ASTM D4045-04(2010)
(Test Method)Standard Test Method for Sulfur in Petroleum Products by Hydrogenolysis and Rateometric Colorimetry
Standard Test Method for Sulfur in Petroleum Products by Hydrogenolysis and Rateometric Colorimetry
SIGNIFICANCE AND USE
In many petroleum refining processes, low levels of sulfur in feed stocks may poison expensive catalysts. This test method can be used to monitor the amount of sulfur in such petroleum fractions.
This test method may also be used as a quality-control tool for sulfur determination in finished products.
SCOPE
1.1 This test method covers the determination of sulfur in petroleum products in the range from 0.02 to 10.00 mg/kg.
1.2 This test method may be extended to higher concentration by dilution.
1.3 This test method is applicable to liquids whose boiling points are between 30 and 371°C (86 and 700°F). Materials that can be analyzed include naphtha, kerosine, alcohol, steam condensate, various distillates, jet fuel, benzene, and toluene.
1.4 The values stated in SI units are to be regarded as standard. The values given in parentheses are for information only.
1.4.1 Certain specifications for the recorder (see 5.5) are excepted.
1.5 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.
General Information
Relations
Standards Content (Sample)
NOTICE: This standard has either been superseded and replaced by a new version or withdrawn.
Contact ASTM International (www.astm.org) for the latest information
Designation: D4045 − 04(Reapproved 2010)
Standard Test Method for
Sulfur in Petroleum Products by Hydrogenolysis and
Rateometric Colorimetry
This standard is issued under the fixed designation D4045; 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 above, to convert sulfur compounds to hydrogen sulfide (H S).
Readout is by the rateometric detection of the colorimetric
1.1 This test method covers the determination of sulfur in
reactionofH Swithleadacetate.Condensablecomponentsare
petroleum products in the range from 0.02 to 10.00 mg/kg.
converted to gaseous products, such as methane, during hy-
1.2 This test method may be extended to higher concentra-
drogenolysis.
tion by dilution.
4. Significance and Use
1.3 This test method is applicable to liquids whose boiling
points are between 30 and 371°C (86 and 700°F). Materials 4.1 In many petroleum refining processes, low levels of
that can be analyzed include naphtha, kerosine, alcohol, steam
sulfur in feed stocks may poison expensive catalysts. This test
condensate, various distillates, jet fuel, benzene, and toluene. method can be used to monitor the amount of sulfur in such
petroleum fractions.
1.4 The values stated in SI units are to be regarded as
standard. The values given in parentheses are for information 4.2 This test method may also be used as a quality-control
only.
tool for sulfur determination in finished products.
1.4.1 Certain specifications for the recorder (see 5.5) are
3,4
5. Apparatus
excepted.
5.1 Pyrolysis Furnace—A furnace that can provide an
1.5 This standard does not purport to address all of the
adjustable temperature from 900 to 1400°C in a 5-mm inside
safety concerns, if any, associated with its use. It is the
diameter or larger tube is required to pyrolyze the sample. The
responsibility of the user of this standard to establish appro-
furnace entry temperature shall allow insertion of the hypoder-
priate safety and health practices and determine the applica-
mic tip to a depth at which the temperature is 550°C to provide
bility of regulatory limitations prior to use.
sample vaporization at the injection syringe tip. This tempera-
2. Referenced Documents ture shall be above the boiling point of the sample and of the
2 sulfur compounds in the sample (see Fig. 1). The pyrolyzer
2.1 ASTM Standards:
tube may be of quartz; however, the lifetime is limited above
D1193 Specification for Reagent Water
1250°C. Ceramic may be used at any temperature.
