1、Designation: D7679 11Standard Test Method forSulfur Content in Carbon Black Feedstock Oils1This standard is issued under the fixed designation D7679; the number immediately following the designation indicates the year oforiginal adoption or, in the case of revision, the year of last revision. A numb
2、er 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 instrumental determinationof sulfur content in samples of carbon black feedstock oils.Values obtained represent
3、 the total sulfur content. Two analysismethods are available for use:Test Method A: High-Temperature Combustion WithInfrared Absorption Detection ProceduresSections 4-10Test Method B: X-Ray Fluorescence Sections 11-151.2 This test method is applicable to carbon black feedstockoils derived from petro
4、leum, coal, and other sources whichinclude fuel oils, residues, tars, pitches, reclaimed oils, andsimilar materials that are normally handled as liquids. This testmethod is applicable to products typically containing 0 to 5mass % sulfur.1.3 The results of these tests can be expressed as mass %sulfur
5、.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 address all of thesafety concerns, if any, associated with its use. It is theresponsibility of the user of this standard to establish app
6、ro-priate safety and health practices and determine the applica-bility of regulatory limitations prior to use.2. Referenced Documents2.1 ASTM Standards:2D1619 Test Methods for Carbon BlackSulfur ContentD4057 Practice for Manual Sampling of Petroleum andPetroleum ProductsD4177 Practice for Automatic
7、Sampling of Petroleum andPetroleum Products3. Significance and Use3.1 Measuring the total sulfur content of feedstock oil isoften a necessary component in calculations for sulfur dioxideemissions.3.2 The carbon black industry measures sulfur content offeedstock oils along with sulfur content of carb
8、on blackproducts per Test Method D1619 in calculations to determinesulfur dioxide emissions for compliance with governmentalreporting requirements.TEST METHOD A: HIGH-TEMPERATURECOMBUSTION WITH INFRARED ABSORPTIONDETECTION PROCEDURES4. Summary of Test Method4.1 In this test method, a sample of feeds
9、tock oil is weighedin a combustion boat containing either a tungsten oxide basedaccelerator, sand or aluminum oxide absorbent, and the sulfurcontent is determined by placing the boat in a tube furnace at1350C in an air or oxygen-enriched atmosphere resulting incomplete combustion. Sulfur in the samp
10、le is completelyoxidized to sulfur dioxide. Moisture and particulates areremoved from the gas stream by traps filled with anhydrousmagnesium perchlorate. The gas stream is then passed througha cell in which sulfur dioxide concentration is measured by aninfrared (IR) absorption detector at a precise
11、wavelength in theIR spectrum. The IR absorption detects sulfur dioxide through-out the entire combustion process. The integral of the detectorsignal is the basis for the total sulfur content of a sample.4.2 This test method is for use with commercially availablesulfur analyzers equipped to carry out
12、 the combustion andmeasurement operations automatically.4.3 The sulfur analyzer shall be calibrated using appropriatecalibration standards (see 6.7).4.4 The instrument may be configured to analyze more thanone element such as a carbon-sulfur analyzer. In this case, theanalyzer has individual detecto
13、rs for each element that arearranged in series.1This test method is under the jurisdiction of ASTM Committee D24 on CarbonBlack and is the direct responsibility of Subcommittee D24.66 on Environment,Health, and Safety.Current edition approved Nov. 1, 2011. Published December 2011. Originallyapproved
14、 in 2010. Last previous edition approved in 2010 as D7679 10. DOI:10.1520/D7679-11.2For referenced ASTM standards, visit the ASTM website, www.astm.org, orcontact ASTM Customer Service at serviceastm.org. For Annual Book of ASTMStandards volume information, refer to the standards Document Summary pa
