1、Designation: D6839 02 (Reapproved 2007)D6839 13Standard 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 ye
2、ar 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. Scope1.1 This test method covers the quantitative determination
3、 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 1There can be an overlap between the C9 and C10 aromatics; however, the total is accura
4、te. 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 method is applicable to spark-ignition engine fuel with total aromatic content up to 50
5、% (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) has been obtained for total volume fractionof aromatics of up to 50 %; a total volume fr
6、action 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 to 50 %
7、 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 specifically dev
8、eloped 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, C3 to C
9、5 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 integ
10、ration, 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 hydrocar
11、bons.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 derived precision data for methanol do not comply with theprecision calculation as present
12、ed 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 orno precisionD5599.data have been determined for these compounds.1.4.1 Other oxygenates
13、can be determined and quantified using Test Method D4815 or D5599.1.5 The method is harmonized with ISO 22854.1.6 The values stated in SI units are to be regarded 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
14、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.1 This test method is under the jurisdiction of ASTM Committee D02 on Petroleum P
15、roducts Products, Liquid Fuels, and Lubricants and is the direct responsibility ofSubcommittee D02.04.0L on Gas Chromatography Methods.Current edition approved Nov. 1, 2007Oct. 1, 2013. Published January 2008November 2013. Originally approved in 2002. Last previous edition approved in 20022007as D68
16、39D6839 02 (2007).02. DOI: 10.1520/D6839-02R07.10.1520/D6839-13.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 possible to adequately depict all
17、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.Copyright ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959
18、. United States12. Referenced Documents2.1 ASTM Standards:2D4307 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 D
19、etermination of Oxygenates in Gasoline by Gas Chromatography and Oxygen Selective FlameIonization Detection2.2 Other Documents:ISO 4259 Petroleum ProductsDetermination and Application of Precision Data in Relation to Methods of Test3ISO 22854 Liquid Petroleum ProductsDetermination of Hydrocarbon Typ
20、es 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 Specific to
21、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 180C180 C in the presence ofhydrogen. The olefins are converted i
22、nto 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 oxygena
23、tes) 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 into
24、 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 times to direct portions of the sample to appropriate columns and traps. As the analysis proc
25、eeds, 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 detected
26、 peaks followed by normalization to 100 %. For samples containing methanol or otheroxygenates 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 Th
27、e liquid volume concentration of each detected 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 i
28、s useful for regulatory compliance, process 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.2 For referencedASTM standards, visit theASTM website, www.astm.org, or
29、contactASTM Customer Service at serviceastm.org. For Annual 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
30、 Dr., Bensalem, PA 19020. If youare aware of alternative 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
31、W. 43rd St., 4th Floor, New York, NY 10036, http:/www.ansi.org.1which you may attend.D6839 1325.3 This test method is not applicable to M85 and E85 fuels, which contain 85 % methanol and ethanol, respectively. methanol.6. Interferences6.1 Some types of sulfur-containing compounds are irreversibly ad
32、sorbed 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 traps.6.2
33、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 water in s
34、park-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 modifications.
35、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, components, or conditions may be utilized provided they are capable of achieving the req
36、uiredcomponent 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 that can be packed (packed column
37、inlet), inlet, a flame ionization detector, necessary flow controllers, andcomputer control.FIG. 1 Typical Instrument ConfigurationD6839 1337.3 Sample Introduction System, automatic liquid sampler, capable of injecting a 0.1 L volume of liquid. The total injectedsample shall be introduced to the chr
38、omatographic 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 the column is not exceeded and that the lin
39、earity 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, hydrogen for the hydrogenator, and hydrogen
40、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):7.5.1 Capacity for 150 peaks for each analysi
41、s.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).7.5.5 Peak
42、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 numerouscolumns and traps, the hydrogenat
43、ion 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 Note 37.6.1). Some of t
44、he 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 temperatures620C620 C of those indicated
45、to accommodate specific systems. Temperature control may be by any means that will meet therequirements listed in 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 and
46、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 tra
47、ps 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 recommended. The valvesshall be intended for gas chromatographic usage and meet the foll
48、owing requirements:7.7.1 The valves must be capable of continuous operation at operating temperatures that will prevent sample condensation.7.7.2 The valves shall be constructed of materials that are nonreactive with the sample under analysis conditions. Stainless steel,PFA, and Vespel4 and Vespelar
49、e satisfactory.7.7.3 The valves shall have a small internal volume but offer little restriction to carrier gas flow under analysis conditions.7.7.4 New valves, tubing, catalyst, columns, traps, and other materials that contact the sample or gasses may requireconditioning prior to operation in accordance with the manufacturers recommendations.4 PFA and Vespel are trademarks of E. I. DuPont de Nemours and Co.TABLE 1 Temperature Control Ranges of System Componentscolwidth=“0.60in“/COLSPECComponentTypical OperatingTemperatureRange, CMaximumHeatingTime, min
