1、Designation: D2163 14Standard Test Method forDetermination of Hydrocarbons in Liquefied Petroleum (LP)Gases and Propane/Propene Mixtures by GasChromatography1This standard is issued under the fixed designation D2163; the number immediately following the designation indicates the year oforiginal adop
2、tion 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 quantitative determinationof individual hydr
3、ocarbons in liquefied petroleum (LP) gasesand mixtures of propane and propene, excluding high-puritypropene in the range of C1to C5. Component concentrationsare determined in the range of 0.01 to 100 volume percent.1.2 This test method does not fully determine hydrocarbonsheavier than C5and non-hydr
4、ocarbon materials, and additionaltests may be necessary to fully characterize an LPG sample.1.3 The values stated in SI units are to be regarded asstandard. The values given in parentheses are for informationonly.1.4 This standard does not purport to address all of thesafety concerns, if any, associ
5、ated 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 Documents2.1 ASTM Standards:2D1265 Practice for Sampling Liquefied Petroleum (LP)Gases,
6、Manual MethodD1835 Specification for Liquefied Petroleum (LP) GasesD2421 Practice for Interconversion of Analysis of C5andLighter Hydrocarbons to Gas-Volume, Liquid-Volume, orMass BasisD2598 Practice for Calculation of Certain Physical Proper-ties of Liquefied Petroleum (LP) Gases from Composi-tiona
7、l AnalysisD3700 Practice for Obtaining LPG Samples Using a Float-ing Piston CylinderD6729 Test Method for Determination of Individual Com-ponents in Spark Ignition Engine Fuels by 100 MetreCapillary High Resolution Gas ChromatographyE355 Practice for Gas Chromatography Terms and Relation-shipsE594 P
8、ractice for Testing Flame Ionization Detectors Usedin Gas or Supercritical Fluid ChromatographyE1510 Practice for Installing Fused Silica Open TubularCapillary Columns in Gas Chromatographs2.2 Canadian General Standards Board Publications:3CAN/CGSB 3.0 No. 14.3 Standard Test Method for theIdentifica
9、tion of Hydrocarbon Components in AutomotiveGasoline Using Gas Chromatography2.3 Gas Processors Association:4GPA Std 2145-03 for hexane3. Terminology3.1 Definitions:3.1.1 Additional terminology related to the practice of gaschromatography can be found in Practice E355.3.1.2 liquefied petroleum gas (
10、LPG), nhydrocarbon gasesthat can be stored or handled in the liquid phase throughcompression or refrigeration, or both.3.1.2.1 DiscussionLPGs generally consist of C3and C4alkanes and alkenes or mixtures thereof and containing lessthan 10 volume percent of higher carbon number material.Vapor pressure
11、 does not normally exceed 2000 kPa at 40C.3.2 Definitions of Terms Specific to This Standard:3.2.1 propane/propene mixtures, nmixtures primarilycomposed of propane and propene where one of these compo-nents is usually in the concentration range of 30 to 85 mass %with the other comprising the majorit
12、y of the remainder.“Commercial Propane in Specification D1835 is typically thissort of product mixture.3.2.1.1 DiscussionOther components may be present,usually at less than 10 mass %.1This test method is under the jurisdiction of ASTM Committee D02 onPetroleum Products, Liquid Fuels, and Lubricants
13、 and is the direct responsibility ofSubcommittee D02.D0.03 on Propylene.Current edition approved Jan. 1, 2014. Published January 2014. Originallyapproved in 1963. Last previous edition approved in 2007 as D216307. DOI:10.1520/D2163-14.2For referenced ASTM standards, visit the ASTM website, www.astm.
