1、Designation: D5600 17Standard Test Method forTrace Metals in Petroleum Coke by Inductively CoupledPlasma Atomic Emission Spectrometry (ICP-AES)1This standard is issued under the fixed designation D5600; the number immediately following the designation indicates the year oforiginal adoption or, in th
2、e 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. Scope*1.1 This test method covers the analysis for commonlydetermined trace metals in test spec
3、imens of raw and calcinedpetroleum coke by inductively coupled plasma atomic emis-sion spectroscopy.1.2 Elements for which this test method is applicable arelisted in Table 1. Detection limits, sensitivity, and optimumranges of the metals will vary with the matrices and model ofspectrometer.1.3 This
4、 test method is applicable only to samples contain-ing less than one mass % ash.1.4 Elements present at concentrations above the upper limitof the working ranges can be determined with additional,appropriate dilutions.1.5 The values stated in SI units are to be regarded as thestandard. The values gi
5、ven in parentheses are for informationonly.1.6 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 regulato
6、ry limitations prior to use.1.7 This international standard was developed in accor-dance with internationally recognized principles on standard-ization established in the Decision on Principles for theDevelopment of International Standards, Guides and Recom-mendations issued by the World Trade Organ
7、ization TechnicalBarriers to Trade (TBT) Committee.2. Referenced Documents2.1 ASTM Standards:2D346 Practice for Collection and Preparation of CokeSamples for Laboratory AnalysisD1193 Specification for Reagent WaterD6299 Practice for Applying Statistical Quality Assuranceand Control Charting Techniqu
8、es to Evaluate AnalyticalMeasurement System PerformanceD7260 Practice for Optimization, Calibration, and Valida-tion of Inductively Coupled Plasma-Atomic EmissionSpectrometry (ICP-AES) for Elemental Analysis of Petro-leum Products and LubricantsE11 Specification for Woven Wire Test Sieve Cloth and T
9、estSieves3. Terminology3.1 Definitions of Terms Specific to This Standard:3.1.1 gross samplethe original, uncrushed, representativeportion taken from a shipment or lot of coke.3.1.2 ICP-AESInductively Coupled PlasmaAtomicEmission Spectrometry.3.1.3 petroleum cokea solid, carbonaceous residue pro-duc
10、ed by thermal decomposition of heavy petroleum fractionsand cracked stocks.4. Summary of Test Method4.1 A test sample of the petroleum coke is ashed at 700 C.The ash is fused with lithium borate. The melt is dissolved indilute hydrochloric acid (HCl), and the resultant solution isanalyzed by inducti
11、vely coupled plasma atomic emissionspectrometry (ICP-AES) using simultaneous, or sequentialmultielemental determination of elements. The solution isintroduced to the ICP instrument by free aspiration or by anoptional peristaltic pump. The concentrations of the tracemetals are then calculated by comp
12、aring the emission intensi-ties from the sample with the emission intensities of thestandards used in calibration.5. Significance and Use5.1 The presence and concentration of various metallicelements in a petroleum coke are major factors in determiningthe suitability of the coke for various end uses
13、. This testmethod provides a means of determining the concentrations ofthese metallic elements in a coke sample.1This test method is under the jurisdiction of ASTM Committee D02 onPetroleum Products, Liquid Fuels, and Lubricantsand is the direct responsibility ofSubcommittee D02.03 on Elemental Anal
14、ysis.Current edition approved May 1, 2017. Published May 2017. Originallyapproved in 1994. Last previous edition approved in 2014 as D5600 14. DOI:10.1520/D5600-17.2For referenced ASTM standards, visit the ASTM website, www.astm.org, orcontact ASTM Customer Service at serviceastm.org. For Annual Boo
15、k of ASTMStandards volume information, refer to the standards Document Summary page onthe ASTM website.*A Summary of Changes section appears at the end of this standardCopyright ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959. United StatesThis international
16、standard was developed in accordance with internationally recognized principles on standardization established in the Decision on Principles for theDevelopment of International Standards, Guides and Recommendations issued by the World Trade Organization Technical Barriers to Trade (TBT) Committee.15
17、.2 The test method provides a standard procedure for useby buyer and seller in the commercial transfer of petroleumcoke to determine whether the petroleum coke meets thespecifications of the purchasing party.6. Interferences6.1 SpectralFollow the instrument manufacturers operat-ing guide to develop
