1、Designation: D5443 04 (Reapproved 2009)1D5443 14Standard Test Method forParaffin, Naphthene, and Aromatic Hydrocarbon TypeAnalysis in Petroleum Distillates Through 200C 200 C byMulti-Dimensional Gas Chromatography1This standard is issued under the fixed designation D5443; the number immediately foll
2、owing 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 NOTEUpdated vendor and pro
3、duct footnotes editorially in December 2009.1. Scope Scope*1.1 This test method covers the determination of paraffins, naphthenes, and aromatics by carbon number in low olefinichydrocarbon streams having final boiling points of 200C 200 C or less. Hydrocarbons with boiling points greater than 200C20
4、0 C and less than 270C 270 C are reported as a single group. Olefins, if present, are hydrogenated and the resultant saturatesare included in the paraffin and naphthene distribution.Aromatics boiling at C9 and above are reported as a single aromatic group.1.2 This test method is not intended to dete
5、rmine individual components except for benzene and toluene that are the only C6and C7 aromatics, respectively, and cyclopentane,cyclopentane that is the only C5 naphthene. The lower limit of detection for asingle hydrocarbon component or group is 0.05 mass %.% by mass.1.3 This test method is applica
6、ble to hydrocarbon mixtures including virgin, catalytically converted, thermally converted,alkylated and blended naphthas.naphtha.1.4 The values stated in SI units are to be regarded as standard. No other units of measurement are included in this standard.1.4.1 The abbreviation for SI unit “coulomb”
7、 is “C”.1.5 This standard does not purport to address all of the safety concerns, if any, associated with its use. It is the responsibilityof the user of this standard to establish appropriate safety and health practices and determine the applicability of regulatorylimitations prior to use. Specific
8、 precautionary statements are given in Section 7 and Table 1.2. Referenced Documents2.1 ASTM Standards:2D4057 Practice for Manual Sampling of Petroleum and Petroleum ProductsD4307 Practice for Preparation of Liquid Blends for Use as Analytical StandardsD5134 Test Method for Detailed Analysis of Petr
9、oleum Naphthas through n-Nonane by Capillary Gas ChromatographyD6839 Test Method for Hydrocarbon Types, Oxygenated Compounds, and Benzene in Spark Ignition Engine Fuels by GasChromatography3. Summary of Test Method3.1 A representative sample is introduced into a gas chromatographic system containing
10、 a series of columns and switchingvalves. As the sample passes through a polar column, the polar aromatic compounds, bi-naphthenes, and high boiling (200C)(200 C) paraffins and naphthenes are retained. The fraction not retained elutes to a platinum column, that hydrogenates olefins,if present, in th
11、is fraction, and then to a molecular sieve column which performs a carbon number separation based on molecularstructure, that is, naphthenes and paraffins. The fraction remaining on the polar column is further divided into three separatefractions that are then separated on a non-polar column by boil
12、ing point. Eluting compounds are detected by a flame ionizationdetector.1 This test method is under the jurisdiction of ASTM Committee D02 on Petroleum Products Products, Liquid Fuels, and Lubricants and is the direct responsibility ofSubcommittee D02.04.0L on Gas Chromatography Methods.Current edit
13、ion approved Dec. 1, 2009June 15, 2014. Published February 2010September 2014. Originally approved in 1993. Last previous edition approved in 20042009as D5443D5443 04 (2009)104 DOI: 10.1520/D5443-04R09E01.10.1520/D5443-14.2 For referencedASTM standards, visit theASTM website, www.astm.org, or contac
14、tASTM Customer Service at serviceastm.org. For Annual Book of ASTM Standardsvolume information, refer to the standards Document Summary page on the ASTM website.This document is not an ASTM standard and is intended only to provide the user of an ASTM standard an indication of what changes have been
15、made to the previous version. Becauseit may not be technically possible to adequately depict all changes accurately, ASTM recommends that users consult prior editions as appropriate. In all cases only the current versionof the standard as published by ASTM is to be considered the official document.*
16、A Summary of Changes section appears at the end of this standardCopyright ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959. United States13.2 The mass concentration of each group is determined by the multiplication of detected peak areas by flame ionization de
