1、Designation: D7807 12Standard Test Method forDetermination of Boiling Range Distribution of Hydrocarbonand Sulfur Components of Petroleum Distillates by GasChromatography and Chemiluminescence Detection1This standard is issued under the fixed designation D7807; the number immediately following the d
2、esignation 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
3、 determination of the boilingrange distribution of petroleum products. The test method isapplicable to petroleum products and fractions having a finalboiling point of 538C (1000F) or lower at atmosphericpressure as measured by this test method. This test method islimited to samples having a boiling
4、range greater than 55C(100F), and having a vapor pressure sufficiently low to permitsampling at ambient temperature.1.1.1 The applicable sulfur concentration range will vary tosome extent depending on the boiling point distribution of thesample and the instrumentation used; however, in most cases,th
5、e test method is applicable to samples containing levels ofsulfur above 10 mg/kg.1.2 This test method requires the use of both FID and SCDfor detection. The hydrocarbon simulated distillation dataobtained from the FID signal should be performed according toTest Method D2887.1.3 The test method is no
6、t applicable for analysis ofpetroleum distillates containing low molecular weight compo-nents (for example, naphthas, reformates, gasolines, crudeoils). Materials containing heterogeneous components (forexample, alcohols, ethers, acids or esters) or residue are not tobe analyzed by this test method.
7、 See Test Methods D3710,D7096, D5307, D7169,orD7500.1.4 This test method does not purport to identify all sulfurspecies in a sample. The detector response to sulfur isequimolar for all sulfur compounds within the scope (1.1)ofthis test method. Thus, unidentified sulfur compounds aredetermined with e
8、qual precision to that of identified sub-stances. Total sulfur content is determined from the total areaof the sulfur detector.1.4.1 This test method uses the principles of simulateddistillation methodology.1.5 The values stated in SI units are to be regarded asstandard. The values given in parenthe
9、ses are for informationonly.1.6 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 limitations
10、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 atReduced PressureD2622 Test Method for Sulfur in Petroleum Products byWavelength Dispersive X-ray Fluorescenc
11、e SpectrometryD2887 Test Method for Boiling Range Distribution of Pe-troleum Fractions by Gas ChromatographyD2892 Test Method for Distillation of Crude Petroleum(15-Theoretical Plate Column)D3120 Test Method for Trace Quantities of Sulfur in LightLiquid Petroleum Hydrocarbons by Oxidative Microcou-l
12、ometryD3710 Test Method for Boiling Range Distribution of Gaso-line and Gasoline Fractions by Gas ChromatographyD4307 Practice for Preparation of Liquid Blends for Use asAnalytical StandardsD4626 Practice for Calculation of Gas ChromatographicResponse FactorsD5307 Test Method for Determination of Bo
13、iling RangeDistribution of Crude Petroleum by Gas Chromatography(Withdrawn 2011)3D5504 Test Method for Determination of Sulfur Compounds1This test method is under the jurisdiction of ASTM Committee D02 onPetroleum Products and Lubricants and is the direct responsibility of SubcommitteeD02.04.0H on C
14、hromatographic Distribution Methods.Current edition approved Dec. 15, 2012. Published April 2013. DOI: 10.1520/D7807-12.2For 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
15、 to the standards Document Summary page onthe ASTM website.3The last approved version of this historical standard is referenced onwww.astm.org.Copyright ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959. United States1in Natural Gas and Gaseous Fuels by Gas Chr
16、omatogra-phy and ChemiluminescenceD5623 Test Method for Sulfur Compounds in Light Petro-leum Liquids by Gas Chromatography and Sulfur Selec-tive DetectionD6299 Practice for Applying Statistical Quality Assuranceand Control Charting Techniques to Evaluate AnalyticalMeasurement System PerformanceD6300
17、 Practice for Determination of Precision and BiasData for Use in Test Methods for Petroleum Products andLubricantsD6352 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 RangeD
18、istribution 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 High Temperature GasChromatographyD7500 Test Method for Determination of Boiling RangeDistribution of Di
