1、Designation: D8088 16Standard Practice forDetermination of the Six Major Rare Earth Elements in FluidCatalytic Cracking Catalysts, Zeolites, Additives, andRelated Materials by Inductively Coupled Plasma OpticalEmission Spectroscopy1This standard is issued under the fixed designation D8088; the numbe
2、r immediately following the designation indicates the year oforiginal adoption or, in the case of revision, the year of last revision. A number in parentheses indicates the year of last reapproval. Asuperscript epsilon () indicates an editorial change since the last revision or reapproval.1. Scope1.
3、1 This practice describes the analysis of fluid catalyticcracking catalysts, rare earth exchanged zeolitic materials,additive and related materials when analyzed by ICP-OES forthe six most common rare earth elements.1.2 The values stated in SI units are to be regarded asstandard. No other units of m
4、easurement are included in thisPractice.1.3 This standard does not purport to address all of thesafety concerns, if any, associated with its use. It is theresponsibility of the user of this standard to establish appro-priate safety and health practices and determine the applica-bility of regulatory
5、limitations prior to use. See Appendix X3.2. Referenced Documents2.1 ASTM Standards:2C1109 Practice for Analysis of Aqueous Leachates fromNuclear Waste Materials Using Inductively CoupledPlasma-Atomic Emission SpectroscopyD1193 Specification for Reagent WaterD3766 Terminology Relating to Catalysts a
6、nd CatalysisD6299 Practice for Applying Statistical Quality Assuranceand Control Charting Techniques to Evaluate AnalyticalMeasurement System PerformanceD6349 Test Method for Determination of Major and MinorElements in Coal, Coke, and Solid Residues from Com-bustion of Coal and Coke by Inductively C
7、oupledPlasmaAtomic Emission SpectrometryD7085 Guide for Determination of Chemical Elements inFluid Catalytic Cracking Catalysts by X-ray FluorescenceSpectrometry (XRF)D7260 Practice for Optimization, Calibration, and Valida-tion of Inductively Coupled Plasma-Atomic EmissionSpectrometry (ICP-AES) for
8、 Elemental Analysis of Petro-leum Products and LubricantsD7442 Practice for Sample Preparation of Fluid CatalyticCracking Catalysts and Zeolites for ElementalAnalysis byInductively Coupled Plasma Optical Emission Spectros-copyE1479 Practice for Describing and Specifying Inductively-Coupled Plasma At
9、omic Emission Spectrometers2.2 EPA Standard:3Method 6010B Inductively Coupled Plasma-Atomic Emis-sion Spectrometry3. Terminology3.1 Definitionssee Terminology D37663.2 Definitions of Terms Specific to This Standard:3.2.1 ICP-OESInductively Coupled Plasma Optical Emis-sion Spectroscopy3.2.2 FCCFluid
10、Catalytic Cracking3.2.3 WaterDefined as ASTM Type I or highest qualityavailable as defined in Specification D1193.4. Summary of Practice4.1 Specimens are prepared using one of the three prepara-tion techniques described in Practice D7442-08a. The resultshould be a clear, dilute acidic solution suita
11、ble for ICP-OES.The final concentration should be 1.0 g of the test specimenprepared and diluted into a 250-mL volumetric flask. The testsolutions are introduced into the plasma torch of the ICPinstrument where excitation occurs. Characteristic atomic lineemission spectra are produced by a radio-fre
12、quency inductivelycoupled plasma. The spectra are dispersed by a high resolutiongrating and the intensities of the individual lines are measured.1This test method is under the jurisdiction of ASTM Committee D32 onCatalysts and is the direct responsibility of Subcommittee D32.03 on ChemicalCompositio
13、n.Current edition approved Nov. 1, 2016. Published November 2016. DOI:10.1520/D808816.2For referenced ASTM standards, visit the ASTM website, www.astm.org, orcontact ASTM Customer Service at serviceastm.org. For Annual Book of ASTMStandards volume information, refer to the standards Document Summary
14、 page onthe ASTM website.3Available from United States Environmental ProtectionAgency (EPA), WilliamJefferson Clinton Bldg., 1200 Pennsylvania Ave., NW, Washington, DC 20460,http:/www.epa.gov.Copyright ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959. United S
15、tates1By comparing emission intensities of the elemental lines in thetest specimens with emission intensities measured in thestandards, the concentration of the elements in the test speci-men can be calculated. The internal standard will compensatefor variations in test specimen introduction efficie
16、ncy.4.2 Details of the instrument components are given inPractice E1479. This Practice provides a good summary ofinstrument calibration and verification techniques.4.3 Practice D7260, although primarily for non-aqueousapplications, provides a good description of the basic compo-nents that make up an
17、 ICP-OES instrument.4.4 This practice describes the analysis of the six major rareearth elements found in catalyst and related materials. It caneasily be extended to any additional elements by following theprotocols outlined in this Practice. Guide D7085 provides a listof the elements above 10 ppm c
