ASTM D2650-2010(2015) Standard Test Method for Chemical Composition of Gases by Mass Spectrometry《采用质谱法测定气体化学成分的标准试验方法》.pdf

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1、Designation: D2650 10 (Reapproved 2015)Standard Test Method forChemical Composition of Gases by Mass Spectrometry1This standard is issued under the fixed designation D2650; the number immediately following the designation indicates the year oforiginal adoption or, in the case of revision, the year o

2、f 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 analysis ofgases containing specific combinations of the following com-pone

3、nts: hydrogen; hydrocarbons with up to six carbon atomsper molecule; carbon monoxide; carbon dioxide; mercaptanswith one or two carbon atoms per molecule; hydrogen sulfide;and air (nitrogen, oxygen, and argon). This test method cannotbe used for the determination of constituents present inamounts le

4、ss than 0.1 mole %. Dimethylbutanes are assumedabsent unless specifically sought.NOTE 1Although experimental procedures described herein areuniform, calculation procedures vary with application. The followinginfluences guide the selection of a particular calculation: qualitativemixture composition;

5、minimum error due to components presumedabsent; minimum cross interference between known components; maxi-mum sensitivity to known components; low frequency and complexity ofcalibration; and type of computing machinery.Because of these influences, a tabulation of calculation proceduresrecommended fo

6、r stated applications is presented in Section 12 (Table 1).NOTE 2This test method was developed on Consolidated Electrody-namics Corporation Type 103 Mass Spectrometers. Users of otherinstruments may have to modify operating parameters and the calibrationprocedure.1.2 The values stated in SI units a

7、re to be regarded asstandard. No other units of measurement are included in thisstandard.1.3 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 practice

8、s and determine the applica-bility of regulatory limitations prior to use.2. Referenced Documents2.1 ASTM Standards:2D1137 Method for Analysis of Natural Gases and RelatedTypes of Gaseous Mixtures by the Mass Spectrometer(Withdrawn 1981)3D1247 Test Method for Sampling Manufactured Gas (With-drawn 19

9、86)3D1265 Practice for Sampling Liquefied Petroleum (LP)Gases, Manual MethodD1302 Test Method for Analysis of Carbureted Water Gasby the Mass Spectrometer (Withdrawn 1967)32.2 American Petroleum Institute Standards:4MPMS 14.1 Collecting and Handling of Natural GasSamples for Custody Transfer2.3 Gas

10、Producers Association Standards:5GPA 2166 Obtaining Natural Gas Samples for Analysis byGas Chromatography3. Terminology3.1 Definitions:3.1.1 base peak of a compoundthe peak used as 100 % incomputing the cracking pattern coefficient.3.1.2 cracked gaseshydrocarbon gases that contain un-saturates.3.1.3

11、 cracking pattern coeffcientthe ratio of a peak at anym/e relative to its parent peak (or in some cases its base peak).3.1.4 GLCa gas-liquid chromatographic column that iscapable of separating the isomers of butenes, pentenes,hexanes, and hexenes.3.1.5 IRinfrared equipment capable of analyzing gases

12、 forthe butene isomers.3.1.6 mass number or m/e value of an ionthe quotient ofthe mass of that ion (given in atomic mass units) and itspositive charge (number of electrons lost during ionization).3.1.7 parent peak of a compoundthe peak at which the m/eis equal to the sum of the atomic mass values fo

13、r thatcompound. This peak is sometimes used as 100 % in comput-ing the cracking pattern coefficients.1This test method is under the jurisdiction of ASTM Committee D02 onPetroleum Products, Liquid Fuels, and Lubricants and is the direct responsibility ofSubcommittee D02.04.0M on Mass Spectroscopy.Cur

14、rent edition approved June 1, 2015. Published July 2015. Originally approvedin 1967. Last previous edition approved in 2010 as D2650 10. DOI: 10.1520/D2650-10R15.2For referenced ASTM standards, visit the ASTM website, www.astm.org, orcontact ASTM Customer Service at serviceastm.org. For Annual Book

15、of ASTMStandards volume information, refer to the standards Document Summary page onthe ASTM website.3The last approved version of this historical standard is referenced onwww.astm.org.4Available from American Petroleum Institute (API), 1220 L. St., NW,Washington, DC 20005-4070, http:/www.api.org.5A