14、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.3Available from CGSB, Canadian General Standards Board, Gatineau, CanadaK1A 1G6. Visit the CGSB website, www.pwgsc.gc.ca/cgsb/
15、4Available from Gas Processors Association (GPA), 6526 E. 60th St., Tulsa, OK74145, http:/.Copyright ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959. United States14. Summary of Test Method4.1 An LPG sample is analyzed via either liquid or gassampling valves
16、by gas chromatography and compared tocorresponding components separated under identical operatingconditions from a reference standard mixture of known com-position or from use of pure hydrocarbons. The chromatogramof the sample is interpreted by comparing peak retention timesand areas with those obt
17、ained for the reference standardmixture or pure hydrocarbons.5. Significance and Use5.1 The hydrocarbon component distribution of liquefiedpetroleum gases and propene mixtures is often required forend-use sale of this material. Applications such as chemicalfeed stocks or fuel require precise composi
18、tional data to ensureuniform quality. Trace amounts of some hydrocarbon impuri-ties in these materials can have adverse effects on their use andprocessing.5.2 The component distribution data of liquefied petroleumgases and propene mixtures can be used to calculate physicalproperties such as relative
19、 density, vapor pressure, and motoroctane (see Practice D2598). Precision and accuracy of com-positional data are extremely important when these data areused to calculate various properties of these petroleum prod-ucts.6. Apparatus6.1 Gas Chromatograph (GC)Any gas chromatographicinstrument provided
20、with a linear temperature programmablecolumn oven. The temperature control must be capable ofobtaining a retention time repeatability of 0.05 min (3 s)throughout the scope of this analysis.6.2 DetectorA flame ionization detector (FID) having asensitivity of 0.5 ppm (mole) or less for the compounds l
21、istedin Table 1 is strongly recommended (see Practice E594).6.2.1 Other detectors may be used (alone or in series)provided that they have sufficient response, linearity, andsensitivity to measure the components of interest at theconcentration levels required.6.3 Data AcquisitionAny commercial integr
22、ator or com-puterized data acquisition system may be used for display ofthe chromatographic detector signal and peak area integration.The device should be capable of calibration and reporting ofthe final response corrected results.6.4 Sample IntroductionWhether liquid or vaporsampling, the combinati
23、on of valve injection size and split ratiomust be selected such that the required sensitivity is achievedand also that no component concentration in a sample is greaterthan the detector upper linearity limit.6.4.1 If capillary columns will be used, then the GC mustinclude a heated splitting type inj
24、ector that is operated isother-mally. Split ratios in the range of 5:1 to 200:1, with a typicalvalue of 100:1, will be used dependent upon the sampleinjection volume and sensitivity required. If packed columnswill be used, then a splitting type injector is not required and asuitable packed inlet por
25、t may be used.6.4.2 Liquid Sampling (recommended)The GC should beequipped with a liquid sampling valve for introduction of thesample aliquot to the splitting injector. Liquid sampling valveswith an internal fixed sample volume between 0.2 to 0.5 L ora size to provide the minimum detection limits giv
26、en in 1.1have been used satisfactorily. The valve shall be rated for atleast 1380 kPa (200 psi) above the vapor pressure of the sampleat the valve operating temperature. A shut-off valve shall beTABLE 1 Expected Retention Order and TimesComponentEstimated Retention Time (min)(using typical Al2O3PLOT
27、 operating conditions)Estimated Retention Time (min)(using typical 100 m Dimethylpolysiloxanecolumn operating conditions)FID TCDC5Olefin/C6+Composite (backflush) NAA. x xAir Composite (O2,Ar,N2, Co) NAA. . xMethane 1.9 6.5 x xEthane 2.1 6.7 x xPropane 2.7 7.3 x xCyclopropane 3.4 . x xPropene 3.5 7.2
28、 x x2-Methyl Propane (Isobutane) 4.0 8.4 x xButane 4.2 9.5 x xPropadiene 4.7 . x xEthyne (Acetylene) 5.0 . x xTrans-2-Butene 5.5 9.9 x x1-Butene 5.6 9.2 x x2-Methyl Propene (Isobutene) 5.7 9.1 x x2,2-Dimethylpropane (Neopentane) 5.9 10.1 x xCis-2-Butene 6.2 10.6 x xCyclopentane 6.7 25.8 x x2-Methyl
29、Butane (Isopentane) 6.8 14.0 x xPentane 7.2 16.9 x x1,3-Butadiene 7.5 9.3 x xPropyne (Methyl Acetylene) 7.9 . x xnC5(Sum C5Olefins and Heavier)B8.1 until end of run . x xANot applicable.BnC5components may be speciated and reported individually.D2163 142provided at the exit of the sampling valve wast
30、e port. A 2 to 7m packed-screen type filter should be provided at the sampleinlet port of the sampling valve to remove possible particulatematerial from the sample. The valve shall provide for arepeatability of at least 2% relative sample volume introduc-tion. The sampling valve shall be located at
31、the GC such thatit can be operated at ambient temperature. The use of floatingpiston sample cylinders is encouraged to minimize or eliminatethe volatilization of lighter components into the headspace.Common 80% filled LPG storage cylinders should be pressur-ized with an inert gas such as helium to f
32、acilitate liquid transferand accurate liquid injections. A minimum pressure of 200 psiabove sample vapor pressure is recommended. A pressuregauge may be used to make this determination. Beforepressurization, verify that the sample cylinder, transfer linesand valves are rated to safely contain the pr
