ASTM D6733-2001(2011) 7500 Standard Test Method for Determination of Individual Components in Spark Ignition Engine Fuels by 50-Metre Capillary High Resolution Gas Chromatography《用.pdf

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1、Designation: D6733 01 (Reapproved 2011)Standard Test Method forDetermination of Individual Components in Spark IgnitionEngine Fuels by 50-Metre Capillary High Resolution GasChromatography1This standard is issued under the fixed designation D6733; the number immediately following the designation indi

2、cates the year oforiginal adoption or, in the case of revision, the year of last revision. A number in parentheses indicates the year of last reapproval. Asuperscript epsilon () indicates an editorial change since the last revision or reapproval.1. Scope1.1 This test method covers the determination

3、of individualhydrocarbon components of spark-ignition engine fuels withboiling ranges up to 225C. Other light liquid hydrocarbonmixtures typically encountered in petroleum refining opera-tions, such as, blending stocks (naphthas, reformates, alkylates,and so forth) may also be analyzed; however, sta

4、tistical datawas obtained only with blended spark-ignition engine fuels.The tables in Annex A1 enumerate the components reported.Component concentrations are determined in the range from0.10 to 15 mass %. The procedure may be applicable to higherand lower concentrations for the individual components

5、; how-ever, the user must verify the accuracy if the procedures areused for components with concentrations outside the specifiedranges.1.2 This test method is applicable also to spark-ignitionengine fuel blends containing oxygenated components. How-ever, in this case, the oxygenate content must be d

6、etermined byTest Methods D5599 or D4815.1.3 Benzene co-elutes with 1-methylcyclopentene. Benzenecontent must be determined by Test Method D3606 or D5580.1.4 Toluene co-elutes with 2,3,3-trimethylpentane. Toluenecontent must be determined by Test Method D3606 or D5580.1.5 Although a majority of the i

7、ndividual hydrocarbonspresent are determined, some co-elution of compounds isencountered. If this procedure is utilized to estimate bulkhydrocarbon group-type composition (PONA) the user of suchdata should be cautioned that error may be encountered due toco-elution and a lack of identification of al

8、l componentspresent. Samples containing significant amounts of naphthenic(for example, virgin naphthas) constituents above n-octanemay reflect significant errors in PONA type groupings. Basedon the interlaboratory cooperative study, this procedure isapplicable to samples having concentrations of ole

9、fins less than20 mass %. However, significant interfering coelution with theolefins above C7is possible, particularly if blending compo-nents or their higher boiling cuts such as those derived fromfluid catalytic cracking (FCC) are analyzed, and the total olefincontent may not be accurate. Many of t

10、he olefins in sparkignition fuels are at a concentration below 0.10 %; they are notreported by this test method and may bias the total olefinresults low.1.5.1 Total olefins in the samples may be obtained orconfirmed, or both, by Test Method D1319 (volume %) orother test methods, such as those based

11、on multidimensionalPONA type of instruments.1.6 If water is or is suspected of being present, its concen-tration may be determined, if desired, by the use of TestMethod D1744. Other compounds containing sulfur, nitrogen,and so forth, may also be present, and may co-elute with thehydrocarbons. If det

12、ermination of these specific compounds isrequired, it is recommended that test methods for these specificmaterials be used, such as Test Method D5623 for sulfurcompounds.1.7 The values stated in SI units are to be regarded as thestandard. The values given in parentheses are provided forinformation o

13、nly.1.8 This standard does not purport to address all of thesafety concerns, if any, associated with its use. It is theresponsibility of the user of this standard to establish appro-priate safety and health practices and determine the applica-bility of regulatory limitations prior to use.2. Referenc

14、ed Documents2.1 ASTM Standards:2D1319 Test Method for Hydrocarbon Types in LiquidPetroleum Products by Fluorescent Indicator AdsorptionD1744 Test Method for Determination of Water in LiquidPetroleum Products by Karl Fischer Reagent3D3606 Test Method for Determination of Benzene and1This test method

15、is under the jurisdiction of ASTM Committee D02 onPetroleum Products and Lubricants and is the direct responsibility of SubcommitteeD02.04.0L on Gas Chromatography Methods.Current edition approved May 1, 2011. Published May 2011. Originallyapproved in 2001. Last previous edition approved in 2006 as

16、D6733 01 (2006).DOI: 10.1520/D6733-01R11.2For referenced ASTM standards, visit the ASTM website, www.astm.org, orcontact ASTM Customer Service at serviceastm.org. For Annual Book of ASTMStandards volume information, refer to the standards Document Summary page onthe ASTM website.3Withdrawn. The last

17、 approved version of this historical standard is referencedon www.astm.org.1Copyright ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959, United States.Toluene in Finished Motor and Aviation Gasoline by GasChromatographyD4057 Practice for Manual Sampling of Petr

18、oleum andPetroleum ProductsD4420 Test Method for Determination of Aromatics inFinished Gasoline by Gas Chromatography3D4815 Test Method for Determination of MTBE, ETBE,TAME, DIPE, tertiary-Amyl Alcohol and C1to C4Alco-hols in Gasoline by Gas ChromatographyD5580 Test Method for Determination of Benze