D6299 Practice for Applying Statistical Quality Assurance
and Control Charting Techniques to Evaluate Analytical 5.2 Rateometric H S Readout— Hydrogenolysis products
Measurement System Performance contain H S in proportion to sulfur in the sample. The HSis
2 2
measuredbymeasuringrateofchangeofreflectancecausedby
3. Summary of Test Method
darkening when lead sulfide is formed. Rateometric
electronics, adapted to provide a first derivative output, allows
3.1 The sample is injected at a constant rate into a flowing
sufficient sensitivity to measure below 0.1 mg/L (see Fig. 2).
hydrogen stream in a hydrogenolysis apparatus. The sample
and hydrogen are pyrolyzed at a temperature of 1300°C, or
5.3 Hypodermic Syringe—A hypodermic having a needle
long enough to reach the 550°C zone is required.Aside port is
This test method is under the jurisdiction of ASTM Committee D02 on
Petroleum Products, Liquid Fuels, and Lubricantsand is the direct responsibility of The apparatus described in 5.1 – 5.4 inclusive is similar in specification to the
Subcommittee D02.03 on Elemental Analysis. equipment available from Houston Atlas, Inc., 22001 North Park Dr., Kingswood,
Current edition approved May 1, 2010. Published May 2010. Originally TX 77339-3804. For further information see Drushel, H. V., “Trace Sulfur
approved in 1987. Last previous edition approved in 2004 as D4045– 04. DOI: Determination Petroleum Fractions,” Analytical Chemistry, Vol 50, 1978, p. 76.
10.1520/D4045-04R10. The sole source of supply of the apparatus known to the committee at this time
For referenced ASTM standards, visit the ASTM website, www.astm.org, or is Houston Atlas, Inc. If you are aware of alternative suppliers, please provide this
contact ASTM Customer Service at service@astm.org. For Annual Book of ASTM information to ASTM International Headquarters. Your comments will receive
Standards volume information, refer to the standard’s Document Summary page on careful consideration at a meeting of the responsible technical committee, which
the ASTM website. you may attend.
Copyright © ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959. United States
D4045 − 04 (2010)
NOTE 1—The humidifier gas wash bottle is optional.
FIG. 1 Hydrogenolysis Flow Diagram
5.6 Thermocouple—A thermocouple suitable for use at 500
to 1400°C, 250-mm long with readout is required. Type K,
⁄16-in. (1.6-mm) diameter, Type 316 stainless steel sheath is
suitable.
6. Reagents and Materials
6.1 Purity of Reagents—Reagent grade chemicals shall be
used in all tests. Unless otherwise indicated, it is intended that
all reagents conform to the specifications of the Committee on
Analytical Reagents of the American Chemical Society where
such specifications are available. Other grades may be used,
provided it is first ascertained that the reagent is of sufficiently
high purity to permit its use without lessening the accuracy of
the determination.
6.2 Purity of Water—Unless otherwise indicated, references
to water shall be understood to mean Type II reagent grade
water conforming to Specification D1193.
6.3 Sensing Tape—Lead acetate impregnated paper of chro-
matographic quality shall be used. (Warning—Lead is a
FIG. 2 Photorateometry H S Readout
cumulative poison.)
6.4 Hydrogen—As no commercial grade of hydrogen has a
convenient for vacuum filling and for flushing the syringe. A
sulfur specification sufficiently low, each new source of supply
100-µL syringe is satisfactory for injection rates down to 3
must be tested. A change in the zero base line of 5 % of full
µL/min and a 25-µL syringe for lower rates. (Warning—
scale from no flow to full flow indicates impure hydrogen.
Exercise caution as hypodermics can cause accidental injury.)
(Warning—Extremely flammable gas under pressure. Hydro-
gen is a flammable gas. Test all flow systems for leaks and
5.4 Syringe Injection Drive—The drive shall provide
purge with inert gas before introducing hydrogen and after
uniform, continuous sample injections. Variation in drive
removing hydrogen. Keep all flow systems as small in volume
injection rate caused by mechanical irregularities of gears will
as practical and provide protective screening for containers
cause noise. The adjustable drive shall be capable of injection
other than sample flow lines. Dispose of exhaust gases in a
from 6 µL/min to 0.06 µL/min over a 6-min interval.
