ASTM D5863-00a(2005)
(Test Method)Standard Test Methods for Determination of Nickel, Vanadium, Iron, and Sodium in Crude Oils and Residual Fuels by Flame Atomic Absorption Spectrometry
Standard Test Methods for Determination of Nickel, Vanadium, Iron, and Sodium in Crude Oils and Residual Fuels by Flame Atomic Absorption Spectrometry
SIGNIFICANCE AND USE
When fuels are combusted, metals present in the fuels can form low melting compounds that are corrosive to metal parts. Metals present at trace levels in petroleum can deactivate catalysts during processing. These test methods provide a means of quantitatively determining the concentrations of vanadium, nickel, iron, and sodium. Thus, these test methods can be used to aid in determining the quality and value of the crude oil and residual oil.
SCOPE
1.1 These test methods cover the determination of nickel, vanadium, iron, and sodium in crude oils and residual fuels by flame atomic absorption spectrometry (AAS). Two different test methods are presented.
1.2 Test Method A, Sections -Flame AAS is used to analyze a sample that is decomposed with acid for the determination of total Ni, V, and Fe.
1.3 Test Method B, Sections -Flame AAS is used to analyze a sample diluted with an organic solvent for the determination of Ni, V, and Na. This test method uses oil-soluble metals for calibration to determine dissolved metals and does not purport to quantitatively determine nor detect insoluble particulates. Hence, this test method may underestimate the metal content, especially sodium, present as inorganic sodium salts.
1.4 The concentration ranges covered by these test methods are determined by the sensitivity of the instruments, the amount of sample taken for analysis, and the dilution volume. A specific statement is given in Note 0.
1.5 For each element, each test method has its own unique precision. The user can select the appropriate test method based on the precision required for the specific analysis.
1.6 The values stated in SI units are to be regarded as the standard. The values given in parentheses are for information only.
1.7 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 warning statements are given in 7.1, 8.2, 8.5, 10 2, 10.4, and 15.1 .
General Information
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Standards Content (Sample)
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:D5863–00a (Reapproved 2005)
Standard Test Methods for
Determination of Nickel, Vanadium, Iron, and Sodium in
Crude Oils and Residual Fuels by Flame Atomic Absorption
Spectrometry
This standard is issued under the fixed designation D5863; 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 These test methods cover the determination of nickel, 2.1 ASTM Standards:
vanadium, iron, and sodium in crude oils and residual fuels by D1193 Specification for Reagent Water
flame atomic absorption spectrometry (AAS). Two different D4057 Practice for Manual Sampling of Petroleum and
test methods are presented. Petroleum Products
1.2 Test Method A, Sections 7–13—Flame AAS is used to D4177 Practice for Automatic Sampling of Petroleum and
analyze a sample that is decomposed with acid for the Petroleum Products
determination of total Ni, V, and Fe. D6299 Practice for Applying Statistical Quality Assurance
1.3 Test Method B, Sections 14–19—Flame AAS is used to and Control Charting Techniques to Evaluate Analytical
analyze a sample diluted with an organic solvent for the Measurement System Performance
determination of Ni, V, and Na. This test method uses oil-
3. Summary of Test Method
soluble metals for calibration to determine dissolved metals
3.1 Test Method A—One to twenty grams of sample are
and does not purport to quantitatively determine nor detect
insoluble particulates. Hence, this test method may underesti- weighed into a beaker and decomposed with concentrated
sulfuric acid by heating to dryness. The residual carbon is
mate the metal content, especially sodium, present as inorganic
sodium salts. burned off by heating at 525°C in a muffle furnace. The
inorganic residue is digested in dilute nitric acid, evaporated to
1.4 The concentration ranges covered by these test methods
are determined by the sensitivity of the instruments, the incipient dryness, dissolved in dilute nitric and made up to
amount of sample taken for analysis, and the dilution volume. volume with dilute nitric acid. Interference suppressant is
added to the dilute nitric acid solution. The solution is
A specific statement is given in Note 1.
