1、Designation: D7500 10Standard Test Method forDetermination of Boiling Range Distribution of Distillatesand Lubricating Base Oilsin Boiling Range from 100 to735C by Gas Chromatography1This standard is issued under the fixed designation D7500; the number immediately following the designation indicates
2、 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. Scope*1.1 This test method covers the determination of t
3、he boilingrange distribution of petroleum products by capillary gaschromatography using flame ionization detection. This stan-dard test method has been developed through the harmoniza-tion of two test methods, Test Method D6352 and IP 480. Asboth of these methods cover the same scope and include ver
4、ysimilar operating conditions, it was agreed that a singlestandard method would benefit the global simulated distillationcommunity.1.2 This test method is not applicable for the analysis ofpetroleum or petroleum products containing low molecularweight components (for example naphthas, reformates, ga
5、so-lines, diesel). Components containing hetero atoms (for ex-ample alcohols, ethers, acids, or esters) or residue are not to beanalyzed by this test method. See Test Methods D7096, D2887,or D7213 for possible applicability to analysis of these types ofmaterials. This method is also not suitable for
6、 samples that willnot elute completely from the gas chromatographic column,leaving residues. For such samples as crude oils and residues,see Test Methods D5307 and D7169.1.3 This test method is applicable to distillates with initialboiling points above 100C and final boiling points below735C (carbon
7、 110); for example, distillates (IBP 100C),base oils and lubricating base stocks.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 wit
8、h 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 Petroleum Products atAtmospheri
9、c PressureD1160 Test Method for Distillation of Petroleum Productsat Reduced PressureD2887 Test Method for Boiling Range Distribution ofPetroleum Fractions by Gas ChromatographyD5307 Test Method for Determination of Boiling RangeDistribution of Crude Petroleum by Gas ChromatographyD6352 Test Method
10、for Boiling Range Distribution ofPetroleum Distillates in Boiling Range from 174 to 700Cby Gas ChromatographyD7096 Test Method for Determination of the Boiling RangeDistribution of Gasoline by Wide-Bore Capillary GasChromatographyD7169 Test Method for Boiling Point Distribution ofSamples with Residu
11、es Such as Crude Oils and Atmo-spheric and Vacuum Residues by High Temperature GasChromatographyD7213 Test Method for Boiling Range Distribution ofPetroleum Distillates in the Boiling Range from 100 to615C by Gas ChromatographyE355 Practice for Gas Chromatography Terms and Rela-tionshipsE594 Practic
12、e for Testing Flame Ionization Detectors Usedin Gas or Supercritical Fluid ChromatographyE1510 Practice for Installing Fused Silica Open TubularCapillary Columns in Gas Chromatographs1This test method is under the jurisdiction of ASTM Committee D02 onPetroleum Products and Lubricants and is the dire
13、ct responsibility of SubcommitteeD02.04.0H on Chromatographic Distribution Methods.Current edition approved May 1, 2010. Published August 2010. Originallyapproved in 2008. Last previous edition approved in 2008 as D7500-08. DOI:10.1520/D7500-10.2For referenced ASTM standards, visit the ASTM website,
14、 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 Changes section appears at the end of this standard.Copyright ASTM International, 100 Barr Harbor Dri
15、ve, PO Box C700, West Conshohocken, PA 19428-2959, United States.2.2 ISO Standard:3ISO 3170 Petroleum Liquids Manual Sampling3. Terminology3.1 DefinitionsThis test method makes reference to manycommon gas chromatographic procedures, terms, and relation-ships. For definitions of these terms used in t
16、his test method,refer to Practices E355, E594, and E1510.3.2 Definitions of Terms Specific to This Standard:3.2.1 area slice, nthe area resulting from the integrationof the chromatographic detector signal within a specifiedretention time interval. In area slice mode (see 6.4.1), peakdetection parame
17、ters are bypassed and the detector signalintegral is recorded as area slices of consecutive, fixed durationtime intervals.3.2.2 corrected area slice, nan area slice corrected forbaseline offset by subtraction of the exactly corresponding areaslice in a previously recorded blank (non-sample) analysis
