1、Designation: D 1977 03Standard Test Method forNickel and Vanadium in FCC Equilibrium Catalysts byHydrofluoric/Sulfuric Acid Decomposition and AtomicSpectroscopic Analysis1This standard is issued under the fixed designation D 1977; the number immediately following the designation indicates the year o
2、foriginal adoption or, in the case of revision, the year of last revision. A number in parentheses indicates the year of last reapproval. Asuperscript epsilon (e) indicates an editorial change since the last revision or reapproval.1. Scope1.1 This test method covers the determination of nickel andva
3、nadium in equilibrium catalysts where the vanadium andnickel concentrations are greater than 50 and 25 mg/kg,respectively.1.2 The values stated in SI units are to be regarded as thestandard. The values given in parentheses are for informationonly.1.3 This standard does not purport to address all of
4、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 limitations prior to use.2. Referenced Documents2.1 ASTM Standards:2D 1193 Specification for
5、Reagent WaterD 3766 Terminology Relating to Catalysts and CatalysisE 105 Practice for Probability Sampling of MaterialsE 177 Practice for Use of the Terms Precision and Bias inASTM Test MethodsE 288 Specification for Laboratory Glass Volumetric FlasksE 456 Terminology Relating to Quality and Statist
6、icsE 691 Practice for Conducting an Interlaboratory Study toDetermine the Precision of a Test Method2.2 U.S. Federal SpecificationFederal Spec NNN-P-395C Tolerance for Class A Pipets33. Terminology3.1 DefinitionsSee Terminology D 3766.4. Summary of Test Method4.1 The test specimen (as received) is d
7、ecomposed withhydrofluoric and sulfuric acids. After complete volatilization ofthe hydrofluoric acid and cooling, the sulfate salts are diluted tothe appropriate concentration range for analysis by flameatomic absorption, direct current plasma emission, or induc-tively coupled plasma emission spectr
8、oscopies. The instrumentis calibrated with matrix-matched standards. Solutions of thetest specimen are analyzed.5. Significance and Use5.1 This test method is a procedure by which catalystsamples may be compared on an inter- or intra-laboratorybasis. Catalyst producers and user should find this test
9、 methodto be of value.6. Interferences6.1 The enhancement of alumina in the samples are over-come by using matrix-matched standards. Any dilutionsneeded to achieve the working ranges for vanadium and nickelmust contain the same Al2O3(7800 ppm) concentration as thestandards.6.2 If using optical emiss
10、ion, consult tables showing inter-fering line near analyte lines; if significant overlap occurs, onemust apply inter-element correction or choose an alternateemission line.7. Apparatus7.1 Analytical Balance, capable of weighing to nearest 0.1mg.7.2 Hot Plate, capable of maintaining 250 6 10C atsurfa
11、ce.7.3 TFE Fluorocarbon Beaker, 250 mL.7.4 Volumetric Flasks, borosilicate glass, 50, 100, 250, 500,and 1000-mL capacity conforming to Specification E 288.1This test method is under the jurisdiction of ASTM Committee D32 onCatalysts and is the direct responsibility of Subcommittee D32.03 on Chemical
12、Composition.Current edition approved Oct. 1, 2003. Published October 2003. Originallyapproved in 1991. Last previous edition approved in 1998 as D 197798.2For referenced ASTM standards, visit the ASTM website, www.astm.org, orcontact ASTM Customer Service at serviceastm.org. For Annual Book of ASTMS
13、tandards volume information, refer to the standards Document Summary page onthe ASTM website.3Available from Standardization Documents Order Desk, Bldg. 4 Section D, 700Robbins Ave., Philadelphia, PA 19111-5094, Attn: NPODS.1Copyright ASTM International, 100 Barr Harbor Drive, PO Box C700, West Cons
