1、Designation: D5600 09D5600 14Standard 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 o
2、r, 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. Scope*1.1 This test method covers the analysis for commonly determined trace metals in
3、test specimens of raw and calcined petroleumcoke by inductively coupled plasma atomic emission spectroscopy.1.2 Elements for which this test method is applicable are listed in Table 1. Detection limits, sensitivity, and optimum ranges ofthe metals will vary with the matrices and model of spectromete
4、r.1.3 This test method is applicable only to samples containing less than one mass % ash.1.4 Elements present at concentrations above the upper limit of the working ranges can be determined with additional,appropriate dilutions.1.5 The values stated in SI units are to be regarded as the standard. Th
5、e values given in parentheses are for information only.1.6 This standard does not purport to address all of the safety concerns, if any, associated with its use. It is the responsibilityof the user of this standard to establish appropriate safety and health practices and determine the applicability
6、of regulatorylimitations prior to use.2. Referenced Documents2.1 ASTM Standards:2D346 Practice for Collection and Preparation of Coke Samples for Laboratory AnalysisD1193 Specification for Reagent WaterD7260 Practice for Optimization, Calibration, and Validation of Inductively Coupled Plasma-Atomic
7、Emission Spectrometry(ICP-AES) for Elemental Analysis of Petroleum Products and LubricantsE11 Specification for Woven Wire Test Sieve Cloth and Test Sieves3. Terminology3.1 Definitions of Terms Specific to This Standard:3.1.1 gross samplethe original, uncrushed, representative portion taken from a s
8、hipment or lot of coke.3.1.2 ICP-AESInductively Coupled PlasmaAtomic Emission Spectrometry.3.1.3 petroleum cokea solid, carbonaceous residue produced by thermal decomposition of heavy petroleum fractions andcracked stocks.4. Summary of Test Method4.1 A test sample of the petroleum coke is ashed at 7
9、00C. The ash is fused with lithium borate. The melt is dissolved in dilutehydrochloric acid (HCl), and the resultant solution is analyzed by inductively coupled plasma atomic emission spectrometry(ICP-AES) using simultaneous, or sequential multielemental determination of elements. The solution is in
10、troduced to the ICPinstrument by free aspiration or by an optional peristaltic pump. The concentrations of the trace metals are then calculated bycomparing the emission intensities from the sample with the emission intensities of the standards used in calibration.1 This test method is under the juri
11、sdiction of ASTM Committee D02 on Petroleum Products Products, Liquid Fuels, and Lubricantsand is the direct responsibility ofSubcommittee D02.03 on Elemental Analysis.Current edition approved Oct. 1, 2009June 1, 2014. Published November 2009 July 2014. Originally approved in 1994. Last previous edi
12、tion approved in 20042009 asD5600D5600 09.04 1. DOI: 10.1520/D5600-09.10.1520/D5600-14.2 For referencedASTM standards, visit theASTM website, www.astm.org, or contactASTM Customer Service at serviceastm.org. For Annual Book of ASTM Standardsvolume information, refer to the standards Document Summary
13、 page on the ASTM website.This document is not an ASTM standard and is intended only to provide the user of an ASTM standard an indication of what changes have been made to the previous version. Becauseit may not be technically possible to adequately depict all changes accurately, ASTM recommends th
14、at users consult prior editions as appropriate. In all cases only the current versionof the standard as published by ASTM is to be considered the official document.*A Summary of Changes section appears at the end of this standardCopyright ASTM International, 100 Barr Harbor Drive, PO Box C700, West
15、Conshohocken, PA 19428-2959. United States15. Significance and Use5.1 The presence and concentration of various metallic elements in a petroleum coke are major factors in determining thesuitability of the coke for various end uses. This test method provides a means of determining the concentrations
16、of these metallicelements in a coke sample.5.2 The test method provides a standard procedure for use by buyer and seller in the commercial transfer of petroleum coke todetermine whether the petroleum coke meets the specifications of the purchasing party.6. Interferences6.1 SpectralFollow the instrum
17、ent manufacturers operating guide to develop and apply correction factors to compensate forthe interferences. To apply interference corrections, all concentrations shall be within the previously established linear responserange of each element.6.2 Spectral interferences are caused by: (1) overlap of
