1、Designation: D 5291 02 (Reapproved 2007)An American National StandardStandard Test Methods forInstrumental Determination of Carbon, Hydrogen, andNitrogen in Petroleum Products and Lubricants1This standard is issued under the fixed designation D 5291; the number immediately following the designation
2、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 (e) indicates an editorial change since the last revision or reapproval.1. Scope*1.1 These test methods cover the instrum
3、ental determinationof carbon, hydrogen, and nitrogen in laboratory samples ofpetroleum products and lubricants. Values obtained representthe total carbon, the total hydrogen, and the total nitrogen.1.2 These test methods are applicable to samples such ascrude oils, fuel oils, additives, and residues
4、 for carbon andhydrogen and nitrogen analysis. These test methods weretested in the concentration range of at least 75 to 87 mass % forcarbon, at least 9 to 16 mass % for hydrogen, and 0.1 to 2mass % for nitrogen.1.3 The nitrogen test method is not applicable to lightmaterials or those containing 0.
5、75 mass % nitrogen, or both,such as gasoline, jet fuel, naphtha, diesel fuel, or chemicalsolvents.1.4 These test methods are not recommended for the analy-sis of volatile materials such as gasoline, gasoline-oxygenateblends, or gasoline type aviation turbine fuels.1.5 The results of these tests can
6、be expressed as mass %carbon, hydrogen or nitrogen.1.6 The values stated in SI units are to be regarded as thestandard.1.7 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-pri
7、ate safety and health practices and determine the applica-bility of regulatory limitations prior to use.2. Referenced Documents2.1 ASTM Standards:2D 4057 Practice for Manual Sampling of Petroleum andPetroleum ProductsD 4177 Practice for Automatic Sampling of Petroleum andPetroleum ProductsD 6299 Pra
8、ctice for Applying Statistical Quality AssuranceTechniques to Evaluate Analytical Measurement SystemPerformance3. Summary of Test Methods3.1 In these test methods, carbon, hydrogen, and nitrogenare determined concurrently in a single instrumental procedure.With some systems, the procedure consists o
9、f simply weighinga portion of the sample, placing the portion in the instrument,and initiating the (subsequently automatic) analytical process.In other systems, the analytical process, to some degree, ismanually controlled.3.2 The actual process can vary substantially from instru-ment to instrument,
10、 since a variety of means can be utilized toeffect the primary requirements of the test methods. Allsatisfactory processes provide for the following:3.2.1 The conversion of the subject materials (in theirentirety) to carbon dioxide, water vapor, and elemental nitro-gen, respectively, and3.2.2 The su
11、bsequent, quantitative determination of thesegases in an appropriate gas stream.3.3 The conversion of the subject materials to their corre-sponding gases takes place largely during combustion of thesample at an elevated temperature in an atmosphere of purifiedoxygen. Here, a variety of gaseous mater
12、ials are produced,including the following:3.3.1 Carbon dioxide from the oxidation of organic andelemental carbon,3.3.2 Hydrogen halides from organic halides (and organichydrogen, as required),3.3.3 Water vapor from the oxidation of (the remaining)organic hydrogen and the liberation of moisture,3.3.4
13、 Nitrogen and nitrogen oxides from the oxidation oforganic nitrogen, and1These test methods are under the jurisdiction of ASTM Committee D02 onPetroleum Products and Lubricants and are the direct responsibility of Subcommit-tee D02.03 on Elemental Analysis.Current edition approved May 1, 2007. Publi
14、shed July 2007. Originally approvedin 1992. Last previous edition approved in 2002 as D 529102.2For 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 Documen
15、t Summary page onthe ASTM website.1*A Summary of Changes section appears at the end of this standard.Copyright ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959, United States.3.3.5 Sulfur oxides from the oxidation of organic sulfur. Insome systems, sulfurous a
16、nd sulfuric acids can also be obtainedfrom a combination of the sulfur oxides and the water vapor.3.4 There are several accepted ways of isolating the desiredgaseous products and quantitatively determining them. Theseare as follows:3.4.1 Test Method A3,4From the combustion product gasstream, oxides
17、of sulfur are removed with calcium oxide in thesecondary combustion zone. A portion of the remaining mixedgases is carried by helium gas over a hot copper train to removeoxygen, and reduce NOxto N2, over NaOH to remove CO2,and over magnesium perchlorate to remove H2O. The remain-ing elemental nitrog
18、en is measured by the thermal conductivitycell. Simultaneously, but separately from the nitrogen measure-ment, the carbon and hydrogen selective infrared cells measurethe CO2and H2O levels.3.4.2 Test Method B4,5 From the combustion product gasstream (which is cleaned from sulfur oxides, excess oxyge
