ASTM D4929-17

Standard Test Method for Determination of Organic Chloride Content in Crude Oil

SIGNIFICANCE AND USE
4.1 Organic chlorides do not occur naturally in crude oil. When present, they result from contamination in some manner, such as disposal of chlorinated solvent used in many dewaxing pipeline or other equipment operations.  
4.1.1 Uncontaminated crude oil will contain no detectable organic chloride, and most refineries can handle very small amounts without deleterious effects.
4.1.1.1 Most trade contracts specify that no organic chloride is present in the crude oil.  
4.1.2 Several pipelines have set specification limits at  
4.1.2.1 To ensure Eq 3).  
4.1.3 Organic chloride present in the crude oil (for example, methylene chloride, perchloroethylene, etc.) is usually distilled into the naphtha fraction. Some compounds break down during fractionation and produce hydrochloric acid, which has a corrosive effect. Some compounds survive fractionation and are destroyed during hydro-treating (desulfurization of the naphtha).  
4.2 Other halides can also be used for dewaxing crude oil; in such cases, any organic halides will have similar impact on the refining operations as the organic chlorides.  
4.3 Organic chloride species are potentially damaging to refinery processes. Hydrochloric acid can be produced in hydrotreating or reforming reactors and the acid accumulates in condensing regions of the refinery. Unexpected concentrations of organic chlorides cannot be effectively neutralized and damage can result. Organic chlorides are not known to be naturally present in crude oils and usually result from cleaning operations at producing sites, pipelines, or tanks. It is important for the oil industry to have common methods available for the determination of organic chlorides in crude oil, particularly when transfer of custody is involved.
SCOPE
1.1 The procedures in this test method cover the determination of organic chloride (above 1 μg/g organically-bound chlorine) in crude oils, using either distillation and sodium biphenyl reduction, distillation and microcoulometry, or distillation and x-ray fluorescence (XRF) spectrometry.  
1.2 The procedures in this test method involve the distillation of crude oil test specimens to obtain a naphtha fraction prior to chloride determination. The chloride content of the naphtha fraction of the whole crude oil can thereby be obtained. See Section 5 regarding potential interferences.  
1.3 Procedure A covers the determination of organic chloride in the washed naphtha fraction of crude oil by sodium biphenyl reduction followed by potentiometric titration.  
1.4 Procedure B covers the determination of organic chloride in the washed naphtha fraction of crude oil by oxidative combustion followed by microcoulometric titration.  
1.5 Procedure C covers the determination of organic chloride in the washed naphtha fraction of crude oil by x-ray fluorescence spectrometry.  
1.6 The values stated in SI units are to be regarded as standard. No other units of measurement are included in this standard.  
1.6.1 The preferred concentration units are micrograms of chloride per gram of sample.  
1.7 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.  
1.8 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: Historical
• Publication Date: 14-Oct-2017
• ICS: 75.040 - Crude petroleum
• Technical Committee: D02 - Petroleum Products, Liquid Fuels, and Lubricants
• Drafting Committee: D02.03 - Elemental Analysis

