ASTM D5504-12
(Test Method)Standard Test Method for Determination of Sulfur Compounds in Natural Gas and Gaseous Fuels by Gas Chromatography and Chemiluminescence
Standard Test Method for Determination of Sulfur Compounds in Natural Gas and Gaseous Fuels by Gas Chromatography and Chemiluminescence
SIGNIFICANCE AND USE
Many sources of natural and petroleum gases contain sulfur compounds that are odorous, corrosive, and poisonous to catalysts used in gaseous fuel processing.
Low ppm amounts of sulfur odorants are added to natural gas and LP gases for safety purposes. Some odorants are unstable and react to form compounds having lower odor thresholds. Quantitative analysis of these odorized gases ensures that odorant injection equipment is performing to specification.
Although not intended for application to gases other than natural gas and related fuels, this test method has been successfully applied to fuel type gases including refinery, landfill, cogeneration, and sewage digester gas. Refinery, landfill, sewage digester and other related fuel type gases inherently contain volatile sulfur compounds that are subject to federal, state, or local control. The methane fraction of these fuel type gases are occasionally sold to distributors of natural gas. For these reasons, both regulatory agencies and production and distribution facilities may require the accurate determination of sulfur to satisfy regulatory, production or distribution requirements. Fuel gases are also used in energy production or are converted to new products using catalysts that are poisoned by excessive sulfur in the feed gas. Industry frequently requires measurement of sulfur in these fuel type gases to protect their catalyst investments.
Analytical Methods—Gas chromatography (GC) is commonly used in the determination of fixed gas and organic composition of natural gas (Test Method D1945). Other standard ASTM methods for the analysis of sulfur in fuel gases include Test Methods D1072 and D4468 for total sulfur and Test Methods D4010 and D4884 for hydrogen sulfide.
SCOPE
1.1 This test method is primarily for the determination of speciated volatile sulfur-containing compounds in high methane content gaseous fuels such as natural gas. It has been successfully applied to other types of gaseous samples including air, digester, landfill, and refinery fuel gas. The detection range for sulfur compounds, reported as picograms sulfur, is ten (10) to one million (1 000 000). This is equivalent to 0.01 to 1 000 mg/m3, based upon the analysis of a 1 cc sample.
1.2 The range of this test method may be extended to higher concentration by dilution or by selection of a smaller sample loop.
Note 1— Dilution will reduce method precision.
1.3 This test method does not purport to identify all sulfur species in a sample. Only compounds that are eluted through the selected column under the chromatographic conditions chosen are determined. The detector response to sulfur is equimolar for all sulfur compounds within the scope (1.1) of this test method. Thus, unidentified compounds are determined with equal precision to that of identified substances. Total sulfur content is determined from the total of individually quantified components.
1.4 The values stated in SI units are standard. The values stated in inch-pound units are for information only.
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
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Designation: D5504 − 12
Standard Test Method for
Determination of Sulfur Compounds in Natural Gas and
Gaseous Fuels by Gas Chromatography and
1
Chemiluminescence
This standard is issued under the fixed designation D5504; the number immediately following the designation indicates the year of
original adoption or, in the case of revision, the year of last revision.Anumber in parentheses indicates the year of last reapproval.A
superscript epsilon (´) indicates an editorial change since the last revision or reapproval.
1. Scope 2. Referenced Documents
2
1.1 This test method is primarily for the determination of 2.1 ASTM Standards:
D1072Test Method for Total Sulfur in Fuel Gases by
speciated volatile sulfur-containing compounds in high meth-
Combustion and Barium Chloride Titration
ane content gaseous fuels such as natural gas. It has been
D1945Test Method for Analysis of Natural Gas by Gas
successfully applied to other types of gaseous samples includ-
Chromatography
ing air, digester, landfill, and refinery fuel gas. The detection
D3609Practice for Calibration Techniques Using Perme-
range for sulfur compounds, reported as picograms sulfur, is
ation Tubes
ten (10) to one million (1 000 000). This is equivalent to 0.01
3
D4468Test Method for Total Sulfur in Gaseous Fuels by
to 1 000 mg/m , based upon the analysis ofa1cc sample.
