ASTM D7493-14 - 1.6.2014
 
Significance and Use

5.1 Gaseous fuels, such as natural gas, petroleum gases and bio-gases, contain sulfur compounds that are naturally occurring or that are added as odorants for safety purposes. These sulfur compounds are odorous, corrosive to equipment, and can inhibit or destroy catalysts employed in gas processing and other end uses. Their accurate continuous measurement is important to gas processing, operation and utilization, and is frequently of regulatory interest.

5.2 Small amounts (typically, total of 4 to 6 ppmv) of sulfur odorants are added to natural gas and other fuel gases for safety purposes. Some sulfur odorants are reactive, and may be oxidized to form more stable sulfur compounds having lower odor thresholds which adversely impact the potential safety of the gas delivery systems and gas users. Gaseous fuels are analyzed for sulfur compounds and odorant levels to assist in pipeline integrity surveillance and to ensure appropriate odorant levels for public safety.

5.3 This method offers an on-line technique to continuously identify and quantify individual target sulfur species in gaseous fuel with automatic calibration and validation.

 
1. Scope

1.1 This test method is for on-line measurement of volatile sulfur-containing compounds in gaseous fuels by gas chromatography (GC) and electrochemical (EC) detection. This test method is applicable to hydrogen sulfide, C1 to C4 mercaptans, sulfides and tetrahydrothiophene (THT).

1.1.1 Carbonyl sulfide (COS) is not covered in this test method.

1.1.2 The detection range for sulfur compounds is approximately from 0.1 to 100 ppmv (mL/m3) or 0.1 to 100 mg/m3. The detection range may vary depending on the sample injection volume, chromatographic peak separation and the sensitivity to the specific EC detector.

1.2 This test method describes a GC-EC method employing packed GC columns and a specific detector for natural gas and other gaseous fuel composed of mainly light (C4 and smaller) hydrocarbons. Alternative GC columns, detector designs and instrument parameters may be used, provided that chromatographic separation, quality control and measurement objectives needed to comply with user, or regulator needs or both, are achieved.

1.3 This test method does not intend to identify and measure all individual sulfur species, and is mainly employed for monitoring naturally occurring reduced sulfur compounds commonly found in natural gas and fuel gases or employed as an odorant in these gases.

1.4 The test method is typically employed in repetitive or continuous on-line monitoring of sulfur components in natural gas and fuel gases using a single sulfur calibration standard. Need for a multipoint calibration curve or quality control procedures can be satisfied by making use of procedures delineated in Test Methods D5504, D5623, D6228, D6968, ISO 19739, or GPA 2199.

1.5 The test method can be used for measurement of all sulfur compounds listed in Table 1 in air or other gaseous matrices, provided that no compounds that can interfere with the GC separation and electrochemical detection are present.

1.6 This test method is written as a companion to Practices D5287, D7165 and D7166.

1.7 The values stated in SI units are to be regarded as standard. No other units of measurement are included in this standard.

1.8 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

D4150-23a

Standard Terminology Relating to Gaseous Fuels (Includes all amendments and changes 7/12/2023).

D4626-23

Standard Practice for Calculation of Gas Chromatographic Response Factors

D6228-19

Standard Test Method for Determination of Sulfur Compounds in Natural Gas and Gaseous Fuels by Gas Chromatography and Flame Photometric Detection

D5504-20

Standard Test Method for Determination of Sulfur Compounds in Natural Gas and Gaseous Fuels by Gas Chromatography and Chemiluminescence

D7165-22

Standard Practice for Gas Chromatograph Based On-line/At-line Analysis for Sulfur Content of Gaseous Fuels

D3609-22

Standard Practice for Calibration Techniques Using Permeation Tubes

D5623-24

Standard Test Method for Sulfur Compounds in Light Petroleum Liquids by Gas Chromatography and Sulfur Selective Detection

D6968-03

Standard Test Method for Simultaneous Measurement of Sulfur Compounds and Minor Hydrocarbons in Natural Gas and Gaseous Fuels by Gas Chromatography and Atomic Emission Detection

D7166-23

Standard Practice for Total Sulfur Analyzer Based On-line/At-line for Sulfur Content of Gaseous Fuels

ISO 19739

Natural gas - Determination of sulfur compounds by gas chromatography

GPA 2199

Determination - Determination of Specific Sulfur Compounds by Capillary Gas Chromatography and Sulfur Chemiluminescence Detection

D5287-25

Standard Practice for Automatic Sampling of Gaseous Fuels