1、Designation: D5291 09Standard Test Methods forInstrumental Determination of Carbon, Hydrogen, andNitrogen in Petroleum Products and Lubricants1This standard is issued under the fixed designation D5291; the number immediately following the designation indicates the year oforiginal adoption or, in the
2、 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 These test methods cover the instrumental determinationof carbon, hydrogen, and nitrog
3、en 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 for carbon andhydrogen and nitrogen analysis. The
4、se 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 0.75 mass % nitrogen, or both,such as gasoline, jet
5、fuel, naphtha, diesel fuel, or chemicalsolvents.1.3.1 However, using Test Method D levels of 0.1 mass%nitrogen in lubricants could be determined.1.4 These test methods are not recommended for the analy-sis of volatile materials such as gasoline, gasoline-oxygenateblends, or gasoline type aviation tu
6、rbine fuels.1.5 The results of these tests can be expressed as mass %carbon, hydrogen or nitrogen.1.6 The values stated in SI units are to be regarded asstandard. No other units of measurement are included in thisstandard.1.7 This standard does not purport to address all of thesafety concerns, if an
7、y, 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:2D4057 Practice for Manual Sampling of Petroleum an
8、dPetroleum ProductsD4177 Practice for Automatic Sampling of Petroleum andPetroleum ProductsD6299 Practice for Applying Statistical Quality Assuranceand Control Charting Techniques to Evaluate AnalyticalMeasurement System Performance3. Summary of Test Methods3.1 In these test methods, carbon, hydroge
9、n, and nitrogenare determined concurrently in a single instrumental procedure.With some systems, the procedure consists of simply weighinga portion of the sample, placing the portion in the instrument,and initiating the (subsequently automatic) analytical process.In other systems, the analytical pro
10、cess, to some degree, ismanually controlled.3.2 The actual process can vary substantially from instru-ment to instrument, 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 su
11、bject materials (in theirentirety) to carbon dioxide, water vapor, and elemental nitro-gen, respectively, and3.2.2 The subsequent, 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 durin
12、g combustion of thesample at an elevated temperature in an atmosphere of purifiedoxygen. Here, a variety of gaseous materials 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,
13、as required),3.3.3 Water vapor from the oxidation of (the remaining)organic hydrogen and the liberation of moisture,3.3.4 Nitrogen and nitrogen oxides from the oxidation oforganic nitrogen, and3.3.5 Sulfur oxides from the oxidation of organic sulfur. Insome systems, sulfurous and sulfuric acids can
14、also be obtainedfrom a combination of the sulfur oxides and the water vapor.1These 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 Dec. 1, 2009.
15、Published January 2010. Originallyapproved in 1992. Last previous edition approved in 2007 as D529102 (2007).DOI: 10.1520/D5291-09.2For referenced ASTM standards, visit the ASTM website, www.astm.org, orcontact ASTM Customer Service at serviceastm.org. For Annual Book of ASTMStandards volume informa
16、tion, refer to the standards Document 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.3.4 There are several accepted ways of isolating
17、the desiredgaseous products and quantitatively determining them. Theseare as follows:3.4.1 Test Method A3,4From the combustion product gasstream, oxides 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
18、 copper train to removeoxygen, and reduce NOxto N2, over NaOH to remove CO2,and over magnesium perchlorate to remove H2O. The remain-ing elemental nitrogen is measured by the thermal conductivitycell. Simultaneously, but separately from the nitrogen measure-ment, the carbon and hydrogen selective in
19、frared cells measurethe CO2and H2O levels.3.4.2 Test Method B4,5 From the combustion product gasstream (which is cleaned from sulfur oxides, excess oxygen,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, te
20、mperature, and pressure. Afterhomogenization, the chamber is depressurized to allow thegases to pass through a heated column, where the gasesseparate as 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
21、 Method C4,6The combustion product gasstream, after full oxidation of component gases, is passed overheated copper to remove excess oxygen and reduce NOxto N2gas. The gases are then passed through a heated chromato-graphic column to separate and elute N2,CO2, and H2O in thatorder. The individual elu
22、ted gases are measured by a thermalconductivity detector.3.4.4 Test Method D4,7The organic samples are packedinto lightweight containers of oxidizable metal and dropped atpreset times into a vertical quartz, inconel, or stainless steelreactor, heated at about 1050C, through which a constant flowof h
23、elium is maintained. When the samples are introduced, thehelium stream is temporarily enriched with pure oxygen. Flashcombustion takes place primed by the oxidation of the con-tainer. Quantitative combustion is then achieved by passing thegases over chromium trioxide and cupric oxide. The mixture of
24、the combustion gases is transferred over copper at about 640C(840C in a steel reactor) to eliminate the excess of oxygen;then without stopping, it is introduced into the chromato-graphic column heated to about 120C (50C for Flash EA1112 units). The individual components are then separated byelution
25、in the order nitrogen, carbon dioxide, and water by adedicated Poropak column (active carbon column for Flash EA1112 units for nitrogen determination) and measured by athermal conductivity detector. With dedicated software thepercentage of elements present in the sample are calculated.The instrument
26、 is calibrated with standard pure organic com-pounds. K-factors or linear regression can be used for instru-ment calibration. The typical operator analysis time for a singlesample is about 4 min, and the total elapsed time is 8 min.3.5 In all cases, the concentrations of carbon, hydrogen andnitrogen
27、 are calculated as functions 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 inclu
28、ded in the instrumentation utilized 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 de
29、termining the complex nature 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
30、itsconcentration can be used 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.