19、stillates and Lubricating Base OilsinBoiling Range from 100 to 735C by Gas Chromatogra-phyE178 Practice for Dealing With Outlying ObservationsE355 Practice for Gas Chromatography Terms and Relation-shipsE594 Practice for Testing Flame Ionization Detectors Usedin Gas or Supercritical Fluid Chromatogr
20、aphyE1510 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. Detailed definitions of these can be found in PracticesE355, E594,
21、and E1510.3.2 Definitions of Terms Specific to This Standard:3.2.1 area slice, nthe area, resulting from the integrationof the chromatographic detector signal, within a specifiedretention time interval. Peak detection parameters are bypassedand the detector signal integral is recorded as area slices
22、 ofconsecutive, fixed duration time intervals.3.2.2 corrected area slice, nan area slice corrected forbaseline offset, by subtraction of the exactly correspondingarea slice in a previously recorded blank (non-sample) analy-sis.3.2.3 cumulative corrected area, nthe accumulated sum ofcorrected area sl
23、ices 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 the total sample area under
24、thechromatogram is obtained.3.2.5 initial boiling point (IBP), nthe temperature (corre-sponding to the retention time) at which a cumulative correctedarea equal to 0.5 % of the total sample area under thechromatogram is obtained.3.2.6 response factor (RF), nthe factor used in order tocalculate the m
25、g/kg Sulfur recovery of the sample.3.2.7 slice rate, nthe time interval used to integrate thecontinuous (analog) chromatographic detector response duringan analysis. The slice rate is expressed in Hz (for example,integrations or slices per second).3.2.8 slice time, nthe cumulative slice rate (analys
26、is time)associated with each area slice throughout the chromatographicanalysis. The slice rate is the time at the end of each contiguousarea slice.3.2.9 total sample area, nthe cumulative corrected areafrom the initial point to the final area point.3.3 AbbreviationsAcommon abbreviation of hydrocarbo
27、ncompounds 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, normal decane n-C10, iso-tetradecane = i-C14).4. Summary of Test Method4.1 The boiling range distributio
28、n determination by distilla-tion is simulated by the use of gas chromatography.Anonpolaropen tubular (capillary) gas chromatographic column is used toelute the hydrocarbon components of the sample in order ofincreasing boiling point. The column temperature is raised at areproducible linear rate and
29、the area under the chromatogram isrecorded throughout the analysis. Boiling points are assignedto the time axis from a calibration curve obtained under thesame chromatographic conditions by analyzing a known mix-ture of hydrocarbons covering the boiling range expected in thesample. A quantitative st
30、andard is used to determine the SCDdetector response factor. Finally, the sample solution is injectedand with the use of the response factor, the amount of samplerecovered is calculated. After converting the retention times ofthe sample slices to temperature, the boiling point distributioncan be cal
31、culated up to the recovered amount. From these data,the boiling range distribution can be obtained.4.1.1 By splitting the column effluent to FID and SulfurChemiluminescence Detector, simultaneous detection for Hy-drocarbon (FID) and Sulfur (SCD) components boiling rangedistribution is obtained. The
32、Hydrocarbon simulated distilla-tion data should be calculated according to Test MethodD2887.4.1.2 Alternatively, the FID may be used with the SCDdetector superimposed over the FID and thus avoiding splittingthe sample through the column exit. This type of arrangementwill lower the sensitivity of the
33、 detector in the sulfur mode.4.2 Asample aliquot is introduced into the chromatographicsystem. Sample vaporization is provided by separate heating ofthe point of injection or in conjunction with column ovenheating.4.3 The column oven temperature is raised at a reproduciblelinear rate to effect separ
34、ation of the sample components inD7807 122order of increasing boiling point. The elution of samplecomponents is quantitatively determined using a flame ioniza-tion detector and a sulfur chemiluminescence detector. Thedetector signal integral is recorded as area slices for consecu-tive retention time
35、 intervals during the analysis.4.4 Retention times of known normal paraffin hydrocarbonsspanning the scope of this test method (C5- C44) are deter-mined and correlated to their theoretical boiling point tempera-tures. The normalized cumulative corrected sample areas foreach consecutive recorded time
