1、Designation: D7213 11Standard Test Method forBoiling Range Distribution of Petroleum Distillates in theBoiling Range from 100 to 615C by Gas Chromatography1This standard is issued under the fixed designation D7213; the number immediately following the designation indicates the year oforiginal adopti
2、on 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. Scope*1.1 This test method covers the determination of the boilingrange distributio
3、n of petroleum products. This test method isapplicable to petroleum distillates having an initial boilingpoint greater than 100C and a final boiling point less than615C at atmospheric pressure as measured by this testmethod.1.2 The test method is not applicable for analysis ofpetroleum distillates c
4、ontaining low molecular weight compo-nents (for example, naphthas, reformates, gasolines, crudeoils). Materials containing heterogeneous components (forexample, alcohols, ethers, acids or esters) or residue are not tobe analyzed by this test method. See Test Methods D3710,D2887, D6352,orD5307.1.3 Th
5、is test method uses the principles of simulated distil-lation methodology.1.4 The values stated in SI units are to be regarded asstandard. No other units of measurement are included in thisstandard.1.5 This standard does not purport to address all of thesafety concerns, if any, associated with its u
6、se. 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. Referenced Documents2.1 ASTM Standards:2D86 Test Method for Distillation of Petroleum Products atAtmospheric Press
7、ureD1160 Test Method for Distillation of Petroleum Productsat Reduced PressureD2887 Test Method for Boiling Range Distribution ofPetroleum Fractions by Gas ChromatographyD2892 Test Method for Distillation of Crude Petroleum(15-Theoretical Plate Column)D3710 Test Method for Boiling Range Distribution
8、 ofGasoline and Gasoline Fractions by Gas ChromatographyD4626 Practice for Calculation of Gas ChromatographicResponse FactorsD5307 Test Method for Determination of Boiling RangeDistribution of Crude Petroleum by Gas ChromatographyD6300 Practice for Determination of Precision and BiasData for Use in
9、Test Methods for Petroleum Products andLubricantsD6352 Test Method for Boiling Range Distribution ofPetroleum Distillates in Boiling Range from 174 to 700Cby Gas ChromatographyE355 Practice for Gas Chromatography Terms and Rela-tionshipsE594 Practice for Testing Flame Ionization Detectors Usedin Gas
10、 or Supercritical Fluid ChromatographyE1510 Practice for Installing Fused Silica Open TubularCapillary Columns in Gas Chromatographs3. Terminology3.1 DefinitionsThis test method makes reference to manycommon gas chromatographic procedures, terms, and relation-ships. Detailed definitions of these can
11、 be found in PracticesE355, E594, and E1510.3.2 Definitions of Terms Specific to This Standard:3.2.1 area slicethe area, resulting from the integration ofthe chromatographic detector signal, within a specified reten-tion time interval. In area slice mode (see 6.4.2), peak detection1This test method
12、is under the jurisdiction of ASTM Committee D02 onPetroleum Products and Lubricants and is the direct responsibility of SubcommitteeD02.04.0H on Chromatographic Distribution Methods.Current edition approved May 1, 2011. Published July 2011. Originally approvedin 2005. Last previous edition approved
13、in 2005 as D7213051. DOI: 10.1520/D7213-11.2For 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.1*A Summary of Cha
14、nges section appears at the end of this standard.Copyright ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959, United States.parameters are bypassed and the detector signal integral isrecorded as area slices of consecutive, fixed duration timeintervals.3.2.2 cor
15、rected area slicean area slice corrected for base-line offset, by subtraction of the exactly corresponding areaslice in a previously recorded blank (non-sample) analysis.3.2.3 cumulative corrected areathe accumulated sum ofcorrected area slices from the beginning of the analysis througha given reten
16、tion time, ignoring any non-sample area (forexample, solvent).3.2.4 final boiling point (FBP)the temperature (corre-sponding to the retention time) at which a cumulative correctedarea count equal to 99.5 % of the total sample area under thechromatogram is obtained.3.2.5 initial boiling point (IBP)th
17、e temperature (corre-sponding to the retention time) at which a cumulative correctedarea count equal to 0.5 % of the total sample area under thechromatogram is obtained.3.2.6 slice ratethe time interval used to integrate thecontinuous (analog) chromatographic detector response duringan analysis. The
18、 slice rate is expressed in Hz (for example,integrations or slices per second).3.2.7 slice timethe cumulative slice rate (analysis time)associated with each area slice throughout the chromatographicanalysis. The slice time is the time at the end of eachcontiguous area slice.3.2.8 total sample areath