18、ommonly found in equilibriumfluid catalytic cracking catalysts. EPAMethod 6010B is a goodprimer for those not familiar with the technique. It describesthe analysis of water and waste water for numerous elements atlow concentration.5. Significance and Use5.1 The chemical composition of catalysts and
19、catalystmaterials is an important indicator of catalyst performance andis a valuable tool for assessing parameters in a FCCU process.This practice will be useful to catalyst manufacturers andpetroleum refiners for quality verification and performanceevaluation, and to environmental authorities at th
20、e state andfederal levels for evaluation and verification of various com-pliance programs (1, 2, 3).6. Reagents6.1 All reagents should conform to American ChemicalSociety (ACS) specifications. Ultra-high purity standards andreference materials are commercially available from recog-nized vendors.6.2
21、Perchloric Acid, concentrated, 69 to 72 %.6.3 Hydroflouric Acid, concentrated, 48 % (Refer to theSafety Information in Appendix X3).6.4 Sulfuric Acid, H2S04, concentrated, 94 %.6.5 Nitric Acid, HNO3, concentrated, 65 %.6.6 Hydrochloric Acid, 1:1 HCl (concentrated HCl, 38,Diluted 1:1).6.7 Hydrogen Pe
22、roxide, 3%.6.8 Lithium Borate Fluxes, lithium tetra-borate or meta-borate, or both.6.9 Boric Acid Solution, 3%.6.10 Water, Type I preferred, or highest quality available.7. Preparation of Calibration Standards7.1 Determine the method that will be used for the prepa-ration of the test specimens. Dete
23、rmine the element that will beused as an internal standard. The sample test specimens shouldcontain no appreciable amount of the element selected as aninternal standard. Common elements used as internal standardsfor catalysts and related materials are cobalt and scandium.7.2 For the purpose of this
24、discussion, we will assume aperchloric acid digestion with cobalt as the internal standard.7.3 Prepare ten 250-mL volumetric flasks. Number eachflask. Fill each flask half full with water and then into eachflask add 20 mL of perchloric acid, 15 mL of 3 % boric acidsolution, and 10 mL of hydrochloric
25、 acid.7.4 Label flask number 1 “Reagent Blank.” Add 1 mL ofinternal standard. For this example, 1 mL of a 10 000 ppmsolution of cobalt and dilute to volume with water.7.5 Into flask number 2, add 25 mL of 10 000 ppmaluminum. Label flask number 2 “Sample Blank.”Add 1 mLofthe internal standard solutio
26、n and dilute to volume with water.7.6 Into flask number 3, add 10 mL of a 1000 ppmlanthanum solution.Add 1 mLof internal standard solution anddilute to volume with water. Label “La Std.”7.7 Into flask number 4, add 10 mL of a 1000 ppm ceriumsolution. Add 1 mL of internal standard solution and dilute
27、 tovolume with water. Label “Ce Std.”7.8 Into flask number 5, add 5 mL of a 1000 ppm neo-dymium solution. Add 1 mL of internal standard solution anddilute to volume with water. Label “Nd Std.”7.9 Into flask number 6, add 5 mL of a 1000 ppm praseo-dymium solution. Add 1 mL of internal standard soluti
28、on anddilute to volume with water. Label “Pr Std.”7.10 Into flask number 7, add 5 mL of a 1000 ppmgadolinium solution. Add 1 mL of internal standard solutionand dilute to volume with water. Label “Gd Std.”7.11 Into flask number 8, add 2 mL of a 1000 ppm solutionof samarium.Add 1 mL of internal stand
29、ard solution and diluteto volume with water. Label “Sm Std.”7.12 Into flask number 9, add:25 mL of 10 000 ppm aluminum solution,10 mL of 1000 ppm lanthanum solution,5 mL of 1000 ppm cerium solution,2 mL of 1000 ppm neodymium solution,5 mL of 1000 ppm praseodymium solution,3 mL of 1000 ppm gadolinium
30、 solution, and2 mL of 1000 ppm samarium solution.7.12.1 Add 1 mL of internal standard solution and dilute tovolume with water. Label “Check Std #1.”7.13 Into flask number 10, add:25 mL of 10 000 ppm aluminum solution,5 mL of 1000 ppm lanthanum solution,10 mL of 1000 ppm cerium solution,5 mL of 1000
31、ppm neodymium solution,2 mL of 1000 ppm praseodymium solution,1 mL of 1000 ppm gadolinium solution, and1 mL of 1000 ppm samarium solution.7.13.1 Add 1 mL of internal standard solution and dilute tovolume with water. Label “Check Std #2.”D8088 1628. Preparation of Apparatus8.1 Consult the manufacture
32、rs instructions. Design differ-ences between the various available units make it impossible tospecify exact operating conditions.8.2 Operating parameters should be established for theinstrument in use. Method development will yield appropriateconditions for the following variables:8.2.1 Torch config
33、uration,8.2.2 Nebulizer conditions,8.2.3 Auxiliary gas,8.2.4 RF power,8.2.5 Nebulizer pressure,8.2.6 Spray chamber type,8.2.7 Plasma gas,8.2.8 Mass flow to nebulizer, and8.2.9 Emission line used.8.3 Operating parameters should be designed for the par-ticular on-board computer. Parameters to be inclu
