ASTM D7798-2013 1875 Standard Test Method for Boiling Range Distribution of Petroleum Distillates with Final Boiling Points up to 538° C by Ultra Fast Gas Chromatography (UF GC).pdf

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1、Designation: D7798 13Standard Test Method forBoiling Range Distribution of Petroleum Distillates withFinal Boiling Points up to 538C by Ultra Fast GasChromatography (UF GC)1This standard is issued under the fixed designation D7798; the number immediately following the designation indicates the year

2、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 the boilingr

3、ange distribution of petroleum products and biodieselformulations, B5, B10, and B20. It is applicable to petroleumdistillates having a final boiling point not greater than 538C orlower at atmospheric pressure as measured by this test method.The difference between the initial boiling point and the fi

4、nalboiling point shall be greater than 55C.1.2 The test method is not applicable for analysis ofpetroleum distillates containing low molecular weight compo-nents (for example naphthas, reformates, gasolines, full rangecrude oils). Materials containing heterogeneous mixtures (forexample, alcohols, et

5、hers, acids or esters, except biodiesels) orresidue are not to be analyzed by this test method. See TestMethods D3710, D7096, D6352,orD7169.1.3 This test method uses the principles of simulated distil-lation methodology. This test method uses gas chromato-graphic components that allow the entire ana

6、lysis from sampleto sample to occur in 5 min or less. In these instruments thecolumn is heated directly at rates 1015 times that of aconventional gas chromatograph and thus the analysis time isreduced from sample to sample.1.4 The values stated in SI units are to be regarded asstandard. No other uni

7、ts of measurement are included in thisstandard.1.4.1 ExceptionAppendix X1 includes temperatures inFahrenheit for information only.1.5 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 establis

8、h 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 atAtmospheric PressureD1160 Test Method for Distillation of Petroleum Products atReduce

9、d PressureD2887 Test Method for Boiling Range Distribution of Pe-troleum Fractions by Gas ChromatographyD2892 Test Method for Distillation of Crude Petroleum(15-Theoretical Plate Column)D3710 Test Method for Boiling Range Distribution of Gaso-line and Gasoline Fractions by Gas ChromatographyD4626 Pr

10、actice for Calculation of Gas ChromatographicResponse FactorsD6352 Test Method for Boiling Range Distribution of Pe-troleum Distillates in Boiling Range from 174 to 700C byGas ChromatographyD6708 Practice for Statistical Assessment and Improvementof Expected Agreement Between Two Test Methods thatPu

11、rport to Measure the Same Property of a MaterialD7096 Test Method for Determination of the Boiling RangeDistribution of Gasoline by Wide-Bore Capillary GasChromatographyD7169 Test Method for Boiling Point Distribution ofSamples with Residues Such as Crude Oils and Atmo-spheric and Vacuum Residues by

12、 High Temperature GasChromatographyE355 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 Gas Chromatographs3. Termin

13、ology3.1 Definitions: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 Jan. 1, 2013. Published April 2013. DOI: 10.1520/D7798

14、-13.2For 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.Copyright ASTM International, 100 Barr Harbor Drive, PO B

15、ox C700, West Conshohocken, PA 19428-2959. United States13.1.1 This test method makes reference to many commongas chromatographic procedures, terms, and relationships.Detailed definitions of these can be found in Practices E355,E594, and E1510.3.1.2 area slice, nin gas chromatography, the area, resu

16、lt-ing from the integration of the chromatographic detectorsignal, within a specified retention time interval.3.1.3 corrected area slice, nin gas chromatography,anarea slice corrected for baseline offset, by subtraction of thecorresponding area slice in a previously recorded blank (non-sample) analy

17、sis.3.1.4 cumulative corrected area, nin gaschromatography, the accumulated sum of corrected area slicesfrom the beginning of the analysis through to a given retentiontime, ignoring any non-sample areas (for example, solventpeak area).3.1.5 Final Boiling Point (FBP), nin gaschromatography, the tempe

18、rature (corresponding to the reten-tion time) at which a cumulative corrected area count equal to99.5 % of the total sample area under the chromatogram isobtained.3.1.6 Initial Boiling Point (IBP), nin gaschromatography, the temperature (corresponding to the reten-tion time) at which a cumulative co

