1、Designation: D3606 17Standard Test Method forDetermination of Benzene and Toluene in Spark IgnitionFuels by Gas Chromatography1This standard is issued under the fixed designation D3606; the number immediately following the designation indicates the year oforiginal adoption or, in the case of revisio
2、n, 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*1.1 This test method covers the determination of benzeneand toluene in finished motor and aviation spark i
3、gnition fuelsby gas chromatography. This test method has two procedures:Procedure A uses capillary column gas chromatography andProcedure B uses packed gas chromatography columns. Pro-cedures A and B have separate precisions.1.2 Benzene can be determined between the levels of: (1)Procedure A 0.1 % a
4、nd 5.0 % by volume and toluene can bedetermined between the levels 0.4 % and 20 % by volume, and(2) Procedure B benzene can be determined between the levelsof 0.1 % and 5 % by volume and toluene can be determinedbetween the levels of 2 % and 20 % by volume.1.3 The precision for this test method was
5、determined usingconventional spark ignition fuel (motor gasolines) as well asthose containing blended ethanol and such ethers as MTBE,ETBE, TAME, and other alcohols such as methanol andbutanols. This method may be used for finished motor andaviation gasolines that contain ethanol blend up to 20 % an
6、dbutanols blend up to 20 %.1.4 M85 and E85 fuels were not included in the precisionfor Procedure A. M85 and E85 fuels cause interference withProcedure B.1.5 Procedure A uses MIBK as the internal standard. Pro-cedure B uses sec-butanol as the internal standard. The use ofProcedure B for fuels contain
7、ing blended butanols requires thatsec-butanol be below the detection limit in the fuels.1.6 The values stated in SI units are to be regarded asstandard. The values given in parentheses are for informationonly.1.7 This standard does not purport to address all of thesafety concerns, if any, associated
8、 with its use. It is theresponsibility of the user of this standard to establish appro-priate safety, health, and environmental practices and deter-mine the applicability of regulatory limitations prior to use.1.8 This international standard was developed in accor-dance with internationally recogniz
9、ed principles on standard-ization established in the Decision on Principles for theDevelopment of International Standards, Guides and Recom-mendations issued by the World Trade Organization TechnicalBarriers to Trade (TBT) Committee.2. Referenced Documents2.1 ASTM Standards:2D4057 Practice for Manua
10、l Sampling of Petroleum andPetroleum ProductsD6299 Practice for Applying Statistical Quality Assuranceand Control Charting Techniques to Evaluate AnalyticalMeasurement System PerformanceE288 Specification for Laboratory Glass Volumetric FlasksE694 Specification for Laboratory Glass Volumetric Appa-r
11、atusE969 Specification for Glass Volumetric (Transfer) PipetsE1044 Specification for Glass Serological Pipets (GeneralPurpose and Kahn)E1293 Specification for Glass Measuring PipetsPROCEDURE ACAPILLARY WCOT GASCHROMATOGRAPHIC SYSTEMS3. Summary of Test Method3.1 An internal standard, methyl isobutyl
12、ketone (MIBK) isadded to the sample which is then introduced into a heatedcapillary or programmed temperature vaporization (PTV) in-jector on a gas chromatograph (GC). The GC is equipped withtwo columns connected in series. The sample passes firstthrough a column with a nonpolar phase. After toluene
13、 haseluted, the flow through the nonpolar column is reversed,flushing out the components heavier than toluene. The tolueneand lighter components enter a second column which separates1This test method is under the jurisdiction of ASTM Committee D02 onPetroleum Products, Liquid Fuels, and Lubricants a
14、nd is the direct responsibility ofSubcommittee D02.04.0L on Gas Chromatography Methods.Current edition approved Dec. 1, 2017. Published April 2018. Originallyapproved in 1977. Last previous edition approved in 2010 as D3606 101. DOI:10.1520/D3606-17.2For referenced ASTM standards, visit the ASTM web
15、site, 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.*A Summary of Changes section appears at the end of this standardCopyright ASTM International, 100 Barr Harbor
16、Drive, PO Box C700, West Conshohocken, PA 19428-2959. United StatesThis international standard was developed in accordance with internationally recognized principles on standardization established in the Decision on Principles for theDevelopment of International Standards, Guides and Recommendations
17、 issued by the World Trade Organization Technical Barriers to Trade (TBT) Committee.1the aromatic and nonaromatic compounds. The eluted compo-nents are detected by a flame ionization detector (FID). Thedetector response is recorded, the peak areas are measured, andthe concentration of each component
