1、Designation: D 6352 04e1An American National StandardStandard Test Method forBoiling Range Distribution of Petroleum Distillates inBoiling Range from 174 to 700C by Gas Chromatography1This standard is issued under the fixed designation D 6352; 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 (e) indicates an editorial change since the last revision or reapproval.e1NOTEVariable definitions were added to 10.15.1.3 and 1
3、0.15.1.4 editorially in August 2004.1. Scope*1.1 This test method covers the determination of the boilingrange distribution of petroleum distillate fractions. The testmethod is applicable to petroleum distillate fractions having aninitial boiling point greater than 174C (345F) and a finalboiling poi
4、nt of less than 700C (1292F) (C10 to C90) atatmospheric pressure as measured by this test method.1.2 The test method is not applicable for the analysis ofpetroleum or petroleum products containing low molecularweight components (for example naphthas, reformates, gaso-lines, crude oils). Materials co
5、ntaining heterogeneous compo-nents (for example alcohols, ethers, acids, or esters) or residueare not to be analyzed by this test method. See Test MethodsD 3710, D 2887, or D 5307 for possible applicability to analy-sis of these types of materials.1.3 The values stated in SI units are to be regarded
6、 asstandard. The values stated in inch-pound units are for infor-mation only and may be included as parenthetical values.1.4 This standard does not purport to address all of thesafety concerns, if any, associated with its use. It is theresponsibility of the user of this standard to establish appro-p
7、riate safety and health practices and determine the applica-bility of regulatory limitations prior to use.2. Referenced Documents2.1 ASTM Standards:2D 86 Test Method for Distillation of Petroleum Products atAtmospheric PressureD 1160 Test Method for Distillation of Petroleum Productsat Reduced Press
8、ureD 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 Test Method for Boiling Range Distribution ofGasoline and Gasoline Fractions by Gas ChromatographyD 4626 Practice
9、for Calculation of Gas ChromatographicResponse FactorsD 5307 Test Method for Determination of Boiling RangeDistribution of Crude Petroleum by Gas ChromatographyE 355 Practice for Gas Chromatography Terms and Rela-tionshipsE 594 Practice for Testing Flame Ionization Detectors Usedin Gas or Supercriti
10、cal 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 relation-ships. For definitions of these terms used in this te
11、st method,refer to Practices E 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 mode (see 6.4.2), peak detectionparameters
12、 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 recorded blank (non-sample) analysis.3.2.
13、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).1This test method is under the jurisdiction of ASTM Committee D02 onPetroleum Products and Lubricants and is the
14、 direct responsibility of SubcommitteeD02.04 on Hydrocarbon Analysis.Current edition approved June 1, 2004. Published July 2004. Originally approvedin 1998. Last previous edition approved in 2003 as D 635203.2For referenced ASTM standards, visit the ASTM website, www.astm.org, orcontact ASTM Custome
15、r 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 Drive, PO Box C700, West Conshohocken, P
16、A 19428-2959, United States.3.2.4 final boiling point (FBP)the 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)the temperature (corre-sponding to t
17、he 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 ratethe time interval used to integrate thecontinuous (analog) chromatographic detector response duringan analysis. The slice rate is expressed in Hz (fo
18、r exampleintegrations or slices per second).3.2.7 slice timethe analysis time associated with each areaslice throughout the chromatographic analysis. The slice timeis the time at the end of each contiguous area slice.3.2.8 total sample areathe cumulative corrected area,from the initial area point to
19、 the final area point, where thechromatographic signal has returned to baseline after completesample elution.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 subscrip
20、ted suffix denotes the number of carbonatoms (for example n-C10for normal-decane, i-C14for iso-tetradecane).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 chromatographi
21、c 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 reducingsolvent and introduced into the chromatographic system.Sample vaporization is provided by separate heating of thepoint of injection or in c
22、onjunction with column oven heating.4.3 The column oven temperature is raised at a specifiedlinear rate 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 detecto
23、r signal is recorded as area slices forconsecutive retention time intervals during the analysis.4.4 Retention 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
24、 areas for each consecutive re-corded time interval are 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 medium and heavyp
25、etroleum distillate fractions provides an insight into thecomposition of feed stocks and products related to petroleumrefining processes (for example, hydrocracking, hydrotreating,visbreaking, or deasphalting). The gas chromatographic simu-lation of this determination can be used to replace conventi
26、onaldistillation methods for control of refining operations. This testmethod can be used for product specification testing with themutual agreement of interested parties.5.2 This test method extends the scope of boiling rangedetermination by gas chromatography to include medium andheavy petroleum di
27、stillate fractions beyond the scope of TestMethod D 2887 (538C).5.3 Boiling range distributions obtained by this test methodhave not been analyzed for correlation to those obtained by lowefficiency distillation, such as with Test Method D 86 orD 1160.6. Apparatus6.1 ChromatographThe gas chromatograp
28、hic systemused shall have the following performance characteristics:6.1.1 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.6.1
29、.2 Column OvenCapable of sustained and linear pro-grammed temperature operation from near ambient (for ex-ample, 30 to 35C) up to 450C.6.1.3 Column Temperature ProgrammerThe chromato-graph shall be capable of linear programmed temperatureoperation up to 450C at selectable linear rates up to 20C/min.
