ASTM D4045-19

Standard Test Method for Sulfur in Petroleum Products by Hydrogenolysis and Rateometric Colorimetry

SIGNIFICANCE AND USE
4.1 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.  
4.2 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 mg/kg 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 °C and 371 °C (86 °F 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, health, and environmental practices and determine the applicability of regulatory limitations prior to use.  
1.6 This international standard was developed in accordance with internationally recognized principles on standardization established in the Decision on Principles for the Development of International Standards, Guides and Recommendations issued by the World Trade Organization Technical Barriers to Trade (TBT) Committee.

General Information

• Status: Published
• Publication Date: 30-Nov-2019
• ICS: 75.080 - Petroleum products in general
• Technical Committee: D02 - Petroleum Products, Liquid Fuels, and Lubricants
• Drafting Committee: D02.03 - Elemental Analysis

Relations

• Refers: ASTM D6299-17a - Standard Practice for Applying Statistical Quality Assurance and Control Charting Techniques to Evaluate Analytical Measurement System Performance
• Effective Date: 15-Nov-2017
• Refers: ASTM D6299-17b - Standard Practice for Applying Statistical Quality Assurance and Control Charting Techniques to Evaluate Analytical Measurement System Performance
• Effective Date: 15-Dec-2017
• Refers: ASTM D6299-17 - Standard Practice for Applying Statistical Quality Assurance and Control Charting Techniques to Evaluate Analytical Measurement System Performance
• Effective Date: 01-Jan-2017

Standards Content (Sample)

This international standard was developed in accordance with internationally recognized principles on standardization established in the Decision on Principles for the
Development of International Standards, Guides and Recommendations issued by the World Trade Organization Technical Barriers to Trade (TBT) Committee.
Designation: D4045 − 19
Standard Test Method for
Sulfur in Petroleum Products by Hydrogenolysis and
1
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* D6299 Practice for Applying Statistical Quality Assurance
and Control Charting Techniques to Evaluate Analytical
1.1 This test method covers the determination of sulfur in
Measurement System Performance
petroleum products in the range from 0.02 mg⁄kg to
10.00 mg⁄kg.
3. Summary of Test Method
1.2 This test method may be extended to higher concentra-
3.1 The sample is injected at a constant rate into a flowing
tion by dilution.
hydrogen stream in a hydrogenolysis apparatus. The sample
and hydrogen are pyrolyzed at a temperature of 1300 °C, or
1.3 This test method is applicable to liquids whose boiling
above, to convert sulfur compounds to hydrogen sulfide (H S).
points are between 30 °C and 371 °C (86 °F and 700 °F).
2
Readout is by the rateometric detection of the colorimetric
Materials that can be analyzed include naphtha, kerosine,
reactionofH Swithleadacetate.Condensablecomponentsare
alcohol,steamcondensate,variousdistillates,jetfuel,benzene,
2
converted to gaseous products, such as methane, during hy-
and toluene.
drogenolysis.
1.4 The values stated in SI units are to be regarded as
standard. The values given in parentheses are for information
4. Significance and Use
only.
4.1 In many petroleum refining processes, low levels of
1.4.1 Certain specifications for the recorder (see 5.5) are
sulfur in feed stocks may poison expensive catalysts. This test
excepted.
method can be used to monitor the amount of sulfur in such
1.5 This standard does not purport to address all of the
petroleum fractions.
safety concerns, if any, associated with its use. It is the
4.2 This test method may also be used as a quality-control
responsibility of the user of this standard to establish appro-
tool for sulfur determination in finished products.
priate safety, health, and environmental practices and deter-
mine the applicability of regulatory limitations prior to use.
5. Apparatus
1.6 This international standard was developed in accor-
5.1 Pyrolysis Furnace—A furnace that can provide an
dance with internationally recognized principles on standard-
adjustable temperature from 900 °C to 1400 °C in a 5 mm
ization established in the Decision on Principles for the
inside diameter or larger tube is required to pyrolyze the
Development of International Standards, Guides and Recom-
sample. The furnace entry temperature shall allow insertion of
mendations issued by the World Trade Organization Technical
the hypodermic tip to a depth at which the temperature is
Barriers to Trade (TBT) Committee.
550 °C to provide sample vaporization at the injection syringe
tip. This temperature shall be above the boiling point of the
2. Referenced Documents
sample and of the sulfur compounds in the sample (see Fig. 1).
2
2.1 ASTM Standards:
The pyrolyzer tube may be of quartz; however, the lifetime is
D1193 Specification for Reagent Water
limited above 1250 °C. Ceramic may be used at any tempera-
ture.
5.2 Rateometric H S Readout—Hydrogenolysis products
1
2
This test method is under the jurisdiction of ASTM Committee D02 on
contain H S in proportion to sulfur in the sample. The HSis
Petroleum Products, Liquid Fuels, and Lubricants and is the direct responsibility of
2 2
Subcommittee D02.03 on Elemental Analysis.
measuredbymeasuringrateofchangeofreflectancecausedby
Current edition approved Dec. 1, 2019. Published December 2019. Originally
darkening when lead sulfide is formed. Rateometric
approved in 1987. Last previous edition approved in 2015 as D4045 – 15. DOI:
electronics, adapted to provide a first derivative output, allows
10.1520/D4045-19.
2
For referenced ASTM standards, visit the ASTM website, www.astm.org, or sufficient sensitivity to measure below 0.1 mg/L (see Fig. 2).
contact ASTM Customer Service at [e-mail]. For Annual Book of ASTM
5.3 Hypodermic Syringe—A hypodermic having a needle
Standards volume information, refer to the standard’s Document Summary page on
the ASTM website. long enough to reach the 550 °C zone is required. A side port
*A Summary of Changes section appears at the end of this standard
Copyright © ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959. United States
1

