ASTM D6730-01(2006)
(Test Method)Standard Test Method for Determination of Individual Components in Spark Ignition Engine Fuels by 100-Metre Capillary (with Precolumn) High-Resolution Gas Chromatography
Standard Test Method for Determination of Individual Components in Spark Ignition Engine Fuels by 100-Metre Capillary (with Precolumn) High-Resolution Gas Chromatography
SCOPE
1.1 This test method covers the determination of individual hydrocarbon components of spark-ignition engine fuels and their mixtures containing oxygenate blends (MTBE, ETBE, ethanol, and so forth) with boiling ranges up to 225°C. Other light liquid hydrocarbon mixtures typically encountered in petroleum refining operations, such as blending stocks (naphthas, reformates, alkylates, and so forth) may also be analyzed; however, statistical data was obtained only with blended spark-ignition engine fuels.
1.2 Based on the cooperative study results, individual component concentrations and precision are determined in the range from 0.01 to approximately 30 mass %. The test method may be applicable to higher and lower concentrations for the individual components; however, the user must verify the accuracy if the test method is used for components with concentrations outside the specified ranges.
1.3 This test method also determines methanol, ethanol, t-butanol, methyl t-butyl ether (MTBE), ethyl t-butyl ether (ETBE), and t-amyl methyl ether (TAME) in spark ignition engine fuels in the concentration range from 1 to 30 mass %. However, the cooperative study data provided insufficient statistical data for obtaining a precision statement for these compounds.
1.4 Although a majority of the individual hydrocarbons present are determined, some co-elution of compounds is encountered. If this test method is utilized to estimate bulk hydrocarbon group-type composition (PONA), the user of such data should be cautioned that some error will be encountered due to co-elution and a lack of identification of all components present. Samples containing significant amounts of naphthenic (for example, virgin naphthas) constituents above n-octane may reflect significant errors in PONA-type groupings. Based on the gasoline samples in the interlaboratory cooperative study, this test method is applicable to samples containing less than 25 mass % of olefins. However, some interfering co-elution with the olefins above C7 is possible, particularly if blending components or their higher boiling cuts such as those derived from fluid catalytic cracking (FCC) are analyzed, and the total olefin content may not be accurate. of this test method compares results of the test method with other test methods for selected components, including olefins, and several group types for several interlaboratory cooperative study samples. Although benzene, toulene, and several oxygenates are determined, when doubtful as to the analytical results of these components, confirmatory analyses can be obtained by using the specific test methods listed in the reference section.
1.4.1 Total olefins in the samples may be obtained or confirmed, or both, if necessary, by Test Method D 1319 (volume %) or other test methods, such as those based on multidimentional PONA-type of instruments.
1.5 If water is or is suspected of being present, its concentration may be determined, if desired, by the use of Test Method D 1744 or equivalent. Other compounds containing oxygen, sulfur, nitrogen, and so forth, may also be present, and may co-elute with the hydrocarbons. If determination of these specific compounds is required, it is recommended that test methods for these specific materials be used, such as Test Methods D 4815 and D 5599 for oxygenates, and Test Method D 5623 for sulfur compounds, or equivalent.
1.6 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.
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An American National Standard
Designation: D 6730 – 01 (Reapproved 2006)
Standard Test Method for
Determination of Individual Components in Spark Ignition
Engine Fuels by 100–Metre Capillary (with Precolumn) High-
Resolution Gas Chromatography
This standard is issued under the fixed designation D6730; 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 (e) indicates an editorial change since the last revision or reapproval.
1. Scope elution with the olefins above C is possible, particularly if
blending components or their higher boiling cuts such as those
1.1 This test method covers the determination of individual
derived from fluid catalytic cracking (FCC) are analyzed, and
hydrocarbon components of spark-ignition engine fuels and
the total olefin content may not be accurate.AnnexA1 of this
their mixtures containing oxygenate blends (MTBE, ETBE,
test method compares results of the test method with other test
ethanol, and so forth) with boiling ranges up to 225°C. Other
methods for selected components, including olefins, and sev-
light liquid hydrocarbon mixtures typically encountered in
eral group types for several interlaboratory cooperative study
petroleum refining operations, such as blending stocks (naph-
samples. Although benzene, toulene, and several oxygenates
thas,reformates,alkylates,andsoforth)mayalsobeanalyzed;
are determined, when doubtful as to the analytical results of
however, statistical data was obtained only with blended
these components, confirmatory analyses can be obtained by
spark-ignition engine fuels.
using the specific test methods listed in the reference section.