19、ne, Tolu-ene, Ethylbenzene, p/m-Xylene, o-Xylene, C9and HeavierAromatics, and Total Aromatics in Finished Gasoline byGas ChromatographyD5599 Test Method for Determination of Oxygenates inGasoline by Gas Chromatography and Oxygen SelectiveFlame Ionization DetectionD5623 Test Method for Sulfur Compoun

20、ds in Light Petro-leum Liquids by Gas Chromatography and Sulfur Selec-tive DetectionE355 Practice for Gas Chromatography Terms and Rela-tionships3. Terminology3.1 DefinitionsThis test method makes reference to manycommon gas chromatographic procedures, terms, and relation-ships. Detailed definitions

21、 can be found in Practice E355.4. Summary of Test Method4.1 Representative samples of the petroleum liquid areintroduced into a gas chromatograph equipped with an opentubular (capillary) column coated with specified stationaryphase(s). Helium carrier gas transports the vaporized samplethrough the co

22、lumn in which it is partitioned into individualcomponents, which are sensed with a flame ionization detectoras they elute from the end of the column. The detector signalis recorded digitally by way of an integrator or integratingcomputer. Each eluting component is identified by comparingits retentio

23、n time to those established by analyzing referencestandards or samples under identical conditions. The concen-tration of each component in mass % is determined by normal-ization of the peak areas after correction of selected compo-nents with detector response factors. The unknowncomponents are repor

24、ted individually as well as a summarytotal.5. Significance and Use5.1 Knowledge of the individual component composition(speciation) of gasoline fuels and blending stocks is useful forrefinery quality control and product specification. Processcontrol and product specification compliance for many indi

25、-vidual hydrocarbons may be determined through the use of thistest method.6. Apparatus6.1 InstrumentationA gas chromatograph capable of op-erating under the conditions outlined in Table 1, equipped witha split injector, a carrier gas pressure control, and a flameionization detector which are require

26、d.6.2 Sample Introduction SystemManual or automatic liq-uid syringe sample injection may be employed.6.3 Data Acquisition SystemAny data system can be usedwith a requirement:6.3.1 Sampling rate of 10 Hz or more with a storage ofsampling data for later processing.6.3.2 Capacity for at least 400 peaks

27、/analysis.6.3.3 Identification of individual components from retentiontime; software can be used to automatically identify the peakswith the index system determined from Table A1.1 or TableA1.2.6.4 SamplingTwo millilitres or more crimp-top vials andaluminum caps with polytetrafluoroethylene (PTFE)-l

28、inedsepta are used to transfer the sample.6.5 Capillary ColumnA 50 m fused silica capillary col-umn with an internal diameter of 0.2 mm, containing a 0.5 mfilm thickness of bonded dimethylpolysiloxane phase is used.The features must be respected to reproduce the separation ofthe reference chromatogr

29、am. The column must meet thecriteria of efficiency, resolution, and polarity defined in Section10.7. Reagents and Materials7.1 Carrier Gas and Make-up, helium, 99.99 mol % pure.(WarningCompressed gas under high pressure.)7.2 Fuel Gas, hydrogen, hydrocarbon free, 99.99 mol %pure. (WarningCompressed g

30、as under high pressure. Ex-tremely flammable.)7.3 Oxidizing Gas, air, 99 mol %. (WarningCompressedgas under high pressure.)7.4 n-Pentane, 99+ mol % pure. (WarningExtremelyflammable. Harmful if inhaled.)7.5 n-Hexane, 99+ % mol % pure. (WarningExtremelyflammable. Harmful if inhaled.)7.6 n-Heptane, 99+

31、 mol % pure. (WarningExtremelyflammable. Harmful if inhaled.)7.7 2-Methylheptane, 99+ mol % pure. (WarningExtremely flammable. Harmful if inhaled.)7.8 4-Methylheptane, 99+ mol % pure. (WarningExtremely flammable. Harmful if inhaled.)7.9 n-Octane, 99+ mol % pure. (WarningExtremelyflammable. Harmful i

32、f inhaled.)TABLE 1 Operating ConditionsTemperatures Method 1 Method 2Column initial isotherm, C 35 10Initial hold time, min. 10 15Rate 1, C/min. 1.1 1.3Final temperature 1, C 114 70Hold time 2, min. 0 0Rate 2, C/min 1.7 1.7Final temperature 2, C 250 250Final hold time 2, min. 5 20Injector, C 250 250

33、Detector, C 280 280Carrier gas helium pressure, kPA (psi) 207 (30) 190 (27)Flow rate (initial isotherm), mL/min. 0.9 0.7Average linear velocity, cm/s 22 21.5InjectionSample size, L 0.5 0.3Splitter ventflow out, mL/min. 250 200D6733 01 (2011)27.10 n-Dodecane, 99+ mol % pure. (WarningExtremelyflammabl

34、e. Harmful if inhaled.)7.11 Toluene, 99+ mol % pure. (WarningExtremelyflammable. Harmful if inhaled.)7.12 System Performance MixtureWeigh an equal amountof n-pentane, n-heptane, n-octane, n-dodecane,2-methylheptane, 4-methylheptane, and toluene. Dilute thismixture in n-hexane to obtain a concentrati

