ASTM D6376-09

Standard Test Method for Determination of Trace Metals in Petroleum Coke by Wavelength Dispersive X-Ray Fluorescence Spectroscopy

SIGNIFICANCE AND USE
The presence and concentration of sulfur and various metallic elements in a petroleum coke are major factors determining the suitability of a coke for various purposes. This test method provides rapid means for measuring sulfur and commercially important metallic elements in coke samples.  
This test method provides a guide for determining conformance to material specifications for use by buyers and sellers in a commercial transfer of petroleum coke.
Sulfur contents can be used to evaluate the potential formation of sulfur oxides (SOx), a source of atmospheric pollution.
SCOPE
1.1 This test method covers the X-ray fluorescence spectrometric determination of total sulfur and trace metals in samples of raw or calcined petroleum coke. Elements determined using this test method are listed in Table 1.
1.2 Detection limits, sensitivity, and optimal element ranges will vary with matrices, spectrometer type, analyzing crystal, and other instrument conditions and parameters.
1.3 All analytes are determined as the element and reported as such. These include all elements listed in Table 1. This test method may be applicable to additional elements or concentration ranges if sufficient standards are available to produce proper calibration equations.
1.4 The values stated in SI units are to be regarded as standard. No other units of measurement are included in this 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.

General Information

• Status: Historical
• Publication Date: 30-Nov-2009
• ICS: 75.160.10 - Solid fuels
• Technical Committee: D02 - Petroleum Products, Liquid Fuels, and Lubricants
• Drafting Committee: D02.05 - Properties of Fuels, Petroleum Coke and Carbon Material

Relations

• Replaces: ASTM D6376-06 - Standard Test Method for Determination of Trace Metals in Petroleum Coke by Wavelength Dispersive X-Ray Fluorescence Spectroscopy
• Effective Date: 01-Dec-2009
• Replaced By: ASTM D6376-10 - Standard Test Method for Determination of Trace Metals in Petroleum Coke by Wavelength Dispersive X-Ray Fluorescence Spectroscopy
• Effective Date: 01-Jul-2010
• Referred By: ASTM D7343-20 - Standard Practice for Optimization, Sample Handling, Calibration, and Validation of X-ray Fluorescence Spectrometry Methods for Elemental Analysis of Petroleum Products and Lubricants
• Effective Date: 01-Dec-2009
• Referred By: ASTM D6969-23 - Standard Practice for Preparation of Calcined Petroleum Coke Samples for Analysis
• Effective Date: 01-Dec-2009

