ASTM D5134-13(2017) Standard Test Method for Detailed Analysis of Petroleum Naphthas through n-Nonane by Capillary Gas Chromatography.pdf

1、Designation: D5134 13 (Reapproved 2017)Standard Test Method forDetailed Analysis of Petroleum Naphthas through n-Nonaneby Capillary Gas Chromatography1This standard is issued under the fixed designation D5134; the number immediately following the designation indicates the year oforiginal adoption or

2、, 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.INTRODUCTIONDespite the many advances in capillary gas chromatography instrumentation and t

3、he remarkableresolution achievable, it has proven difficult to standardize a test method for the analysis of a mixtureas complex as petroleum naphtha. Because of the proliferation of numerous, similar columns and theendless choices of phase thickness, column internal diameter, length, etc., as well

4、as instrumentoperating parameters, many laboratories use similar but not identical methods for the capillary GCanalysis of petroleum naphthas. Even minute differences in column polarity or column oventemperature, for example, can change resolution or elution order of components and make theiridentif

5、ication an individual interpretive process rather than the desirable, objective application ofstandard retention data. To avoid this, stringent column specifications and temperature and flowconditions have been adopted in this test method to ensure consistent elution order and resolution andreproduc

6、ible retention times. Strict adherence to the specified conditions is essential to the successfulapplication of this test method.1. Scope1.1 This detailed hydrocarbon analysis (DHA) test methodcovers the determination of hydrocarbon components paraffins,naphthenes, and monoaromatics (PNA) of petrole

7、um naphthasas enumerated in Table 1. Components eluting after n-nonane(bp 150.8 C) are determined as a single group.1.2 This test method is applicable to olefin-free (C7.1.5 Detailed hydrocarbon components in olefin containingsamples may be determined by DHA Test Methods D6729,D6730,orD6733.1.6 The

8、values stated in SI units are to be regarded asstandard. No other units of measurement are included in thisstandard.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

9、 safety, health, and environmental practices and deter-mine the applicability of regulatory limitations prior to use.Specific warning statements are given in Section 7.1.8 This international standard was developed in accor-dance with internationally recognized principles on standard-ization establis

10、hed in the Decision on Principles for theDevelopment of International Standards, Guides and Recom-mendations issued by the World Trade Organization TechnicalBarriers to Trade (TBT) Committee.2. Referenced Documents2.1 ASTM Standards:2D1319 Test Method for Hydrocarbon Types in Liquid Petro-leum Produ

11、cts by Fluorescent Indicator Adsorption1This test method is under the jurisdiction of ASTM Committee D02 onPetroleum Products, Liquid Fuels, and Lubricants and is the direct responsibility ofSubcommittee D02.04.0L on Gas Chromatography Methods.Current edition approved Oct. 1, 2017. Published Novembe

12、r 2017. Originallyapproved in 1990. Last previous edition approved in 2013 as D5134 13. DOI:10.1520/D5134-13R17.2For 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 to the

13、standards Document Summary page onthe ASTM website.Copyright ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959. United StatesThis international standard was developed in accordance with internationally recognized principles on standardization established in the

14、 Decision on Principles for theDevelopment of International Standards, Guides and Recommendations issued by the World Trade Organization Technical Barriers to Trade (TBT) Committee.1TABLE 1 Typical Retention Characteristics of Naphtha ComponentsNOTE 1The abbreviations N and P refer to unidentified n

15、aphthenes and paraffins respectively.Compound Retention Time, minAdjusted RetentionTime, minKovats RetentionIndex 35 CLinear Retention IndexMethane 3.57 0.00 100.0 .Ethane 3.65 0.08 200.0 .Propane 3.84 0.27 300.0 .Isobutane 4.14 0.57 367.3 .n-Butane 4.39 0.82 400.0 .2,2-Dimethylpropane 4.53 0.96 415

16、.5 .Isopentane 5.33 1.76 475.0 .n-Pentane 5.84 2.27 500.0 .2,2-Dimethylbutane 6.81 3.24 536.2 .Cyclopentane 7.83 4.26 564.1 .2,3-Dimethylbutane 7.89 4.32 565.5 .2-Methylpentane 8.06 4.49 569.5 .3-Methylpentane 8.72 5.15 583.4 .n-Hexane 9.63 6.06 600.0 .2,2-Dimethylpentane 11.22 7.65 624.2 .Methylcyc

