ASTM D6730-01(2011)
(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
SIGNIFICANCE AND USE
Knowledge of the individual component composition (speciation) of gasoline fuels and blending stocks is useful for refinery quality control and product specification. Process control and product specification compliance for many individual hydrocarbons can be determined through the use of this test method.
This test method is adopted from earlier development and enhancement. , , , The chromatographic operating conditions and column tuning process, included in this test method, were developed to provide and enhance the separation and subsequent determination of many individual components not obtained with previous single-column analyses. The column temperature program profile is selected to afford the maximum resolution of possible co-eluting components, especially where these are of two different compound types (for example, a paraffin and a naphthene).
Although a majority of the individual hydrocarbons present in petroleum distillates are determined, some co-elution of compounds is encountered. If this test method is utilized to determine 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 olefinic or naphthenic, or both, constituents above octane may reflect significant errors in PONA-type groupings.
If water is or is suspected of being present, its concentration is determined by the use of Test Method D1744. Other compounds containing oxygen, sulfur, nitrogen, and so forth may also be present, and may co-elute with the hydrocarbons. When known co-elution exists, these are noted in the test method data tables. If determination of these specific compounds is required, it is recommended that test methods for these specific materials be used, such as Test Method D4815 and D5599 for oxygenates, Test Method D5580 for aromatics, and Test Method D5623 for sulfur compounds.
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 olef...
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Designation: D6730 − 01(Reapproved 2011)
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 (´) indicates an editorial change since the last revision or reapproval.
1. Scope (for example, virgin naphthas) constituents above n-octane
may reflect significant errors in PONA-type groupings. Based
1.1 This test method covers the determination of individual
on the gasoline samples in the interlaboratory cooperative
hydrocarbon components of spark-ignition engine fuels and
study, this test method is applicable to samples containing less
their mixtures containing oxygenate blends (MTBE, ETBE,
than 25 mass % of olefins. However, some interfering co-
ethanol, and so forth) with boiling ranges up to 225°C. Other
elution with the olefins above C is possible, particularly if
light liquid hydrocarbon mixtures typically encountered in
blending components or their higher boiling cuts such as those
petroleum refining operations, such as blending stocks
derived from fluid catalytic cracking (FCC) are analyzed, and
(naphthas, reformates, alkylates, and so forth) may also be
the total olefin content may not be accurate. AnnexA1 of this
analyzed; however, statistical data was obtained only with
test method compares results of the test method with other test
blended spark-ignition engine fuels.
methods for selected components, including olefins, and sev-
1.2 Based on the cooperative study results, individual com-
eral group types for several interlaboratory cooperative study
ponent concentrations and precision are determined in the
samples. Although benzene, toulene, and several oxygenates
range from 0.01 to approximately 30 mass %.The test method
are determined, when doubtful as to the analytical results of
may be applicable to higher and lower concentrations for the
these components, confirmatory analyses can be obtained by
individual components; however, the user must verify the
using the specific test methods listed in the reference section.
accuracy if the test method is used for components with
1.4.1 Total olefins in the samples may be obtained or
concentrations outside the specified ranges.
confirmed, or both, if necessary, by Test Method D1319
1.3 This test method also determines methanol, ethanol,
(volume %) or other test methods, such as those based on
t-butanol, methyl t-butyl ether (MTBE), ethyl t-butyl ether
multidimentional PONA-type of instruments.
(ETBE), and t-amyl methyl ether (TAME) in spark ignition
1.5 If water is or is suspected of being present, its concen-
engine fuels in the concentration range from 1 to 30 mass %.
tration may be determined, if desired, by the use of Test
However, the cooperative study data provided insufficient
Method D1744 or equivalent. Other compounds containing
statistical data for obtaining a precision statement for these
oxygen,sulfur,nitrogen,andsoforth,mayalsobepresent,and
compounds.
may co-elute with the hydrocarbons. If determination of these
1.4 Although a majority of the individual hydrocarbons
specific compounds is required, it is recommended that test
present are determined, some co-elution of compounds is
methods for these specific materials be used, such as Test
encountered. If this test method is utilized to estimate bulk
Methods D4815 and D5599 for oxygenates, and Test Method
hydrocarbongroup-typecomposition(PONA),theuserofsuch
D5623 for sulfur compounds, or equivalent.
data should be cautioned that some error will be encountered
1.6 The values stated in SI units are to be regarded as
duetoco-elutionandalackofidentificationofallcomponents
standard. No other units of measurement are included in this
present. Samples containing significant amounts of naphthenic
standard.
1.7 This standard does not purport to address all of the
This test method is under the jurisdiction of ASTM Committee D02 on
Petroleum Products, Liquid Fuels, and Lubricantsand is the direct responsibility of
safety concerns, if any, associated with its use. It is the
Subcommittee D02.04.0L on Gas Chromatography Methods.
responsibility of the user of this standard to establish appro-
Current edition approved May 1, 2011. Published May 2011. Originally
ε1 priate safety and health practices and determine the applica-
approved in 2001. Last previous edition approved in 2006 as D6730–01(2006) .
