1、Designation: D 7183 07e1Standard Test Method forDetermination of Total Sulfur in Aromatic Hydrocarbons andRelated Chemicals by Ultraviolet Fluorescence1This standard is issued under the fixed designation D 7183; the number immediately following the designation indicates the year oforiginal adoption
2、or, in the case of revision, the year of last revision. A number in parentheses indicates the year of last reapproval. Asuperscript epsilon (e) indicates an editorial change since the last revision or reapproval.e1NOTEResearch report was added editorially in September 2007.1. Scope1.1 This test meth
3、od covers the determination of sulfur inaromatic hydrocarbons, their derivatives, and related chemi-cals.1.2 This test method is applicable to samples with sulfurconcentrations from 0.5 to 100 mg/kg.1.3 The following applies for the purposes of determiningthe conformance of the test results using th
4、is test method toapplicable specifications, results shall be rounded off in accor-dance with the rounding-off method of Practice E29.1.4 The values stated in SI units are to be regarded asstandard. No other units of measurement are included in thisstandard.1.5 This standard does not purport to addre
5、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. For specific hazardstatements, see Section 9.2. Reference
6、d Documents2.1 ASTM Standards:2D 1555 Test Method for Calculation of Volume and Weightof Industrial Aromatic Hydrocarbons and CyclohexaneD 3437 Practice for Sampling and Handling Liquid CyclicProductsD 6809 Guide for Quality Control and Quality AssuranceProcedures for Aromatic Hydrocarbons and Relat
7、ed Ma-terialsE29 Practice for Using Significant Digits in Test Data toDetermine Conformance with SpecificationsE 691 Practice for Conducting an Interlaboratory Study toDetermine the Precision of a Test Method2.2 Other DocumentsOSHA Regulations, 29 CFR, paragraphs 1910.1000 and1910.120033. Terminolog
8、y3.1 oxidative pyrolysis, na process in which a sample iscombusted in an oxygen-rich atmosphere at high temperatureto break down the components of the sample into elementaloxides.3.2 ultraviolet fluorescence, nradiation in the region ofthe electromagnetic spectrum including wavelength from 100to 390
9、0A that excites SO2to (SO2*).4. Summary of Test Method4.1 A specimen is either directly injected or placed in asample boat. The boat is then inserted into a high temperaturecombustion tube where the sulfur is oxidized to sulfur dioxide(SO2) in an oxygen-rich atmosphere. Water produced duringthe samp
10、le combustion is removed and the sample combustiongases are next exposed to ultraviolet (UV) light. The SO2absorbs the energy from the UV light and is converted toexcited sulfur dioxide (SO2*). As it returns to a stable state,light is emitted and detected by a photomultiplier tube and theresulting s
11、ignal is a measure of the sulfur contained in thespecimen.5. Significance and Use5.1 Some process catalysts used in petroleum and chemicalrefining can be poisoned when trace amounts of sulfur-bearingmaterials are contained in the feedstocks. This test method canbe used to determine sulfur in process
12、 feeds, sulfur in finishedproducts, and can also be used for purposes of regulatorycontrol.6. Interferences6.1 Halogens present in the specimen in concentrationsgreater than 10 % and nitrogen concentrations of 1500 mg/kgor greater can interfere.1This test method is under the jurisdiction of ASTM Com
13、mittee D16 onAromatic Hydrocarbons and Related Chemicals and is the direct responsibility ofSubcommittee D16.04 on Instrumental Analysis.Current edition approved Jan. 15, 2007. Published April 2007.2For referenced ASTM standards, visit the ASTM website, www.astm.org, orcontact ASTM Customer Service
14、at serviceastm.org. For Annual Book of ASTMStandards volume information, refer to the standards Document Summary page onthe ASTM website.3Available from U.S. Government Printing Office Superintendent of Documents,732 N. Capitol St., NW, Mail Stop: SDE, Washington, DC 20401, http:/www.access.gpo.gov.