1.5 For each element, each test method has its own unique nebulized into the flame of an atomic absorption spectrometer.
A nitrous oxide/acetylene flame is used for vanadium and an
precision.Theusercanselecttheappropriatetestmethodbased
on the precision required for the specific analysis. air/acetylene flame is used for nickel and iron. The instrument
is calibrated with matrix-matched standard solutions. The
1.6 The values stated in SI units are to be regarded as
standard. No other units of measurement are included in this measuredabsorptionintensitiesarerelatedtoconcentrationsby
the appropriate use of calibration data.
standard.
1.7 This standard does not purport to address all of the 3.2 Test Method B—Sample is diluted with an organic
solvent to give a test solution containing either 5 % (m/m) or
safety concerns, if any, associated with its use. It is the
responsibility of the user of this standard to establish appro- 20 % (m/m) sample. The recommended sample concentration
is dependent on the concentrations of the analytes in the
priate safety and health practices and determine the applica-
bility of regulatory limitations prior to use. Specific warning sample. For the determination of vanadium, interference sup-
pressant is added to the test solution. The test solution is
statements are given in 7.1, 8.2, 8.5, 10.2, 10.4, and 15.1.
nebulized into the flame of an atomic absorption spectrometer.
A nitrous oxide/acetylene flame is used for vanadium and an
These test methods are under the jurisdiction of ASTM Committee D02 on
Petroleum Products and Lubricants and are the direct responsibility of Subcommit-
tee D02.03 on Elemental Analysis. For referenced ASTM standards, visit the ASTM website, www.astm.org, or
Current edition approved May 1, 2005. Published June 2005. Originally contact ASTM Customer Service at service@astm.org. For Annual Book of ASTM
approved in 1995. Last previous edition approved in 2000 as D5863–00a. DOI: Standards volume information, refer to the standard’s Document Summary page on
10.1520/D5863-00AR05. the ASTM website.
Copyright © ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959, United States.
D5863–00a (2005)
air/acetylene flame is used for nickel and sodium. The mea-
sured absorption intensities are related to concentrations by the
appropriate use of calibration data.
4. Significance and Use
4.1 When fuels are combusted, metals present in the fuels
can form low melting compounds that are corrosive to metal
parts.Metalspresentattracelevelsinpetroleumcandeactivate
catalysts during processing. These test methods provide a
means of quantitatively determining the concentrations of
vanadium, nickel, iron, and sodium. Thus, these test methods
can be used to aid in determining the quality and value of the
crude oil and residual oil.
5. Purity of Reagents
5.1 Reagent grade chemicals shall be used for all tests.
Unless otherwise indicated, it is intended that all reagents
conform to the specifications of the Committee on Analytical
Reagents of the American Chemical Society where such
specifications are available. Other grades may be used, pro-
FIG. 1 Decomposition Apparatus
vided it is first ascertained that the reagent is of sufficiently
high purity to permit its use without lessening the accuracy of
the determination.
400-mL beaker for the test solution, an air bath (Fig. 2) that
5.2 When determining metals at concentrations less than 1
rests on a hot plate and a 250 W infrared lamp supported 2.5
mg/kg, use ultra-pure grade reagents.
cm above the air bath. A variable transformer controls the
5.3 Purity of Water—Unless otherwise indicated, reference
voltage applied to the lamp.
towatershallbeunderstoodtomeanreagentwaterconforming
7.3 Glassware—Borosilicate glass 400-mL beakers, volu-
to Type II of Specification D1193.
metric flasks of various capacities and pipettes of various
capacities. When determining concentrations below 1 mg/kg,
6. Sampling and Sample Handling
allglasswaremustbethoroughlycleaned(orsoakedovernight)
6.1 The objective of sampling is to obtain a sample for
with 5 % HNO and rinsed five times with water.
testing purposes that is representative of the entire quantity.
7.4 Electric Muffle Furnace, capable of maintaining 525 6
Only representative samples obtained as specified in Practices
25°C and sufficiently large to accommodate 400-mL beakers.
D4057 and D4177 shall be used. Do not fill the sample
The capability of an oxygen bleed is advantageous and
container more than two-thirds full
optional.