5.5 Recorder—A chart recorder with 10-V full scale and
10 000-Ω input or greater and having a chart speed of 0.2 to 1
Reagent Chemicals, American Chemical Society Specifications, American
Chemical Society, Washington, DC. For Suggestions on the testing of reagents not
in./min (approximately 0.5 to 3 cm/min) is required. An
listed by the American Chemical Society, see Annual Standards for Laboratory
attenuator can be used for more sensitive recorders. Newer
Chemicals, BDH Ltd., Poole, Dorset, U.K., and the United States Pharmacopeia
instruments that display the results are acceptable in lieu of a
and National Formulary, U.S. Pharmacopeial Convention, Inc. (USPC), Rockville,
chart recorder. MD.
D4045 − 04 (2010)
fume hood or by vacuuming to a safe area. If gas cylinders are erratic pulses of fast drive do not occur when the drive range
used handle carefully as rupture of the valve or cylinder is is switched. Pulses of high sample flow above 15 µL/min will
dangerous.) cause carboning and spurious readings.
6.5 Reference Standards: 7.4 Install sensing tape, and turn H S readout analyzer on.
6.5.1 2,2,4 Trimethyl Pentane (Isooctane)— (Warning—
7.5 Connect the recorder and adjust the zero to desired
Extremely flammable.)
position with hydrogen flowing.
6.5.1.1 ASTM Knock Test Reference Fuel may be used as
7.6 Fill syringe with blank reference standard solution,
the solvent. However, when this material is used, each new lot
typically isooctane, insert the needle through the septum to the
shall be tested for sulfur by this procedure because the
550°C temperature zone, and clamp to the syringe drive. At
specifications are not rigorous enough for this application.
hightemperaturethehotneedlemayabsorbsulfurandatlower
NOTE1—Heptaneorequivalentmaterialmayalsobeusedbutprecision
temperature heavy compounds may not evaporate. Set the
data is based on the use of isooctane.
syringe drive rate desired, normally 6 µL/min, maximum with
6.6 Acetic Acid Solution—Mix glacial acetic acid 1 part by
200 mL/min hydrogen flow. Drive rate may be increased for
volume into 19 parts water (see 6.2). (Warning—Corrosive.)
increased sensitivity up to the point at which carbon is formed.
(Hydrogen flow at 500 mL/min allows injection of 15 µL/min;
6.7 Di-n-Butyl Sulfide—(CH CH CH CH ) S) is used to
3 2 2 2 2
however, dibenzothiophene conversion will be low.)
prepare standards. Equivalent sulfur compound may be used if
care is exercised to prevent more volatile compounds from
8. Calibration Standard
evaporating during preparation or use of standards.
8.1 Prepare a reference standard-solution or solutions of
6.8 Helium or Nitrogen Purge Gas. (Warning—
strength near that expected in the unknown. Measurements can
Compressed gas under high pressure.)
be made by weight or by volume for carrier liquid.
7. Preparation of Apparatus
8.2 Units of sulfur in milligrams per litre of sample are
preferred as this is independent of the density of the carrier
7.1 Turn on the furnace with temperature controls at mini-
liquid. The following equation is used to calculate the volume
mum. Gradually increase furnace control over a 3-h period to
of solvent required to dissolve a precise weight of sulfur
approximately 1300°C to minimize thermal shock. Reverse the
compound, of known composition and purity to prepare a
procedurewhenpreparingforlong-termstorage.Forshutdown
liquid standard:
atnightandoverweekends,reducetemperaturetoabout900°C
but do not turn off the furnace. Furnace and quartz tubing life
b
z 5 3 d 3 e 310 / a or alternatively: (1)
S D ~ !
are extended by not cooling to room temperature.
c
7.2 Connect all tubing and fill prehumidifier outside the
b
a 5 3 d 3 e 310 / z (2)
S D ~ !
