ASTM D7423-09(2014)

Standard Test Method for Determination of Oxygenates in C2, C3, C4, and C5 Hydrocarbon Matrices by Gas Chromatography and Flame Ionization Detection

SIGNIFICANCE AND USE
5.1 The determination of oxygenates is important in the manufacture of ethene, propene, 1-3 butadiene, C4 hydrocarbons, and C5 hydrocarbons. Alcohols, ethers, aldehydes, and ketones are trace impurities in these hydrocarbons. Oxygenates decrease catalyst activity in downstream polymerization processes.
SCOPE
1.1 This test method covers the gas chromatographic procedure for the quantitative determination of organic oxygenates in C2, C3, C4, and C5 matrices by multidimensional gas chromatography and flame ionization detection. This test method is applicable when the hydrocarbon matrices have a final boiling point not greater than 200°C. Oxygenate compounds include, but are not limited to, those listed in Table 1. The linear working range for oxygenates is 0.50 mg/kg to 100 mg/kg.  
1.2 This test method is intended to determine the mass concentration of each oxygenate in the hydrocarbon matrix. Oxygenate compound identification is determined by reference standards and column elution retention order.  
1.3 The values stated in SI units are to be regarded as standard. No other units of measurement are included in this standard.  
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

• Status: Historical
• Publication Date: 30-Apr-2014
• ICS: 71.080.01 - Organic chemicals in general
• Technical Committee: D02 - Petroleum Products, Liquid Fuels, and Lubricants
• Drafting Committee: D02.D0.04 - C4 and C5 Hydrocarbons

Relations

• Replaces: ASTM D7423-09 - Standard Test Method for Determination of Oxygenates in C2, C3, C4, and C5 Hydrocarbon Matrices by Gas Chromatography and Flame Ionization Detection
• Effective Date: 01-May-2014
• Referred By: ASTM D5273-18 - Standard Guide for Analysis of Propylene Concentrates
• Effective Date: 01-May-2014

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NOTICE: This standard has either been superseded and replaced by a new version or withdrawn.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
Designation: D7423 − 09(Reapproved 2014)
Standard Test Method for
Determination of Oxygenates in C2, C3, C4, and C5
Hydrocarbon Matrices by Gas Chromatography and Flame
1
Ionization Detection
This standard is issued under the fixed designation D7423; 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 gas chromatographic pro-
Measurement System Performance
cedureforthequantitativedeterminationoforganicoxygenates
D6849 Practice for Storage and Use of Liquefied Petroleum
in C2, C3, C4, and C5 matrices by multidimensional gas
Gases (LPG) in Sample Cylinders for LPG Test Methods
chromatography and flame ionization detection. This test
E355 Practice for Gas Chromatography Terms and Relation-
method is applicable when the hydrocarbon matrices have a
ships
final boiling point not greater than 200°C. Oxygenate com-
pounds include, but are not limited to, those listed in Table 1.
3. Terminology
The linear working range for oxygenates is 0.50 mg/kg to 100
3.1 Additional terminology related to the practice of gas
mg/kg.
chromatography can be found in Practice E355.
1.2 This test method is intended to determine the mass
3.2 Definitions:
concentration of each oxygenate in the hydrocarbon matrix.
3.2.1 liquefied petroleum gas (LPG), n—a mixture of nor-
Oxygenate compound identification is determined by reference
mally gaseous hydrocarbons, predominantly propane or
standards and column elution retention order.
butane, or both, that has been liquefied by compression or
1.3 The values stated in SI units are to be regarded as
cooling, or both, to facilitate storage, transport, and handling.
standard. No other units of measurement are included in this
D4175
standard.
3.2.2 oxygenate, n—an oxygen-containing ashless organic
1.4 This standard does not purport to address all of the
compound, such as an alcohol or ether, which may be used as
safety concerns, if any, associated with its use. It is the
a fuel or fuel supplement. D4175
responsibility of the user of this standard to establish appro-
3.3 Definitions of Terms Specific to This Standard:
priate safety and health practices and determine the applica-
3.3.1 Dean’s switching method—representative aliquot of
bility of regulatory limitations prior to use.
sampleisinjectedon-columnusingasamplevalve(orviaagas
chromatograph split inlet). The sample passes onto a nonpolar
2. Referenced Documents
column, which elutes the lighter hydrocarbons in boiling point
2
2.1 ASTM Standards:
order to the analytical column and backflushes the heavier
D1265 Practice for Sampling Liquefied Petroleum (LP)
hydrocarbons to vent. The oxygenate compounds elute from
Gases, Manual Method
the analytical column and are detected via a flame ionization
D1835 Specification for Liquefied Petroleum (LP) Gases
detector.
D4175 Terminology Relating to Petroleum, Petroleum
3.3.2 Dean’s switching method direct inject—gas chromato-
Products, and Lubricants
graphic valve configuration equipped with a valve connected
directlytotheprecolumn.Thistechniqueiscommonlyusedfor
1 the determination of oxygenates in ethene and propene con-
This test method is under the jurisdiction of ASTM Committee D02 on
Petroleum Products, Liquid Fuels, and Lubricants and is the direct responsibility of centrates. This configuration provides the lowest detection
Subcommittee D02.D0.04 on C4 Hydrocarbons.
limitssuchasthosecommonlyrequiredforetheneandpropene
CurrenteditionapprovedMay1,2014.PublishedJuly2014.Originallyapproved
concentrates.
in 2009. Last pervious edition approved in 2009 as D7423 – 09. DOI: 10.1520/
D7423-09R14.
3.3.3 Dean’s switching method equipped with a split inlet—
2
For referenced ASTM standards, visit the ASTM website, www.astm.org, or
gas chromatographic valve configuration equipped with a gas
contact ASTM Customer Service at [e-mail]. For Annual Book of ASTM
chromatograph split inlet for sample introduction into the
Standards volume information, refer to the standard’s Document Summary page on
the ASTM website. precolumn. This configuration is commonly used for the
Copyright © ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959. United States
1

