Designation: D 6667 – 01 An American National Standard

Standard Test Method for

Determination of Total Volatile Sulfur in Gaseous
Hydrocarbons and Liquefied Petroleum Gases by Ultraviolet
Fluorescence1
This standard is issued under the fixed designation D 6667; 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 D 6299 Practice for Applying Statistical Quality Assurance

1.1 This test method covers the determination of total Techniques to Evaluate Analytical Measurement System
volatile sulfur in gaseous hydrocarbons and liquefied petro- Performance6
leum (LP) gases. It is applicable to analysis of natural, F 307 Practice for Sampling Pressurized Gas for Gas Analy-
processed, and final product materials containing sulfur in the sis7
range of 1 to 100 mg/kg (Note 1). 2.2 Gas Processor Association (GPA) Standards:8
GPA 2166 Obtaining Natural Gas Samples for Analysis by
NOTE 1—An estimate of pooled limit of quantification (PLOQ), infor- Gas Chromatography
mation regarding sample stability and other general information derived
from the inter-laboratory study on precision can be referenced in ASTM
GPA 2174 Obtaining Liquid Hydrocarbon Samples for
research report RR: D02-1506.2 Analysis by Gas Chromatography
1.2 This test method may not detect sulfur compounds that 3. Summary of Test Method
do not vaporize under the conditions of the test. 3.1 A heated sample valve is used to inject gaseous samples.
1.3 This test method is applicable for total volatile sulfur Liquefied petroleum gas (LPG) samples are injected by a
determination in LP gases containing less than 0.35 % (mass/ sample valve connected to a heated expansion chamber. The
mass) halogen(s). gaseous sample then enters a high temperature combustion
1.4 The values stated in SI units are to be regarded as tube where sulfur is oxidized to sulfur dioxide (SO2) in an
standard. oxygen rich atmosphere. Water produced during the sample
1.5 This standard does not purport to address all of the combustion is removed and the sample combustion gases are
safety concerns, if any, associated with its use. It is the next exposed to ultraviolet (UV) light. The SO2 absorbs the
responsibility of the user of this standard to establish appro- energy from the UV light and is converted to an excited sulfur
priate safety and health practices and determine the applica- dioxide (SO2). Fluorescence emitted from the excited SO2* as
bility of regulatory limitations prior to use. See paragraphs 3.1, it returns to a stable state SO2* is detected by a photomultiplier
6.3, and Section 7 for specific safety statements. tube, the resulting signal is a measure of the sulfur contained in
2. Referenced Documents the sample. (Warning—Exposure to excessive quantities of
ultraviolet light is injurious to health. The operator shall avoid
2.1 ASTM Standards: exposing their person, especially their eyes, not only to direct
D 1070 Test Methods for Relative Density (Specific Grav- UV light but also to secondary or scattered radiation that is
ity) of Gaseous Fuels3 present.)
D 1265 Practice for Sampling Liquefied Petroleum (LP)
Gases (Manual Method)4 4. Significance and Use
D 3700 Practice for Containing Hydrocarbon Fluid Samples 4.1 The sulfur content of LPG, used for fuel purposes,
Using a Floating Piston Cylinder5 contributes to SOx emissions and can lead to corrosion in
D 5287 Practice for the Automatic Sampling of Gaseous engine and exhaust systems. Some process catalysts used in
Fuels3 petroleum and chemical refining can be poisoned by sulfur
bearing materials in the feed stocks. This test method can be
1
This test method is under the jurisdiction of ASTM Committee D02 on used to determine sulfur in process feeds, to measure sulfur in
Petroleum Products and Lubricantsand is the direct responsibility of Subcommittee finished products, and can also be used for compliance deter-
D02.03on Elemental Analysis. minations when acceptable to a regulatory authority.
Current edition approved May 10, 2001. Published July 2001.
2
Available from ASTM Headquarters. Request RR:D02–1506.
3 6
Annual Book of ASTM Standards, Vol 05.06. Annual Book of ASTM Standards, Vol 05.04.
4 7
Annual Book of ASTM Standards, Vol 05.01. Annual Book of ASTM Standards, Vol 15.03.
5 8
Annual Book of ASTM Standards, Vol 05.02. Available from Gas Processors Assoc., 6526 East 60th, Tulsa, OK 74145.

Copyright © ASTM, 100 Barr Harbor Drive, West Conshohocken, PA 19428-2959, United States.