18、.3.2.3 cumulative corrected area, nthe accumulated sumof corrected area slices from the beginning of the analysisthrough a given retention time, ignoring any non-sample area(for example, solvent).3.2.4 final boiling point (FBP), nthe temperature (corre-sponding to the retention time) at which a cumu
19、lative correctedarea count equal to 99.5 % of the total sample area under thechromatogram is obtained.3.2.5 initial boiling point (IBP), nthe 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
20、obtained.3.2.6 slice rate, nthe frequency used in sampling (analog)the chromatographic detector signal during an analysis. Theslice rate is expressed in Hz (for example integrations or slicesper second).3.2.7 slice time, nthe inverse function of the acquisitionrate. It is the time duration of each s
21、ampling pulse usuallyexpressed in seconds. The slice time is the time at the end ofeach contiguous area slice.3.2.8 total sample area, nthe cumulative corrected area,from the initial area point to the final area point, where thechromatographic signal has returned to baseline after completesample elu
22、tion.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 n-C10for normal-decane, i-C14for iso-tetradeca
23、ne).4. Summary of Test Method4.1 The boiling range distribution determination by distilla-tion is simulated by the use of gas chromatography. Anon-polar open tubular (capillary) gas chromatographic col-umn is used to elute the hydrocarbon components of the samplein order of increasing boiling point.
24、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 raised at a specifiedlinear rate
25、to affect 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 is recorded as area slices forconsecutive retention time intervals during the analysis.4.4 Rete
26、ntion times of known normal paraffin hydrocarbons,spanning the scope of the test method, are determined andcorrelated to their boiling point temperatures. The normalizedcumulative corrected sample areas for each consecutive re-corded time interval are used to calculate the boiling rangedistribution.
27、 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 medium and heavypetroleum distillate fractions provides an insight into thecomposition of feed stocks and products relate
28、d to petroleumrefining processes (for example, hydrocracking, hydrotreating,visbreaking, or deasphalting). The gas chromatographic simu-lation of this determination can be used to replace conventionaldistillation methods for control of refining operations. This testmethod can be used for product spe
29、cification testing with themutual agreement of interested parties.5.2 This test method extends the scope of boiling rangedetermination by gas chromatography to include distillates(IBP 100C) and heavy petroleum distillate fractions beyondthe scope of Test Method D2887 (538C).5.3 Boiling range distrib
30、utions obtained by this test methodhave not been analyzed for correlation to those obtained by lowefficiency distillation, such as with Test Method D86 or D1160.This test method does not claim agreement between thesephysical distillations and simulated distillation. Efforts toresolve this question w
31、ill continue. When successful resolu-tions of the questions are determined, this test method will berevised accordingly.6. Apparatus6.1 ChromatographThe gas chromatographic systemused shall have the following performance characteristics:6.1.1 Carrier Gas Flow ControlThe chromatograph shallbe equippe
32、d with carrier gas pressure or flow control capable ofmaintaining constant carrier gas flow to 61 % throughout thecolumn temperature program cycle.6.1.2 Column OvenCapable of sustained and linear pro-grammed temperature operation from near ambient (for ex-ample, 30 to 35C) up to 430C.6.1.3 Column Te
33、mperature ProgrammerThe chromato-graph shall be capable of linear programmed temperatureoperation up to 430C at selectable linear rates up to 10C/min.The programming rate shall be sufficiently reproducible toobtain the retention time repeatability of 0.1 min (6 s) for eachcomponent in the calibratio
34、n mixture described in 7.5.3Available from American National Standards Institute (ANSI), 25 W. 43rd St.,4th Floor, New York, NY 10036, http:/www.ansi.org.D7500 1026.1.4 DetectorThis test method requires the use of a flameionization detector (FID). The detector shall meet or exceed thefollowing speci
