ASTM D5186-2003(2009) Standard Test Method for Determination of Aromatic Content and Polynuclear Aromatic Content of Diesel Fuels and Aviation Turbine Fuels by Supercritical Fluid .pdf

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1、Designation: D 5186 03 (Reapproved 2009)Standard Test Method forDetermination of the Aromatic Content and PolynuclearAromatic Content of Diesel Fuels and Aviation Turbine FuelsBy Supercritical Fluid Chromatography1This standard is issued under the fixed designation D 5186; the number immediately fol

2、lowing the designation 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 () indicates an editorial change since the last revision or reapproval.1. Scope1.1 This test metho

3、d covers the determination of the totalamounts of monoaromatic and polynuclear aromatic hydrocar-bon compounds in motor diesel fuels, aviation turbine fuels,and blend stocks by supercritical fluid chromatography (SFC).The range of aromatics concentration to which this test methodis applicable is fro

4、m 1 to 75 mass %. The range of polynucleararomatic hydrocarbon concentrations to which this test methodis applicable is from 0.5 to 50 mass %.1.2 The values stated in SI units are to be regarded asstandard. The values stated in inch-pound units are for infor-mation only.1.3 This standard does not pu

5、rport 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 regulatory limitations prior to use.2. Referenced Documents2.1 ASTM Standards:2D

6、 1319 Test Method for Hydrocarbon Types in LiquidPetroleum Products by Fluorescent Indicator AdsorptionD 1655 Specification for Aviation Turbine FuelsD 2425 Test Method for Hydrocarbon Types in MiddleDistillates by Mass SpectrometryD 6299 Practice for Applying Statistical Quality Assuranceand Contro

7、l Charting Techniques to Evaluate AnalyticalMeasurement System Performance3. Terminology3.1 Definitions of Terms Specific to This Standard:3.1.1 critical pressure, nthat pressure needed to condensea gas at the critical temperature.3.1.2 critical temperature, nthe highest temperature atwhich a gaseou

8、s fluid may be converted to a liquid by meansof compression.3.1.3 mononuclear aromatic hydrocarbons, nhydro-carbon compounds containing exactly one aromatic ring. Thisgroup includes benzene, alkyl-substituted benzenes, indans,tetralins, alkyl-substituted indans, and alkyl-substituted tetra-lins.3.1.

9、4 polynuclear aromatic hydrocarbons, nall hydrocar-bon compounds containing two or more aromatic rings. Theserings may be fused as in naphthalene and phenanthrene, orseparate as in biphenyl.3.1.5 restrictor, na device, attached to the outlet of achromatographic column, to restrict the mobile phase f

10、lowsuch that the mobile phase is maintained in the supercriticalstate throughout the chromatographic column.3.1.6 supercritical fluid, na fluid maintained in a thermo-dynamic state above its critical temperature and critical pres-sure.3.1.7 supercritical fluid chromatography, na class ofchromatograp

11、hy that employs supercritical fluids as mobilephases.4. Summary of Test Method4.1 A small aliquot of the fuel sample is injected onto apacked silica adsorption column and eluted using supercriticalcarbon dioxide mobile phase. Monoaromatics and polynucleararomatics in the sample are separated from no

12、naromatics anddetected using a flame ionization detector.4.2 The detector response to hydrocarbons is recordedthroughout the analysis time. The chromatographic areascorresponding to the monoaromatic, polynuclear aromatic, and1This test method is under the jurisdiction of ASTM Committee D02 onPetrole

13、um Products and Lubricants and is the direct responsibility of SubcommitteeD02.04.0C on Liquid Chromatography.Current edition approved April 15, 2009. Published July 2009. Originallyapproved in 1991. Last previous edition approved in 2003 as D 518603.2For referenced ASTM standards, visit the ASTM we

14、bsite, www.astm.org, orcontact ASTM Customer Service at serviceastm.org. For Annual Book of ASTMStandards volume information, refer to the standards Document Summary page onthe ASTM website.1Copyright ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959, United St

15、ates.nonaromatic components are determined and the mass %content of each of these groups in the fuel is calculated by areanormalization.5. Significance and Use5.1 The aromatic hydrocarbon content of motor diesel fuelsis a factor that can affect their cetane number and exhaustemissions. The aromatic

16、hydrocarbon content and the naphtha-lenes content of aviation turbine fuels affect their combustioncharacteristics and smoke-forming tendencies. These proper-ties represent specifications for aviation turbine fuels (seeSpecification D 1655).5.2 The United States Environmental Protection Agency(USEPA

17、) regulates the aromatic content of diesel fuels. Cali-forniaAir Resources Board (CARB) regulations place limits onthe total aromatics content and polynuclear aromatic hydrocar-bon content of motor diesel fuel, thus requiring an appropriateanalytical determination to ensure compliance with the regu-