15、1Copyright ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959, United States.Copyright by ASTM Intl (all rights reserved); Mon Apr 14 02:14:21 EDT 2008Downloaded/printed byGuo Dehua (CNIS) pursuant to License Agreement. No further reproductions authorized.6.2 Mo
16、isture produced during the combustion step caninterfere if not removed prior to the gas entering the detectorcell.7. Apparatus7.1 Pyrolysis FurnaceAn electric furnace capable ofmaintaining a temperature sufficient to volatilize and pyrolyzeall the sample and oxidize sulfur to SO2. The actual tempera
17、-ture should be recommended by specific instrument manufac-turer.7.2 Quartz Pyrolysis TubeCapable of withstanding 900 to1200C. The tube should be recommended by the instrumentmanufacturer.7.3 Microlitre SyringeCapable of delivering from 5 to250 L of sample. Check with the instrument manufacturer for
18、recommendations for specific sample requirements.7.4 Constant Rate Injector SystemIf the sample is to beintroduced into the pyrolysis furnace via syringe, use aconstant rate injector or a liquid introduction module.7.5 Liquid Auto-SamplerCapable of injecting 5 to 250 Lof sample.7.6 Automatic Boat Dr
19、ive SystemIf the instrument isequipped with an inlet system, a device for driving the boatinto the furnace at a controlled and repeatable rate is required.7.7 Flow ControlThe instrument must be equipped withflow controllers capable of maintaining a constant supply ofoxygen and carrier gas.7.8 Drier
20、TubeThe instrument must be equipped with amechanism for removal of water vapor.8. Reagents8.1 Purity of ReagentsReagent grade chemicals shall beused in all tests. It is intended that all reagents shall conform tothe specifications of the Committee on Analytical Reagents ofthe American Chemical Socie
21、ty,4where such specifications areavailable, unless otherwise indicated. Other grades may beused, provided it is first ascertained that the reagent is ofsufficiently high purity to permit its use without lessening theaccuracy of the determination.8.2 Inert GasEither argon (Ar) or helium (He) may beus
22、ed. The purity should be no less than 99.99 mol %.8.3 Oxygen GasThe purity should be no less than 99.99mol %.8.4 SolventThe solvent chosen should be capable ofdissolving the sulfur compound. The solvent of choice shouldhave a boiling point similar to the sample being analyzed.Suggested possibilities
23、 include, but not limited to methanol,iso-octane, and p-xylene (see Note 1 and Note 2).NOTE 1A quick screening can be conducted by injecting the solventand sample once or twice and comparing relative area counts.NOTE 2All solvents should have known sulfur content or known to beless than what will in
24、terfere with results.8.5 DibenzothiopheneFW184.26, 17.399 % (m/m) Sulfur(see Note 3).NOTE 3A correction for chemical impurity is required. Normally98 %.8.6 Quartz WoolIf needed.8.7 Sulfur Stock Solution, approximately 870 to 1044 gS/mlThis standard may be purchased if desired. Prepare astock solutio
25、n by accurately weighing approximately 0.5 to 0.6g of dibenzothiophene to the nearest 0.1 mg into a tared 100mL volumetric flask. Record the weight. Dilute to volume withthe selected solvent. Use Eq 1 to determine the concentrationof stock solution. This stock solution can be further diluted todesir
26、ed sulfur concentrations (see Note 4 and Note 5). Alter-nate volumes of solutions may be prepared so long as thepreparation meets the concentration specified.g S/ml solvent 5gofDBT!3.174!3Purity of DBT!3106!100 ml of Solvent(1)where:DBT = dibenzothiopheneSinDBT = 17.3994 %NOTE 4Working standards sho
27、uld be remixed on a regular basisdepending upon frequency of use and age. Typically, stock solutions havea useful life of about 3 months.NOTE 5Check all new calibration standards against the previousstandard.9. Hazards9.1 Consult the current version OSHA regulations, suppli-ers Material Data Sheets,
28、 and local regulations for all mate-rials used in this test method.9.2 High temperature is employed in this test method. Extracare must be exercised when using flammable materials nearthe furnace.9.3 WarningExposure to excessive quantities of ultravio-let light is injurious to health. The operator m
29、ust avoidexposing any part of their person, especially their eyes, notonly to direct UV light but also to secondary or scatteredradiation that is present.10. Sampling10.1 Consult guidelines for taking samples from bulk con-tainers in accordance with Practice D 3437.11. Preparation of Apparatus11.1 S
30、et-up the instrument in accordance with manufactur-ers instructions.11.2 Adjust gas flows and pyrolysis temperature(s) to theoperating conditions recommended by the manufacturer.11.3 The actual operation of injecting a sample will varydepending upon the instrument manufacturer and the type ofinlet s
31、ystem used.11.4 An auto-sampler or a constant rate injector must beused when using an instrument equipped with a verticalfurnace.11.5 Prebake the sample boats to be used for the determi-nation.4Reagent Chemicals, American Chemical Society Specifications, AmericanChemical Society, Washington, DC. For
32、 suggestions on the testing of reagents notlisted by the American Chemical Society, see Analar Standards for LaboratoryChemicals, BDH Ltd., Poole, Dorset, U.K., and the United States Pharmacopeiaand National Formulary, U.S. Pharmacopeial Convention, Inc. (USPC), Rockville,MD.D718307e12Copyright by A
