ASTM D7041-04(2010)e1
(Test Method)Standard Test Method for Determination of Total Sulfur in Light Hydrocarbons, Motor Fuels, and Oils by Online Gas Chromatography with Flame Photometric Detection
Standard Test Method for Determination of Total Sulfur in Light Hydrocarbons, Motor Fuels, and Oils by Online Gas Chromatography with Flame Photometric Detection
SIGNIFICANCE AND USE
4.1 This test method can be used to determine total sulfur levels in process feeds and finished products that fall within the scope of this test method.
4.2 Low levels of sulfur in process feed stocks can poison expensive catalysts used in petroleum refining processes. This test method can be used to monitor sulfur levels in these feedstocks.
SCOPE
1.1 This test method covers the determination of total sulfur in liquid hydrocarbons with a final boiling point less than 450°C by gas chromatography using a flame photometric detector.
1.2 This test method is applicable for total sulfur levels from 0.5 to 100 mg S/kg.Note 1—The pooled limit of quantification (PLOQ) derived from the 2002 interlaboratory cooperative test program was determined to be 1 mgS/kg.Note 2—Samples can also be tested at other total sulfur levels, but the precision statements may not apply.
1.3 The values stated in SI units are to be regarded as standard.
1.4 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. For specific hazard statements see Section 7.
General Information
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Standards Content (Sample)
NOTICE: This standard has either been superseded and replaced by a new version or withdrawn.
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Designation: D7041 − 04(Reapproved 2010)
Standard Test Method for
Determination of Total Sulfur in Light Hydrocarbons, Motor
Fuels, and Oils by Online Gas Chromatography with Flame
Photometric Detection
This standard is issued under the fixed designation D7041; 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.
ε NOTE—Table 3 was editorially reinstated in February 2013.
1. Scope D4177 Practice for Automatic Sampling of Petroleum and
Petroleum Products
1.1 This test method covers the determination of total sulfur
E840 PracticeforUsingFlamePhotometricDetectorsinGas
in liquid hydrocarbons with a final boiling point less than
Chromatography
450°C by gas chromatography using a flame photometric
detector.
3. Summary of Test Method
1.2 Thistestmethodisapplicablefortotalsulfurlevelsfrom
3.1 The sample is analyzed by gas chromatography with a
0.5 to 100 mg S/kg.
flame photometric detector. A fixed amount of sample is
NOTE 1—The pooled limit of quantification (PLOQ) derived from the
2002 interlaboratory cooperative test program was determined to be 1 injected into the gas chromatograph where it is vaporized. The
mgS/kg.
air carrier stream carries the vaporized sample into a high
NOTE 2—Samples can also be tested at other total sulfur levels, but the
temperature zone (>900°C) where the compounds present in
precision statements may not apply.
the sample are oxidized. Sulfur compounds are converted to
1.3 The values stated in SI units are to be regarded as
sulfur dioxide (SO ). The carrier stream carries the oxidation
standard.
components onto a chromatographic column where they are
1.4 This standard does not purport to address all of the separated and the SO is quantified by the flame photometric
safety concerns, if any, associated with its use. It is the detector.Calibrationofthedetectorisachievedbytheuseofan
responsibility of the user of this standard to establish appro- appropriate external standard.
priate safety and health practices and determine the applica-
bility of regulatory limitations prior to use. For specific hazard
4. Significance and Use
statements see Section 7.
4.1 This test method can be used to determine total sulfur
levelsinprocessfeedsandfinishedproductsthatfallwithinthe
2. Referenced Documents
scope of this test method.
2.1 ASTM Standards:
4.2 Low levels of sulfur in process feed stocks can poison
D1298 Test Method for Density, Relative Density, or API
expensive catalysts used in petroleum refining processes. This
Gravity of Crude Petroleum and Liquid Petroleum Prod-
test method can be used to monitor sulfur levels in these
ucts by Hydrometer Method
feedstocks.
D4052 Test Method for Density, Relative Density, and API
Gravity of Liquids by Digital Density Meter
5. Apparatus
D4057 Practice for Manual Sampling of Petroleum and
Petroleum Products
5.1 Gas Chromatograph, equipped with automatically con-
trolled valves, capable of automatic calibration with an exter-
This test method is under the jurisdiction of ASTM Committee D02 on
nal standard and having a flame photometric detector with an
Petroleum Products, Liquid Fuels, and Lubricants and is the direct responsibility of
overall sensitivity to detect at least 0.5 mg/kg of SO . It must
Subcommittee D02.03 on Elemental Analysis.
be able to automatically control all valve switching times.
Current edition approved May 1, 2010. Published May 2010. Originally
Although originally developed with online analytical measure-
approved in 2004. Last previous edition approved in 2004 as D7041–04. DOI:
10.1520/D7041-04R10E01.
mentequipmentinanofflinemodeofoperation,suitableonline
For referenced ASTM standards, visit the ASTM website, www.astm.org, or
or laboratory gas chromatographs may apply this test method
contact ASTM Customer Service at service@astm.org. For Annual Book of ASTM
as described. Typical instrument parameters are listed in Table
Standards volume information, refer to the standard’s Document Summary page on
the ASTM website. 1.