Hydrogenolysis and Rateometric Colorimetry
1.2 Therangeofthistestmethodmaybeextendedtohigher
E177Practice for Use of the Terms Precision and Bias in
concentration by dilution or by selection of a smaller sample
ASTM Test Methods
loop.
E594Practice for Testing Flame Ionization Detectors Used
NOTE 1— Dilution will reduce method precision.
in Gas or Supercritical Fluid Chromatography
E691Practice for Conducting an Interlaboratory Study to
1.3 This test method does not purport to identify all sulfur
Determine the Precision of a Test Method
species in a sample. Only compounds that are eluted through
the selected column under the chromatographic conditions
3. Summary of Test Method
chosen are determined. The detector response to sulfur is
3.1 The analysis of gaseous sulfur compounds is challeng-
equimolar for all sulfur compounds within the scope (1.1)of
ing due to the reactivity of these substances. They are difficult
thistestmethod.Thus,unidentifiedcompoundsaredetermined
tosampleandanalyze.Ideally,analysisisperformedon-siteto
with equal precision to that of identified substances. Total
eliminatesampledeteriorationasafactorinanalysis.Sampling
sulfur content is determined from the total of individually
must be performed using non-reactive containers, such as
quantified components.
3 4
Silcosteel lined vessels, Tedlar bags with polypropylene
1.4 The values stated in SI units are standard. The values 4
fittings or the equivalent. Tedlar bag samples require protec-
stated in inch-pound units are for information only.
tionfromlightandheat.Laboratoryequipmentmustbeinertor
1.5 This standard does not purport to address all of the
passivated to ensure reliable results.
safety concerns, if any, associated with its use. It is the
3.2 A one cc (mL) sample is injected into a gas chromato-
responsibility of the user of this standard to establish appro-
graphwhereitiselutedthroughamegabore,thickfilm,methyl
priate safety and health practices and determine the applica-
siliconeliquidphase,opentubularpartitioningcolumnorother
bility of regulatory limitations prior to use.
suitable column, and separated into its individual constituents.
2
For referenced ASTM standards, visit the ASTM website, www.astm.org, or
1
ThistestmethodisunderthejurisdictionofASTMCommitteeD03onGaseous contact ASTM Customer Service at service@astm.org. For Annual Book of ASTM
Fuels and is the direct responsibility of Subcommittee D03.05 on Determination of Standards volume information, refer to the standard’s Document Summary page on
Special Constituents of Gaseous Fuels. the ASTM website.
3
Current edition approved June 1, 2012. Published November 2012. Originally Silcosteel is a trademark of Restek Corporation, 110 Benner Circle Bellefonte,
approved in 1994. Last previous edition approved in 2008 as D5504–08. DOI: PA, 16823.
4
10.1520/D5504-12. Tedlar is a trademark of DuPont.
Copyright © ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959. United States
1
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D5504 − 12
3.3 Sulfur Chemiluminescence Detection—As sulfur com- 5. Apparatus
pounds elute from the gas chromatographic column, they are
5.1 Chromatograph—Any gas chromatograph of standard
processed in a flame ionization detector (FID) or a heated
manufacture, with hardware necessary for interfacing to a
combustionzone.Theproductsarecollectedandtransferredto
chemiluminescence detector and containing all features neces-
a sulfur chemiluminesce
...
This document is not anASTM standard and is intended only to provide the user of anASTM standard an indication of what changes have been made to the previous version. Because
it may not be technically possible to adequately depict all changes accurately,ASTM recommends that users consult prior editions as appropriate. In all cases only the current version
of the standard as published by ASTM is to be considered the official document.
