An American National Standard

Designation: D 5274 – 00 (Reapproved 2005)

Standard Guide for

Analysis of 1,3–Butadiene Product1
This standard is issued under the fixed designation D 5274; 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 (e) indicates an editorial change since the last revision or reapproval.

1. Scope D 4423 Test Method for Determination of Carbonyls in C4

1.1 This guide covers the analysis of 1,3–butadiene prod- Hydrocarbons
ucts produced in North America. It includes possible compo- D 4468 Test Method for Total Sulfur in Gaseous Fuels by
nents and test methods, both ASTM and other, either actually Hydrogenolysis and Rateometric Colorimetry
used or believed to be in use, to test for these components. This D 4629 Test Method for Trace Nitrogen in Liquid Petro-
guide is not intended to be used or construed as a set of leum Hydrocarbons by Syringe/Inlet Oxidative Combus-
specifications for butadiene products. tion and Chemiluminescence Detection
1.2 The values stated in SI units are to be regarded as the D 4864 Test Method for Determination of Traces of Metha-
standard. The values given in parentheses are for information nol in Propylene Concentrates by Gas Chromatography
only. D 5799 Test Method for Determination of Peroxides in
1.3 This standard does not purport to address all of the Butadiene
safety concerns, if any, associated with its use. It is the 3. Terminology
responsibility of the user of this standard to establish appro-
priate safety and health practices and determine the applica- 3.1 Definitions:
bility of regulatory limitations prior to use. 3.1.1 1,3-butadiene—hydrocarbon product containing more
than 99 % 1,3-butadiene.
2. Referenced Documents 3.2 Symbols:
2.1 ASTM Standards: 2 3.2.1 BHT—butyl hydroxy toluene.
D 1025 Test Method for Nonvolatile Residue of Polymer- 3.2.2 GC—gas chromatography.
ization Grade Butadiene 3.2.3 pTBC—paratertiary butyl catechol.
D 1157 Test Method for Total Inhibitor Content (TBC) of 3.2.4 4VCH-1—4-vinyl cyclo hexene (1,3-butadiene
Light Hydrocarbons dimer).
D 1550 ASTM Butadiene Measurement Tables
4. Significance and Use
D 2384 Test Methods for Traces of Volatile Chlorides in
Butane-Butene Mixtures 4.1 This guide is intended to provide information on the
D 2426 Test Method for Butadiene Dimer and Styrene in possible composition of 1,3-butadiene products and possible
Butadiene Concentrates by Gas Chromatography ways to test them. Since there are currently not enough ASTM
D 2593 Test Method for Butadiene Purity and Hydrocarbon standards for determining all components of interest, this guide
Impurities by Gas Chromatography provides information on other potentially available test meth-
D 3246 Test Method for Sulfur in Petroleum Gas by Oxi- ods.
dative Microcoulometry 4.2 Although this guide is not to be used for specifications,
D 3700 Practice for Obtaining LPG Samples Using a Float- it can provide a starting point for parties to develop mutually
ing Piston Cylinder agreed-upon specifications that meet their respective require-
D 4178 Practice for Calibrating Moisture Analyzers ments. It can also be used as a starting point in finding suitable
test methods for 1,3-butadiene components.
5. Sampling
1
This guide is under the jurisdiction of ASTM Committee D02 on Petroleum 5.1 General:
Products and Lubricants and is the direct responsibility of Subcommittee D02.D0.04
on C4 Hydrocarbons. 5.1.1 1,3-butadiene is a very reactive hydrocarbon. It reacts
Current edition approved Nov. 1, 2005. Published November 2005. Originally with oxygen to form peroxides and to polymerize. It also
approved in 1992. Last previous edition approved in 2000 as D 5274 – 00.
2
dimerizes at a rate that is temperature dependent. Below 10°C
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
(50°F), the dimerization rate is less than 1 mg/kg by mass/h;
Standards volume information, refer to the standard’s Document Summary page on but, at 20°C (77°F), it increases to 3 to 4 mg/kg mass/h; and at
the ASTM website. 40°C (104°F), to 14 to 20 mg/kg mass/h. 1,3-butadiene is also

Copyright © ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959, United States.