18、 is calculated with refer-ence to the internal standard.4. Significance and Use4.1 Knowledge of the concentration of benzene may berequired for regulatory use, control of gasoline blending,and/or process optimizations.5. Apparatus and Chemicals5.1 ChromatographAny gas chromatograph that has thecapab
19、ility of performing multidimensional chromatographythat can be operated at approximately the conditions describedin this method, and meets all the required chromatographicspecifications and method criteria specified in 7.5 and 11.5.1.1 Sample Introduction SystemAutomated sample in-jection system suc
20、h as a liquid autosampler.5.1.2 InjectorCapillary split/splitless injector.5.1.3 DetectorAt least one flame ionization detector (FID)is required. In a two FID configuration, the optional seconddetector is used to monitor the effluent from the pre-column(refer to configuration A in 7.1.1).5.2 Columns
21、:5.2.1 Pre-columnNon-polar, boiling point column, whichperforms the first separation of the hydrocarbons. A dimethylpolysiloxane phase column with dimensions of 30 m by0.25 mm by 0.50 m has been used successfully. Any columnwith equivalent or better chromatographic efficiency and se-lectivity may be
22、 used.5.2.2 Analytical ColumnThis column separates aromaticand non-aromatic compounds. A polyethylene glycol (polarwax) column with the dimensions 60 m by 0.32 mm by 1.0m has been used successfully.Any column capable of meetingthe resolution requirement in 7.5 may be employed.5.2.3 RestrictorUncoate
23、d deactivated fused silica. A100 m by 42.5 cm restrictor was successfully used whendeveloping this method.5.3 Chromatography Data System (CDS)An electronicdevice capable of graphical presentation and integration of thechromatogram peaks.5.4 MicrosyringeCapable of making injections from0.5 L to 1.0 L
24、.5.5 Volumetric Pipets, Class A0.5 mL, 1 mL, 5 mL,10 mL, 15 mL, and 20 mL capacities (see Specifications E694and E969).5.6 Measuring Pipets1 mL and 2 mL capacities calibratedin 0.01 mL; 5 mL calibrated in 0.1 mL, for use in dispensingvolumes of benzene and toluene not covered by the volumetricpipets
25、 (see Specifications E1044 and E1293) during prepara-tion of standard samples (see 8.1).NOTE 1Other manual or automated volume dispensing equipmentcapable of delivering the specified volumes within the stated tolerancelimits may be used as an alternative to the requirements stated in 5.5 and5.6.5.7
26、FlasksVolumetric, 25 mL and 100 mL capacity (seeSpecification E288).5.8 GC Carrier GasHelium or hydrogen 99.999 % pure.(WarningCompressed gas under high pressure; hydrogenflammable.) A hydrogen generator may be used.NOTE 2When using hydrogen carrier gas, use precautions such asinstallation of hydrog
27、en sensors in the gas chromatograph oven. It isrecommended that the hydrogen excess flow, such as from the splitterinlet, should be vented to a safe area such as a ventilated hood orappropriate exhaust approved for such use. Use caution when performingmaintenance by isolating the hydrogen source.5.9
28、 FID GasAir chromatographic grade, dry (WarningCompressed gas under high pressure.)An air generator may beused with purifier.5.10 FID GasHydrogen, 99.999 % pure (WarningCompressed gas under high pressure; hydrogen flammable.) Ahydrogen generator may be used.5.11 FID Make-up Gas, if Required (Refer t
29、o Manufactur-ers Requirements)Nitrogen, 99.999 % pure. (WarningCompressed gas under high pressure.)NOTE 3Reference the instrument manual for specifics on how toestablish required flow rates for a particular vendors instrument.5.12 Chemicals(WarningThese chemicals aredangerous, harmful, or fatal if s
30、wallowed or inhaled. They areflammable to extremely flammable. Vapors can cause flashfires.)5.12.1 Internal StandardMethyl Isobutyl Ketone (MIBK)99.5 % pure.5.13 Calibration Standards:5.13.1 Benzene99.5 % minimum purity. (WarningCarcinogen.)5.13.2 Toluene99.5 % minimum purity.5.13.3 Isooctane (2,2,4
31、trimethyl pentane)99.5 % mini-mum purity. This is the solvent used for dilution.5.14 Method Chemicals for Resolution Validation:5.14.1 Sec-butanol99.5 % minimum purity.5.14.2 Iso-butanol99.5 % minimum purity.5.14.3 n-butanol99.5 % minimum purity.5.14.4 n-propanol99.5 % minimum purity.5.14.5 Ethanol9
32、9.5 % minimum purity (200 proof).6. Sampling6.1 Gasoline(WarningExtremely flammable. Vaporsharmful if inhaled.) Samples to be analyzed by this test methodshall be obtained using the procedures outlined in PracticeD4057.7. Apparatus, Configurations, and Method Setup7.1 ConfigurationIllustrated and di
33、scussed in this testmethod are three configurations used by the laboratories thathave participated in the interlaboratory study (ILS). Figs. A1.5and A1.6 contain graphical representations of these configura-tions and Table A1.1 provides the method parameters. Valve-based systems for backflushing may
34、 be used and such aconfiguration is displayed in Fig.A1.7 and was also used in theILS. Other configurations may be used provided all of therequirements and criteria in this test method are met, such asD3606 172signal to noise (S/N), resolution, calibration, quality controlrequirements, and so forth,