18、lations. Producers of diesel fuels will require similar determi-nations for process and quality control. This test method can beused to make such determinations.5.3 This test method is applicable to materials in the boilingrange of motor diesel fuels and is unaffected by fuel coloration.Test Method

19、D 1319, which has been mandated by the USEPAfor the determination of aromatics in motor diesel fuel,excludes materials with final boiling points greater than 315C(600F) from its scope. Test Method D 2425 is applicable tothe determination of both total aromatics and polynucleararomatic hydrocarbons i

20、n diesel fuel, but is much more costlyand time-consuming to perform.5.4 Results obtained by this test method have been shown tobe statistically more precise than those obtained from TestMethod D 1319 for typical diesel fuels, and this test methodhas a shorter analysis time.3Cooperative study data4ha

21、vefound this test method to be more precise than the publishedprecision of Test Method D 1319 when applied to aviationturbine fuels and diesel fuels. Results from this test method fortotal polynuclear aromatic hydrocarbons are also expected tobe at least as precise as those of Test Method D 2425.6.

22、Apparatus6.1 Supercritical Fluid Chromatograph (SFC)Any SFCinstrumentation can be used that has the following capabilitiesand meets the performance requirements in Section 8.6.1.1 PumpThe SFC instrumentation must include apump capable of delivering supercritical carbon dioxide to thecolumn without p

23、ressure fluctuations and at constant flow. Thepump is typically a single-stroke-type (syringe) pump or ahighly dampened reciprocating pump with pressure fluctua-tions not exceeding 60.3 % of the operating pressure.6.1.2 DetectorThis test method is limited to the use of theflame ionization detector (

24、FID). The detector must havesufficient sensitivity to detect 0.1 mass % toluene in hexade-cane under instrument conditions employed in this test method.6.1.3 Column Temperature ControlThe chromatographmust be capable of column temperature control of at least60.5C (1F) at the operating temperature.6.

25、1.4 Sample Inlet SystemA liquid sample injection valveis required, capable of reproducibly introducing samples in the0.05 to 0.50-L liquid volume range. The inlet system shouldbe operated at between 25 and 30C. The sample inlet systemmust be connected to the chromatographic column so that lossof chr

26、omatographic efficiency is avoided.6.1.5 Post-column RestrictorA device capable of main-taining mobile phase supercritical conditions within the col-umn and up to the detector inlet must be connected to the endof the column.6.1.6 ColumnAny liquid or supercritical fluid chromato-graphic column may be

27、 used that provides separation ofnonaromatic, monoaromatic, and polynuclear aromatic hydro-carbons and meets the performance requirements of Section 8.Some columns and conditions that have been used successfullyare shown in Table 1.6.1.7 IntegratorMeans must be provided for the determi-nation of bot

28、h discrete chromatographic peak areas and theaccumulated area under the chromatogram. This can be done3Supporting data (obtained in a comparison study of Test Methods D 1319 andD 5186) have been filed at ASTM International Headquarters and may be obtainedby requesting Research Report RR: D02-1276.4S

29、upporting data have been filed at ASTM International Headquarters and maybe obtained by requesting Research Report RR: D02-1388.TABLE 1 Typical Operating ConditionsParameter A B C DColumn Vendor Chromegasphere Suprex YMC Hewlett-PackardPacking SI 60 Petro-Pak SASI 60 HP-HydrocarbonLength (mm) 250 25

30、0 500 250ID (mm) 2 2 1 4.6Particle size, mm 5 5 10 5Temperature, C 30 40 30 28CO2pressure, atm 115 125 115 197BFlow rate, mL/minC40 37 33 20Injection, L 0.1 0.1 0.06 0.5FID, temperature, C 350 385 350 350Air, mL/min 300 800 280 400H2, mL/min 50 80 33 50Air makeup, mL/min 15 n/a n/a n/aAnalysis time,

31、 min 1520 15 24 5ATrademark.BPost-column (downstream) pressure regulation.CDecompressed, gaseous CO2flow, measured at column exit.D 5186 03 (2009)2by means of a computer or electronic integrator. The computeror integrator must have the capability of correcting for baselineshifts during the run.7. Re

32、agents and Materials7.1 Purity of ReagentsReagent grade chemicals shall beused in all tests. Unless otherwise indicated, it is intended thatall reagents conform to the specifications of the Committee onAnalytical Reagents of the American Chemical Society wheresuch specifications are available.5Other

33、 grades may be used,provided it is first ascertained that the reagent is of sufficientlyhigh purity to permit its use without lessening the accuracy ofthe determination.7.2 AirZero grade (hydrocarbon-free) is used as the FIDoxidant. (WarningAir is usually supplied as a compressedgas under high press