19、rrected area count equal to0.5 % of the total sample area under the chromatogram isobtained.3.1.7 slice rate, nin gas chromatography, the time intervalused to integrate the continuous (analog) chromatographicdetector response during an analysis, expressed in Hz.3.1.7.1 Discussionfor example, integra

20、tions or slices persecond.3.1.8 slice time, nin gas chromatography, the time dura-tion of the slice, in seconds.The slice time is the time at the endof each contiguous area slice.3.1.9 total sample area, nin gas chromatography, thecumulative corrected area, from the initial area point to thefinal ar

21、ea point.3.2 Abbreviations:3.2.1 Acommon abbreviation of hydrocarbon compounds isto designate the number of carbon atoms in the compound. Aprefix is used to indicate the carbon chain form, while asubscripted suffix denotes the number of carbon atoms (forexample, n-Cl0normal decane; iCl4= iso tetrade

22、cane).4. Summary of Test Method4.1 The boiling range distribution of hydrocarbon fractionsobtained by physical distillation is simulated by the use of gaschromatography (GC). The GC column heating is accom-plished by supplying heat to the column directly instead of anoven with a consequence that the

23、 elution time is considerablyshortened. Thus, cycle times of 5 min or less (heating andcooling) is achieved. A non-polar capillary gas chromato-graphic column is used to separate the hydrocarbon compo-nents of the sample and cause them to elute in order ofincreasing boiling point.4.2 Depending on th

24、e analyzer and column used, a samplealiquot is diluted with a viscosity reducing solvent or intro-duced neat into the chromatographic system. Sample vaporiza-tion is provided by separate heating of the point of injection orin conjunction with column oven heating.4.3 The column temperature is raised

25、at a reproduciblelinear rate to effect separation 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 integral is recorded as areaslices for consecutive retention time

26、intervals during theanalysis.4.4 Retention times of known normal paraffin hydrocarbons,spanning the scope of the test method (C5C44), are determinedand correlated to their boiling point temperatures. (Refer toTable 1.) The normalized cumulative corrected sample areasfor each consecutive recorded tim

27、e interval are used tocalculate the boiling range distribution. The boiling pointtemperature at each reported percent off increment is calculatedfrom the retention time calibration.5. Significance and Use5.1 The boiling range distribution of petroleum distillatefractions provides an insight into the

28、 composition of feedstocks and products related to petroleum refining processes. Amajor advantage of the fast analysis time obtained by this testmethod is increasing product through put and reduced labtesting time by a minimum factor of 3. This gas chromato-graphic determination of boiling range may

29、 be used to replaceconventional distillation methods for control of refining opera-tions and for product specification testing with the mutualagreement of interested parties.5.2 Boiling range distributions obtained by this test methodare essentially equivalent to those obtained by true boilingpoint

30、(TBP) distillation (see Test Method D2892). They are notequivalent to results from low efficiency distillations such asthose obtained with Test Method D86 or D1160.6. Apparatus6.1 ChromatographThe gas chromatographic system usedshall have the following performance characteristics:6.1.1 Column Heatin

31、g AssemblyCapable of sustaining aprogrammed temperature operation from 40C up to 400C.6.1.2 Column Temperature ProgrammerThe columnshould be capable of linear programmed temperature operationup to 400C at selectable linear rates from a minimum of60C/min up to 350C/min. The programming rate shall bes

32、ufficiently reproducible to obtain the retention time repeatabil-ity for the mixture described in 7.6.6.1.3 DetectorThis test method requires a flame ioniza-tion detector (FID). The detector shall meet or exceed thefollowing specifications as detailed in Practice E594. Theflame jet should have an or

33、ifice of approximately 0.018 inchesor 0.45 mm or as specified by the manufacturer.6.1.3.1 Operating Temperature approximately 380400C.6.1.3.2 Sensitivity 0.005 coulombs/ g carbon.6.1.3.3 Minimum Detectability110-12g carbon / s forn-C13.D7798 1326.1.3.4 Linear Range 106.6.1.3.5 Connection of the colu

34、mn to the detector shall besuch that no temperature below the column inlet temperatureexists. Refer to E1510 for proper installation and conditioningof the capillary column.6.1.4 Sample Inlet SystemAny sample inlet system ca-pable of operating continuously at a temperature equivalent tothe maximum c

35、olumn temperature employed. Programmedtemperature vaporization (PTV) and programmable cool on-column injection and split injection systems have been usedsuccessfully. Table 2 gives some examples of operating con-ditions of commercially available instrumentation. The inletshould be capable to continu