19、e cumulative corrected area,from the initial point to the final area point.3.3 AbbreviationsA common abbreviation of hydrocar-bon compounds is to designate the number of carbon atoms inthe compound. A prefix is used to indicate the carbon chainform, while a subscripted suffix denotes the number of c
20、arbonatoms (for example, normal decane n-Cl0; iso-tetradecane =i-Cl4).4. Summary of Test Method4.1 The boiling range distribution by distillation is simu-lated by the use of gas chromatography. The solvent should notinterfere with measurement of the sample in the 100 to 615Crange, and it should be a
21、polar. A non-polar open tubular(capillary) gas chromatographic column is used to elute thehydrocarbon components of the sample in order of increasingboiling point.4.2 A sample aliquot is diluted with a viscosity reducingsolvent and introduced into the chromatographic system.Sample vaporization is pr
22、ovided by separate heating of thepoint of injection or in conjunction with column oven heating.4.3 The column oven temperature is raised at a reproduciblelinear rate to effect separation of the hydrocarbon componentsin order of increasing boiling point. The elution of samplecomponents is quantitativ
23、ely determined using a flame ioniza-tion detector. The detector signal integral is recorded as areaslices for consecutive retention time intervals during theanalysis.4.4 Retention times of known normal paraffin hydrocarbonsspanning the scope of this test method (C5-C60) are determinedand correlated
24、to their boiling point temperatures. The normal-ized cumulative corrected sample areas for each consecutiverecorded time interval are used to calculate the boiling rangedistribution. The boiling point temperature at each reportedpercent off increment is calculated from the retention timecalibration.
25、5. Significance and Use5.1 The boiling range distribution of light and mediumpetroleum distillate fractions provides an insight into thecomposition of feed stocks and products related to petroleumrefining process, This gas chromatographic determination ofboiling range can be used to replace conventi
26、onal distillationmethods for control of refining operations. This test methodcan be used for product specification testing with the mutualagreement of interested parties.5.2 This test method extends the scope of boiling rangedetermination by gas chromatography to include light andmedium petroleum di
27、stillate fractions beyond the scope of TestMethod D2887 (538C) and below Test Method D6352(700C).5.3 Boiling range distributions obtained by this test methodare theoretically equivalent to those obtained by true boilingpoint (TBP) distillation (see Test Method D2892). They are notequivalent to resul
28、ts from low efficiency distillation such asthose obtained with Test Method D86 or D1160.6. Apparatus6.1 ChromatographThe gas chromatographic systemused shall have the following performance characteristics:6.1.1 Column OvenCapable of sustained and linear pro-grammed temperature operation from near am
29、bient (for ex-ample, 35 to 50C) up to 400C.6.1.2 Column Temperature ProgrammerThe chromato-graph shall be capable of linear programmed temperatureoperation up to 400C at selectable linear rates up to 20C/min.The programming rate shall be sufficiently reproducible toobtain the retention time repeatab
30、ility of 0.1 min (6 s) for eachcomponent in the calibration mixture described in 7.5.6.1.3 DetectorThis test method requires a flame ioniza-tion detector (FID). The detector shall meet or exceed thefollowing specifications as detailed in Practice E594. Theflame jet should have an orifice of approxim
31、ately 0.05 to 0.07mm.6.1.3.1 Operating Temperature, , 400C.6.1.3.2 Sensitivity, 0.005 coulombs/g carbon.6.1.3.3 Minimum Detectability,13 10-11g carbon/s.6.1.3.4 Linear Range, 106.6.1.3.5 Connection of the column to the detector shall besuch that no temperature below the column temperature exists.Ref
32、er to Practice E1510 for proper installation and condition-ing of the capillary column.6.1.4 Sample Inlet SystemAny sample inlet system ca-pable of meeting the performance specification in 7.6 may beused. Programmed temperature vaporization (PTV) and pro-grammable cool on-column injection systems ha
33、ve been usedsuccessfully.6.1.5 Carrier Gas Flow ControlThe chromatograph shallbe equipped with carrier gas pressure or flow control capable ofmaintaining constant carrier gas flow control through thecolumn throughout the column temperature program cycle.D7213 1126.2 MicrosyringeA microsyringe with a
34、 23 gauge orsmaller stainless steel needle is used for on-column sampleintroduction. Syringes of 0.1 to 10 L capacity are available.6.2.1 Automatic syringe injection is recommended toachieve best precision.6.3 ColumnThis test method is limited to the use ofnon-polar wall coated open tubular (WCOT) c