DOI: 10.1520/D6730-01R11. bility of regulatory limitations prior to use.
Copyright © ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959. United States
D6730 − 01 (2011)
2. Referenced Documents reference standards or samples under identical conditions. The
2 concentration of each component in mass % is determined by
2.1 ASTM Standards:
normalization of the peak areas after correction with detector
D1319TestMethodforHydrocarbonTypesinLiquidPetro-
response factors. Unknown components are reported as a total
leum Products by Fluorescent Indicator Adsorption
unknown mass %.
D1744Test Method for Determination of Water in Liquid
Petroleum Products by Karl Fischer Reagent
5. Significance and Use
D3700Practice for Obtaining LPG Samples Using a Float-
5.1 Knowledge of the individual component composition
ing Piston Cylinder
(speciation) of gasoline fuels and blending stocks is useful for
D4057Practice for Manual Sampling of Petroleum and
refinery quality control and product specification. Process
Petroleum Products
control and product specification compliance for many indi-
D4177Practice for Automatic Sampling of Petroleum and
vidual hydrocarbons can be determined through the use of this
Petroleum Products
test method.
D4307Practice for Preparation of Liquid Blends for Use as
5.2 This test method is adopted from earlier development
Analytical Standards
3,4,5,6
D4626Practice for Calculation of Gas Chromatographic and enhancement. The chromatographic operating condi-
Response Factors tions and column tuning process, included in this test method,
D4815Test Method for Determination of MTBE, ETBE, were developed to provide and enhance the separation and
TAME, DIPE, tertiary-Amyl Alcohol and C to C Alco- subsequent determination of many individual components not
1 4
hols in Gasoline by Gas Chromatography obtained with previous single-column analyses. The column
D5580Test Method for Determination of Benzene,Toluene, temperatureprogramprofileisselectedtoaffordthemaximum
Ethylbenzene, p/m-Xylene, o-Xylene, C and Heavier resolutionofpossibleco-elutingcomponents,especiallywhere
Aromatics, and Total Aromatics in Finished Gasoline by these are of two different compound types (for example, a
Gas Chromatography paraffin and a naphthene).
D5599Test Method for Determination of Oxygenates in
5.3 Although a majority of the individual hydrocarbons
Gasoline by Gas Chromatography and Oxygen Selective
present in petroleum distillates are determined, some co-
Flame Ionization Detection
elution of compounds is encountered. If this test method is
D5623Test Method for Sulfur Compounds in Light Petro-
utilized to determine bulk hydrocarbon group-type composi-
leum Liquids by Gas Chromatography and Sulfur Selec-
tion (PONA), the user of such data should be cautioned that
tive Detection
some error will be encountered due to co-elution and a lack of
E355PracticeforGasChromatographyTermsandRelation-
identification of all components present. Samples containing
ships
significantamountsofolefinicornaphthenic,orboth,constitu-
E594Practice for Testing Flame Ionization Detectors Used
ents above octane may reflect significant errors in PONA-type
in Gas or Supercritical Fluid Chromatography
groupings.
E1510Practice for Installing Fused Silica Open Tubular
5.4 If water is or is suspected of being present, its concen-
Capillary Columns in Gas Chromatographs
tration is determined by the use of Test Method D1744. Other
compounds containing oxygen, sulfur, nitrogen, and so forth
3. Terminology
may also be present, and may co-elute with the hydrocarbons.
3.1 Definitions—This test method makes reference to many
When known co-elution exists, these are noted in the test
common gas chromatographic procedures, terms, and relation-
method data tables. If determination of these specific com-
ships. Detailed definitions can be found in Practice E355.
pounds is required, it is recommended that test methods for
these specific materials be used, such as Test Method D4815
4. Summary of Test Method
and D5599 for oxygenates, Test Method D5580 for aromatics,
4.1 A representative sample of the petroleum liquid is
and Test Method D5623 for sulfur compounds.
introduced into a gas chromatograph equipped with an open
tubular (capillary) column coated with a methyl silicone liquid 6. Apparatus
phase,modifiedwithacapillaryprecolumn.Heliumcarriergas
6.1 Gas Chromatograph—Instrumentation capable of col-
transports the vaporized sample through the column, in which
umn oven temperature programming, from subambient (5°C)
it is partitioned into individual components which are sensed
with a flame ionization detector as they elute from the end of
Johansen, N.G., and Ettre, L.S., “Retention Index Values of Hydrocarbons on
the column. The detector signal is presented on a strip chart
Open Tubular Columns Coated with Methyl Silicone Liquid Phases,”
recorder or digitally, or both, by way of an integrator or
Chromatographia, Vol 5, No. 10, October 1982.