17、lopentane 11.39 7.82 626.5 .2,4-Dimethylpentane 11.68 8.11 630.3 .2,2,3-Trimethylbutane 12.09 8.52 635.4 .Benzene 13.29 9.72 649.1 .3,3-dimethylpentane 13.84 10.27 654.8 .Cyclohexane 14.19 10.62 658.3 .2-Methylhexane 15.20 11.63 667.8 .2,3-Dimethylpentane 15.35 11.78 669.1 .1,1-Dimethylcyclopentane

18、15.61 12.04 671.4 .3-Methylhexane 16.18 12.61 676.2 .cis-1,3-Dimethylcyclopentane 16.88 13.31 681.8 .trans-1,3-Dimethylcyclopentane 17.22 13.65 684.4 .3-Ethylpentane 17.44 13.87 686.1 .trans-1,2-Dimethylcyclopentane 17.57 14.00 687.0 .2,2,4-Trimethylpentane 17.80 14.23 688.7 .n-Heptane 19.43 15.86 7

19、00.0 .Methylcyclohexane + cis-1,2-Dimethylcyclopentane 22.53 18.96 718.6A.1,1,3-Trimethylcyclopentane + 2,2-Dimethylhexane 23.05 19.48 721.4A.Ethylcyclopentane 24.59 21.02 729.3A.2,5-Dimethylhexane + 2,2,3-Trimethylpentane 25.12 21.55 731.9A.2,4-Dimethylhexane 25.47 21.90 733.5A.1,trans-2,cis-4-Trim

20、ethylcyclopentane 26.43 22.86 738.0A.3,3-Dimethylhexane 26.79 23.22 739.6A.1,trans-2,cis-3-Trimethylcyclopentane 28.01 24.44 744.9A.2,3,4-Trimethylpentane 28.70 25.13 747.8A.Toluene + 2,3,3-Trimethylpentane 29.49 25.92 751.1A730.2B1,1,2-Trimethylcyclopentane 31.21 27.64 . 741.7B2,3-Dimethylhexane 31

21、.49 27.92 . 743.6B2-Methyl-3-ethylpentane 31.69 28.12 . 744.9A2-Methylheptane 33.06 29.49 . 754.1B4-Methylheptane + 3-Methyl-3-ethylpentane 33.34 29.77 . 756.0B3,4-Dimethylhexane 33.49 29.92 . 757.0B1,cis-2,trans-4-Trimethylcyclopentane + 1,cis-2,cis-4-Trimethylcyclopentane 33.73 30.16 . 758.6Bcis-1

22、,3-Dimethylcyclohexane 34.45 30.88 . 763.4B3-Methylheptane + 1,cis-2,trans-3-Trimethylcyclopentane 34.64 31.07 . 764.7B3-Ethylhexane + trans-1,4-Dimethylcyclohexane 34.83 31.26 . 766.0B1,1-Dimethylcyclohexane 35.81 32.24 . 772.5B2,2,5-Trimethylhexane + trans-1,3-Ethylmethylcyclopentane 36.75 33.18 .

23、 778.8Bcis-1,3-Ethylmethylcyclopentane 37.14 33.57 . 781.4Btrans-1,2-Ethylmethylcyclopentane 37.39 33.82 . 783.1B2,2,4-Trimethylhexane + 1,1-Ethylmethylcyclopentane 37.68 34.11 . 785.1Btrans-1,2-Dimethylcylohexane 38.14 34.57 . 788.1B1,cis-2,cis-3-Trimethylcyclopentane 39.21 35.64 . 795.3Btrans-1,3-

24、Dimethylcyclohexane + cis-1,4-Dimethylcyclohexane 39.54 35.97 . 797.5n-Octane 39.91 36.34 . 800.0Isopropylcyclopentane + 2,4,4-Trimethylhexane 40.76 37.19 . 805.7Unidentified C9-Naphthene 40.88 37.31 . 806.5Unidentified C8-Naphthene 41.52 37.95 . 810.8Unidentified C9-Naphthene 41.88 38.31 . 813.2cis

