ASTM D6352-2014 4472 Standard Test Method for Boiling Range Distribution of Petroleum Distillates in Boiling Range from 174&thinsp &deg C to 700&thinsp &deg C by Gas Chromatography.pdf

1、Designation: D6352 14Standard Test Method forBoiling Range Distribution of Petroleum Distillates inBoiling Range from 174 C to 700 C by GasChromatography1This standard is issued under the fixed designation D6352; the number immediately following the designation indicates the year oforiginal adoption

2、 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 the boilingrange distribution

3、of petroleum distillate fractions. The testmethod is applicable to petroleum distillate fractions having aninitial boiling point greater than 174 C (345 F) and a finalboiling point of less than 700 C (1292 F) (C10 to C90) atatmospheric pressure as measured by this test method.1.2 The test method is

4、not applicable for the analysis ofpetroleum or petroleum products containing low molecularweight components (for example naphthas, reformates,gasolines, crude oils). Materials containing heterogeneouscomponents (for example alcohols, ethers, acids, or esters) orresidue are not to be analyzed by this

5、 test method. See TestMethods D3710, D2887,orD5307 for possible applicability toanalysis 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 may be included as parenthetical values.1.4 This s

6、tandard 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 limitations prior to use.2. Referenced Documents2.

7、1 ASTM Standards:2D86 Test Method for Distillation of Petroleum Products atAtmospheric PressureD1160 Test Method for Distillation of Petroleum Products atReduced PressureD2887 Test Method for Boiling Range Distribution of Pe-troleum Fractions by Gas ChromatographyD2892 Test Method for Distillation o

8、f Crude Petroleum(15-Theoretical Plate Column)D3710 Test Method for Boiling Range Distribution of Gaso-line and Gasoline Fractions by Gas Chromatography(Withdrawn 2014)3D4626 Practice for Calculation of Gas ChromatographicResponse FactorsD5307 Test Method for Determination of Boiling RangeDistributi

9、on of Crude Petroleum by Gas Chromatography(Withdrawn 2011)3E355 Practice for Gas Chromatography Terms and Relation-shipsE594 Practice for Testing Flame Ionization Detectors Usedin Gas or Supercritical Fluid ChromatographyE1510 Practice for Installing Fused Silica Open TubularCapillary Columns in Ga

10、s 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 E355, E594, and E1510.3.2 Definitions of Terms Specific to This Standard:3

11、.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 6.4.2), peak detectionparameters are bypassed and the detector signal integral isrecorded as area slices of consecutive, fixed duration

12、 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 accumulated sum ofcorrected area slices from the beginning of the an

13、alysis througha given retention time, ignoring any non-sample area (forexample, solvent).1This test method is under the jurisdiction of ASTM Committee D02 onPetroleum Products, Liquid Fuels, and Lubricants and is the direct responsibility ofSubcommittee D02.04.0H on Chromatographic Distribution Meth

14、ods.Current edition approved Oct. 1, 2014. Published December 2014. Originallyapproved in 1998. Last previous edition approved in 2012 as D6352 12. DOI:10.1520/D6352-14.2For referenced ASTM standards, visit the ASTM website, www.astm.org, orcontact ASTM Customer Service at serviceastm.org. For Annua

15、l Book of ASTMStandards volume information, refer to the standards Document Summary page onthe ASTM website.3The last approved version of this historical standard is referenced onwww.astm.org.*A Summary of Changes section appears at the end of this standardCopyright ASTM International, 100 Barr Harb

16、or Drive, PO Box C700, West Conshohocken, PA 19428-2959. United States13.2.4 final boiling point (FBP), nthe temperature (corre-sponding to the retention time) at which a cumulative correctedarea count equal to 99.5 % of the total sample area under thechromatogram is obtained.3.2.5 initial boiling p

17、oint (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 time interval used to integrate thecontinuous (analog) chromatographic detector response duri

18、ngan analysis. The slice rate is expressed in Hz (for exampleintegrations or slices per second).3.2.7 slice time, nthe analysis time associated with eacharea slice throughout the chromatographic analysis. The slicetime is the time at the end of each contiguous area slice.3.2.8 total sample area, nth

19、e 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 hydrocarboncompounds is to designate the number of carbon atoms in thecompound. A prefix is

20、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 distribution determination by distilla-tion is simulated by the use of gas chromatography.

