ASTM D6730-01(2006)e1
(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.4 ,5 ,6 ,7 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 D 1744. 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 D 4815 and D 5599 for oxygenates, Test Method D 5580 for aromatics, and Test Method D 5623 for sulfur comp...
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 o...
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Designation: D6730 – 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 (´) indicates an editorial change since the last revision or reapproval.
´ NOTE—Corrected Referenced Documents editorially in April 2007.
1. Scope on the gasoline samples in the interlaboratory cooperative
study, this test method is applicable to samples containing less
1.1 This test method covers the determination of individual
than 25 mass % of olefins. However, some interfering co-
hydrocarbon components of spark-ignition engine fuels and
elution with the olefins above C is possible, particularly if
their mixtures containing oxygenate blends (MTBE, ETBE, 7
blending components or their higher boiling cuts such as those
ethanol, and so forth) with boiling ranges up to 225°C. Other
derived from fluid catalytic cracking (FCC) are analyzed, and
light liquid hydrocarbon mixtures typically encountered in
the total olefin content may not be accurate.AnnexA1 of this
petroleum refining operations, such as blending stocks (naph-
test method compares results of the test method with other test
thas,reformates,alkylates,andsoforth)mayalsobeanalyzed;
methods for selected components, including olefins, and sev-
however, statistical data was obtained only with blended
eral group types for several interlaboratory cooperative study
spark-ignition engine fuels.
samples. Although benzene, toulene, and several oxygenates
1.2 Based on the cooperative study results, individual com-
are determined, when doubtful as to the analytical results of
ponent concentrations and precision are determined in the
these components, confirmatory analyses can be obtained by
range from 0.01 to approximately 30 mass %.The test method
using the specific test methods listed in the reference section.
may be applicable to higher and lower concentrations for the
1.4.1 Total olefins in the samples may be obtained or
individual components; however, the user must verify the
confirmed, or both, if necessary, by Test Method D1319
accuracy if the test method is used for components with
(volume %) or other test methods, such as those based on
concentrations outside the specified ranges.
multidimentional PONA-type of instruments.
1.3 This test method also determines methanol, ethanol,
1.5 If water is or is suspected of being present, its concen-
t-butanol, methyl t-butyl ether (MTBE), ethyl t-butyl ether
tration may be determined, if desired, by the use of Test
(ETBE), and t-amyl methyl ether (TAME) in spark ignition
Method D1744 or equivalent. Other compounds containing
engine fuels in the concentration range from 1 to 30 mass %.
oxygen,sulfur,nitrogen,andsoforth,mayalsobepresent,and
However, the cooperative study data provided insufficient
may co-elute with the hydrocarbons. If determination of these
statistical data for obtaining a precision statement for these
specific compounds is required, it is recommended that test
compounds.
methods for these specific materials be used, such as Test
1.4 Although a majority of the individual hydrocarbons
Methods D4815 and D5599 for oxygenates, and Test Method
present are determined, some co-elution of compounds is
D5623 for sulfur compounds, or equivalent.
encountered. If this test method is utilized to estimate bulk
1.6 This standard does not purport to address all of the
hydrocarbongroup-typecomposition(PONA),theuserofsuch
safety concerns, if any, associated with its use. It is the
data should be cautioned that some error will be encountered
responsibility of the user of this standard to establish appro-
duetoco-elutionandalackofidentificationofallcomponents
priate safety and health practices and determine the applica-
present. Samples containing significant amounts of naphthenic
bility of regulatory limitations prior to use.
(for example, virgin naphthas) constituents above n-octane
may reflect significant errors in PONA-type groupings. Based
2. Referenced Documents
2.1 ASTM Standards:
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 Nov. 1, 2006. Published January 2007. Originally contact ASTM Customer Service at service@astm.org. For Annual Book of ASTM
approved in 2001. Last previous edition approved in 2001 as D6730–01. DOI: Standards volume information, refer to the standard’s Document Summary page on
10.1520/D6730-01R06E01. the ASTM website.
Copyright © ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959, United States.