Designation:D5504–08 Designation: D5504 – 12
Standard Test Method for
Determination of Sulfur Compounds in Natural Gas and
Gaseous Fuels by Gas Chromatography and
1
Chemiluminescence
This standard is issued under the fixed designation D5504; the number immediately following the designation indicates the year of
original adoption or, in the case of revision, the year of last revision.Anumber in parentheses indicates the year of last reapproval.A
superscript epsilon (ϵ) indicates an editorial change since the last revision or reapproval.
1. Scope
1.1 This test method is primarily for the determination of speciated volatile sulfur-containing compounds in high methane
contentgaseousfuelssuchasnaturalgas.Ithasbeensuccessfullyappliedtoothertypesofgaseoussamplesincludingair,digester,
landfill, and refinery fuel gas. The detection range for sulfur compounds, reported as picograms sulfur, is ten (10) to one million
3
(1 000 000). This is equivalent to 0.01 to 1 000 mg/m , based upon the analysis ofa1cc sample.
1.2 Therangeofthistestmethodmaybeextendedtohigherconcentrationbydilutionorbyselectionofasmallersampleloop.
NOTE 1— Dilution will reduce method precision.
1.3 This test method does not purport to identify all sulfur species in a sample. Only compounds that are eluted through the
selected column under the chromatographic conditions chosen are determined.The detector response to sulfur is equimolar for all
sulfur compounds within the scope (1.1) of this test method. Thus, unidentified compounds are determined with equal precision
to that of identified substances. Total sulfur content is determined from the total of individually quantified components.
1.4 The values stated in SI units are standard. The values stated in inch-pound units are for information only.
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.
2. Referenced Documents
2
2.1 ASTM Standards:
D1072 Test Method for Total Sulfur in Fuel Gases by Combustion and Barium Chloride Titration
D1945 Test Method for Analysis of Natural Gas by Gas Chromatography
D3609 Practice for Calibration Techniques Using Permeation Tubes
D4468 Test Method for Total Sulfur in Gaseous Fuels by Hydrogenolysis and Rateometric Colorimetry
E177 Practice for Use of the Terms Precision and Bias in ASTM Test Methods
E594 Practice for Testing Flame Ionization Detectors Used in Gas or Supercritical Fluid Chromatography Practice for Testing
Flame Ionization Detectors Used in Gas or Supercritical Fluid Chromatography
E691 Practice for Conducting an Interlaboratory Study to Determine the Precision of a Test Method
3. Summary of Test Method
3.1 The analysis of gaseous sulfur compounds is challenging due to the reactivity of these substances. They are difficult to
sample and analyze. Ideally, analysis is performed on-site to eliminate sample deterioration as a factor in analysis. Sampling must
3 4
be performed using non-reactive containers, such as Silcosteel lined vessels, Tedlar bags with polypropylene fittings or the
4
equivalent.Tedlar bagsamplesrequireprotectionfromlightandheat.Laboratoryequipmentmustbeinertorpassivatedtoensure
reliable results.
3.2 Aonecc(mL)sampleisinjectedintoagaschromatographwhereitiselutedthroughamegabore,thickfilm,methylsilicone
liquid phase, open tubular partitioning column or other suitable column, and separated into its individual constituents.
1
This test method is under the jurisdiction of ASTM Committee D03 on Gaseous Fuels and is the direct responsibility of Subcommittee D03.05 on Determination of
Special Constituents of Gaseous Fuels.
Current edition approved June 15, 2008.1, 2012. Published July 2008.November 2012. Originally approved in 1994. Last previous edition approved in 20062008 as
D5504–01(2006).D5504–08. DOI: 10.1520/D5504-08.10.1520/D5504-12.
2
ForreferencedASTMstandards,visittheASTMwebsite,www.astm.org,orcontactASTMCustomerServiceatservice@astm.org.ForAnnualBookofASTMStandards
volume information, refer to the standard’s Document Summary page on the ASTM website.
3
Silcosteel is a trademark of Restek Corporation, 110 Benner Circle Bellefonte, PA, 16823.
4
Tedlar is a trademark of DuPont.
Copyright © ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959, United States.
1
---------------------- Page: 1 ----------------------
D5504 – 12
3.3 Sulfur Chemilu
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