ASTM D5443-93(1998)
(Test Method)Standard Test Method for Paraffin, Naphthene, and Aromatic Hydrocarbon Type Analysis in Petroleum Distillates Through 200°C by Multi-Dimensional Gas Chromatography
Standard Test Method for Paraffin, Naphthene, and Aromatic Hydrocarbon Type Analysis in Petroleum Distillates Through 200°C by Multi-Dimensional Gas Chromatography
SCOPE
1.1 This test method provides for the determination of paraffins, naphthenes, and aromatics by carbon number in low olefinic hydrocarbon streams having final boiling points of 200°C or less. Hydrocarbons with boiling points greater than 200°C and less than 270°C are reported as a single group. Olefins, if present, are hydrogenated and the resultant saturates are included in the paraffin and naphthene distribution. Aromatics boiling at C 9 and above are reported as a single aromatic group.
1.2 This test method is not intended to determine individual components except for benzene and toluene that are the only C 6 and C 7 aromatics, respectively, and cyclopentane, that is the only C 5 naphthene. The lower limit of detection for a single hydrocarbon component or group is 0.05 mass %.
1.3 This test method is applicable to hydrocarbon mixtures including virgin, catalytically converted, thermally converted, alkylated and blended naphthas.
1.4 The values stated in SI (metric) units are to be regarded as the standard.
1.5 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. Specific precautionary statements are given in Notes 1 and 2 and Table 2.
General Information
Relations
Standards Content (Sample)
NOTICE: This standard has either been superceded and replaced by a new version or discontinued.
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Designation: D 5443 – 93 (Reapproved 1998)
Standard Test Method for
Paraffin, Naphthene, and Aromatic Hydrocarbon Type
Analysis in Petroleum Distillates Through 200°C by Multi-
Dimensional Gas Chromatography
This standard is issued under the fixed designation D 5443; 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.
TABLE 1 Hydrocarbon Test Mixture
1. Scope
Hydrocarbons Warning
1.1 This test method provides for the determination of
Cyclopentane (Warning—Extremely Flammable. Harmful if inhaled.)
paraffins, naphthenes, and aromatics by carbon number in low
Pentane (Warning—Extremely Flammable. Harmful if inhaled.)
olefinic hydrocarbon streams having final boiling points of
Cyclohexane (Warning—Extremely Flammable. Harmful if inhaled.)
200°C or less. Hydrocarbons with boiling points greater than
2,3-Dimethylbutane (Warning—Extremely Flammable. Harmful if inhaled.)
Hexane (Warning—Extremely Flammable. Harmful if inhaled.)
200°C and less than 270°C are reported as a single group.
1-Hexene (Warning—Extremely Flammable. Harmful if inhaled.)
Olefins, if present, are hydrogenated and the resultant saturates
Methylcyclohexane (Warning—Extremely Flammable. Harmful if inhaled.)
are included in the paraffin and naphthene distribution. Aro-
4-Methyl-1-hexene (Warning—Extremely Flammable. Harmful if inhaled.)
Heptane (Warning—Flammable. Harmful if inhaled.)
matics boiling at C and above are reported as a single aromatic
1,cis-2-Dimethylcyclohexane (Warning—Extremely Flammable. Harmful if
group.
inhaled.)
1.2 This test method is not intended to determine individual
2,2,4-Trimethylpentane (iso-octane) (Warning—Flammable. Harmful if inhaled.)
Octane (Warning—Flammable. Harmful if inhaled.)
components except for benzene and toluene that are the only
1,cis-2,cis-4-Trimethylcyclohexane (Warning—Flammable. Harmful if inhaled.)
C and C aromatics, respectively, and cyclopentane, that is the
6 7
Nonane (Warning—Flammable. Harmful if inhaled.)
only C naphthene. The lower limit of detection for a single Decane (Warning—Flammable. Harmful if inhaled.)