18、 a spectral line from another element; (2) unresolved overlap of molecularband spectra; (3) background contribution from continuous or recombination phenomena; and (4) stray light from the line emissionof high-concentration elements. Spectral overlap can be compensated for by computer-correcting the
19、 raw data after monitoring andmeasuring the interfering element. Unresolved overlap requires selection of an alternate wavelength. Background contribution andstray light can usually be compensated for by a background correction adjacent to the analyte line.6.3 Physical interferences are effects asso
20、ciated with the sample nebulization and transport processes. Changes in viscosity andsurface tension can cause significant inaccuracies, especially in samples containing high dissolved solids or high acidconcentrations. If physical interferences are present, they shall be reduced by diluting the sam
21、ple, by using a peristaltic pump, orby using the standard additions method. Another problem that can occur with high dissolved solids is salts buildup at the tip ofthe nebulizer, which can affect aerosol flow rate and cause instrumental drift. This problem can be controlled by wetting the argonprior
22、 to nebulization, using a tip washer, or diluting the sample.6.4 See Practice D7260 for explanation of ICP-AES interferences and other operational details.7. Apparatus7.1 Balance, top loading, with automatic tare, capable of weighing to 0.0001 g, 150 g capacity.7.2 Ceramic Cooling Plate, desiccator
23、plates have been found effective.7.3 Crucible Support, nichrome wire triangles.7.4 Furnaces, electric, capable of regulation of temperature at 700 6 10C and 1000 6 10C, with allowances for exchangeof combustion gases and air.7.5 Inductively Coupled Plasma Atomic Emission SpectrometerEither sequentia
24、l or simultaneous spectrometer is suitable.7.6 Magnetic Stirring Bars, polytetrafluoroethylene (PTFE) coated, approximately 12 mm (12 in.) in length.7.7 Magnetic Stirring Hot Plate.TABLE 1 Elements Determined and Suggested WavelengthsElement Wavelengths, nmA ,B ConcentrationRange, mg/kgCAluminum 237
25、.313, 256.799, 308.216, 396.152 15110Barium 455.403, 493.410 165Calcium 317.933, 393.367, 396.847 10140Iron 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
26、 334.941, 337.280 17Vanadium 292.402 2480Zinc 202.548, 206.200, 213.856 120A The wavelengths listed were 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 spe
27、ctralinterference (see 6.1). In time, other elements may be added as more informationbecomes available and as required.B Alternative 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.,
28、 Elsevier, 1985.C Based on this round robin study. This test method can be applicable to otherelements or concentration ranges but precision data is not available.D5600 1427.8 Meker Type Forced Air Burner.7.9 NebulizerAhigh-solids nebulizer is strongly recommended. This type of nebulizer reduces the
29、 possibility of clogging andminimizes aerosol particle effects.7.10 Peristaltic PumpA peristaltic pump is strongly recommended to provide a constant flow of solution.7.11 Platinum Dish, 50 to 58 mL capacity.7.12 Platinum Dish, 100 to 200 mL capacity.7.13 Platinum-tipped Tongs.7.14 Ring Stand, with c
30、rucible support.7.15 Sieves, 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 retentio
31、n.8. Reagents8.1 Purity of ReagentsReagent-grade chemicals shall be used in all tests. It is intended that all reagents shall conform to thespecifications of the Committee onAnalytical Reagents of theAmerican Chemical Society where such specifications are available.3Other grades may be used, provide
32、d it is first ascertained that the reagent is of sufficiently high purity to permit its use withoutlessening the accuracy of the determination.8.2 Purity of WaterUnless otherwise indicated, references to water shall be understood to mean Type II reagent water asdefined in Specification D1193.8.3 Arg
33、on Gas Supply, welding grade.8.4 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 concentrated HCl diluted to 2000 mL wi
34、th water).8.6 Solution No. 2, Standard and Sample Solution Additive. Weigh 20.0 6 0.1 g of lithium borate into a 100 to 200 mLplatinumdish. Place in a furnace at 1000C for 5 min to fuse to a liquid. Remove and cool. Place the cooled platinum dish containing thefused recrystallized lithium borate and
