1、Designation: D 7169 05An American National StandardStandard Test Method forBoiling Point Distribution of Samples with Residues Suchas Crude Oils and Atmospheric and Vacuum Residues byHigh Temperature Gas Chromatography1This standard is issued under the fixed designation D 7169; the number immediatel
2、y following the designation 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 (e) indicates an editorial change since the last revision or reapproval.1. Scope1.1 This test
3、 method covers the determination of the boilingpoint distribution and cut point intervals of crude oils andresidues by using high temperature gas chromatography. Theamount of residue (or sample recovery) is determined using anexternal standard.1.2 This test method extends the applicability of simula
4、teddistillation to samples that do not elute completely from thechromatographic system. This test method is used to determinethe boiling point distribution through a temperature of 720C.This temperature corresponds to the elution of n-C100.1.3 This test method is used for the determination of boilin
5、gpoint distribution of crude oils. This test method uses capillarycolumns with thin films, which results in the incompleteseparation of C4-C8in the presence of large amounts of carbondisulfide, and thus yields an unreliable boiling point distribu-tion corresponding to this elution interval. In addit
6、ion, quench-ing of the response of the detector employed to hydrocarbonseluting during carbon disulfide elution, results in unreliablequantitative analysis of the boiling distribution in the C4-C8region. Since the detector does not quantitatively measure thecarbon disulfide, its subtraction from the
7、 sample using asolvent-only injection and corrections to this region viaquenching factors, results in an approximate determination ofthe net chromatographic area.Aseparate, higher resolution gaschromatograph (GC) analysis of the light end portion of thesample may be necessary in order to obtain a mo
8、re accuratedescription of the boiling point curve in the interval in question(see Appendix X1).1.4 This test method is also designed to obtain the boilingpoint distribution of other incompletely eluting samples such asatmospheric residues, vacuum residues, etc., that are charac-terized by the fact t
9、hat the sample components are resolvedfrom the solvent.1.5 This test method is not applicable for the analysis ofmaterials containing a heterogeneous component such aspolyesters and polyolefins.1.6 The values stated in inch-pound units are to be regardedas standard. The values given in parentheses a
10、re mathematicalconversions to SI units that are provided for information onlyand are not considered standard.1.7 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
11、 and health practices and determine the applica-bility of regulatory limitations prior to use. Specific warningstatements are given in Section 8.2. Referenced Documents2.1 ASTM Standards:2D 2887 Test Method for Boiling Range Distribution ofPetroleum Fractions by Gas ChromatographyD 2892 Test Method
12、for Distillation of Crude Petroleum(15-Theoretical Plate Column)D 4057 Practice for Manual Sampling of Petroleum andPetroleum ProductsD 6352 Test Method for Boiling Range Distribution ofPetroleum Distillates in Boiling Range from 174 to 700Cby Gas ChromatographyD 6729 Test Method for Determination o
13、f Individual Com-ponents in Spark Ignition Engine Fuels by 100m Capil-lary High Resolution Gas ChromatographyD 6730 Test Method for Determination of Individual Com-ponents in Spark Ignition Engine Fuels by 100m Capil-lary (with Precolumn) High-Resolution Gas Chromatogra-phyE 594 Practice for Testing
14、 Flame Ionization Detectors Usedin Gas or Supercritical Fluid ChromatographyE 1510 Practice for Installing Fused Silica Open TubularCapillary Columns in Gas Chromatographs3. Terminology3.1 Definitions of Terms Specific to This Standard:1This test method is under the jurisdiction of ASTM Committee D0
15、2 onPetroleum Products and Lubricants and is the direct responsibility of SubcommitteeD02.04 on Hydrocarbon Analysis.Current edition approved July 1, 2005. Published September 2005.2For referenced ASTM standards, visit the ASTM website, www.astm.org, orcontact ASTM Customer Service at serviceastm.or
16、g. For Annual Book of ASTMStandards volume information, refer to the standards Document Summary page onthe ASTM website.1Copyright ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959, United States.3.1.1 cut point interval, nthe mass % obtained betweentwo selecte
17、d temperatures of the interval.3.1.2 data acquisition rate, nthe speed of conversion ofthe analog signal to a digital signal, expressed in Hz (cycles/second).3.1.3 final boiling point (FBP), nthe temperature, forfully eluting samples (recovery = 100 %), at which 99.5 % ofthe sample is eluted.3.1.4 f
