1、Designation: D7524 10IP 568/08Standard Test Method forDetermination of Static Dissipater Additives (SDA) inAviation Turbine Fuel and Middle Distillate FuelsHighPerformance Liquid Chromatograph (HPLC) Method1This standard is issued under the fixed designation D7524; the number immediately following t
2、he 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. Scope1.1 This test method covers
3、 the determination of staticdissipater additive (SDA) content of aviation turbine fuel andmiddle distillate fuels.1.2 The precision of this test method has been establishedfor aviation turbine fuel over the concentration range of 1 to12 mg/L. Higher concentrations can be determined by dilution,but t
4、he precision of the test method will not apply.NOTE 1The SDA used to develop this test method was STADIS 4502for aviation fuels and STADIS 450 and 4252for middle distillates.1.3 The test method includes a procedure to concentrate thesulfonic acid component in the SDA prior to analysis.1.4 The test m
5、ethod only applies to SDAs that contain alkylsubstituted sulfonic acid.1.5 The values stated in SI units are to be regarded asstandard. No other units of measurement are included in thisstandard.1.6 This standard does not purport to address all of thesafety concerns, if any, associated with its use.
6、 It is theresponsibility of the user of this standard to establish appro-priate safety and health practices and determine the applica-bility of regulatory limitations prior to use.2. Referenced Documents2.1 ASTM Standards:3D4057 Practice for Manual Sampling of Petroleum andPetroleum ProductsD4177 Pr
7、actice for Automatic Sampling of Petroleum andPetroleum Products2.2 ISO Standards:4EN ISO 3696 Water for analytical laboratory useSpecifications and test methods2.3 Energy Institute Standards:5IP 568/08 Determination of the static dissipater additives(SDA) in aviation turbine fuel and middle distill
8、atefuelsHPLC method3. Terminology3.1 Definitions:3.1.1 middle distillate fuels, ngeneric refinery/supplierterm that usually denotes a fuel primarily intended for use incompression ignition/diesel engine applications, and also innon-aviation gas turbine engines and other non-automotiveapplications su
9、ch as a burner fuel.3.2 Definitions of Terms Specific to This Standard:3.2.1 aviation turbine fuel, nfuel used for powering jetand turbo-prop engine aircraft.3.2.2 conductivity improver additive, nmaterial added to afuel in very small amounts to increase its electrical conductiv-ity and thereby redu
10、ce relaxation time.3.2.2.1 DiscussionConductivity improver additives arealso known as static dissipater additives (SDAs) or antistaticadditives.4. Summary of Test Method4.1 A solid phase extraction procedure is used to concen-trate the sulfonic acid component of SDApresent in an aviation1This test m
11、ethod is under the jurisdiction of ASTM Committee D02 onPetroleum Products and Lubricants and is the direct responsibility of SubcommitteeD02.04.0C on Liquid Chromatography.Current edition approved Feb. 15, 2010. Published April 2010. DOI:10.1520/D752410.2Stadis 450 and 425 are registered trademarks
12、 marketed by Innospec, Inc.,Innospec Manufacturing Park, Oil Sites Road, Ellesmere Port, Cheshire Ch65 4EY,UK.3For referenced ASTM standards, visit the ASTM website, www.astm.org, orcontact ASTM Customer Service at serviceastm.org. For Annual Book of ASTMStandards volume information, refer to the st
13、andards Document Summary page onthe ASTM website.4Available from International Organization for Standardization (ISO), 1, ch. dela Voie-Creuse, Case postale 56, CH-1211, Geneva 20, Switzerland, http:/www.iso.ch.5Available from Energy Institute, 61 New Cavendish St., London, WIG 7AR,U.K., http:/www.e
