ASTM D6730-01
(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 225C. 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
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 blending components or their higher boiling cuts such as those
derived from fluid catalytic cracking (FCC) are analyzed, and
1.1 This test method covers the determination of individual
the total olefin content may not be accurate.AnnexA1 of this
hydrocarbon components of spark-ignition engine fuels and
test method compares results of the test method with other test
their mixtures containing oxygenate blends (MTBE, ETBE,
methods for selected components, including olefins, and sev-
ethanol, and so forth) with boiling ranges up to 225°C. Other
eral group types for several interlaboratory cooperative study
light liquid hydrocarbon mixtures typically encountered in
samples. Although benzene, toulene, and several oxygenates
petroleum refining operations, such as blending stocks (naph-
are determined, when doubtful as to the analytical results of
thas,reformates,alkylates,andsoforth)mayalsobeanalyzed;
these components, confirmatory analyses can be obtained by
however, statistical data was obtained only with blended
using the specific test methods listed in the reference section.
spark-ignition engine fuels.
1.4.1 Total olefins in the samples may be obtained or
1.2 Based on the cooperative study results, individual com-
confirmed, or both, if necessary, by Test Method D1319
ponent concentrations and precision are determined in the
(volume %) or other test methods, such as those based on
range from 0.01 to approximately 30 mass %.The test method
multidimentional PONA-type of instruments.
may be applicable to higher and lower concentrations for the
1.5 If water is or is suspected of being present, its concen-
individual components; however, the user must verify the
tration may be determined, if desired, by the use of Test
accuracy if the test method is used for components with
Method D1744 or equivalent. Other compounds containing
concentrations outside the specified ranges.
oxygen,sulfur,nitrogen,andsoforth,mayalsobepresent,and
1.3 This test method also determines methanol, ethanol,
may co-elute with the hydrocarbons. If determination of these
t-butanol, methyl t-butyl ether (MTBE), ethyl t-butyl ether
specific compounds is required, it is recommended that test
(ETBE), and t-amyl methyl ether (TAME) in spark ignition
methods for these specific materials be used, such as Test
engine fuels in the concentration range from 1 to 30 mass %.
Methods D4815 and D5599 for oxygenates, andTest Method
However, the cooperative study data provided insufficient
D5623 for sulfur compounds, or equivalent.
statistical data for obtaining a precision statement for these
1.6 This standard does not purport to address all of the
compounds.
safety concerns, if any, associated with its use. It is the
1.4 Although a majority of the individual hydrocarbons
responsibility of the user of this standard to establish appro-
present are determined, some co-elution of compounds is
priate safety and health practices and determine the applica-
encountered. If this test method is utilized to estimate bulk
bility of regulatory limitations prior to use.
hydrocarbongroup-typecomposition(PONA),theuserofsuch
data should be cautioned that some error will be encountered
2. Referenced Documents
duetoco-elutionandalackofidentificationofallcomponents
2.1 ASTM Standards:
present. Samples containing significant amounts of naphthenic
D1319 Test Method for Hydrocarbon Types in Liquid
(for example, virgin naphthas) constituents above n-octane
Petroleum Products by Fluorescent Indicator Adsorption
may reflect significant errors in PONA-type groupings. Based
D1744 Test Method for Determination of Water in Liquid
on the gasoline samples in the interlaboratory cooperative
Petroleum Products by Karl Fisher Reagent
study, this test method is applicable to samples containing less
D3700 PracticeforContainingHydrocarbonFluidSamples
than 25 mass % of olefins. However, some interfering co-
Using a Floating Piston Cylinder
elution with the olefins above C is possible, particularly if
D4057 Practice for Manual Sampling of Petroleum and
This test method is under the jurisdiction of ASTM Committee D02 on
PetroleumProductsandLubricantsandisthedirectresponsibilityofSubcommittee Annual Book of Standards, Vol 05.01.
D02.04.0Lon Gas Chromatographic Methods. Discontinued; see 1999 Annual Book of ASTM Standards, Vol 05.01.
Current edition approved Nov. 10, 2001. Published January 2002. Annual Book of Standards, Vol 05.02.
Copyright © ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959, United States.
D6730–01
Petroleum Products control and product specification compliance for many indi-
D4177 Practice for Automatic Sampling of Petroleum and vidual hydrocarbons can be determined through the use of this
Petroleum Products test method.
D4307 PracticeforPreparationofLiquidBlendsforUseas 5.2 This test method is adopted from earlier development
, , ,
4 78910
Analytical Standards and enhancement. The chromatographic operating con-
D4626 Practice for Calculation of Gas Chromatographic ditions and column tuning process, included in this test
Response Factors method,weredevelopedtoprovideandenhancetheseparation
D4815 Test Method for Determination of MTBE, ETBE, and subsequent determination of many individual components
TAME, DIPE, tertiary-Amyl Alcohol and C to C Alco- not obtained with previous single-column analyses. The col-
1 4
hols in Gasoline by Gas Chromatography umn temperature program profile is selected to afford the
D5580 Test Method for Determination of Benzene, Tolu- maximum resolution of possible co-eluting components, espe-
ene,Ethylbenzene, p/m-Xylene, o-Xylene,C andHeavier cially where these are of two different compound types (for
Aromatics and Total Aromatics in Finished Gasoline by example, a paraffin and a naphthene).