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: D4929 − 17
Standard Test Method for
1
Determination of Organic Chloride Content in Crude Oil
This standard is issued under the fixed designation D4929; 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* 2. Referenced Documents
2
1.1 The procedures in this test method cover the determi- 2.1 ASTM Standards:
nation of organic chloride (above 1 µg/g organically-bound D86 Test Method for Distillation of Petroleum Products and
chlorine) in crude oils, using either distillation and sodium Liquid Fuels at Atmospheric Pressure
biphenyl reduction, distillation and microcoulometry, or distil- D1193 Specification for Reagent Water
lation and x-ray fluorescence (XRF) spectrometry. D4057 Practice for Manual Sampling of Petroleum and
Petroleum Products
1.2 The procedures in this test method involve the distilla-
D4177 Practice for Automatic Sampling of Petroleum and
tion of crude oil test specimens to obtain a naphtha fraction
Petroleum Products
prior to chloride determination. The chloride content of the
D6299 Practice for Applying Statistical Quality Assurance
naphtha fraction of the whole crude oil can thereby be
and Control Charting Techniques to Evaluate Analytical
obtained. See Section 5 regarding potential interferences.
Measurement System Performance
1.3 Procedure A covers the determination of organic chlo-
D6300 Practice for Determination of Precision and Bias
ride in the washed naphtha fraction of crude oil by sodium
Data for Use in Test Methods for Petroleum Products and
biphenyl reduction followed by potentiometric titration.
Lubricants
D6708 Practice for StatisticalAssessment and Improvement
1.4 Procedure B covers the determination of organic chlo-
ride in the washed naphtha fraction of crude oil by oxidative of Expected Agreement Between Two Test Methods that
Purport to Measure the Same Property of a Material
combustion followed by microcoulometric titration.
D7343 Practice for Optimization, Sample Handling,
1.5 Procedure C covers the determination of organic chlo-
Calibration, and Validation of X-ray Fluorescence Spec-
ride in the washed naphtha fraction of crude oil by x-ray
trometry Methods for Elemental Analysis of Petroleum
fluorescence spectrometry.
Products and Lubricants
1.6 The values stated in SI units are to be regarded as
standard. No other units of measurement are included in this
3. Summary of Test Method
standard.
3.1 A crude oil distillation is performed to obtain the
1.6.1 The preferred concentration units are micrograms of
naphtha cut at 204 °C (400 °F). The distillation method was
chloride per gram of sample.
adaptedfromTestMethodD86forthedistillationofpetroleum
1.7 This standard does not purport to address all of the
products. The naphtha cut is washed with caustic, repeatedly
safety concerns, if any, associated with its use. It is the
when necessary, until all hydrogen sulfide is removed. The
responsibility of the user of this standard to establish appro-
naphtha cut, free of hydrogen sulfide, is then washed with
priate safety, health, and environmental practices and deter-
water, repeatedly when necessary, to remove inorganic halides
mine the applicability of regulatory limitations prior to use.
(chlorides).
1.8 This international standard was developed in accor-
3.2 There are three alternative procedures for determination
dance with internationally recognized principles on standard-
of the organic chloride in the washed naphtha fraction, as
ization established in the Decision on Principles for the
follows.
Development of International Standards, Guides and Recom-
3.2.1 Procedure A, Sodium Biphenyl Reduction and
mendations issued by the World Trade Organization Technical
Potentiometry—The washed naphtha fraction of a crude oil
Barriers to Trade (TBT) Committee.
specimen is weighed and transferred to a separatory funnel
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
2
Subcommittee D02.03 on Elemental Analysis. For referenced ASTM standards, visit the ASTM website, www.astm.org, or
Current edition approved Oct. 15, 2017. Published December 2017. Originally contact ASTM Customer Service at [e-mail]. For Annual Book of ASTM
approved in 1989. Last previous edition approved in 2016 as D4929 – 16. DOI: Standards volume information, refer to the standard’s Document Summary page on
10.1520/D4929-17. 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 Cons
...

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: D4929 − 16 D4929 − 17
Standard Test Method for
1
Determination of Organic Chloride Content in Crude Oil
This standard is issued under the fixed designation D4929; 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 The procedures in this test method cover the determination of organic chloride (above 1 μg/g organically-bound chlorine)
in crude oils, using either distillation and sodium biphenyl reduction reduction, distillation and microcoulometry, or distillation and
microcoulometry. x-ray fluorescence (XRF) spectrometry.
1.2 The procedures in this test method involve the distillation of crude oil test specimens to obtain a naphtha fraction prior to
chloride determination. The chloride content of the naphtha fraction of the whole crude oil can thereby be obtained. See Section
5 regarding potential interferences.
1.3 Procedure A covers the determination of organic chloride in the washed naphtha fraction of crude oil by sodium biphenyl
reduction followed by potentiometric titration.
1.4 Procedure B covers the determination of organic chloride in the washed naphtha fraction of crude oil by oxidative
combustion followed by microcoulometric titration.
1.5 Procedure C covers the determination of organic chloride in the washed naphtha fraction of crude oil by x-ray fluorescence
spectrometry.
1.6 The values stated in SI units are to be regarded as standard. No other units of measurement are included in this standard.
1.6.1 The preferred concentration units are micrograms of chloride per gram of sample.
1.7 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.
1.8 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:
D86 Test Method for Distillation of Petroleum Products and Liquid Fuels at Atmospheric Pressure
D1193 Specification for Reagent Water
D4057 Practice for Manual Sampling of Petroleum and Petroleum Products
D4177 Practice for Automatic Sampling of Petroleum and Petroleum Products
D6299 Practice for Applying Statistical Quality Assurance and Control Charting Techniques to Evaluate Analytical Measure-
ment System Performance
D6300 Practice for Determination of Precision and Bias Data for Use in Test Methods for Petroleum Products and Lubricants
D6708 Practice for Statistical Assessment and Improvement of Expected Agreement Between Two Test Methods that Purport
to Measure the Same Property of a Material
D7343 Practice for Optimization, Sample Handling, Calibration, and Validation of X-ray Fluorescence Spectrometry Methods
for Elemental Analysis of Petroleum Products and Lubricants
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 Oct. 1, 2016Oct. 15, 2017. Published October 2016December 2017. Originally approved in 1989. Last previous edition approved in 20152016
as D4929 – 15a.16. DOI: 10.1520/D4929-16.10.1520/D4929-17.
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

---------------------- Page: 1 ----------------------
D4929 − 17
3. Summary of Test Method
3.1 A crude oil distillation is performed to obtain the naphtha cut at 204 °C (400 °F). The distillation method was adapted from
Test Method D86 for the distillation of petroleum products. The naphtha cut is washed with caustic, repeatedly when nec
...