ASTM D5134-98(2008)e1

Standard Test Method for Detailed Analysis of Petroleum Naphthas through n-Nonane by Capillary Gas Chromatography

SIGNIFICANCE AND USE
A knowledge of the hydrocarbon components comprising a petroleum naphtha, reformate, or alkylate is useful in valuation of crude oils, in alkylation and reforming process control, in product quality assessment, and for regulatory purposes. Detailed hydrocarbon composition is also used as input in the mathematical modeling of refinery processes.
Separation of naphtha components by the procedure described in this test method can result in some peaks that represent coeluting compounds. This test method cannot attribute relative concentrations to the coelutants. In the absence of supporting information, use of the results of this test method for purposes which require such attribution is not recommended.
SCOPE
1.1 This test method covers the determination of hydrocarbon components of petroleum naphthas as 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 (2 % olefins by liquid volume) liquid hydrocarbon mixtures including virgin naphthas, reformates, and alkylates. Olefin content can be determined by Test Method D 1319. The hydrocarbon mixture must have a 98 % point of 250°C or less as determined by Test Method D 3710.
1.3 Components that are present at the 0.05 mass % level or greater can be determined.
1.4 The values stated in SI units are to be regarded as standard. No other units of measurement are included in this standard.
1.5 This standard does not purport to address all of the safety concerns, if any, associated with its use. It is the responsibility of the user of this standard to establish appropriate safety and health practices and determine the applicability of regulatory limitations prior to use. Specific warning statements are given in Section 7.

General Information

• Status: Historical
• Publication Date: 30-Apr-2008
• ICS: 71.080.10 - Aliphatic hydrocarbons
• Technical Committee: D02 - Petroleum Products, Liquid Fuels, and Lubricants
• Drafting Committee: D02.04.0L - Gas Chromatography Methods

Relations

• Replaces: ASTM D5134-98(2003) - Standard Test Method for Detailed Analysis of Petroleum Naphthas through <i>n</i>-Nonane by Capillary Gas Chromatography
• Effective Date: 01-May-2008
• Referred By: ASTM D5443-23 - Standard Test Method for Paraffin, Naphthene, and Aromatic Hydrocarbon Type Analysis in Petroleum Distillates Through 200 °C by Multi-Dimensional Gas Chromatography
• Effective Date: 01-May-2008
• Referred By: ASTM D7900-23 - Standard Test Method for Determination of Light Hydrocarbons in Stabilized Crude Oils by Gas Chromatography
• Effective Date: 01-May-2008
• Referred By: ASTM D2892-20 - Standard Test Method for Distillation of Crude Petroleum (15-Theoretical Plate Column)
• Effective Date: 01-May-2008

Standards Content (Sample)

