ASTM D4929-15a
(Test Method)Standard Test Methods for Determination of Organic Chloride Content in Crude Oil
Standard Test Methods 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 These test methods 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 These test methods 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 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 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.
1.6 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.
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Designation: D4929 − 15a
StandardTest Methods 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* D4177 Practice for Automatic Sampling of Petroleum and
Petroleum Products
1.1 These test methods cover the determination of organic
D6299 Practice for Applying Statistical Quality Assurance
chloride (above 1 µg/g organically-bound chlorine) in crude
and Control Charting Techniques to Evaluate Analytical
oils, using either distillation and sodium biphenyl reduction or
Measurement System Performance
distillation and microcoulometry.
1.2 These test methods involve the distillation of crude oil
3. Summary of Test Method
test specimens to obtain a naphtha fraction prior to chloride
3.1 A crude oil distillation is performed to obtain the
determination. The chloride content of the naphtha fraction of
naphtha cut at 204 °C (400 °F). The distillation method was
the whole crude oil can thereby be obtained. See Section 5
adaptedfromTestMethodD86forthedistillationofpetroleum
regarding potential interferences.
products. The naphtha cut is washed with caustic, repeatedly
1.3 Test Method A covers the determination of organic
when necessary, until all hydrogen sulfide is removed. The
chloride in the washed naphtha fraction of crude oil by sodium
naphtha cut, free of hydrogen sulfide, is then washed with
biphenyl reduction followed by potentiometric titration.
water, repeatedly when necessary, to remove inorganic halides
1.4 Test Method B covers the determination of organic
(chlorides).
chloride in the washed naphtha fraction of crude oil by
3.2 There are two alternative test methods for determination
oxidative combustion followed by microcoulometric titration.
of the organic chloride in the washed naphtha fraction, as
1.5 The values stated in SI units are to be regarded as
follows.
standard. No other units of measurement are included in this
3.2.1 Test Method A, Sodium Biphenyl Reduction and
standard. The preferred concentration units are micrograms of
Potentiometry—The washed naphtha fraction of a crude oil
chloride per gram of sample.
specimen is weighed and transferred to a separatory funnel
1.6 This standard does not purport to address all of the
containing sodium biphenyl reagent in toluene. The reagent is
safety concerns, if any, associated with its use. It is the
an addition compound of sodium and biphenyl in ethylene
responsibility of the user of this standard to establish appro-
glycol dimethyl ether. The free radical nature of this reagent
priate safety and health practices and determine the applica-
promotes very rapid conversion of the organic halogen to
bility of regulatory limitations prior to use.
inorganic halide. In effect this reagent solubilizes metallic
sodium in organic compounds. The excess reagent is
2. Referenced Documents
decomposed, the mixture acidified, and the phases separated.
2
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
3.2.2 Test Method B, Combustion and Microcoulometry
D1193 Specification for Reagent Water
—The washed naphtha fraction of a crude oil specimen is
D4057 Practice for Manual Sampling of Petroleum and
injected into a flowing stream of gas containing about 80 %
Petroleum Products
oxygen and 20 % inert gas, such as argon, helium, or nitrogen.
The gas and sample flow through a combustion tube main-
1
tained at about 800 °C. The chlorine is converted to chloride
These test methods are under the jurisdiction of ASTM Committee D02 on
Petroleum Products, Liquid Fuels, and Lubricants and are the direct responsibility
and oxychlorides, which then flow into a titration cell where
of Subcommittee D02.03 on Elemental Analysis.
they react with the silver ions in the titration cell. The silver
Current edition approved Dec. 1, 2015. Published December 2015. Originally
ions thus consumed are coulometrically replaced. The total
approved in 1989. Last previous edition approved in 2015 as D4929 – 15. DOI:
10.1520/D4929-15A. current required to replace the silver ions is a measure of the
2
For referenced ASTM standards, visit the ASTM website, www.astm.org, or
chlorine present in the injected samples.
contact ASTM Customer Service at service@astm.org. For Annual Book of ASTM
3.2.3 The reaction occurring in the titration cell as chloride
Standards volume information, refer to the standard’s Doc
...
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 − 15 D4929 − 15a
Standard Test Methods 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 methods 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 These test methods 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 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 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.
1.6 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 for determination of the organic chloride in the washed naphtha fraction, as follows.
3.2.1 Test Method 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 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
1
These test methods are under the jurisdiction of ASTM Committee D02 on Petroleum Products, Liquid Fuels, and Lubricants and are the direct responsibility of
Subcommittee D02.03 on Elemental Analysis.
Current edition approved June 1, 2015Dec. 1, 2015. Published June 2015December 2015. Originally approved in 1989. Last previous edition approved in 20142015 as
D4929 – 07 (2014).D4929 – 15. DOI: 10.1520/D4929-15.10.1520/D4929-15A.
2
For referenced ASTM standards, visit the ASTM website, www.astm.org, or contact ASTM Customer Service at service@astm.org. 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 − 15a
excess reagent is decomposed, the mixture acidified, and the phases separated. The aqueous phase is evaporated to 25 mL to
30 mL, acetone is added, and the solution titrated potentiometrically.
3.2.2 Test Method B, Combustion and Microcoulometr
...
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