Undecane (Warning—Flammable. Harmful if inhaled.)
hydrocarbon component or group is 0.05 mass %.
Dodecane (Warning—Flammable. Harmful if inhaled.)
1.3 This test method is applicable to hydrocarbon mixtures
Benzene (Warning—Extremely Flammable. Harmful if inhaled.)
including virgin, catalytically converted, thermally converted,
Methylbenzene (Toluene) (Warning—Flammable. Harmful if inhaled.)
trans-Decahydronaphthalene (Decalin) (Warning—Flammable. Harmful if
alkylated and blended naphthas.
inhaled.)
1.4 The values stated in SI (metric) units are to be regarded
Tetradecane (Warning—Harmful if inhaled.)
as the standard. Ethylbenzene (Warning—Extremely Flammable. Harmful if inhaled.)
1,2-Dimethylbenzene (o-Xylene) (Warning—Extremely Flammable. Harmful if
1.5 This standard does not purport to address all of the
inhaled.)
safety concerns, if any, associated with its use. It is the
Propylbenzene (Warning—Extremely Flammable. Harmful if inhaled.)
responsibility of the user of this standard to establish appro- 1,2,4-Trimethylbenzene (Warning—Extremely Flammable. Harmful if inhaled.)
1,2,3-Trimethylbenzene (Warning—Extremely Flammable. Harmful if inhaled.)
priate safety and health practices and determine the applica-
1,2,4,5-Tetramethylbenzene (Warning—Flammable. Harmful if inhaled.)
bility of regulatory limitations prior to use. Specific precau-
Pentamethylbenzene (Warning—Harmful if inhaled.)
tionary statements are given in Note 1 and Note 2 and Table 1.
2. Referenced Documents
3. Summary of Test Method
2.1 ASTM Standards:
3.1 A representative sample is introduced into a gas chro-
D 4057 Practice for Manual Sampling of Petroleum and
matographic system containing a series of columns and switch-
Petroleum Products
ing valves. As the sample passes through a polar column, the
D 4307 Practice for Preparation of Liquid Blends for Use
polar aromatic compounds, bi-naphthenes, and high boiling
As Analytical Standards
(>200°C) paraffins and naphthenes are retained. The fraction
not retained elutes to a platinum column, that hydrogenates
olefins, if present, in this fraction, and then to a molecular sieve
This test method is under the jurisdiction of ASTM Committee D-2 on
column which performs a carbon number separation based on
Petroleum Products and Lubricants and is the direct responsibility of Subcommittee
molecular structure, that is, naphthenes and paraffins. The
D02.04.0L on Gas Chromatography.
fraction remaining on the polar column is further divided into
Current edition approved Aug. 15, 1993. Published October 1993.
Annual Book of ASTM Standards, Vol 05.02. three separate fractions that are then separated on a non-polar
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NOTICE: This standard has either been superceded and replaced by a new version or discontinued.
Contact ASTM International (www.astm.org) for the latest information.
D 5443 – 93 (1998)
column by boiling point. Eluting compounds are detected by a 6.2 Sample Introduction System—Manual or automatic liq-
flame ionization detector. uid sample system operated in a splitless mode. Although this
3.2 The mass concentration of each group is determined by test method is intended primarily for use with syringe sample
the multiplication of detected peak areas by flame ionization injection, automatic sampling valves have also been found
detector response factors and normalization to 100 %. satisfactory. Devices capable of a reproducible injection vol-
ume of 0.1 to 0.5 μL are suitable. The sample introduction
4. Significance and Use
system must be capable of heating the sample to a temperature
4.1 A knowledge of the composition of hydrocarbon refin-
that ensures total sample vaporization. A temperature range of
ery streams is useful for process control and quality assurance.
120 to 180°C has been found suitable.