NOTICE: This standard has either been superseded and replaced by a new version or withdrawn.
Contact ASTM International (www.astm.org) for the latest information
´1
Designation: D5134 − 98(Reapproved 2008)
Standard Test Method for
Detailed Analysis of Petroleum Naphthas through n-Nonane
by Capillary Gas Chromatography
This standard is issued under the fixed designation D5134; the number immediately following the designation indicates the year of
original adoption or, in the case of revision, the year of last revision.Anumber in parentheses indicates the year of last reapproval.A
superscript epsilon (´) indicates an editorial change since the last revision or reapproval.
´ NOTE—Updated sole source of supply footnotes editorially in May 2008.
INTRODUCTION
Despite the many advances in capillary gas chromatography instrumentation and the remarkable
resolution achievable, it has proven difficult to standardize a test method for the analysis of a mixture
as complex as petroleum naphtha. Because of the proliferation of numerous, similar columns and the
endless choices of phase thickness, column internal diameter, length, etc., as well as instrument
operating parameters, many laboratories use similar but not identical methods for the capillary GC
analysis of petroleum naphthas. Even minute differences in column polarity or column oven
temperature, for example, can change resolution or elution order of components and make their
identification an individual interpretive process rather than the desirable, objective application of
standard retention data. To avoid this, stringent column specifications and temperature and flow
conditionshavebeenadoptedinthistestmethodtoensureconsistentelutionorderandresolutionand
reproducible retention times. Strict adherence to the specified conditions is essential to the successful
application of this test method.
1. Scope responsibility of the user of this standard to establish appro-
priate safety and health practices and determine the applica-
1.1 This test method covers the determination of hydrocar-
bility of regulatory limitations prior to use. Specific warning
boncomponentsofpetroleumnaphthasasenumeratedinTable
statements are given in Section 7.
1. Components eluting after n-nonane (bp 150.8°C) are deter-
mined as a single group.
2. Referenced Documents
1.2 This test method is applicable to olefin-free (<2%
2.1 ASTM Standards:
olefins by liquid volume) liquid hydrocarbon mixtures includ-
D1319TestMethodforHydrocarbonTypesinLiquidPetro-
ing virgin naphthas, reformates, and alkylates. Olefin content
leum Products by Fluorescent Indicator Adsorption
can be determined by Test Method D1319. The hydrocarbon
D3700Practice for Obtaining LPG Samples Using a Float-
mixturemusthavea98%pointof250°Corlessasdetermined
ing Piston Cylinder
by Test Method D3710.
D3710TestMethodforBoilingRangeDistributionofGaso-
1.3 Componentsthatarepresentatthe0.05mass%levelor
line and Gasoline Fractions by Gas Chromatography
greater can be determined.
D4057Practice for Manual Sampling of Petroleum and
Petroleum Products
1.4 The values stated in SI units are to be regarded as
standard. No other units of measurement are included in this
3. Summary of Test Method
standard.
3.1 A representative sample of the naphtha is introduced
1.5 This standard does not purport to address all of the
into a gas chromatograph equipped with a methyl silicone
safety concerns, if any, associated with its use. It is the
bondedphasefusedsilicacapillarycolumn.Heliumcarriergas
transports the vaporized sample through the column in which
This test method is under the jurisdiction of ASTM Committee D02 on
PetroleumProductsandLubricantsandisthedirectresponsibilityofSubcommittee
D02.04.0L on Gas Chromatography Methods. For referenced ASTM standards, visit the ASTM website, www.astm.org, or
Current edition approved May 1, 2008. Published September 2008. Originally contact ASTM Customer Service at [e-mail]. For Annual Book of ASTM
approved in 1990. Last previous edition approved in 2003 as D5134–98(2003). Standards volume information, refer to the standard’s Document Summary page on
DOI: 10.1520/D5134-98R08E01. the ASTM website.
Copyright © ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959. United States
´1
D5134 − 98 (2008)
TABLE 1 Typical Retention Characteristics of Naphtha Components
NOTE 1—The abbreviations N and P refer to unidentified naphthenes and paraffins respectively.
Adjusted Retention Kovats Retention
Compound Retention Time, min Linear Retention Index
Time, min Index @ 35°C
Methane 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 0.96 415.5 .
