ASTM D5291-10(2015)

NOTICE: This standard has either been superseded and replaced by a new version or withdrawn.
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Designation: D5291 − 10(Reapproved 2015)
Standard Test Methods for
Instrumental Determination of Carbon, Hydrogen, and
Nitrogen in Petroleum Products and Lubricants
This standard is issued under the fixed designation D5291; 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 2. Referenced Documents
1.1 Thesetestmethodscovertheinstrumentaldetermination 2.1 ASTM Standards:
of carbon, hydrogen, and nitrogen in laboratory samples of D4057 Practice for Manual Sampling of Petroleum and
petroleum products and lubricants. Values obtained represent Petroleum Products
the total carbon, the total hydrogen, and the total nitrogen. D4177 Practice for Automatic Sampling of Petroleum and
Petroleum Products
1.2 These test methods are applicable to samples such as
D6299 Practice for Applying Statistical Quality Assurance
crude oils, fuel oils, additives, and residues for carbon and
and Control Charting Techniques to Evaluate Analytical
hydrogen and nitrogen analysis. These test methods were
Measurement System Performance
tested in the concentration range of at least 75 mass % to 87
mass % for carbon, at least 9 mass % to 16 mass % for
3. Summary of Test Methods
hydrogen, and <0.1 mass % to 2 mass % for nitrogen.
3.1 In these test methods, carbon, hydrogen, and nitrogen
1.3 The nitrogen test method is not applicable to light
aredeterminedconcurrentlyinasingleinstrumentalprocedure.
materials or those containing <0.75 mass % nitrogen, or both,
With some systems, the procedure consists of simply weighing
such as gasoline, jet fuel, naphtha, diesel fuel, or chemical
a portion of the sample, placing the portion in the instrument,
solvents.
and initiating the (subsequently automatic) analytical process.
1.3.1 However, using Test Method D levels of 0.1 mass %
In other systems, the analytical process, to some degree, is
nitrogen in lubricants could be determined.
manually controlled.
1.4 These test methods are not recommended for the analy-
3.2 The actual process can vary substantially from instru-
sis of volatile materials such as gasoline, gasoline-oxygenate
ment to instrument, since a variety of means can be utilized to
blends, or gasoline type aviation turbine fuels.
effect the primary requirements of the test methods. All
satisfactory processes provide for the following:
1.5 The results of these tests can be expressed as mass %
3.2.1 The conversion of the subject materials (in their
carbon, hydrogen or nitrogen.
entirety) to carbon dioxide, water vapor, and elemental
1.6 The values stated in SI units are to be regarded as
nitrogen, respectively, and
standard. No other units of measurement are included in this
3.2.2 The subsequent, quantitative determination of these
standard.
gases in an appropriate gas stream.
1.7 This standard does not purport to address all of the
3.3 The conversion of the subject materials to their corre-
safety concerns, if any, associated with its use. It is the
sponding gases takes place largely during combustion of the
responsibility of the user of this standard to establish appro-
sample at an elevated temperature in an atmosphere of purified
priate safety and health practices and determine the applica-
oxygen. Here, a variety of gaseous materials are produced,
bility of regulatory limitations prior to use.
including the following:
3.3.1 Carbon dioxide from the oxidation of organic and
elemental carbon,
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. For referenced ASTM standards, visit the ASTM website, www.astm.org, or
Current edition approved April 1, 2015. Published June 2015. Originally contact ASTM Customer Service at service@astm.org. For Annual Book of ASTM
approved in 1992. Last previous edition approved in 2010 as D5291 – 10. DOI: Standards volume information, refer to the standard’s Document Summary page on
10.1520/D5291-10R15. 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
D5291 − 10 (2015)
3.3.2 Hydrogen halides from organic halides (and organic combustion takes place primed by the oxidation of the con-
hydrogen, as required), tainer. Quantitative combustion is then achieved by passing the
3.3.3 Water vapor from the oxidation of (the remaining) gasesoverchromiumtrioxideandcupricoxide.Themixtureof
organic hydrogen and the liberation of moisture, the combustion gases is transferred over copper at about
3.3.4 Nitrogen and nitrogen oxides from the oxidation of 640 °C (840 °C in a steel reactor) to eliminate the excess of
organic nitrogen, and oxygen; then without stopping, it is introduced into the
3.3.5 Sulfur oxides from the oxidation of organic sulfur. In chromatographic column heated to about 120 °C (50 °C for
somesystems,sulfurousandsulfuricacidscanalsobeobtained Flash EA 1112 units). The individual components are then
from a combination of the sulfur oxides and the water vapor. separated by elution in the order nitrogen, carbon dioxide, and
water by a dedicated Poropak column (active carbon column
3.4 There are several accepted ways of isolating the desired
for Flash EA 1112 units for nitrogen determination) and
gaseous products and quantitatively determining them. These
measured by a thermal conductivity detector. With dedicated
are as follows:
3,4 software the percentage of elements present in the sample are
3.4.1 Test Method A —From the combustion product gas
calculated. The instrument is calibrated with standard pure
stream, oxides of sulfur are removed with calcium oxide in the
organic compounds. K-factors or linear regression can be used
secondary combustion zone.Aportion of the remaining mixed
for instrument calibration. The typical operator analysis time
gasesiscarriedbyheliumgasoverahotcoppertraintoremove
for a single sample is about 4 min, and the total elapsed time
oxygen, and reduce NO to N , over NaOH to remove CO ,
x 2 2
is 8 min.
