ASTM D8088-16(2022)
(Practice)Standard Practice for Determination of the Six Major Rare Earth Elements in Fluid Catalytic Cracking Catalysts, Zeolites, Additives, and Related Materials by Inductively Coupled Plasma Optical Emission Spectroscopy
Standard Practice for Determination of the Six Major Rare Earth Elements in Fluid Catalytic Cracking Catalysts, Zeolites, Additives, and Related Materials by Inductively Coupled Plasma Optical Emission Spectroscopy
SIGNIFICANCE AND USE
5.1 The chemical composition of catalysts and catalyst materials is an important indicator of catalyst performance and is a valuable tool for assessing parameters in a FCCU process. This practice will be useful to catalyst manufacturers and petroleum refiners for quality verification and performance evaluation, and to environmental authorities at the state and federal levels for evaluation and verification of various compliance programs (1, 2, 3).
SCOPE
1.1 This practice describes the analysis of fluid catalytic cracking catalysts, rare earth exchanged zeolitic materials, additive and related materials when analyzed by ICP-OES for the six most common rare earth elements.
1.2 The values stated in SI units are to be regarded as standard. No other units of measurement are included in this Practice.
1.3 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, health, and environmental practices and determine the applicability of regulatory limitations prior to use. See Appendix X3.
1.4 This international standard was developed in accordance with internationally recognized principles on standardization established in the Decision on Principles for the Development of International Standards, Guides and Recommendations issued by the World Trade Organization Technical Barriers to Trade (TBT) Committee.
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Standards Content (Sample)
This international standard was developed in accordance with internationally recognized principles on standardization established in the Decision on Principles for the
Development of International Standards, Guides and Recommendations issued by the World Trade Organization Technical Barriers to Trade (TBT) Committee.
Designation: D8088 − 16 (Reapproved 2022)
Standard Practice for
Determination of the Six Major Rare Earth Elements in Fluid
Catalytic Cracking Catalysts, Zeolites, Additives, and
Related Materials by Inductively Coupled Plasma Optical
Emission Spectroscopy
This standard is issued under the fixed designation D8088; 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 Measurement System Performance
D6349 Test Method for Determination of Major and Minor
1.1 This practice describes the analysis of fluid catalytic
Elements in Coal, Coke, and Solid Residues from Com-
cracking catalysts, rare earth exchanged zeolitic materials,
bustion of Coal and Coke by Inductively Coupled
additive and related materials when analyzed by ICP-OES for
Plasma—Atomic Emission Spectrometry
the six most common rare earth elements.
D7085 Guide for Determination of Chemical Elements in
1.2 The values stated in SI units are to be regarded as
Fluid Catalytic Cracking Catalysts by X-ray Fluorescence
standard. No other units of measurement are included in this
Spectrometry (XRF)
Practice.
D7260 Practice for Optimization, Calibration, and Valida-
1.3 This standard does not purport to address all of the tion of Inductively Coupled Plasma-Atomic Emission
safety concerns, if any, associated with its use. It is the
Spectrometry (ICP-AES) for ElementalAnalysis of Petro-
responsibility of the user of this standard to establish appro- leum Products and Lubricants
priate safety, health, and environmental practices and deter-
D7442 Practice for Sample Preparation of Fluid Catalytic
mine the applicability of regulatory limitations prior to use. CrackingCatalystsandZeolitesforElementalAnalysisby
See Appendix X3.
