1、Designation: D 7213 05An 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 indic
2、ates 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 (e) indicates an editorial change since the last revision or reapproval.1. Scope1.1 This test method covers the determination
3、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 testmethod.1.2 The test method is not applicable for ana
4、lysis 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 analyzed by this test method. See Test Methods D
5、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 as thestandard. The values given in parentheses are for informationonly.1.5 This standard does not purport to address all of thesafety con
6、cerns, 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 Standards:2D86 Test Method for Distillation of Pe
7、troleum 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 Petroleum(15-Theoretical Plate Column)D 3710 Te
8、st 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 Gas ChromatographyD 6300 Practice for Determin
9、ation 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 Chromatography Terms and Rela-tionshipsE 594 Practice for
10、 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 gas chromatographic procedures, terms, and re
11、lation-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 specified reten-tion time interval. In area slice
12、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 on Hydrocarbon Analysis.Current edition approved Nov. 1, 2005. Published January 2006.2For referenced ASTM stan
13、dards, 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 International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken,
14、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 subtraction of the exactly corresponding areaslice in a previously r
15、ecorded 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 final boiling point (FBP)the temperature (corre-sponding to the re
16、tention 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 cumulative correctedarea count equal to 0.5 % of the total sample area
17、 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 per second).3.2.7 slice timethe cumulative slice rate (analysis tim
18、e)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 point.3.3 AbbreviationsA common abbreviation of hydrocar-bon comp
19、ounds 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).4. Summary of Test Method4.1 The boiling range distribution by d
20、istillation 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 is used to elute thehydrocarbon components of the sample in orde
21、r 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 with column oven heating.4.3 The column oven temperature is rais
22、ed 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 signal integral is recorded as areaslices for consecutive retention ti
23、me 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 corrected sample areas for each consecutiverecorded time interval are
24、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 and mediumpetroleum distillate fractions provides an insight into t
25、hecomposition 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 test methodcan be used for product specification testing with the mu
26、tualagreement 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 below Test Method D 6352(700C).5.3 Boiling range distributions obt
27、ained 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 Test Method D86or D 1160.6. Apparatus6.1 ChromatographThe gas chroma
28、tographic 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 Temperature ProgrammerThe chromato-graph shall be capable of linear program
29、med 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 mixture described in 7.5.6.1.3 DetectorThis test method requires a flam
30、e 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.6.1.3.2 Sensitivity, 0.005 coulombs/g carbon.6.1.3.3 Minimum Detectabil
31、ity,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 of the capillary column.6.1.4 Sample Inlet SystemAny sample inlet
32、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 chromatograph shallbe equipped with carrier gas pressure or flow contr
33、ol capable ofmaintaining constant carrier gas flow control through thecolumn throughout the column temperature program cycle.D72130526.2 MicrosyringeA microsyringe with a 23 gauge orsmaller stainless steel needle is used for on-column sampleintroduction. Syringes of 0.1 to 10 L capacity are availabl
34、e.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 stainless steel col-umns, with a 0.53 mm diameter have been successfully
35、 used.Cross-linked or bonded 100 % dimethyl-polysiloxane station-ary phases with film thickness of 0.5 to 1.0 mm have beenused. The column length and liquid phase film thickness shallallow the elution of at least C60n-paraffin (BP = 615C). Thecolumn and conditions shall provide separation of typical
36、petroleum 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 usingthis test methods operating conditions.6.4 Data Acquisition System:6.4.1 RecorderA 0 to 1 mV range recording potentiom-eter o
37、r 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 electronic integrator or computer-basedchromatography data system. The
38、 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 detector signal into area slices offixed duration (area slice mode)
39、. 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/electrometer system used.NOTE 1Some gas chromatographs have an algorithm
40、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 bleed. Some integration systems also store and automaticallysubtra
41、ct 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 extremely flammable gasunder high pressure.) These gases may be used
42、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 water, oxygen, andhydrocarbons.Available pressure shall be sufficien
43、t 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.)7.3 AirHigh purity (for example, hydrocarbon-free) com-pressed a
44、ir 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 specifications of the committee onanalytical Reagents of the American C
45、hemical 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 Carbon Disulfide (CS2)(99+ % pure) may be usedas a viscosity redu
46、cing 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 FID. The quality (hydrocarbon content)should be determined by this
47、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, it responds well to the FID. The quality(hydrocarbon content) s
48、hould 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 concentration should be approximately onepart of n-paraffin mixture to
49、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 (for example, Polywax 5004) in a volatile solvent (forexample, carbon
