1、Designation: D7213 12Standard 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 Products atReduced PressureD2887 Test Method for Boiling Range Distribution of Pe-troleum Fractions by Gas ChromatographyD2892 Test Method for Distillation of Crude Petroleum(15-Theoretical Plate Column)D3710 Test Method for Boiling Range Distributi
8、on of Gaso-line 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FactorsD5307 Test Method for Determination of Boiling RangeDistribution of Crude Petroleum by Gas Chromatography(Withdrawn 2011)3D6352 Test Method for Boiling Range Distribution
9、of Pe-troleum Distillates in Boiling Range from 174 to 700C byGas ChromatographyE355 Practice for Gas Chromatography Terms and Relation-shipsE594 Practice for Testing Flame Ionization Detectors Usedin Gas or Supercritical Fluid ChromatographyE1510 Practice for Installing Fused Silica Open TubularCap
10、illary 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 be found in PracticesE355, E594, and E1510.3.2 Definitions of Terms Specific to This Standard:3
11、.2.1 area slice, nthe area, resulting from the integrationof the chromatographic detector signal, within a specifiedretention time interval. In area slice mode (see 6.4.2), peakdetection parameters are bypassed and the detector signalintegral is recorded as area slices of consecutive, fixed duration
12、time intervals.3.2.2 corrected area slice, nan area slice corrected forbaseline offset, by subtraction of the exactly correspondingarea slice in a previously recorded blank (non-sample) analy-sis.1This test method is under the jurisdiction of ASTM Committee D02 onPetroleum Products and Lubricants an
13、d is the direct responsibility of SubcommitteeD02.04.0H on Chromatographic Distribution Methods.Current edition approved Dec. 1, 2012. Published December 2012. Originallyapproved in 2005. Last previous edition approved in 2011 as D721311. DOI:10.1520/D7213-12.2For referenced ASTM standards, visit th
14、e 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.3The last approved version of this historical standard is referenced onwww.astm.org.*A Summary of Cha
15、nges section appears at the end of this standardCopyright ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959. United States13.2.3 cumulative corrected area, nthe accumulated sum ofcorrected area slices from the beginning of the analysis througha given retention
16、time, ignoring any non-sample area (forexample, solvent).3.2.4 final boiling point (FBP), nthe 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), nt
17、he 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 rate, nthe time interval used to integrate thecontinuous (analog) chromatographic detector response duringan analysis.
18、 The slice rate is expressed in Hz (for example,integrations or slices per second).3.2.7 slice time, nthe 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
19、 area, nthe cumulative corrected area,from the initial point to the final area point.3.3 AbbreviationsAcommon abbreviation of hydrocarboncompounds is to designate the number of carbon atoms in thecompound. A prefix is used to indicate the carbon chain form,while a subscripted suffix denotes the numb
20、er of carbon atoms(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 sho
21、uld be apolar. 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 vaporizati
22、on is provided 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 qua
23、ntitatively 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 cor
24、related 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 timecali
25、bration.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
26、conventional 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 petr
27、oleum distillate 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
28、to results from low efficiency distillation such asthose obtained with Test Method D86 or D1160.6. Apparatus6.1 ChromatographThe gas chromatographic system usedshall have the following performance characteristics:6.1.1 Column OvenCapable of sustained and linear pro-grammed temperature operation from
29、 near ambient (forexample, 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 re
30、peatability 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 ap
31、proximately 0.45 to 0.50mm.6.1.3.1 Operating Temperature, 400C.6.1.3.2 Sensitivity, 0.005 coulombs/g carbon.6.1.3.3 Minimum Detectability, 110-11g 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.
32、Refer 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
33、 have 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.6.2 MicrosyringeA microsyringe with a 23 ga
34、uge orsmaller stainless steel needle is used for on-column sampleintroduction. Syringes of 0.1 to 10 L capacity are available.D7213 1226.2.1 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
35、) columns of highthermal stability. Glass, fused silica, and stainless steelcolumns, with a 0.53 mm diameter have been successfullyused. Cross-linked or bonded 100 % dimethyl-polysiloxanestationary phases with film thickness of 0.5 to 1.0 m havebeen used. The column length and liquid phase film thic
36、knessshall allow the elution of at least C60n-paraffin (BP = 615C).The column and conditions shall provide separation of typicalpetroleum hydrocarbons in order of increasing boiling pointand meet the column resolution requirements of 8.2.1. Thecolumn shall provide a resolution between one and ten us
37、ingthis test methods operating conditions.6.4 Data Acquisition System:6.4.1 RecorderA0 to 1 mV range recording potentiometeror equivalent, with a full-scale response time of2sorless maybe used to provide a graphical display.6.4.2 IntegratorMeans shall be provided for determiningthe accumulated area
38、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 system
39、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) shall
40、 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 detector si
41、gnal 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 Materials47.1 Carrier GasHelium or hydrogen of high purity.(WarningHelium and hydrogen are compre
42、ssed 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 molecu
43、lar 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). (WarningHydrogen i
44、s 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, it
45、is intended thatall solvents conform to the specifications of the committee onanalytical Reagents of the American Chemical Society wheresuch specifications are available.4Other grades may be usedprovided it is first ascertained that the solvent is of sufficientlyhigh purity to permit its use without
46、 lessening the accuracy ofthe determination.7.4.1 Carbon Disulfide (CS2)(99+ % pure) may be used asa viscosity reducing solvent and as a means of reducing massof sample introduced onto the column to ensure linear detectorresponse and reduced peak skewness. It is miscible withasphaltic hydrocarbons a
47、nd provides a relatively small re-sponse with the FID. The quality (hydrocarbon content) shouldbe determined by this test method prior to use as a samplediluent. (Warning Carbon disulfide is extremely flammableand toxic.)7.5 Cyclohexane (C6H12)(99+ % pure) may be used as aviscosity reducing solvent.
48、 It is miscible with asphaltichydrocarbons, however, it responds well to the FID. Thequality (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 C6
49、0) 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 mix
