ASTM D6352-2004(2009) 781 Standard Test Method for Boiling Range Distribution of Petroleum Distillates in Boiling Range from 174 to 700&176 C by Gas Chromatography《用气相色谱法测试174℃-700.pdf

1、Designation: D 6352 04 (Reapproved 2009)An 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 des

2、ignation indicates 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 d

3、etermination 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 point of less than 700C (1292F) (C10 to C90) atatmospheric pressure as measured b

4、y 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 containing heterogeneous compo-nents (for example alcohols, ethers, acids, or es

5、ters) or residueare not to be analyzed by this test method. See Test MethodsD 3710, D 2887,orD 5307 for possible applicability to analy-sis of these types of materials.1.3 The values stated in SI units are to be regarded asstandard. The values stated in inch-pound units are for infor-mation only and

6、 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-priate safety and health practices and determine the applica-bility of regulatory

7、 limitations prior to use.2. Referenced Documents2.1 ASTM Standards:2D86 Test Method for Distillation of Petroleum Products atAtmospheric PressureD 1160 Test Method for Distillation of Petroleum Productsat Reduced PressureD 2887 Test Method for Boiling Range Distribution ofPetroleum Fractions by Gas

8、 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 for Calculation of Gas ChromatographicResponse FactorsD 5307 Test Method for Dete

9、rmination 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 Supercritical Fluid ChromatographyE 1510 Practice for Installing Fused Silica Open TubularC

10、apillary 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 test method,refer to Practices E 355, E 594, and E 1510.3.2 Definitions of Terms Sp

11、ecific 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 are bypassed and the detector signal integral isrecorded as area slices of conse

12、cutive, 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.3.2.3 cumulative corrected areathe accumulated sum ofcorrected area slices from the b

13、eginning 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 retention time) at which a cumulative correctedarea count equal to 99.5 % of the total sample area under thechromatogram is

14、 obtained.1This test method is under the jurisdiction of ASTM Committee D02 onPetroleum Products and Lubricants and is the direct responsibility of SubcommitteeD02.04.0H on Chromatographic Distribution Methods.Current edition approved April 15, 2009. Published July 2009. Originallyapproved in 1998.

15、Last previous edition approved in 2004 as D 6352 041.2For 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.1Copyrig

16、ht ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959, United States.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 under thechromatogram i

17、s 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 exampleintegrations or slices per second).3.2.7 slice timethe analysis time associated with each areaslice throughout the

18、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 the final area point, where thechromatographic signal has returned to baseline after completesample elution.3.3 Abbreviatio

19、nsA 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 of Te

20、st 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 aliquot

21、 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 separation

22、 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 known

23、 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 point t

24、emperature 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 petroleumrefini

25、ng 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 testing w

26、ith themutual agreement of interested parties.5.2 This test method extends the scope of boiling rangedetermination by gas chromatography to include medium andheavy petroleum distillate fractions beyond the scope of TestMethod D 2887 (538C).5.3 Boiling range distributions obtained by this test method

27、have not been analyzed for correlation to those obtained by lowefficiency distillation, such as with Test Method D86 orD 1160.6. Apparatus6.1 ChromatographThe gas chromatographic systemused shall have the following performance characteristics:6.1.1 Carrier Gas Flow ControlThe chromatograph shallbe e

28、quipped with carrier gas pressure or flow control capable ofmaintaining constant carrier gas flow control through thecolumn throughout the column 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) u

29、p 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.The programming rate shall be sufficiently reproducible toobtain the retention time repeatability of 0.1 min (6 s) for eachco

30、mponent 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 thefollowing specifications in accordance with Practice E 594.The flame jet should have an orifice of approximately 0.05 to0.070

31、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 Range1066.1.4.5 Connection of the column to the detector shall besuch that no temperature below the column temperature existsbetween t

32、he 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 of meeting the performance specification in 7.6 and 8.2.2may be used. Programmable temperature vaporization (PTV)and cool on

33、-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. Syringes of 0.1 to 10-L capacity are available.6.2.1 Automatic syringe injection is recommended toachieve best precision.6.3

34、 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 stainlesssteel columns with 0.53 to 0.75-mm internal diameter havebeen successfully used. Cross-linked or bonded 100 %dimethyl-polysiloxan

35、e 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 C90n-paraffin (BP = 700C). The column and conditions shallprovide separation of typical petroleum hydrocarbons in orderof increasing boiling p

36、oint and meet the column performanceD 6352 04 (2009)2requirements of 8.2.1. The column shall provide a resolutionbetween three (3) and ten (10) using the test method operatingconditions.NOTE 1Based on recent information that suggests that true boilingpoints (atmospheric equivalent temperatures) vers

37、us 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 robin evaluation of the test method is completed.6.4 Data Acquisition System:6.4.1 RecorderA 0 to 1 mV range recording

38、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 IntegratorMeans shall be provided for determiningthe accumulated area under the chromatogram. This can bedone by means of an electro

39、nic integrator or computer-basedchromatography data system. The 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 dete

40、ctor signal into area slices offixed duration. These contiguous area slices, collected for theentire analysis, are stored for later processing. The electronicrange of the integrator/computer (for example 1 V, 10 V) shallbe operated within the linear range of the detector/electrometersystem used.NOTE

41、 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 automatically subtractedfrom the detector signal on subsequent sample runs to compensate for thecolumn bleed. Some integratio

42、n systems also store and automaticallysubtract a blank analysis from subsequent analytical determinations.7. Reagents and Materials7.1 Carrier GasHelium, hydrogen, or nitrogen of highpurity (WarningHelium and nitrogen are compressed gasesunder high pressure). Additional purification is recommendedby

43、 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 HydrogenHydrogen of high purity (for example, hy-drocarbon free) is used as fuel for the FID. Hydrogen can alsobe used

44、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 the FID. (WarningCompressed air is a gas under high pressure and supportscombustion).7.4 SolventsUnless otherwise ind

45、icated, it is intended thatall solvents conform to the specifications of the Committee onAnalytical Reagents of the American Chemical Society wheresuch specifications are available.3Other grades may be used,provided it is first ascertained that the solvent is of sufficientlyhigh purity to permit its

46、 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 introduced onto the column to ensure linear detectorresponse and reduced peak skewness. It is miscible withasphaltic hydroc

47、arbons 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. (WarningCS2is extremely flammable and toxic.)7.4.2 Cyclohexane (C6H12)(99+ % pure) may be used inplace of CS2for the preparation o

48、f the calibration mixture.7.5 Calibration MixtureA qualitative mixture ofn-paraffins (nominally C10 to C100) dissolved in a suitablesolvent. The final concentration should be approximately onepart of n-paraffin mixture to 200 parts of solvent. At least onecompound in the mixture shall have a boiling

49、 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 obtained by dissolvinga hydrogenated polyethylene wax (for example, Polywax 655 or Polywax1000) in a volatile solve