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:D6376–09
Standard Test Method for
Determination of Trace Metals in Petroleum Coke by
1
Wavelength Dispersive X-ray Fluorescence Spectroscopy
This standard is issued under the fixed designation D6376; the number immediately following the designation indicates the year of
original adoption or, in the case of revision, the year of last revision.Anumber in parentheses indicates the year of last reapproval.A
superscript epsilon (´) indicates an editorial change since the last revision or reapproval.
TABLE 1 Applicable Concentration Ranges
1. Scope*
Element Concentration Range, (ppm)
1.1 This test method covers the X-ray fluorescence spectro-
Na 50–500
metricdeterminationoftotalsulfurandtracemetalsinsamples
Al 50–500
of raw or calcined petroleum coke. Elements determined using
Si 20–500
this test method are listed in Table 1.
S, % 0.10–7.0
Ca 20–500
1.2 Detectionlimits,sensitivity,andoptimalelementranges
Ti 10–200
will vary with matrices, spectrometer type, analyzing crystal,
V 20–2000
and other instrument conditions and parameters.
Mn 10–200
Fe 20–1000
1.3 All analytes are determined as the element and reported
Ni 20–500
as such. These include all elements listed in Table 1. This test
method may be applicable to additional elements or concen-
tration ranges if sufficient standards are available to produce
Inductively Coupled Plasma Atomic Emission Spectrom-
proper calibration equations.
etry (ICP-AES)
1.4 The values stated in SI units are to be regarded as
E11 SpecificationforWovenWireTestSieveClothandTest
standard. No other units of measurement are included in this
Sieves
standard.
1.5 This standard does not purport to address all of the
3. Terminology
safety concerns, if any, associated with its use. It is the
3.1 Definitions:
responsibility of the user of this standard to establish appro-
3.1.1 calcined petroleum coke, n—petroleum coke that has
priate safety and health practices and determine the applica-
been thermally treated to drive off the volatile matter and to
bility of regulatory limitations prior to use.
develop crystalline structure.
3.1.2 green petroleum coke, n—same as raw petroleum
2. Referenced Documents
coke.
2
2.1 ASTM Standards:
3.1.3 petroleum coke, n—a solid, carbonaceous residue
D346 Practice for Collection and Preparation of Coke
produced by thermal decomposition of heavy petroleum frac-
Samples for Laboratory Analysis
tions or cracked stocks, or both
D1552 Test Method for Sulfur in Petroleum Products
3.1.4 raw petroleum coke, n—petroleum coke that has not
(High-Temperature Method)
been calcined.
D4057 Practice for Manual Sampling of Petroleum and
3.2 Definitions of Terms Specific to This Standard:
Petroleum Products
3.2.1 alpha, n—correction factor used to compensate for
D5056 TestMethodforTraceMetalsinPetroleumCokeby
interferences.
Atomic Absorption
3.2.2 analytical sample, n—a representative fraction taken
D5600 TestMethodforTraceMetalsinPetroleumCokeby
from a larger mass of petroleum coke and reduced by grinding
to pass a 75 µm (No. 200 mesh) sieve.
3.2.3 pellet, n—a blend of dried sample and binder milled
1
This test method is under the jurisdiction of ASTM Committee D02 on
together and then formed into a pellet by pressure.
PetroleumProductsandLubricantsandisthedirectresponsibilityofSubcommittee
3.2.4 reference samples, n—samples of known concentra-
D02.05 on Properties of Fuels, Petroleum Coke and Carbon Material.
tions to be used in the calibration of the X-ray fluorescence
Current edition approved Dec. 1, 2009. Published February 2010. Originally
approved in 1999. Last previous edition approved in 2006 as D6376–06. DOI: spectrometer.
10.1520/D6376-09.
2
For referenced ASTM standards, visit the ASTM website, www.astm.org, or
4. Summary of Test Method
contact ASTM Customer Service at [e-mail]. For Annual Book of ASTM
4.1 A representative sample of petroleum coke is dried to
Standards volume information, refer to the standard’s Document Summary page on
the ASTM website. constantmassat110 610°Candthencrushedtopassa75µm
*A Summary of Changes section appears at the end of this standard.
Copyright ©ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA19428-2959, United States.
1

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D6376–09
(No. 200 mesh) sieve. A weighed portion of this analytical 7.2 Hydraulic Press, capable of exerting a force of not less
sample is mixed with stearic acid, or other suitable binder, and than 276 MPa (40 000 psi).
thenmilledandcompressedintoasmall,smoothpelletsuitable 7.3 Mill or Grinder, capable of reducing 20 g of petroleum
for analysis. The pellet is irradiated by an X-ray beam. The coketoasamplepassing75µm(No.200mesh)inlessthan10
characteristic X rays of the elements analyzed are excited, min, without introducing contamination.
separated, and detec
...

