ASTM D2427-2006(2015) Standard Test Method for Determination of C2 through C5 Hydrocarbons in Gasolines by Gas Chromatography《使用气相色谱法测定汽油中C2至C5烃的标准试验方法》.pdf

1、Designation: D2427 06 (Reapproved 2015)Standard Test Method forDetermination of C2through C5Hydrocarbons in Gasolinesby Gas Chromatography1This standard is issued under the fixed designation D2427; the number immediately following the designation indicates the year oforiginal adoption or, in the cas

2、e 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 two(C2) through five(C5-) carbon paraffins

3、 and mono-olefins ingasolines. The concentrations by volume or mass (weight) ofthe following components are generally reported:1.1.1 Ethylene plus ethane1.1.2 Propane1.1.3 Propylene1.1.4 Isobutane1.1.5 n-Butane1.1.6 Butene-1 plus isobutylene1.1.7 trans-Butene-21.1.8 cis-Butene-21.1.9 Isopentane1.1.1

4、0 3-Methylbutene-11.1.11 n-Pentane1.1.12 Pentene-11.1.13 2-Methylbutene-11.1.14 trans-Pentene-21.1.15 cis-Pentene-21.1.16 2-Methylbutene-21.2 This test method does not cover the determination ofcyclic olefins, diolefins, or acetylenes. These are usually minorcomponents in finished gasolines.1.3 Samp

5、les to be analyzed should not contain significantamounts of material boiling lower than ethylene.1.4 The values stated in SI units are to be regarded asstandard. No other units of measurement are included in thisstandard.1.4.1 ExceptionAlternative units, in common usage, arealso provided to improve

6、the clarity and aid the user of this testmethod.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 establish appro-priate safety and health practices and determine the applica-bility of reg

7、ulatory limitations prior to use.2. Referenced Documents2.1 ASTM Standards:2D2001 Test Method for Depentanization of Gasoline andNaphthas3. Summary of Test Method3.1 The sample is injected into a gas-liquid partition col-umn. The components are separated as they pass through thecolumn with an inert

8、carrier gas and their presence in theeffluent is detected and recorded as a chromatogram. Materialscontaining components having more than five carbon atomscan either be backflushed from the system withoutmeasurement, or recorded as a broad peak by reversing thedirection of the carrier gas through th

9、e column at such time asto regroup the higher-boiling portion (C6and heavier) of thesample. If backflushing is used, the concentration of C2through C5hydrocarbons may be related to the whole sampleby adding a known quantity of low-boiling internal standard tothe sample prior to analysis. Alternative

10、ly, a known amount ofsample can be charged and compared to a standard sample rununder the same conditions. Sample composition is determinedfrom the chromatogram by comparing peak areas with thoseobtained using known amounts of calibration standards or asynthetic blend.4. Significance and Use4.1 In h

11、ydrocarbon type analyses of gasolines, highly vola-tile fuels can need to be stabilized by depentanization (TestMethod D2001) prior to analysis. A knowledge of the compo-sition of light hydrocarbons in the overhead from the depen-tanization process is useful in converting analyses of thedepentanized

12、 fraction to a total sample basis.5. Apparatus5.1 ChromatographAny chromatograph having a thermo-stated oven and a detection system of adequate sensitivity may1This test method is under the jurisdiction of ASTM Committee D02 onPetroleum Products, Liquid Fuels, and Lubricants and is the direct respon

13、sibility ofSubcommittee D02.04.0L on Gas Chromatography Methods.Current edition approved Oct. 1, 2015. Published December 2015. Originallyapproved in 1965. Last previous edition approved in 2011 as D2427 06 (2011).DOI: 10.1520/D2427-06R15.2For referenced ASTM standards, visit the ASTM website, www.a

14、stm.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 Box C700, West Conshohocken, PA 19428-2959. United States1be used.

15、 The detection system must have sufficient sensitivityto produce a recorder deflection of at least 5 mm for 0.1 liquidvolume percent of pentene-1 in the sample or synthetic blendbeing analyzed.NOTE 1If the sensitivity of a given system is inadequate, it can beincreased by using a more sensitive reco

16、rder or detector, or by using moresample if the resolution is substantially unaffected.5.2 RecorderA 1 mV to 10 mV recorder with a full-scaleresponse time of 2 s or less and a noise level no greater than60.3 % of full scale.5.3 Columns:5.3.1 A description of columns and valving arrangementsthat meet