Inductively Coupled Plasma Optical Emission Spectros-
1.4 This international standard was developed in accor- copy
dance with internationally recognized principles on standard-
E1479 Practice for Describing and Specifying Inductively
ization established in the Decision on Principles for the Coupled Plasma Atomic Emission Spectrometers
Development of International Standards, Guides and Recom-
2.2 EPA Standard:
mendations issued by the World Trade Organization Technical
Method 6010B Inductively Coupled Plasma-Atomic Emis-
Barriers to Trade (TBT) Committee.
sion Spectrometry
2. Referenced Documents 3. Terminology
2.1 ASTM Standards: 3.1 Definitions—See Terminology D3766.
C1109 Practice for Analysis of Aqueous Leachates from
3.2 Definitions of Terms Specific to This Standard:
Nuclear Waste Materials Using Inductively Coupled
3.2.1 ICP-OES—InductivelyCoupledPlasmaOpticalEmis-
Plasma-Atomic Emission Spectroscopy
sion Spectroscopy
D1193 Specification for Reagent Water
3.2.2 FCC—Fluid Catalytic Cracking
D3766 Terminology Relating to Catalysts and Catalysis
3.2.3 Water—Defined as ASTM Type I or highest quality
D6299 Practice for Applying Statistical Quality Assurance
available as defined in Specification D1193.
and Control Charting Techniques to Evaluate Analytical
4. Summary of Practice
This practice is under the jurisdiction of ASTM Committee D32 on Catalysts
4.1 Specimens are prepared using one of the three prepara-
and is the direct responsibility of Subcommittee D32.03 on Chemical Composition.
tion techniques described in Practice D7442-08a. The result
Current edition approved April 1, 2022. Published May 2022. Originally
should be a clear, dilute acidic solution suitable for ICP-OES.
approved in 2016. Last previous edition approved in 2016 as D8088 – 16. DOI:
10.1520/D8088-16R22.
For referenced ASTM standards, visit the ASTM website, www.astm.org, or
contact ASTM Customer Service at service@astm.org. For Annual Book of ASTM AvailablefromUnitedStatesEnvironmentalProtectionAgency(EPA),William
Standards volume information, refer to the standard’s Document Summary page on Jefferson Clinton Bldg., 1200 Pennsylvania Ave., NW, Washington, DC 20460,
the ASTM website. http://www.epa.gov.
Copyright © ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959. United States
D8088 − 16 (2022)
The final concentration should be 1.0 g of the test specimen 6.10 Water, Type I preferred, or highest quality available.
prepared and diluted into a 250 mL volumetric flask. The test
solutions are introduced into the plasma torch of the ICP
7. Preparation of Calibration Standards
instrument where excitation occurs. Characteristic atomic line
7.1 Determine the method that will be used for the prepa-
emissionspectraareproducedbyaradio-frequencyinductively
rationofthetestspecimens.Determinetheelementthatwillbe
coupled plasma. The spectra are dispersed by a high resolution
used as an internal standard.The sample test specimens should
grating and the intensities of the individual lines are measured.
contain no appreciable amount of the element selected as an
By comparing emission intensities of the elemental lines in the
internal standard. Common elements used as internal standards
test specimens with emission intensities measured in the
for catalysts and related materials are cobalt and scandium.
standards, the concentration of the elements in the test speci-
7.2 For the purpose of this discussion, we will assume a
men can be calculated. The internal standard will compensate
perchloric acid digestion with cobalt as the internal standard.
for variations in test specimen introduction efficiency.
7.3 Prepare ten 250 mL volumetric flasks. Number each
4.2 Details of the instrument components are given in
flask. Fill each flask half full with water and then into each
Practice E1479. This Practice provides a good summary of
flask add 20 mL of perchloric acid, 15 mL of 3 % boric acid
instrument calibration and verification techniques.
solution, and 10 mL of hydrochloric acid.
4.3 Practice D7260, although primarily for non-aqueous
7.4 Label flask number 1 “Reagent Blank.” Add 1 mL of
applications, provides a good description of the basic compo-
internal standard. For this example, 1 mL of a 10 000 ppm
nents that make up an ICP-OES instrument.
solution of cobalt and dilute to volume with water.
