ASTM_D_4045_-_15.pdf

Designation:D404515Standard Test Method forSulfur in Petroleum Products by Hydrogenolysis andRateometric Colorimetry1This standard is issued under the fixed designation D4045;the number 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.Scope*1.1 This test method covers the determination of sulfur inpetroleum products in the range from 0.02 mg kg to10.00 mgkg.1.2 This test method may be extended to higher concentra-tion by dilution.1.3 This test method is applicable to liquids whose boilingpoints are between 30 C and 371 C(86 F and 700 F).Materials that can be analyzed include naphtha,kerosine,alcohol,steam condensate,various distillates,jet fuel,benzene,and toluene.1.4 The values stated in SI units are to be regarded asstandard.The values given in parentheses are for informationonly.1.4.1 Certain specifications for the recorder(see 5.5)areexcepted.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 appro-priate safety and health practices and determine the applica-bility of regulatory limitations prior to use.2.Referenced Documents2.1 ASTM Standards:2D1193 Specification for Reagent WaterD6299 Practice for Applying Statistical Quality Assuranceand Control Charting Techniques to Evaluate AnalyticalMeasurement System Performance3.Summary of Test Method3.1 The sample is injected at a constant rate into a flowinghydrogen stream in a hydrogenolysis apparatus.The sampleand hydrogen are pyrolyzed at a temperature of 1300 C,orabove,to convert sulfur compounds to hydrogen sulfide(H2S).Readout is by the rateometric detection of the colorimetricreaction of H2S with lead acetate.Condensable components areconverted to gaseous products,such as methane,during hy-drogenolysis.4.Significance and Use4.1 In many petroleum refining processes,low levels ofsulfur in feed stocks may poison expensive catalysts.This testmethod can be used to monitor the amount of sulfur in suchpetroleum fractions.4.2 This test method may also be used as a quality-controltool for sulfur determination in finished products.5.Apparatus3,45.1 Pyrolysis FurnaceA furnace that can provide anadjustable temperature from 900 C to 1400 C in a 5 mminside diameter or larger tube is required to pyrolyze thesample.The furnace entry temperature shall allow insertion ofthe hypodermic tip to a depth at which the temperature is550 C to provide sample vaporization at the injection syringetip.This temperature shall be above the boiling point of thesample and of the sulfur compounds in the sample(see Fig.1).The pyrolyzer tube may be of quartz;however,the lifetime islimited above 1250 C.Ceramic may be used at any tempera-ture.5.2 Rateometric H2S ReadoutHydrogenolysis productscontain H2S in proportion to sulfur in the sample.The H2S ismeasured by measuring rate of change of reflectance caused bydarkeningwhenleadsulfideisformed.Rateometricelectronics,adapted to provide a first derivative output,allowssufficient sensitivity to measure below 0.1 mg/L(see Fig.2).1This test method is under the jurisdiction of ASTM Committee D02 onPetroleum Products,Liquid Fuels,and Lubricantsand is the direct responsibility ofSubcommittee D02.03 on Elemental Analysis.Current edition approved April 1,2015.Published April 2015.Originallyapproved in 1987.Last previous edition approved in 2010 as D4045 04(2010).DOI:10.1520/D4045-15.2For 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 page onthe ASTM website.3The apparatus described in 5.1 5.4 inclusive is similar in specification to theequipment available from Analytical Systems Keco,9215 Solon Rd.,Suite A4,Houston,TX 77064.For further information see Drushel,H.V.,“Trace SulfurDetermination Petroleum Fractions,”Analytical Chemistry,Vol 50,1978,p.76.4The sole source of supply of the apparatus known to the committee at this timeisAnalytical Systems Keco.If you are aware of alternative suppliers,please providethis information to ASTM International Headquarters.Your comments will receivecareful consideration at a meeting of the responsible technical committee,1whichyou may attend.*A Summary of Changes section appears at the end of this standardCopyright ASTM International,100 Barr Harbor Drive,PO Box C700,West Conshohocken,PA 19428-2959.United States1 5.3 Hypodermic SyringeA hypodermic having a needlelong enough to reach the 550 C zone is required.A side portis convenient for vacuum filling and for flushing the syringe.A100 L syringe is satisfactory for injection rates down to3 Lmin and a 25 L syringe for lower rates.(WarningExercise caution as hypodermic