35、olumns of highthermal stability. Glass, fused silica, and stainless steel col-umns, with a 0.53 mm diameter have been successfully used.Cross-linked or bonded 100 % dimethyl-polysiloxane station-ary phases with film thickness of 0.5 to 1.0 m have been used.The column length and liquid phase film thi
36、ckness shall allowthe elution of at least C60n-paraffin (BP = 615C). The columnand conditions shall provide separation of typical petroleumhydrocarbons in order of increasing boiling point and meet thecolumn resolution requirements of 8.2.1. The column shallprovide a resolution between one and ten u
37、sing this testmethods operating conditions.6.4 Data Acquisition System:6.4.1 RecorderA 0 to 1 mV range recording potentiom-eter or equivalent, with a full-scale response time of2sorlessmay be used to provide a graphical display.6.4.2 IntegratorMeans shall be provided for determiningthe accumulated a
38、rea under the chromatogram. This can bedone by means of an electronic integrator or computer-basedchromatography data system. The integrator/computer systemshall have normal chromatographic software for measuring theretention time and areas of eluting peaks (peak detectionmode). In addition, the sys
39、tem shall be capable of convertingthe continuously integrated detector signal into area slices offixed duration (area slice mode). These contiguous area slices,collected for the entire analysis, are stored for later processing.The electronic range of the integrator/computer (for example, 1V, 10 V) s
40、hall be operated within the linear range of thedetector/electrometer system used.NOTE 1Some gas chromatographs have an algorithm built into theiroperating software that allows a mathematical model of the baselineprofile to be stored in memory. This profile is automatically subtractedfrom the detecto
41、r signal on subsequent sample runs to compensate for thecolumn bleed. Some integration systems also store and automaticallysubtract a blank analysis from subsequent analytical determinations.7. Reagents and Materials37.1 Carrier GasHelium or hydrogen of high purity.(WarningHelium and hydrogen are co
42、mpressed gases underhigh pressure; hydrogen is an extremely flammable gas underhigh pressure.) These gases may be used as the carrier gas andshould not contain more than 5 mL/m3of oxygen. The totalamount of impurities should not exceed 10 mL/m3. Additionalpurification is recommended by the use of mo
43、lecular sieves orother suitable agents to remove water, oxygen, and hydrocar-bons.Available pressure shall be sufficient to ensure a constantcarrier gas flow rate.7.2 HydrogenHydrogen of high purity (for example,hydrocarbon-free) is used as fuel for the flame ionizationdetector (FID). (WarningHydrog
44、en is an extremely flam-mable gas under high pressure.)7.3 AirHigh purity (for example, hydrocarbon-free) com-pressed air is used as the oxidant for the flame ionizationdetector (FID). (WarningCompressed air is a gas under highpressure and supports combustion.)7.4 SolventsUnless otherwise indicated,
45、 it is intended thatall solvents conform to the specifications of the committee onanalytical Reagents of the American Chemical Society wheresuch specifications are available.3Other grades may be usedprovided it is first ascertained that the solvent is of sufficientlyhigh purity to permit its use wit
46、hout lessening the accuracy ofthe determination.7.4.1 Carbon Disulfide (CS2)(99+ % pure) may be usedas a viscosity reducing solvent and as a means of reducingmass of sample introduced onto the column to ensure lineardetector response and reduced peak skewness. It is misciblewith asphaltic hydrocarbo
47、ns and provides a relatively smallresponse with the FID. The quality (hydrocarbon content)should be determined by this test method prior to use as asample diluent. (WarningCarbon disulfide is extremelyflammable and toxic.)7.5 Cyclohexane (C6H12)(99+ % pure) may be used as aviscosity reducing solvent
48、. It is miscible with asphaltic hydro-carbons, however, it responds well to the FID. The quality(hydrocarbon content) should be determined by this testmethod prior to use as a sample diluent. (WarningCyclohexane is flammable.)7.6 Calibration MixtureA qualitative mixture ofn-paraffins (nominally C5to
49、 C60) dissolved in a suitablesolvent. The final concentration should be approximately onepart of n-paraffin mixture to one hundred parts of solvent. Atleast one compound in the mixture shall have a boiling pointlower than the initial boiling point of the sample beinganalyzed, as defined in the scope of this test method (1.1). Thecalibration mixture shall contain at least 13 known n-paraffins(for example, C6,C7,C8,C9,C10,C12,C16,C20,C30,C40,C50,C52,C60). Boiling points of n-paraffins are listed in Table 1.NOTE 2A suitable calibration
