1、Designation: D 7500 08Standard 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 D 7500; the number immediately following the designation indicat
2、es 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. Scope1.1 This test method covers the determination of
3、the 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 D 6352 and IP 480. Asboth of these methods cover the same scope and include v
4、erysimilar 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,
5、gaso-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 D 7096,D 2887, or D 7213 for possible applicability to analysis ofthese types of materials. This method is also not suitabl
6、e forsamples that will not elute completely from the gas chromato-graphic column, leaving residues. For such samples as crudeoils and residues, see Test Methods D 5307 and D 7169.1.3 This test method is applicable to distillates with initialboiling points above 100C and final boiling points below735
7、C (carbon 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, assoc
8、iated 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 Petroleum Products atA
9、tmospheric PressureD 1160 Test Method for Distillation of Petroleum Productsat Reduced PressureD 2887 Test Method for Boiling Range Distribution ofPetroleum Fractions by Gas ChromatographyD 5307 Test Method for Determination of Boiling RangeDistribution of Crude Petroleum by Gas ChromatographyD 6352
10、 Test Method for Boiling Range Distribution ofPetroleum Distillates in Boiling Range from 174 to 700Cby Gas ChromatographyD 7096 Test Method for Determination of the BoilingRange Distribution of Gasoline by Wide-Bore CapillaryGas ChromatographyD 7169 Test Method for Boiling Point Distribution ofSamp
11、les with Residues Such as Crude Oils and Atmo-spheric and Vacuum Residues by High Temperature GasChromatographyD 7213 Test Method for Boiling Range Distribution ofPetroleum Distillates in the Boiling Range from 100 to615C by Gas ChromatographyE 355 Practice for Gas Chromatography Terms and Rela-tion
12、shipsE 594 Practice for Testing Flame Ionization Detectors Usedin Gas or Supercritical Fluid ChromatographyE 1510 Practice for Installing Fused Silica Open TubularCapillary Columns in Gas Chromatographs2.2 ISO Standard:ISO 3170 Petroleum Liquids Manual Sampling31This test method is under the jurisdi
13、ction of ASTM Committee D02 onPetroleum Products and Lubricants and is the direct responsibility of SubcommitteeD02.04.0H on Chromatographic Distribution Methods.Current edition approved Dec. 1, 2008. Published February 2009.2For referenced ASTM standards, visit the ASTM website, www.astm.org, orcon
14、tact ASTM Customer Service at serviceastm.org. For Annual Book of ASTMStandards volume information, refer to the standards Document Summary page onthe ASTM website.3Available from American National Standards Institute (ANSI), 25 W. 43rd St.,4th Floor, New York, NY 10036, http:/www.ansi.org.1Copyrigh
15、t ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959, United States.3. Terminology3.1 DefinitionsThis test method makes reference to manycommon gas chromatographic procedures, terms, and relation-ships. For definitions of these terms used in this test method,ref
16、er to Practices E 355, E 594, and E 1510.3.2 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 parameters are bypasse
17、d 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.3.2.3 cumulativ
18、e 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 cumulative corrected
19、area 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 obtained.3.2.6 s
20、lice 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 sampling pulse us
21、uallyexpressed 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 elution.3.3 Abbrevi
22、ationsA 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-tetradecane).4. Summary o
23、f 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.4.2 A sample ali
24、quot 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 to affect separa
25、tion 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 Retention times of k
26、nown 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. The boiling poi
27、nt 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 related to petroleumre
28、fining 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 specification testi
29、ng 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 D 2887 (538C).5.3 Boiling range distributions obtained
30、 by this test methodhave not been analyzed for correlation to those obtained by lowefficiency distillation, such as with Test Method D 86 orD 1160. This test method does not claim agreement betweenthese physical distillations and simulated distillation. Efforts toresolve this question will continue.
31、 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 equipped with carrie
32、r 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 Temperature Pro
33、grammerThe 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 calibration mixture des
34、cribed in 7.5.6.1.4 DetectorThis test method requires the use of a flameionization detector (FID). The detector shall meet or exceed thefollowing specifications in accordance with Practice E 594.Check the detector according the instrument manufacturersinstructions.6.1.4.1 Operating Temperature100 to
35、 430C.D75000826.1.4.2 Connection of the column to the detector shall besuch that no temperature below the column temperature existsbetween the column and the detector. Refer to Practice E 1510for proper installation and conditioning of the capillary col-umn.6.1.5 Sample Inlet SystemAny sample inlet
36、system ca-pable of meeting the performance specification in Annex A3and execute the conditions of Table 2. Programmable tempera-ture vaporization (PTV) and cool on-column (COC) injectionsystems have been used successfully.6.2 MicrosyringeA microsyringe with a 23-gauge orsmaller stainless steel needl
37、e 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) columns of highthermal stability. Fused si
38、lica (aluminum coated) and stainlesssteel columns with 0.53 to 0.75-mm internal diameter havebeen successfully used. Cross-linked or bonded 100 %dimethyl-polysiloxane stationary phases with film thickness of0.09 to 0.17 m have been used. The column length and liquidphase film thickness shall allow t
39、he elution of C110n-paraffin(BP = 735C). The column and conditions shall provideseparation of typical petroleum hydrocarbons in order ofincreasing boiling point 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
40、 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 area under the chro-matogram. This can be done by means of an electronicintegrator or computer-based chromatography data system. Theintegra
41、tor/computer system shall have normal chromato-graphic software for measuring the retention time and areas ofeluting peaks (peak processing mode). In addition, the systemshall be capable of converting the continuously integrateddetector signal into area slices of fixed duration (slice mode).These co
42、ntiguous area slices, collected for the entire analysis,are stored for later processing. A similar collection of contigu-ous slices is also collected for the blank run. It is necessary thatthe number of slices collected for sample and blank analysisare the same. The electronic range of the integrato
43、r/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 algorithm built into theiroperating software that allows a mathematical model of the baselineprofile to be stored in memory. This profile is autom
44、atically subtractedfrom the detector 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 Materials7.1 Liquid Stationary PhaseA methyl silicone stat
45、ionaryphase 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 safety instructions from the filtersupplier.) Total impurities not to exceed 10 mL/m3. Helium orNitrogen (99.999 %) can also be used as de
46、tector 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 flame 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
47、,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 204Polywax is a registered trademark of Baker Petrolite, 12645 WestAirport Blvd.,Sugar Land, TX 77478.TABLE 1 Reference Material 5010A% OFFAverage,
48、F95.5% CI, FAllowableDifferenceAverage,C95.5% CI, CAllowableDifferenceIBP 801 16 428 95 891 5 477 310 918 5 493 315 936 5 502 320 950 6 510 325 963 6 518 430 975 7 524 435 987 7 531 440 998 8 537 445 1008 8 543 450 1019 8 548 555 1030 8 554 460 1040 8 560 465 1051 8 566 470 1062 8 572 475 1073 9 578
49、 580 1086 8 585 485 1099 7 593 490 1116 8 602 495 1140 7 616 4FBP 1213 32 655 18AConsensus results obtained from 14 laboratories in 2000 as reported in TestMethod D 6352.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 0.17Initial column temperature, C 35Initial hold time, min 0Final column temperature, C 430Final hold time, min 10Program rate, C/min 10Injector initial temperature, C 100Inje