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...

This document is not an ASTM standard and is intended only to provide the user of an ASTM 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: D4045 − 15 D4045 − 19
Standard Test Method for
Sulfur in Petroleum Products by Hydrogenolysis and
1
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*
1.1 This test method covers the determination of sulfur in petroleum products in the range from 0.02 mg ⁄kg 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 °C and 371 °C (86 °F 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 safety, health, and healthenvironmental practices and determine the
applicability of regulatory limitations prior to use.
1.6 This international standard was developed in accordance with internationally recognized principles on standardization
established in the Decision on Principles for the Development of International Standards, Guides and Recommendations issued
by the World Trade Organization Technical Barriers to Trade (TBT) Committee.
2. Referenced Documents
2
2.1 ASTM Standards:
D1193 Specification for Reagent Water
D6299 Practice for Applying Statistical Quality Assurance and Control Charting Techniques to Evaluate Analytical Measure-
ment System Performance
3. Summary of Test Method
3.1 The sample is injected at a constant rate into a flowing hydrogen stream in a hydrogenolysis apparatus. The sample and
hydrogen are pyrolyzed at a temperature of 1300 °C, or above, to convert sulfur compounds to hydrogen sulfide (H S). Readout
2
is by the rateometric detection of the colorimetric reaction of H S with lead acetate. Condensable components are converted to
2
gaseous products, such as methane, during hydrogenolysis.
4. Significance and Use
4.1 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.
4.2 This test method may also be used as a quality-control tool for sulfur determination in finished products.
,
5. Apparatus
5.1 Pyrolysis Furnace—A furnace that can provide an adjustable temperature from 900 °C to 1400 °C in a 5 mm inside diameter
or larger tube is required to pyrolyze the sample. The furnace entry temperature shall allow insertion of the hypodermic tip to a
depth at which the temperature is 550 °C to provide sample vaporization at the injection syringe tip. This temperature shall be
1
This test method is under the jurisdiction of ASTM Committee D02 on Petroleum Products, Liquid Fuels, and Lubricants and is the direct responsibility of Subcommittee
D02.03 on Elemental Analysis.
Current edition approved April 1, 2015Dec. 1, 2019. Published April 2015December 2019. Originally approved in 1987. Last previous edition approved in 20102015 as
D4045 – 04 (2010).D4045 – 15. DOI: 10.1520/D4045-15.10.1520/D4045-19.
2
For referenced ASTM standards, visit the ASTM website, www.astm.org, or contact ASTM Customer Service at [e-mail]. For Annual Book of ASTM Standards
volume information, refer to the standard’s Document Summary page on the ASTM website.
*A Summary of Changes section appears at the end of this standard
Copyright © ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959. United States
1

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D4045 − 19
above the boiling point of the sample and of the sulfur compounds in the sample (see Fig. 1). The pyrolyzer tube may be of quartz;
however, the lifetime is limited above 1250 °C. Ceramic may be used at any temperature.
5.2 Rateometric H S Readout—Hydrogenolysis products contain H S in proportion to sulfur in the sample. The H S is measured
2 2 2
by measuring rate of change of reflectance caused by darkening when lea
...