14、nergyinst.org.uk.1Copyright ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959, United States.turbine fuel or middle distillate fuel sample prior to analysis. Afixed volume of the concentrated test fraction is injected into acalibrated high performance liquid ch
15、romatograph. An analyti-cal column is used to separate the sample components of thetest fraction by polarity.4.2 The analytical column is attached to a liquid chroma-tography detector where the sulfonic acid components arereadily detected by UV absorption as they elute from thecolumn. The electronic
16、 signal from the liquid chromatographydetector is continually monitored by a chromatography datasystem. The amplitudes of the signal (peak area) from thesulfonic acids are compared with those obtained from previ-ously measured calibration standards in order to calculate thepercent m/V SDA present in
17、 the sample.4.3 The test method only applies to SDAs that contain alkylsubstituted sulfonic acids.5. Significance and Use5.1 This test method will allow the determination of staticdissipater additive in jet and middle distillate. These additivesreduce the hazardous effects of static electricity gene
18、rated bytransfer and movement of jet and middle distillate fuels.6. Apparatus6.1 High Performance Liquid Chromatograph (HPLC)Any HPLC capable of pumping an isocratic mobile phase atflow rates between 0.1 and 1.5 mL/min, with a precision betterthan 0.5% and a pulsation of 1% full scale deflection und
19、erthe test method conditions.6.2 Variable Wavelength Ultraviolet Photometric Detectoror Photometric Diode Array DetectorCapable of operationat 225 and 234 nm.6.3 Manual or Automatic Sample Injection ValveCapableof injecting 10 to 25 L, using either partial or full loop mode,with a repeatability 61%.
20、6.3.1 An equal and constant volume of the calibration andsample solutions is injected into the chromatograph. Bothmanual and automatic sample injection systems (using eithercomplete or partial filling of the sample loop) will, when usedcorrectly, meet the repeatability requirements specified in 6.3.
21、NOTE 2When using the partial loop-filling mode, it is recommendedthat the injection volume should be less than half the total loop volume.For complete filling of the loop, best results are obtained by overfilling theloop at least six times.6.4 Chromatography Data SystemAny data system can beused, pr
22、ovided it is compatible with the liquid chromatographydetector, has a minimum sampling rate of 1 Hz, and is able tomeasure peak areas and retention times and perform post-rundata processing such as baseline correction and re-integration.6.5 Analytical Column6Any stainless steel HPLC columnpacked wit
23、h C6alkyl-bonded reversed-phase, 5 m particlesize, 250 3 4.6 mm ID is suitable, provided that it meets theresolution requirements specified in 9.3.6.6 HPLC Column OvenAny suitable HPC column ovenblock heating or air circulating) capable of maintaining aconstant temperature of 61C within the range fr
24、om 20 to40C.NOTE 3Alternative forms of temperature control are permitted, forexample, temperature-controlled laboratories.6.7 Analytical BalanceAccurate to 60.0001 g.6.8 Solid Phase Extraction (SPE) Columns Reservoirs6Amino bonded silica, 6500 mg (A) or 100 mg (B) capacity.6.8.1 Reservoirs with Conn
25、ectorsApproximately 60 mLcapacity and connectors.6.9 Solid Phase Extraction Vacuum ManifoldOptional.6.10 Volumetric FlasksClass A, of 2 mL, 5 mL, 10 mL,25 mL, and 100 mL capacity.6.11 Graduated PipetteClass A, of 1 mL, 2 mL, 10 mL,and 50 mL capacity. Capable of delivering volumes of therange 0.5 to