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 D 6667
5. Apparatus used in tests. Unless otherwise indicated, it is intended that all
5.1 Furnace—An electric furnace held at a temperature reagents shall conform to the specifications of the Committee
(1075 6 25°C) sufficient to pyrolyze the entire sample and on Analytical Reagents of the American Chemical Society,9
oxidize sulfur to SO2. where such specifications are available. Other grades may be
5.2 Combustion Tube—A quartz combustion tube con- used, provided it is first ascertained that the reagent is of
structed to allow the direct injection of the sample into the sufficiently high purity to permit its use without lessening the
heated oxidation zone of the furnace. The combustion tube accuracy of the determination.
shall have side arms for the introduction of oxygen and carrier 6.2 Inert Gas—Argon or helium only, high purity grade
gas. The oxidation section shall be large enough (see Fig. 1) to (that is, chromatography or zero grade), 99.998 % min purity,
ensure complete combustion of the sample (see 11.3). Fig. 1 moisture 5 mg/kg max. (Warning—Argon or helium may be a
depicts a typical combustion tube. Other configurations are compressed gas under high pressure (7.1)).
acceptable when precision is not degraded. 6.3 Oxygen—High purity (that is chromatography or zero
5.3 Flow Control—The apparatus shall be equipped with grade), 99.75 % min purity, moisture 5 mg/kg max, dried over
flow controllers capable of maintaining a constant supply of molecular sieves. (Warning—Oxygen vigorously accelerates
oxygen and carrier gas at the specified rates. combustion and may be compressed gas under high pressure
5.4 Drier Tube—The apparatus shall be equipped with a (7.1)).
mechanism for the removal of water vapor formed during 6.4 Calibration Standards—Certified calibration standards
sample combustion. This can be accomplished with a mem- from commercial sources or calibration gases prepared using
brane drying tube, or a permeation dryer that utilizes a certified permeation tube devices are required. Table 1 lists the
selective capillary action for water removal. sulfur source material and diluent matrices used during the
5.5 UV Fluorescence Detector—A quantitative detector ca- inter-laboratory study (Notes 2 and 3).
pable of measuring light emitted from the fluorescence of NOTE 2—Other sulfur sources and diluent materials may be used if
sulfur dioxide by UV light. precision and accuracy are not degraded.
5.6 Sample Inlet System—The system provides a heated NOTE 3—Calibration standards are typically re-mixed and re-certified
gas-sampling valve, or a LP gas-sampling valve, or both, with on a regular basis depending upon frequency of use and age. These
a heated expansion chamber, connected to the inlet of the calibration standards may have a useful life of about 6 to 12 months.
oxidation area, Fig. 2. The system is swept by an inert carrier 6.5 Quality Control (QC) Samples, preferably are portions
gas and shall be capable of allowing the quantitative delivery of one or more gas or LP gas materials that are stable and
of the material to be analyzed into the oxidation zone at a representative of the samples of interest.
controlled and repeatable rate of approximately 30 mL/min.
Fig. 3 provides an example.
5.7 Strip Chart Recorder, equivalent electronic data logger, 9
Reagent Chemicals, American Chemical Society Specifications, American
integrator or, recorder (optional). 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 Chemicals, BDH Ltd., Poole, Dorset, U.K., and the United States Pharmacopeia
and National Formulary, U.S. Pharmacopeial Convention, Inc. (USPC), Rockville,
6.1 Purity of Reagents—Reagent grade chemicals shall be MD.

FIG. 1 Example of a Typical Direct Inject Quartz Pyrolysis Tube

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 D 6667

FIG. 2 Example of Orientation of Total Sulfur Analyzer and Gas or Liquid Sampling Valve