14、hohocken, PA 19428-2959, United States.7.5 Pipettes, borosilicate glass, 5, 10, and 25 mL, conform-ing to Federal Specification NNN-P-395C.7.6 Bottles, polyethylene, 100 and 1000 mL.8. Reagents8.1 Purity of ReagentsReagent grade chemicals shall beused in all tests. Unless otherwise indicated, it is
15、intended thatall reagents conform to the specifications of the Committee onAnalytical Reagents of the American Chemical Society, wheresuch specifications are available.4Other grades may be used,provided it is first ascertained that the reagent is of sufficientpurity to permit its use without lesseni
16、ng the accuracy of thedetermination.8.2 Purity of WaterUnless otherwise indicated, referencesto water shall be understood to mean type IV reagent water, asdefined in Specification D 1193.8.3 Required Reagents:8.3.1 Hydrofluoric Acid (HF), concentrated, 48 %.8.3.2 Sulfuric Acid,(H2SO4), concentrated,
17、 98 %.8.3.3 Sulfuric Acid, 49 volume %, add slowly, while stirring,one part of concentrated H2SO4(98 %) to one part of water,then cool.8.3.4 Hydrochloric Acid, concentrated, 38 %.8.3.5 Hydrochloric Acid, 19 volume %, add slowly, whilestirring, one part of concentrated HCl (38 %) to one part ofwater,
18、 then cool.8.3.6 Nitric Acid (HNO3), concentrated, 70 %.8.3.7 Reference Standard Solution1000 mg/L nickel (seeNote 1).NOTE 1If emission spectrometry is to be used, standards must containno interfering element(s) in concentration(s) great enough to yield aninterference of more than 0.1% of the analyt
19、ical response.8.3.8 Reference Standard Solution1000 mg/L vanadium(see Note 1).8.3.9 Aluminum Chloride, reagent grade, AlCl36H2O8.3.10 Aluminum Stock Solution39 000 mg/L Al2O3dissolve 184.5 grams of AlCl36H2O in water and dilute to 1liter and store in a polyethylene bottle.8.3.11 Hydrogen Peroxide3 %
20、 solution.9. Preparation of Standards9.1 NickelPrepare standard solutions containing 0, 5.0,20.0, and 50.0 mg/L Ni in a matrix of 7800 mg/L Al2O3and10 % hydrochloric acid by transferring 0, 5.0, 20.0, and 50.0mL of the 1000mg/L solution to 1000-mL volumetric flaskscontaining 200 mL of the 39 000mg/L
21、 Al2O3solution and 100mL concentrated hydrochloric acid. Dilute solutions to volumewith distilled water and store in polyethylene bottles.9.2 VanadiumPrepare standard solutions containing 0,10.0, 25.0, 50.0 and 100.0 mg/L V in a matrix of 7800 mg/LAl2O3and 10 % hydrochloric acid by transferring 0, 1
22、0.0, 25.0,50.0, and 100.0 mL of the 1000mg/L solution to 1000-mLvolumetric flasks containing 200 mL of the 39 000 mg/LAl2O3solution and 100 mL concentrated hydrochloric acid.Dilute solutions to volume with distilled water and store inpolyethylene bottles.10. Sampling10.1 The selection of a represent
23、ative analytical samplefrom the bulk material is outside the scope of this test method.Parties using this test method for comparison purposes willhave agreed on the selection of an analytical sample. If asampling procedure is desired, Practice E 105 is recommended.11. Procedure11.1 Weigh three test
24、specimens of approximately 2.0 geach to the nearest 0.1 mg and transfer to 250-mL TFE-fluorocarbon beakers. A reagent blank should be carried alongwith each set of samples.11.2 Add 10 mL 48 % sulfuric acid, 10 mL concentratednitric acid, and 10 mL concentrated hydrofluoric acid.11.3 Transfer beaker
25、and contents to a hot plate (no hotterthan 250C to avoid melting the beaker) and evaporate to neardryness.11.4 Remove beaker from hot plate and cool to ambienttemperature.11.5 Add 20 mL 19 % hydrochloric acid and 30 mL 3%hydrogen peroxide, cover with watch glass and return beaker tohot plate.11.6 He
26、at solution to boiling and continue to boil until allthe salts are dissolved.11.7 After dissolution is complete, remove beaker from hotplate and cool to ambient temperature.11.8 Wash watch glass, catching washings in the beaker, andtransfer solution quantitatively to a 100-mL volumetric flask.Dilute