Gas Chromatography 5.3 Although a majority of the individual hydrocarbons
D5599 Test Method for Determination of Oxygenates in present in petroleum distillates are determined, some co-
Gasoline by Gas Chromatography and Oxygen Selective elution of compounds is encountered. If this test method is
Flame Ionization Detection utilized to determine bulk hydrocarbon group-type composi-
D5623 Test Method for Sulfur Compounds in Light Petro- tion (PONA), the user of such data should be cautioned that
leum Liquids by Gas Chromatography and Sulfur Selec- some error will be encountered due to co-elution and a lack of
tive Detection identification of all components present. Samples containing
E355 Practice for Gas Chromatography Terms and Rela- significantamountsofolefinicornaphthenic,orboth,constitu-
tionships ents above octane may reflect significant errors in PONA-type
E594 Practice forTesting Flame Ionization Detectors Used groupings.
in Gas or Supercritical Fluid Chromatography 5.4 If water is or is suspected of being present, its concen-
E1510 Practice for Installing Fused Silica Open Tubular tration is determined by the use of Test Method D1744. Other
Capillary Columns in Gas Chromatography compounds containing oxygen, sulfur, nitrogen, and so forth
may also be present, and may co-elute with the hydrocarbons.
3. Terminology
When known co-elution exists, these are noted in the test
method data tables. If determination of these specific com-
3.1 Definitions—This test method makes reference to many
pounds is required, it is recommended that test methods for
common gas chromatographic procedures, terms, and relation-
these specific materials be used, such as Test Method D4815
ships. Detailed definitions can be found in Practice E355.
andD5599foroxygenates,TestMethodD5580foraromatics,
and Test Method D5623 for sulfur compounds.
4. Summary of Test Method
4.1 A representative sample of the petroleum liquid is
6. Apparatus
introduced into a gas chromatograph equipped with an open
6.1 Gas Chromatograph—Instrumentation capable of col-
tubular (capillary) column coated with a methyl silicone liquid
umn oven temperature programming, from subambient (5°C)
phase,modifiedwithacapillaryprecolumn.Heliumcarriergas
to at least 200°C, in 0.1°C/min or less rate increments, is
transports the vaporized sample through the column, in which
required. Multi-step column oven temperature programming is
it is partitioned into individual components which are sensed
required, consisting of an initial hold time, an initial tempera-
with a flame ionization detector as they elute from the end of
ture program followed by an isothermal temperature hold and
the column. The detector signal is presented on a strip chart
another programmed temperature rise.Aheated flash vaporiz-
recorder or digitally, or both, by way of an integrator or
ing injector designed to provide a linear sample split injection
integrating computer. Each eluting component is identified by
(that is, 200:1) is required for proper sample introduction. The
comparing its retention time to that established by analyzing
associatedcarriergascontrolsmustbeofsufficientprecisionto
reference standards or samples under identical conditions. The
provide reproducible column flows and split ratios in order to
concentration of each component in mass % is determined by
maintain analytical integrity. A hydrogen flame ionization
normalization of the peak areas after correction with detector
response factors. Unknown components are reported as a total
unknown mass %.
Johansen, N.G., and Ettre, L.S., “Retention Index Values of Hydrocarbons on
Open Tubular Columns Coated with Methyl Silicone Liquid Phases,” Chro-
5. Significance and Use
matographia, Vol 5, No. 10, October 1982.
Johansen, N.G., Ettre, L.S., and Miller, R.L., “Quantitative Analysis of
5.1 Knowledge of the individual component composition
Hydrocarbons by Structural Group Type in Gasolines and Distillates. Part 1,”
(speciation) of gasoline fuels and blending stocks is useful for
Journal of Chromatography, 256, 1983, pp. 393-417.
refinery quality control and product specification. Process 9
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
Quality Improvement Research Program,” SAE Paper No. 930143, March 1993.
Schubert,A.J. and Johansen, N.J., “Cooperative Study to Evaluate a Standard
Annual Book of Standards, Vol 05.03. Test Method for the Speciation of Gasolines by Capillary Gas Chromatography,”
Annual Book of Standards, Vol 14.02. SAE Paper No. 930144, March 1993.
D6730–01
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
Analytical Reagents of the American Chemical Society
must be determined in accordance with Section 10.
where such specifications are available. Other grades may be
6.3 Electronic Integrator—Any electronic integration de-
used, provided it is first ascertained that the reagent is of
vice used for quantitating these analyses shall meet or exceed
sufficiently high purity to permit its use without lessening the
these minimum requirements:
accuracy of 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
selectivity, which is typically slightly more than that exhibited
8.1 Hydrocarbon liquids with Reid vapor pressures of 110
by current commercially available columns. Some older col-
kPa(16psi)orlessmaybesampledeitherintoafloatingpiston
umns, and columns that have a sample residue from repeated
cylinder or into an open container (Practices D4057 and
use without conditioning, may exhibit the required polarity.
D4177). If the sample as received does not meet the upper
Until adequate columns are commercially available, th
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