1、Designation: D6839 15D6839 16Standard Test Method forHydrocarbon Types, Oxygenated Compounds, and Benzenein Spark Ignition Engine Fuels by Gas Chromatography1This standard is issued under the fixed designation D6839; the number immediately following the designation indicates the year oforiginal adop
2、tion 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.NOTEPreviously balloted and approved material was included and the year date changed
3、 on April 20, 2016.1. Scope*1.1 This test method covers the quantitative determination of saturates, olefins, aromatics, and oxygenates in spark-ignitionengine fuels by multidimensional gas chromatography. Each hydrocarbon type can be reported either by carbon number (see Note1) or as a total.NOTE 1
4、There can be an overlap between the C9 and C10 aromatics; however, the total is 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.1.3 This test me
5、thod is applicable to spark-ignition engine fuel with total aromatic content up to 50 % (V/V), total olefiniccontent up to 30 % (V/V) and oxygen compounds up to 15 % (V/V).divided into two parts, Part A and Part B.1.3.1 PartAis applicable to automotive motor gasoline for which precision (Table 9) ha
6、s been obtained for total volume fractionof aromatics of up to 50 %; a total volume 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 %. A
7、lthough this test method can be used to determine higher-olefin contents of up to 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
8、 but no precision data has been determined.1.3.1.1 This test method is specifically 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
9、the procedure for the analysis of oxygenated groups (ethanol, methanol, ethers, C3 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
10、20 % before the analysis by GC. The diluting solventshould not be considered in the 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 Oxy
11、genates as specified inTest Method D4815 have been verified not to interfere with hydrocarbons.Within the round robinsample set, the following oxygenates have been tested: MTBE, ethanol, ETBE, TAME, iso-propanol, isobutanol, tertand TAME.Other oxygenates can be determined -butanol and methanol. The
12、derived precision data for methanol do not comply with theprecision calculation as presented in this International Standard. Applicability of this test method has also been verified for thedetermination of n-propanol, acetone, and quantifieddi using Test Method-isopropyl ether (DIPE). However, D4815
13、 orno precisionD5599.data have been determined for these compounds.1.4.1 Other oxygenates can be determined and quantified using Test Method D4815 or D5599.1.5 The method is harmonized with ISO 22854.1.6 This test method includes a relative bias section for U.S. EPA spark-ignition engine fuel regula
14、tions for total olefinsreporting based on Practice D6708 accuracy assessment between Test Method D6839 and Test Method D1319 as a possible TestMethod D6839 alternative to Test Method D1319. The Practice D6708 derived correlation equation is only applicable for fuels in1 This test method is under the
15、 jurisdiction ofASTM Committee D02 on Petroleum Products, Liquid Fuels, and Lubricants and is the direct responsibility of SubcommitteeD02.04.0L on Gas Chromatography Methods.Current edition approved Dec. 1, 2015April 20, 2016. Published December 2015April 2016. Originally approved in 2002. Last pre
16、vious edition approved in 20132015as D6839 13.D6839 15. DOI: 10.1520/D6839-15.10.1520/D6839-16.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 made to the previous version. Becauseit may not be technically pos
17、sible 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.*A Summary of Changes section appears at the end of this standardCo
18、pyright ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959. United States1the total olefins concentration range from 0.2 % to 18.2 % by volume as measured by Test Method D6839. The applicable TestMethod D1319 range for total olefins is from 0.6 % to 20.6 % by vo
19、lume as reported by Test Method D1319.1.7 The values stated in SI units are to be regarded as standard. No other units of measurement are included in this standard.1.8 This standard does not purport to address all of the safety concerns, if any, associated with its use. It is the responsibilityof th
20、e user of this standard to establish appropriate safety and health practices and determine 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
21、Practice for Preparation of Liquid Blends for Use as Analytical StandardsD4815 Test Method 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
22、Oxygen Selective FlameIonization DetectionD6708 Practice for Statistical Assessment and 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 R
23、elation to Methods of Test3ISO 22854 Liquid Petroleum ProductsDetermination of Hydrocarbon 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
24、fuel supplement, for example,various alcohols and ethers.3.2 Definitions of Terms Specific 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
25、platinum at a temperature of 180 C in the presence ofhydrogen. The olefins are converted 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 utilize
26、d to selectively retain specific portions (individual or groups of hydrocarbons or oxygenates) 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 DI
27、PEdi-isopropylether4. Summary of Test Method4.1 A representative sample is introduced into a computer controlled gas chromatographic system consisting of switchingvalves, columns, and an olefin hydrogenation catalyst, all operating at various temperatures. The valves are actuated atpredetermined tim
28、es to direct portions of the sample to appropriate columns and traps. As the analysis 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 hydrocar
29、bon group is determined by the application of responsefactors to the areas of the detected 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 An
30、nual Book of ASTM Standardsvolume information, refer to the standards Document Summary page on the ASTM website.3 The sole source of supply of the AC Reformulyzer known to the committee at this time is AC Analytical Controls, Inc., 3494 Progress Dr., Bensalem, PA 19020. If youare aware of alternativ
31、e suppliers, please provide this information to ASTM International Headquarters. Your comments will receive careful consideration at a meeting ofthe responsible technical committee,Available from American National Standards Institute (ANSI), 25 W. 43rd St., 4th Floor, New York, NY 10036, http:/www.a
32、nsi.org.1which you may attend.D6839 162oxygenates that cannot be determined by this 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 detect
33、ed compound or hydrocarbon group is determined by application of densityfactors to the 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
34、control, and qualityassurance.5.2 The quantitative determination of olefins and other 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 and ethanol, respectively.
35、methanol.6. Interferences6.1 Some types of sulfur-containing compounds are irreversibly 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
36、fuels have been analyzed without significant performance deterioration of these traps.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 en
37、gine fuels have been found not to interfere with this test method.6.4 Dissolved water 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 con
38、trolledgas chromatograph, automated sample injector, and specific hardware modifications. 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 54). Other configurations
39、, components, or conditions may be utilized provided they are capable of achieving the 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 tempe
40、ratures, equipped with a heated flashvaporization inlet that can be packed (packed column inlet), inlet, a flame ionization detector, necessary flow controllers, andcomputer control.7.3 Sample Introduction System, automatic liquid sampler, capable of injecting a 0.1 L volume of liquid. The total inj
41、ectedsample shall be introduced to the chromatographic system thus excluding the use of split injections or carrier gas purging of theinlet septum.An auto injector is recommended but optional.using an automatic liquid injector, the injection volume shall be chosenin a way such that the capacity of t
42、he column is not exceeded and that the linearity of the detector is valid.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 helium the carriergas to the chromatographic system, hy
43、drogen for the hydrogenator, and hydrogen and air for the flame ionization detector. Controlof 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
44、.1 Capacity for 150 peaks for each 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
45、to give 10 points across peak).7.5.5 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 Components ComponentsThe independent temperature control of
46、 numerouscolumns and traps, the hydrogenation 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
47、 temperatures (see Note 37.6.1). Some 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
48、 temperatures 620 C ofthose indicated to accommodate specific systems. Temperature control may be by any means that will meet the requirements listedin Table 1.D6839 1637.6.1 The system components and temperatures listed in Table 1 and Section 8 are specific to the analyzer used to obtain theprecisi
49、on data shown in Section 14. Other columns and 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 SwitchingAutomated, rotary Suitable automated switching valves are r
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