4.4 This practice describes the analysis of the six major rare
7.5 Into flask number 2, add 25 mL of 10 000 ppm alumi-
earth elements found in catalyst and related materials. It can
num. Label flask number 2 “Sample Blank.” Add 1 mL of the
easily be extended to any additional elements by following the
internal standard solution and dilute to volume with water.
protocols outlined in this Practice. Guide D7085 provides a list
of the elements above 10 ppm commonly found in equilibrium
7.6 Into flask number 3, add 10 mL of a 1000 ppm lantha-
fluid catalytic cracking catalysts. EPAMethod 6010B is a good
num solution. Add 1 mL of internal standard solution and
primer for those not familiar with the technique. It describes
dilute to volume with water. Label “La Std.”
theanalysisofwaterandwastewaterfornumerouselementsat
7.7 Into flask number 4, add 10 mL of a 1000 ppm cerium
low concentration.
solution. Add 1 mL of internal standard solution and dilute to
volume with water. Label “Ce Std.”
5. Significance and Use
7.8 Into flask number 5, add 5 mL of a 1000 ppm neo-
5.1 The chemical composition of catalysts and catalyst
dymium solution. Add 1 mL of internal standard solution and
materials is an important indicator of catalyst performance and
dilute to volume with water. Label “Nd Std.”
is a valuable tool for assessing parameters in a FCCU process.
7.9 Into flask number 6, add 5 mL of a 1000 ppm praseo-
This practice will be useful to catalyst manufacturers and
dymium solution. Add 1 mL of internal standard solution and
petroleum refiners for quality verification and performance
dilute to volume with water. Label “Pr Std.”
evaluation, and to environmental authorities at the state and
federal levels for evaluation and verification of various com-
7.10 Into flask number 7, add 5 mL of a 1000 ppm gado-
pliance programs (1, 2, 3).
linium solution. Add 1 mL of internal standard solution and
dilute to volume with water. Label “Gd Std.”
6. Reagents
7.11 Into flask number 8, add 2 mL of a 1000 ppm solution
6.1 All reagents should conform to American Chemical
of samarium.Add 1 mLof internal standard solution and dilute
Society (ACS) specifications. Ultra-high purity standards and
to volume with water. Label “Sm Std.”
reference materials are commercially available from recog-
7.12 Into flask number 9, add:
nized vendors.
25 mL of 10 000 ppm aluminum solution,
6.2 Perchloric Acid, concentrated, 69 to 72 %.
10 mL of 1000 ppm lanthanum solution,
5 mL of 1000 ppm cerium solution,
6.3 Hydroflouric Acid, concentrated, 48 % (Refer to the
2 mL of 1000 ppm neodymium solution,
Safety Information in Appendix X3).
5 mL of 1000 ppm praseodymium solution,
6.4 Sulfuric Acid, H S0 , concentrated, 94 %.
2 4
3 mL of 1000 ppm gadolinium solution, and
6.5 Nitric Acid, HNO , concentrated, 65 %.
2 mL of 1000 ppm samarium solution.
7.12.1 Add 1 mL of internal standard solution and dilute to
6.6 Hydrochloric Acid, 1:1 HCl (concentrated HCl, 38,
volume with water. Label “Check Std #1.”
Diluted 1:1).
7.13 Into flask number 10, add:
6.7 Hydrogen Peroxide,3%.
25 mL of 10 000 ppm aluminum solution,
6.8 Lithium Borate Fluxes, lithium tetra-borate or meta-
5 mL of 1000 ppm lanthanum solution,
borate, or both.
10 mL of 1000 ppm cerium solution,
6.9 Boric Acid Solution,3%. 5 mL of 1000 ppm neodymium solution,
D8088 − 16 (2022)
2 mL of 1000 ppm praseodymium solution, suppress the intensity of the element of interest, and a special
1 mL of 1000 ppm gadolinium solution, and formofmatrixeffectthatoccurswhenitaffectsthebackground
1 mL of 1000 ppm samarium solution. measurement.
7.13.1 Add 1 mL of internal standard solution and dilute to
8.10 Appendix X2 includes a simple procedure that can be
volume with water. Label “Check Std #2.”
used to verify that the interference(s) have been properly
compensated. The procedure is widely known as the Standard
8. Preparation of Apparatus
Addition Method (SAM).