7. Hazards 9.3 Adjust instrument sensitivity and baseline stability and

7.1 High temperature, flammable hydrocarbons, and gases perform instrument-blanking procedures following manufac-
under high pressures occur in the test method. Use materials turer’s guidelines.
that are rated for containing these pressurized hydrocarbons in 10. Calibration and Standardization
all sample containers and sample transfer apparatus. Exercise 10.1 Based on the anticipated sulfur concentration, select
extra care when using flammable materials near the oxidative one of the curve ranges from Table 3, preferably using a sulfur
furnace. compound and a diluent type representative of the samples to
be analyzed (Note 4).
8. Sampling
8.1 Obtain a sample in accordance with Practices F 307, NOTE 4—The number of standards used per curve may vary.
D 1265, D 3700, D 5287, or GPA-2174 or GPA-2166. Analyze 10.2 With the sample valve in the load position, connect the
samples as soon as possible after taking from bulk supplies to pressurized sample container to the sample valve of the sample
prevent loss of sulfur or contamination due to exposure or inlet system.
contact with sample containers. 10.3 Obtain a quantitative measurement of the injected
8.2 If the sample is not used immediately, then thoroughly material by filling the sample loop of the sample valve system
mix it in its container prior to taking a test specimen. The use for the matrix being analyzed (see Table 2) (Notes 5 and 6).
of segregated or specially treated sample containers can help NOTE 5—Injection of a constant or similar sample size for all materials
reduce sample cross-contamination and improve sample sta- analyzed in a selected operating range promotes consistent combustion
bility. conditions and may simplify result calculations.
NOTE 6—An automatic sample transfer and injection device may be
9. Preparation of Apparatus used.
9.1 Assemble and check the apparatus for leaks according to 10.3.1 Flush the sample loop with sufficient calibrant to
manufacturer’s instructions. assure that the material to be injected is representative.
9.2 Typical apparatus adjustments and conditions are listed 10.3.2 For LPG samples, if bubbles are present in the
in Table 2. viewable portion of the liquid column, flush the sample loop to

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 D 6667

FIG. 3 Sample Inlet System Flow Path

TABLE 1 Typical Standard Materials 10.5.1.2 Calibrate the analyzer according to the manufac-
Sulfur Source Diluent turer’s instructions to yield sulfur concentration (see Section
Dimethyl sulfide n, butane 13). This curve is typically linear and system performance shall
iso-butane be checked at least once per day, each day of use. (Note 7).
propylene
propane NOTE 7—Other calibration curve techniques may be used when accu-
racy and precision are not degraded. The frequency of calibration may be
determined by the use of quality control charts or other quality assurance/
TABLE 2 Typical Operating Conditions quality control techniques.
Sample inlet system temperature 85 6 20°C
10.5.2 One-point Calibration:
Sample injection system carrier gas 25–30 mL/min
Furnace temperature 1075 6 25°C 10.5.2.1 Utilize a calibration standard (6.4) with a sulfur
Furnace oxygen flow meter setting 375–450 mL/min content close to that of the samples to be analyzed (625 %
Inlet oxygen flow meter setting 10–30 mL/min
Inlet carrier flow meter setting 130–160 mL/min
max.).
Gas sample size 10–20 mL 10.5.2.2 Follow the instrument manufacturer’s instructions
LPG sample size 15 µL to establish an instrument zero (instrument blank) by conduct-
ing an analysis run without injection of the calibration stan-
dard.
TABLE 3 Sulfur Standards
10.5.2.3 Perform measurements of the calibration standard a
Curve I Curve II
Sulfur mg/kg Sulfur mg/kg minimum of three times.
Blank Blank 10.5.2.4 Calculate a calibration factor K, in counts per
5.00 10.00 nanogram of sulfur (counts/ng S) as described in 12.2.
10.00 50.00
100.00
11. Procedure
11.1 Obtain a test specimen using the procedure described
introduce a new liquid-full sample portion. in Section 8. Typically the sulfur concentration in the test
10.4 Start the analyzer and inject the calibration material specimen is less than the concentration of the highest standard
according to the manufacturer’s instructions. and greater than the concentration of the lowest standard used
10.5 Calibrate the instrument using one of the following in the calibration.
techniques. 11.2 Measure the response for the test specimen using one
10.5.1 Multi-point Calibration: of the procedures described in 10.2-10.4.
10.5.1.1 When the apparatus features an internal self- 11.3 Inspect the combustion tube and other flow path
calibration routine, analyze the calibration standards and blank components to verify complete oxidation of the test specimen.
three times using the procedures described in 10.2-10.4. 11.3.1 Reduce the rate of injection or the sample size, or

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 D 6667
both, of the specimen into the furnace when coke or sooting is A
S 5 M 3 K 3 Fg (5)
observed.
11.4 Cleaning and Re-calibration—Clean any coked or or
sooted parts according to the manufacturer’s instructions. After A
any cleaning or adjustment, assemble and check the apparatus S 5 V 3 K 3 Fv (6)
for leaks. Repeat instrument calibration prior to reanalysis of
the test specimen. where:
K = calibration factor, in counts per nanogram of sulfur,
11.5 To obtain one result, measure each test specimen three and
times and calculate the average detector response. M = mass of test specimen solution injected, in milligrams,
11.6 Density values needed for calculations are to be either measured directly or calculated from measured
measured using Test Methods D 1070 or equivalent, at the volume injected and density.
temperature at which the sample was tested (Note 8). M5V3D (7)