26、4.0 mL with an accuracy of 60.0005 mL.6.12 Measuring Cylinder50 and 500 mL capacity.6.13 pH meter.7. Reagents and Materials7.1 Dinonylnaphthalene Sulfonic Acid (DINNSA)50 %(m/m) solution in heptane.7.2 Dodecylbenzene Sulfonic Acid (DDBSA)70 % (m/m)solution in 2-propanol.7.3 TetrahydrofuranHPLC grade
27、. (WarningHPLCgrade tetrahydrofuran does not contain inhibitor, hence explo-sive peroxides may form. Highly flammable and may causeirritation by inhalation, ingestion or skin contact.)7.4 Hydrochloric Acid37%.7.5 MethanolHPLC grade. (WarningMethanol ishighly flammable and toxic by inhalation, ingest
28、ion or skincontact.)7.6 Methanolic Hydrochloric AcidMix approximately1 mL of hydrochloric acid (see 7.4) with approximately 9 mLof methanol (see 7.5).7.7 Orthophosphoric Acid.7.8 Sodium Hydroxide Pellets.7.9 Sodium Hydroxide SolutionApproximately 1M. Dis-solve approximately4gofsodium hydroxide (see
29、7.8)inapproximately 100 mL of water.7.10 Buffered Phosphoric AcidAdd approximately 2 mLof orthophosphoric acid (see 7.7) to approximately 1l mL ofwater and buffer to 2.5 pH using sodium hydroxide solution(see 7.9).7.11 IsohexaneHPLC grade. (WarningIsohexane ishighly flammable, and may cause irritati
30、on by inhalation,ingestion or skin contact.)7.12 Solid Phase Extraction (SPE) Columns andCartridgesAmino-bonded silica, 500 and 100 mg.7.13 Mobile PhaseMix approximately 400 mL methanol(see 7.5), approximately 400 mL THF (see 7.3), and approxi-mately 50 mL of buffered phosphoric acid (see 7.10).7.14
31、 NitrogenOptional.NOTE 4It is recommended practice to degas HPLC mobile phasebefore use; this can be done conveniently, on-line or off-line, by heliumsparging, vacuum degassing, or ultrasonic agitation. A failure to degas themobile phase may lead to negative peaks.6The sole source of supply of the a
32、pparatus known to the committee at this timeis Waters Corp. 34 Maple St., Milford, MA 01757. If you are aware of alternativesuppliers, please provide this information to ASTM International Headquarters.Your comments will receive careful consideration at a meeting of the responsibletechnical committe
33、e,1which you may attend.D7524 1027.15 Calibration Stock SolutionsAccurately weigh, to thenearest 0.0001 g, between 0.078 and 0.082 g of DINNSAsolution (7.1) into a 100 mL volumetric flask and make up tothe mark with heptane or mobile phase (7.13). Accuratelyweigh, to the nearest 0.0001 g, between 0.
34、028 to 0.032 g ofDDBSA solution (7.2) into a 100 mL volumetric flask andmake up to the mark with heptane or mobile phase (7.13).7.16 Calibration StandardsFrom the calibration stocksolutions (7.15), prepare a set of five calibration standards inthe mobile phase (7.13) to cover the concentration range
35、sindicated in the table:SPE Column Size DINNSA DDBSA500 mg 0.8 to 16 mg/mL 0.7 to 8.5 mg/mL100 mg 0.32 to 9 mg/mL 0.35 to 4.5 mg/mLNOTE 5A suggested procedure to prepare these standards is given inAnnex A1.7.17 Calibration Check Solutions2.0 mg/L DINNSA and2.8 mg/L DBSA.7.17.1 Prepare a 500 mg/L DIN
36、NSA solution by accuratelyweighing, to the nearest 0.0001 g, about 0.05 g DINNSA (7.1)into a 50 mL volumetric flask and making up to the mark withheptane. Pipette 1 mL of this solution into a 25 mL volumetricflask and make up to the mark with heptane (20 mg/LDINNSAsolution). Pipette 1 mL of the 20 m
37、g/L DINNSA solution intoa 10 mL volumetric flask and make up to volume with mobilephase (7.13) to give a 2.0 mg/L check solution.7.17.2 Prepare a 700 mg/L DDBSA solution by accuratelyweighing, to the nearest 0.0001 g, 0.05 g DDBSA (7.2) into a50 mL volumetric flask and making up to the mark withhept
38、ane. Pipette 1 mL of this solution into a 25 mL volumetricflask and make up to the mark with heptane (28 mg/L DDBSAsolution). Pipette 1 mL of the 28 mg/L DDBSA solution into a10 mL volumetric flask and make up to volume with mobilephase (7.13) to give a 2.8 mg/L check solution.7.18 WaterGrade 3 of E