33、STM Intl (all rights reserved); Mon Apr 14 02:14:21 EDT 2008Downloaded/printed byGuo Dehua (CNIS) pursuant to License Agreement. No further reproductions authorized.12. Calibration and Standardization12.1 Using the sulfur standard stock solution (see 8.7),make a series of calibrations standards cove
34、ring the range ofexpected sulfur concentration. If the expected levels include 0to 1.0 mg/kg and 1 to 100 mg/kg, then two curves should bemade to cover the entire range, one from 0 to 1.0 mg/kg (lowcurve) and one from 1.0 to 100 mg/kg (high curve).NOTE 6When looking for levels of sulfur below 1 mg/k
35、g make acalibration curve using an auto-sampler or constant rate injector andstandards, made from the sulfur stock solution, to cover the expectedrange of samples. Follow manufacturers recommendations for construct-ing the curve.NOTE 7When looking for concentrations from 1 mgS/kg to 100mgS/kg, follo
36、w manufacturers recommendations for constructing thecurve.12.2 The sample size can be determined either volumetri-cally, by syringe or by mass.12.3 Volumetric measurement can be utilized by filling thesyringe with standard, carefully eliminating all bubbles, andpushing the plunger to a calibrated ma
37、rk on the syringe, andrecording the volume of liquid in the syringe. After injectingthe standard, read the volume remaining in the syringe. Thedifference between the two volume readings is the volume ofstandard injected. This test method requires the known ormeasured density, to the third decimal pl
38、ace.12.4 Alternatively, the syringe may be weighed before andafter the injection to determine the weight of the sampleinjected. This technique provides greater precision than thevolume delivery method, provided a balance with a precisionof 60.0001 g is used.12.5 Follow the instrument manufacturers r
39、ecommendationfor introducing samples into the instrument.12.6 If there are any problems with the calibration standardsfollow the instrument manufacturers recommendations tocorrect.12.7 Construct a linear regression curve (g S versus Area)using as many points as recommended by the instrumentmanufactu
40、rer.12.8 The linear regression curve should have a minimum of0.99 correlation coefficient. If it does not, examine each pointon the curve to determine which point or points are out. Correctthe problem and run new Standards.13. Procedure13.1 Obtain a test specimen using the procedure describedin Sect
41、ion 10. The sulfur concentration in the test specimenmust be less than the concentration of the highest standard andgreater than the concentration of the lowest standard used inthe calibration.13.2 Follow the instrument manufacturers recommenda-tions for sample size.13.3 Follow the instrument manufa
42、cturers recommenda-tions for introducing samples into the instrument.13.4 Determine the sulfur concentration, by the average ofthree determinations, calculated by the instrument software.Make sure replicates are repeatable.14. Calculation14.1 All calculations are performed by the software, andresult
43、s are displayed and printed out in ppm (mg/kg) asappropriate. The density is input during sample data entry andis used by the instrument to convert from wt./vol. to wt./wt.14.2 Use Test Method D 1555 for measurements utilizingvolume and known density in milligrams per kilograms asfollows:Sulfur, mg/
44、kg 5MB!V 3 D(2)14.3 Measurement utilizing weight of sample:sulfur, mg/kg 5M2B!w(3)where:M = measured sulfur value, gB = blank measured sulfur value, gV = sample injection volume, mLD = density of sample g/mLw = weight of sample, g15. Report15.1 Report the sulfur results as (mg/kg ) of the sample tot
45、he nearest 0.01 mg/kg for samples less than 1 mg/kg. Reportto the nearest .1 for sample greater than 1 mg/kg.16. Precision and Bias516.1 The precision of this test method is based on guidelinesof Practice E 691, an interlaboratory study determination ofTotal Sulfur in Aromatic Hydrocarbons and Relat
46、ed Chemicalsby Ultraviolet Fluorescence, conducted in 2004. Each of 19laboratories tested 5 different materials for sulfur concentra-tions between 0.05 and 0.9 mg/kg (Table 1). In a correspondingeffort, 25 laboratories joined in the evaluation of 3 materialswith sulfur concentrations between 15 and
47、90 mg/kg (Table 2).Each test result was average of 3 individual determinations.Participating laboratories reported 3 replicate test results foreach material. All samples were prepared from high purityp-xylene with known quantities of sulfur added.16.1.1 RepeatabilityTwo test results obtained within
48、onelaboratory shall be judged not equivalent if they differ by morethan the “r” value for that material; “r” is the intervalrepresenting the critical difference between two test results forthe same material, obtained by the same operator using thesame equipment on the same day in the same laboratory
49、.16.1.2 ReproducibilityTwo test results should be judgednot equivalent if they differ by more than the “R” value for thatmaterial; “R” is the interval representing the difference be-tween two test results for the same material, obtained bydifferent operators using different equipment in different labo-ratories.16.1.3 Any judgement in accordance with these two state-ments would have an approximate 95 % probability of beingcorrect.5Supporting data have been filed at ASTM International Headquarters and maybe obtained by requesting Resea
