ASTM D4045-99
(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
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 The method may be extended to higher concentration by dilution.
1.3 The method is applicable to liquids whose boiling points are between 30 to 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 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NOTICE: This standard has either been superseded and replaced by a new version or withdrawn.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
An American National Standard
Designation: D 4045 – 99
Standard Test Method for
Sulfur in Petroleum Products by Hydrogenolysis and
Rateometric Colorimetry
This standard is issued under the fixed designation D 4045; 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 (e) indicates an editorial change since the last revision or reapproval.
1. Scope 4. Significance and Use
4.1 In many petroleum refining processes, low levels of
1.1 This test method covers the determination of sulfur in
petroleum products in the range from 0.02 to 10.00 mg/kg. sulfur in feed stocks may poison expensive catalysts. This test
1.2 The method may be extended to higher concentration by method can be used to monitor the amount of sulfur in such
dilution. petroleum fractions.
1.3 The method is applicable to liquids whose boiling points 4.2 This test method may also be used as a quality-control
are between 30 and 371°C (86 and 700°F). Materials that can tool for sulfur determination in finished products.
be analyzed include naphtha, kerosine, alcohol, steam conden-
,
4 5
5. Apparatus
sate, various distillates, jet fuel, benzene, and toluene.
1.4 The values in acceptable SI units are to be regarded as 5.1 Pyrolysis Furnace—A furnace that can provide an
adjustable temperature from 900 to 1400°C in a 5-mm inside
the standard. The values in parentheses are for information
only. diameter or larger tube is required to pyrolyze the sample. The
furnace entry temperature shall allow insertion of the hypoder-
1.4.1 Certain specifications for the recorder (see 5.5) are
excepted. mic tip to a depth at which the temperature is 550°C to provide
sample vaporization at the injection syringe tip. This tempera-
1.5 This standard does not purport to address all of the
safety concerns, if any, associated with its use. It is the ture shall be above the boiling point of the sample and of the
sulfur compounds in the sample (see Fig. 1). The pyrolyzer
responsibility of the user of this standard to establish appro-
priate safety and health practices and determine the applica- tube may be of quartz; however, the lifetime is limited above
1250°C. Ceramic may be used at any temperature.
bility of regulatory limitations prior to use.
5.2 Rateometric H S Readout— Hydrogenolysis products
2. Referenced Documents
contain H S in proportion to sulfur in the sample. The H Sis
2 2
2.1 ASTM Standards: measured by measuring rate of change of reflectance caused by
D 1193 Specification for Reagent Water darkening when lead sulfide is formed. Rateometric electron-
D 6299 Practice for Applying Statisitical Quality Assurance ics, adapted to provide a first derivative output, allows suffi-
Techniques to Evaluate Analytical Measurement System cient sensitivity to measure below 0.1 mg/L (see Fig. 2).
Performance 5.3 Hypodermic Syringe—A hypodermic having a needle
long enough to reach the 550°C zone is required. A side port is
3. Summary of Test Method
convenient for vacuum filling and for flushing the syringe.
3.1 The sample is injected at a constant rate into a flowing
A100-μL syringe is satisfactory for injection rates down to 3
hydrogen stream in a hydrogenolysis apparatus. The sample μL/min and a 25-μL syringe for lower rates.
and hydrogen are pyrolyzed at a temperature of 1300°C, or
NOTE 1—Warning: Exercise caution as hypodermics can cause acci-
above, to convert sulfur compounds to hydrogen sulfide (H S).
dental injury.
Readout is by the rateometric detection of the colorimetric
5.4 Syringe Injection Drive—The drive shall provide uni-
reaction of H S with lead acetate. Condensable components are
form, continuous sample injections. Variation in drive injection
converted to gaseous products, such as methane, during hydro-
genolysis.
The apparatus described in 5.1-5.4 inclusive is similar in specification to the
This test method is under the jurisdiction of ASTM Committee D-2 on equipment available from Houston Atlas, Inc., 22001 North Park Dr., Kingswood,
Petroleum Products and Lubricants and is the direct responsibility of Subcommittee TX 77339-3804. For further information see Drushel, H. V., “Trace Sulfur
D02.03 on Elemental Analysis. Determination Petroleum Fractions,” Analytical Chemistry, Vol 50, 1978, p. 76.
Current edition approved Jan. 10, 1999. Published March 1999. Originally Houston Atlas, Inc. is the sole source of supply of the apparatus known to the
published as D 4045 – 87. Last previous edition D 4045 – 96. committee at this time. If you are aware of alternative suppliers, please provide this
Annual Book of ASTM Standards, Vol 11.01. information to ASTM Headquarters. Your comments will receive careful consider-
3 1
Annual Book of ASTM Standards, Vol 05.03. ation at a meeting of the responsible technical committee, which you may attend.
Copyright © ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959, United States.
D 4045
NOTE 1—The humidifier gas wash bottle is optional.
FIG. 1 Hydrogenolysis Flow Diagram
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 D 1193.
