1、Designation: D7963 14Standard Test Method forDetermination of Contamination Level of Fatty Acid MethylEsters in Middle Distillate and Residual Fuels Using FlowAnalysis by Fourier Transform Infrared SpectroscopyRapid Screening Method1This standard is issued under the fixed designation D7963; the numb
2、er immediately following the 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
3、.1 This test method specifies a rapid screening methodusing flow analysis by Fourier Transform Infrared (FA-FTIR)spectroscopy with partial least squares (PLS) processing for thequantitative determination of the fatty acid methyl ester(FAME) contamination of middle distillates, in the range of20 mg k
4、g to 1000 mg kg, and of middle distillates and residualfuels, following dilution, for levels above 0.1 %.NOTE 1Annex A2 describes a dilution procedure to significantlyexpand the measurement range above 1000 mg/kg for distillates and toenable measurement of residual oilsNOTE 2This test method detects
5、 all FAME components, with peak IRabsorbance at approximately 1749 cm-1and C8to C22molecules, asspecified in standards such as D6751 and EN 14214. The accuracy of thetest method is based on the molecular mass of C16to C18FAME species;the presence of other FAME species with different molecular masses
6、 couldaffect the accuracy.NOTE 3Additives such as antistatic agents, antioxidants, and corro-sion inhibitors are measured with the FAME by the FTIR spectrometer.However any potential interference effects of these additives are elimi-nated by the flow analysis processing.NOTE 4Precision for middle di
7、stillate and residual fuel is provided inpreliminary form at this time, details are given in Appendix X1.NOTE 5The scope of this test method does not include aviationturbine fuel which is addressed by Test Method D7797.1.2 All stated values are in SI units.1.3 This standard does not purport to addre
8、ss all of thesafety concerns, if any, associated with its use. 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:2D1298 Test Meth
9、od for Density, Relative Density, or APIGravity of Crude Petroleum and Liquid Petroleum Prod-ucts by Hydrometer MethodD4052 Test Method for Density, Relative Density, and APIGravity of Liquids by Digital Density MeterD4057 Practice for Manual Sampling of Petroleum andPetroleum ProductsD4177 Practice
10、 for Automatic Sampling of Petroleum andPetroleum ProductsD6751 Specification for Biodiesel Fuel Blend Stock (B100)for Middle Distillate FuelsD7797 Test Method for Determination of the Fatty AcidMethyl Esters Content of Aviation Turbine Fuel UsingFlow Analysis by Fourier Transform Infrared Spectros-
11、copy Rapid Screening MethodE1655 Practices for Infrared Multivariate QuantitativeAnalysis2.2 CEN Standard:3EN 14214 Automotive FuelsFatty Acid Methyl Esters(FAME) for Diesel EnginesRequirements and TestMethods2.3 Energy Institute Standards:4IP 583 Test Method for Determination of the Fatty AcidMethy
12、l Esters Content of Aviation Turbine Fuel UsingFlow Analysis by Fourier Transform InfraredSpectroscopyRapid Screening Method1This test method is under the jurisdiction of ASTM Committee D02 onPetroleum Products, Liquid Fuels, and Lubricants and is the direct responsibility ofSubcommittee D02.14 on S
13、tability and Cleanliness of Liquid Fuels.Current edition approved Oct. 1, 2014. Published October 2014. DOI: 10.1520/D7963-14.2For referenced ASTM standards, visit the ASTM website, www.astm.org, orcontact ASTM Customer Service at serviceastm.org. For Annual Book of ASTMStandards volume information,
14、 refer to the standards Document Summary page onthe ASTM website.3Available from the American National Standards Institute (ANSI) 25W 43rdSt,4thFloor. New York, NY 10036.4Available from the Energy Institute, 61 New Cavendish Street, London,W1G7AR, U.K. www.energyinst.org.uk.Copyright ASTM Internatio
15、nal, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959. United States13. Terminology3.1 Definitions:3.1.1 FAME, nfatty acid methyl esters, also known asbiodiesel.3.1.1.1 DiscussionUsed as a component in automotivediesel fuel and the potential source of contamination in fuelsdue to
16、 multi-fuel tankers and pipelines.3.2 Definitions of Terms Specific to This Standard:3.2.1 FA-FTIR, nflow analysis by Fourier Transform In-frared technique uses a flow-through measurement cell to makea number of measurements on a stream of test specimen.3.2.1.1 DiscussionThe test specimen is analyze
17、d beforeand after passing through a sorbent that is designed to retardthe FAME contamination to be measured. The results arecompared to enable the amount of FAME present in the fuel tobe determined.3.2.2 sorbent cartridge, na cartridge through which thetest specimen flows, containing a specific sorb
