1、Designation: D6839 13D6839 15Standard Test Method forHydrocarbon Types, Oxygenated Compounds,Compoundsand Benzene in Spark Ignition Engine Fuels by GasChromatography1This standard is issued under the fixed designation D6839; the number immediately following the designation indicates the year oforigi
2、nal 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. Scope Scope*1.1 This test method covers the quantitative determination of
3、 saturates, olefins, aromatics,aromatics and oxygenates inspark-ignition engine fuels by multidimensional gas chromatography. Each hydrocarbon type can be reported either by carbonnumber (see Note 1) or as a total.NOTE 1There can be an overlap between the C9 and C10 aromatics; however, the total is
4、accurate. Isopropyl benzene is resolved from the C8 aromaticsand is included with the other C9 aromatics.1.2 This test method is not intended to determine individual hydrocarbon components except benzene.1.2 This test method is divided into two parts, Part A and Part B.applicable to spark-ignition e
5、ngine fuel with total aromaticcontent up to 50 % (V/V), total olefinic content up to 30 % (V/V) and oxygen compounds up to 15 % (V/V).1.3.1 PartAis applicable to automotive motor gasoline for which precision (Table 9) has been obtained for total volume fractionof aromatics of up to 50 %; a total vol
6、ume fraction of olefins from about 1.5 % up to 30 %; a volume fraction of oxygenates, from0.8 % up to 15 %; a total mass fraction of oxygen from about 1.5 % to about 3.7 %; and a volume fraction of benzene of up to2 %. Although this test method can be used to determine higher-olefin contents of up t
7、o 50 % volume fraction, the precision forolefins was tested only in the range from about 1.5 % volume fraction to about 30 % volume fraction. The method has also beentested for an ether content up to 22% volume fraction but no precision data has been determined.1.3.1.1 This test method is specifical
8、ly developed for the analysis of automotive motor gasoline that contains oxygenates, butit also applies to other hydrocarbon streams having similar boiling ranges, such as naphthas and reformates.1.3.2 Part B describes the procedure for the analysis of oxygenated groups (ethanol, methanol, ethers, C
9、3 to C5 alcohols) inethanol fuels containing an ethanol volume fraction between 50 % and 85 % (17 to 29 % oxygen). The gasoline is diluted withan oxygenate-free component to lower the ethanol content to a value below 20 % before the analysis by GC. The diluting solventshould not be considered in the
10、 integration, this makes it possible to report the results of the undiluted sample after normalizationto 100 %1.3 This test method is not intended to determine individual hydrocarbon components except benzene.1.4 Oxygenates as specified inTest Method D4815 have been verified not to interfere with hy
11、drocarbons.Within the round robinsample set, the following oxygenates have been tested: MTBE, ethanol, ETBE, TAME, iso-propanol, isobutanol, tert-butanol andmethanol. The derived precision data for methanol do not comply with the precision calculation as presented in this InternationalStandard. Appl
12、icability of this test method has also been verified for the determination of n-propanol, acetone, and TAME. Otheroxygenates can be determined and diquantified-isopropyl ether (DIPE). However, no using Test Method D4815 precisionorD5599data have been determined for these compounds. .1.4.1 Other oxyg
13、enates can be determined and quantified using Test Method D4815 or D5599.1.5 This test method includes a relative bias section for U.S. EPA spark-ignition engine fuel regulations for total olefinsreporting based on Practice D6708 accuracy assessment between Test Method D6839 and Test Method D1319 as
14、 a possible TestMethod D6839 alternative to Test Method D1319. The methodPractice D6708is harmonized with ISO 22854. derived correlationequation is only applicable for fuels in the total olefins concentration range from 0.2 % to 18.2 % by volume as measured by TestMethod D6839. The applicable Test M
15、ethod D1319 range for total olefins is from 0.6 % to 20.6 % by volume as reported by TestMethod D1319.1 This test method is under the jurisdiction ofASTM Committee D02 on Petroleum Products, Liquid Fuels, and Lubricants and is the direct responsibility of SubcommitteeD02.04.0L on Gas Chromatography
16、Methods.Current edition approved Oct. 1, 2013Dec. 1, 2015. Published November 2013December 2015. Originally approved in 2002. Last previous edition approved in 20072013as D6839 02 (2007).D6839 13. DOI: 10.1520/D6839-13.10.1520/D6839-15.This document is not an ASTM standard and is intended only to pr
17、ovide the user of an ASTM standard an indication of what changes have been 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 th