19、n,etc. as in 3.4.1), the remaining CO2, water vapor, and N2areflushed into a mixing chamber and are thoroughly homog-enized at a precise volume, temperature, and pressure. Afterhomogenization, the chamber is depressurized to allow thegases to pass through a heated column, where the gasesseparate as
20、a function of selective retention times. The sepa-ration occurs in a stepwise steady-state manner for nitrogen,carbon dioxide, and water.3.4.3 Test Method C4,6The combustion product gasstream, after full oxidation of component gases, is passed overheated copper to remove excess oxygen and reduce NOx
21、to N2gas. The gases are then passed through a heated chromato-graphic column to separate and elute N2,CO2, and H2O in thatorder. The individual eluted gases are measured by a thermalconductivity detector.3.5 In all cases, the concentrations of carbon, hydrogen andnitrogen are calculated as functions
22、 of the following:3.5.1 The measured instrumental responses,3.5.2 The values for response per unit mass for the elements(established via instrument calibration), and3.5.3 The mass of the sample.3.6 A capability for performing these computations auto-matically can be included in the instrumentation u
23、tilized forthese test methods.4. Significance and Use4.1 This is the first ASTM standard covering the simulta-neous determination of carbon, hydrogen, and nitrogen inpetroleum products and lubricants.4.2 Carbon, hydrogen, and particularly nitrogen analysesare useful in determining the complex nature
24、 of sample typescovered by this test method. The CHN results can be used toestimate the processing and refining potentials and yields in thepetrochemical industry.4.3 The concentration of nitrogen is a measure of thepresence of nitrogen containing additives. Knowledge of itsconcentration can be used
25、 to predict performance. Somepetroleum products also contain naturally occurring nitrogen.Knowledge of hydrogen content in samples is helpful inaddressing their performance characteristics. Hydrogen tocarbon ratio is useful to assess the performance of upgradingprocesses.5. Apparatus5.1 Since a vari
26、ety of instrumental components and configu-rations can be satisfactorily utilized for these test methods, nospecifications are given here with respect to overall systemdesign.5.2 Functionally, however, the following are specified for allinstruments:5.2.1 The conditions for combustion of the sample m
27、ust besuch that (for the full range of applicable samples) the subjectcomponents are completely converted to carbon dioxide, watervapor (except for hydrogen associated with volatile halides andsulfur oxides), and nitrogen or nitrogen oxides. Generally,instrumental conditions that affect complete com
28、bustion in-clude availability of the oxidant, temperature, and time.5.2.2 Representative aliquots of the combustion gases mustthen be treated:5.2.2.1 To liberate (as water vapor) hydrogen present ashydrogen halides and sulfur oxyacids, and5.2.2.2 To reduce (to the element) nitrogen present asnitroge
29、n oxides.5.2.3 The water vapor and nitrogen so obtained must beincluded with the materials originally present in these aliquots.5.2.4 Additional treatment of the aliquots (prior to detec-tion) depends on the detection scheme utilized for the instru-ment (see Note 1).NOTE 1These additional treatments
30、 can be provided by the instru-mental components utilized to satisfy 5.2.2.5.2.5 The detection system (in its full scope) must deter-mine the analytical gases individually and without interference.Additionally, for each analyte, either:5.2.5.1 The detectors must provide linear responses withrespect
31、to concentration over the full range of possible con-centrations from the applicable samples, or5.2.5.2 The system must include provisions for appropri-ately evaluating nonlinear responses so that they can beaccurately correlated with these concentrations.5.2.6 Such provisions can be integral to the
32、 instrumentation,or they can be provided by (auxiliary) computation schemes.5.2.7 Lastly, except for those systems where the concentra-tion data are output directly, the instrument must include anappropriate readout device for the detector responses.5.3 Additionally consumables needed for the analys
33、es in-clude:5.3.1 Tin Capsules, large and small,3The sole source of supply of the Leco CHN-600 instrument known to thecommittee at this time is Leco Corporation, 3000 Lakeview Ave., St. Joseph, MI49085.4If you are aware of alternative suppliers, please provide this information toASTM International H
34、eadquarters. Your comments will receive careful consider-ation at a meeting of the responsible technical committee1, which you may attend.5The sole source of supply of the Perkin Elmer 240C, 2400 series and CEC240XA and 440 instruments known to the committee at this time is Perkin ElmerCorporation,