35、 which are discussed in 7.5 andSection 11.7.1.1 Configuration AHas the capability of monitoring theeffluent from the pre-column via a restrictor. This is a dualdetector system. One FID is used to monitor the analyticalcolumns effluent, and the other to monitor the effluent from thepre-column. The se
36、cond FID provides a quicker approach indetermining backflush time. Figs. A1.1 and A1.2 representexamples of this configuration.7.1.2 Configuration BHas the capability of monitoring theeffluent from the pre-column via a restrictor; however, only oneFID is installed. Figs.A1.3 and A1.4 represent examp
37、les of thisconfiguration.7.1.3 Configuration CDoes not have the capability tomonitor the effluent from the pre-column. Figs. A1.5 and A1.6represent an example of this configuration.7.2 Conditioning ColumnInstall the pre-column, analyti-cal column, and the restrictor, if the restrictor is being used
38、asin configurations A and B. Condition the columns per manu-facturers instructions.7.3 Determine Time to Backflush (BF)Or backflush time,must be empirically determined for each system and columnset used by the laboratory. Optimization of backflush time isdependent upon the configuration used.7.3.1 C
39、onfiguration A, Dual Detector ConfigurationFollow the instrument setup as shown in Figs. A1.1 and A1.2.7.3.1.1 Establish analytical parameters set forth in TableA1.1 or parameters that have met method separation criteria asoutlined in 7.5. Ensure both detector channels are beingcollected by the CDS.
40、7.3.1.2 Inject 0.1 L to 0.5 L of standard #1 (8.2)orthebutanol composite mix (8.5.2) depending on ethanol or butanolblended gasoline, respectively. If the gasoline being tested isblended with ethanol and not butanol, the composite mixdescribed in 8.5.2 for butanol blend does not need to beprepared.
41、However, if the laboratory wants to prepare thiscomposite mix, the composite mix described in 8.5.2 may beused for establishing backflush time for both blended fuels.7.3.1.3 Record the time when toluene returns to baselinefrom the pre-column via the restrictor. A chromatogram fromthe pre-column thro
42、ugh the restrictor demonstrating this isshown in Fig. A1.8 for standard #1, and in Fig. A1.9 for thecomposite mix in 8.5.2.7.3.1.4 Next monitor the effluent from the analytical columnusing the backflush time established in 7.3.1.3. Inject standard#1 (8.2) or composite mix for butanol blend (8.5.2).
43、Record thearea for toluene.7.3.1.5 Reduce the backflush time by 0.02 min. Injectstandard #1 or composite mix. Record the area for toluene.Repeat this step until the response for toluene begins todecrease.7.3.1.6 The backflush time for the method will be the timerecorded before the time when toluene
44、decreased. An examplechromatogram from the analytical column of standard #1 is inFig. A1.10 and an example chromatogram of composite mixdescribed in 8.5.2 is located in Fig. A1.11.7.3.2 Configuration B, Single Detector ConfigurationTomonitor the flow from the pre-column to establish the back-flush t
45、ime, the analytical column is removed from the FID andleft in the GC oven as displayed in Fig. A1.3.(WarningUsecaution if using hydrogen as carrier gas; if possible, ventexternally of the gas chromatographs oven.) The restrictor isinstalled into the FID.7.3.2.1 Follow procedures from 7.3.1.1 through
46、 7.3.1.3.7.3.2.2 Remove restrictor from the detector and install theanalytical column in the detector for analysis as shown in Fig.A1.4.7.3.2.3 Follow procedures from 7.3.1.4 to 7.3.1.6.7.3.3 Configuration C, No Pre-column ConfigurationThisconfiguration is not capable of monitoring the chromatograph
47、yfrom the pre-column. An example of this configuration isshown in Figs. A1.5 and A1.6 configuration C.7.3.3.1 Inject 0.1 L to 0.5 L of standard #1 (8.2)orthecomposite mix (8.5) depending on ethanol or butanol blendedgasoline using a backflush time equal to the run-time.7.3.3.2 Decrease the backflush
48、 time by 1 min intervals untiltoluene is no longer present in the chromatogram.7.3.3.3 Increase the backflush time by 0.02 min until tolu-ene provides a stable area count. The shortest time when thetoluene has a stable response is the backflush time.7.4 Re-establishing Backflush TimeAs the column ag
49、eswith use, retention times will become shorter. If the qualitycontrol samples fail, backflush time may need to be re-established on the same column, set especially if a retentiontime shift is when a new pre-column, analytical column, and/orrestrictor are employed, the backflush time will need to bere-established.7.5 Method Criteria:7.5.1 Verify Resolution for Gasoline Blended WithEthanolUsing the injection volume and other parameters thatwill be used for sample analysis, inject either composite mixdescribed in 8.
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