ASTM D2505-88(2015)

NOTICE: This standard has either been superseded and replaced by a new version or withdrawn.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: D2505 − 88 (Reapproved 2015)
Standard Test Method for
Ethylene, Other Hydrocarbons, and Carbon Dioxide in High-
Purity Ethylene by Gas Chromatography
This standard is issued under the fixed designation D2505; 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 helium as the carrier gas. Methane and ethane are determined
by using a silica gel column. Propylene and heavier hydrocar-
1.1 This test method covers the determination of carbon
bons are determined using a hexamethylphosphoramide
dioxide, methane, ethane, acetylene, and other hydrocarbons in
(HMPA) column. Acetylene is determined by using, in series,
high-purity ethylene. Hydrogen, nitrogen, oxygen, and carbon
a hexadecane column and a squalane column. Carbon dioxide
monoxide are determined in accordance with Test Method
is determined using a column packed with activated charcoal
D2504. The percent ethylene is obtained by subtracting the
impregnated with a solution of silver nitrate in β,β'-
sum of the percentages of the hydrocarbon and nonhydrocar-
oxydipropionitrile. Columns other than those mentioned above
bon impurities from 100. The method is applicable over the
may be satisfactory (see 5.3). Calibration data are obtained
range of impurities from 1 to 500 parts per million volume
using standard samples containing the impurities, carbon
(ppmV).
dioxide, methane, and ethane in the range expected to be
1.2 This standard does not purport to address all of the
encountered. Calibration data for acetylene are obtained as-
safety concerns, if any, associated with its use. It is the
suming that acetylene has the same peak area response on a
responsibility of the user of this standard to establish appro-
weight basis as methane. The acetylene content in a sample is
priate safety and health practices and determine the applica-
calculated on the basis of the ratio of peak area of the acetylene
bility of regulatory limitations prior to use. For some specific
peak to the peak area of a known amount of methane.
hazard statements, see Section 6.
Calculations for carbon dioxide, methane, and ethane are
1.3 The values stated in SI units are to be regarded as the
carried out by the peak-height measurement method.
standard. The values in parentheses are for information only.
2. Referenced Documents 4. Significance and Use
2.1 ASTM Standards:
4.1 High-purity ethylene is required as a feedstock for some
D2504 Test Method for Noncondensable Gases in C and manufacturing processes, and the presence of trace amounts of
Lighter Hydrocarbon Products by Gas Chromatography
carbon dioxide and some hydrocarbons can have deleterious
D4051 Practice for Preparation of Low-Pressure Gas Blends effects. This method is suitable for setting specifications, for
E260 Practice for Packed Column Gas Chromatography
use as an internal quality control tool and for use in develop-
F307 Practice for Sampling Pressurized Gas for Gas Analy- ment or research work.
sis
5. Apparatus
3. Summary of Test Method
5.1 Any chromatographic instrument with an overall sensi-
3.1 The sample is separated in a gas chromatograph system
tivity sufficient to detect 2 ppmV or less of the compounds
utilizing four different packed chromatographic columns with
listed with a peak height of at least 2 mm without loss of
resolution.
This test method is under the jurisdiction of ASTM Committee D02 on
Petroleum Products, Liquid Fuels, and Lubricantsand is the direct responsibility of
5.2 Detectors—Thermal Conductivity—If a methanation re-
Subcommittee D02.D0.02 on Ethylene.
actor is used, a flame ionization detector is also required. To
Current edition approved June 1, 2015. Published July 2015. Originally approved
determine carbon dioxide with a flame ionization detector, a
in 1966. Last previous edition approved in 2010 as D2505 – 88 (2010). DOI:
10.1520/D2505-88R15.
methanation reactor must be inserted between the column and
For referenced ASTM standards, visit the ASTM website, www.astm.org, or
the detector and hydrogen added as a reduction gas (see Test
contact ASTM Customer Service at service@astm.org. For Annual Book of ASTM
Method D2504, Appendix X1, Preparation of Methanation
Standards volume information, refer to the standard’s Document Summary page on
the ASTM website. Reactor).
Copyright © ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959. United States
D2505 − 88 (2015)
FIG. 2 Gas-Blending Manifold
FIG. 1 Typical Chromatogram for Propylene
6.3 Active Solids—Activated carbon, 30 mesh to 40 mesh,
silica gel, 100 to 200-mesh. Other sizes may be satisfactory.