1.2 Based on the cooperative study results, individual com-
1.4.1 Total olefins in the samples may be obtained or
ponent concentrations and precision are determined in the
confirmed, or both, if necessary, by Test Method D1319
range from 0.01 to approximately 30 mass %.The test method
(volume %) or other test methods, such as those based on
may be applicable to higher and lower concentrations for the
multidimentional PONA-type of instruments.
individual components; however, the user must verify the
1.5 If water is or is suspected of being present, its concen-
accuracy if the test method is used for components with
tration may be determined, if desired, by the use of Test
concentrations outside the specified ranges.
Method D1744 or equivalent. Other compounds containing
1.3 This test method also determines methanol, ethanol,
oxygen,sulfur,nitrogen,andsoforth,mayalsobepresent,and
t-butanol, methyl t-butyl ether (MTBE), ethyl t-butyl ether
may co-elute with the hydrocarbons. If determination of these
(ETBE), and t-amyl methyl ether (TAME) in spark ignition
specific compounds is required, it is recommended that test
engine fuels in the concentration range from 1 to 30 mass %.
methods for these specific materials be used, such as Test
However, the cooperative study data provided insufficient
Methods D4815 and D5599 for oxygenates, andTest Method
statistical data for obtaining a precision statement for these
D5623 for sulfur compounds, or equivalent.
compounds.
1.6 This standard does not purport to address all of the
1.4 Although a majority of the individual hydrocarbons
safety concerns, if any, associated with its use. It is the
present are determined, some co-elution of compounds is
responsibility of the user of this standard to establish appro-
encountered. If this test method is utilized to estimate bulk
priate safety and health practices and determine the applica-
hydrocarbongroup-typecomposition(PONA),theuserofsuch
bility of regulatory limitations prior to use.
data should be cautioned that some error will be encountered
duetoco-elutionandalackofidentificationofallcomponents
2. Referenced Documents
present. Samples containing significant amounts of naphthenic
2.1 ASTM Standards:
(for example, virgin naphthas) constituents above n-octane
D1319 Test Method for Hydrocarbon Types in Liquid
may reflect significant errors in PONA-type groupings. Based
Petroleum Products by Fluorescent Indicator Adsorption
on the gasoline samples in the interlaboratory cooperative
D1744 Test Method for Determination of Water in Liquid
study, this test method is applicable to samples containing less
Petroleum Products by Fluorescent Indicator Adsorption
than 25 mass % of olefins. However, some interfering co-
1 2
This test method is under the jurisdiction of ASTM Committee D02 on For referenced ASTM standards, visit the ASTM website, www.astm.org, or
PetroleumProductsandLubricantsandisthedirectresponsibilityofSubcommittee contact ASTM Customer Service at service@astm.org. For Annual Book of ASTM
D02.04.0L on Gas Chromatography Methods. Standards volume information, refer to the standard’s Document Summary page on
Current edition approved Nov. 1, 2006. Published January 2007. Originally the ASTM website.
approved in 2001. Last previous edition approved in 2001 as D6730–01. Withdrawn.
Copyright © ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959, United States.
NOTICE: This standard has either been superseded and replaced by a new version or withdrawn. Please
contact ASTM International (www.astm.org) for the latest information.
D 6730 – 01 (2006)
D3700 Practice for Obtaining LPG Samples Using a Float- control and product specification compliance for many indi-
ing Piston Cylinder vidual hydrocarbons can be determined through the use of this
D4057 Practice for Manual Sampling of Petroleum and test method.