39、N ISO 3696.8. Sampling8.1 Use only representative samples obtained as describedin Practice D4057 or D4177, unless otherwise specified.9. Sample Preparation9.1 Clamp the SPE column, 6.8(A) or 6.8(B), vertically orattach to a vacuum manifold if used. Add a 60 mL reservoir tothe 500 mg SPE column (6.8(
40、A) using a connector (6.8.1); the100 mg SPE column has an integral reservoir.9.2 With a pipette, transfer the test specimen (see Table 1)tothe SPE reservoir and allow the fuel to percolate through thecolumn under gravity or vacuum at a flow rate of 2 mL/min orless. Discard the eluate.9.3 After all t
41、he fuel has eluted from the SPE column, rinsethe reservoir and SPE adsorbent with portions of isohexane (orheptane) and then methanol, discarding the eluate (see Table1).9.4 Elute the sulfonic acid (DINNSA or DDBSA) from the100 or 500 mg SPE column using approximately 2 or 5 mL ofmobile phase (7.13)
42、, respectively, and collect the eluate in a 2or 5 mL volumetric flask (6.10), making up to the mark withmobile phase (7.13) if necessary. Replace stopper in volumetricflask and shake well.9.5 Sample and eluent volumes are summarized in Table 1.10. Preparation of Apparatus10.1 Set up the pump, inject
43、or, detector, and data systemaccording to the manufacturers instructions. Set the UVdetector to 234 nm for DINNSA and 225 nm for DDBSA.10.2 Install the HPLC column and set the mobile phase flowrate to 0.5 mL/min.NOTE 6Set the temperature of the column oven, if used, to at least10C above ambient, for
44、 example, 40C.10.3 When operating conditions are steady, inject a fixedvolume (10 L to 25 L) of the middle calibration standard(7.16), and ensure the chromatogram resembles those shown inFig. 1 (DINNSA) or Fig. 2 (DDBSA).NOTE 7The sulfonic acid peak around 4 min may exhibit somebroadening due to the
45、 presence of isomers but no fine structure.NOTE 8Small adjustments in the buffered phosphoric acid content ofthe mobile phase may improve the chromatographic profile of the sulfonicacid.10.4 Inject a fixed volume (10 to 25 L) of the lowestconcentration calibration standard (7.16) to check systemsens
46、itivity. The detector shall have a signal to noise ratio (S/N)greater than 10 for the lowest concentration calibration stan-dard; increase the injection volume if necessary.10.5 Inject the same volume (10 to 25 L) of middlecalibration standard (7.16) five times to check system repeat-ability (less t
47、han 1 %).10.6 Inject the same volume (10 to 25 L) of all calibrationstandards (7.16) to check system linearity (correlation co-efficient greater than 0.995).10.7 Inject the same (10 to 25 L) of the highest concen-tration standard (7.16) followed by blank (mobile phase)injection to check for analyte
48、carryover (less than 0.05 %).10.8 Determination of Injection VolumeWhen operatingconditions are steady, as indicated by a stable horizontalbaseline of the liquid chromatography detector, inject a fixedvolume (10 to 25 L) of the lowest calibration standard (E) andrecord the chromatogram with the chro
49、matography data systemto check system sensitivity. Select a fixed injection volume thatprovides a detector response (that is, signal to baseline noiseratio) of at least 10 for standard (E). Use the same selectedinjection volume for all analyses in this test method.NOTE 9At a mobile phase flow rate of 0.5 mL/min, the analysis timeshould be approximately 20 min.10.9 Evaluate Injection System RepeatabilityInject afixed volume of middle calibration (C) standard five times,recording each chromatogram with the chromatograph