16、vailable from Gas Processors Association (GPA), 6526 E. 60th St., Tulsa, OK74145, www.gpaglobal.org.Copyright ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959. United States1TABLE 1 Calculation Procedures for Mass Spectrometer Gas AnalysisNOTE 1Coding of calcu

17、lation procedures is as follows:O = Order peaks are used in the calculation expressed serially from 1 to n, n being the total number of components.P=m/e of peak used and prefix, M, if monoisotopic.M = Method of computationU = Unicomponent Peak MethodMa= Simultaneous equations where “a” identifies th

18、e particular set of equations if more than one is used.C = Chemically removed.Residual = m/e of peak suitable as an independent check on the method.SerialNo. 123456Name or ApplicationD1137ANatural GasD1302BCarburetedWater GasH2-C6ReformerGasC3,C4iC4Component O P M O P M OCPCMOPMOCPCMOPMHydrogen . .

19、. 6 2 M 16 2 U 17 2 M 0 . . . . .Methane 15 16 U 71516 M 15 16 U 16 16 M 0 . . . . .Ethylene 13 27 M2 12 27 M 13 26 U 15 26 M 0 . . . . .Ethane 12 30 M2 8 30 M 12 30 U 13 30 M 0 . . . . .Propene 10 42 M2 11 42 M 8 42 M2 12 42 M 6 42 M . . MPropane 9 29 M2 9 29 M 3 44 M1 14 29 M 9 29 M 3 29 MButadien

20、e . . . 9 . . 3 . . 10 54 M 9 . M . . MButene-1 8 56 M2 5 56 U 9 41 M2 8 56 M 8 41 M . . MButene-2 8 56 M2 5 56 U 10 55 M2 8 56 M 4 56 M . . MIsobutene 8 56 M2 5 56 U 11 56 M2 8 56 M 5 39 M . . MIsobutane 7 43 M2 5 . . 4 M43 M1 11 43 M 7 43 M 2 43 Mn-Butane 6 58 M2 4 58 U 5 58 M1 6 58 M 2 58 M 1 58

21、MPentenes . . . 3 70 U 2 70 U 9 55 M 3 70 M . . MIsopentane . . . 3 . . 6 M57 M1 7 57 M 1 72 M . . .n-Pentane 4 72 M2 2 72 U 7 72 M2 5 72 M . . . . . .Benzene . . . 2 . . 7 . . 4 78 M . . . . . .Hexanes . . . 2 . . 7 . . . . M . . . . . .C6cyclic paraffins . . . 2 . . 7 . . 3 84 M . . . . . .Hexanes

22、 5 57 M2 2 . . 1 71 U 2 86 M . . . . . .Toluene . . . 2 . . 1 . . 1 92 M . . . . . .Hydrogen sulfide 2 34 M1 2 . . 1 . . 21 34 M . . . . . .Carbon dioxide 11 44 M2 10 44 M 1 . C 20 44 M . . . . . .Carbon monoxide . . . 13 12 M 1 . C 18 28 M . . . . . .Nitrogen 14 28 M2 14 14 M 14 28 U 19 14 M . . .

23、. . .Air 3 32 M1 1 32 U 14 . . 22 32 M 1 32 U . . .Helium 1 4 U 1 . . 14 . .DD. . . . . . .SerialNo. 7 8 9 10 11 12 13Name or ApplicationCommercialPropaneCommercialButaneBB Stream(CrackedButanes)Dry GasCrackedFuel GasMixed Isoand NormalButanesReformerMake-UpGasUnstabi-lized FuelGasComponent O P M O

24、P M OCPCMOPMOPMOPMOCPCMHydrogen . . . . . . . . . 15 2 M . . . 10 2 M 16 2 MMethane . . . . . . . . . 14 16 M . . . 9 16 M 15 16 MEthyleneE7 26 M . . . . . . 12 26 M . . . . . . 13 26 MEthane 6 30 M . . . . . . 11 30 M . . . 7 30 M 12 30 MPropene 5 42 M 7 42 M 6 42 M 10 42 M . . . . . . 8 42 MPropan

25、e 3 44 M 4 44 M 4 44 M 7 44 M 3 44 M 5 44 M 6 44 MButadiene . . . . . . 1 54 M 3 54 M . . . . . . 2 54 MButene-1 1 56 M 1 56 M 7 41 M 1 . . . . . . . . 9 41 MButene-2 1 56 M 1 56 M 8 56 M 1 56 M . . . . . . 10 56 MIsobutene 1FFM1FF939M 1F. 4 43 M . . . 11 39 MIsobutane 4 43 M 5 43 M 5 43 M 8 43 M 1