18、e standard as published by ASTM is to be considered the official document.*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 States11.6 The values stated in SI units are to be reg
19、arded as standard. No other units of measurement are included in this standard.1.7 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 dete
20、rmine the applicability of regulatorylimitations prior to use.2. Referenced Documents2.1 ASTM Standards:2D1319 Test Method for Hydrocarbon Types in Liquid Petroleum Products by Fluorescent Indicator AdsorptionD4307 Practice for Preparation of Liquid Blends for Use as Analytical StandardsD4815 Test M
21、ethod for Determination of MTBE, ETBE, TAME, DIPE, tertiary-Amyl Alcohol and C1 to C4 Alcohols inGasoline by Gas ChromatographyD5599 Test Method for Determination of Oxygenates in Gasoline by Gas Chromatography and Oxygen Selective FlameIonization DetectionD6708 Practice for Statistical Assessment a
22、nd Improvement of Expected Agreement Between Two Test Methods that Purportto Measure the Same Property of a Material2.2 Other Documents:ISO 4259 Petroleum ProductsDetermination and Application of Precision Data in Relation to Methods of Test3ISO 22854 Liquid Petroleum ProductsDetermination of Hydroc
23、arbon Types and Oxygenates in Automotive-MotorGasolineMultidimensional Gas Chromatography Method33. Terminology3.1 Definitions:3.1.1 oxygenate, nan oxygen-containing organic compound, which may be used as a fuel or fuel supplement, for example,various alcohols and ethers.3.2 Definitions of Terms Spe
24、cific to This Standard:3.2.1 hydrogenation, nthe process of adding hydrogen to olefin molecules as a result of a catalytic reaction.3.2.1.1 DiscussionHydrogenation is accomplished when olefins in the sample contact platinum at a temperature of 180 C in the presence ofhydrogen. The olefins are conver
25、ted into hydrogen saturated compounds of the same carbon number and structure. Monoolefinsand diolefins convert to paraffins while cycloolefins and cyclodienes convert to cycloparaffins.3.2.2 trap, na device utilized to selectively retain specific portions (individual or groups of hydrocarbons or ox
26、ygenates) ofthe test sample and to release the retained components by changing the trap temperature.3.3 Acronyms:3.3.1 ETBEethyl-tert-butylether3.3.2 MTBEmethyl-tert-butylether3.3.3 TAMEtert-amyl-methylether3.3.4 DIPEdi-isopropylether4. Summary of Test Method4.1 A representative sample is introduced
27、 into a computer controlled gas chromatographic system3 consisting of switchingvalves, columns, and an olefin hydrogenation catalyst, all operating at various temperatures. The valves are actuated atpredetermined times to direct portions of the sample to appropriate columns and traps. As the analysi
28、s proceeds, the columnsseparate these sample portions sequentially into groups of different hydrocarbon types that elute to a flame ionization detector.4.2 The mass concentration of each detected compound or hydrocarbon group is determined by the application of responsefactors to the areas of the de
29、tected peaks followed by normalization to 100 %. For samples containing methanol or other2 For referencedASTM standards, visit theASTM website, www.astm.org, or contactASTM Customer Service at serviceastm.org. For Annual Book of ASTM Standardsvolume information, refer to the standards Document Summa
30、ry page on the ASTM website.3 Available from American National Standards Institute (ANSI), 25 W. 43rd St., 4th Floor, New York, NY 10036, http:/www.ansi.org.The sole source of supply of theAC Reformulyzer known to the committee at this time is AC Analytical Controls, Inc., 3494 Progress Dr., Bensale
31、m, PA 19020. If you are aware of alternative suppliers,please provide this information to ASTM International Headquarters. Your comments will receive careful consideration at a meeting of the responsible technical committee,1which you may attend.D6839 152oxygenates that cannot be determined by this
32、test method, the hydrocarbon results are normalized to 100 % minus the value of theoxygenates as determined by another test method such as Test Method D4815 or D5599.4.3 The liquid volume concentration of each detected compound or hydrocarbon group is determined by application of densityfactors to t
33、he calculated mass concentration of the detected peaks followed by normalization to 100 %.5. Significance and Use5.1 A knowledge of spark-ignition engine fuel composition is useful for regulatory compliance, process control, and qualityassurance.5.2 The quantitative determination of olefins and othe
34、r hydrocarbon types in spark-ignition engine fuels is required to complywith government regulations.5.3 This test method is not applicable to M85 and E85 fuels, which contain 85 % methanol. methanol and ethanol, respectively.6. Interferences6.1 Some types of sulfur-containing compounds are irreversi