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 .
Methylcyclopentane 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 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 15.86 700.0 .
A
Methylcyclohexane + cis-1,2-Dimethylcyclopentane 22.53 18.96 718.6 .
A
1,1,3-Trimethylcyclopentane + 2,2-Dimethylhexane 23.05 19.48 721.4 .
A
Ethylcyclopentane 24.59 21.02 729.3 .
A
2,5-Dimethylhexane + 2,2,3-Trimethylpentane 25.12 21.55 731.9 .
A
2,4-Dimethylhexane 25.47 21.90 733.5 .
A
1,trans-2,cis-4-Trimethylcyclopentane 26.43 22.86 738.0 .
A
3,3-Dimethylhexane 26.79 23.22 739.6 .
A
1,trans-2,cis-3-Trimethylcyclopentane 28.01 24.44 744.9 .
A
2,3,4-Trimethylpentane 28.70 25.13 747.8 .
A B
Toluene + 2,3,3-Trimethylpentane 29.49 25.92 751.1 730.2
B
1,1,2-Trimethylcyclopentane 31.21 27.64 . 741.7
B
2,3-Dimethylhexane 31.49 27.92 . 743.6
A
2-Methyl-3-ethylpentane 31.69 28.12 . 744.9
B
2-Methylheptane 33.06 29.49 . 754.1
B
4-Methylheptane + 3-Methyl-3-ethylpentane 33.34 29.77 . 756.0
B
3,4-Dimethylhexane 33.49 29.92 . 757.0
B
1,cis-2,trans-4-Trimethylcyclopentane + 1,cis-2,cis-4-Trimethylcyclopentane 33.73 30.16 . 758.6
B
cis-1,3-Dimethylcyclohexane 34.45 30.88 . 763.4
B
3-Methylheptane + 1,cis-2,trans-3-Trimethylcyclopentane 34.64 31.07 . 764.7
B
3-Ethylhexane + trans-1,4-Dimethylcyclohexane 34.83 31.26 . 766.0
B
1,1-Dimethylcyclohexane 35.81 32.24 . 772.5
B
2,2,5-Trimethylhexane + trans-1,3-Ethylmethylcyclopentane 36.75 33.18 . 778.8
B
cis-1,3-Ethylmethylcyclopentane 37.14 33.57 . 781.4
B
trans-1,2-Ethylmethylcyclopentane 37.39 33.82 . 783.1
B
2,2,4-Trimethylhexane + 1,1-Ethylmethylcyclopentane 37.68 34.11 . 785.1
B
trans-1,2-Dimethylcylohexane 38.14 34.57 . 788.1
B
1,cis-2,cis-3-Trimethylcyclopentane 39.21 35.64 . 795.3
trans-1,3-Dimethylcyclohexane + cis-1,4-Dimethylcyclohexane 39.54 35.97 . 797.5
n-Octane 39.91 36.34 . 800.0
Isopropylcyclopentane + 2,4,4-Trimethylhexane 40.76 37.19 . 805.7
Unidentified C9-Naphthene 40.88 37.31 . 806.5
Unidentified C8-Naphthene 41.52 37.95 . 810.8
Unidentified C9-Naphthene 41.88 38.31 . 813.2
cis-1,2-Ethylmethylcyclopentane + 2,3,5-Trimethylhexane 42.55 38.98 . 817.7
2,2-Dimethylheptane 43.20 39.63 . 822.0
cis-1,2-Dimethylcyclohexane 43.43 39.86 . 823.6
2,2,3-Trimethylhexane + 9N 43.76 40.19 . 825.8
2,4-Dimethylheptane 43.88 40.31 . 826.6
4,4-Dimethylheptane + 9N 44.09 40.52 . 828.0
Ethylcyclohexane + n-Propylcyclopentane 44.36 40.79 . 829.8
2-Methyl- 4-Ethylhexane 44.74 41.17 . 832.4
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D5134 − 98 (2008)
TABLE 1 Continued
Adjusted Retention Kovats Retention
Compound Retention Time, min Linear Retention Index
Time, min Index @ 35°C
2,6-Dimethylheptane + 9N 44.95 41.38 . 833.8
1,1,3-Trimethylcyclohexane 45.21 41.64 . 835.5
Unidentified C9-Naphthene 45.56 41.99 . 837.8
2,5-Dimethylheptane + 9P 45.92 42.35 . 840.3
3,5-Dimethylheptane + 3,3-Dimethylheptane + N 46.09 42.52 . 841.4
Unidentified C9-Naphthene 46.31 42.74 . 842.9
Unidentified C9-Naphthene 46.55 42.98 . 844.5
Ethyl Benzene 47.15 43.58 . 848.5
Unidentified C9-Naphthene 47.37 43.80 . 850.0
Unidentified Naphthene + 2,3,4-Trimethylhexane 47.53 43.96 . 851.0
Unidentified Naphthenes 47.78 44.21 . 852.7
Unidentified Naphthene + Paraffin 48.13 44.56 . 855.1
m-Xylene 48.49 44.92 . 857.5
p-Xylene 48.63 45.06 . 858.4
2,3-Dimethylheptane 48.93 45.36 . 860.4
C
3,4-Dimethylheptane + N 49.10 45.53 . 861.6
C
3,4-Dimethylheptane 49.29 45.72 . 862.8
Unidentified Naphthene 49.41 45.84 . 863.6
4-Ethylheptane + N 49.65 46.08 . 865.2
4-Methyloctane 50.10 46.53 . 868.3
2-Methyloctane 50.26 46.69 . 869.3
Unidentified Naphthene 50.41 46.84 . 870.3
Unidentified Naphthene 50.73 47.16 . 872.5
3-Ethylheptane + N 50.96 47.39 . 874.0
3-Methyloctane 51.15 47.58 . 875.3
Unidentified Naphthene 51.35 47.78 . 876.6
o-Xylene + 1,1,2-Trimethylcyclohexane 51.54 47.97 . 877.9
Unidentified Naphthene + 2,4,6-Trimethylheptane 51.74 48.17 . 879.2
Unidentified Naphthene 52.12 48.55 . 881.8
Unidentified Paraffin 52.24 48.67 . 882.6
Unidentified Naphthenes 52.56 48.99 . 884.7
Unidentified Naphthene 52.85 49.28 . 886.7
Unidentified Naphthene + Paraffin 53.06 49.49 . 888.1
Unidentified Naphthene 53.26 49.69 . 889.4
Unidentified Naphthene 53.46 49.89 . 890.8
Unidentified Naphthene 54.02 50.45 . 894.5
Unidentified Naphthene 54.40 50.83 . 897.1
n-Nonane 54.84 51.27 . 900.0
Unidentified Naphthene 54.98 51.41 . 900.9
A
Extrapolated from n-C and n-C . See A1.1.3.
6 7
B
Extrapolated from n-C and n-C . See A1.2.3.
8 9
C
Stereoisomers.
the components are separated. Components are sensed by a control, in product quality assessment, and for regulatory