18、inal elution time (FEt), nthe retention time of thecomponent of the reference time standard sample that elutes atthe end of the temperature ramp of the oven.3.1.5 final elution temperature (FET), nthe boiling pointof the normal paraffin that elutes at the time when the ovenreaches its final temperat
19、ure.3.1.6 initial boiling point (IBP), nthe temperature corre-sponding to an accumulated 0.5 % of the total area of the elutedsample after correcting for the percent of sample recovery.3.1.7 quenching factor (QF), na number that corrects forthe diminished response due to the solvent profile co-eluti
20、ngwith sample components.3.1.7.1 DiscussionData acquired during the quenchinginterval (QI) shall be corrected by applying the quenchingfactor.3.1.8 quenching interval (QI), nthe time interval of thestart and end of elution of the CS2used as a solvent.3.1.8.1 DiscussionSample components that elute du
21、ringthis time interval shall be corrected by a factor due to theirdiminished response resulting from the co-elution of therelatively large amount of solvent present in the sample withthe light sample components.3.1.9 residue (R), nthe mass % of the sample that has noteluted at the temperature of cal
22、culation.3.1.9.1 DiscussionResidue is calculated from the %recov-ery.3.1.10 response factor (RF), nthe factor used in order tocalculate the %recovery of the sample.3.1.10.1 DiscussionThe response factor is determinedfrom the net area of the standard (ASTD), mass of standard(MSTD), and mass of solven
23、t (MSLSTD) used in the solution ofthe standard. A fully eluting sample, such as Reference Oil5010, is used in obtaining the response factor.3.1.11 sample area obtained (ASMP), nthe net chromato-graphic area (after baseline subtraction) obtained for thesample at the final elution time or temperature.
24、3.1.12 slice, nthe reciprocal of the data acquisition rate;the time interval used to accumulate data, expressed in sec-onds.3.1.12.1 DiscussionNormally 0.1 s is used. In caseswhere sample elutes immediately after injection, 0.05 s is used.3.1.13 start elution temperature (SET), nthe temperatureat wh
25、ich the first amount of hydrocarbon is detected by theflame ionization detector above a predetermined threshold.3.1.14 %recovery (RC), npercentage of the sample eluted.3.1.14.1 Discussion%Recovery is calculated from thesample area (ASMP), the response factor (RF), the sample mass,(MSMP), and the sol
26、vent mass (MSLSMP) used in sampledissolution.3.1.15 %recovery threshold (Rt), nif the %recovery fallsabove a preset limit, the sample is considered fully eluted andits recovery is assumed to be 100 %.3.1.15.1 DiscussionIf the %recovery values found forduplicate analyses of a nearly completely elutin
27、g sample are99.6 and 101.2 %, the %recovery threshold (Rt) may be set to99.6 % and thus either of these results may be considered asfully eluted and set to 100 %.3.2 Symbols:ASMP= net area of the sampleASTD= net area of the response factor standardMSL= mass of solvent used in preparing sample soluti
28、onMSLSTD= mass of solvent used in preparing the responsefactor standard solutionMSMP= sample mass used in sample preparationMSTD= mass of the standard used in preparing the responsefactor solution4. Summary of Test Method4.1 This is a gas chromatographic method utilizing an inletand a capillary colu
29、mn, both of which are subject to atemperature program. A flame ionization detector is used as atransducer that converts mass to an electrical signal A dataacquisition system operating in the slice mode and chromatog-raphy software is used to accumulate the electronic signal. Aretention time calibrat
30、ion mixture is used to develop a retentiontime versus boiling point curve.Asolution of the Reference Oil5010, which fully elutes from the column under the conditionsof the test method and whose boiling point distribution hasbeen characterized in Test Method D 6352, is used to deter-mine the detector
31、 response factor. Solvent injections are made,and the resulting signal is subtracted from both the responsefactor standard and the sample chromatogram. Finally, thesample solution is injected and with the use of the responsefactor, the amount of sample recovered is calculated. Afterconverting the re
32、tention times of the sample slices to tempera-ture, the boiling point distribution can be calculated up to therecovered amount.5. Significance and Use5.1 The determination of the boiling point distribution ofcrude oils and vacuum residues, as well as other petroleumfractions, yields important inform
33、ation for refinery operation.These boiling point distributions provide information as to thepotential mass percent yield of products. This test method mayprovide useful information that can aid in establishing opera-tional conditions in the refinery. Knowledge of the amount ofresidue produced is imp
34、ortant in determining the economics ofthe refining process.6. Apparatus6.1 Gas ChromatographA gas chromatograph providedwith a cryogenic valve for cooling the oven to sub ambienttemperatures is required. The conditions of operating the GasChromatograph are given in Table 1. It shall also have thefol