6.3 Sensing Tape—Lead acetate impregnated paper of chro-
matographic quality shall be used. (Warning: See Note 2.)
NOTE 2—Warning: Lead is a cumulative poison.
6.4 Hydrogen—As no commercial grade of hydrogen has a
sulfur specification sufficiently low, each new source of supply
must be tested. A change in the zero base line of 5 % of full
scale from no flow to full flow indicates impure hydrogen.
(Warning: See Notes 3 and 4.)
NOTE 3—Warning: Extremely flammable gas under pressure.
NOTE 4—Warning: Hydrogen is a flammable gas. Test all flow systems
FIG. 2 Photorateometry H S Readout
for leaks and purge with inert gas before introducing hydrogen and after
removing hydrogen. Keep all flow systems as small in volume as practical
and provide protective screening for containers other than sample flow
rate caused by mechanical irregularities of gears will cause
lines. Dispose of exhaust gases in a fume hood or by vacuuming to a safe
noise. The adjustable drive shall be capable of injection from 6
area. If gas cylinders are used handle carefully as rupture of the valve or
μL/min to 0.06 μL/min over a 6-min interval.
cylinder is dangerous.
5.5 Recorder—A chart recorder with 10-V full scale and
6.5 Reference Standards:
10 000-V input or greater and having a chart speed of 0.2 to 1
6.5.1 2,2,4 Trimethyl Pentane (Isooctane)—(Warning:
in./min (approximately 0.5 to 3 cm/min) is required. An
See Note 5.)
attenuator can be used for more sensitive recorders.
NOTE 5—Warning: Extremely flammable.
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.
Reagent Chemicals, American Chemical Society Specifications, American
Chemical Society, Washington, DC. For suggestions on the testing of reagents not
listed by the American Chemical Society, see Analar Standards for Laboratory
6. Reagents and Materials
Chemicals, BDH Ltd., Poole, Dorset, U.K., and the United States Pharmacopeia
6.1 Purity of Reagents—Reagent grade chemicals shall be
and National Formulary, U.S. Pharmacopeial Convention, Inc. (USPC), Rockville,
used in all tests. Unless otherwise indicated, it is intended that MD.
D 4045
6.5.1.1 ASTM Knock Test Reference Fuel may be used as syringe drive rate desired, normally 6 μL/min, maximum with
the solvent. However, when this material is used, each new lot 200 mL/min hydrogen flow. Drive rate may be increased for
shall be tested for sulfur by this procedure because the increased sensitivity up to the point at which carbon is formed.
specifications are not rigorous enough for this application. (Hydrogen flow at 500 mL/min allows injection of 15 μL/min;
however, dibenzothiophene conversion will be low.)
NOTE 6—Heptane or equivalent material may also be used but precision
data is based on the use of isooctane.
8. Calibration Standard
6.6 Acetic Acid Solution—Mix glacial acetic acid 1 part by
8.1 Prepare a reference standard-solution or solutions of
volume into 19 parts water (see 6.2). (Warning: See Note 7.)
strength near that expected in the unknown. Measurements can
NOTE 7—Warning: Corrosive.
be made by weight or by volume for carrier liquid.
6.7 Di-n-Butyl Sulfide—(CH CH CH CH ) S) is used to
8.2 Units of sulfur in milligrams per litre of sample are
3 2 2 2 2
prepare standards. Equivalent sulfur compound may be used if preferred as this is independent of the density of the carrier
care is exercised to prevent more volatile compounds from liquid. The following equation is used to calculate the volume
evaporating during preparation or use of standards. of solvent required to dissolve a precise weight of sulfur
6.8 Helium or Nitrogen Purge Gas.(Warning: See Note 8.) compound, of known composition and purity to prepare a
liquid standard:
NOTE 8—Warning: Compressed gas under high pressure.
b
z 5 3 d 3 e 3 10 /~a! or alternatively : (1)
S D
7. Preparation of Apparatus
c
7.1 Turn on the furnace with temperature controls at mini-
b
a 5 3 d 3 e 3 10 /~z! (2)
S D
mum. Gradually increase furnace control over a 3-h period to
c
approximately 1300°C to minimize thermal shock. Reverse the
where:
procedure when preparing for long-term storage. For shutdown
a 5 desired concentration of sulfur, mg/L, of the standard
at night and over weekends, reduce temperature to about 900°C
solution of z millilitre of volume,
but do not turn off the furnace. Furnace and quartz tubing life
b 5 molecular weight of sulfur: 32.06,
are extended by not cooling to room temperature.
c 5 molecular weight of the sulfur compound to be used to
7.2 Connect all tubing and fill prehumidifier outside the
prepare the standard.
cabinet with water if this apparatus is being used, and final
d 5 mass of the sulfur compound used to prepare the
humidifier inside the cabinet with
...
Questions, Comments and Discussion
Ask us and Technical Secretary will try to provide an answer. You can facilitate discussion about the standard in here.