18、ent.3.2.2.1 DiscussionThe sorbent cartridge is discarded aftereach test.4. Summary of Test Method4.1 The test specimen is automatically analyzed, by anFTIR spectrometer, in a 2 mm effective path length flow-through cell, before and after flowing through a cartridgecontaining a sorbent designed to ha
19、ve a relatively long resi-dence time for FAME.4.2 The spectroscopic absorbance differences of the IRspectra, between the measurements, are processed in conjunc-tion with a PLS-1 model to determine the presence andamplitude of the carbonyl peak of FAME at approximately1749 cm-1.4.3 The flow analysis
20、by FTIR enables the effects ofpotential interferences to be removed by using their relativeretardance times through the sorbent in conjunction with theirabsorbance at specific wavelengths.4.4 Test time is typically less than 20 min.5. Significance and Use5.1 The present and growing international gov
21、ernmentalrequirements to add FattyAcid Methyl Esters (FAME) to dieselfuel has had the unintended side-effect of leading to potentialFAME contamination of fuels in multi-fuel transport facilitiessuch as cargo tankers and pipelines, and industry wide con-cerns. This has led to a requirement to measure
22、 contaminationlevels in diesel and other fuels to assist custody transfer issues.5.2 Analytical methods have been developed with the capa-bility of measuring down to 1000 mg/kg (See Annex A2).7.6 Sorbent Cartridge6see Fig. A1.2, individually packedin a sealed envelope, one per test.8. Sampling8.1 Un
23、less otherwise specified, take a sample of at least 60mL in accordance with Practices D4057 or D4177, and/or inaccordance with the requirements of national standards orregulations for the sampling of petroleum products.8.2 Use new opaque glass or epoxy-lined metal containerswith inert closures.5The
24、following reagents and materials were used to develop the preliminaryprecision statements: Seta Verification and Calibration fluids for Seta FIJI.Stanhope-Seta, Chertsey, Surrey, KT16 8AP, UK. This is not an endorsement orcertification by ASTM. The sole source of supply of Seta Verification andCalib
25、ration fluids for Seta FIJI known to the committee at this time is Stanhope-Seta, Chertsey, Surrey, KT16 8AP, UK. If you are aware of alternative suppliers,please provide this information to ASTM International Headquarters. Your com-ments will receive careful consideration at a meeting of the respon
26、sible technicalcommittee,1which you may attend.6The sole source of supply of the apparatus known to the committee at this timeis Seta FIJI and cartridge (including filter) available from Stanhope-Seta, Chertsey,Surrey, KT16 8AP, UK. If you are aware of alternative suppliers, please provide thisinfor
27、mation to ASTM International Headquarters. Your comments will receivecareful consideration at a meeting of the responsible technical committee,1whichyou may attend.D7963 1428.2.1 Used sample containers are permitted provided it canbe confirmed they have not been used for unknown fluids or forfluids
28、containing 5 % FAME.8.2.1.1 New sample containers are strongly recommendeddue to concerns over the difficulty in removing all traces ofFAME retained from previous samples.8.2.2 Rinse all sample containers with heptane (7.1)oranother suitable solvent and drain. Then rinse with the productto be sample
29、d at least three times. Each rinse shall use productwith a volume of 10 % to 20 % of the container volume. Eachrinse shall include closing and shaking the container for aminimum of 5 s and then draining the product.9. Apparatus and Sample Preparation9.1 Follow the manufacturers instructions and on-s
30、creeninstructions for the correct set-up and shut-down of theapparatus.9.2 Run a flushing sequence using heptane (7.1) in accor-dance with the manufacturers instructions if the last testsample contained FAME in excess of 1000 mg/kg.9.3 Wipe dry the sample input tube with a lint-free cloth(7.4) befor
31、e commencing a test.9.4 Ensure that the verification and calibration of the instru-ment are in accordance with Section 10.9.5 Gently swirl the middle distillate sample for homoge-neity before drawing the test specimen. For residual fuels,warm the sample up to 50 C and agitate the sample to providemi
32、xing, such as orbiting the container horizontally.9.6 If the expected concentration of FAME is 1000 mg/kgor the sample is residual fuel, follow Annex A2 to dilute thesample.9.7 Determine the density of the middle distillate sampleusing the density measuring device (6.4) if the density is notknown. F
33、or samples previously diluted according to AnnexA2,determine the density of the diluted sample using the densitymeasuring device (6.4) if the density is not known.9.8 Use a new test specimen container, or if there is enoughtest sample available, it is permissible to clean and dry the testspecimen co
34、ntainer thoroughly before each test using heptaneand then partially fill with the test sample, swirl and drain.Repeat three times.NOTE 6New specimen containers are strongly recommended due toconcerns over the difficulty in removing all traces of FAME retained fromprevious test specimens.10. Calibrat