---------------------- Page: 1 ----------------------
D7423 − 09 (2014)
TABLE 1 Oxygenates and Typical Retention Times
Components Retention Time (min)
Dimethyl ether 6.18
Diethyl ether 8.44
Acetaldehyde 8.89
Ethyl tert-butyl ether 10.66
Methyl tert-butyl ether (MTBE) 10.92
Diisopropyl ether 11
...

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: D7423 − 09 D7423 − 09 (Reapproved 2014)
Standard Test Method for
Determination of Oxygenates in C2, C3, C4, and C5
Hydrocarbon Matrices by Gas Chromatography and Flame
1
Ionization Detection
This standard is issued under the fixed designation D7423; 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 gas chromatographic procedure for the quantitative determination of organic oxygenates in C2,
C3, C4, and C5 matrices by multidimensional gas chromatography and flame ionization detection. This test method is applicable
when the hydrocarbon matrices have a final boiling point not greater than 200°C. Oxygenate compounds include, but are not
limited to, those listed in Table 1. The linear working range for oxygenates is 0.50 mg/kg to 100 mg/kg.
1.2 This test method is intended to determine the mass concentration of each oxygenate in the hydrocarbon matrix. Oxygenate
compound identification is determined by reference standards and column elution retention order.
1.3 The values stated in SI units are to be regarded as standard. No other units of measurement are included in this standard.
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.
2. Referenced Documents
2
2.1 ASTM Standards:
D1265 Practice for Sampling Liquefied Petroleum (LP) Gases, Manual Method
D1835 Specification for Liquefied Petroleum (LP) Gases
D4175 Terminology Relating to Petroleum, Petroleum Products, and Lubricants
D6299 Practice for Applying Statistical Quality Assurance and Control Charting Techniques to Evaluate Analytical Measure-
ment System Performance
D6849 Practice for Storage and Use of Liquefied Petroleum Gases (LPG) in Sample Cylinders for LPG Test Methods
E355 Practice for Gas Chromatography Terms and Relationships
3. Terminology
3.1 Additional terminology related to the practice of gas chromatography can be found in Practice E355.
3.2 Definitions:
3.2.1 liquefied petroleum gas (LPG), n—a mixture of normally gaseous hydrocarbons, predominantly propane or butane, or
both, that has been liquefied by compression or cooling, or both, to facilitate storage, transport, and handling. D4175
3.2.2 oxygenate, n—an oxygen-containing ashless organic compound, such as an alcohol or ether, which may be used as a fuel
or fuel supplement. D4175
3.3 Definitions of Terms Specific to This Standard:
3.3.1 Dean’s switching method—representative aliquot of sample is injected on-column using a sample valve (or via a gas
chromatograph split inlet). The sample passes onto a nonpolar column, which elutes the lighter hydrocarbons in boiling point order
1
This test method is under the jurisdiction of ASTM Committee D02 on Petroleum Products Products, Liquid Fuels, and Lubricants and is the direct responsibility of
Subcommittee D02.D0.04 on C4 Hydrocarbons.
Current edition approved July 1, 2009May 1, 2014. Published September 2009July 2014. Originally approved in 2009. Last pervious edition approved in 2009 as
D7423 – 09. DOI: 10.1520/D7423-09.10.1520/D7423-09R14.
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.
Copyright © ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959. United States
1

---------------------- Page: 1 ----------------------
D7423 − 09 (2014)
TABLE 1 Oxygenates and Typical Retention Times
Components Retention Time (min)
Dimethyl ether 6.18
Diethyl ether 8.44
Acetaldehyde 8.89
Ethyl tert-butyl ether 10.66
Methyl tert-butyl ether (MTBE) 10.92
Diisopropyl ether 11.22
Propionaldehyde (Propanal) 12.00
Tertiary amyl methyl ether (TAME) 13.19
Propyl ether 14.00
Isobutylaldehyde 14.10
Butylaldehyde 14.50
Methanol 14.91
Acetone 15.39
Isovaleraldehyde 16.00
Valeraldehyde 16.10
2-Butanone (MEK) 17.14
Ethanol 17.51
N-propyl alcohol and isopropanol 19.20 (co-elution)
Allyl Alcohol 20.00
Isobutanol, Tert-butyl alcohol, Sec-Butanol 20.24 (co-elution)
N-butanol 20.84
to the a
...