18、and apply correction factors to compen-sate for the interferences. To apply interference corrections, allconcentrations shall be within the previously established linearresponse range of each element.6.2 Spectral interferences are caused by: (1) overlap of aspectral line from another element; (2) un
19、resolved overlap ofmolecular band spectra; (3) background contribution fromcontinuous or recombination phenomena; and (4) stray lightfrom the line emission of high-concentration elements. Spec-tral overlap can be compensated for by computer-correcting theraw data after monitoring and measuring the i
20、nterfering ele-ment. Unresolved overlap requires selection of an alternatewavelength. Background contribution and stray light canusually be compensated for by a background correction adja-cent to the analyte line.6.3 Physical interferences are effects associated with thesample nebulization and trans
21、port processes. Changes in vis-cosity and surface tension can cause significant inaccuracies,especially in samples containing high dissolved solids or highacid concentrations. If physical interferences are present, theyshall be reduced by diluting the sample, by using a peristalticpump, or by using
22、the standard additions method. Anotherproblem that can occur with high dissolved solids is saltsbuildup at the tip of the nebulizer, which can affect aerosol flowrate and cause instrumental drift. This problem can be con-trolled by wetting the argon prior to nebulization, using a tipwasher, or dilut
23、ing the sample.6.4 See Practice D7260 for explanation of ICP-AES inter-ferences and other operational details.7. Apparatus7.1 Balance, top loading, with automatic tare, capable ofweighing to 0.0001 g, 150 g capacity.7.2 Ceramic Cooling Plate, desiccator plates have beenfound effective.7.3 Crucible S
24、upport, nichrome wire triangles.7.4 Furnaces, electric, capable of regulation of temperatureat 700 C 6 10 C and 1000 C 6 10 C, with allowances forexchange of combustion gases and air.7.5 Inductively Coupled Plasma Atomic EmissionSpectrometerEither sequential or simultaneous spectrometeris suitable.7
25、.6 Magnetic Stirring Bars, polytetrafluoroethylene (PTFE)coated, approximately 12 mm (12 in.) in length.7.7 Magnetic Stirring Hot Plate.7.8 Meker-Type Forced Air Burner.7.9 NebulizerA high-solids nebulizer is strongly recom-mended. This type of nebulizer reduces the possibility ofclogging and minimi
26、zes aerosol particle effects.7.10 Peristaltic PumpA peristaltic pump is strongly rec-ommended to provide a constant flow of solution.7.11 Platinum Dish, 50 mL to 58 mL capacity.7.12 Platinum Dish, 100 mL to 200 mL capacity.7.13 Platinum-tipped Tongs.7.14 Ring Stand, with crucible support.7.15 Sieves
27、, 0.250 mm (No. 60) and 0.075 mm (No. 200),conforming to Specification E11.7.16 Tungsten Carbide Mill, laboratory size.7.17 Vacuum Filtration Apparatus.7.18 Filter Paper, sized to fit vacuum filtration apparatus,fine porosity, slow flow rate, 2.5 micron particle retention.8. Reagents8.1 Purity of Re
28、agentsReagent-grade chemicals shall beused in all tests. It is intended that all reagents shall conform tothe specifications of the Committee on Analytical Reagents ofthe American Chemical Society where such specifications areavailable.3Other grades may be used, provided it is firstascertained that
29、the reagent is of sufficiently high purity topermit its use without lessening the accuracy of the determi-nation.8.2 Purity of WaterUnless otherwise indicated, referencesto water shall be understood to mean Type II reagent water asdefined in Specification D1193.8.3 Argon Gas Supply, welding grade.3R
30、eagent Chemicals, American Chemical Society Specifications, AmericanChemical Society, Washington, DC. For Suggestions on the testing of reagents notlisted by the American Chemical Society, see Annual Standards for LaboratoryChemicals, BDH Ltd., Poole, Dorset, U.K., and the United States Pharmacopeia
31、and National Formulary, U.S. Pharmacopeial Convention, Inc. (USPC), Rockville,MD.TABLE 1 Elements Determined and Suggested WavelengthsElement Wavelengths, nmA ,BConcentrationRange, mg/kgCAluminum 237.313, 256.799, 308.216, 396.152 15110Barium 455.403, 493.410 165Calcium 317.933, 393.367, 396.847 101
32、40Iron 259.940 40700Magnesium 279.079, 279.553 550Manganese 257.610, 294.920 17Nickel 231.604, 241.476, 352.454 3220Silicon 212.412, 251.611, 288.159 60290Sodium 588.995, 589.3, 589.592 30160Titanium 334.941, 337.280 17Vanadium 292.402 2480Zinc 202.548, 206.200, 213.856 120AThe wavelengths listed we
33、re utilized in the round robin because of theirsensitivity. Other wavelengths can be substituted if they can provide the neededsensitivity and are treated with the same corrective techniques for spectralinterference (see 6.1). In time, other elements may be added as more informationbecomes available
34、 and as required.BAlternative wavelengths can be found in references such as “Inductively CoupledPlasma Atomic Emission Spectroscopy,” Winge, R. K., Fassel, V. A., Peterson, V.J., and Floyd, M. A., Elsevier, 1985.CBased on this round-robin study. This test method can be applicable to otherelements o