5.3 Column—Any column or set of columns can be used
6.4 Liquid Phases—Hexamethylphosphoramide (HMPA ),
that separates carbon dioxide, methane, acetylene and C and
6 6
hexadecane. Squalene, silver nitrate, and β,β'-
heavier compounds. There may be tailing of the ethylene peak
oxydipropionitrile. Other liquid phases may be satisfactory.
but do not use any condition such that the depth of the valleys
(Warning—Combustible solvents. See A1.7.) (Warning—
ahead of the trace peak is less than 50 % of the trace peak
HMPA may be harmful if inhaled. Causes irritation. A potential
height. (See Fig. 1 for example.)
carcinogen (lungs). See A1.5.)
5.4 Recorder—A recorder with a full-scale response of 2 s
6.5 Helium. ( Warning—Compressed Gas, Hazardous Pres-
or less and a maximum rate of noise of 60.3 % of full scale.
sure. See A1.2.)
5.5 Gas-Blending Apparatus—A typical gas-blending appa-
6.6 Hydrogen. ( Warning—Flammable Gas, Hazardous
ratus is shown in Fig. 2. A high-pressure manifold equipped
Pressure. See A1.6.)
with a gage capable of accurately measuring ethylene pressures
6.7 Acetone. ( Warning—Extremely Flammable. See
up to 3.4 MN ⁄m gage (500 psig) is required. Other types of
A1.1.)
gas-blending equipment, such as described in Practice D4051,
6.8 Gases for Calibration—Pure or research grade carbon
can be used.
dioxide, methane, ethane, acetylene, ethylene, propane, and
NOTE 1— Practice E260 contains information that will be helpful to
those using this method.
A fraction sieved in the laboratory to 30 to 40 mesh from medium activity
6. Reagents and Materials charcoal, 20 to 60 mesh, sold by Central Scientific Co., 1700 Irving Park Road,
Chicago, IL 60613, has been found satisfactory for this purpose. If you are aware of
6.1 Copper or Aluminum, or Stainless Steel Tubing, 6.4 mm alternative suppliers, please provide this information to ASTM International
1 1 Headquarters. Your comments will receive careful consideration at a meeting of the
( ⁄4 in. ) outside diameter, and nylon tubing, 3.2 mm ( ⁄8-in.)
responsible technical committee , which you may attend.
outside diameter. 5
The sole source of supply of the apparatus known to the committee at this time
is Silica gel Code 923 available from the Davison Chemical Co., Baltimore, Md.
6.2 Solid Supports—Crushed firebrick or calcined diatoma-
21203. If you are aware of alternative suppliers, please provide this information to
ceous earth, such as Chromosorb P, 35 mesh to 80 mesh and ASTM International Headquarters. Your comments will receive careful consider-
ation at a meeting of the responsible technical committee , which you may attend.
80 mesh to 100 mesh. Other supporting materials or mesh
The sole source of supply of the apparatus known to the committee at this time
sieves can be satisfactory.
is available from the Fisher Scientific Co., St. Louis, MO. If you are aware of
alternative suppliers, please provide this information to ASTM International
Headquarters. Your comments will receive careful consideration at a meeting of the
responsible technical committee , which you may attend.
3 7
The sole source of supply of the apparatus is available from the Celite Division, β,β'-oxydipropionitrile, sold by Distillation Products Industries, Division of
Johns Mansville Co., New York, NY. If you are aware of alternative suppliers, Eastman Kodak Co., Rochester, NY, has been found to be satisfactory. If you are
please provide this information to ASTM International Headquarters. Your com- aware of alternative suppliers, please provide this information to ASTM Interna-
ments will receive careful consideration at a meeting of the responsible technical tional Headquarters. Your comments will receive careful consideration at a meeting
1 1
committee , which you may attend. of the responsible technical committee , which you may attend.
D2505 − 88 (2015)
TABLE 1 Suggested Composition of a Concentrate of Impurities
propylene. Certified calibration blends are commercially avail-
Used in Preparing Standard Mixtures for Calibration Purposes
able from numerous sources and may be used. (Warning—
Component Percent
Flammable Gases, Hazardous Pressure. See A1.2 and A1.3.)
Carbon dioxide 10
6.9 Methanol. ( Warning—Flammable. Vapor Harmful. See
Methane 45
Ethane 25
A1.4.)
Propylene 20
NOTE 2—The use of copper tubing is not recommended with samples
containing acetylene as this could lead to the formation of potentially
explosive copper acetylide.
stirred during drying to ensure uniform distribution. When the
7. Sampling acetone has evaporated, add a portion of the packing to a 7 m
(25 ft) length of 3.2 mm ( ⁄8 in.) outside diameter nylon tubing
7.1 Samples should be supplied to the laboratory in high
which has been plugged at one end with glass wool. Vibrate the
pressure sample cylinders, obtained using the procedures
column while filling to ensure more uniform packing. Fill the
described in Practice F307, or similar methods.
