【astm標(biāo)準(zhǔn)】d 6730 - 01 (2011)

1、Designation:D6730?01(Reapproved2011)StardTestMethodfDeterminationofIndividualComponentsinSparkIgnitionEngineFuelsby100–MetreCapillary(withPrecolumn)HighResolutionGasChromatography1Thisstardisissuedunderthefixeddesignatio

2、nD6730thenumberimmediatelyfollowingthedesignationindicatestheyearofiginaladoptioninthecaseofrevisiontheyearoflastrevision.Anumberinparenthesesindicatestheyearoflastreapproval.Asuperepsilon()indicatesaneditialchangesincet

3、helastrevisionreapproval.1.Scope1.1Thistestmethodcoversthedeterminationofindividualhydrocarboncomponentsofsparkignitionenginefuelstheirmixturescontainingoxygenateblends(MTBEETBEethanolsofth)withboilingrangesupto225C.Othe

4、rlightliquidhydrocarbonmixturestypicallyencounteredinpetroleumrefiningoperationssuchasblendingstocks(naphthasrefmatesalkylatessofth)mayalsobeanalyzedhoweverstatisticaldatawasobtainedonlywithblendedsparkignitionenginefuel

5、s.1.2Basedonthecooperativestudyresultsindividualcomponentconcentrationsprecisionaredeterminedintherangefrom0.01toapproximately30mass%.Thetestmethodmaybeapplicabletohigherlowerconcentrationsftheindividualcomponentshowever

6、theusermustverifytheaccuracyifthetestmethodisusedfcomponentswithconcentrationsoutsidethespecifiedranges.1.3Thistestmethodalsodeterminesmethanolethanoltbutanolmethyltbutylether(MTBE)ethyltbutylether(ETBE)tamylmethylether(

7、TAME)insparkignitionenginefuelsintheconcentrationrangefrom1to30mass%.Howeverthecooperativestudydataprovidedinsufficientstatisticaldatafobtainingaprecisionstatementfthesecompounds.1.4Althoughamajityoftheindividualhydrocar

8、bonspresentaredeterminedsomecoelutionofcompoundsisencountered.Ifthistestmethodisutilizedtoestimatebulkhydrocarbongrouptypecomposition(PONA)theuserofsuchdatashouldbecautionedthatsomeerrwillbeencounteredduetocoelutionalack

9、ofidentificationofallcomponentspresent.Samplescontainingsignificantamountsofnaphthenic(fexamplevirginnaphthas)constituentsabovenoctanemayreflectsignificanterrsinPONAtypegroupings.Basedonthegasolinesamplesintheinterlabaty

10、cooperativestudythistestmethodisapplicabletosamplescontaininglessthan25mass%ofolefins.HoweversomeinterferingcoelutionwiththeolefinsaboveC7ispossibleparticularlyifblendingcomponentstheirhigherboilingcutssuchasthosederived

11、fromfluidcatalyticcracking(FCC)areanalyzedthetotalolefincontentmaynotbeaccurate.AnnexA1ofthistestmethodcomparesresultsofthetestmethodwithothertestmethodsfedcomponentsincludingolefinsseveralgrouptypesfseveralinterlabatyco

12、operativestudysamples.Althoughbenzenetouleneseveraloxygenatesaredeterminedwhendoubtfulastotheanalyticalresultsofthesecomponentsconfirmatyanalysescanbeobtainedbyusingthespecifictestmethodslistedinthereferencesection.1.4.1

13、TotalolefinsinthesamplesmaybeobtainedconfirmedbothifnecessarybyTestMethodD1319(volume%)othertestmethodssuchasthosebasedonmultidimentionalPONAtypeofinstruments.1.5Ifwaterisissuspectedofbeingpresentitsconcentrationmaybedet

14、erminedifdesiredbytheuseofTestMethodD1744equivalent.Othercompoundscontainingoxygensulfurnitrogensofthmayalsobepresentmaycoelutewiththehydrocarbons.Ifdeterminationofthesespecificcompoundsisrequireditisrecommendedthattestm

15、ethodsfthesespecificmaterialsbeusedsuchasTestMethodsD4815D5599foxygenatesTestMethodD5623fsulfurcompoundsequivalent.1.6ThevaluesstatedinSIunitsaretoberegardedasstard.Nootherunitsofmeasurementareincludedinthisstard.1.7This

16、starddoesnotpurpttoaddressallofthesafetyconcernsifanyassociatedwithitsuse.Itistheresponsibilityoftheuserofthisstardtoestablishappropriatesafetyhealthpracticesdeterminetheapplicabilityofregulatylimitationspritouse.1Thiste

17、stmethodisunderthejurisdictionofASTMCommitteeD02onPetroleumProductsLiquidFuelsLubricantsisthedirectresponsibilityofSubcommitteeD02.04.0LonGasChromatographyMethods.CurrenteditionapprovedMay12011.PublishedMay2011.iginallya

18、pprovedin2001.Lastpreviouseditionapprovedin2006asD6730–01(2006)ε1.DOI:10.1520D673001R11.Copyright?ASTMInternational100BarrHarbDrivePOBoxC700WestConshohockenPA194282959.UnitedStates1toatleast200Cin0.1Cminlessrateincrement

19、sisrequired.Multistepcolumnoventemperatureprogrammingisrequiredconsistingofaninitialholdtimeaninitialtemperatureprogramfollowedbyanisothermaltemperatureholdanotherprogrammedtemperaturerise.Aheatedflashvapizinginjectdesig

20、nedtoprovidealinearsamplesplitinjection(thatis200:1)isrequiredfpropersampleintroduction.Theassociatedcarriergascontrolsmustbeofsufficientprecisiontoprovidereproduciblecolumnflowssplitratiosindertomaintainanalyticalintegr

21、ity.AhydrogenflameionizationdetectwithassociatedgascontrolselectronicsdesignedfoptimumresponsewithopentubularcolumnsshallconfmtothespecificationsasdescribedinPracticeE594aswellashavinganoperatingtemperaturerangeofuptoatl

22、east250C.6.2SampleIntroduction—Manualautomaticliquidsampleinjectiontothesplittinginjectmaybeemployed.Automatedinjectionsarehighlyrecommended.Microsyringesautosyringesamplersvalvescapableof0.1to0.5L.injectionsaresuitable.