Petroleum Products 5.2 This test method is adopted from earlier development
, , ,
D4117 Performance Specification for Women’s and Girls’ and enhancement. The chromatographic operating condi-
Woven Robe, Negligee, Nightgown, Pajama, Slip, and tions and column tuning process, included in this test method,
Lingerie Fabrics were developed to provide and enhance the separation and
D4307 PracticeforPreparationofLiquidBlendsforUseas subsequent determination of many individual components not
Analytical Standards obtained with previous single-column analyses. The column
D4626 Practice for Calculation of Gas Chromatographic temperatureprogramprofileisselectedtoaffordthemaximum
Response Factors resolutionofpossibleco-elutingcomponents,especiallywhere
D4815 Test Method for Determination of MTBE, ETBE, these are of two different compound types (for example, a
TAME, DIPE, tertiary-Amyl Alcohol and C to C Alco- paraffin and a naphthene).
1 4
hols in Gasoline by Gas Chromatography 5.3 Although a majority of the individual hydrocarbons
D5580 Test Method for Determination of Benzene, Tolu- present in petroleum distillates are determined, some co-
ene,Ethylbenzene, p/m-Xylene, o-Xylene,C andHeavier elution of compounds is encountered. If this test method is
Aromatics, and Total Aromatics in Finished Gasoline by utilized to determine bulk hydrocarbon group-type composi-
Gas Chromatography tion (PONA), the user of such data should be cautioned that
D5599 Test Method for Determination of Oxygenates in some error will be encountered due to co-elution and a lack of
Gasoline by Gas Chromatography and Oxygen Selective identification of all components present. Samples containing
Flame Ionization Detection significantamountsofolefinicornaphthenic,orboth,constitu-
D5623 Test Method for Sulfur Compounds in Light Petro- ents above octane may reflect significant errors in PONA-type
leum Liquids by Gas Chromatography and Sulfur Selec- groupings.
tive Detection 5.4 If water is or is suspected of being present, its concen-
E355 Practice for Gas Chromatography Terms and Rela- tration is determined by the use ofTest Method D1744. Other
tionships compounds containing oxygen, sulfur, nitrogen, and so forth
E594 Practice forTesting Flame Ionization Detectors Used may also be present, and may co-elute with the hydrocarbons.
in Gas or Supercritical Fluid Chromatography When known co-elution exists, these are noted in the test
E1510 Practice for Installing Fused Silica Open Tubular method data tables. If determination of these specific com-
Capillary Columns in Gas Chromatographs pounds is required, it is recommended that test methods for
these specific materials be used, such as Test Method D4815
3. Terminology andD5599foroxygenates,TestMethodD5580foraromatics,
and Test Method D5623 for sulfur compounds.
3.1 Definitions—This test method makes reference to many
common gas chromatographic procedures, terms, and relation-
6. Apparatus
ships. Detailed definitions can be found in Practice E355.
6.1 Gas Chromatograph—Instrumentation capable of col-
umn oven temperature programming, from subambient (5°C)
4. Summary of Test Method
to at least 200°C, in 0.1°C/min or less rate increments, is
4.1 A representative sample of the petroleum liquid is
required. Multi-step column oven temperature programming is
introduced into a gas chromatograph equipped with an open
required, consisting of an initial hold time, an initial tempera-
tubular (capillary) column coated with a methyl silicone liquid
ture program followed by an isothermal temperature hold and
phase,modifiedwithacapillaryprecolumn.Heliumcarriergas
another programmed temperature rise.Aheated flash vaporiz-
transports the vaporized sample through the column, in which
ing injector designed to provide a linear sample split injection
it is partitioned into individual components which are sensed
(that is, 200:1) is required for proper sample introduction. The
with a flame ionization detector as they elute from the end of
associatedcarriergascontrolsmustbeofsufficientprecisionto
the column. The detector signal is presented on a strip chart
provide reproducible column flows and split ratios in order to
recorder or digitally, or both, by way of an integrator or
maintain analytical integrity. A hydrogen flame ionization
integrating computer. Each eluting component is identified by
comparing its retention time to that established by analyzing
reference standards or samples under identical conditions. The
Johansen, N.G., and Ettre, L.S., “Retention Index Values of Hydrocarbons on
concentration of each component in mass % is determined by
Open Tubular Columns Coated with Methyl Silicone Liquid Phases,” Chro-
normalization of the peak areas after correction with detector
matographia, Vol 5, No. 10, October 1982.
response factors. Unknown components are reported as a total Johansen, N.G., Ettre, L.S., and Miller, R.L., “Quantitative Analysis of
Hydrocarbons by Structural Group Type in Gasolines and Distillates. Part 1,”
unknown mass %.