17、tectorresponse factors and normalization to 100 %.3.3 This test method provides limited identification of individual hydrocarbon components. Test Method D5134 may be usedto obtain speciation of a number of individual compounds. For samples containing olefins, Test Method D6839 provides carbonnumber
18、distributions of hydrocarbon types (PIONA).4. Significance and Use4.1 A knowledge of the composition of hydrocarbon refinery streams is useful for process control and quality assurance.4.2 Aromatics in gasoline are soon to be limited by federal mandate. This test method can be used to provide such i
19、nformation.5. Interferences5.1 Chemicals of a non-hydrocarbon composition may elute within the hydrocarbon groups, depending on their polarity, boilingpoint, and molecular size. Included in this group are ethers (for example, methyl-tertiary butyl ether) and alcohols (for example,ethanol).6. Apparat
20、us6.1 ChromatographA gas chromatograph capable of isothermal operation at 130130 C 6 0.1C. 0.1 C. The gaschromatograph must contain the following:6.1.1 A heated flash vaporization sample inlet system capable of operation in a splitless mode.6.1.2 Associated gas controls with adequate precision to pr
21、ovide reproducible flows and pressures.6.1.3 A flame ionization detection system optimized for use with packed columns and capable of the following:Isothermal temperature operation 150 to 170CIsothermal temperature operation 150 C to 170 CSensitivity 0.015 coulombs/gSensitivity 0.015 C/gMinimum dete
22、ctability 5 1012 g carbon/secondMinimum detectability 5 1012 g carbon/sLinearity 107Some instruments will produce a non-linear response for benzene, above approximately 5.5 mass %, % by mass, and for tolueneabove approximately 15 mass %. % by mass. The linearity of these components above these conce
23、ntrations must be verified withappropriate blends. Where non-linearity has been shown to exist, samples, that contain no higher than C13, can be analyzed if theTABLE 1 Hydrocarbon Test MixtureHydrocarbons WarningCyclopentane (WarningExtremely Flammable. Harmful if inhaled.)Pentane (WarningExtremely
24、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 Flammable. Harmful if inhaled.)Methylcyclohexane (Warning
25、Extremely 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-Trimethylpentane (iso-octane) (WarningFlammable. Harmful if inh
26、aled.)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. Harmful if inhaled.)Dodecane (WarningFlammable. Harmfu
27、l if inhaled.)Benzene (WarningExtremely Flammable. Harmful if inhaled.)Methylbenzene (Toluene) (WarningFlammable. Harmful if inhaled.)trans-Decahydronaphthalene (Decalin) (WarningFlammable. Harmful if in-haled.)Tetradecane (WarningHarmful if inhaled.)Ethylbenzene (WarningExtremely Flammable. Harmful
28、 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 (WarningExtremely Flammable. Harmful if inhaled.)1
29、,2,4,5-Tetramethylbenzene (WarningFlammable. Harmful if inhaled.)Pentamethylbenzene (WarningHarmful if inhaled.)D5443 142sample is diluted with n-C15 and the instrument is equipped with a prefractionating column. The sample may also be diluted witha component that is not present in the sample and th
30、is component will then not be included in the normalized report.6.2 Sample Introduction SystemManual or automatic liquid sample system operated in a splitless mode. Although this testmethod is intended primarily for use with syringe sample injection, automatic sampling valves have also been found sa
31、tisfactory.Devices capable of a reproducible injection volume of 0.10.1 L to 0.5 L are suitable. The sample introduction system must becapable of heating the sample to a temperature that ensures total sample vaporization.Atemperature range of 120120 C to 180C180 C has been found suitable.6.3 Electro
32、nic Data Acquisition SystemThe data acquisition and integration device used for detection and integration mustmeet or exceed the following specifications:6.3.1 Capacity for at least 75 peaks for each analysis,6.3.2 Normalized area percent calculation,6.3.3 Noise and spike rejection capability,6.3.4
33、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 method requires the temperature control of five columns, column switchingvalves and sample lines. The c
34、olumns consist of polar, non-polar, Tenax3, platinum, and molecular sieve columns. Thespecifications for these columns are listed in Table 2. The polar column, non-polar column, column switching valves, and samplelines require isothermal operation at a temperature equivalent to the temperature of th