25、-1,2-Ethylmethylcyclopentane + 2,3,5-Trimethylhexane 42.55 38.98 . 817.72,2-Dimethylheptane 43.20 39.63 . 822.0cis-1,2-Dimethylcyclohexane 43.43 39.86 . 823.62,2,3-Trimethylhexane + 9N 43.76 40.19 . 825.82,4-Dimethylheptane 43.88 40.31 . 826.64,4-Dimethylheptane + 9N 44.09 40.52 . 828.0Ethylcyclohex

26、ane + n-Propylcyclopentane 44.36 40.79 . 829.82-Methyl- 4-Ethylhexane 44.74 41.17 . 832.4D5134 13 (2017)2D3700 Practice for Obtaining LPG Samples Using a Float-ing Piston CylinderD3710 Test Method for Boiling Range Distribution of Gaso-line and Gasoline Fractions by Gas Chromatography(Withdrawn 2014

27、)3D4057 Practice for Manual Sampling of Petroleum andPetroleum ProductsD5443 Test Method for Paraffin, Naphthene, and AromaticHydrocarbon Type Analysis in Petroleum DistillatesThrough 200 C by Multi-Dimensional Gas Chromatog-raphyD6839 Test Method for Hydrocarbon Types, OxygenatedCompounds, and Benz

28、ene in Spark Ignition Engine Fuelsby Gas ChromatographyD6729 Test Method for Determination of Individual Com-ponents in Spark Ignition Engine Fuels by 100 MetreCapillary High Resolution Gas ChromatographyD6730 Test Method for Determination of Individual Com-ponents in Spark Ignition Engine Fuels by

29、100MetreCapillary (with Precolumn) High-Resolution Gas Chro-matographyD6733 Test Method for Determination of Individual Com-ponents in Spark Ignition Engine Fuels by 50-MetreCapillary High Resolution Gas ChromatographyD7096 Test Method for Determination of the Boiling RangeDistribution of Gasoline b

30、y Wide-Bore Capillary GasChromatography3. Summary of Test Method3.1 A representative sample of the naphtha is introducedinto a gas chromatograph equipped with a methyl siliconebonded phase fused silica capillary column. Helium carrier gastransports the vaporized sample through the column in whichthe

31、 components are separated. Components are sensed by aflame ionization detector as they elute from the column. Thedetector signal is processed by an electronic data acquisitionsystem or integrating computer. Each eluting peak is identifiedby comparing its retention index to a table of retention indic

32、es3The last approved version of this historical standard is referenced onwww.astm.org.TABLE 1 ContinuedCompound Retention Time, minAdjusted RetentionTime, minKovats RetentionIndex 35 CLinear Retention Index2,6-Dimethylheptane + 9N 44.95 41.38 . 833.81,1,3-Trimethylcyclohexane 45.21 41.64 . 835.5Unid

33、entified C9-Naphthene 45.56 41.99 . 837.82,5-Dimethylheptane + 9P 45.92 42.35 . 840.33,5-Dimethylheptane + 3,3-Dimethylheptane + N 46.09 42.52 . 841.4Unidentified C9-Naphthene 46.31 42.74 . 842.9Unidentified C9-Naphthene 46.55 42.98 . 844.5Ethyl Benzene 47.15 43.58 . 848.5Unidentified C9-Naphthene 4

34、7.37 43.80 . 850.0Unidentified Naphthene + 2,3,4-Trimethylhexane 47.53 43.96 . 851.0Unidentified Naphthenes 47.78 44.21 . 852.7Unidentified Naphthene + Paraffin 48.13 44.56 . 855.1m-Xylene 48.49 44.92 . 857.5p-Xylene 48.63 45.06 . 858.42,3-Dimethylheptane 48.93 45.36 . 860.43,4-DimethylheptaneC+ N 4

35、9.10 45.53 . 861.63,4-DimethylheptaneC49.29 45.72 . 862.8Unidentified Naphthene 49.41 45.84 . 863.64-Ethylheptane + N 49.65 46.08 . 865.24-Methyloctane 50.10 46.53 . 868.32-Methyloctane 50.26 46.69 . 869.3Unidentified Naphthene 50.41 46.84 . 870.3Unidentified Naphthene 50.73 47.16 . 872.53-Ethylhept

36、ane + N 50.96 47.39 . 874.03-Methyloctane 51.15 47.58 . 875.3Unidentified Naphthene 51.35 47.78 . 876.6o-Xylene + 1,1,2-Trimethylcyclohexane 51.54 47.97 . 877.9Unidentified Naphthene + 2,4,6-Trimethylheptane 51.74 48.17 . 879.2Unidentified Naphthene 52.12 48.55 . 881.8Unidentified Paraffin 52.24 48.