NOTE 8—When sample matrix compositions are known, other tech- where:
niques may be used to derive sample density, provided accuracy and D = density of test specimen solution at measurement
precision are not degraded. temperature, g/mL,
V = volume of the test specimen solution injected, µL,
12. Calculation A = integrated detector response for sample, in counts
12.1 For analyzers calibrated using an internal self- number,
calibration, calculate the sulfur content in the test specimen as Fg = gravimetric dilution factor, mass of test specimen/
follows: mass of test specimen and solvent, g/g, and
Fv = volumetric dilution factor, mass of test specimen/
G3d volume of test specimen and solvent, g/mL.
Sulfur, mg/kg 5 s (1)

13. Quality Control

where:
d = density of standard mixture, g/mL, 13.1 Confirm the performance of the instrument or the test
s = density of sample, g/mL, and procedure by analyzing a quality control (QC) sample (see 6.5)
G = sulfur found in test specimen, mg/kg. after each calibration and at least each day of use thereafter
12.2 For analyzers calibrated using a one point calibration, (see 11.5).
calculate the calibration factor, (10.5.2.4). 13.1.1 When QC/quality assurance (QA) protocols are al-
ready established in the testing facility, these may be used
Ac when they confirm the reliability of the test result.
K 5 Mc 3 Scg (2)
13.1.2 When there is no QC/QA protocol established in the
or testing facility, Appendix X1 can be used as the QC/QA
Ac
system.
K 5 Vc 3 Scv (3)
14. Precision and Bias
where: 14.1 The following precision and bias data was derived
Ac = integrated detector response for calibration standard, from an inter-laboratory study that included samples in
in counts, and n-butane, isobutane, and propane/propylene mix.10,11
Mc = mass of calibration standard injected, in milligrams, 14.2 Repeatability—The difference between two test results
either measured directly or calculated from measured obtained by the same operator with the same apparatus under
volume injected and density. constant operating conditions on identical test material would,
Mc 5 V 3 Dc (4) in the long run, in the normal and correct operation of the test
method, exceed the following values in only 1 case in 20,
where: where X = the average of the two test results.
Dc = density of calibration standard at measurement tem-
r 5 0.1152~X!
perature, g/mL,
Vc = volume of calibration standard injected, µL, 14.3 Reproducibility—The difference between two single
Scg = sulfur content of calibration standard, mL/kg, and and independent results obtained by different operators work-
Scv = sulfur content of calibration standard, mg/L. ing in different laboratories on identical test material would, in
12.2.1 Calculate the average of the calibration factor (K)
and check that the standard deviation is within the tolerance
10
accepted. This calibration factor shall be established every day. The following equipment, as listed in RR:D02–1506, was used to develop this
precision statement: (Antek Model 9000 Total Sulfur Analyzer configured with
12.2.2 Calculate the sulfur content, S, of the sample, in Model 734 Sample Inlet System, manufactured by Antek Instruments, 300 Bammel
mg/kg, using the following equation: Westfield Rd, Houston, TX, 77090. To date no other equipment has demonstrated,
through ASTM interlaboratory testing, the ability to meet the precision of this test.
This is not an endorsement or certification by ASTM.
11
Supporting data available from ASTM Headquarters, Request RR:D02–1506.

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 D 6667
the long run, in the normal and correct operation of the test TABLE 4 Repeatability (r) and Reproducibility (R)
method, exceed the following values in only 1 case in 20, Concentration
r R
where X = the average of the two test results, (mg/kg S)
1 0.1 0.3
R 5 0.3130~X! 5 0.6 1.6
14.4 Bias—Bias for this test method was studied during the 10 1.2 3.1
25 2.9 7.8
inter-laboratory study by analysis of certified-gravimetrically 50 5.8 15.6
prepared calibration standards and sample materials and pub- 100 11.5 31.3
lished in 2000 as a research report.11 This report indicated that
the results obtained were within the repeatability of the test
method. isobutane; LP; LPG; liquefied; petroleum; propane; sulfur;
14.5 Examples of the above precision estimates for selected ultraviolet
absolute values of X are set out in Table 4.
15. Keywords
15.1 analysis; butane; fluorescence; gases; hydrocarbon;

APPENDIXES

(Nonmandatory Information)