35、fications in accordance with Practice E594.Check the detector according the instrument manufacturersinstructions.6.1.4.1 Operating Temperature100 to 430C.6.1.4.2 Connection of the column to the detector shall besuch that no temperature below the column temperature existsbetween the column and the de
36、tector. Refer to Practice E1510for proper installation and conditioning of the capillary col-umn.6.1.5 Sample Inlet SystemAny sample inlet system ca-pable of meeting the performance specification in Annex A3and execute the conditions of Table 2. Programmable tempera-ture vaporization (PTV) and cool
37、on-column (COC) injectionsystems have been used successfully.6.2 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 available.6.2.1 Automatic syringe injection is recommended toachieve best precis
38、ion.6.3 ColumnThis test method is limited to the use ofnon-polar wall coated open tubular (WCOT) columns of highthermal stability. Fused silica (aluminum coated) and stainlesssteel columns with 0.53 to 0.75-mm internal diameter havebeen successfully used. Cross-linked or bonded 100 %dimethyl-polysil
39、oxane stationary phases with film thickness of0.09 to 0.17 m have been used. The column length and liquidphase film thickness shall allow the elution of C110n-paraffin(BP = 735C). The column and conditions shall provideseparation of typical petroleum hydrocarbons in order ofincreasing boiling point
40、and meet the column performancerequirements of A3.2.1. The column shall provide a resolutionnot less than 2 and not higher than 4 using the test methodoperating conditions in Table 2.6.4 Data Acquisition System:6.4.1 Integrator/Computer SystemMeans shall be pro-vided for determining the accumulated
41、area under the chro-matogram. This can be done by means of an electronicintegrator or computer-based chromatography data system. Theintegrator/computer system shall have normal chromato-graphic software for measuring the retention time and areas ofeluting peaks (peak processing mode). In addition, t
42、he systemshall be capable of converting the continuously integrateddetector signal into area slices of fixed duration (slice mode).These contiguous area slices, collected for the entire analysis,are stored for later processing. A similar collection of contigu-ous slices is also collected for the bla
43、nk run. It is necessary thatthe number of slices collected for sample and blank analysisare the same. The electronic range of the integrator/computer(for example 1 V, 10 V) shall be operated within the linearrange of the detector/electrometer system used.NOTE 1Some gas chromatographs have an algorit
44、hm 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 automaticallysub
45、tract a blank analysis from subsequent analytical determinations.7. Reagents and Materials7.1 Liquid Stationary PhaseA methyl silicone stationaryphase for the column.7.2 Carrier GasesHelium, of at least 99.999 % (v/v)purity. Any oxygen present is removed by a chemical resinfilter. (WarningFollow the
46、 safety instructions from the filtersupplier.) Total impurities not to exceed 10 mL/m3. Helium orNitrogen (99.999 %) can also be used as detector makeup gas.7.3 Hydrogen99.999 % Grade suitable for flame ioniza-tion detectors. Total impurities not to exceed 10 mL/m3.7.4 Compressed AirRegulated for fl
47、ame ionization detec-tors. Total impurities not to exceed 10 mL/m3.7.5 AlkanesNormal alkanes of at least 98 % (m/m) purityfrom C5to C10,C12,C14,C16,C18,C20,C24,C26, and C28, areto be used with Polywax 655 or 1000.4A solution of thesealkanes is prepared by adding 500 mg of each alkane into a 20mL via
48、l.Additionally n-tetracontane (C40) can also be added tofor ease of carbon counting. This solution is used to spike thePolywax4solution.7.6 Polywax 655 or 1000.44Polywax is a registered trademark of Baker Petrolite, 12645 WestAirport Blvd.,Sugar Land, TX 77478.TABLE 1 Reference Material 5010A%Dist.m
49、/m C F r,C R,C r,F R,FIBP 421 789 3 9 5 165 476 888 2 4 4 810 491 916 2 4 3 720 510 950 2 5 3 930 524 975 2 5 3 940 536 998 2 5 3 950 548 1018 2 5 3 960 559 1039 2 5 3 970 572 1061 2 5 3 980 585 1085 2 5 3 990 602 1116 2 5 3 995 617 1142 2 5 3 9FBP 661 1223 9 17 16 31AValues obtained from including Reference Oil 5010 in the ILS sample set.TABLE 2 Typical Operating Conditions for Gas ChromatographColumn length, m 5Column internal diameter, mm 0.53Column material MetalStationary phase type methyl siliconeFilm thickness, m 0.09 to 0.17I