17、 the requirements of this method are described inAnnex A1. Persons using other column materials must estab-lish that the column gives results that meet the precisionrequirements of Section 10.5.3.2 Analyzer ColumnThe column system used must becapable of resolving the individual C2to C5paraffins ando

18、lefins well enough so that the individual hydrocarbons listedin Section 1 may be reported. The resolution should be suchthat at the operating conditions selected, the distance from thebase line in the valley between two peaks representing com-pounds reported is not greater than 50 % of the height of

19、 thesmaller peak. If an internal standard is used, it must becompletely resolved from the other components.5.3.3 Precut ColumnThis column must be capable ofseparating the C5and lighter olefins and paraffins from the C6and heavier olefins and paraffins. The resolution should be suchthat at the operat

20、ing conditions selected, the distance from thebase line to the valley between 2-methylbutene-2 and 2,2-dimethylbutane is not greater than 50 % of the height of thesmaller peak. If an internal standard is used, it must be elutedwith the C5and lighter materials.6. Reagents and Materials6.1 Compounds f

21、or calibration shall be of a purity of notless than 99 mole %. Calibrants should include compounds1.1.5 1.1.16 as listed in Section 1. The concentration ofethylene, ethane, propylene, and propane is generally so low inmost samples that calibration with these materials is unneces-sary (WarningExtreme

22、ly flammable gas under pressure.Extremely flammable liquids.) Commercially available certi-fied blends of light hydrocarbons may be used to establishcalibration data where their compositions are applicable. If aninternal standard is used to relate the concentration of lighthydrocarbons to the whole

23、sample it must be included as acalibrant.6.2 Carrier GasA carrier gas appropriate to the type ofdetector used should be employed. Helium or hydrogen can beused with thermal conductivity detector (WarningCompressed gas under high pressure.) (WarningHydrogenis extremely flammable under pressure.) Nitr

24、ogen or argon canbe used with ionization or gas density detectors (WarningCompressed gas under high pressure).6.3 Liquid PhaseSee Annex A1.6.4 Solid Support, for use in packed column; usuallycrushed firebrick or diatomaceous earth. Mesh size should beappropriate to the system selected from the suppl

25、ement.7. Preparation of Apparatus7.1 Column PreparationThe method used to prepare thecolumn is not critical as long as the finished column producesthe desired separation. Preparation of the packing is notdifficult once the support, partitioning liquid, and loading levelhave been determined. Some sta

26、tionary phases are susceptibleto oxidation and must be protected from excessive exposure toair during the evaporation and drying steps. The followinggeneral directions have been found to produce columns ofacceptable characteristics:7.1.1 Weigh out the desired quantity of support, usuallytwice that r

27、equired to fill the column.7.1.2 Calculate and weigh out the required quantity ofpartitioning agent. Dissolve the partitioning agent in a volumeof chemically inert, low-boiling solvent equal to approximatelytwice the volume of support.7.1.3 Gradually add the support material to the solution withgent

28、le stirring.7.1.4 Slowly evaporate the solvent while gently agitatingthe mixture until the packing is nearly dry and no free liquid isapparent.7.1.5 Spread the packing in thin layers on a nonabsorbentsurface and air or oven dry as required to remove all traces ofsolvent.7.1.6 Resieve the packing to

29、remove fines and agglomeratesproduced in the impregnation step.7.1.7 Fill the column tubing with packing by plugging oneend with a wad of glass wool and pouring the packing into theother end through a small funnel. Vibrate the tubing continu-ously over its entire length while filling. When the packi

30、ngceases to flow, tap the column gently on the floor or bench topwhile vibrating is continued.Add packing as necessary until nofurther settling occurs during a 2 min period. Remove a smallamount of packing from the open end, plug with a wad of glasswool, and shape the column to fit the chromatograph

31、.7.1.8 If multiple columns are joined by tubing unions, thedead volume in the union should be filled with columnpacking.7.2 ChromatographMount the column in the chromato-graph and establish the operating conditions required to givethe desired separation (see Annex A1). Allow sufficient timefor the i

32、nstrument to reach equilibrium as indicated by a stablerecorder base line. Control the oven temperature so that it isconstant to within 0.5 C without thermostat cycling whichcauses an uneven base line. Set the carrier gas flow rate,measured with a soap film meter, so that it is constant to within1 m

33、L/min of the selected value.8. Procedure8.1 CalibrationDetermine the relative area response ofthe compounds to be reported by injecting known quantities ofthe pure compounds or by using synthetic blends of knowncomposition. For those compounds that are normally gases atroom temperature it is advanta