cabinet with water if this apparatus is being used, and final
c
humidifier inside the cabinet with 5 % by volume acetic acid
where:
solution. Purge with inert gas, then close valve. Check all
a = desired concentration of sulfur, mg/L, of the standard
connections and repair any leaks that are found.
solution of z millilitre of volume,
(Warning—On instruments where electronics are in close
b = molecular weight of sulfur: 32.06,
proximity with the flow systems, exercise care if leak checking
c = molecular weight of the sulfur compound to be used to
with a soap solution.Asuitable method is to block the line that
prepare the standard.
goes to the final humidifier and observe the flow meter. If the
d = mass of the sulfur compound used to prepare the
flow drops to zero, the flow systems are adequately leak-free.)
standard, g,
Set hydrogen flow at 200 mL/min, and allow temperature to
e = purity of sulfur compound expressed as a decimal, and
stabilize.(Warning—Extremely flammable gas under pres-
z = millilitres of standard solution required to give the
sure.) Make final temperature adjustment to 1315 6 15°C. Use
desired concentration a.
a standard thermocouple to verify temperature by inserting
Example:
through a septum with hydrogen flowing at the rate noted
Calculatethevolumeofsulfurfree isooctanewithvolumeof
above.Determinedepthofinsertionrequired,andalwaysinsert
sulfur compound necessary to dissolve 0.5013 g of 98 % by
the hypodermic tip to the 550°C point (see
weight di-n-butyl sulfide to obtain a standard containing 1000
7.6).(Warning—The use of a humidifier gas wash bottle filled
mg/L of sulfur in a solution.
with approximately 250 mL of water is a potential safety
hazard as hydrogen pressure may build up inside the container.
a = 1000 mg/L
The user of this test method should take appropriate safety
b = 32.06
measures to prevent an accidental injury, if the humidifier gas
c = 146.29 di-n-butyl sulfide (CH CH CH CH ) S
3 2 2 2 2
wash bottle is used in the analysis.)
d = 0.5013 g
e = 0.98
7.3 Prepare the sample injection drive. Check to be sure
32.06 / 146.29 30.501330.98310
@ #
z =
desired injection rate is obtained at various settings.Verify that
5107.66 mL
Isooctane is added to bring the solution to a total volume of
Available from Phillips Petroleum Co., P.O. Drawer O, Borger, TX 79071. 107.66mL.Whenresultsaretobereportedinmassofpartsper
D4045 − 04 (2010)
million mg/kg, the conversion from milligrams per litre should
R = response for unknown sample, and
s
be done as the last step in the calculations.
R = response for standard reference material.
std
8.3 To prepare a sulfur standard with a sulfur concentration
11.2 Report mass of parts per million of sulfur as follows:
of 1000 mg/L, as previously described, obtain a clean 125-mL
S, ppm 5 ~mg/L!/~density! 5 mg/kg (4)
glass container, a 100-mL flask, and a 20-mL graduated glass
pipet. Rinse each thoroughly with 2,2,4-trimethyl pentane
since density of sample is in grams per cubic centimetres.
(isooctane). (Warning—Extremely flammable.) Pour approxi-
mately 90 mL of isooctane into the 100-mL flask. Weigh
12. Quality Assurance/Quality Control (QA/QC)
approximately 0.5 g of di- n-butyl sulfide directly into the flask
12.1 Confirm the performance of the instrument and the test
and record the mass added, to 650 µg. Add additional
procedure by analyzing a control (QC) sample.
isooctane to the flask to 100 mL. Transfer the mixture to the
12.1.1 When QA/QC protocols are already established in
125-mL container and add isooctane equal to the difference of
the testing facility, these may be used when they confirm the
z minus 100 mL. Keep containers closed as much as possible.
reliability of test result.
Do not open containers of pure sulfur compound in the vicinity
12.1.2 When there is no QA/QC protocol established in the
of sulfur free stocks or
...
Questions, Comments and Discussion
Ask us and Technical Secretary will try to provide an answer. You can facilitate discussion about the standard in here.