ASTM D2504-88(2015)

NOTICE: This standard has either been superseded and replaced by a new version or withdrawn.
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Designation: D2504 − 88 (Reapproved 2015)
Standard Test Method for
Noncondensable Gases in C and Lighter Hydrocarbon
Products by Gas Chromatography
This standard is issued under the fixed designation D2504; 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 concentration of the gases to be determined is calculated from
the recorded peak heights or peak areas. Argon can be used as
1.1 This test method covers the determination of hydrogen,
a carrier gas for the determination of hydrogen in concentra-
nitrogen, oxygen, and carbon monoxide in the parts per million
tions below 100 ppmv. Argon, if present in the sample,
volume (ppmv) range in C and lighter hydrocarbon products.
interferes with oxygen determination.
This test method should be applicable to light hydrocarbons
other than ethylene, but the test program did not include them.
4. Significance and Use
1.2 The values stated in SI units are to be regarded as the
4.1 The presence of trace amounts of hydrogen, oxygen, and
standard. The values given in parentheses are for information
carbon monoxide can have deleterious effects in certain pro-
only.
cesses using hydrocarbon products as feed stock. This test
1.3 This standard does not purport to address all of the
method is suitable for setting specifications, for use as an
safety concerns, if any, associated with its use. It is the
internal quality control tool and for use in development or
responsibility of the user of this standard to establish appro-
research work.
priate safety and health practices and determine the applica-
5. Apparatus
bility of regulatory limitations prior to use. For some specific
hazard statements, see the Annex A1.
5.1 Chromatograph—Any chromatographic instrument
having either a thermal conductivity or ionization detector with
2. Referenced Documents
an overall sensitivity sufficient to detect 2 ppmv or less of the
2.1 ASTM Standards:
compounds listed in the scope, with a peak height of at least
D2505 Test Method for Ethylene, Other Hydrocarbons, and
2 mm without loss of resolution.
Carbon Dioxide in High-Purity Ethylene by Gas Chroma-
5.2 Detectors—Thermal Conductivity—If a methanation re-
tography
actor is used, a flame ionization detector is also required. To
E260 Practice for Packed Column Gas Chromatography
determine carbon monoxide with a flame ionization detector, a
F307 Practice for Sampling Pressurized Gas for Gas Analy-
methanation reactor must be inserted between the column and
sis
the detector and hydrogen added as a reduction gas. Details on
2.2 Other Standard:
the preparation and use of the reactor are given in Appendix
Compressed Gas Association Booklets G-4 and G-4.1 on the
X1.
use of oxygen.
5.3 Constant-Volume Gas Sampling Valve.
3. Summary of Test Method
5.4 Column—Any column or set of columns that is capable
3.1 The sample is separated in a gas-solid chromatographic
of resolving the components listed in the scope can be used.
system using molecular sieves as the solid adsorbent. The
Copper, stainless steel, or aluminum tubing may be used. The
columns chosen must afford a resolution such that the depth of
the valleys ahead of the trace peak is no less than 50 % of the
This test method is under the jurisdiction of ASTM Committee D02 on
Petroleum Products, Liquid Fuels, and Lubricants and is the direct responsibility of
trace peak height.
Subcommittee D02.D0.02 on Ethylene.
5.5 Recorder—A recorder with a full-scale response of 2 s
Current edition approved June 1, 2015. Published July 2015. Originally approved
in 1966. Last previous edition approved in 2010 as D2504 – 88 (2010). DOI:
or less and a maximum rate of noise of 60.3 % of full scale.
10.1520/D2504-88R15.
5.6 Oven—The oven used for activating molecular sieves
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
must be maintained at 260 °C to 288 °C (500 °F to 550 °F) and
Standards volume information, refer to the standard’s Document Summary page on
should be designed so that the gases may be displaced
the ASTM website.
3 continuously by a stream of inert gas. The oven may be a
Available from Compressed Gas Association (CGA), 4221 Walney Rd., 5th
Floor, Chantilly, VA 20151-2923, http://www.cganet.com. thermostated piece of 1 in. pipe about 0.3 m (1 ft) in length.
Copyright © ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959. United States
D2504 − 88 (2015)
Electrical heating tapes or other means may be used for heating erate the column in the oven in the same manner as described
provided the heat is distributed uniformly. in 8.1 whenever the oxygen is not completely separated from
the nitrogen peak.
NOTE 1—The use of copper tubing is not recommended with samples
containing acetylene as this could lead to the formation of potentially
9. Calibration
explosive copper acetylide.
9.1 Bring the equipment and column to equilibrium and
6. Reagents and Materials
maintain a constant carrier gas rate and temperature.