15、ge onthe ASTM website.1Copyright ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959, United States.5. Apparatus5.1 There are a number of commercially available instru-ments designed to measure sulfur content in organic materialsincluding sulfur and carbon-sulfur
16、 combustion analyzers. Thistest method makes no specifications regarding system designs.5.2 Functionally, however, the following are specified for allinstruments:5.2.1 An analytical balance, or equivalent, that is capable ofa weighing sensitivity of 0.1 mg or better resolution.5.2.2 The combustion t
17、ube and boat are made of a suitablematerial such as mullite, porcelain, or zircon.5.2.3 The sample is absorbed onto a solid which mayinclude the following materials: (1) tungsten oxide basedaccelerator; (2) Sea sand; (3) Aluminum oxide. Refer to theinstrument manufacturers recommendations.5.2.4 The
18、sample is combusted at a temperature of 1350 615C in an air or oxygen-enriched atmosphere.5.2.5 The combustion gas is passed through an absorbent(anhydrous magnesium perchlorate) to remove water vapor.5.2.6 The detection system measures sulfur dioxide using anIR absorption detector at a wavelength s
19、uitable for linearresponses with respect to the concentration over the full rangeof possible concentrations.6. Reagents6.1 Purity of ReagentsReagent-grade chemicals shall beused in all tests. Unless otherwise indicated, it is intended thatall reagents shall conform to the specifications of the Commi
20、t-tee on Analytical Reagents of the American Chemical Societywhere such specifications are available.3Other 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.6.2 Magnesium Perchlorat
21、e.6.3 Oxygen, high purity, 99.9 %.6.4 Tungsten (VI) Oxide Accelerator, containing potassiumdihydrogen-phosphate (optional).6.5 Sea Sand, purified by acid and calcinated (optional).6.6 Aluminum Oxide, optional.6.7 Calibration Standards.47. Sampling7.1 Collect feedstock oil as specified in Practices D
22、4057 orD4177.7.2 SampleThis is the portion or aliquot of the feedstockoil for use in obtaining a result.7.3 PreparationWarm viscous samples until they are fluidand shake for 5 s.7.4 TransferUse any convenient, clean syringe or pipet totransfer a sample to the combustion boat as described inSection 1
23、0.8. Preparation of Apparatus8.1 Assemble the apparatus according to the manufacturersinstructions.8.2 Stabilize the furnace temperature at 1350 6 15C.8.3 Make a minimum of two determinations to condition theequipment or follow the manufacturers recommendation tocondition equipment before calibratin
24、g the instrument.9. Calibration9.1 Calibrate the instrument per the manufacturers recom-mendation using appropriate sulfur calibration standards.9.2 Adjustment of Response of Measurement SystemWeigh approximately 0.1 to 0.2 g of calibration standard or usethe recommended mass per manufacturer. Analy
25、ze the sample(see Section 10). Repeat this procedure. Adjust the instrumentas recommended by the manufacturer until the absence of driftis indicated. Insure the minimum analysis time is sufficient forcomplete combustion of the sample.9.3 Calibration ProcedureFollow the calibration proce-dure recomme
26、nded by the manufacturer. Confirm the calibra-tion by analyzing a reference material of known sulfur con-centration. Reference standards should be similar to feedstockoils with sulfur content in the range of approximately 0 to 5 %.The measured value should be within allowable limits of theknown valu
27、e. If not, repeat the procedure. If acceptable resultsare not obtained, refer to the manufacturers instructions forcalibration.10. Procedure10.1 Stabilize and verify calibration of the analyzer (seeSections 8 and 9).10.2 Confirm the furnace temperature is 1350 6 15C.10.3 Weigh an appropriate mass of
28、 accelerator or absorbentinto the combustion boat.NOTE 1Use a material and mass recommended by the instrumentmanufacturer suitable for the combustion boat in use. Calibration stan-dards and feedstock samples should be analyzed using a similar mass ofaccelerator or absorbent.10.4 Weigh approximately
29、0.1 to 0.2 g of the sample intothe combustion boat on top of the accelerator or absorbent.10.5 Record the sample weight.10.6 A portion of the accelerator or absorbent within theboat may be used to cover the sample, or alternatively,additional accelerator or absorbent may be weighed and addedto cover