4.2 Aromatics in gasoline are soon to be limited by federal
6.3 Electronic Data Acquisition System—The data acquisi-
mandate. This test method can be used to provide such
tion and integration device used for detection and integration
information.
must meet or exceed the following specifications:
6.3.1 Capacity for at least 75 peaks for each analysis,
5. Interferences
6.3.2 Normalized area percent calculation,
5.1 Chemicals of a non-hydrocarbon composition may elute
6.3.3 Noise and spike rejection capability,
within the hydrocarbon groups, depending on their polarity,
6.3.4 Sampling rates for fast (<2 s) peaks,
boiling point, and molecular size. Included in this group are
6.3.5 Peak width detection for narrow and broad peaks, and
ethers (for example, methyl-tertiary butyl ether) and alcohols
6.3.6 Perpendicular drop and tangent skimming as required.
(for example, ethanol).
6.4 Independent Temperature Control—This test method
requires the temperature control of five columns, column
6. Apparatus
switching valves and sample lines. The columns consist of
6.1 Chromatograph—A gas chromatograph capable of iso- 3
polar, non-polar, Tenax , platinum, and molecular sieve col-
thermal operation at 130 6 0.1°C. The gas chromatograph
umns. The specifications for these columns are listed in Table
must contain the following:
2. The polar column, non-polar column, column switching
6.1.1 A heated flash vaporization sample inlet system ca-
valves, and sample lines require isothermal operation at a
pable of operation in a splitless mode.
temperature equivalent to the temperature of the gas chromato-
6.1.2 Associated gas controls with adequate precision to
graph oven. These components may be located in the gas
provide reproducible flows and pressures. 3
chromatograph oven. The Tenax column, platinum column,
6.1.3 A flame ionization detection system optimized for use
and molecular sieve column require operation at temperatures
with packed columns and capable of the following:
other than the gas chromatograph oven temperature. These
Isothermal temperature operation 150 to 170°C
columns may be temperature controlled by any means that will
Sensitivity >0.015 coulombs/g
−12
meet the following specifications:
Minimum detectability 5 3 10 g carbon/second
Linearity >10 6.4.1 Ability to control the temperature of the Tenax
column within a range from 60 to 280°C, with a tolerance of
Some instruments will produce a non-linear response for
65°C at any point. The time required to heat this column
benzene, above approximately 5.5 mass %, and for toluene
between any two points must be no more than 1 min. The time
above approximately 15 mass %. The linearity of these
required to cool this column between any two points must be
components above these concentrations must be verified with
no more than 5 min,
appropriate blends. Where non-linearity has been shown to
6.4.2 Ability to control the temperature of the molecular
exist, samples, that contain no higher than C , can be analyzed
sieve column within a range from 100 and 490°C, with a
if the sample is diluted with n-C and the instrument is
equipped with a prefractionating column. The sample may also
be diluted with a component that is not present in the sample
and this component will then not be included in the normalized
Tenax is a registered trademark of AKZO, Velperiveg 76, P.O. Box 9300, 6800
report. SB Arnhem, The Netherlands.
TABLE 2 Typical Column Specifications
Column Type
Specification
3 A A
Polar Non-Polar Tenax Molsieve Platinum
Column length, m 3 4 0.16 to 0.18 1.8 0.002 to 0.06
Column inside diameter, mm 2.0 to 2.1 1.8 to 2.0 2.5 1.6 to 2.0 1.6
B B
Liquid phase OV-275 OV-101 . . .
Percent liquid phase 30 4–5 . . .
C C
Support material Chromasorb Chromasorb . . .
PAW WAW . . .
3 D,E
Packing material . . Tenax Molecular sieve 13X .
Mesh size 60/80 80/100 80/100 . .
A
Available from AC Analytical Controls, 3448 Progress Dr., Bensalem, PA 19020.
B
OV- 101 and OV-275 are registered trademarks of Ohio Valley Specialty Chemical Co., 115 Industry Rd., Marietta, OH 45750.
C
Chromasorb is a registered trademark of Manville Corp., Box 519, Lompoc, CA 93438.
D
Sodium form of molecular sieve 13X.
