1、Designation: D5443 04 (Reapproved 2009)1Standard Test Method forParaffin, Naphthene, and Aromatic Hydrocarbon TypeAnalysis in Petroleum Distillates Through 200C by Multi-Dimensional Gas Chromatography1This standard is issued under the fixed designation D5443; the number immediately following the des
2、ignation 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.1NOTEUpdated vendor and product footnotes
3、 editorially in December 2009.1. Scope1.1 This test method covers the determination of paraffins,naphthenes, and aromatics by carbon number in low olefinichydrocarbon streams having final boiling points of 200C orless. Hydrocarbons with boiling points greater than 200C andless than 270C are reported
4、 as a single group. Olefins, ifpresent, are hydrogenated and the resultant saturates areincluded in the paraffin and naphthene distribution. Aromaticsboiling at C9and above are reported as a single aromatic group.1.2 This test method is not intended to determine individualcomponents except for benze
5、ne and toluene that are the onlyC6and C7aromatics, respectively, and cyclopentane, that is theonly C5naphthene. The lower limit of detection for a singlehydrocarbon component or group is 0.05 mass %.1.3 This test method is applicable to hydrocarbon mixturesincluding virgin, catalytically converted,
6、thermally converted,alkylated and blended naphthas.1.4 The values stated in SI units are to be regarded asstandard. No other units of measurement are included in thisstandard.1.5 This standard does not purport to address all of thesafety concerns, if any, associated with its use. It is theresponsibi
7、lity 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. Specific precau-tionary statements are given in Section 7 and Table 1.2. Referenced Documents2.1 ASTM Standards:2D4057 Practice for Manual
8、Sampling of Petroleum andPetroleum ProductsD4307 Practice for Preparation of Liquid Blends for Use asAnalytical Standards3. Summary of Test Method3.1 A representative sample is introduced into a gas chro-matographic system containing a series of columns and switch-ing valves. As the sample passes th
9、rough a polar column, thepolar aromatic compounds, bi-naphthenes, and high boiling(200C) paraffins and naphthenes are retained. The fractionnot retained elutes to a platinum column, that hydrogenatesolefins, if present, in this fraction, and then to a molecular sievecolumn which performs a carbon nu
10、mber separation based onmolecular structure, that is, naphthenes and paraffins. The1This test method is under the jurisdiction of ASTM Committee D02 onPetroleum Products and Lubricants and is the direct responsibility of SubcommitteeD02.04.0L on Gas Chromatography Methods.Current edition approved De
11、c. 1, 2009. Published February 2010. Originallyapproved in 1993. Last previous edition approved in 2004 as D544304. DOI:10.1520/D5443-04R09E01.2For referenced ASTM standards, visit the ASTM website, www.astm.org, orcontact ASTM Customer Service at serviceastm.org. For Annual Book of ASTMStandards vo
12、lume information, refer to the standards Document Summary page onthe ASTM website.TABLE 1 Hydrocarbon Test MixtureHydrocarbons WarningCyclopentane (WarningExtremely Flammable. Harmful if inhaled.)Pentane (WarningExtremely Flammable. Harmful if inhaled.)Cyclohexane (WarningExtremely Flammable. Harmfu
13、l if inhaled.)2,3-Dimethylbutane (WarningExtremely Flammable. Harmful if inhaled.)Hexane (WarningExtremely Flammable. Harmful if inhaled.)1-Hexene (WarningExtremely Flammable. Harmful if inhaled.)Methylcyclohexane (WarningExtremely Flammable. Harmful if inhaled.)4-Methyl-1-hexene (WarningExtremely F
14、lammable. Harmful if inhaled.)Heptane (WarningFlammable. Harmful if inhaled.)1,cis-2-Dimethylcyclohexane (WarningExtremely Flammable. Harmful ifinhaled.)2,2,4-Trimethylpentane (iso-octane) (WarningFlammable. Harmful if inhaled.)Octane (WarningFlammable. Harmful if inhaled.)1,cis-2,cis-4-Trimethylcyc
15、lohexane (WarningFlammable. Harmful if inhaled.)Nonane (WarningFlammable. Harmful if inhaled.)Decane (WarningFlammable. Harmful if inhaled.)Undecane (WarningFlammable. Harmful if inhaled.)Dodecane (WarningFlammable. Harmful if inhaled.)Benzene (WarningExtremely Flammable. Harmful if inhaled.)Methylb
16、enzene (Toluene) (WarningFlammable. Harmful if inhaled.)trans-Decahydronaphthalene (Decalin) (WarningFlammable. Harmful ifinhaled.)Tetradecane (WarningHarmful if inhaled.)Ethylbenzene (WarningExtremely Flammable. Harmful if inhaled.)1,2-Dimethylbenzene (o-Xylene) (WarningExtremely Flammable. Harmful
17、 ifinhaled.)Propylbenzene (WarningExtremely Flammable. Harmful if inhaled.)1,2,4-Trimethylbenzene (WarningExtremely Flammable. Harmful if inhaled.)1,2,3-Trimethylbenzene (WarningExtremely Flammable. Harmful if inhaled.)1,2,4,5-Tetramethylbenzene (WarningFlammable. Harmful if inhaled.)Pentamethylbenz