column with packing to only 4 m (15 ft) of the length of the
column. Fill the remainder of the column with squalane
8. Preparation of Apparatus
packing prepared in the same manner as the hexadecane
8.1 Silica Gel Column—Dry the silica gel in an oven at
packing. Plug the open end of the tubing with glass wool and
204 °C (400 °F) for 3 h, cool in a desiccator, and store in
shape the column to fit into the chromatograph with the
screw-cap bottles. Pour the activated silica gel into a 0.9 m
hexadecane portion of the column at the front end of the
(3 ft) length of 6.4 mm ( ⁄4 in.) outside diameter copper or
column. The column shall be purged under test conditions (no
aluminum tubing plugged with glass wool at one end. Tap or
sample added) until a constant baseline is obtained.
vibrate the tube while adding the silica gel to ensure uniform
NOTE 3—Columns made with liquid phases listed above were used
packing and plug the top end with glass wool. Shape the
satisfactorily in cooperative work. Other columns may be used (see 5.3).
column to fit into the chromatograph.
8.2 Silver Nitrate—β,β'-Oxydipropionitrile—Activated Car- 9. Calibration
bon Column—Weigh 10 g of β,β'-oxydipropionitrile into a
9.1 Preparation of Standard Mixtures:
brown 125 mL (4 oz) bottle. Add 5 g of silver nitrate (AgNO )
9.1.1 Preparation of Concentrate—Prepare a concentrate of
crystals. With occasional shaking, dissolve as much AgNO as
the impurities expected to be encountered. A certified calibra-
possible, and allow the bottle to stand overnight to ensure
tion blend containing the expected impurities can be obtained
saturation. Prepare this solution fresh, as required. Without
and used as the concentrate. An example of a satisfactory
disturbing the crystals at the bottom of the bottle, weigh 2.5 g
concentrate is given in Table 1. The concentrate can be
of supernatant AgNO solution into a 250 mL beaker and add
prepared using the gas blending manifold as shown in Fig. 2 or
50 mL of methanol. While stirring this mixture, slowly add
using a similar apparatus as follows: Evacuate the apparatus
22.5 g of activated carbon. Place the beaker on a steam bath to
and add the components in the order of increasing vapor
evaporate the methanol. When the impregnated activated
pressure; that is, propylene, carbon dioxide, ethane and meth-
carbon appears to be dry, remove the beaker from the steam
ane. Record the increase in pressure on the manometer as each
bath and finish drying in an oven at 100 °C to 110 °C for 2 h.
component is added. Close the reservoir and evacuate the
Plug one end of a 4 ft (1.2 m) length of 6.4 mm ( ⁄4 in.) outside
manometer after each addition.
diameter aluminum or stainless steel tubing with glass wool.
9.1.2 Dilution of Concentrate—Dilute the concentrate with
Hold the tubing vertically with the plugged end down and pour
high-purity ethylene in a ratio of approximately 1:4000. This
freshly dried column packing into it, vibrating the column
can be done by adding the calculated amount of the concentrate
during filling to ensure uniform packing. Plug the top end with
and high purity ethylene to an evacuated cyclinder using the
glass wool and shape the tubing so that it may be mounted
gas-blending apparatus (Fig. 2). Use a source of high-pressure,
conveniently in the chromatograph.
high-purity ethylene equipped with a needle valve and a
8.3 Hexamethylphosphoramide Column (HMPA)—Dry the pressure gage capable of accurately measuring the pressure of
35 mesh to 80 mesh inert support at 204 °C (400 °F). Weigh the blend as the ethylene is added to the cylinder containing the
75 g into a wide-mouth 500 mL (16 oz) bottle. Add 15 g of concentrate. Add the calculated amount of ethylene; warm one
HMPA to the inert support and shake and roll the mixture until end of the cylinder to ensure mixing of the blend. Allow the
the support appears to be uniformly wet with the HMPA. Pour temperature to reach equilibrium before recording the final
the packing into a 6 m (20 ft) length of 6.4 mm ( ⁄4 in.) outside pressure on the cylinder. Prepare at least three calibration
diameter copper of aluminum tubing plugged at one end with samples containing the compounds to be determined over the
glass wool. Vibrate the tubing while filling to ensure more range of concentration desired in the products to be analyzed.
uniform packing. Plug the top end of the column with glass
9.2 Calculation of Composition of Standard Mixtures—
wool and shape the column to fit into the chromatograph.
Calculate the exact ratio of the concentrate dilution with
8.4 Hexadecane-Squalane Column—Dissolve 30 g of hexa- ethylene by correcting the pressure of the ethylene added for
decane into approximately 100 mL of acetone. Add 70 g of the compressibility of ethylene (Table 2). Multiply the dilution
80 mesh to 100 mesh inert support. Mix thoroughly and pour ratio or factor by the perce
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