27、 to volume with water and mix well.11.9 Using direct current argon plasma spectrometry (DCP),inductively coupled argon plasma spectrometry (ICP), oratomic absorption spectrophotometry (AAS), determine con-centration of analytes in solutions of test specimens. If appar-ent concentration is greater th
28、an that of the most concentratedstandard, perform an additional dilution so that result isbracketed by two or more standards.12. Calculations12.1 Calculate the concentration of nickel and vanadium asfollows:mg/L metal 5C 3 DS(1)where:C = Concentration of metal in solution, mg/kgD = Volume equivalent
29、 of dilution used for analysis; ifsolution 10.8 is used directly, D = 100 mL. If a furtherdilution is needed, D = 100 mL 3 V2/V1, where V1isthe aliquot of solution 10.8 and V2is the volume towhich it was diluted.S = Sample mass.4Reagent Chemicals, American Chemical Society Specifications, AmericanCh
30、emical 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 Pharmacopeiaand National Formulary, U.S. Pharmacopeial Convention, Inc. (USPC), Ro
31、ckville,MD.D197703213. Precision and Bias13.1 Test ProgramAn interlaboratory study was con-ducted in which the named property was measured in threeseparate test materials in eight separate laboratories. PracticeE 691, modified for non-uniform data sets, was followed forthe data reduction period.13.2
32、 PrecisionPairs of test results obtained by a proce-dure similar to that described in the study are expected to differin absolute value by less than 2.772 S, where 2.772 S is the95 % probability interval limit on the difference between twotest results, and S is the appropriate estimate of standardde
33、viation. Definitions and usage are given in TerminologyE 456 and Practice E 177, respectively.Test Resultsfor Ni(Consensus Mean)95 % RepeatabilityInterval(Within Laboratory)95 % ReproducibilityInterval(Between Laboratories)208 mg/kg 8 mg/kg(3.9 % of mean)14 mg/kg(6.7 % of mean)152 mg/kg 5 mg/kg(3.3
34、% of mean)24 mg/kg(15.8 % of mean)437 mg/kg 9 mg/kg(2.1 % of mean)31 mg/kg(7.1 % of mean)Test Results for V(Consensus Mean)95 % RepeatabilityInterval(Within Laboratory)95 % ReproducibilityInterval(Between Laboratories)1191 mg/kg 43 mg/kg(3.6 % of mean)201 mg/kg(16.9 % of mean)1898 mg/kg 72 mg/kg(3.8
35、 % of mean)303 mg/kg(16.0 % of mean)3346 mg/kg 82 mg/kg(2.4% of mean)531 mg/kg(15.9 % of mean)13.3 BiasThis test method described is without knownbias since there is by definition no absolute standard forcomparison.14. Keywords14.1 acid decomposition; atomic spectroscopy; ECAT; FCCequilibrium cataly
36、sts; Nickel; VanadiumASTM International takes no position respecting the validity of any patent rights asserted in connection with any item mentionedin this standard. Users of this standard are expressly advised that determination of the validity of any such patent rights, and the riskof infringemen
37、t of such rights, are entirely their own responsibility.This standard is subject to revision at any time by the responsible technical committee and must be reviewed every five years andif not revised, either reapproved or withdrawn. Your comments are invited either for revision of this standard or f
38、or additional standardsand should be addressed to ASTM International Headquarters. Your comments will receive careful consideration at a meeting of theresponsible technical committee, which you may attend. If you feel that your comments have not received a fair hearing you shouldmake your views know
39、n to the ASTM Committee on Standards, at the address shown below.This standard is copyrighted by ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959,United States. Individual reprints (single or multiple copies) of this standard may be obtained by contacting ASTM at the aboveaddress or at 610-832-9585 (phone), 610-832-9555 (fax), or serviceastm.org (e-mail); or through the ASTM website(www.astm.org).D1977033