1
 D 5274 – 00 (2005)
TABLE 1 1,3-Butadiene Test Methods (ASTM) 5.1.1.2 Eliminate or keep to an absolute minimum the
Property Units Test Method
Concentration inclusion of oxygen during and after sampling, and
Range
5.1.1.3 Sample the product at as low a temperature as
Amines mg/kg See Table 2 <1 to 25 possible, maintain the sample at a low temperature, and
Ammonia mg/kg See Table 2 <1 to 25
Benzene mg/kg See Table 2 <0.1 to 10 analyze it as soon as possible. Do not allow it to sit outdoors in
1,2-butadiene mg/kg D 2593 <1 to 100 the sun after sampling.
1,3-butadiene dimer mg/kg D 2426 <100 to 200
(4VCH-1) 5.1.2 In addition to 5.1.1.1-5.1.1.3, 1,3-butadiene to be
C5 hydrocarbons mg/kg D 2593 <1 to 1000 analyzed for trace components should be sampled by a
C6+ hydrocarbons mg/kg See Table 2 <1 to 1000 technique that minimizes or eliminates loss of light compo-
Carbonyls mg/kg D 4423 <1 to 100
Chlorides mg/kg See Table 2 <1 to 25 nents and concentration of heavy ones. The subsections below
Ethylene glycol mg/kg See Table 2 <1 to 100 list some different sampling methods and principles. However,
Inhibitor (p-TBC) mg/kg D 1157 <1 to 500 it is not the intent of this guide to list procedures that are
See Table 2
Methanol and other mg/kg D 4864 <1 to 25 applicable to all sampling situations. It is strongly recom-
alcohols See Table 2 mended that samples be obtained under the supervision of a
Moisture mg/kg D 4178 <1 to saturated person with wide knowledge and experience in sampling
See Table 2
Nonvolatile residue mass % D 1025 <0.001 to 0.2 1,3-butadiene.
Oxygen in vapor space mass % See Table 2 <0.001 to 0.3 5.1.3 Also, even though this guide does not address the
Peroxides mg/kg D 5799 <1 to 10
Propadiene mg/kg D 2593 <1 to 25 location of a sampling point in a line or vessel, the importance
Propane mg/kg D 2593 <1 to 25 of the proper sampling location cannot be overemphasized.
Propylene mg/kg D 2593 <1 to 25
Purity of 1,3-butadiene mass % D 2593 99.0 min
5.2 Floating Piston Cylinder—Practice D 3700 meets the
Relative density 15.6/15.6 D 1550 0.625 to 0.630 criterion of minimizing or eliminating loss of light components
Toluene mg/kg See Table 2 <1 to 500 and concentration of heavy ones. However, some labs have
Total acetylenes mg/kg D 2593 <1 to 100
Total nitrogen mg/kg See Table 2 <1 to 25
safety codes preventing use of rupture-disc piston containers.
Total sulfur mg/kg See Table 2 <1 to 25 Alternative procedures must be used in these labs.
5.3 Conventional “Outaging” Method—The widely used
“outaging” technique (that is, the practice of removing a
TABLE 2 1,3-Butadiene Test Methods (Non-ASTM Methods)A portion of the fluid contents from a conventional sampling
Property Possible Test Method cylinder after filling in order to provide expansion room)
Amines Adaption of Test Method D 4629 causes a partial loss of light components into the vapor space.
Ammonia Acid absorption with Nessler finish Subsequent handling to recapture these light ends in the liquid
Acid absorption with specific ion finish
Benzene Capillary gas chromatography phase of the sample, such as repressurization of the cylinder
Chlorides Organic chlorides by GC, with hall detector; contents with an inert gas, is usually successful, since 1,3-
also, Test Methods D 2384
butadiene seldom contains noncondensables. However, if per-
Ethylene glycol Capillary gas chromatography
Inhibitor (BHT) Capillary gas chromatography or titration manent gases are present and are to be determined, an alternate
method procedure may be required.
Inhibitor (pTBC) Test Method D 1157; also, gas
chromatography and titration methods using 5.4 Vaporization Methods—Vaporization of the sample, ei-
ceric ammonium sulfate ther at the source or in the lab prior to analysis, may cause loss
Methanol and other Adaption of Test Method D 4864 of heavier components, if present, and concentration of lighter
alcohols
Moisture Panametrics moisture instrument; adaption of ones. Also, since 1,3-butadiene is so reactive, the heat required
Karl Fisher titration to vaporize may cause undesirable changes in the composition
Oxygen Adaption of Panometric or Teledyne oxygen of the sample. For these reasons, vaporization is not recom-
analyzers
Toluene Capillary gas chromatography mended for 1,3-butadiene.
Total sulfur Adaption of Test Methods D 3246 or D 4468 5.5 Reactive Components—Determination of reactive com-
Total nitrogen Adaption of Test Method D 4629; also, micro-
coulometry ponents, such as certain sulfur compounds, is generally be-
A
The above are possible butadiene test methods or techniques which are
lieved to require special sample containers, such as TFE-
believed to be in use in the industry for testing. Inclusion of any test method in this fluorocarbon-lined cylinders.
list is not to be construed as a recommendation by ASTM for its use. Some of the
test methods in this list are ASTM test methods that are specified for other
products but are being used by some labs for butadiene analysis. However, use of 6. Composition and Test Methods
ASTM test methods beyond their scope is not recommended by ASTM. Precision
and bias may be adversely affected.
6.1 Table 1 indicates possible composition ranges and
ASTM methods for 1,3-butadiene product. Table 2 lists other
test methods known or believed to be in use.
classified as toxic and as a potential health hazard, having been
found carcinogenic to laboratory animals. Therefore, sampling
7. Keywords
of 1,3-butadiene must adhere to the following three principles:
5.1.1.1 Minimize personnel exposure. See the appropriate 7.1 1,3-butadiene;1,3-butadiene product;1,3-butadiene test
OSHA Material Safety Data Sheet for guidance, methods

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 D 5274 – 00 (2005)
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