35、Main Ave., Norwalk, CT 06856.6The sole source of supply of the Carlo Erba 1106, 1108, and 1500 instrumentsknown to the committee at this time is Carlo Erba Strumentazione, Strada Rivoltana,20090 Rodano, Milan, Italy.D 5291 02 (2007)25.3.2 Ceramic Crucibles,5.3.3 Copper Capsules,5.3.4 Tin Plugs,5.3.5
36、 Tin Boats,5.3.6 Copper Plugs,5.3.7 Aluminum Capsules,5.3.8 Combustion Tubes,5.3.9 Adsorption Tubes,5.3.10 Nickel Capsules, and5.3.11 Reduction Tubes.5.4 Analytical Balance, capable of weighing to the nearest0.00001 g.5.5 Syringes or Pipettes, to transfer the test specimens tocapsules.6. Reagents6.1
37、 Purity of ReagentsReagent grade chemicals shall beused in all tests. Unless otherwise indicated, it is intended thatall reagents shall conform to the specifications of the Commit-tee on Analytical Reagents of the American Chemical Society,where such specifications are available.7Other grades may be
38、used, provided it is first ascertained that the reagent is ofsufficiently high purity to permit its use without lessening theaccuracy of the determination.6.2 Calibration StandardsTable 1 lists the pure organiccompounds most commonly used to calibrate the instrumentsoperated according to 3.4.1-3.4.3
39、; other suitable pure com-pounds can also be used.6.3 Carrier and Combustion Gases:6.3.1 Oxygen, high purity (99.998 %),6.3.2 Helium, high purity (99.995 %),6.3.3 Compressed Air, Nitrogen, or Argon, for operatingpneumatic valves, if needed, and6.3.4 Carbon Dioxide.6.4 Additional Reagents (as Specifi
40、ed by the InstrumentManufacturer)This specification covers the reagents utilizedto provide for the functional requirements cited in 5.2.2 and5.2.3. These reagents can vary substantially for differentinstruments. Consequently, these reagents shall be those rec-ommended by the manufacturer. Specifical
41、ly, these reagentswill be for:6.4.1 Test Method A3,4:6.4.1.1 Sodium Hydroxide Coated Silica,6.4.1.2 Quartz Wool,6.4.1.3 Magnesium Perchlorate,6.4.1.4 Copper Turnings,6.4.1.5 Coated Calcium Oxide (Furnace Reagent),6.4.1.6 Nitrogen Catalyst, and6.4.1.7 Magnesium Oxide,4,8for liquids.6.4.2 Test Method
42、B4,5:6.4.2.1 EA 1000 Reagent,4,96.4.2.2 Silver Tungstate on MgO,6.4.2.3 Silver Vanadate,6.4.2.4 Quartz Wool,6.4.2.5 Silver Gauze,6.4.2.6 Copper Oxide,106.4.2.7 Tungstic Oxide,6.4.2.8 Cobalt Oxide,6.4.2.9 Copper Powder,6.4.2.10 Sodium Hydroxide Coated Silica,6.4.2.11 Alumina,6.4.2.12 Magnesium Perchl
43、orate, and6.4.2.13 Platinum Gauze.6.4.3 Test Method C4,6:6.4.3.1 Quartz Wool,6.4.3.2 Chromic Oxide (oxidation catalyst),6.4.3.3 Silver Coated Cobalt Oxide,6.4.3.4 Reduced Copper (reduction catalyst),6.4.3.5 Magnesium Perchlorate,6.4.3.6 Molecular Sieve,3A116 in. (1.6 mm),6.4.3.7 Sodium Hydroxide Coa
44、ted Silica,6.4.3.8 Chromosorb, (Absorber,11for liquid samples; cal-cined silica), and6.4.3.9 Copper Grains.6.5 Quality Control (QC) Samples, preferably are portionsof one or more liquid petroleum materials that are stable andrepresentative of the samples of interest. These QC samples7Reagent Chemica
45、ls, American Chemical Society Specifications, AmericanChemical Society, Washington, DC. For suggestions on the testing of reagents notlisted by the American Chemical Society, see Analar Standards for LaboratoryChemicals, BDH Ltd., Poole, Dorset, U.K., and the United States Pharmacopeiaand National F
46、ormulary, U.S. Pharmacopeial Convention, Inc. (USPC), Rockville,MD.8The sole source of supply of Com-aid, a registered trademark of Leco, knownto the committee at this time is Leco Corporation, 3000 Lakeview Ave., St Joseph,MI 49085.9The sole source of supply of the EA 1000 Reagent, a registered tra
47、demark ofPerkin Elmer, known to the committee at this time is Perkin Elmer Corporation,Main Ave., Norwalk, CT 06856.10The sole source of supply of Cuprox, a registered trademark of Perkin Elmer,known to the committee at this time is Perkin Elmer Corporation, Main Ave.,Norwalk, CT 06856.11The sole so
48、urce of supply of Chromosorb, a registered trademark of Carlo ErbaStrumentazione, known to the committee at this time is Carlo Erba Strumentazione,Strada Rivoltana, 20090 Rodano, Milan, Italy.TABLE 1 Calibration Standards for CHN Instrumental AnalysisA,BCompoundMolecularFormulaCarbon,Mass%HydrogenMa
49、ss %NitrogenMass %Acetanilide C8H9NO 71.09 6.71 10.36Atropine C17H23NO370.56 8.01 4.84Benzoic acid C7H6O268.84 4.95 . . .Cyclohexanone- C12H14N4O451.79 5.07 20.142,4-dinitrophenylhydrazoneCystine C6H12N2O4S229.99 5.03 11.66Diphenyl C12H1093.46 6.54 . .EDTA C10H16N2O841.10 5.52 9.59Imidazol C3H4N252.92 5.92 41.15Nicotinic acid C6H5NO258.53 4.09 11.38Stearic acid C18H36O275.99 12.76 . .Succinamide C4H8N2O241.37 6.94 24.13Sucrose C12H22O1142.10 6.48 . .Sulphanilamide C6H8N2O2S 41.84 4.68 16.27Triethanol amine C6H15NO348.30 10.13 9.39AThe Merck Index, 10th Edition, Merck and Compa
