ASTM D4929-16

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 or distillation and microcoulometry.  
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 The values stated in SI units are to be regarded as standard. No other units of measurement are included in this standard.  
1.5.1 The preferred concentration units are micrograms of chloride per gram of sample.  
1.6 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-Sep-2016
• 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 − 16
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* D4057 Practice for Manual Sampling of Petroleum and
Petroleum Products
1.1 The procedures in this test method cover the determi-
D4177 Practice for Automatic Sampling of Petroleum and
nation of organic chloride (above 1 µg/g organically-bound
Petroleum Products
chlorine) in crude oils, using either distillation and sodium
D6299 Practice for Applying Statistical Quality Assurance
biphenyl reduction or distillation and microcoulometry.
and Control Charting Techniques to Evaluate Analytical
1.2 The procedures in this test method involve the distilla-
Measurement System Performance
tion of crude oil test specimens to obtain a naphtha fraction
prior to chloride determination. The chloride content of the
3. Summary of Test Method
naphtha fraction of the whole crude oil can thereby be
3.1 A crude oil distillation is performed to obtain the
obtained. See Section 5 regarding potential interferences.
naphtha cut at 204 °C (400 °F). The distillation method was
1.3 Procedure A covers the determination of organic chlo-
adaptedfromTestMethodD86forthedistillationofpetroleum
ride in the washed naphtha fraction of crude oil by sodium
products. The naphtha cut is washed with caustic, repeatedly
biphenyl reduction followed by potentiometric titration.
when necessary, until all hydrogen sulfide is removed. The
1.4 Procedure B covers the determination of organic chlo-
naphtha cut, free of hydrogen sulfide, is then washed with
ride in the washed naphtha fraction of crude oil by oxidative
water, repeatedly when necessary, to remove inorganic halides
combustion followed by microcoulometric titration.
(chlorides).
1.5 The values stated in SI units are to be regarded as
3.2 There are two alternative procedures for determination
standard. No other units of measurement are included in this
of the organic chloride in the washed naphtha fraction, as
standard.
follows.
1.5.1 The preferred concentration units are micrograms of
3.2.1 Procedure A, Sodium Biphenyl Reduction and
chloride per gram of sample.
Potentiometry—The washed naphtha fraction of a crude oil
1.6 This standard does not purport to address all of the
specimen is weighed and transferred to a separatory funnel
safety concerns, if any, associated with its use. It is the
containing sodium biphenyl reagent in toluene. The reagent is
responsibility of the user of this standard to establish appro-
an addition compound of sodium and biphenyl in ethylene
priate safety and health practices and determine the applica-
glycol dimethyl ether. The free radical nature of this reagent
bility of regulatory limitations prior to use.
promotes very rapid conversion of the organic halogen to
inorganic halide. In effect this reagent solubilizes metallic
2. Referenced Documents
sodium in organic compounds. The excess reagent is
2
decomposed, the mixture acidified, and the phases separated.
2.1 ASTM Standards:
The aqueous phase is evaporated to 25 mL to 30 mL, acetone
D86 Test Method for Distillation of Petroleum Products and
is added, and the solution titrated potentiometrically.
Liquid Fuels at Atmospheric Pressure
D1193 Specification for Reagent Water 3.2.2 Procedure B, Combustion and Microcoulometry
—The washed naphtha fraction of a crude oil specimen is
injected into a flowing stream of gas containing about 80 %
1
This test method is under the jurisdiction of ASTM Committee D02 on
oxygen and 20 % inert gas, such as argon, helium, or nitrogen.
Petroleum Products, Liquid Fuels, and Lubricants and is the direct responsibility of
The gas and sample flow through a combustion tube main-
Subcommittee D02.03 on Elemental Analysis.
tained at about 800 °C. The chlorine is converted to chloride
Current edition approved Oct. 1, 2016. Published October 2016. Originally
and oxychlorides, which then flow into a titration cell where
approved in 1989. Last previous edition approved in 2015 as D4929 – 15a. DOI:
10.1520/D4929-16.
they react with the silver ions in the titration cell. The silver
2
For referenced ASTM standards, visit the ASTM website, www.astm.org, or
ions thus consumed are coulometrically replaced. The total
contact ASTM Customer Service at [e-mail]. For Annual Book of ASTM
current required to replace the silver ions is a measure of the
Standards volume information, refer to the standard’s Document Summary page on
the ASTM website. chlorine present in the injected sa
...

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 − 15a D4929 − 16
Standard Test MethodsMethod 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 These test methodsThe 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 or distillation and microcou-
lometry.
1.2 These test methodsThe 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 Test Method 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 Test Method 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 The values stated in SI units are to be regarded as standard. No other units of measurement are included in this standard.
The preferred concentration units are micrograms of chloride per gram of sample.
1.5.1 The preferred concentration units are micrograms of chloride per gram of sample.
1.6 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:
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
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 necessary,
until all hydrogen sulfide is removed. The naphtha cut, free of hydrogen sulfide, is then washed with water, repeatedly when
necessary, to remove inorganic halides (chlorides).
3.2 There are two alternative test methods procedures for determination of the organic chloride in the washed naphtha fraction,
as follows.
3.2.1 Test Method Procedure A, Sodium Biphenyl Reduction and Potentiometry—The washed naphtha fraction of a crude oil
specimen is weighed and transferred to a separatory funnel containing sodium biphenyl reagent in toluene. The reagent is an
1
TheseThis test methods aremethod is under the jurisdiction of ASTM Committee D02 on Petroleum Products, Liquid Fuels, and Lubricants and areis the direct
responsibility of Subcommittee D02.03 on Elemental Analysis.
Current edition approved Dec. 1, 2015Oct. 1, 2016. Published December 2015October 2016. Originally approved in 1989. Last previous edition approved in 2015 as
D4929 – 15.D4929 – 15a. DOI: 10.1520/D4929-15A.10.1520/D4929-16.
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
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D4929 − 16
addition compound of sodium and biphenyl in ethylene glycol dimethyl ether. The free radical nature of this reagent promotes very
rapid conversion of the organic halogen to inorganic halide. In effect this reagent solubilizes metallic sodium in organic
compounds. The excess reagent is decomposed, th
...