36、ously deliver the sample compo-nents in to the column by maintaining the temperature higherthan the column temperature.6.1.5 Carrier Gas Flow ControlThe chromatograph shallbe equipped with carrier gas pressure or flow control capable ofmaintaining constant carrier gas flow control through thecolumn

37、throughout the column temperature program cycle.The flow shall not vary by more than 1 % from the initialtemperature to the end column temperature.6.2 MicrosyringeSyringes of 0.1 to 5 L capacity aresuitable for this test method. Consult manufacturer for specificdetails on requirements for syringes c

38、ompatible with autosam-pler and injection technique used.6.2.1 Automatic syringe injection is required to achieve bestprecision.6.3 ColumnThis test method is limited to the use ofnon-polar wall coated open tubular (WCOT) columns of highthermal stability. Fused silica, and stainless steel columns, wi

39、tha 0.320.18 mm inside diameter have been successfully used.Cross-linked or bonded 100 % dimethyl-polysiloxane station-ary phases with film thickness of 0.1 to 1.0 m have been used.It is required that the choice of these two variables (column i.d.and phase thickness) allow the elution of C5to C44dur

40、ing thetemperature programming phase of the column. The columnand conditions shall provide separation of typical petroleumhydrocarbons in order of increasing boiling point and meet thecolumn resolution requirements of 8.2.1. The column shallprovide a resolution of at least three (3) using the test m

41、ethodoperating conditions. Table 2 gives some examples of columnsused successfully.6.4 Data Acquisition System:6.4.1 ComputerMeans shall be provided for determiningthe accumulated area under the chromatogram. This can bedone by means of a computer based chromatography datasystem. The computer system

42、 shall have normal chromato-graphic software for measuring the retention time and areas ofeluting peaks (peak detection mode). In addition, the systemshall be capable of converting the continuously integrateddetector signal into area slices of fixed duration (area slicemode). These contiguous area s

43、lices, collected for the entireanalysis, are stored for later processing. Gas Chromatographswith analog to digital conversion of the detector signal, shall beoperated within the linear range of the detector/electrometersystem used. Since the chromatogram is developing in a veryshort time and since t

44、he peaks elute at a fast rate, it is necessaryto acquire the signals at 50100 hz.7. Reagents and Materials7.1 Carrier GasHelium, or hydrogen of high purity(99.999 %) have been used as shown in Table 2.(WarningSee Notes 1 and 2.)Additional purification is recommended bythe use of molecular sieves or

45、other suitable agents to removewater, oxygen, and hydrocarbons. Available pressure shall besufficient to ensure a constant carrier gas flow rate.NOTE 1Warning: Helium and Hydrogen are compressed gases underhigh pressure.NOTE 2Warning: Hydrogen is an extremely flammable gas.TABLE 1 Boiling Points of

46、n-ParaffinsA,BCarbonNumberBoilingPoint, CBoilingPoint, F536976 69 1567 98 2098 126 2589 151 30310 174 34511 196 38512 216 42113 235 45614 254 48815 271 51916 287 54817 302 57618 316 60119 330 62620 344 65121 356 67422 369 69523 380 71624 391 73625 402 75526 412 77427 422 79128 431 80829 440 82530 44

47、9 84031 458 85632 466 87033 474 88534 481 89835 489 91236 496 92537 503 93738 509 94839 516 96140 522 97241 528 98242 534 99343 540 100444 545 1013AAPI Project 44, October 31, 1972 is believed to have provided the original normalparaffin boiling point data that are listed in Table 1. However, over t

48、he years someof the data contained in both API Project 44 (Thermodynamics Research CenterHydrocarbon Project) and Test Method D2887 have changed, and they are nolonger equivalent. Table 1 represents the current normal paraffin boiling pointvalues accepted by Subcommittee D02.04 and found in all test

49、 methods under thejurisdiction of Section D02.04.0H.BTest Method D2887 has traditionally used n-paraffin boiling points rounded to thenearest whole degree for calibration. The boiling points listed in Table 1 are correctto the nearest whole number in both degrees Celsius and degrees Fahrenheit.However, if a conversion is made from one unit to the other and then rounded toa whole number, the result will not agree with the table value for a few carbonnumbers. For example, the boiling point of n-heptane is 98.425C, which iscorrectly rounded to