ASTM D7398-07
(Test Method)Standard Test Method for Boiling Range Distribution of Fatty Acid Methyl Esters (FAME) in the Boiling Range from 100 to 615C by Gas Chromatography
Standard Test Method for Boiling Range Distribution of Fatty Acid Methyl Esters (FAME) in the Boiling Range from 100 to 615C by Gas Chromatography
SCOPE
1.1 This test method covers the determination of the boiling range distribution of fatty acid methyl esters (FAME). This test method is applicable to FAMES (biodiesel, B100) having an initial boiling point greater than 100C and a final boiling point less than 615C at atmospheric pressure as measured by this test method.
1.2 The test method can also be applicable to blends of diesel and biodiesel (B1 through B100), however precision for these samples types has not been evaluated.
1.3 The test method is not applicable for analysis of petroleum containing low molecular weight components (for example naphthas, reformates, gasolines, crude oils).
1.4 Boiling range distributions obtained by this test method are not equivalent to results from low efficiency distillation such as those obtained with Test Method D 86 or D 1160, especially the initial and final boiling points.
1.5 This test method uses the principles of simulated distillation methodology. See Test Methods D 2887, D 6352, and D 7213.
1.6 &si-value;
1.7 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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Designation: D7398 – 07
Standard Test Method for
Boiling Range Distribution of Fatty Acid Methyl Esters
(FAME) in the Boiling Range from 100 to 615°C by Gas
Chromatography
This standard is issued under the fixed designation D7398; the number immediately following the designation indicates the year of
original adoption or, in the case of revision, the year of last revision. A number in parentheses indicates the year of last reapproval. A
superscript epsilon (´) indicates an editorial change since the last revision or reapproval.
1. Scope D86 Test Method for Distillation of Petroleum Products at
Atmospheric Pressure
1.1 This test method covers the determination of the boiling
D1160 Test Method for Distillation of Petroleum Products
range distribution of fatty acid methyl esters (FAME).This test
at Reduced Pressure
method is applicable to FAMES (biodiesel, B100) having an
D2887 Test Method for Boiling Range Distribution of
initialboilingpointgreaterthan100°Candafinalboilingpoint
Petroleum Fractions by Gas Chromatography
less than 615°C at atmospheric pressure as measured by this
D2892 Test Method for Distillation of Crude Petroleum
test method.
(15-Theoretical Plate Column)
1.2 The test method can also be applicable to blends of
D4626 Practice for Calculation of Gas Chromatographic
diesel and biodiesel (B1 through B100), however precision for
Response Factors
these samples types has not been evaluated.
D6352 Test Method for Boiling Range Distribution of
1.3 The test method is not applicable for analysis of
Petroleum Distillates in Boiling Range from 174 to 700°C
petroleum containing low molecular weight components (for
by Gas Chromatography
example naphthas, reformates, gasolines, crude oils).
D6751 Specification for Biodiesel Fuel Blend Stock (B100)
1.4 Boiling range distributions obtained by this test method
for Middle Distillate Fuels
are not equivalent to results from low efficiency distillation
D7213 Test Method for Boiling Range Distribution of
such as those obtained with Test Method D86 or D1160,
Petroleum Distillates in the Boiling Range from 100 to
especially the initial and final boiling points.
615°C by Gas Chromatography
1.5 This test method uses the principles of simulated distil-
E355 Practice for Gas Chromatography Terms and Rela-
lation methodology. See Test Methods D2887, D6352, and
tionships
D7213.
E594 Practice for Testing Flame Ionization Detectors Used
1.6 The values stated in SI units are to be regarded as
in Gas or Supercritical Fluid Chromatography
standard. The values given in parentheses are for information
E1510 Practice for Installing Fused Silica Open Tubular
only.
Capillary Columns in Gas Chromatographs
1.7 This standard does not purport to address all of the
safety concerns, if any, associated with its use. It is the
3. Terminology
responsibility of the user of this standard to establish appro-
3.1 Definitions:
priate safety and health practices and determine the applica-
3.1.1 This test method makes reference to many common
bility of regulatory limitations prior to use.
gas chromatographic procedures, terms, and relationships.
2. Referenced Documents Detailed definitions of these can be found in Practices E355,
E594, and E1510.
2.1 ASTM Standards:
3.1.2 biodiesel, n—fuel composed of mono-alkyl esters of
long chain fatty acids derived from vegetable oils or animal
This test method is under the jurisdiction of ASTM Committee D02 on
fats, designated B100.
Petroleum Products and Lubricants and is the direct responsibility of Subcommittee
3.2 Definitions of Terms Specific to This Standard:
D02.04.0H on Chromatographic Distribution Methods.
3.2.1 area slice, n—area resulting from the integration of
Current edition approved Nov. 1, 2007. Published December 2007. DOI:
10.1520/D7398-07.
the chromatographic detector signal within a specified reten-
For referenced ASTM standards, visit the ASTM website, www.astm.org, or
tion time interval. In area slice mode (6.4.2), peak detection
contact ASTM Customer Service at service@astm.org. For Annual Book of ASTM
Standards volume information, refer to the standard’s Document Summary page on
the ASTM website.