and over magnesium perchlorate to remove H O. The remain-
ingelementalnitrogenismeasuredbythethermalconductivity 3.5 In all cases, the concentrations of carbon, hydrogen and
cell. Simultaneously, but separately from the nitrogen nitrogen are calculated as functions of the following:
measurement, the carbon and hydrogen selective infrared cells 3.5.1 The measured instrumental responses,
measure the CO and H O levels. 3.5.2 The values for response per unit mass for the elements
2 2
4,5
3.4.2 Test Method B —From the combustion product gas (established via instrument calibration), and
stream (which is cleaned from sulfur oxides, excess oxygen, 3.5.3 The mass of the sample.
etc. as in 3.4.1), the remaining CO , water vapor, and N are
2 2
3.6 A capability for performing these computations auto-
flushed into a mixing chamber and are thoroughly homog-
matically can be included in the instrumentation utilized for
enized at a precise volume, temperature, and pressure. After
these test methods.
homogenization, the chamber is depressurized to allow the
gases to pass through a heated column, where the gases 4. Significance and Use
separate as a function of selective retention times. The sepa-
4.1 This is the firstASTM standard covering the simultane-
ration occurs in a stepwise steady-state manner for nitrogen,
ous determination of carbon, hydrogen, and nitrogen in petro-
carbon dioxide, and water.
leum products and lubricants.
4,6
3.4.3 Test Method C —The combustion product gas
4.2 Carbon, hydrogen, and particularly nitrogen analyses
stream, after full oxidation of component gases, is passed over
are useful in determining the complex nature of sample types
heated copper to remove excess oxygen and reduce NO to N
x 2
covered by this test method. The CHN results can be used to
gas. The gases are then passed through a heated chromato-
estimatetheprocessingandrefiningpotentialsandyieldsinthe
graphic column to separate and elute N ,CO , and H O in that
2 2 2
petrochemical industry.
order. The individual eluted gases are measured by a thermal
conductivity detector.
4.3 The concentration of nitrogen is a measure of the
4,7
3.4.4 Test Method D —The organic samples are packed
presence of nitrogen containing additives. Knowledge of its
into lightweight containers of oxidizable metal and dropped at
concentration can be used to predict performance. Some
preset times into a vertical quartz, inconel, or stainless steel
petroleum products also contain naturally occurring nitrogen.
reactor,heatedatabout1050 °C,throughwhichaconstantflow
Knowledge of hydrogen content in samples is helpful in
of helium is maintained. When the samples are introduced, the
addressing their performance characteristics. Hydrogen to
helium stream is temporarily enriched with pure oxygen. Flash
carbon ratio is useful to assess the performance of upgrading
processes.
5. Apparatus
The sole source of supply of the Leco CHN-600 instrument known to the
committee at this time is Leco Corporation, 3000 Lakeview Ave., St. Joseph, MI
5.1 Sinceavarietyofinstrumentalcomponentsandconfigu-
49085.
rations can be satisfactorily utilized for these test methods, no
If you are aware of alternative suppliers, please provide this information to
specifications are given here with respect to overall system
ASTM International Headquarters. Your comments will receive careful consider-
design.
ation at a meeting of the responsible technical committee , which you may attend.
The sole source of supply of the Perkin Elmer 240C, 2400 series and CEC
5.2 Functionally,however,thefollowingarespecifiedforall
240XA and 440 instruments known to the committee at this time is Perkin Elmer
instruments:
Corporation, Main Ave., Norwalk, CT 06856.
The sole source of supply of the Carlo Erba 1106, 1108, and 1500 instruments
5.2.1 The conditions for combustion of the sample must be
knowntothecommitteeatthistimeisCarloErbaStrumentazione,StradaRivoltana,
such that (for the full range of applicable samples) the subject
20090 Rodano, Milan, Italy.
components are completely converted to carbon dioxide, water
The sole source of supply of the Flash EAinstruments known to the committee
at this time is Thermo Fisher Scientific, Strada Rivoltana, 20090 Milano, Italy. vapor(exceptforhydrogenassociatedwithvolatilehalidesand
D5291 − 10 (2015)
A,B
TABLE 1 Calibration Standards for CHN Instrumental Analysis
sulfur oxides), and nitrogen or nitrogen oxides. Generally,
Molecular Carbon, Hydrogen Nitrogen
instrumental conditions that affect complete combustion in-
Compound
Formula Mass% Mass % Mass %
clude availability of the oxidant, temperature, and time.