Journal of Chromatography, 256, 1983, pp. 393-417.
Kopp, V.R., Bones, C.J., Doerr, D.G., Ho, S.P., and Schubert, A.J., “Heavy
5. Significance and Use
Hydrocarbon/Volatility Study: Fuel Blending and Analysis for the Auto/Oil Air
Quality Improvement Research Program,” SAE Paper No. 930143, March 1993.
5.1 Knowledge of the individual component composition
Schubert, A.J. and Johansen, N.J., “Cooperative Study to Evaluate a Standard
(speciation) of gasoline fuels and blending stocks is useful for
Test Method for the Speciation of Gasolines by Capillary Gas Chromatography,”
refinery quality control and product specification. Process SAE Paper No. 930144, March 1993.
NOTICE: This standard has either been superseded and replaced by a new version or withdrawn. Please
contact ASTM International (www.astm.org) for the latest information.
D 6730 – 01 (2006)
detector,withassociatedgascontrolsandelectronics,designed 7. Reagents and Materials
for optimum response with open tubular columns, shall con-
7.1 Carrier Gas—Helium, 99.999% pure. (Warning—
form to the specifications as described in Practice E594, as
Helium, air, nitrogen, compressed gas under pressure.)
well as having an operating temperature range of up to at least
7.2 Oxidant—Air, 99.999% pure. (Warning—see 7.1.)
250°C.
7.3 Detector Makeup Gas—Nitrogen, 99.999 % pure.
6.2 Sample Introduction—Manual or automatic liquid
(Warning—see 7.1.)
sample injection to the splitting injector may be employed. 7.4 Fuel Gas—Hydrogen, 99.999% pure. (Warning—
Automated injections are highly recommended. Micro- Hydrogen, flammable gas under high pressure.)
syringes,auto-syringesamplers,orvalvescapableof0.1to0.5 7.5 Reference Standards:
µL. injections are suitable. It should be noted that some 7.5.1 Purity of Reagents—Reagentgradechemicalsshallbe
syringes and improper injection techniques as well as inad- used in all tests. Unless otherwise indicated, it is intended that
equatesplitterdesigncouldresultinsamplefractionation.This all reagents conform to the specifications of the Committee on
AnalyticalReagentsoftheAmericanChemicalSociety where
must be determined in accordance with Section 10.
such specifications are available. Other grades may be used,
6.3 Electronic Integrator—Any electronic integration de-
provided it is first ascertained that the reagent is of sufficiently
vice used for quantitating these analyses shall meet or exceed
high purity to permit its use without lessening the accuracy of
these minimum requirements:
the determination.
6.3.1 Capacity to handle 400 or more peaks per analysis.
7.5.2 Methanol—(Warning—These materials are flam-
6.3.2 Normalized area percent calculation with response
mable and may be harmful or fatal, if ingested or inhaled.).
factors.
7.5.3 Ethanol—Only absolute ethanol of 99.5 minimum
6.3.3 Noise and spike rejection.
percent meets the requirements of this test method.
6.3.4 Accurateareadeterminationoffast(1to2s)peaks(10 (Warning—see 7.5.2.)
Hz or greater sampling rate). 7.5.4 Hydrocarbon and Other Component References—
Individual and mixed component reference materials are com-
6.3.5 Maintain peak detection sensitivity for narrow and
mercially available and may be used to establish qualitative
broad peaks.
and quantitative calibration. (Warning—see 7.5.2.)
6.3.6 Positive and negative sloping baseline correction.
7.5.5 System and Column Evaluation Mixture—Aquantita-
6.3.7 Perpendicular drop and tangent skimming as needed.
tively prepared mixture, complying with Practice D4307,of
6.3.8 Display of baseline used to ensure correct peak area
individual hydrocarbons and oxygenates of interest is used for
determination.
system and column evaluation (see Table 1). (Warning—see
6.4 Open Tubular Column—The column used for this test
7.5.2.) Fig. 1 is a chromatogram of the recommended mixture
method consists of a primary (100 m) analytical column and a
in Table 1.
precolumn. The ability to provide the required component
separations is dependent on the precise control of the column 8. Sampling
selectiv
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