37、67 . 882.6Unidentified Naphthenes 52.56 48.99 . 884.7Unidentified Naphthene 52.85 49.28 . 886.7Unidentified Naphthene + Paraffin 53.06 49.49 . 888.1Unidentified Naphthene 53.26 49.69 . 889.4Unidentified Naphthene 53.46 49.89 . 890.8Unidentified Naphthene 54.02 50.45 . 894.5Unidentified Naphthene 54.

38、40 50.83 . 897.1n-Nonane 54.84 51.27 . 900.0Unidentified Naphthene 54.98 51.41 . 900.9AExtrapolated from n-C6and n-C7. See A1.1.3.BExtrapolated from n-C8and n-C9. See A1.2.3.CStereoisomers.D5134 13 (2017)3and by visual matching with a standard chromatogram. Thetable of retention indices has been est

39、ablished by runningreference compounds under identical conditions or by gaschromatographicmass spectrometric (GC/MS) analysis ofreference samples under the same conditions, or both.3.2 The mass concentration of each component is deter-mined by area normalization with response factors. Peakseluting a

40、fter n-nonane are summed and reported as C10+.4. Significance and Use4.1 A knowledge of the hydrocarbon components compris-ing a petroleum naphtha, reformate, or alkylate is useful invaluation of crude oils, in alkylation and reforming processcontrol, in product quality assessment, and for regulator

41、ypurposes. Detailed hydrocarbon composition is also used asinput in the mathematical modeling of refinery processes.4.2 Separation of naphtha components by the proceduredescribed in this test method can result in some peaks thatrepresent coeluting compounds. This test method cannot attri-bute relati

42、ve concentrations to the coelutants. In the absence ofsupporting information, use of the results of this test methodfor purposes which require such attribution is not recom-mended.5. Interferences5.1 If present, olefinic hydrocarbons with boiling points lessthan 150 C will be separated and detected

43、along with thesaturates and aromatics. Some of the olefins will coelute withsaturates or aromatics and give erroneously high concentra-tions for those components. Some coelutions of PNA compo-nents above C7 may occur and results may not be completelyaccurate. Test Method D5443 may be used for carbon

44、 numberdistribution above C7 to verify results from this test method.5.2 Alcohols, ethers, and other organic compounds of simi-lar volatility can also interfere by coeluting with saturate oraromatic hydrocarbons thereby causing erroneously high val-ues to be determined.6. Apparatus6.1 Instrumentatio

45、nA gas chromatograph capable of col-umn oven temperature programming from 35 C to 200 C in1 Cmin increments is required. A heated flash vaporizinginjector designed to provide a linear sample split injection (forexample, 200:1) is also required for proper sample introduc-tion. The associated carrier

46、gas controls must be of adequateprecision to provide reproducible column flows and split ratiosin order to maintain analytical integrity. A hydrogen flameionization detector designed for optimum response with capil-lary columns (with the required gas controls and electronics)must meet or exceed the

47、following specifications:Operating temperature 100 C to 300 CSensitivity 0.015 C/gMinimum detectability 5 1012g carbon/secondLinearity 1076.2 Sample Introduction SystemManual or automatic liq-uid syringe sample injection to the splitting injector may beemployed. Devices capable of 0.2 L to 1.0 L inj

48、ections aresuitable. It should be noted that inadequate splitter design orpoor injection technique, or both, can result in sample frac-tionation. Operating conditions which preclude fractionationshould be determined in accordance with Section 11.6.3 Electronic Data Acquisition SystemAny data acquisi

49、-tion and integration device used for quantitation of theseanalyses must meet or exceed these minimum requirements:6.3.1 Capacity for at least 250 peaks/analysis.6.3.2 Normalized area percent calculation with responsefactors.6.3.3 Identification of individual components by retentiontime.6.3.4 Noise and spike rejection capa