18、ene (WarningHarmful if inhaled.)1Copyright ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959, United States.fraction remaining on the polar column is further divided intothree separate fractions that are then separated on a non-polarcolumn by boiling point. Elu
19、ting compounds are detected by aflame ionization detector.3.2 The mass concentration of each group is determined bythe multiplication of detected peak areas by flame ionizationdetector response factors and normalization to 100 %.4. Significance and Use4.1 A knowledge of the composition of hydrocarbo
20、n refin-ery streams is useful for process control and quality assurance.4.2 Aromatics in gasoline are soon to be limited by federalmandate. This test method can be used to provide suchinformation.5. Interferences5.1 Chemicals of a non-hydrocarbon composition may elutewithin the hydrocarbon groups, d
21、epending on their polarity,boiling point, and molecular size. Included in this group areethers (for example, methyl-tertiary butyl ether) and alcohols(for example, ethanol).6. Apparatus6.1 ChromatographA gas chromatograph capable of iso-thermal operation at 130 6 0.1C. The gas chromatographmust cont
22、ain the following:6.1.1 A heated flash vaporization sample inlet system ca-pable of operation in a splitless mode.6.1.2 Associated gas controls with adequate precision toprovide reproducible flows and pressures.6.1.3 A flame ionization detection system optimized for usewith packed columns and capabl
23、e of the following:Isothermal temperature operation 150 to 170CSensitivity 0.015 coulombs/gMinimum detectability 5 3 1012g carbon/secondLinearity 107Some instruments will produce a non-linear response forbenzene, above approximately 5.5 mass %, and for tolueneabove approximately 15 mass %. The linea
24、rity of thesecomponents above these concentrations must be verified withappropriate blends. Where non-linearity has been shown toexist, samples, that contain no higher than C13, can be analyzedif the sample is diluted with n-C15and the instrument isequipped with a prefractionating column. The sample
25、 may alsobe diluted with a component that is not present in the sampleand this component will then not be included in the normalizedreport.6.2 Sample Introduction SystemManual or automatic liq-uid sample system operated in a splitless mode. Although thistest method is intended primarily for use with
26、 syringe sampleinjection, automatic sampling valves have also been foundsatisfactory. Devices capable of a reproducible injection vol-ume of 0.1 to 0.5 L are suitable. The sample introductionsystem must be capable of heating the sample to a temperaturethat ensures total sample vaporization. A temper
27、ature range of120 to 180C has been found suitable.6.3 Electronic Data Acquisition SystemThe data acquisi-tion and integration device used for detection and integrationmust meet or exceed the following specifications:6.3.1 Capacity for at least 75 peaks for each analysis,6.3.2 Normalized area percent
28、 calculation,6.3.3 Noise and spike rejection capability,6.3.4 Sampling rates for fast (2 s) peaks,6.3.5 Peak width detection for narrow and broad peaks, and6.3.6 Perpendicular drop and tangent skimming as required.6.4 Independent Temperature ControlThis test methodrequires the temperature control of
29、 five columns, columnswitching valves and sample lines. The columns consist ofpolar, non-polar, Tenax3, platinum, and molecular sieve col-umns. The specifications for these columns are listed in Table2. The polar column, non-polar column, column switchingvalves, and sample lines require isothermal o
30、peration at atemperature equivalent to the temperature of the gas chromato-graph oven. These components may be located in the gaschromatograph oven. The Tenax3column, platinum column,and molecular sieve column require operation at temperaturesother than the gas chromatograph oven temperature. Thesec
31、olumns may be temperature controlled by any means that willmeet the following specifications:6.4.1 Ability to control the temperature of the Tenax3column within a range from 60 to 280C, with a tolerance of65C at any point. The time required to heat this columnbetween any two points must be no more t
32、han 1 min. The timerequired to cool this column between any two points must beno more than 5 min,3Tenax is a registered trademark of AKZO, Velperiveg 76, P.O. Box 9300, 6800SB Arnhem, The Netherlands.TABLE 2 Typical Column SpecificationsSpecificationColumn TypePolar Non-Polar Tenax3Molsieve Platinum
33、Column length, m 3 4 0.16 to 0.18 1.8 0.002 to 0.06Column inside diameter, mm 2.0 to 2.1 1.8 to 2.0 2.5 1.6 to 2.0 1.6Liquid phase OV-275AOV-101A. . .Percent liquid phase 30 45 . . .Support material ChromasorbBChromasorbB. . .PAW WAW . . .Packing material . . Tenax3Molecular sieve 13XC,D.Mesh size 6
34、0/80 80/100 80/100 . .AOV- 101 and OV-275 are registered trademarks of Ohio Valley Specialty Chemical Co., 115 Industry Rd., Marietta, OH 45750.BChromasorb is a registered trademark of World Minerals, Corp., Santa Barbara, CA.CSodium form of molecular sieve 13X.DMay also contain a mix of molecular s