6.1 Molecular Sieves, 5A, 13A, or 13X—Any mesh sizes can
NOTE 4—Carrier gas rates of 36 mL ⁄min to 60 mL ⁄min and tempera-
be used so long as sensitivity and resolution are maintained tures of 50 °C to 60 °C have been used successfully.
(see Note 2). If a 40 mesh to 60 mesh sieve size is desired, but
9.2 Prepare at least three synthetic standard samples con-
is not available, it may be prepared as described in 8.1.
taining the compounds to be determined over the range of
concentration desired in the products to be analyzed, using the
6.2 Coconut Charcoal, 30 mesh to 60 mesh sieve size (op-
pure gases or the certified blend. For the preparation of the
tional).
second, third, and following calibration samples it is always
NOTE 2—Columns that have been found to give the desired separation
preferable not to dilute the first sample.
include a 1 m by 3.175 mm outside diameter column of 100 mesh to
120 mesh 5A molecular sieve, a 3 m by 6.35 mm outside diameter column
NOTE 5—Synthetic standard samples should be prepared as described in
of 40 mesh to 60 mesh 5A sieve, and a 7.7 m by 6.35 mm outside diameter
Test Method D2505.
column with 13A or 13X sieve in the first 7.4 m and charcoal in the 0.3 m.
9.3 Inject a known volume of one of the standard samples,
6.3 Gases for Calibration—Pure or research grade
using a minimum of 1 mL for detecting 2 ppmv.
hydrogen, oxygen, nitrogen, and carbon monoxide will be
NOTE 6—Use of a reverse-flow arrangement will facilitate removal of
needed to prepare synthetic standard samples as described in
heavier gases and decrease the elapsed time of analysis.
Test Method D2505. (Warning—Flammable gases. Hazardous
9.4 Record all of the desired peaks on each of the synthetic
pressure. See Annexes A1.1 – A1.5.) (Warning—Flammable.
blends prepared.
Poison. Harmful if inhaled. Dangerous when exposed to flame.
See Annex A1.5.) (Warning—Hazardous pressure. See Annex
9.5 Prepare a chart for each compound, plotting the peak
A1.2.) Certified calibration blends are commercially available
height of the compound or peak area of the compound against
from numerous sources and can be used as the synthetic
the concentration of the compounds in ppmv. The peak area
standard samples.
can be determined by any method that meets the precision
6.4 Carrier Gases—Argon or helium. requirements of Section 12. Methods found to be acceptable
include planimetering, integration (electronic or mechanical or
NOTE 3—Practice E260 contains information that will be helpful to
computer processing), and triangulation.
those using this test method.
10. Procedure
7. Sampling
10.1 Connect the sample cylinder containing a gaseous
7.1 Samples shall be supplied to the laboratory in high-
sample to the gas sample valve with a metal tube and allow the
pressure sample cylinders, obtained using the procedures
sample to flow from the sample tube for about ⁄2 min. at a rate
described in Practice F307 or similar methods.
of 70 to 100 mL/min.
10.2 Inject into the instrument the same volume of sample
8. Preparation of Apparatus
as used for calibration, (pressure of sample and calibration gas
8.1 Chromatographic Column Packing—Crush in a porce-
must be the same in the sample loop) and record the peak areas
lain mortar and sieve to 40 mesh to 60 mesh size about 200 g
or peak heights desired.
of molecular sieves 5A in order to have enough for several
columns. All work of preparing molecular sieves and packing
11. Calculation
columns with this material shall be done rapidly, preferably
11.1 From the peak height or area of the compound in the
under a blanket of dry nitrogen in order to minimize moisture
sample, determine the moles per million of the compound
absorption. Heat the screened molecular sieves in an oven at
using the charts prepared in calibration. A typical characteriza-
274 °C 6 14 °C (525 °F 6 25 °F) for 24 h purging with dry
tion showing hydrogen, oxygen, and nitrogen in ethylene is
nitrogen at a rate of about 5 mL/min during this time. The
presented in Fig. 1.
nitrogen rate is not critical and can be measured by any
convenient means such as an orifice meter, rotameter, 12. Precision and Bias
manometer, etc. Do not use a wet test meter.
12.1 The precision of this test method as determined by
8.2 Chromatographic Column—Purge the metal tubing with statistical examination of interlaboratory results is as follows:
dry nitrogen. Insert a small amount of glass wool in the end. 12.1.1 Repeatability—The difference between successive
Fill rapidly with the screened and activated molecular sieves, test results, obtained by the same operator with the same
adding the latter in 1 g increments. Vibrate the column, adding apparatus under constant operating conditions on identical test
additional sieves during this peri
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