35、e gas chromatograph oven.These componentsmay be located in the gas chromatograph oven.TheTenax column, platinum column, and molecular sieve column require operationat temperatures other than the gas chromatograph oven temperature. These columns may be temperature controlled by any meansthat will mee
36、t the following specifications:specifications in Table 2.6.4.1 Ability to control the temperature of the Tenax column within a range from 6060 C to 280C, 280 C, with a toleranceof 65C 65 C at any point. The time required to heat this column between any two points must be no more than 1 min. The time
37、required to cool this column between any two points must be no more than 5 min,6.4.2 Ability to control the temperature of the molecular sieve column within a range from 100100 C and 490C, 490 C, witha tolerance of 610C 610 C at any point. The time required to heat this column between any two points
38、 must be no more than10 min. The time required to cool this column from 450450 C to 100C 100 C must be no more than 15 min, and6.4.3 Ability to control the platinum column within a temperature range of 170170 C and 350C. 350 C. During routineanalysis, this column is operated within a temperature ran
39、ge of 170170 C to 220C.220 C.NOTE 1Newer analyzers may have updated hardware and/or separation columns types and traps dimensions. Precision using using newer hardwareconfigurations or conditions have not been studied by ASTM. The precision listed in this method was obtained with hardware described
40、in this testmethod.7. Materials7.1 Carrier GasesFor carrier gases, it is recommended to install commercial active oxygen scrubbers and water dryers, suchas molecular sieves, ahead of the instrument to protect the systems chromatographic columns. Follow supplier instructions in theuse of such gas pur
41、ifiers and replace as necessary.7.1.1 Hydrogen, 99.995 % by mol minimum purity, 0.10.1 L ppm L H2O. (WarningExtremely flammable gas underhigh pressure.)3 Tenax is a registered trademark of AKZO, VelperivegVelperweg 76, P.O. Box 9300, 6800 SB Arnhem, The Netherlands.TABLE 2 Typical Column Specificati
42、onsSpecification Column TypePolar Non-Polar Tenax3 Molsieve PlatinumColumn 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-275A OV-101A . . .Percent liquid phase 30 45 . . .Support material ChromasorbB ChromasorbB . . .PA
43、W WAW . . .Packing material . . Tenax3 Molecular sieve 13XC ,D .Mesh size 60/80 80/100 80/100 . .A OV- 101 OV-101 and OV-275 are registered trademarks of Ohio Valley Specialty Chemical Co., 115 Industry Rd., Marietta, OH 45750.B Chromasorb is a registered trademark of World Minerals, Corp., Santa Ba
44、rbara, CA.C Sodium form of molecular sieve 13X.D May also contain a mix of molecular sieves 13X and 5A to separate normal and iso-paraffins.D5443 1437.1.2 Helium, 99.995 % by mol minimum purity, 0.1 ppmL/L H2O. (WarningCompressed gas under high pressure.)7.2 Detector Gases:7.2.1 Hydrogen, 99.99 % by
45、 mol minimum purity. (WarningExtremely flammable gas under high pressure.)7.2.2 Air, less than 1010 L ppm L each of total hydrocarbons and water. (WarningCompressed gas under high pressure.)7.3 Valve Actuation GasThis test method permits the use of any type of valve switching or valve actuation. Whe
46、n pneumaticvalves are used, air of any grade that will result in no water condensation or will not introduce oil or other contaminates in theswitching valves may be used. Air from a piston operated compressor equipped with a water and oil separator has been foundsuitable. Column switching valves tha
47、t do not require air to operate do not have this air requirement.7.4 ColumnsFive columns, as described in Table 2. These column specifications are to be considered as guidelines and havebeen found to be acceptable. Other materials or combinations of materials may also provide acceptable performance.
48、 Thesuitability of each column is determined by test criteria as defined in Section 8.NOTE 2It is not the intention of this test method to include detailed column preparation steps. Columns may be prepared in any way that followsaccepted safety practices and results in columns that will meet the per
49、formance requirements of Section 9.7.5 ValvesThis test method uses valves for column switching and flow switching.Any commercially available valves may beused that are intended for, or adapted for use in gas chromatography that meet the following specifications:7.5.1 The column switching valves are generally installed in the gas chromatograph oven. These valves must be capable ofcontinuous operation at the operating temperature of the GC oven.7.5.2 Materials used in the constructi