34、ded areelement, wavelength (see Table A1.1 for suggestedwavelengths), background correction points, integration time,number of repeat integrations (two minimum), automaticinternal standard correction, and re-calibration frequency.Analysis of a check standard every 5 test specimens isrecommended.8.4
35、Data tables should be developed in the computer forcalibration curve coefficients and inter-element correction.Inter-element correction is very important to eliminate inter-ferences and will guide the selection of emission line wave-lengths.8.5 Check all expected spectral interferences for the ele-m
36、ents listed in Table A1.1. Follow the manufacturers instruc-tions to develop and apply correction factors to compensate forinterferences.8.6 To properly apply interference correction factors, youmust first establish the linear response range for each element.8.7 Correct wavelength profiling is impor
37、tant and willreveal any spectral interference. Follow the manufacturersinstructions for wavelength profiling before proceeding withthe calibration.8.8 Spectral interferences can usually be avoided by select-ing the proper emission line wavelength. When they cannot beavoided, computer software provid
38、ed by the manufacturer canbe used. If this is not available, then the empirical method inPractice C1109 may be used.8.9 When analyzing unknown materials, the analyst mustalways be alert to the presence of interfering elements. Thereare three basic types of interferences that require correction:spect
39、ral line overlap, matrix effects that either enhance orsuppress the intensity of the element of interest, and a specialform of matrix effect that occurs when it affects the backgroundmeasurement.8.10 Appendix X2 includes a simple procedure that can beused to verify that the interference(s) have been
40、 properlycompensated. The procedure is widely known as the StandardAddition Method (SAM).9. Calibration9.1 Prepare the equipment according to the manufacturersinstructions. Unless otherwise specified by the manufacturer,warm the instrument up for at least 30 minutes.9.2 Perform wavelength profiling
41、for each element of inter-est using the solutions prepared in Section 7. The sample blankand all six rare earth standards should be analyzed at eachanalytical wavelength to determine if background or inter-element corrections are necessary. Do not analyze flasks 9 and10 at this point. If spectral in
42、terferences are noted, follow themanufacturers instructions.9.3 In this example, we are using a simple two pointcalibration, the blank (zero) and a high standard. Manymanufacturers systems will handle multiple calibration stan-dards. This is usually preferable and will validate the linearrange for e
43、ach analyte.9.4 Analyze the two “Check” standards to validate the linearrange.10. Procedure10.1 Analyze the test specimen solutions in the samemanner as the calibration standards.10.2 The computer system will present the concentration ofeach analyte as micrograms per milliliter (g/mL).10.3 Re-analyz
44、e the check standards every 5 test specimensto verify the calibration.10.4 Test specimens with analyte concentrations above thelinear range will need to be diluted. Care must be taken to keepthe internal standard concentration at the correct level. It isrecommended that dilutions be done with the “R
45、eagent Blank.”11. Calculation11.1 Frequently, the calculation procedure can be set up inthe on-board computer. In this situation, the results may bereported as the element or as the corresponding oxide. Themanual calculations are:Mass % 5C x V x DS x 106g/g!x 100 % (1)where:C = concentration g/mLV =
46、 volume, normally 250 mLD = dilution factor, normally 1S = actual mass of test specimen, nominally 1 g.12. Calculation Example12.1 1.0000 g of a test specimen was digested and diluted to250 mL. The analysis of the solution revealed a lanthanumconcentration of 30.0 g/mL.12.2Mass%5C x V x DS x 106g/g!
47、x 100 % (2)12.3Mass%530.0 g/mL x 250 mL x 11.0000g x 106g/g!x 100 % (3)D8088 16312.4Mass%57500.0 g10 000.0 g(4)Mass% 5 0.75% lanathum (5)13. Keywords13.1 catalysts; FCC; FCCU; fluid catalytic cracking; ICP;ICP-OES; inductively coupled plasma optical emission spec-troscopy; rare earthsANNEX(Mandatory
48、 Information)A1. RECOMMENDED WAVELENGTHSA1.1 Detection limits are estimates for radial view. Axialview are generally an order of magnitude better.A1.2 Recommended wavelengths are to be used for initialset-up. The ultimate choice of wavelength will depend onsample matrix and any interferences that ma
49、y be encountered.Appendix X1 lists alternate wavelengths and knowninterferences.APPENDIXES(Nonmandatory Information)X1. ALTERNATE WAVELENGTHS WITH KNOWN INTERFERENCESAt. No. Element Wavelength (nm) Known Interferences57 Lanthanum 333.749 408.672 Th412.323 Ce, Th58 Cerium 413.765 Ce418.660 Zr453.975 59 Praseodymium 414.314 Ce417.939 Ce, Cr422.535 V, U60 Neodymium 401.225 Ti, Cr430.358 406.109 Ce62 Samarium 359.260 W, Th442.434 Ce, Ca428.079 Ce, Cr64 Gadolinium 342.247 Th, U336.223 Th, Ca335.047 Ce, CaTABLE A1.1 Recommended WavelengthsElement Wavelength (nm)