23、Itshouldbenotedthatsomesyringesimproperinjectiontechniquesaswellasinadequatesplitterdesigncouldresultinsamplefractionation.ThismustbedeterminedinaccdancewithSection10.6.3ElectronicIntegrat—Anyelectronicintegrationdeviceu

24、sedfquantitatingtheseanalysesshallmeetexceedtheseminimumrequirements:6.3.1Capacitytohle400mepeaksperanalysis.6.3.2Nmalizedareapercentcalculationwithresponsefacts.6.3.3Noisespikerejection.6.3.4Accurateareadeterminationoff

25、ast(1to2s)peaks(10Hzgreatersamplingrate).6.3.5Maintainpeakdetectionsensitivityfnarrowbroadpeaks.6.3.6Positivenegativeslopingbaselinecrection.6.3.7Perpendiculartangentskimmingasneeded.6.3.8Displayofbaselineusedtoensurecre

26、ctpeakareadetermination.6.4OpenTubularColumn—Thecolumnusedfthistestmethodconsistsofaprimary(100m)analyticalcolumnaprecolumn.Theabilitytoprovidetherequiredcomponentseparationsisdependentontheprecisecontrolofthecolumnivity

27、whichistypicallyslightlymethanthatexhibitedbycurrentcommerciallyavailablecolumns.Someoldercolumnscolumnsthathaveasampleresiduefromrepeatedusewithoutconditioningmayexhibittherequiredpolarity.Untiladequatecolumnsarecommerc

28、iallyavailablethecurrentlyusedmethylsiliconecolumnscanbemodifiedtunedtomeetthemethodcolumnspecifications.SeeSection11fadeionofthecolumnperfmancespecificationsAnnexA1fadeionofthecolumnmodificationprocedure.6.4.1Theprimary

29、gaschromatographiccolumnusedfthistestmethodwillmeetthefollowingspecifications.MaterialfusedsilicaLength100mInternaldiameter0.25mmLiquidphasemethylsiliconeFilmthickness0.50mTheeticalplatesnpentaneat35C400000to500000Retent

30、ionfactkpentaneat35C0.45to0.50ResolutionRtbutanol2methylbutene2at35C3.25to5.25Peaksymmetrytbutanolat35C1.0to5.06.4.2Precolumn—Avariablelength(1to4m)of5%phenyl95%dimethylpolysiloxanefusedsilicaopentubularcolumn(0.25mminsi

31、dediameter)isaddedtothefront(inject)endofthe100mcolumnasdescribedinAnnexA1.7.ReagentsMaterials7.1CarrierGas—Helium99.999%pure.(Warning—Heliumairnitrogencompressedgasunderpressure.)7.2Oxidant—Air99.999%pure.(Warning—see7.

32、1.)7.3DetectMakeupGas—Nitrogen99.999%pure.(Warning—see7.1.)7.4FuelGas—Hydrogen99.999%pure.(Warning—Hydrogenflammablegasunderhighpressure.)7.5ReferenceStards:7.5.1PurityofReagents—Reagentgradechemicalsshallbeusedinalltest

33、s.UnlessotherwiseindicateditisintendedthatallreagentsconfmtothespecificationsoftheCommitteeonAnalyticalReagentsoftheAmericanChemicalSociety7wheresuchspecificationsareavailable.Othergradesmaybeusedprovideditisfirstertaine

34、dthatthereagentisofsufficientlyhighpuritytopermititsusewithoutlesseningtheaccuracyofthedetermination.7.5.2Methanol—(Warning—Thesematerialsareflammablemaybeharmfulfatalifingestedinhaled.).7.5.3Ethanol—Onlyabsoluteethanolo

35、f99.5minimumpercentmeetstherequirementsofthistestmethod.(Warning—see7.5.2.)7.5.4HydrocarbonOtherComponentReferences—Individualmixedcomponentreferencematerialsarecommerciallyavailablemaybeusedtoestablishqualitativequantit

36、ativecalibration.(Warning—see7.5.2.)7.5.5SystemColumnEvaluationMixture—AquantitativelypreparedmixturecomplyingwithPracticeD4307ofindividualhydrocarbonsoxygenatesofinterestisusedfsystemcolumnevaluation(seeTable1).(Warning

37、—see7.5.2.)Fig.1isachromatogramoftherecommendedmixtureinTable1.8.Sampling8.1HydrocarbonliquidswithReidvappressuresof110kPa(16psi)lessmaybesampledeitherintoafloatingpistoncylinderintoanopencontainer(PracticesD4057D4177).I

38、fthesampleasreceiveddoesnotmeettheupper7ReagentChemicalsAmericanChemicalSocietySpecificationsAmericanChemicalSocietyWashingtonDC.FsuggestionsonthetestingofreagentsnotlistedbytheAmericanChemicalSocietyseeAnalarStardsfLaba