Copyright © ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959, United States.
D7398 – 07
parameters are bypassed and the detector signal integral is provided by separate heating of the point of injection or in
recorded as area slices of consecutive, fixed duration time conjunction with column oven heating.
intervals. 4.3 The column oven temperature is raised at a reproducible
3.2.2 atmospheric equivalent temperature (AET), linear rate to effect separation of the FAME components in
n—temperature converted from the measured vapor tempera- order of increasing boiling point relative to a n-paraffin
ture obtained at sub-ambient pressure to atmospheric equiva- calibration mixture. The elution of sample components is
lenttemperature(AET)correspondingtotheequivalentboiling quantitatively determined using a flame ionization detector.
point at atmospheric pressure, 101.3 kPa (760 mm Hg), The The detector signal integral is recorded as area slices for
AET is the expected distillate temperature if the distillation consecutive retention time intervals during the analysis.
was performed at atmospheric pressure and there was no 4.4 Retentiontimesofknownnormalparaffinhydrocarbons,
thermal decomposition. spanning the scope of the test method (C –C ), are deter-
5 60
3.2.3 corrected area slice, n—area slice corrected for base- mined and correlated to their boiling point temperatures. The
line offset, by subtraction of the exactly corresponding area normalized cumulative corrected sample areas for each con-
slice in a previously recorded blank (non-sample) analysis. secutiverecordedtimeintervalareusedtocalculatetheboiling
3.2.4 cumulative corrected area, n—accumulated sum of range distribution. The boiling point temperature at each
correctedareaslicesfromthebeginningoftheanalysisthrough reported percent off increment is calculated from the retention
a given retention time, ignoring any non-sample area (for time calibration.
example, solvent). 4.5 The retention time versus boiling point curve is cali-
3.2.5 initial boiling point (IBP), n—temperature (corre- brated with normal paraffin hydrocarbons since these boiling
spondingtotheretentiontime)atwhichacumulativecorrected points are well defined. A mixture of FAMEs is analyzed to
area count equal to 0.5 % of the total sample area under the check column resolution. A triglyceride is analyzed to verify
chromatogram is obtained. the system’s ability to detect unreacted oil.
3.2.6 final boiling point (FBP), n—temperature (corre-
5. Significance and Use
spondingtotheretentiontime)atwhichacumulativecorrected
5.1 The boiling range distribution of FAMES provides an
area count equal to 99.5 % of the total sample area under the
insight into the composition of product related to the transes-
chromatogram is obtained.
terificationprocess.Thisgaschromatographicdeterminationof
3.2.7 slice rate, n—frequency of data sampling or the
boiling range can be used to replace conventional distillation
frequency of data bunching provided that the frequency of data
methods for product specification testing with the mutual
acquisition is larger than the frequency of bunching. The unit
agreement of interested parties.
of frequency is points/seconds or Hz.
5.2 Biodiesel (FAMES) exhibits a boiling point rather than
3.2.8 slice time, n—cumulative slice rate (analysis time)
a distillation curve. The fatty acid chains in the raw oils and
associatedwitheachareaslicethroughoutthechromatographic
fats from which biodiesel is produced are mainly comprised of
analysis. The slice time is the time at the end of each
straight chain hydrocarbons with 16 to 18 carbons that have
contiguous area slice.
3.2.9 total sample area, n—cumulative corrected area, from similar boiling temperatures. The atmospheric boiling point of
biodiesel generally ranges from 330 to 357°C. The Specifica-
the initial point to the final area point.
3.3 Abbreviations: tion D6751 value of 360°C max at 90 % off by Test Method
D1160 was incorporated as an precaution to ensure the fuel has
3.3.1 Acommonabbreviationofhydrocarboncompoundsis
to designate the number of carbon atoms in the compound. A not been adulterated with high boiling contaminants.
prefix is used to indicate the carbon chain form, while a
6. Apparatus
subscripted suffix denotes the number of carbon atoms (for
6.1 Chromatograph—The following gas chromatographic
example, normal decane n-C ; iso-tetradecane = i-C ).
10 14
system performance characteristics are required:
3.3.2 A common abbreviation for FAME compounds is to
6.1.1 Column Oven—Capable of sustained and linear pro-
designate the number of carbon atoms and number of double
grammed temperature operation from near ambient (for ex-
bonds in the compound. The number of carbon atoms is
ample 35 to 50°C) up to 400°C.
denoted by a number after the “C” and the number following
6.1.2 Column Temperature Programmer—The chromato-
a colon indicates the number of double bonds (for example,
graph must be capable of linear programmed temperature
C16:2; FAME with 16 carbon atoms and 2 double bonds).
operationupto400°Catselectablelinearratesupto20°C/min.