Johansen, N.G., Ettre, L.S., and Miller, R.L., “Quantitative Analysis of
integrating computer. Each eluting component is identified by
Hydrocarbons by Structural Group Type in Gasolines and Distillates. Part 1,”
comparing its retention time to that established by analyzing
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
Hydrocarbon/Volatility Study: Fuel Blending and Analysis for the Auto/Oil Air
For referenced ASTM standards, visit the ASTM website, www.astm.org, or Quality Improvement Research Program,” SAE Paper No. 930143, March 1993.
contact ASTM Customer Service at service@astm.org. For Annual Book of ASTM Schubert, A.J. and Johansen, N.J., “Cooperative Study to Evaluate a Standard
Standards volume information, refer to the standard’s Document Summary page on Test Method for the Speciation of Gasolines by Capillary Gas Chromatography,”
the ASTM website. SAE Paper No. 930144, March 1993.
D6730 − 01 (2011)
to at least 200°C, in 0.1°C/min or less rate increments, is
Material fused silica
Length 100 m
required. Multi-step column oven temperature programming is
Internal diameter 0.25 mm
required, consisting of an initial hold time, an initial tempera-
Liquid phase methyl silicone
ture program followed by an isothermal temperature hold and Film thickness 0.50 µm
Theoretical plates, n, pentane at 35°C ; 400 000 to 500 000
another programmed temperature rise.Aheated flash vaporiz-
Retention factor, k, pentane at 35°C 0.45 to 0.50
ing injector designed to provide a linear sample split injection
Resolution, R, t-butanol and 2-methylbutene-2 at 3.25 to 5.25
35°C
(that is, 200:1) is required for proper sample introduction. The
Peak symmetry, t-butanol at 35°C > 1.0 to < 5.0
associatedcarriergascontrolsmustbeofsufficientprecisionto
6.4.2 Precolumn—A variable length (1 to 4 m) of 5%
provide reproducible column flows and split ratios in order to
phenyl/95% dimethylpolysiloxane fused silica open tubular
maintain analytical integrity. A hydrogen flame ionization
column (0.25 mm inside diameter) is added to the front
detector,withassociatedgascontrolsandelectronics,designed
(injector) end of the 100 m column, as described in AnnexA1.
for optimum response with open tubular columns, shall con-
formtothespecificationsasdescribedinPracticeE594,aswell
7. Reagents and Materials
as having an operating temperature range of up to at least
7.1 Carrier Gas—Helium, 99.999% pure. (Warning—
250°C.
Helium, air, nitrogen, compressed gas under pressure.)
6.2 Sample Introduction—Manual or automatic liquid
7.2 Oxidant—Air, 99.999% pure. (Warning—see 7.1.)
sample injection to the splitting injector may be employed.
7.3 Detector Makeup Gas—Nitrogen, 99.999 % pure.
Automated injections are highly recommended. Micro-
(Warning—see 7.1.)
syringes,auto-syringesamplers,orvalvescapableof0.1to0.5
7.4 Fuel Gas—Hydrogen, 99.999% pure. (Warning—
µL. injections are suitable. It should be noted that some
Hydrogen, flammable gas under high pressure.)
syringes and improper injection techniques as well as inad-
equatesplitterdesigncouldresultinsamplefractionation.This
7.5 Reference Standards:
must be determined in accordance with Section 10.
7.5.1 Purity of Reagents—Reagent grade chemicals shall be
used in all tests. Unless otherwise indicated, it is intended that
6.3 Electronic Integrator—Any electronic integration de-
all reagents conform to the specifications of the Committee on
vice used for quantitating these analyses shall meet or exceed
AnalyticalReagentsoftheAmericanChemicalSociety where
these minimum requirements:
such specifications are available. Other grades may be used,
6.3.1 Capacity to handle 400 or more peaks per analysis.
provided it is first ascertained that the reagent is of sufficiently
6.3.2 Normalized area percent calculation with response
high purity to permit its use without lessening the accuracy of
factors.
the determination.
7.5.2 Methanol—(Warning—These materials are flam-
6.3.3 Noise and spike rejection.
mable and may be harmful or fatal, if ingested or inhaled.).
6.3.4 Accurateareadeterminationoffast(1to2s)peaks(10
7.5.3 Ethanol—Only absolute ethanol of 99.5 minimum
Hz or greater sampling rate).
percent meets the requirements of this test method.
6.3.5 Maintain peak detection sensitivity for narrow and
(Warning—see 7.5.2.)
broad peaks.
7.5.4 Hydrocarbon and Other Component References—
6.3.6 Positive and negative sloping baseline correction.
Individual and mixed component reference materials are com-
mercially available and may be used to establish qualitative
6.3.7 Perpendicular drop and tangent skimming as needed.
and quantitative calibration. (Warning —see 7.5.2.)
6.3.8 Display of baseline used to ensure correct peak area
7.5.5 System and Column Evaluation Mixture—A quantita-
determination.
tively prepared mixture, complying with Practice D4307,of
6.4 Open Tubular Column—The column used for this test
individual hydrocarbons and oxygenates of interest is used for
method consists of a primary (100 m) analytical col
...
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