36、 interval are used to calculatethe boiling range distribution. The boiling point temperature ateach reported percent off increment is calculated from theretention time calibration.4.5 Sulfur Chemiluminescence DetectionAs sulfur com-pounds elute from the gas chromatographic column, they areprocessed
37、in a heated combustion zone. The products arecollected and transferred to a sulfur chemiluminescence detec-tor (SCD). This technique provides a sensitive, selective, linearresponse to volatile sulfur compounds and is used for theselective sulfur detection, while collecting hydrocarbon datafrom the F
38、ID.4.6 Alternative DetectorsThis test method is written forthe sulfur chemiluminescence detector but other sulfur specificdetectors can be used provided they have sufficient linearity,sensitivity and have equimolar response to all eluted sulfurcompounds, do not suffer from interferences, and satisfy
39、quality assurance criteria. Regulatory agencies may requiredemonstration of equivalency of alternative detection systemsto the SCD.5. Significance and Use5.1 The boiling range distribution of light and mediumpetroleum distillate fractions provides an insight into thecomposition of feed stocks and pr
40、oducts related to petroleumrefining processes. This gas chromatographic determination ofboiling range can be used to replace conventional distillationmethods for control of refining operations. This test methodcan be used for product specification testing with the mutualagreement of interested parti
41、es.5.2 This test method extends the scope of Test MethodD2887 (538C) boiling range determination by gas chroma-tography to include sulfur boiling range distribution in thepetroleum distillate fractions. Knowledge of the amount ofsulfur and its distribution in hydrocarbons is economicallyimportant in
42、 determining product value and in determininghow best to process or refine intermediate products. Sulfurcompounds are known to affect numerous properties of petro-leum and petrochemical products. The corrosion of metals andpoisoning of catalysts is of particular concern. In addition, thecontent of s
43、ulfur in various refined products may be subject togovernmental regulations. Test Methods, such as, D2622,D3120, D5504 and D5623, are available to determine totalsulfur content or content of individual sulfur compounds inpetroleum and petroleum products. Test Methods, such as,D86, D1160, D2887, D371
44、0, D2892, are also available todetermine the hydrocarbon boiling ranges of such samples. Thegas chromatographic determination of the sulfur boiling rangeassists in process development, in treatment and control ofrefining operations and is useful for assessing product quality.This determination produ
45、ces detailed information about thesulfur distribution in a sample that cannot be obtained by eithertotal sulfur analysis or analysis of sulfur in discreet distillationcuts.5.2.1 The hydrocarbon boiling range distributions obtainedby Test Method D2887 are theoretically equivalent to thoseobtained by
46、true boiling point (TBP) distillation (see TestMethod D2892). They are not equivalent to results from lowefficiency distillation such as those obtained with Test MethodD86 or D1160.6. Apparatus6.1 ChromatographAny gas chromatograph, with hard-ware necessary for interfacing to a chemiluminescence det
47、ectorand containing all features necessary for the intended applica-tion(s) can be used. The gas chromatographic system used shallhave the following performance characteristics:6.2 Column Temperature ProgrammerThe chromatographmust be capable of linear programmed temperature operationover a range su
48、fficient to elute compounds up to a boilingtemperature of 538C (1000F) before reaching the upper endof the temperature program. The programming rate must besufficiently reproducible to obtain retention time repeatabilityof 0.01 min (0.6 s, corresponding to approximately 0.5C) foreach component in th
49、e calibration mixture described in 7.7.6.3 DetectorsThis test method requires a Flame IonizationDetector (FID) and a Sulfur Chemiluminescence Detector(SCD).6.3.1 FIDThe FID shall meet or exceed the followingspecifications in accordance with Practice E594. Check thedetector according the instrument manufacturers instructions.6.3.2 SCDThe sulfur chemiluminescence detector shallmeet or exceed the following specifications: (1) greater than103linearity, (2) less than 1 pg S/s sensitivity, (3) greater than106selectivity for sulfur compounds over hydrocarbons, (