34、ure and supports combustion.)7.3 Carbon Dioxide (CO2)Supercritical fluid chromato-graphic grade, 99.99 % minimum purity, supplied pressurizedin a cylinder equipped with a dip tube for removal of liquidCO2.(WarningLiquid at high pressure. Release of pressureresults in production of extremely cold sol

35、id CO2and gas,which can dilute available atmospheric oxygen.)7.4 Check StandardA commercial standard reference ma-terial, which has accepted reference values, in accordance within Section 6 on Reference Materials in Practice D 6299.Alternatively, samples subjected to round robin may be used ascheck

36、standards. It is important that the standard deviation ofthe values of the laboratory exchange program not be statisti-cally greater than the reproducibility for the test method.7.5 HydrogenHydrogen of high quality (hydrocarbon-free) is used as the fuel for the flame ionization detector.(WarningHydr

37、ogen is usually supplied under high pressureand is extremely flammable.)7.6 Performance MixtureA quantitative mixture of ap-proximately 75 mass % hexadecane (n-C16), 20 mass %toluene, 3 mass % tetralin (1,2,3,4-tetrahydronaphthalene), and2 mass % naphthalene is used for performance checks.7.7 Qualit

38、y Control SampleAhomogeneous material hav-ing similar physical and chemical properties to the samples tobe analyzed. The choice of such material should be guided bySection 6 on Reference Materials in Practice D 6299. Ex-amples of such material can be motor diesel fuel, aviationturbine fuel or other

39、typical samples containing aromatics andpolynuclear aromatics similar to the samples to be analyzed.8. Preparation of Apparatus8.1 Install the SFC instrumentation in accordance with themanufacturers instructions. System operating conditions willdepend upon the column used and optimization of perfor-

40、mance. Conditions listed in Table 1 have been used success-fully. If the performance characteristics in terms of retentionand resolution, specified in 8.2, are not achieved, modify thetemperature, pressure, or mobile phase flow rate to achievecompliance. A column of low activity may be reactivated b

41、ysolvent rinsing using established liquid chromatography acti-vation techniques.NOTE 1This temperature can be increased (up to 40C) if theresolution between the monoaromatics and polynuclear aromatics is notsatisfactory. Lower temperatures are suggested to improve resolutionbetween nonaromatics and

42、monoaromatics.8.2 System Performance:8.2.1 ResolutionAnalyze the performance mixture pre-pared in 7.6. The resolution between the nonaromatics andmonoaromatics (RNM) must be at least four and resolutionbetween the monoaromatics and polynuclear aromatics (RMD)must be at least two when calculated in a

43、ccordance with thefollowing equations:RNM52 3 t22 t1!1.699 3 y21 y1!(1)RMD52 3 t42 t3!1.699 3 y41 y3!(2)where:t1= time for the n-C16peak apex, s,t2= time for the toluene peak apex, s,t3= time for the tetralin peak apex, s,t4= time for the naphthalene peak apex, s,y1= peak width at half height of n-C

44、16peak, s,y2= peak width at half height of toluene, s,y3= peak width at half height of tetralin, s, andy4= peak width at half height of naphthalene, s.8.2.2 Retention Time ReproducibilityRepeated injectionsof the performance mixture must show a retention timerepeatability (maximum difference between

45、 duplicate runs) ofnot more than 0.5 % for n-C16and toluene peaks.8.2.3 Detector Accuracy TestThis test method assumesthat the FID response approximates the theoretical unit carbonresponse. To verify this assumption, analyze the performancemixture and calculate the response factors, relative to hexa

46、de-cane (RRFi), for each of the components in the performancemix, using the following equations:RFi5AiMi(3)RRFi5RFiRFC16(4)where:Ai= Component i in performance mix, area %,Mi= Component i in performance mix, known mass%,RFi= response factor of Component i,RFC16= response factor of hexadecane in perf

47、ormancemix, andRRFi= relative response factor of Component i.These values can then be compared to the theoreticalresponse factor for each component in the performance mix ascalculated by the following equation:RRFtheo5S12.01 3 nMWD3S226.412.01 3 16D(5)5Reagent Chemicals, American Chemical Society Sp

48、ecifications, 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 Pharmacopeiaand National Formulary, U.S. Pharmacopeial Con

49、vention, Inc. (USPC), Rockville,MD.D 5186 03 (2009)3where:12.01 = atomic mass of carbon,n = number of carbon atoms in component molecule,MW = molecular mass of component,226.4 = molecular mass of hexadecane, and16 = number of carbon atoms in hexadecane molecule.The measured RRF for each component in the test mixturemust be within 610 % of the theoretical value as calculatedwith Eq 5 or summarized in Table 2. If this is not attained, itwill be necessary to vary the injection volume, restrictorposition, or detector gas flows, or combinatio