39,347,5 2,57,0 5,07,6 Palmitoleicacid C16:1 0,050,6 0,050,6 0,050,3 Stearicacid C18:0

42、 3,56,0 0,83,0 2,76,5 Oleicacid C18:1 36,044,0 51,070,0 14,039,4 Linoleicacid C18:2 9,012,0 15,030,0 48,374,0 Linolenicacid C18:3 0,050,5 5,014,0 0,050,3 Arachidicacid C20:0 0,051,0 0,21,2 0,10,5 Gadoleicacid C20:1 0,050,4 0,14,3 0,050,3 Behenicacid C22:0 0,050,2 0,050,6 0,31,5 Erucicacid C22:1 0,05

43、 0,052,0 0,050,3 Lignocericacid C24:0 0,05 0,050,3 0,050,6 a loweruciccontentEN14331:2004(E) 10 Bibliography 1 EN14103:2003,FatandoilderivativesFattyAcidMethylEsters(FAME)Determinationofesterand linolenicacidmethylestercontents. 2 CODEXSTAN210,1999Revision1(2001), NamedVegetableOils,Volume8 ,CodexAlimentarius,Joint FAO/WHOFoodStandardsProgramme,FoodandAgricultureOrganizationoftheUnitedNations,Italy (http:/).blankBS EN 14331:2004 BSI 389 Chiswick High Road London W4 4AL BSI British Standards Institution BSI is the independent national body respo