flame ionization detector as they elute from the column. The purposes. Detailed hydrocarbon composition is also used as
detector signal is processed by an electronic data acquisition input in the mathematical modeling of refinery processes.
system or integrating computer. Each eluting peak is identified
4.2 Separation of naphtha components by the procedure
by comparing its retention index to a table of retention indices
described in this test method can result in some peaks that
and by visual matching with a standard chromatogram. The
represent coeluting compounds. This test method cannot attri-
table of retention indices has been established by running
buterelativeconcentrationstothecoelutants.Intheabsenceof
reference compounds under identical conditions or by gas
supporting information, use of the results of this test method
chromatographic—mass spectrometric (GC/MS) analysis of
for purposes which require such attribution is not recom-
reference samples under the same conditions, or both.
mended.
3.2 The mass concentration of each component is deter-
mined by area normalization with response factors. Peaks
5. Interferences
eluting after n-nonane are summed and reported as C .
10+
5.1 Ifpresent,olefinichydrocarbonswithboilingpointsless
4. Significance and Use
than 150°C will be separated and detected along with the
4.1 A knowledge of the hydrocarbon components compris- saturates and aromatics. Some of the olefins will coelute with
saturates or aromatics and give erroneously high concentra-
ing a petroleum naphtha, reformate, or alkylate is useful in
valuation of crude oils, in alkylation and reforming process tions for those components.
´1
D5134 − 98 (2008)
5.2 Alcohols, ethers, and other organic compounds of simi- 7.4 n-Heptane, 99+mol %. (Warning—Flammable. Harm-
lar volatility can also interfere by coeluting with saturate or ful if inhaled.)
aromatic hydrocarbons thereby causing erroneously high val-
7.5 Methane—(Warning—Extremely flammable gas.)
ues to be determined.
7.6 2-Methylheptane, 99+mol %. (Warning—Flammable.
Harmful if inhaled.)
6. Apparatus
7.7 4-Methylheptane, 99+mol %. (Warning—Flammable.
6.1 lnstrumentation—Agas chromatograph capable of col-
Harmful if inhaled.)
umn oven temperature programming from 35°C to 200°C in
1°C/min increments is required. A heated flash vaporizing 7.8 2-Methylpentane, 99+mol %. (Warning—Extremely
flammable. Harmful if inhaled.)
injector designed to provide a linear sample split injection (for
example, 200:1) is also required for proper sample introduc-
7.9 n-Octane, 99+mol %. (Warning—Flammable. Harm-
tion. The associated carrier gas controls must be of adequate
ful if inhaled.)
precision to provide reproducible column flows and split ratios
7.10 Toluene, 99+mol %. (Warning—Flammable. Vapor
in order to maintain analytical integrity. A hydrogen flame
harmful.)
ionization detector designed for optimum response with capil-
7.11 2,3,3-Trimethylpentane, 99+ mol %. (Warning—
lary columns (with the required gas controls and electronics)
must meet or exceed the following specifications: Extremely flammable. Harmful if inhaled.)
Operating temperature 100°C to 300°C
7.12 Column Evaluation Mixture, a qualitative synthetic
Sensitivity >0.015 C/g
mixture of pure liquid hydrocarbons with the following ap-
−12
Minimum detectability 5 × 10 g carbon/second
proximate composition: 0.5% toluene, 1% n-heptane, 1%
Linearity >10
2,3,3-trimethylpentane, 1 % 2-methylheptane, 1 %
6.2 Sample Introduction System —Manual or automatic
4-methylheptane, 1% n-octane in 2-methylpentane solvent.
liquid syringe sample injection to the splitting injector may be
employed. Devices capable of 0.2 µL to 1.0 µL injections are 7.13 Reference Alkylate, actual refinery alkylation product
suitable. It should be noted that inadequate splitter design or used to prepare Fig. 1.(Warning—Extremely flammable.
poor injection technique, or both, can result in sample frac- Harmful if inhaled.)
tionation. Operating conditions which preclude fractionation 3
7.14 Reference Naphtha, actual refinery stream used to
should be determined in accordance with Section 11.
prepare Fig. 2.(Warning—Extremely flammable. Harmful if
inhaled.)
6.3 Electronic Data Acquisition System—Any data acquisi-
tion and integration device used for quantitation of these
7.15 Reference Reformate, actual refinery reformer product
analyses must meet or exceed these minimum requirements:
used to prepare Fig. 3.(Warning—Extremely flammable.
6.3.1 Capacity for at least 250 peaks/analysis.
Harmful if inhaled.)
6.3.2 Normalized area percent calculation
...