26、58 M 6 43 M 7 43 Mn-Butane 2 58 M 2 58 M 2 58 M 4 58 M . . . 2 58 M 3 58 MPentenes . . . 6 70 MG70 U 9 70 M . . . 3 57 M . 70 UIsopentane . . . 3 57 M 3 57 M 5 57 M 2 57 M 4 72 M 4 57 Mn-Pentane . . . . . . . . . 6 72 M . . . . . . 5 72 MBenzene . . . . . . . . . . . . . . . . . .HHDHexanes . . . .

27、. . . . . . . . . . . . . .HHDC6cyclic paraffins . . . . . . . . . . . . . . . . . .HHDHexanes . . . . . . . . . . . . . . . . . .HHDToluene . . . . . . . . . . . . . . . . . .HHDHydrogen sulfide . . . . . . . . .I. C . . .IICIICCarbon dioxide . . . . . . . . .I. C . . .IICIICCarbon monoxide . . . .

28、 . . . . . 13 28 M . . . 8 28 M 14 28 MNitrogen . . . . . . . . . . . . . . . . . . . . .Air . . . . . . . . . 2 32 M . . . 1 32 M 1 32 MAcid Gases . . . . . . . . .I. C . . .IICIICResidualE8 27 M 8 27 M 10 27 M 16 14 M 5 27 M 11 14 M 17 14 MResidualE9 29 M 9 29 M 11 29 M 17 15 M 6 29 M 12 15 M 18 1

29、5 MResidualE. . . . . . . . . 18 27 M . . . 13 27 M 19 27 MResidualE. . . . . . . . . 19 29 M . . . 14 29 M 20 29 MD2650 10 (2015)23.1.8 partial pressurethe pressure of any component inthe inlet system before opening the expansion bottle to leak.3.1.9 sensitivitythe height of any peak in the spectru

30、m ofthe pure compound divided by the pressure prevailing in theinlet system of the mass spectrometer immediately beforeopening the expansion bottle to leak.3.1.10 straight-run gaseshydrocarbon gases that do notcontain unsaturates.4. Summary of Test Method4.1 The molecular species which make up a gas

31、eous mix-ture are dissociated and ionized by electron bombardment. Thepositive ions of the different masses thus formed are acceler-ated in an electrostatic field and separated in a magnetic field.The abundance of each mass present is recorded. The mixturespectrum obtained is resolved into individua

32、l constituents bymeans of simultaneous equations derived from the massspectra of the pure compounds.5. Significance and Use5.1 A knowledge of the composition of refinery gases isuseful in diagnosing the source of plant upsets, in determiningthe suitability of certain gas streams for use as fuel, or

33、asfeedstocks for polymerization and alkylation, and for monitor-ing the quality of commercial gases.6. Interferences6.1 In setting up an analysis, it is possible that a constituentwas ignored. Also, an impure calibration may have been used.The spectrum calculated from the composition found is to,TAB

34、LE 1 ContinuedSerialNo. 14 15 16Name or Application H2-C6Cracked Gas H2-C6Straight Run Gas Light Refinery GasComponent O P M O P M O P MHydrogen 1 2 M 1 2 M 20 2 UMethane 2 16 M 2 16 M 17 16 MEthylene 4 26 M . . . 14 26 MEthane 7 30 M 5 30 M 13 30 MPropene 11 42 M . . . 12 42 MPropane 6 29 M 4 29 M

35、10 29 MButadiene 15 54 M . . . . . .Butane-1 . . . . . . 11 56 MButene-2 16 56 M . . . . . .Isobutene . . . . . . . . .Isobutane 12 43 M 9 43 M 9 43 Mn-Butane 18 58 M 14 58 M 8 58 MPentenes 21 70 M . . . 15 70 MIsopentane 17 57 M 13 57 M 7 57 Mn-Pentane 22 72 M 18 72 M 6 72 MBenzene . . . 19 78 M 5

