1、Designation: D 5443 04An American National StandardStandard 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 D 5443; the number immediately follo
2、wing 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 (e) indicates an editorial change since the last revision or reapproval.1. Scope*1.1 This test metho
3、d 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 as a single group. Olefins, ifpresent, are hydrogenated
4、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 benzene and toluene that are the onlyC6and C7aromatics, respec
5、tively, 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, thermally converted,alkylated and blended naphthas.1.4 Th
6、e values stated in SI units are to be regarded as thestandard. The values given in parentheses are for informationonly.1.5 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. Specific precau-tionary statements are given in Section 7 and Table 1.2. Referenced Documents2.1 ASTM Standards:2D 4057 Practice for Manual Sampling of Petroleum andPetroleum ProductsD 4307 Pract
8、ice 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 through a polar column, thepolar aromatic compounds, bi-
9、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 number separation based onmolecular structure, that is,
10、naphthenes and paraffins. Thefraction remaining on the polar column is further divided intothree separate fractions that are then separated on a non-polarcolumn by boiling point. Eluting compounds are detected by aflame ionization detector.1This test method is under the jurisdiction of ASTM Committe
11、e D02 onPetroleum Products and Lubricants and is the direct responsibility of SubcommitteeD02.04 on Hydrocarbon Analysis.Current edition approved Nov. 1, 2004. Published November 2004. Originallyapproved in 1993. Last previous edition approved in 2003 as D 544393(2003)e1.2For referenced ASTM standar
12、ds, 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 Document Summary page onthe ASTM website.TABLE 1 Hydrocarbon Test MixtureHydrocarbons WarningCyclopentane (WarningExtremely Flamma
13、ble. Harmful if inhaled.)Pentane (WarningExtremely Flammable. Harmful if inhaled.)Cyclohexane (WarningExtremely Flammable. Harmful if inhaled.)2,3-Dimethylbutane (WarningExtremely Flammable. Harmful if inhaled.)Hexane (WarningExtremely Flammable. Harmful if inhaled.)1-Hexene (WarningExtremely Flamma
14、ble. Harmful if inhaled.)Methylcyclohexane (WarningExtremely Flammable. Harmful if inhaled.)4-Methyl-1-hexene (WarningExtremely Flammable. Harmful if inhaled.)Heptane (WarningFlammable. Harmful if inhaled.)1,cis-2-Dimethylcyclohexane (WarningExtremely Flammable. Harmful ifinhaled.)2,2,4-Trimethylpen
15、tane (iso-octane) (WarningFlammable. Harmful if inhaled.)Octane (WarningFlammable. Harmful if inhaled.)1,cis-2,cis-4-Trimethylcyclohexane (WarningFlammable. Harmful if inhaled.)Nonane (WarningFlammable. Harmful if inhaled.)Decane (WarningFlammable. Harmful if inhaled.)Undecane (WarningFlammable. Har
16、mful if inhaled.)Dodecane (WarningFlammable. Harmful if inhaled.)Benzene (WarningExtremely Flammable. Harmful if inhaled.)Methylbenzene (Toluene) (WarningFlammable. Harmful if inhaled.)trans-Decahydronaphthalene (Decalin) (WarningFlammable. Harmful ifinhaled.)Tetradecane (WarningHarmful if inhaled.)
17、Ethylbenzene (WarningExtremely Flammable. Harmful if inhaled.)1,2-Dimethylbenzene (o-Xylene) (WarningExtremely Flammable. Harmful ifinhaled.)Propylbenzene (WarningExtremely Flammable. Harmful if inhaled.)1,2,4-Trimethylbenzene (WarningExtremely Flammable. Harmful if inhaled.)1,2,3-Trimethylbenzene (
18、WarningExtremely Flammable. Harmful if inhaled.)1,2,4,5-Tetramethylbenzene (WarningFlammable. Harmful if inhaled.)Pentamethylbenzene (WarningHarmful if inhaled.)1*A Summary of Changes section appears at the end of this standard.Copyright ASTM International, 100 Barr Harbor Drive, PO Box C700, West C
19、onshohocken, PA 19428-2959, United States.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 hydrocarbon refin-ery stre
20、ams 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, depending on thei
21、r 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 contain the followin
22、g: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 capable of the followi
23、ng: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 linearity of thesecom
24、ponents 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 may alsobe dilu
25、ted 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 syringe samplei
26、njection, 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 temperature range of12
27、0 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 calculation,6.3
28、.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 five columns, c
29、olumnswitching 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 operation at atem
30、perature 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. Thesecolumns may be te
31、mperature 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 than 1 min. The t
32、imerequired to cool this column between any two points must beno more than 5 min,6.4.2 Ability to control the temperature of the molecularsieve column within a range from 100 and 490C, with a3Tenax is a registered trademark of AKZO, Velperiveg 76, P.O. Box 9300, 6800SB Arnhem, The Netherlands.TABLE
33、2 Typical Column SpecificationsSpecificationColumn TypePolar Non-Polar Tenax3MolsieveAPlatinumAColumn 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-275BOV-101B. . .Percent liquid phase 30 45 . . .Support material Chroma
34、sorbCChromasorbC. . .PAW WAW . . .Packing material . . Tenax3Molecular sieve 13XD,E.Mesh size 60/80 80/100 80/100 . .AAvailable from AC Analytical Controls, 3448 Progress Dr., Bensalem, PA 19020.BOV- 101 and OV-275 are registered trademarks of Ohio Valley Specialty Chemical Co., 115 Industry Rd., Ma
35、rietta, OH 45750.CChromasorb is a registered trademark of Manville Corp., Box 519, Lompoc, CA 93438.DSodium form of molecular sieve 13X.EMay also contain a mix of molecular sieves 13X and 5A to separate normal and iso-paraffins.D5443042tolerance of 610C at any point. The time required to heat thisco
36、lumn between any two points must be no more than 10 min.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 r
37、ange of 170 to220C.7. Materials7.1 Carrier GasesFor carrier 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 pur
38、ifiers and replace as necessary.7.1.1 Hydrogen, 99.995 % 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. (Warning
39、Extremely flammable gas under high pressure.)7.2.2 Air, 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 an
40、y grade that will result inno water condensation or will 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 h
41、ave this airrequirement.7.4 ColumnsFive columns, as described 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 determi
42、ned by test criteria asdefined in Section 8.NOTE 1It is 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 Valve
43、sThis test method uses valves for columnswitching and flow 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 o
44、ven. These valves must be capable ofcontinuous operation 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 suita
45、ble.7.5.3 Valves must be sized such that they offer little 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 performa
46、nce.7.6 Hydrocarbon Test MixtureA quantitative syntheticmixture 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 t
47、o those listed in Table 1, may be used to aid in theanalysis. 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 individualcomp
48、onents may have an adverse effect on the quantitativeaspect 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-clohexa
49、ne will both be determined as C9naphthenes. Each ofthe individual hydrocarbon components used for this testmixture must have a minimum purity level of 99 mol %. Referto Practice D 4307 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