35、ion and Standardization10.1 Verification:10.1.1 Follow the apparatus and test specimen preparationinstructions (see Section 9) and check the validity of theverification fluids to be used.10.1.2 Verify the correct operation of the instrument usingthe verification fluid (7.2.1), in accordance with the
36、 manufac-turers instructions, at least every six months. More frequentperformance checks shall be carried out according to localquality control requirements.10.1.3 Verify the correct operation of the instrument usingall verification fluids (7.2.1 7.2.4) in accordance with themanufacturers instructio
37、ns at least every 12 months or imme-diately after any maintenance on the measurement system.10.1.4 If the result is not within R/2 plus the uncertainty ofthe verification fluids certified value or within the tolerancessupplied with the verification fluid, recheck the validity date ofthe verification
38、 fluid.NOTE 7In 10.1.4, R is the reproducibility of the test method at thecertified FAME concentration.10.1.5 Follow the manufacturers instructions regardingfault finding and calibration if it is not possible meet the criteriain 10.1.4 to verify the correct operation of the instrument.10.2 Calibrati
39、on:10.2.1 Calibrate the instrument according to the manufac-turers instructions when it is not possible to meet the criteriain to verify the correct operation of the instrument.10.2.1.1 Calibration uses nine calibration standards (7.3)covering the scope of the test method, containing knownamounts (m
40、g/kg) of FAME in a known fluid.11. Procedure (see Fig. 1)11.1 Commence the test measurement sequence (see Sec-tion 9), input the test specimen density in kilograms per metrecubed and sample identification in accordance with the manu-facturers instructions and the on-screen instructions.11.2 Insert a
41、 new sorbent cartridge (A1.1.2) and attach anew filter (A1.1.8) to the exit (bottom) of the sorbent cartridge;follow the manufacturers instructions to fit the input tube tothe cartridge.11.3 Pour approximately 50 mL of sample, which has beenprepared as described in Section 9, into the test specimenc
42、ontainer (A1.1.3), locate in position, and attach the containerlid and sample input tube.11.4 Ensure that an empty waste container, lid, and outputtube (A1.1.4) are in position.11.5 Start the test to commence the following automaticsequences as the test specimen is drawn through the instrumentby the
43、 programmed pump (see Fig. 1 and Fig. A1.1):FIG. 1 Test SequenceD7963 14311.5.1 Primes and flushes the tubing and the flow-throughmeasurement cell with the test specimen,11.5.2 Measures the spectrum of the test specimen to checkfor contamination and to obtain a reference spectrum,11.5.3 Measures the
44、 spectra of the output from the sorbentcartridge until a stable value is reached and compares with thereference spectrum,11.5.4 Re-measures the spectrum of the test specimen toobtain a second reference spectrum,11.5.5 Analyzes and compares the flow analysis spectra (see11.5.3) with the reference spe
45、ctrum and determines the FAMEpeak amplitude using a PLS-1 model (see A1.1.9) over thenominal 1660 cm-1to 1800 cm-1range,11.5.6 Calculates the FAME concentration in mg/kg usingthe apparatus calibration, the determined peak, the stored valueof the calibrant materials density, and the samples density(s
46、ee 9.7).11.5.7 Flushes the system with the remainder of the testspecimen and finally purges with air, and11.5.8 Displays the result numerically and graphically.11.6 Record the test result and follow the manufacturersinstructions to remove and dispose of the used sorbent car-tridge and filter.12. Cal
47、culation12.1 For samples measured directly, report the amount ofFAME in the sample to the nearest 0.01 mg/kg. For samplesprepared following Annex A2, report the amount of FAME(percent by mass) in the sample to the nearest 0.01 %.12.2 For samples measured directly, calculate the FAMEconcentration as
48、follows:FAME mg/kg 5 Cm! 3SPcPsD(1)where:Cm= value directly from the integral apparatus calibration inmg/kg,Ps= density of the sample in kg/m3, andPc= density of the calibrant material in kg/m3,12.3 For samples prepared following Annex A2, calculatethe FAME concentration as follows:FAME percent 5 FA
49、ME mg/kg! 3DF10 000(2)where:FAME percent = FAME, by mass percent,FAME mg/kg = value obtained from Eq 1 for the dilutedsample, andDF = dilution factor obtained from Eq A2.1 inAnnex A2.13. Report13.1 The test report shall contain at least the followinginformation:13.1.1 A reference to this test method,13.1.2 All details necessary for complete identification ofthe product tested,13.1.3 The result of the test (see Section 12),13.1.4 Any deviations, by agreement or otherwise, from theprocedures specified, and13.1.5 The time and date of the test.14.