Acetanilide C H NO 71.09 6.71 10.36
8 9
5.2.2 Representative aliquots of the combustion gases must
Atropine C H NO 70.56 8.01 4.84
17 23 3
Benzoic acid C H O 68.84 4.95 . . .
then be treated:
7 6 2
Cyclohexanone- C H N O 51.79 5.07 20.14
12 14 4 4
5.2.2.1 To liberate (as water vapor) hydrogen present as
2,4-dinitrophenylhydrazone
hydrogen halides and sulfur oxyacids, and Cystine C H N O S 29.99 5.03 11.66
6 12 2 4 2
Diphenyl C H 93.46 6.54 . .
12 10
5.2.2.2 To reduce (to the element) nitrogen present as
EDTA C H N O 41.10 5.52 9.59
10 16 2 8
nitrogen oxides.
Imidazol C H N 52.92 5.92 41.15
3 4 2
Nicotinic acid C H NO 58.53 4.09 11.38
6 5 2
5.2.3 The water vapor and nitrogen so obtained must be
Stearic acid C H O 75.99 12.76 . .
18 36 2
included with the materials originally present in these aliquots.
Succinamide C H N O 41.37 6.94 24.13
4 8 2 2
Sucrose C H O 42.10 6.48 . .
5.2.4 Additional treatment of the aliquots (prior to detec- 12 22 11
Sulphanilamide C H N O S 41.84 4.68 16.27
6 8 2 2
tion) depends on the detection scheme utilized for the instru-
Triethanol amine C H NO 48.30 10.13 9.39
6 15 3
ment (see Note 1).
A
The Merck Index, 10th Edition, Merck and Company, Inc., Rahway, New Jersey,
1983.
NOTE 1—These additional treatments can be provided by the instru-
B
Many of these compounds can be obtained from the National Institute of
mental components utilized to satisfy 5.2.2.
Standards and Technology as well as other commercial chemical manufacturers,
such as Aldrich, Alfa, Kodak and others. See 6.1 for the purity of these reagents.
5.2.5 The detection system (in its full scope) must deter-
minetheanalyticalgasesindividuallyandwithoutinterference.
Additionally, for each analyte, either:
where such specifications are available. Other grades may be
5.2.5.1 The detectors must provide linear responses with
used, provided it is first ascertained that the reagent is of
respect to concentration over the full range of possible con-
sufficiently high purity to permit its use without lessening the
centrations from the applicable samples, or
accuracy of the determination.
5.2.5.2 The system must include provisions for appropri-
6.2 Calibration Standards—Table 1 lists the pure organic
ately evaluating nonlinear responses so that they can be
compounds most commonly used to calibrate the instruments
accurately correlated with these concentrations.
operated according to 3.4.1 – 3.4.3; other suitable pure
5.2.6 Suchprovisionscanbeintegraltotheinstrumentation,
compounds can also be used.
or they can be provided by (auxiliary) computation schemes.
6.3 Carrier and Combustion Gases:
5.2.7 Lastly, except for those systems where the concentra-
6.3.1 Oxygen, high purity (99.998 %),
tion data are output directly, the instrument must include an
6.3.2 Helium, high purity (99.995 %),
appropriate readout device for the detector responses.
6.3.3 Compressed Air, Nitrogen, or Argon, for operating
5.3 Additionally consumables needed for the analyses in-
pneumatic valves, if needed, and
clude:
6.3.4 Carbon Dioxide.
5.3.1 Tin Capsules, large and small,
6.4 Additional Reagents (as Specified by the Instrument
5.3.2 Ceramic Crucibles,
Manufacturer)—This specification covers the reagents utilized
5.3.3 Copper Capsules,
to provide for the functional requirements cited in 5.2.2 and
5.2.3. These reagents can vary substantially for different
5.3.4 Tin Plugs,
instruments. Consequently, these reagents shall be those rec-
5.3.5 Tin Boats,
ommended by the manufacturer. Specifically, these reagents
5.3.6 Copper Plugs,
will be for:
5.3.7 Aluminum Capsules,
3,4
6.4.1 Test Method A :
5.3.8 Combustion Tubes,
6.4.1.1 Sodium Hydroxide Coated Silica,
5.3.9 Adsorption Tubes,
6.4.1.2 Quartz Wool,
5.3.10 Nickel Capsules, and
...