35、ieves 13X and 5A to separate normal and iso-paraffins.D5443 04 (2009)126.4.2 Ability to control the temperature of the molecularsieve column within a range from 100 and 490C, with atolerance of 610C at any point. The time required to heat thiscolumn between any two points must be no more than 10 min
36、.The time required to cool this column from 450 to 100C mustbe no more than 15 min, and6.4.3 Ability to control the platinum column within atemperature range of 170 and 350C. During routine analysis,this column is operated within a temperature range of 170 to220C.7. Materials7.1 Carrier GasesFor car
37、rier gases, it is recommended toinstall commercial active oxygen scrubbers and water dryers,such as molecular sieves, ahead of the instrument to protect thesystems chromatographic columns. Follow supplier instruc-tions in the use of such gas purifiers and replace as necessary.7.1.1 Hydrogen, 99.995
38、% minimum purity, 0.1 ppm H2O.(WarningExtremely flammable gas under high pressure.)7.1.2 Helium, 99.995 % minimum purity, 0.1 ppm H2O.(WarningCompressed gas under high pressure.)7.2 Detector Gases:7.2.1 Hydrogen, 99.99 % minimum purity. (WarningExtremely flammable gas under high pressure.)7.2.2 Air,
39、 less than 10 ppm each of total hydrocarbons andwater. (WarningCompressed gas under high pressure.)7.3 Valve Actuation GasThis test method permits the useof any type of valve switching or valve actuation. Whenpneumatic valves are used, air of any grade that will result inno water condensation or wil
40、l not introduce oil or othercontaminates in the switching valves may be used. Air from apiston operated compressor equipped with a water and oilseparator has been found suitable. Column switching valvesthat do not require air to operate do not have this airrequirement.7.4 ColumnsFive columns, as des
41、cribed in Table 2. Thesecolumn specifications are to be considered as guidelines andhave been found to be acceptable. Other materials or combi-nations of materials may also provide acceptable performance.The suitability of each column is determined by test criteria asdefined in Section 8.NOTE 1It is
42、 not the intention of this test method to include detailedcolumn preparation steps. Columns may be prepared in any way thatfollows accepted safety practices and results in columns that will meet theperformance requirements of Section 9.7.5 ValvesThis test method uses valves for columnswitching and f
43、low switching. Any commercially availablevalves may be used that are intended for, or adapted for use ingas chromatography that meet the following specifications:7.5.1 The column switching valves are generally installed inthe gas chromatograph oven. These valves must be capable ofcontinuous operatio
44、n at the operating temperature of the GCoven.7.5.2 Materials used in the construction of the valves mustbe unreactive to hydrocarbons present in the sample underanalysis conditions. Stainless steel, PFA, and vespel materialshave been found suitable.7.5.3 Valves must be sized such that they offer lit
45、tle restric-tion to carrier gas flow under the analysis conditions defined inthis test method.7.5.4 Care must be taken to prevent the introduction of anyform of foreign material or contaminant into the valve that mayadversely affect its performance.7.6 Hydrocarbon Test MixtureA quantitative syntheti
46、cmixture of pure hydrocarbons, an example of which is identi-fied in Table 1, is used to tune the instrument analysisconditions and establish that the instrument is performingwithin specifications. Individual hydrocarbon components, inaddition to those listed in Table 1, may be used to aid in theana
47、lysis. The concentration level of each component in thehydrocarbon test mixture is not critical as long as the concen-tration is accurately known. Percentage ranges from 1.0 to 6.0mass % have been found suitable. Impurities in the individualcomponents may have an adverse effect on the quantitativeas
48、pect of the analysis. If an impurity is of the same carbonnumber and basic molecular structure as the main componentitself, it will be correctly grouped and quantitated within thegroup. As an example, isobutylcyclopentane and isopropylcy-clohexane will both be determined as C9naphthenes. Each ofthe
49、individual hydrocarbon components used for this testmixture must have a minimum purity level of 99 mol %. Referto Practice D4307 for instructions on the preparation of liquidblends for use as analytical standards.7.7 Gas Flows and Pressures:7.7.1 Carrier Gases:7.7.1.1 The helium carrier gas through the injection port,polar column, platinum column and molecular sieve column isflow controlled. Flow rates of 16 to 23 mL/min have beenfound suitable. A helium supply pressure of 620 kDa (90 psi)has been found suitable to meet