35、 a magnetic stirring bar into a 2-Lglass beaker.Add 1000 mLof Solution No. 1 (20 % HCl).Heat gently and stir the solution on a magnetic stirring hot plate until the lithium borate completely dissolves. After dissolution,remove the platinum dish with a glass rod. Rinse the platinum dish and glass rod
36、 with water into the lithium borate solution.Immediately transfer the warm solution quantitatively to a 2-L volumetric flask. Dilute to about 1800 mL with water to avoidcrystallization. Mix the solution and cool to room temperature. Dilute to volume with water, mix thoroughly, and vacuum-filterthe e
37、ntire solution through filter paper.NOTE 1Fifty millilitres of Solution No. 2 contains exactly 0.5 g lithium borate and 25 mL Solution No. 1.8.7 Standard Stock SolutionsPrepare standard stock solutions from high purity (99.9 % or better) metals, oxides, or salts.Stock solutions of 1000 g/mL (ppm) fo
38、r each metal are needed for preparation of dilute standards in the range from 1.0 to 50g/mL (ppm).NOTE 2To minimize the potential of contamination, prepare the platinum ware by boiling in dilute HCl (5 volume % HCl + 95 volume % water) andrinsing thoroughly with water. After this initial cleaning, h
39、andle the platinum ware with clean platinum tipped tongs and protect from all sources ofcontamination. Similarly acid clean all glassware used in the analyses.NOTE 3Commercially available standards and other reagents solutions may be used in place of laboratory preparations.9. Sample Preparation9.1
40、Crush and divide the gross sample to obtain a laboratory analysis sample. Crush to pass a 0.250 mm (No. 60) sieve usingPractice D346.9.2 Use a tungsten carbide mill to crush approximately a 30 g 30 g representative portion of the minus 0.250 mm (No. 60) sieveanalysis sample, as prepared in 9.1, to p
41、ass through a 0.075 mm (No. 200) sieve. Dry this sample to constant mass at 110 to 115Cand store in a desiccator until cool and needed for the analysis.3 Reagent Chemicals, American Chemical Society Specifications, American Chemical Society, Washington, DC. For Suggestions on the testing of reagents
42、 not listed bythe American Chemical Society, see Annual Standards for Laboratory Chemicals, BDH Ltd., Poole, Dorset, U.K., and the United States Pharmacopeia and NationalFormulary, U.S. Pharmacopeial Convention, Inc. (USPC), Rockville, MD.D5600 1439.2.1 Preparation of the minus 0.075 mm analysis sam
43、ples, from the minus 0.250 mm analysis samples, shall neither removemetals through loss nor increase metals through contamination. Full dissolution of the ash is required.10. Preparation of Apparatus10.1 ICP-AES InstrumentConsult the manufacturers instructions for operation of the inductively couple
44、d plasma atomicemission spectrometer.10.2 Peristaltic PumpWhen a peristaltic pump is used, inspect the pump tubing and replace it, as necessary, before startingeach day. Verify the solution uptake rate and adjust it to the desired rate.10.3 ICP Excitation SourceInitiate the plasma source at least 30
45、 min before performing the analysis. Some manufacturersrecommend even longer warm-up periods.10.4 Wavelength ProfilingPerform any wavelength profiling that is required in the normal operation of the instrument.10.5 Operating ParametersAssign the appropriate operating parameter to the instrument task
46、 file so that the desired elementscan be determined. Parameters to be included are element, wavelength, background correction points (optional), inter-elementcorrection factors (optional), integration time, and internal standard correction (optional).10.6 Each analyst shall determine the sensitivity
47、 and linear range of calibration of their own equipment and chooseconcentration ranges for standards compatible with the samples and instrument specific to their own work. Sample dilutions canbe required for the determination of some elements (see 11.6).10.7 The linear response range shall be establ
48、ished for each particular instrument being used. This is accomplished by runningintermediate standards between the blank and the calibration standard and by running standards containing higher concentrationsthan the calibration standard within the linear range of response.11. Procedure11.1 Weigh 5 g
49、 (to 0.1 mg) of the dried petroleum coke prepared in Section 9 into a labeled 50 to 58 mL platinum dish.11.2 Place the platinum dish in a cold muffle furnace and heat directly to 700 6 10C until all carbonaceous matter is removed.Transfer the platinum dish to a desiccator and cool to room temperature.11.3 To convert the ash into a solution, weigh, on an analytical balance, onto a tared weighing paper, 0.5 g (60.0005 g) oflithium borate powder. Sprinkle the lithium borate evenly over the ash. Use platinum tipped tongs to place the plati