35、r concentration ranges but precision data is not available.D5600 1728.4 Lithium Borate, either, or a blend containing both.8.4.1 Lithium Metaborate (LiBO2), powder (high purity).8.4.2 Lithium Tetraborate (Li2B4O7), powder (high purity).8.5 Solution No. 1, Hydrochloric Acid, 20 % by volume(400 mL of
36、concentrated HCl diluted to 2000 mL with water).8.6 Solution No. 2, Standard and Sample SolutionAdditiveWeigh 20.0 g 6 0.1 g of lithium borate into a100 mL to 200 mL platinum dish. Place in a furnace at 1000 Cfor 5 min to fuse to a liquid. Remove and cool. Place the cooledplatinum dish containing th
37、e fused recrystallized lithium borateand a magnetic stirring bar into a 2 L glass beaker. Add1000 mL of Solution No. 1 (20 % HCl). Heat gently and stirthe solution on a magnetic stirring hot plate until the lithiumborate completely dissolves. After dissolution, remove theplatinum dish with a glass r
38、od. Rinse the platinum dish andglass rod with water into the lithium borate solution. Immedi-ately transfer the warm solution quantitatively to a 2 L volu-metric flask. Dilute to about 1800 mL with water to avoidcrystallization. Mix the solution and cool to room temperature.Dilute to volume with wat
39、er, mix thoroughly, and vacuum-filter the entire solution through filter paper.NOTE 1Fifty millilitres of Solution No. 2 contains exactly 0.5 glithium borate and 25 mL Solution No. 1.8.7 Standard Stock SolutionsPrepare standard stock solu-tions from high purity (99.9 % or better) metals, oxides, ors
40、alts. Stock solutions of 1000 g/mL (ppm) for each metal areneeded for preparation of dilute standards in the range from1.0 g mL to 50 g/mL (ppm).NOTE 2To minimize the potential of contamination, prepare theplatinum ware by boiling in dilute HCl (5 volume % HCl + 95 volume %water) and rinsing thoroug
41、hly with water. After this initial cleaning,handle the platinum ware with clean platinum-tipped tongs and protectfrom all sources of contamination. Similarly acid clean all glassware usedin the analyses.NOTE 3Commercially available standards and other reagents solu-tions may be used in place of labo
42、ratory preparations.8.8 Quality Control MaterialsNIST SRM 2718A greenpetroleum coke or 2719 calcined petroleum coke can be usedas QC materials for this analysis.49. Sample Preparation9.1 Crush and divide the gross sample to obtain a laboratoryanalysis sample. Crush to pass a 0.250 mm (No. 60) sieveu
43、sing Practice D346.9.2 Use a tungsten carbide mill to crush approximately a30 g representative portion of the minus 0.250 mm (No. 60)sieve analysis sample, as prepared in 9.1, to pass through a0.075 mm (No. 200) sieve. Dry this sample to constant mass at110 C to 115 C and store in a desiccator until
44、 cool andneeded for the analysis.9.2.1 Preparation of the minus 0.075 mm analysis samples,from the minus 0.250 mm analysis samples, shall neitherremove metals through loss nor increase metals throughcontamination. Full dissolution of the ash is required.10. Preparation of Apparatus10.1 ICP-AES Instr
45、umentConsult the manufacturers in-structions for operation of the inductively coupled plasmaatomic emission spectrometer.10.2 Peristaltic PumpWhen a peristaltic pump is used,inspect the pump tubing and replace it, as necessary, beforestarting each day. Verify the solution uptake rate and adjust itto
46、 the desired rate.10.3 ICP Excitation SourceInitiate the plasma source atleast 30 min before performing the analysis. Some manufac-turers recommend even longer warm-up periods.10.4 Wavelength ProfilingPerform any wavelength profil-ing that is required in the normal operation of the instrument.10.5 O
47、perating ParametersAssign the appropriate oper-ating parameter to the instrument task file so that the desiredelements can be determined. Parameters to be included areelement, wavelength, background correction points (optional),inter-element correction factors (optional), integration time,and intern
48、al standard correction (optional).10.6 Each analyst shall determine the sensitivity and linearrange of calibration of their own equipment and chooseconcentration ranges for standards compatible with the samplesand instrument specific to their own work. Sample dilutionscan be required for the determi
49、nation of some elements (see11.6).10.7 The linear response range shall be established for eachparticular instrument being used. This is accomplished byrunning intermediate standards between the blank and thecalibration standard and by running standards containinghigher concentrations than the calibration standard within thelinear range of response.11. Procedure11.1 Weigh 5 g (to 0.1 mg) of the dried petroleum cokeprepared in Section 9 into a labeled 50 mL to 58 mL platinumdish.11.2 Place the platinum dish in a cold muffle fu