Copyright © ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959. United States
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D7041 − 04 (2010)
TABLE 1 Typical Instrument Parameters
all reagents shall conform to the specifications of the Commit-
Carrier gas Zero air tee onAnalytical Reagents of theAmerican Chemical Society,
Carrier flow rate 30 mL/min
where such specifications are available. Other grades may be
Hydrogen flow rate 60 mL/min
used, provided it is first ascertained that the reagent is of
Detector Flame photometric detector
Detector temperature 120°C sufficiently high purity to permit its use without lessening the
Injector temperature 285°C
accuracy of the determination.
Furnace temperature 1000°C
Column 40 ft by ⁄8 in. stainless steel
6.2 Carrier-Gas—Zero grade air is recommended.
tubing,
(Warning—Compressed air is a gas under high pressure that
12 % polyphenyl ether/1.5 %
supports combustion.)
H PO
3 4
on 40/60 Chromosorb T
6.3 Hydrogen—Chromatographic grade recommended,
Column temperature 115°C
minimum purity 99.995 %. (Warning— Hydrogen is an ex-
tremely flammable gas under high pressure.)
6.4 Solvent (Reagent Grade)—the solvent chosen should be
5.1.1 Carrier and Detector Gas Control—The chromato-
capable of dissolving the sulfur-containing compound used to
graph must be equipped with flow controllers or pressure
prepare the standard. The solvent of choice should have a
controllers capable of maintaining a constant supply of carrier
density similar to the samples being analyzed and it should
gas and detector supply gases. Electronic pressure or flow
have sulfur concentrations less than the instrument detection
control is highly recommended.
limit. Mixed solvents such as an isooctane / toluene mixture
5.1.2 Sample Injection System—An automatic sample injec-
can be used to reach the desired density. (Warning— Solvents
tion device is required. The injector must allow the introduc-
used as reagents such as toluene and iso octane are flammable
tion of small sample sizes (0.1 to 1 µL). The sample must be
and may be harmful or fatal if ingested or inhaled.)
accurately and repeatably injected into the gas chromatograph.
6.5 Standards for Calibration and Peak Identification—
Rotary or stem type liquid injection valves or auto injectors are
Standards are used for peak identification and retention time
recommended. The valve or injector must be equipped with a
determination. Also standards of known concentrations are
heated vaporizer section capable of being heated to at least
required for external standard calibration of the gas chromato-
285°C.
graph.
5.2 Pyrolysis Furnace—Afurnace capable of maintaining a
6.5.1 Preparation of Stock Solution (mass/volume), 100 µg
sufficient temperature (>900°C) to pyrolyze the entire sample
S/mL (see Notes 3 and 4).Accurately weigh to the nearest 0.1
and oxidize the sulfur compounds to SO .
mg, 0.0456 g of butyl sulfide into a suitable container such as
5.3 Quartz Combustion Tube—Quartz tube capable of with-
a 100 mL volumetric flask. Dilute to volume with the selected
standing temperatures up to 1200°C. The oxidation section
solvent.Thisstocksolutioncanbefurtherdilutedtothedesired
shall be large enough to ensure complete oxidation of the
sulfur concentration. Other sulfur containing compounds such
sample.
as thiophene or thianaphthene can be substituted for n-butyl
sulfide if desired. The concentration of the stock solution can
5.4 Column—A column that can provide complete separa-
be calculated as follows:
tion of SO from the CO quench and the other oxidized
2 2
components such as H O.
µg S/mL 5 ~M 332.06! 3 ~1 310 !~µg/g!/~100 mL 3 FW! (1)
5.5 Detector—Any flame photometric detector (FPD) can
where:
be used, provided it can detect a minimum peak height twice
M = exact mass of sulfur reference compound (g), and
that of the baseline noise fora1µL injection of a 0.5 mg S/kg
FW = formula weight of sulfur reference compound.
standard. Detector linearity shall be at least equal to or greater
NOTE 3—Commercial standards can be used provided they are checked
than 10 .The user is referred to Practice E840 for assistance in
for accuracy.
NOTE 4—Stock solutions will have a shelf life of approximately 2 to 3
optimizing the operation and performance of the FPD.
months and should be remixed accordingly.
5.6 Data Acquisition System—Use any integrator or com-
6.5.2 Preparation of Stock Solution: (mass/mass), 100 µg
puterized data acquisition system for peak area integration, as
S/g (see Notes 3 and 4). Accurately weigh to the nearest 0.1
well as for recording the chromatographic trace. The device
mg, 0.0456 g of butyl sulfide into a suitable container.Add 100
and software must have the following capabilities:
g (accurately weighed to the nearest 0.1 g) of the selected
5.6.1 Identification of peak by retention time.
solvent.Thisstocksolutioncanbefurtherdilutedtothedesired
5.6.2 Calculation and use of response factors.
sulfur concentration. Other sulfur containing compounds such
5.6.3 External standard calibration calculation.
as thiophene or thianaphthene can be substituted for butyl
5.6.4 Graphic presentation of the chromatogram.
5.7 Analytical Balance—Any balance capable of accurately
weighing materials to the nearest 0.01 mg. 3
Reagent Chemicals, American
...
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