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D6730 – 01 (2006)
D1319 Test Method for Hydrocarbon Types in Liquid 5. Significance and Use
Petroleum Products by Fluorescent Indicator Adsorption
5.1 Knowledge of the individual component composition
D1744 Test Method for Determination of Water in Liquid
(speciation) of gasoline fuels and blending stocks is useful for
Petroleum Products by Fluorescent Indicator Adsorption
refinery quality control and product specification. Process
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
4,5,6,7
D4177 Practice for Automatic Sampling of Petroleum and
and enhancement. The chromatographic operating condi-
Petroleum Products
tions and column tuning process, included in this test method,
D4307 Practice for Preparation of Liquid Blends for Use as
were developed to provide and enhance the separation and
Analytical Standards
subsequent determination of many individual components not
D4626 Practice for Calculation of Gas Chromatographic
obtained with previous single-column analyses. The column
Response Factors
temperatureprogramprofileisselectedtoaffordthemaximum
D4815 Test Method for Determination of MTBE, ETBE,
resolutionofpossibleco-elutingcomponents,especiallywhere
TAME, DIPE, tertiary-Amyl Alcohol and C to C Alco-
1 4 these are of two different compound types (for example, a
hols in Gasoline by Gas Chromatography
paraffin and a naphthene).
D5580 Test Method for Determination of Benzene, Tolu-
5.3 Although a majority of the individual hydrocarbons
ene,Ethylbenzene, p/m-Xylene, o-Xylene,C andHeavier
present in petroleum distillates are determined, some co-
Aromatics, and Total Aromatics in Finished Gasoline by
elution of compounds is encountered. If this test method is
Gas Chromatography
utilized to determine bulk hydrocarbon group-type composi-
D5599 Test Method for Determination of Oxygenates in
tion (PONA), the user of such data should be cautioned that
Gasoline by Gas Chromatography and Oxygen Selective
some error will be encountered due to co-elution and a lack of
Flame Ionization Detection
identification of all components present. Samples containing
D5623 Test Method for Sulfur Compounds in Light Petro-
significantamountsofolefinicornaphthenic,orboth,constitu-
leum Liquids by Gas Chromatography and Sulfur Selec-
ents above octane may reflect significant errors in PONA-type
tive Detection
groupings.
E355 Practice for Gas Chromatography Terms and Rela-
5.4 If water is or is suspected of being present, its concen-
tionships
tration is determined by the use of Test Method D1744. Other
E594 Practice for Testing Flame Ionization Detectors Used
compounds containing oxygen, sulfur, nitrogen, and so forth
in Gas or Supercritical Fluid Chromatography
may also be present, and may co-elute with the hydrocarbons.
E1510 Practice for Installing Fused Silica Open Tubular
When known co-elution exists, these are noted in the test
Capillary Columns in Gas Chromatographs
method data tables. If determination of these specific com-
pounds is required, it is recommended that test methods for
3. Terminology
these specific materials be used, such as Test Method D4815
3.1 Definitions—This test method makes reference to many
and D5599 for oxygenates, Test Method D5580 for aromatics,
common gas chromatographic procedures, terms, and relation-
and Test Method D5623 for sulfur compounds.
ships. Detailed definitions can be found in Practice E355.
6. Apparatus
4. Summary of Test Method
6.1 Gas Chromatograph—Instrumentation capable of col-
4.1 A representative sample of the petroleum liquid is
umn oven temperature programming, from subambient (5°C)
introduced into a gas chromatograph equipped with an open
to at least 200°C, in 0.1°C/min or less rate increments, is
tubular (capillary) column coated with a methyl silicone liquid
required. Multi-step column oven temperature programming is
phase,modifiedwithacapillaryprecolumn.Heliumcarriergas
required, consisting of an initial hold time, an initial tempera-
transports the vaporized sample through the column, in which
ture program followed by an isothermal temperature hold and
it is partitioned into individual components which are sensed
another programmed temperature rise.Aheated flash vaporiz-
with a flame ionization detector as they elute from the end of
ing injector designed to provide a linear sample split injection
the column. The detector signal is presented on a strip chart
recorder or digitally, or both, by way of an integrator or
integrating computer. Each eluting component is identified by
Johansen, N.G., and Ettre, L.S., “Retention Index Values of Hydrocarbons on
Open Tubular Columns Coated with Methyl Silicone Liquid Phases,” Chro-
comparing its retention time to that established by analyzing
matographia, Vol 5, No. 10, October 1982.