31、5. Apparatus5.1 Since a variety 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 fo
32、r combustion of the sample must 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 conditi
33、ons that affect complete combustion 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
34、) nitrogen present asnitrogen oxides.5.2.3 The water vapor and nitrogen so obtained must beincluded with the materials originally present in these aliquots.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
35、, MI49085.4If you are aware of alternative suppliers, please provide this information toASTM International Headquarters. 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, 2
36、400 series and CEC240XA and 440 instruments known to the committee at this time is Perkin ElmerCorporation, 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,200
37、90 Rodano, Milan, Italy.7The sole source of supply of the Flash EA instruments known to the committeeat this time is Thermo Fisher Scientific, Strada Rivoltana, 20090 Milano, Italy.D5291 0925.2.4 Additional treatment of the aliquots (prior to detec-tion) depends on the detection scheme utilized for
38、the instru-ment (see Note 1).NOTE 1These additional treatments 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.
39、2.5.1 The detectors must provide linear responses withrespect 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 the
40、se concentrations.5.2.6 Such provisions can be integral to the 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 detecto
41、r responses.5.3 Additionally consumables needed for the analyses in-clude:5.3.1 Tin Capsules, large and small,5.3.2 Ceramic Crucibles,5.3.3 Copper Capsules,5.3.4 Tin Plugs,5.3.5 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,
42、 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 Purity of ReagentsReagent grade chemicals shall beused in all tests. Unless otherwise indicated, it is intended thatall re
43、agents shall conform to the specifications of the Commit-tee on Analytical Reagents of the American Chemical Society,where such specifications are available.8Other grades may beused, provided it is first ascertained that the reagent is ofsufficiently high purity to permit its use without lessening t
44、heaccuracy 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; 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
45、.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 Specified by the InstrumentManufacturer)This specification covers the reagents utilizedto provide for the functional requirements
46、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. Specifically, 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 Mag
47、nesium 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,4,9for liquids.6.4.2 Test Method B4,5:6.4.2.1 EA 1000 Reagent,4,106.4.2.2 Silver Tungstate on MgO,6.4.2.3 Silver Vanadate,6.4.2.4 Quartz Wool,6.4.2.5 Silver
48、 Gauze,6.4.2.6 Copper Oxide,116.4.2.7 Tungstic Oxide,6.4.2.8 Cobalt Oxide,6.4.2.9 Copper Powder,8Reagent Chemicals, American Chemical Society Specifications, AmericanChemical Society, Washington, DC. For Suggestions on the testing of reagents notlisted by the American Chemical Society, see Annual St
49、andards for LaboratoryChemicals, BDH Ltd., Poole, Dorset, U.K., and the United States Pharmacopeiaand National Formulary, U.S. Pharmacopeial Convention, Inc. (USPC), Rockville,MD.9The 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 49085.10The sole source of supply of the EA 1000 Reagent, a registered trademark ofPerkin Elmer, known to the committee at this time is Perkin Elmer Corporation,Main Ave., Norwalk, CT 06856.11The sole source of supply of Cuprox, a registe