33、essurized sample. Itis customary to add a check valve between the helium cylinderand the sample cylinder to prevent contamination in the eventthe sample cylinder is higher in pressure than the pressurizingcylinder.6.4.3 Vapor Sampling (optional)A six-port gas samplingvalve or a ten-port sampling/col
34、umn switching valve with1.6 mm (116 in.) fittings and a 200 L fixed sampling loop maybe provided. This valve shall be contained in a heatedenclosure and operated at a temperature above the boiling pointof the highest boiling component in the sample. The use of a 2to 7 m frit or packed-screen type fi
35、lter ahead of the sampleintroduction port is recommended. The valve shall provide fora repeatability of at least 2% relative sample volume introduc-tion.6.5 Gas ControlsThe GC shall be provided with suitablefacilities for delivery and control of carrier gas and the detectorgases. This will consist o
36、f the appropriate tank and down-stream regulators and supply tubing as well as the mass orpressure controls for the precise regulation of the instrumentoperation.NOTE 1Most GC suppliers will provide these devices or recommendthe proper supplies.6.6 Column Series/Reversal Switching ValveIf desired, a
37、multi-port valve mentioned may be used to provide the C5olefin/C6+ determination for this analysis. The back-flushconfiguration should be configured according to the manufac-turers recommendations.6.7 ColumnsCondition all columns used according to themanufacturers suggestions prior to use.6.7.1 Anal
38、ytical ColumnThe recommended analytical col-umn is a 50 m by 0.53 mm (I.D) Na2SO4deactivated Al2O3porous layer open tubular (PLOT) column. Relative retentionorder is dependent upon the deactivation method for thecolumn. (WarningSpecifically test the column to ensure thatthe column does not adsorb pr
39、opadiene and butadienes. Thiscondition can exist depending upon the degree of columndeactivation.)6.7.1.1 Routine re-conditioning of the column may berequired to maintain column performance.6.7.1.2 Alternatively, any column(s) that provides the ap-propriate component separations may be used. Columns
40、 (100m by 0.25 mm (ID) by 0.5 m film thickness) employed instandard methods Test Method D6729 and CGSB 3.0 No. 14.3have been successfully used.6.7.2 Pre-column (optional)If an initial back flush of theC5olefins or hexane plus (C6+) components, or both, throughthe use of the sequence reversal/back fl
41、ush valve is desired, asecond column is required. Any pre-column that providesseparation between the components of interest and the com-posite heavier components may be used. Choices may includelengths of column such as a 10 to 30 m section of 0.53 mm(I.D.) 1 m film thickness dimethylpolysiloxane or
42、 polyethyl-ene glycol capillary column ora9to15cmsection of the samecolumn material as the analytical column or any pre-columnthat provides the desired retention of C5olefins, hexanes, andheavier components. This pre-column acts to keep the heaviercomponents away from the analytical column and to ba
43、ck flushthe heavier components as a composite peak to the detector forquantitation. A pre-column that also has the ability to retainwater and oxygenated hydrocarbon compounds is recom-mended to keep those materials from entering the analyticalcolumn.7. Reagents and Materials7.1 Carrier GasesFor carr
44、ier gases, it is recommended toinstall commercial active oxygen scrubbers and water dryers,such as molecular sieves, ahead of the instrument to protect thesystems chromatographic columns. Follow supplier instruc-tions in the use of such gas purifiers and replace as necessary.7.1.1 Hydrogen, 99.995%
45、minimum purity, nC5(C5=and heavier) 0.885ARF values obtained from Test Method D6729.All response factors are relative to that of methane according to the following equation:RRFi5 sMWi/NCid 3s1/MWmethanedwhere:RRFi= relative response factor of each component with respect to methane,MWi= the molecular
46、 weight of the component,NCi= the number of carbon atoms in the component molecule, andMWmethane= the molecular weight of methane.D2163 147valve several times prior to injection provides some localcooling, and it provides for more repeatable liquid injections.When liquid is flowing through the valve
47、, quickly close thewaste shut-off valve, then rotate the liquid sampling valve toinject the sample.10.2.3 If the back flush option is being used, switch the backflush valve at the pre-determined time to elute the C5=/C6+composite to the detector.10.3 Gas Sample Valve Injection (optional)Vaporize the
48、liquid sample according to the procedure given in 10.3.1through 10.3.5, or using an on-line heated vaporizing devicethat is heat-traced to the gas sampling valve, as described in10.3.6. Flush a gas sample loop with 5 to 10 mL of sample,close cylinder valve, and allow the sample pressure to equili-br
49、ate to atmospheric pressure (stopped flow) before introduc-ing the sample into the carrier gas stream.10.3.1 In a hood, prior to connecting the cylinder, invert thecylinder and purge a small aliquot of the sample through thevalve on the sample cylinder to remove any moisture orparticulate matter which might be present.10.3.2 Attach a secondary sampling vessel, consisting oftwo ball valves joined together and having an internal volumeof approximately one mL to the liquid outlet on the samplevessel.10.3.3 Evacuate the secondary ves