35、lowing components:6.1.1 Flame Ionization Detector (FID)A flame ionizationdetector capable of maintaining a temperature 5 to 10C higherD7169052than the highest column temperature. The flame ionizationdetector should possess a jet orifice of about 0.018 in. (0.45mm) in order to delay the plugging of t
36、he orifice due to columnbleed. The FID should possess a sensitivity of 0.005coulombs/g (see Practice E 594) and should have a linear rangeof 106.6.1.2 InletEither a temperature programmable inlet with aglass liner or a cool-on-column inlet can be used. The inletshall be capable of operating in a tem
37、perature-programmedmode from 50C to the final temperature of the oven. It isimportant that the temperature of the inlet, at any time duringthe analysis, be either equal to or greater than the oventemperature. With the use of either inlet, frequent replacementof the liner or removal of a section of t
38、he column may berequired due to accumulation of non-volatile sample compo-nents. It is important that a leak free seal be reestablished afterreplacement of the liner or the removal of a small section of thecolumn.6.2 Carrier Gas Purification SystemGas purifiers are usedin order to remove traces of o
39、xygen as well as moisture andother impurities present in the carrier gas. The purificationsystem should contain a hydrocarbon trap and an oxygen trap.The latter should preferably have a visible indicator in order toassess the remaining capacity of the oxygen trap.6.3 Data SystemA data system compose
40、d of a computerand software for data acquisition, which digitizes the detectorsignal, is recommended. Some instrumentation digitizes thesignal at the electrometer board in order to reduce noise. Thedata system is used at acquisition rates of about 10 Hz, whichcorrespond to slices of 0.1 s. This rate
41、 of data acquisition isnecessary to obtain a minimum number of slices void ofsample or solvent elution immediately after injection. Dataacquisition systems facilitate the inspection of the baselineunder high magnification and allow the inspection of theretention time calibration mixture chromatogram
42、. Retentiontime shifts can be measured. Overlaying chromatograms is alsopossible to ascertain similar signal amplitude.6.4 IntegratorAn integrator that digitizes the signal canalso be used to acquire chromatograms of the retention timecalibration mixture, the sample, the solvent and the referenceoil
43、 standard.6.5 Automatic Sample InjectorIt is mandatory to use anauto sampler since the external standard technique used in thisanalysis requires identical volumes for all injections.Addition-ally, small volumes (0.1 to 0.2 L) shall be injected in areproducible manner. Syringes of 5 to 10 L having ne
44、edlegauges of size 23 to 26 are to be used.6.6 Carrier Gas ControlThe gas chromatograph shall beoperated under constant flow conditions. The flow rate at thebeginning of the oven temperature program shall not differ bymore than 1 % from the flow measured at the final oventemperature. Electronic pneu
45、matic control is highly recom-mended.7. Column and Column Performance Criteria7.1 A100 % bonded polydimethylsiloxane column having anominal inside diameter of 0.5 mm and a film thickness of 0.09to 0.17 m is used.7.2 The column used should be capable of sustainingtemperatures of 435C under temperatur
46、e programming. Alu-minum covered fused silica and metal columns have beensuccessfully used.7.3 The column should be capable of eluting carbon number100 at its highest temperature. It is important that C100beeluted during the temperature program cycle of the oven.7.4 Column resolution is determined f
47、rom the separation ofcarbons 50 and 52 in the retention time calibration mixturechromatogram. The resolution should be between 1.8 to 4.0.See Eq 1 in 13.1.7.5 The column shall be capable of allowing the start of theelution of n-C5prior to the solvent elution, which is CS2,at20C. The descending edge
48、of the n-C5peak co-elutes withthe solvent. It is to be noted that at these low temperaturesliquid phases may turn solid, and retention shifts may beobserved during the elution of compounds at these low oventemperatures.7.6 Column OverloadingThe prevention of column over-loading is carried out by det
49、ermining the skewness of aselected peak among the components of the retention timecalibration mixture chromatogram. Any paraffin with a carbonnumber between C12and C24may be chosen. The skewnessshould be between 0.8 to 1.2. See Eq 2 in 13.2.7.7 Column FlowHelium is used as carrier. Column flowrate is set to 20 mL/min.8. Reagents and Materials8.1 Carbon Disulfide (CS2), 99+ % pure. (WarningExtremely flammable and toxic liquid.) Used as a solvent todilute the sample and standards as well.8.2 Polywax 655 or Polywax 1000Used as a componentof the