6.2 Prior to weighing, stir the sample and then shake the
7.5 Steam Bath.
sample in its container. If the sample does not readily flow at
7.6 Temperature Controlled Hot Plate, (optional).
room temperature, heat the sample to a sufficiently high and
7.7 Drying Oven,(optional),explosion-proof,ifusedtoheat
safe temperature to ensure adequate fluidity.
crude oils to obtain fluidity.
TEST METHOD A—FLAME ATOMIC ABSORPTION
8. Reagents
AFTER ACID DECOMPOSITION OF THE SAMPLE
8.1 Aqueous Standard Solutions—Individual aqueous stan-
7. Apparatus dards with 1000 mg/kg concentrations of vanadium, nickel,
and iron, purchased or prepared in acid matrix to ensure
7.1 Atomic Absorption Spectrometer, complete instrument
stability.
with hollow cathode lamps and burners with gas supplies to
8.2 Nitric Acid—Concentrated nitric acid, HNO .
support air-acetylene and nitrous oxide-acetylene flames. 3
(Warning—Poison, oxidizer. Causes severe burns. Harmful or
(Warning—Hazardous. Potentially toxic and explosive. Refer
fatal if swallowed or inhaled.)
to the manufacturer’s instrument manual for associated safety
8.3 Nitric Acid 50 % (V/V)—Carefully add, with stirring,
hazards.)
one volume of concentrated nitric acid to one volume of water.
7.2 Sample Decomposition Apparatus (optional)—This ap-
8.4 Dilute Nitric Acid, 5 % (V/V)—Carefully add, with
paratus is described in Fig. 1. It consists of a borosilicate glass
stirring, one volume of concentrated nitric acid to 19 volumes
of water.
8.5 Sulfuric Acid—Concentrated sulfuric acid, H SO .
Reagent Chemicals, American Chemical Society Specifications, American
2 4
Chemical Society, Washington, DC. For suggestions on the testing of reagents not
(Warning—Poison, oxidizer. Causes severe burns. Harmful or
listed by the American Chemical Society, see Analar Standards for Laboratory
fatal if swallowed or inhaled.)
Chemicals, BDH Ltd., Poole, Dorset, U.K., and the United States Pharmacopeia
8.6 Aluminum Nitrate, Al(NO ) 9HOH.
and National Formulary, U.S. Pharmacopeial Convention, Inc. (USPC), Rockville, 3 3
MD. 8.7 Potassium Nitrate, KNO .
D5863–00a (2005)
TABLE 1 AAS Conditions for the Determination of Vanadium,
Nickel, and Iron Following Acid Sample Decomposition
Wavelength, Concentration Interference
Element Flame
nm Range, µg/mL Suppressant
Vanadium 318.4 0.5–20 250 µg/mL Al, N O-
Al(NO ) in 5 % C H
3 3 2 2
(V/V)
HNO
Nickel 232.0 0.5–20 None Air-C H
2 2
Iron 248.3 3.0–10 None Air-C H
2 2
10. Preparation of Test Solutions
10.1 Into a beaker, weigh an amount of sample estimated to
contain between 0.0025 and 0.12 mg of each metal to be
determined. A typical mass is 10 g. Add 0.5 mL of H SO for
2 4
each gram of sample.
NOTE 1—If it is desired to extend the lower concentration limits of the
test method, it is recommended that the decomposition be done in 10-g
incrementsuptoamaximumof100g.Itisnotnecessarytodestroyallthe
organic matter each time before adding additional amounts of the sample
andacid.Whenitisdesiredtodeterminehigherconcentrations,reducethe
sample size accordingly.
10.2 At the same time prepare reagent blanks using the
same amount of sulfuric acid as used for sample decomposi-
Note—All parts 16 gage (1.5 mm, 0.060 in.) aluminum. All dimensions are in tion. Reagent blanks should be carried through the same
inches.
procedure as the samples. (Warning—Reagent blanks are
critical when determining concentrations below 1 mg/kg. To
Metric Equivalents
simplify the analysis, use the same volume of acid and the
in. mm in. mm
same dilutions as used for the samples. For example, if 20 g of
1 25.4 3 ⁄8 98.4
sampleisbeingdecomposed,use10mLofsulfuricacidforthe
1 ⁄2 38.1 5 127
2 50.8 6 ⁄2 165.1 reagent blank.)