This document is not anASTM standard and is intended only to provide the user of anASTM standard an indication of what changes have been made to the previous version. Because
it may not be technically possible to adequately depict all changes accurately,ASTM recommends that users consult prior editions as appropriate. In all cases only the current version
of the standard as published by ASTM is to be considered the official document.
Designation:D6376–06 Designation:D6376–09
Standard Test Method for
Determination of Trace Metals in Petroleum Coke by
1
Wavelength Dispersive X-ray Fluorescence Spectroscopy
This standard is issued under the fixed designation D6376; the number immediately following the designation indicates the year of
original adoption or, in the case of revision, the year of last revision.Anumber in parentheses indicates the year of last reapproval.A
superscript epsilon (´) indicates an editorial change since the last revision or reapproval.
1. Scope*
1.1 This test method covers the X-ray fluorescence spectrometric determination of total sulfur and trace metals in samples of
raw or calcined petroleum coke. Elements determined using this test method are listed in Table 1.
1.2 Detection limits, sensitivity, and optimal element ranges will vary with matrices, spectrometer type, analyzing crystal, and
other instrument conditions and parameters.
1.3 All analytes are determined as the element and reported as such. These include all elements listed in Table 1. This test
method may be applicable to additional elements or concentration ranges if sufficient standards are available to produce proper
calibration equations.
1.4The values stated in SI units are to be regarded as standard. The values given in parentheses are for information only.
1.4 The values stated in SI units are to be regarded as standard. No other units of measurement are included in this 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.
2. Referenced Documents
2
2.1 ASTM Standards:
D346 Practice for Collection and Preparation of Coke Samples for Laboratory Analysis
D1552 Test Method for Sulfur in Petroleum Products (High-Temperature Method)
D4057 Practice for Manual Sampling of Petroleum and Petroleum Products
D5056 Test Method for Trace Metals in Petroleum Coke by Atomic Absorption
D5600 Test Method for Trace Metals in Petroleum Coke by Inductively Coupled Plasma Atomic Emission Spectrometry
(ICP-AES)
E11 Specification for Woven Wire Test Sieve Cloth and Test Sieves
3. Terminology
3.1 Definitions:
3.1.1 calcined petroleum coke, n—raw petroleum —petroleum coke that has been thermally treated to drive off the volatile
matter and to develop crystalline structure.
3.1.2 green petroleum coke, n—same as raw petroleum coke.
3.1.3 petroleum coke, n—a solid, carbonaceous residue produced by thermal decomposition of heavy petroleum fractions or
cracked stocks, or both
3.1.4 raw petroleum coke, n—petroleum coke that has not been calcined.
3.2 Definitions of Terms Specific to This Standard:
3.2.1 alpha, n—correction factor used to compensate for interferences.
3.2.2 analytical sample, n—a representative fraction taken from a larger mass of petroleum coke and reduced by grinding to
pass a 75 µm (No. 200 mesh) sieve.
3.2.3 pellet, n—a blend of dried sample and binder milled together and then formed into a pellet by pressure.
3.2.4 reference samples, n—samples of known concentrations to be used in the calibration of the X-ray fluorescence
spectrometer.
1
This test method is under the jurisdiction ofASTM Committee D02 on Petroleum Products and Lubricants and is the direct responsibility of Subcommittee D02.05 on
Properties of Fuels, Petroleum Coke and Carbon Material.
Current edition approved JulyDec. 1, 2006.2009. Published July 2006.February 2010. Originally approved in 1999. Last previous edition approved in 20052006 as
D6376–05.D6376–06. DOI: 10.1520/D6376-069.
2
ForreferencedASTMstandards,visittheASTMwebsite,www.astm.org,[e-mail] Annual Book of ASTM Standards
volume information, refer to the standard’s Document Summary page on 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, PA19428-2959, United States.
1

---------------------- Page: 1 ----------------------
D6376–09
TABLE 1 Applicable Concentration Ranges
Element Concentration Range, (ppm)
Na 50–500
Al 50–500
Si 20–500
S, % 0.10–7.0
Ca 20–500
Ti 10–200
V 20–2000
Mn 10–200
Fe 20–1000
Ni 20–500
4. Summary of Test Method
4.1 Arepresentative sample of petroleum coke is dried to constant mass at 110 6 10°C and then crushed to pass a 75 µm (No.
200 mesh) sieve.Aweighed portion of this analytical sa
...