30、 the sample.NOTE 2When covering the sample use care to insure none of thesample is accidentally removed from the combustion boat due to contactwith a spatula or other tool used to transfer or position the accelerator orabsorbent.10.7 Initiate the analysis and place the boat in the instru-ment using
31、a boat puller or an auto-sampler mechanism.10.8 When the analysis is complete, the instrument shouldindicate the sulfur value. Refer to the manufacturers recom-mended procedure.3Reagent Chemicals, American Chemical Society Specifications, AmericanChemical Society, Washington, DC. For Suggestions on
32、the testing of reagents notlisted by the American Chemical Society, see Annual Standards for LaboratoryChemicals, BDH Ltd., Poole, Dorset, U.K., and the United States Pharmacopeiaand National Formulary, U.S. Pharmacopeial Convention, Inc. (USPC), Rockville,MD.4Sulfur calibration and reference standa
33、rds are typically available from theinstrument manufacturer, National Institute of Standards and Technologys (NIST),http:/www.nist.gov, and are also available from Alpha Resources, 3090 JohnsonRoad, Stevensville, MI 49127, .D7679 112TEST METHOD B: X-RAY FLUORESCENCE11. Summary of Test Method11.1 X-r
34、ay fluorescence may be used to determine sulfur incarbon black feedstock oils. Each element has a unique energyresponse (fluorescence) when exposed to x-ray energy that canbe used to identify the element. An x-ray source excites thesulfur atoms in the sample material. The instrument detects theexcit
35、ed sulfur atoms and produces a numeric value.11.2 The sulfur analyzer shall be calibrated using appropri-ate calibration standards (see 14.3).12. Apparatus12.1 X-ray Fluorescence Instrument, designed specificallyfor the test of trace amounts of sulfur, with x-ray source(radioisotope or x-ray tube),
36、detection, and numeric display.X-ray fluorescence instruments are either wavelength disper-sive or energy dispersive. Energy dispersive instruments havea lower detectable limit of 15 ppm while wavelength dispersiveinstruments have a lower detectable limit of less than 1 ppm.Since the sulfur in oil f
37、urnace type carbon blacks is usuallypresent in percent levels, either instrument type is suitable.13. Sampling13.1 Collect feedstock oil as specified in Practices D4057 orD4177.13.2 SampleThis is the portion or aliquot of the feedstockoil for use in obtaining a result.13.3 PreparationWarm viscous sa
38、mples until they arefluid and shake for 5 s.14. Calibration14.1 The ability of the instrument to detect an elementsenergy signature is strongly influenced by the sample matrix.Therefore, the materials used to calibrate the instrument needto be as similar as possible to the unknown sample to be teste
39、d.If the unknown sample is a liquid, slurry, powder, or solid, thecalibration materials need to be a similar liquid, slurry, powder,or solid. The preferred calibration materials will be made by (orcome from) the same process as the unknown sample.14.2 Calibrate the instrument according to the manufa
40、ctur-ers instructions using appropriate calibration standards.414.3 The following Sulfur Standards in Residual Fuel Oilare available from NIST:SRM Description1620c Sulfur in Residual Fuel Oil (4.0 %)1623e Sulfur in Residual Fuel Oil (0.3 %)1622e Sulfur in Residual Fuel Oil (2.0 %)1621e Sulfur in Res
41、idual Fuel Oil (1.0 %)1619b Sulfur in Residual Fuel Oil (0.7 %)15. Procedure15.1 Follow manufacturers instructions for operation of thetest equipment.16. Report16.1 The percent sulfur value is obtained directly from theapparatus.17. Precision and Bias17.1 PrecisionThe repeatability standard deviatio
42、n hasbeen determined to be _. The reproducibility of this testmethod is being determined and will be available within fiveyears.17.2 BiasThe bias of this test method will be availablewithin five years.18. Keywords18.1 carbon black; combustion; feedstock; hydrocarbon oil;sulfur content; x-ray fluores
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