30、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 7.5.6.1.4 DetectorThis test method requires the use of a flameionization detector (FID). The detector shall meet or exceed thef
31、ollowing specifications in accordance with Practice E 594.The flame jet should have an orifice of approximately 0.05 to0.070 mm (0.020 to 0.030 in.).6.1.4.1 Operating Temperature100 to 450C.6.1.4.2 Sensitivity0.005 C/g carbon.6.1.4.3 Minimum Detectability1 3 10-11 g carbon/s.6.1.4.4 Linear Range1066
32、.1.4.5 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 system ca-pable
33、 of meeting the performance specification in 7.6 and 8.2.2may be used. Programmable temperature vaporization (PTV)and cool on-column injection systems have been used success-fully.6.2 MicrosyringeA microsyringe with a 23-gage orsmaller stainless steel needle is used for on-column sampleintroduction.
34、 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 (see Note 1). Glass, fused silica, and stainlessstee
35、l 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 of0.10 to 0.20 m have been used. The column length and liquidphase film thickness shall allow the elution of at least C90D635204e12n-pa
36、raffin (BP = 700C). The column and conditions shallprovide separation of typical petroleum hydrocarbons in orderof increasing boiling point and meet the column performancerequirements of 8.2.1. The column shall provide a resolutionbetween three (3) and ten (10) using the test method operatingconditi
37、ons.NOTE 1Based on recent information that suggests that true boilingpoints (atmospheric equivalent temperatures) versus retention times for allcomponents do not fall on the same line, other column systems that canmeet this criteria will be considered. These criteria will be specified aftera round r
38、obin evaluation of the test method is completed.6.4 Data Acquisition System:6.4.1 RecorderA 0 to 1 mV range recording potentiom-eter or equivalent with a full-scale response time of2sorlessmay be used. It is, however, not a necessity if an integrator/computer data system is used.6.4.2 IntegratorMean
39、s 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 integrator/computer systemshall have normal chromatographic software for measuring theretention time and areas of elut
40、ing peaks (peak detectionmode). In addition, the system shall be capable of convertingthe continuously integrated detector signal into area slices offixed duration. These contiguous area slices, collected for theentire analysis, are stored for later processing. The electronicrange of the integrator/
41、computer (for example 1 V, 10 V) shallbe operated within the linear range of the detector/electrometersystem used.NOTE 2Some 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 automat
42、ically 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 Carrier GasHelium, hydrogen, or nitrogen of hig
43、hpurity (WarningHelium and nitrogen are compressed gasesunder high pressure). Additional purification is recommendedby the use of molecular sieves or other suitable agents toremove water, oxygen, and hydrocarbons. Available pressureshall be sufficient to ensure a constant carrier gas flow rate.7.2 H
44、ydrogenHydrogen of high purity (for example, hy-drocarbon free) is used as fuel for the FID. Hydrogen can alsobe used as the carrier gas. (WarningHydrogen is an ex-tremely flammable gas under high pressure).7.3 AirHigh purity (for example, hydrocarbon free) com-pressed air is used as the oxidant for
45、 the FID. (WarningCompressed air is a gas under high pressure and supportscombustion).7.4 SolventsUnless otherwise indicated, it is intended thatall solvents conform to the specifications of the Committee onAnalytical Reagents of the American Chemical Society wheresuch specifications are available.3
46、Other grades may be used,provided 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) is used as aviscosity-reducing solvent and as a means of reducing mass ofsample intro
47、duced onto the column to ensure linear detectorresponse and reduced peak skewness. It is miscible withasphaltic hydrocarbons and 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. (WarningCS2i
48、s extremely flammable and toxic.)7.4.2 Cyclohexane (C6H12)(99+ % pure) may be used inplace of CS2for the preparation of the calibration mixture.7.5 Calibration MixtureA qualitative mixture ofn-paraffins (nominally C10 to C100) dissolved in a suitablesolvent. The final concentration should be approxi
49、mately onepart of n-paraffin mixture to 200 parts of solvent. At least onecompound in the mixture shall have a boiling point lower thanthe initial boiling point and one shall have a boiling pointhigher than the final boiling point of the sample beinganalyzed, as defined in 1.1. The calibration mixture shallcontain at least eleven known n-paraffins (for example C10,C12, C16, C20, C30, C40, C50, C60, C70, C80, and C90).Atmospheric equivalent boiling points of n-paraffins are listedin Table 1.NOTE 3A suitable calibration mixture can be