reference standards or samples under identical conditions. The
Johansen, N.G., Ettre, L.S., and Miller, R.L., “Quantitative Analysis of
concentration of each component in mass % is determined by
Hydrocarbons by Structural Group Type in Gasolines and Distillates. Part 1,”
normalization of the peak areas after correction with detector
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
response factors. Unknown components are reported as a total
Hydrocarbon/Volatility Study: Fuel Blending and Analysis for the Auto/Oil Air
unknown mass %.
Quality Improvement Research Program,” SAE Paper No. 930143, March 1993.
Schubert, A.J. and Johansen, N.J., “Cooperative Study to Evaluate a Standard
Test Method for the Speciation of Gasolines by Capillary Gas Chromatography,”
Withdrawn. SAE Paper No. 930144, March 1993.
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D6730 – 01 (2006)
(that is, 200:1) is required for proper sample introduction. The column (0.25 mm inside diameter) is added to the front
associatedcarriergascontrolsmustbeofsufficientprecisionto (injector) end of the 100 m column, as described inAnnexA1.
provide reproducible column flows and split ratios in order to
maintain analytical integrity. A hydrogen flame ionization 7. Reagents and Materials
detector,withassociatedgascontrolsandelectronics,designed
7.1 Carrier Gas—Helium, 99.999% pure. (Warning—
for optimum response with open tubular columns, shall con-
Helium, air, nitrogen, compressed gas under pressure.)
formtothespecificationsasdescribedinPracticeE594,aswell
7.2 Oxidant—Air, 99.999% pure. (Warning—see 7.1.)
as having an operating temperature range of up to at least
7.3 Detector Makeup Gas—Nitrogen, 99.999 % pure.
250°C.
(Warning—see 7.1.)
6.2 Sample Introduction—Manual or automatic liquid
7.4 Fuel Gas—Hydrogen, 99.999% pure. (Warning—
sample injection to the splitting injector may be employed.
Hydrogen, flammable gas under high pressure.)
Automated injections are highly recommended. Micro-
7.5 Reference Standards:
syringes,auto-syringesamplers,orvalvescapableof0.1to0.5
7.5.1 Purity of Reagents—Reagentgradechemicalsshallbe
µL. injections are suitable. It should be noted that some
used in all tests. Unless otherwise indicated, it is intended that
syringes and improper injection techniques as well as inad-
all reagents conform to the specifications of the Committee on
equatesplitterdesigncouldresultinsamplefractionation.This
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—
6.3.5 Maintain peak detection sensitivity for narrow and
Individual and mixed component reference materials are com-
broad peaks.
mercially available and may be used to establish qualitative
6.3.6 Positive and negative sloping baseline correction.
and quantitative calibration. (Warning—see 7.5.2.)
6.3.7 Perpendicular drop and tangent skimming as needed.
7.5.5 System and Column Evaluation Mixture—Aquantita-
6.3.8 Display of baseline used to ensure correct peak area
tively prepared mixture, complying with Practice D4307,of
determination.
individual hydrocarbons and oxygenates of interest is used for
6.4 Open Tubular Column—The column used for this test
system and column evaluation (see Table 1). (Warning—see
method consists of a primary (100 m) analytical column and a
7.5.2.) Fig. 1 is a chromatogram of the recommended mixture
precolumn. The ability to provide the required component
in Table 1.
separations is dependent on the precise control of the column
selectivity, which is typically slightly more than that exhibited
8. Sampling
by current commercially available columns. Some older col-
8.1 Hydrocarbon liquids with Reid vapor pressures of 110
umns, and columns that have a s
...
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