X1. QUALITY CONTROL MONITORING

X1.1 Confirm the performance of the instrument or the test criticality of the quality being measured, the demonstrated
procedure by analyzing quality control (QC) sample(s). stability of the testing process, and customer requirements.
Generally, a QC sample should be analyzed each testing day
X1.2 Prior to monitoring the measurement process, the user with routine samples. The QC frequency should be increased if
of the test method needs to determine the average value and a large number of samples are routinely analyzed. However,
control limits of the QC sample. See Practice D 6299 and when it is demonstrated that the testing is under statistical
MNL7.12 control, the QC testing frequency may be reduced. The QC
X1.3 Record the QC results and analyze by control charts sample testing precision should be periodically checked against
or other statistically equivalent techniques to ascertain the the ASTM method precision to ensure data quality. See
statistical control status of the total testing process. See Practice D 6299 and MNL7.12
Practice D 6299 and MNL7.12,13 Investigate any out-of-control
data for root cause(s). The results of this investigation may, but X1.5 It is recommended that, if possible, the type of QC
not necessarily, result in instrument re-calibration. sample that is regularly tested be representative of the material
routinely analyzed. An ample supply of QC sample material
X1.4 The frequency of QC testing is dependent on the should be available for the intended period of use, and must be
homogenous and stable under the anticipated storage condi-
tions.
12
ASTM MNL 7, “Manual on Presentation of Data Control Chart Analysis,” 6th
Ed., Section 3, available from ASTM Headquarters.
13
In the absence of explicit requirements given in the test method, this clause X1.6 See Practice D 6299 and MNL712 for further guid-
provides guidance on QC testing frequency. ance on QC and control charting techniques.

X2. OPERATION HINTS AND SAFETY CONSIDERATIONS

X2.1 Prior to sample injection, fully stabilize and ready the analysis has completed (instrument has returned to baseline
apparatus for analysis according to the manufacturers’ instruc- and integration has finished.)
tions.
X2.5 The length of time required for detector response will
X2.2 Valves in the sample inlet system typically remain in depend upon the type of pyrotube utilized, carrier gas, sample
the load position except during sample analysis. size or sulfur concentration, or both. From 20 s to 1 min can be
X2.3 Once the sample valve has been filled and allowed to typical (see Fig. X2.1).
equilibrate, accomplish sample injection by executing a prompt
X2.6 Sample inlet system carrier gas flows can be used to
and full rotation to the sample valve to the inject position.
manipulate sample combustion and detection characteristics.
X2.4 Leave the sampling valve in the inject position until However, excessive carrier flow rates (greater than 30 mL/min)

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FIG. X2.1 Typical Injection Profile

can cause incomplete sample combustion (sooting). X2.11 The use of low or iron-free alloys and/or inert treated
materials can enhance the analysis for low level sulfur con-
X2.7 Allow time for return of signal to baseline between tamination.
injections.
X2.12 The use of a strip-chart recorder or a software peak
X2.8 For sample cylinders containing liquefied petroleum
display can aid in the set up and normal operation of the sample
gases, use sufficient pressure (typically greater than 200 psig
container pressure) to allow the transfer of sample to the inlet system.
sample inlet system without the formation of bubbles in the
transfer tubing and sight glass. X2.13 Quality analytical results are best obtained when
calibration materials match the matrix of the samples analyzed.
X2.9 Use standard gas flow conditions for your analyzer. Injection of solvent (room temperature) liquids as calibrants or
See Section 9 of the test method. samples is discouraged and can cause severe coking (sooting)
of sample flow path components and yield poor analytical
X2.10 The use of a filtering device prior to sample results.
introduction is strongly recommended. This can greatly extend
valve service and prevent transfer line (tubing) blockage.

X3. SAFETY CONSIDERATIONS

X3.1 Routinely inspect transfer lines and fittings used to 750 psig. Do not exceed the general overall pressure rating
connect the sample container to the sample inlet system for (900 psig) of the sample inlet system or the capacity of the
leaks and stress weakening that can be caused by frequent sample transfer apparatus being employed.
bending, age, or use.
X3.5 Use slow to moderate purge rates when filling the
X3.2 Inspect Quick-Connect fittings and other sample sample loops during the sample-loading phase of the sampling
transfer and venting apparatus routinely for leaks and proper procedure.
operation.
X3.6 After sample loop loading, allow pressure within the
X3.3 Vent waste gases from the sample inlet system to an loop and vent system to equilibrate. Use of a secure gas-bubble
area away from the instrument operating environment and monitoring device that vents to an area free of potential
potential ignition sources. ignition sources can provide visual confirmation and aid in
ensuring the injection of consistent sample sizes.
X3.4 Pressures employed to maintain contents of sampling
cylinders and to enable sample transfer are typically less than X3.7 After sampling is complete, a controlled venting or

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relief of pressure of the sample transfer line is advised. position, an inert gas connected to the sample inlet system can
be utilized to purge sample residue.
X3.8 After analysis, with the sample valves in the load

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