E
May also contain a mix of molecular sieves 13X and 5A to separate normal and iso-paraffins.
NOTICE: This standard has either been superceded and replaced by a new version or discontinued.
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D 5443 – 93 (1998)
tolerance of 610°C at any point. The time required to heat this 7.5.3 Valves must be sized such that they offer little restric-
column between any two points must be no more than 10 min. tion to carrier gas flow under the analysis conditions defined in
The time required to cool this column from 450 to 100°C must this test method.
be no more than 15 min, and
7.5.4 Care must be taken to prevent the introduction of any
6.4.3 Ability to control the platinum column within a
form of foreign material or contaminant into the valve that may
temperature range of 170 and 350°C. During routine analysis,
adversely affect its performance.
this column is operated within a temperature range of 170 to
7.6 Hydrocarbon Test Mixture—A quantitative synthetic
220°C.
mixture of pure hydrocarbons, an example of which is identi-
fied in Table 1 is used to tune the instrument analysis
7. Materials
conditions and establish that the instrument is performing
7.1 Carrier Gases:
within specifications. Individual hydrocarbon components, in
7.1.1 Hydrogen, 99.999 % pure, <0.1 ppm H O.
2 addition to those listed in Table 1, may be used to aid in the
(Warning—See Note 1.)
analysis. The concentration level of each component in the
hydrocarbon test mixture is not critical as long as the concen-
NOTE 1—Warning: Extremely flammable gas under high pressure.
tration is accurately known. Percentage ranges from 1.0 to 6.0
7.1.2 Helium, 99.999 % pure, <0.1 ppm H O. (Warning—
mass % have been found suitable. Impurities in the individual
See Note 2.)
components may have an adverse effect on the quantitative
NOTE 2—Warning: Compressed gas under high pressure. aspect of the analysis. If an impurity is of the same carbon
number and basic molecular structure as the main component
7.2 Detector Gases:
itself, it will be correctly grouped and quantitated within the
7.2.1 Hydrogen, 99.99 % minimum purity. (Warning—See
group. As an example, isobutylcyclopentane and isopropylcy-
Note 1.)
clohexane will both be determined as C naphthenes. Each of
7.2.2 Air, less than 10 ppm each of total hydrocarbons and
the individual hydrocarbon components used for this test
water. (Warning—See Note 2.)
mixture must have a minimum purity level of 99 mol %. Refer
7.3 Valve Actuation Gas—This test method permits the use
to Practice D 4307 for instructions on the preparation of liquid
of any type of valve switching or valve actuation. When
blends for use as analytical standards.
pneumatic valves are used, air of any grade that will result in
7.7 Gas Flows and Pressures:
no water condensation or will not introduce oil or other
7.7.1 Carrier Gases:
contaminates in the switching valves may be used. Air from a
piston operated compressor equipped with a water and oil 7.7.1.1 The helium carrier gas through the injection port,
polar column, platinum column and molecular sieve column is
separator has been found suitable. Column switching valves
that do not require air to operate do not have this air flow controlled. Flow rates of 16 to 23 mL/min have been
found suitable. A helium supply pressure of 620 kDa (90 psi)
requirement.
7.4 Columns—Five columns, as described in Table 2. These has been found suitable to meet the helium flow requirement.
The helium carrier gas flow will be referred to as the A flow
column specifications are to be considered as guidelines and
have been found to be acceptable. Other materials or combi- within this test method.
nations of materials may also provide acceptable performance. 7.7.1.2 The helium carrier gas used as the make up gas
The suitability of each column is determined by test criteria as when the polar column is in stop flow is set to the same flow
defined in Section 8. rate as the helium carrier gas through the injection port.
7.7.1.3 The hydrogen carrier gas flow through the Tenax
NOTE 3—It is not the intention of this test method to include detailed
column and non-polar column is flow controlled. Flow rates of
column preparation steps. Columns may be prepared in any way t
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