35、bly adsorbed in the olefin trap reducing its capacity to retain olefins.Sulfur containing compounds are also adsorbed in the alcohol and ether-alcohol-aromatic (EAA) traps. However, a variety ofspark-ignition engine fuels have been analyzed without significant performance deterioration of these trap
36、s.6.2 Commercial dyes used to distinguish between grades and types of spark-ignition engine fuels have been found not tointerfere with this test method.6.3 Commercial detergent additives utilized in spark-ignition engine fuels have been found not to interfere with this test method.6.4 Dissolved wate
37、r in spark-ignition engine fuels has been found not to interfere with this test method.7. Apparatus7.1 The complete system that was used to obtain the precision data shown in Section 14 is comprised of a computer controlledgas chromatograph, automated sample injector, and specific hardware modificat
38、ions. These modifications include columns, traps,a hydrogenator, and valves, which are described in 7.7, 7.8, and in Section 8. Fig. 1 illustrates a typical instrument configuration(see Note 45). Other configurations, components, or conditions may be utilized provided they are capable of achieving t
39、he requiredcomponent separations and produce a precision that is equivalent to, or better than, that shown in the precision tables.7.2 Gas Chromatograph, capable of temperature programmed operation at specified temperatures, equipped with a heated flashvaporization inlet, inlet that can be packed (p
40、acked column inlet), a flame ionization detector, necessary flow controllers, andcomputer control.7.3 Sample Introduction System, using an automatic liquid injector, the injection volume shall be chosen in a way such that thecapacity of the column is not exceeded and that the linearity of the detect
41、or is valid.automatic liquid sampler, capable of injectingFIG. 1 Typical Instrument ConfigurationD6839 153a 0.1 L volume of liquid. The total injected sample shall be introduced to the chromatographic system thus excluding the use ofsplit injections or carrier gas purging of the inlet septum. An aut
42、o injector is recommended but optional.7.3.1 An injection volume of 0.1 L has been found satisfactory.7.4 Gas Flow and Pressure Controllers, with adequate precision to provide reproducible flow and pressure of the carrier gashelium to the chromatographic system, hydrogen for the hydrogenator, and hy
43、drogen and air for the flame ionization detector.Control of air flow for cooling specific system components and for automated valve operation is also required.7.5 Electronic Data Acquisition System, shall meet or exceed the following specifications (see Note 2):7.5.1 Capacity for 150 peaks for each
44、analysis.7.5.2 Normalized area percent calculation with response factors.7.5.2.1 Area summation of peaks that are split or of groups of components that elute at specific retention times.7.5.3 Noise and spike rejection capability.7.5.4 Sampling rate for fast (20 Hz to give 10 points across peak).7.5.
45、5 Peak width detection for narrow and broad peaks.7.5.6 Perpendicular drop and tangent skimming, as required.NOTE 2Standard supplied software is typically satisfactory.7.6 Temperature Controllers of System ComponentsComponents The independent temperature control of numerouscolumns and traps, the hyd
46、rogenation catalyst, column switching valves, and sample lines is required. All of the systemcomponents that contact the sample shall be heated to a temperature that will prevent condensation of any sample component.Table 1 lists the system components and operating temperatures (see 7.6.1Note 3). So
47、me of the components require isothermaloperation, some require rapid heating and cooling, while one requires reproducible temperature programming. The indicatedtemperatures are typical; however, the control systems utilized shall have the capability of operating at temperatures 620 C ofthose indicat
48、ed to accommodate specific systems. Temperature control may be by any means that will meet the requirements listedin Table 1.7.6.1 The system components and temperatures listed in Table 1 and Section 8 are specific to the analyzer used to obtain theprecision data shown in Section 14. Other columns a
49、nd traps that can adequately perform the required separations are alsosatisfactory but may require different temperatures.NOTE 3The system components and temperatures listed in Table 1 and Section 8 are specific to the analyzer used to obtain the precision data shownin Section 14. Other columns and traps that can adequately perform the required separations are also satisfactory but may require different temperatures.7.7 Valves, Column and Trap SwitchingSuitable automated switchingAutomated, rotary valves are recommended. The valvesshall be intended for ga
