1、Designation: D 7213 051An American National StandardStandard 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 D 7213; 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.1NOTECorrected 6.3 editorially in October 2008.1. Scop
3、e1.1 This test method covers the determination of the boilingrange distribution 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 testmetho
4、d.1.2 The test method is not applicable for analysis ofpetroleum distillates containing 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 an
5、alyzed by this test method. See Test Methods D 3710,D 2887, D 6352,orD 5307.1.3 This 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 do
6、es 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. Referenced Documents2.1 ASTM Sta
7、ndards:2D86 Test Method for Distillation of Petroleum Products atAtmospheric PressureD 1160 Test Method for Distillation of Petroleum Productsat Reduced PressureD 2887 Test Method for Boiling Range Distribution ofPetroleum Fractions by Gas ChromatographyD 2892 Test Method for Distillation of Crude P
8、etroleum(15-Theoretical Plate Column)D 3710 Test Method for Boiling Range Distribution ofGasoline and Gasoline Fractions by Gas ChromatographyD 4626 Practice for Calculation of Gas ChromatographicResponse FactorsD 5307 Test Method for Determination of Boiling RangeDistribution of Crude Petroleum by
9、Gas ChromatographyD 6300 Practice for Determination of Precision and BiasData for Use in Test Methods for Petroleum Products andLubricantsD 6352 Test Method for Boiling Range Distribution ofPetroleum Distillates in Boiling Range from 174 to 700Cby Gas ChromatographyE 355 Practice for Gas Chromatogra
10、phy Terms and Rela-tionshipsE 594 Practice for Testing Flame Ionization Detectors Usedin Gas or Supercritical Fluid ChromatographyE 1510 Practice for Installing Fused Silica Open TubularCapillary Columns in Gas Chromatographs3. Terminology3.1 DefinitionsThis test method makes reference to manycommon
11、 gas chromatographic procedures, terms, and relation-ships. Detailed definitions of these can be found in PracticesE 355, E 594, and E 1510.3.2 Definitions of Terms Specific to This Standard:3.2.1 area slicethe area, resulting from the integration ofthe chromatographic detector signal, within a spec
12、ified reten-tion time interval. In area slice mode (see 6.4.2), peak detection1This test method 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 approv
13、ed Nov. 1, 2005. Published January 2006.2For 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.1Copyright ASTM Inter
14、national, 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 corrected area slicean area slice corrected for base-line offset, by sub
15、traction 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 retention time, ignoring any non-sample area (forexample, solvent).3.2.4 f
16、inal 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)the temperature (corre-sponding to the retention time) at which a cumul
17、ative 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 slice rate is expressed in Hz (for example,integrations or slices pe
18、r 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 areathe cumulative corrected area,from the initial point to the final area
19、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 carbonatoms (for example, normal decane n-Cl0; iso-tetradecane =i-Cl4)
20、.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 apolar. A non-polar open tubular(capillary) gas chromatographic column
21、 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 provided by separate heating of thepoint of injection or in conjunction
22、 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 quantitatively determined using a flame ioniza-tion detector. The detector signa
23、l 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 to their boiling point temperatures. The normal-ized cumulative corre
24、cted 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.5. Significance and Use5.1 The boiling range distribution of light an
25、d 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 conventional distillationmethods for control of refining operations. This tes
26、t 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 distillate fractions beyond the scope of TestMethod D 2887 (538C) and b
27、elow Test Method D 6352(700C).5.3 Boiling range distributions obtained by this test methodare theoretically equivalent to those obtained by true boilingpoint (TBP) distillation (see Test Method D 2892). They arenot equivalent to results from low efficiency distillation such asthose obtained with Tes
28、t Method D86or D 1160.6. 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 ambient (for ex-ample, 35 to 50C) up to 400C.6.1.2 Column Temperatur
29、e 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 repeatability of 0.1 min (6 s) for eachcomponent in the calibration mixtur
30、e 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 E 594. Theflame jet should have an orifice of approximately 0.05 to 0.07mm.6.1.3.1 Operating Temperature, , 400C.6.1.3.
31、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.Refer to Practice E 1510 for proper installation and condition-ing o
32、f 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 have been usedsuccessfully.6.1.5 Carrier Gas Flow ControlThe chrom
33、atograph shallbe equipped with carrier gas pressure or flow control capable ofmaintaining constant carrier gas flow control through thecolumn throughout the column temperature program cycle.D721305126.2 MicrosyringeA microsyringe with a 23 gauge orsmaller stainless steel needle is used for on-column
34、 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) columns of highthermal stability. Glass, fused silica, and stainl
35、ess 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 thickness shall allowthe elution of at least C60n-paraffin (BP = 61
36、5C). 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 using this testmethods operating conditions.6.4 Data Acquisition
37、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 area under the chromatogram. This can bedone by means of an elect
38、ronic 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 system shall be capable of convertingthe continuously integrated de
39、tector 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) shall be operated within the linear range of thedetector/electrom
40、eter 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 detector signal on subsequent sample runs to compensate for thecolumn b
41、leed. Some integration systems also store and automaticallysubtract a blank analysis from subsequent analytical determinations.7. Reagents and Materials37.1 Carrier GasHelium, nitrogen or hydrogen of highpurity. (WarningHelium and nitrogen are compressed gasesunder high pressure; hydrogen is an extr
42、emely flammable gasunder high pressure.) These gases may be used as the carriergas and should not contain more than 5 mL/m3of oxygen. Thetotal amount of impurities should not exceed 10 mL/m3.Additional purification is recommended by the use of molecu-lar sieves or other suitable agents to remove wat
43、er, oxygen, andhydrocarbons.Available pressure shall be sufficient to ensure aconstant carrier gas flow rate.7.2 HydrogenHydrogen of high purity (for example,hydrocarbon-free) is used as fuel for the flame ionizationdetector (FID). (WarningHydrogen is an extremely flam-mable gas under high pressure.
44、)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, it is intended thatall solvents conform to the specif
45、ications 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 without lessening the accuracy ofthe determination.7.4.1
46、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 hydrocarbons and provides a relatively smallresponse with the FI
47、D. 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. It is miscible with asphaltic hydro-carbons, however
48、, 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 C60) dissolved in a suitablesolvent. The final concen
49、tration 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 mixture can be obtained by dissolvinga polyolefin wax
