1、Designation: D7500 14Standard Test Method forDetermination of Boiling Range Distribution of Distillatesand Lubricating Base Oilsin Boiling Range from 100 C to735 C by Gas Chromatography1This standard is issued under the fixed designation D7500; the number immediately following the designation indica
2、tes 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 o
3、f 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 D6352 and IP 480. Asboth of these methods cover the same scope and include
4、verysimilar 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、gasolines, diesel). Components containing hetero atoms (forexample alcohols, ethers, acids, or esters) or residue are not tobe analyzed by this test method. See Test Methods D7096,D2887,orD7213 for possible applicability to analysis of thesetypes of materials. This method is also not suitable for sa
6、mplesthat will not elute completely from the gas chromatographiccolumn, leaving residues. For such samples as crude oils andresidues, see Test Methods D5307 and D7169.1.3 This test method is applicable to distillates with initialboiling points above 100 C and final boiling points below735 C (carbon
7、110); for example, distillates (IBP 100 C),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 Products atReduced PressureD2887 Test Method for Boiling Range Distribution of Pe-troleum Fractions by Gas ChromatographyD5307 Test Method for Determination of Boiling RangeDistribution of Crude Petroleum by Gas Chromatography(Withdrawn 2011)
10、3D6352 Test Method for Boiling Range Distribution of Pe-troleum Distillates in Boiling Range from 174 to 700C byGas ChromatographyD7096 Test Method for Determination of the Boiling RangeDistribution of Gasoline by Wide-Bore Capillary GasChromatographyD7169 Test Method for Boiling Point Distribution
11、ofSamples with Residues Such as Crude Oils and Atmo-spheric and Vacuum Residues by High Temperature GasChromatographyD7213 Test Method for Boiling Range Distribution of Pe-troleum Distillates in the Boiling Range from 100 to615C by Gas ChromatographyE355 Practice for Gas Chromatography Terms and Rel
12、ation-shipsE594 Practice for Testing Flame Ionization Detectors Usedin Gas or Supercritical Fluid ChromatographyE1510 Practice for Installing Fused Silica Open TubularCapillary Columns in Gas Chromatographs2.2 ISO Standard:4ISO 3170 Petroleum Liquids Manual Sampling1This test method is under the jur
13、isdiction of ASTM Committee D02 onPetroleum Products, Liquid Fuels, and Lubricants and is the direct responsibility ofSubcommittee D02.04.0H on Chromatographic Distribution Methods.Current edition approved Oct. 1, 2014. Published December 2014. Originallyapproved in 2008. Last previous edition appro
14、ved in 2012 as D7500 12. DOI:10.1520/D7500-14.2For 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.3The last appro
15、ved version of this historical standard is referenced onwww.astm.org.4Available from American National Standards Institute (ANSI), 25 W. 43rd St.,4th Floor, New York, NY 10036, http:/www.ansi.org.*A Summary of Changes section appears at the end of this standardCopyright ASTM International, 100 Barr
16、Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959. United States13. 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,refer to Practices E355, E594, and
17、 E1510.3.2 Definitions of Terms Specific to This Standard:3.2.1 area slice, nthe area resulting from the integration ofthe chromatographic detector signal within a specified reten-tion time interval. In area slice mode (see 6.4.1), peak detectionparameters are bypassed and the detector signal integr
18、al isrecorded as area slices of consecutive, fixed duration timeintervals.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 cumulative corrected area, nthe accumulat
19、ed 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), nthe temperature (corre-sponding to the retention time) at which a cumulative correctedarea count equal to 99.5 % of th
20、e 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 slice rate, nthe frequency used i
21、n 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 usuallyexpressed in seconds. The s
22、lice 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 AbbreviationsAcommon abbreviation of hy
23、drocarboncompounds 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 number of carbon atoms(for example n-C10for normal-decane, i-C14for iso-tetradecane).4. Summary of Test Method4.1 The boiling range
24、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 aliquot is diluted with a viscosity re
25、ducingsolvent 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 separation of the hydrocarbon componentsi
26、n 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 known normal paraffin hydrocarbons,s
27、panning 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 point temperature at each reportedperc
28、ent 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 petroleumrefining processes (for example, hydr
29、ocracking, 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 testing with themutual agreement of inte
30、rested parties.5.2 This test method extends the scope of boiling rangedetermination by gas chromatography to include distillates(IBP 100 C) and heavy petroleum distillate fractions beyondthe scope of Test Method D2887 (538 C).5.3 Boiling range distributions obtained by this test methodhave not been
31、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 will continue. When successful resolu-tions of the
32、 questions are determined, this test method will berevised accordingly.6. Apparatus6.1 ChromatographThe gas chromatographic system usedshall have the following performance characteristics:6.1.1 Carrier Gas Flow ControlThe chromatograph shallbe equipped with carrier gas pressure or flow control capab
33、le 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 (forexample, 30 C to 35 C) up to 430 C.6.1.3 Column Temperature ProgrammerThe chromato-graph shall be
34、 capable of linear programmed temperatureoperation up to 430 C at selectable linear rates up to10 C min. The programming rate shall be sufficiently repro-ducible to obtain the retention time repeatability of 0.1 min(6 s) for each component in the calibration mixture describedin 7.5.D7500 1426.1.4 De
35、tectorThis test method requires the use of a flameionization detector (FID). The detector shall meet or exceed thefollowing specifications in accordance with Practice E594.Check the detector according the instrument manufacturersinstructions.6.1.4.1 Operating Temperature100 C to 430 C.6.1.4.2 Connec
36、tion of the column to the detector shall besuch that no temperature below the column temperature existsbetween the column and the detector. 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 th
37、e 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 needle is used for on-column sampl
38、eintroduction. 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 silica (aluminum coated) and st
39、ainlesssteel columns with 0.53 mm to 0.75 mm internal diameter havebeen successfully used. Cross-linked or bonded 100 %dimethyl-polysiloxane stationary phases with film thickness of0.09 m to 0.17 m have been used. The column length andliquid phase film thickness shall allow the elution of C110n-para
40、ffin (BP = 735 C). The column and conditions shallprovide separation of typical petroleum hydrocarbons in orderof increasing 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 test methodoperating
41、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. Theintegrator/computer system sh
42、all 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 contiguous area slices,
43、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 integrator/computer(for example
44、 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 automatically subtractedfro
45、m 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 stationaryphase for the co
46、lumn.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 detector makeup gas.The
47、use of alternative carrier gases hydrogen and nitrogen isdescribed in Appendix X1.7.3 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 Alka
48、nesNormal alkanes of at least 98 % (m/m) purityfrom C5to C10,C12,C14,C16,C18,C20,C24,C26, and C28, areTABLE 1 Reference Material 5010A% Dist.m/mC F r, C R, C r, F R, FIBP 421 789 3 9 5 1654768 24481091916243725050253930249745368253950 548 101860 559 1039 253970 572 106180 585 1085 253990602165174225
49、39FBP 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 0.17Initial column temperature, C 35Initial hold time, min 0Final column temperature, C 430Final hold time, min 10Program rate, C/min 10Injector initial temperature, C 100Injector final temperature, C 430Injector program rate, C/min 15