21、 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 reducingsolvent and introduced into the chromatographic system.Sample vaporization is provid

22、ed 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 componentsin order of increasing boiling point. The elution of samplecomponents is quantitatively det

23、ermined 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,spanning the scope of the test method, are determined andcorrelated to their boiling point

24、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 reportedpercent off increment is calculated from the retention timecalibration.5. Significance and Use

25、5.1 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, hydrocracking, hydrotreating,visbreaking, or deasphalting). The gas chromatographic simu-latio

26、n 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 interested parties.5.2 This test method extends the scope of boiling rangedetermination by gas

27、 chromatography to include medium andheavy petroleum distillate fractions beyond the scope of TestMethod D2887 (538 C).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 D86 or D

28、1160.6. 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 capable ofmaintaining constant carrier gas flow control through thecolu

29、mn throughout the column 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 450 C.6.1.3 Column Temperature ProgrammerThe chromato-graph shall be capable of linear programmed temperatureoperat

30、ion up to 450 C at selectable linear rates up to20 Cmin. The programming rate shall be sufficiently repro-ducible to obtain the retention time repeatability of 0.1 min (6s) for each component in the calibration mixture described in7.5.6.1.4 DetectorThis test method requires the use of a flameionizat

31、ion detector (FID). The detector shall meet or exceed thefollowing specifications in accordance with Practice E594. Theflame jet should have an orifice of approximately 0.05 mm to0.070 mm (0.020 in. to 0.030 in.).6.1.4.1 Operating Temperature100 C to 450 C.6.1.4.2 Sensitivity0.005 C/g carbon.6.1.4.3

32、 Minimum Detectability1 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 the column and the detector. Refer to Practice E1510for proper installation and conditioning of the capillary c

33、ol-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-column injection systems have been used success-fully.6.2 MicrosyringeA microsyringe with a 23-gage orsmaller

34、stainless steel needle is used for on-column sampleintroduction. Syringes of 0.1 L to 10 L capacity are avail-able.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 highD63

35、52 142thermal stability (see Note 1). Glass, fused silica, and stainlesssteel 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 of0.10 m to 0.20 m have been used. The column length and

36、liquid phase film thickness shall allow the elution of at leastC90 n-paraffin (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 resoluti

37、onbetween three (3) and ten (10) using the test method operatingconditions.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 crite

38、ria 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 mV to 1 mV range recording potenti-ometer or equivalent with a full-scale response time of2sorless may be used. It is, however, not a n

39、ecessity if anintegrator/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 electronic integrator or computer-basedchromatography data system. The integrator/computer systemshall have normal

40、chromatographic software for measuring theretention time and areas of eluting 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 analysi

41、s, 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 2Some gas chromatographs have an algorithm built into theiroperating software that allows a mathematical mo

42、del 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 automaticallysubtract a blank analysis from subsequent analytical determinations.7.

43、 Reagents and Materials7.1 Carrier GasHelium, hydrogen, or nitrogen of highpurity. The use of alternative carrier gases hydrogen andnitrogen is described in Appendix X2.(WarningHelium andnitrogen are compressed gases under high pressure)Additionalpurification is recommended by the use of molecular s

44、ieves orother suitable agents to remove water, oxygen, and hydrocar-bons.Available pressure shall be sufficient to ensure a constantcarrier 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 as the carrier gas. (Wa

45、rningHydrogen 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 indicated, it is intended

46、thatall solvents conform to the specifications of the Committee onAnalytical Reagents of the American Chemical Society wheresuch specifications are available.4Other grades may be used,provided it is first ascertained that the solvent is of sufficientlyhigh purity to permit its use without lessening

47、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 hydrocarbons and provides a r

48、elatively 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 of the calibration mixtu

49、re.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 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,