36、78 UHexanes 23 84 M . . . 4 84 UC6cyclic paraffins . . . 20 84 M . . .Hexanes . . . 17 71 M 3 86 UToluene . . . 21 92 M . . .Hydrogen sulfide 9 34 M 7 34 M 1 34 UCarbon dioxide 13 44 M 10 44 M 16 44 UCarbon monoxide . . . . . . 18 12 UNitrogen 5 28 M . . . 19 28 UAir 8 32 M 6 32 M 2 32 UWater 3 18 M

37、 3 18 M . . .Cyclobutane . . . 12 56 M . . .Cyclopentene 20 67 M . . . . . .Pentadienes 20 67 M . . . . . .Cyclopentane . . . 16 70 M . . .Methylmercaptan 14 48 M 11 48 M . . .Ethylmercaptan 19 62 M 15 62 M . . .Residual 41 10 41 M 8 41 M . . .Residual 14 24 14 M 22 14 M . . .AMethod D1137.BMethod D

38、1302.CThe mass spectrometer analysis for isomeric butenes is far less accurate than for the other hydrocarbon components. The inaccuracies involved in the isomeric buteneanalysis by mass spectrometer range from 1.0 to 4.0 mole %, depending upon the concentration, ranges, and extent of drifts in inst

39、rument calibrations. These inaccuracieswill range still higher when pentenes are present in larger than 0.5 % concentrations. See Analytical Chemistry, Vol 22, 1950, p. 991; Ibid, Vol 21, 1949, p. 547; and Ibid, Vol 21, 1949, p. 572.DIn Method 4, butylenes and pentenes spectra are composites based o

40、n typical GLC analyses. Hexene and hexane spectra are from appropriately corrected spectra ofrepresentative fractions.EResiduals Groups A: m/e 72, 58, 57, 44, 43; Group B: m/e 56, 42, 30, 29, 14. All Group A residual shall be 0.2 division or less with the residual of the largest peak alsobeing less

41、than 0.3 % of its total peak height. All Group B residuals shall be less than 1 % of the peak height or 0.2 division, whichever is greater.FButenes are grouped if they are less than 5 %.GIf pentenes exceed 1 %, they are determined by other means and the spectrum removed from the poly spectrum.HRemov

42、ed from sample by distillation.IChemically removed.D2650 10 (2015)3therefore, be compared with the observed spectrum of themixture at masses independent of the original calculation.Differences so computed, called residuals, should as a generalrule be less than 1 % of the original mixture peak for an

43、acceptable analysis. Masses suitable for this calculation aretabulated with each calculation procedure.NOTE 3Another strategy employed to reduce interferences andincrease accuracy consists of using spectra which have been corrected forcontributions caused by the rare isotopes of carbon and hydrogen.

44、7. Apparatus7.1 Mass SpectrometerAny mass spectrometer can beused with this test method that shall be proven by performancetests described herein.8. Reference Standards8.1 The mass spectrometer must be calibrated with each ofthe components constituting the unknown mixture to beanalyzed. The calibrat

45、ing compounds must be of high purity.Research grade calibrants are readily available from a numberof sources. In general, the mass spectrometer is capable ofdetecting impurities in calibrants and the contribution of suchimpurities to the calibration spectrum can be removed.NOTE 4Some of the calculat

46、ion procedures require the use ofcombined spectra, for example, air and butylenes. Three frequently usedpossibilities for producing combined spectra are as follows: (1) Repre-sentative fraction from a specific source, (2) Multiplication factors toconvert the spectrum of a pure constituent to a simul

47、ated spectrum of themixture, and (3) Proportionality factors for combining actual calibrations.Arecommended concentration limit for combined mixtures is given.Atthe level recommended, the residual spectrum contribute less than 0.1 %error in any one result when the concentration of any constituent in

48、 thecombined mixture is doubled.9. Sampling9.1 Samples shall be collected by methods known to pro-vide a representative mixture of the material to be analyzed.Samples can be collected in accordance with Test MethodD1247, Practice D1265, API MPMS 14.1, or GPA 2166.10. Calibration and Standardization1

49、0.1 ApparatusDetermine whether operating conditionsremain normal by making certain tests periodically, followinginstructions furnished by the manufacturer of the apparatus.Include in these tests rate of leak, ion-beam control settings,pattern reproducibility, and galvanometer calibrations.10.1.1 To ascertain pattern stability, the following scheduleis provided both for laboratories that have mass spectrometerswith conventional temperature control and for laboratories thatvary the temperature of the ionization chamber to obtainconstant patterns:Run Number Compou