34、geous to use commerciallyD2427 06 (2015)2available certified light hydrocarbon blends. Sample lighthydrocarbon blends contained in pressure containers from theliquid phase ( WarningExtremely flammable gas underpressure.) Blends of those hydrocarbons that are normallyliquid at room temperature are ea

35、sily prepared by volume withsufficient accuracy to establish relative response factors(WarningExtremely flammable liquids.) If measurement ofthe C6and heavier material by reverse flow through thedetector is intended, an average calibration factor for theseheavy materials must be determined. Gasoline

36、s that have beendepentanized by laboratory distillation may be used as cali-brants for this purpose (WarningExtremely flammable.) Ifuse of an internal standard is contemplated, the internalstandard selected should be included in the calibration pro-gram.8.2 Analysis:8.2.1 Backflush MethodWhen the ba

37、ckflush technique isused, add a known quantity of internal standard equal to about5 % to the sample. The internal standard can be added on eithera weight or volume basis depending upon the method ofreporting. One method of adding the internal standard that hasbeen found convenient is given in Annex

38、A1. Alternatively,quantitative results can be obtained by injecting repeatablequantities of the sample and of a known blend, and comparingthe peak areas obtained for the sample with those obtained forthe known concentration of components in the blend.8.2.1.1 Precut ColumnIf a precut column is used,

39、adjustthe valving so that carrier gas is flowing in the normal directionthrough both the precut and analysis columns. Using a chilledsyringe, charge sufficient sample to ensure a minimum of 10 %recorder deflection for a 0.1 % sample concentration of2-methylbutene-2 at the most sensitive setting of t

40、he instru-ment. When all of the C5and lighter hydrocarbons plus internalstandard, if used, have entered the analyzer column, positionthe valves so that backflushing of the precut column isinitiated. The time at which backflushing is commenced iscritical and may have to be determined by trial and err

41、or. Ifproperly done, it results in the elimination of any interferencefrom low-boiling six-carbon paraffins and produces a chro-matogram that exhibits peaks for C2through C5paraffins andolefins only (Fig. 1). When the last compound has been eluted,remove the chromatogram and proceed as described in

42、9.1.1.8.2.1.2 Single ColumnIf a single column is used, it may bebackflushed if an appropriate valving system has been in-stalled. The operations described above are performed exceptthat backflushing is commenced only when all the C5andlighter hydrocarbons and internal standard have been eluted.The p

43、urpose of backflushing in this case is not to improve theseparation, but merely to shorten the total analysis time andavoid passage of higher boiling hydrocarbons through thedetector.8.2.2 Reverse Flow MethodIf reverse flow of the C6andheavier portion through the detector is employed, the additionof

44、 an internal standard is unnecessary if adequate calibrationhas been performed and the composition of the C6and heavierportion does not differ significantly from that of the depenta-nized gasolines used as calibrants. An internal standard can beused periodically to assure that analytical accuracy is

45、 main-tained (Note 2).Adjust the valving so that carrier gas is flowingthrough the instrument in the normal direction. Charge suffi-cient sample to ensure a minimum of 10 % recorder deflectionfor a 0.1 percent sample concentration of 2-methylbutene-2 atthe highest sensitivity. As soon as the last pe

46、ntene peak(2-methylbutene-2) has been eluted, position the valving soColumn:Precut: SF96-50 silicone fluidAnalyzer: tricresylphosphate plus DC 550 silicone fluid 4.5/1 by wt followed by ethylene glycol in series.FIG. 1 Typical Chromatogram of Light Components in a Catalytic GasolineD2427 06 (2015)3t

47、hat the carrier gas flow is reversed. After the flow hasstabilized, adjust the base line. Attenuate for the C6+ portionas necessary. The run is complete when the recorder returns tothe base line after elution of the C6portion. This part of thesample will generally emerge as one broad peak with onlys

48、light indications of any separation. Proceed as described in9.1.2.NOTE 2All reverse flow determinations, including the C6and heaviercalibration runs should be made in the same carrier gas flow direction. Allsingle-peak determinations and corresponding calibrations will then bemade in the opposite ca

49、rrier gas flow direction. The column should be keptfree of high-boiling residues by periodically sweeping with carrier gas forseveral hours in the reverse direction. A level base line will quickly beattained in either flow direction when the column is clean and the systemis free of leaks.9. Calculation9.1 Calculate the percentage of the individual componentsusing the following procedure that applies and report to thenearest 0.1 %.9.1.1 Backflush MethodMeasure the areas of all of thepeaks representing compounds to be reported and that of theinternal stand