8.1 Consult the manufacturer’s instructions. Design differ-
9. Calibration
encesbetweenthevariousavailableunitsmakeitimpossibleto
9.1 Prepare the equipment according to the manufacturer’s
specify exact operating conditions.
instructions. Unless otherwise specified by the manufacturer,
8.2 Operating parameters should be established for the
warm the instrument up for at least 30 minutes.
instrument in use. Method development will yield appropriate
9.2 Perform wavelength profiling for each element of inter-
conditions for the following variables:
est using the solutions prepared in Section 7.The sample blank
8.2.1 Torch configuration,
and all six rare earth standards should be analyzed at each
8.2.2 Nebulizer conditions,
analytical wavelength to determine if background or inter-
8.2.3 Auxiliary gas,
element corrections are necessary. Do not analyze flasks 9 and
8.2.4 RF power,
10 at this point. If spectral interferences are noted, follow the
8.2.5 Nebulizer pressure,
manufacturer’s instructions.
8.2.6 Spray chamber type,
9.3 In this example, we are using a simple two point
8.2.7 Plasma gas,
calibration, the blank (zero) and a high standard. Many
8.2.8 Mass flow to nebulizer, and
manufacturers systems will handle multiple calibration stan-
8.2.9 Emission line used.
dards. This is usually preferable and will validate the linear
range for each analyte.
8.3 Operating parameters should be designed for the par-
ticular on-board computer. Parameters to be included are
9.4 Analyzethetwo“Check”standardstovalidatethelinear
element, wavelength (see Table A1.1 for suggested
range.
wavelengths), background correction points, integration time,
10. Procedure
number of repeat integrations (two minimum), automatic
10.1 Analyze the test specimen solutions in the same
internal standard correction, and re-calibration frequency.
Analysis of a check standard every 5 test specimens is manner as the calibration standards.
recommended.
10.2 The computer system will present the concentration of
each analyte as micrograms per milliliter (µg/mL).
8.4 Data tables should be developed in the computer for
calibration curve coefficients and inter-element correction.
10.3 Re-analyze the check standards every 5 test specimens
Inter-element correction is very important to eliminate inter-
to verify the calibration.
ferences and will guide the selection of emission line wave-
10.4 Test specimens with analyte concentrations above the
lengths.
linear range will need to be diluted. Care must be taken to keep
8.5 Check all expected spectral interferences for the ele-
the internal standard concentration at the correct level. It is
ments listed in TableA1.1. Follow the manufacturer’s instruc-
recommendedthatdilutionsbedonewiththe“ReagentBlank.”
tions to develop and apply correction factors to compensate for
11. Calculation
interferences.
11.1 Frequently, the calculation procedure can be set up in
8.6 To properly apply interference correction factors, you
the on-board computer. In this situation, the results may be
must first establish the linear response range for each element.
reported as the element or as the corresponding oxide. The
8.7 Correct wavelength profiling is important and will
manual calculations are:
reveal any spectral interference. Follow the manufacturer’s
C x V x D
instructions for wavelength profiling before proceeding with
Mass % 5 x 100 % (1)
S x 10 µg/g
~ !
the calibration.
where:
8.8 Spectral interferences can usually be avoided by select-
C = concentration µg/mL
ing the proper emission line wavelength. When they cannot be
V = volume, normally 250 mL
avoided, computer software provided by the manufacturer can
D = dilution factor, normally 1
be used. If this is not available, then the empirical method in
S = actual mass of test specimen, nominally 1 g.
Practice C1109 may be used.
12. Calculation Example
8.9 When analyzing unknown materials, the analyst must
always be alert to the presence of interfering elements. There 12.1 1.0000 gofatestspecimenwasdigestedanddilutedto
are three basic types of interferences that require correction: 250 mL. The analysis of the solution revealed a lanthanum
spectral line overlap, matrix effects that either enhance or concentration of 30.0 µg⁄mL.
D8088 − 16 (2022)
12.2 7500.0 µg
Mass% 5 (4)
10 000.0 µg
C x
...
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