4. Summary of Test Method
The programming rate must be sufficiently reproducible to
4.1 The boiling range distribution by distillation is simu- obtaintheretentiontimerepeatabilityof0.03min(3s)foreach
lated by the use of gas chromatography. A non-polar open component in the calibration mixture described in 7.3.
tubular(capillary)gaschromatographiccolumnisusedtoelute 6.1.3 Detector—This test method requires a flame ioniza-
the hydrocarbon and FAME components of the sample in order tion detector (FID). The detector must meet or exceed the
of increasing boiling point. following specifications as detailed in Practice E594. The
4.2 A sample aliquot is diluted with a viscosity reducing specification of flame jet orifice is approximately 0.45 mm
solvent and introduced into the chromatographic system. The (0.018 in.).
solvent shall be apolar and not interfere with measurement of 6.1.3.1 Operating Temperature, 400°C.
the sample in the 100 to 615°C range. Sample vaporization is 6.1.3.2 Sensitivity, >0.005 coulombs/ g carbon.
D7398 – 07
-11
6.1.3.3 Minimum Detectability,1 3 10 g carbon / s. 7. Reagents and Materials
6.1.3.4 Linear Range, >10
7.1 Gases—Thefollowingcompressedgasesareutilizedfor
6.1.3.5 Connection of the column to the detector must be
the operation of the gas chromatograph.
such that no temperature below the column temperature exists.
7.1.1 Helium, 99.999 %. (Warning—Compressed gas un-
Refer to Practice E1510 for proper installation and condition-
der high pressure.) This gas can be used as carrier gas. Ensure
ing of the capillary column.
sufficient pressure for a constant carrier gas flow rate. It is not
6.1.4 Sample Inlet System—Any sample inlet system ca-
to contain more than 5 mL/m of oxygen and the total amount
pable of meeting the performance specification in 6.1.5 and 7.3
of impurities are not to exceed 10 mL/m .
may be used. Programmed temperature vaporization (PTV)
7.1.2 Nitrogen, 99.999 %. (Warning—Compressed gas un-
and programmable cool on-column injection systems have
der high pressure.) This gas can be used as carrier gas. Ensure
been used successfully.
sufficient pressure for a constant carrier gas flow rate. It is not
6.1.5 Carrier Gas Flow Control—The chromatograph shall
to contain more than 5 mL/m of oxygen and the total amount
be equipped with carrier flow control capable of maintaining
of impurities are not to exceed 10 mL/m .
constant carrier gas flow control through the column through-
7.1.3 Hydrogen, 99.999 %. (Warning—Extremely flam-
out the column temperature program cycle as measured with
mable gas under high pressure.) The total impurities are not to
the use of flow a sensor. Flow rate must be maintained within
exceed 10 mL/m . This gas can be used as carrier gas. Ensure
1 % through out the temperature program.
sufficient pressure for a constant carrier gas flow rate. It is also
6.2 Microsyringe—A microsyringe with a 23 gauge or
used as fuel for the flame ionization detector (FID).
smaller stainless steel needle is used for on-column sample
7.1.4 Air, 99.999 %. (Warning—Compressed gas under
introduction. Syringes of 0.1 to 10 µL capacity are available.
high pressure and supports combustion.) Total impurities are
6.2.1 Automatic syringe injection is recommended to
nottoexceed10mL/m .Thisgasisusedtosustaincombustion
achieve best precision.
in the flame ionization detector (FID).
6.3 Column—This test method is limited to the use of
7.2 Solvents—Unless otherwise indicated, it is intended that
non-polar wall coated open tubular (WCOT) columns of high
all solvents conform to the specifications of the committee on
thermal stability. Glass, fused silica, and stainless steel col-
analytical Reagents of the American Chemical Society where
umns, with a 0.53 mm diameter have been successfully used.
such specifications are available. Other grades may be used
Cross-linked or bonded 100 % dimethyl-polysiloxane station-
provided it is first ascertained that the solvent is of sufficiently
ary phases with film thickness of 0.5 to 1.0 µm have been used.
high purity to permit its use without lessening the accuracy of
The column length and liquid phase film thickness shall allow
the determination.
the elution of at least C n-paraffin (BP= 615°C) and triolein.
60 7.2.1 Carbon Disulfide (CS ), 99+ % pure. (Warning—
The column and conditions shall provide separation of typical
Extremely flammable and toxic liquid.) Used as a viscosity
petroleum hydrocarbons and saturated FAMES in order of
reducing solvent and as a means of reducing mass of sample
increasing boiling point and meet the column resolution
introduced onto the column to ensure linear detector response
requirements of 8.2.1. The column shall provide a resolution
and reduced peak skewness. It is miscible with FAMES and
between five (5) and fifteen (15) using the test method
provides a relatively small response with the FID. The quality
operating conditions.
(hydrocarbon content) is determined by this test method prior
6.4 Data Acquisition System:
to use as a sample diluent.
6.4.1 Recorder—A 0 to 1 mV range recording potentiom-
7.2.2 Cyclohexane (C H ), (99+ % pure) (Warning—
6 12
eter or equivalent, with a full-scale response time of2sor less
Flammable. Health hazard.) Used as a viscosity reducing
may be used to provide a graphical display.
solvent. It is miscible with asphaltic hydrocarbons, however, it
6.4.2 Integrator—Means shall be provided for determining
responds well
...
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