35、on of 2 mass % foreach compound.8. Sampling8.1 Container SamplingSamples shall be taken as de-scribed in Practice D4057 for instructions on manual samplinginto open container.8.2 The sample and a 2mL vial must be cooled at 4C. Partof the sample is transferred to the vial up to 80 % of its volume,and

36、 aluminum cap with septum is crimped.9. Preparation of Apparatus9.1 InstallationInstall and condition column in accor-dance with the suppliers instruction.9.2 Operating ConditionsTwo sets of operating condi-tions are proposed in Table 1, the first with an initial columntemperature above the ambient

37、temperature, the second with asub-ambient column temperature profile. Adjust the operatingconditions of the gas chromatograph to conform to the first orsecond method.9.3 Carrier Gas PressureSet a correct carrier gas pressureusing the system performance mixture such that the retentiontime of n-Heptan

38、e, n-Octane and n-Dodecane are between thevalues given in Table 2.10. System Performance Evaluation10.1 Evaluation of the column and linearity of the splitinjection are carried out with a system performance mixturedefined in 7.12 and with the column temperature conditionsdefined in the following tab

39、le.Initial temperature 35CHold time 50 min.Final temperature 220CHold time 20 min.Rate 3C/min.10.2 Column EvaluationTo perform the required separa-tion, the column must meet three criteria of separation:efficiency, resolution, and polarity.10.2.1 EffciencyThe number of theoretical plates is cal-cula

40、ted with the normal octane peak using Eq 1:n 5 5.545Rt/W0.5!2(1)where:n = number of theoretical plates,Rt = retention time of normal octane, andW0.5= mid-height peak width of normal octane in thesame unit as retention time.10.2.1.1 The number of theoretical plates must be greaterthan 200 000.10.2.2

41、ResolutionResolution is determined between thepeaks of 2-methylheptane and 4-methylheptane using Eq 2:R 52Rta! Rtb!1.699W0.5a!1 W0.5b!(2)where:Rt(a)= retention time of 4-methylheptane,Rt(b)= retention time of 2-methylheptane,W0.5(a)= mid-height peak width of 4-methylheptane inthe same unit as retent

42、ion time, andW0.5(b)= mid-height peak width of 2-methylheptane inthe same unit as retention time.10.2.2.1 The resolution must be equal to 4or greater than1.20.10.2.3 PolarityPolarity is defined by the McReynoldsconstant of toluene, using Eq 3:Rntol5 Kiana Kisqualane(3)where:Kisqualane= toluene Kovat

43、s index on Squalane at35C = 742.6, andKiana= toluene Kovats index on the analytical col-umn at 35C.10.2.3.1 Toluene Kovats index is calculated using Eq 4:Kiana5 700 1 100Slog T8Rt! log T8Rh!log T8Ro! log T8Rh!D(4)where:T8R(t)= adjusted retention time for toluene,T8R(h)= adjusted retention time for n

44、-heptane, andT8R(o)= adjusted retention time for n-octane.10.2.3.2 Adjusted retention time of a peak is determined bysubtracting the retention time of an unretained compound (airor methane) from the retention time of the peak. The McReyn-olds constant must be less than 10.10.2.4 Base Line StabilityB

45、ase line stability is calculatedwith the difference between area slices at the beginning and atthe end of analysis, divided by the maximum area slice ofN-octane obtained with the system performance mixture.10.2.4.1 Measurement of the StabilityCarry out one tem-perature programming defined in 10.1 wi

46、thout injecting anysample. Subtract the area slices at the start of the analysis withthose corresponding to 120 min (average of three slices).10.2.4.2 Stability StandardizationStandardization is car-ried out using the system performance mixture defined in 7.12with the column temperature conditions d

47、efined in 10.1. Thevalue obtained in 10.2.4.1 is divided by the maximum areaslice of N-octane and multiplied by 100. The value obtainedmust be less than 2 %. If this is not the case, check for possibleleaks, or recondition the column according to the manufactur-ers recommendations.TABLE 2 Reference

48、Retention Times of Normal ParaffinsNOTEMinutes and tenths of a minute.Method 1 Method 1 Method 1 Method 2 Method 2 Method 2n-Paraffins LowerTimeReferenceTimeUpperTimeLowerTimeReferenceTimeUpperTimen-Heptane 18.5 19.4 20.3 39.5 40.7 42.0n-Octane 32.0 33.0 34.0 57.0 57.8 59.0n-Dodecane 92.8 94.0 95.2

49、106.4 107.6 108.8D6733 01 (2011)310.3 Evaluation of the Linearity of the Split InjectorEvaluation is carried out using the system performance mixturedefined in 7.12 with the column temperature conditions definedin 10.1. The % (m/m) of each compound is determined fromthe corrected area % using the response factors for eachcompound given in Table A1.1 or Table A1.2. The relativepercent error is determined from the known mixture concen-trations according to Eq 5:Relative % error 5100 calculated concentration know