3 ⁄16 77.8 . .
10.3 The use of the air bath apparatus (Fig. 2) is optional.
FIG. 2 Air Bath
Place the beaker in the air bath, which is located in the hood.
The hot plate is off at this time. Heat gently from the top with
the infrared lamp (Fig. 1) while stirring the test solution with a
9. Preparation of Standards
glass rod. As decomposition proceeds (indicated by a frothing
9.1 Multi-Element Standard—Using the aqueous standard and foaming), control the heat of the infrared lamp to maintain
steady evolution of fumes. Give constant attention to each
solutions, prepare a multi-element standard containing 100
mg/kg each of vanadium, nickel, and iron. Standards should be sample mixture until all risk of spattering and foaming is past.
Then, gradually increase the temperature of both the hot plate
prepared to ensure accuracy and stability and should be stored
in clean containers to safeguard against physical degradation. and lamp until the sample is reduced to a carbonaceous ash.
10.4 If the air bath apparatus is not used, heat the sample
9.2 Working Standards—Prepare at least two working stan-
dards to cover the concentration ranges specified in Table 1. and acid on a temperature controlled hot plate.As described in
10.3, monitor the decomposition reaction and adjust the
For vanadium, add the specified interference suppressant. Each
working standard must contain 5 % (V/V) nitric acid. Stan- temperature of the hot plate accordingly. (Warning—Hot
fuming concentrated sulfuric acid is very corrosive and a
dards should be prepared to ensure accuracy and stability and
should be stored in clean containers to safeguard against strong oxidizing acid. The analyst should work in a well-
ventilated hood and wear rubber gloves and a suitable face
physical degradation.
9.3 Standard Blank, the standard blank contains 5 % (V/V) shield to protect against spattering acid.)
10.5 Place the sample in the muffle furnace maintained at
nitric acid and any interference suppressant specified in Table
1. 525 6 25°C. Optionally, introduce a gentle stream of oxygen
into the furnace to expedite oxidation. Continue to heat until
9.4 Check Standard—Prepare a calibration check standard
in the same way as the working standards and at analyte the carbon is completely removed.
concentrations that are typical of the specimens being ana- 10.6 Dissolve the inorganic residue by washing down the
lyzed. wallofthebeakerwithabout10mLofthe1 + 1HNO .Digest
D5863–00a (2005)
TABLE 2 AAS Conditions for the Determination of Vanadium,
on a steam bath for 15 to 30 min. Transfer to a hot plate and
Nickel, and Sodium Following Solvent Dilution of the Sample
gently evaporate to incipient dryness.
Wavelength, Concentration Interference
10.7 Wash down the wall of the beaker with about 10 mLof
Element Flame
nm Range, mg/kg Suppressant
dilute nitric acid (5 % V/V). Digest on the steam bath until all
A
Vanadium 318.4 0.5–15 15 mg/kg Al N O-C H
2 2 2
salts are dissolved. Allow to cool. Transfer quantitatively to a
Nickel 232.0 0.5–20 None Air-C H
2 2
volumetric flask of suitable volume and make up to volume
Sodium 589.0 0.1–5 None Air-C H
2 2
with dilute nitric acid. This is the test solution.
A
Prepared from an organometallic standard, mineral oil, and dilution solvent.
10.8 Pipette aliquots of the test solution into two separate
volumetric flasks. Retain one flask for the determination of
nickel and iron. To the other flask add aluminum interference
TEST METHOD B—FLAME ATOMIC ABSORPTION
suppressant for vanadium determination (refer to Table 1) and
WITH AN ORGANIC SOLVENT TEST SOLUTION
dilute up to mark with dilute nitric acid (5 % V/V). Similarly,
prepare a reagent blank solution for vanadium analysis.
14. Apparatus
11. Preparation of Apparatus 14.1 Refer to Section 7.1.
14.2 Test Solution Containers—Glass or plastic vials or
11.1 Consult the manufacturer’s instructions for the opera-
bottles, with screw caps and a capacity of between 50 to 100
tion of the atomic absorption
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