1、Designation: D1552 161Standard Test Method forSulfur in Petroleum Products by High TemperatureCombustion and Infrared (IR) Detection or ThermalConductivity Detection (TCD)1This standard is issued under the fixed designation D1552; the number immediately following the designation indicates the year o
2、foriginal 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.This standard has been approved for use by agencies of the U.S. Depart
3、ment of Defense.1NOTEThe title was corrected editorially in February 2017.1. Scope*1.1 This test method covers procedures for the determina-tion of total sulfur in petroleum products including lubricatingoils containing additives, and in additive concentrates. This testmethod is applicable to sample
4、s boiling above 177 C (350 F)and containing a mass fraction of sulfur between 0.22 % and24.2 %. Other sulfur concentrations may be analyzed, but theprecision stated may or may not apply. These procedures useIR detection or TCD following combustion in a furnace.1.2 Petroleum coke containing a mass fr
5、action of sulfurbetween 2.53 % to 3.79 % sulfur may be analyzed. Other sulfurconcentrations may be analyzed, but the precision stated mayor may not apply.NOTE 1The D155208 (2014) version of this standard contained twoother procedures using iodate titrations. Since these procedures are nolonger being
6、 used in the industry laboratories based on a survey ofD02.SC 3 laboratories conducted in September 2014, they are beingdeleted. For earlier information on the deleted procedures, D155208(2014) may be perused.1.3 The values stated in SI units are to be regarded as thestandard. The values given in pa
7、rentheses are for informationonly.1.4 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 limita
8、tions prior to use.2. Referenced Documents2.1 ASTM Standards:2D4057 Practice for Manual Sampling of Petroleum andPetroleum ProductsD4177 Practice for Automatic Sampling of Petroleum andPetroleum ProductsD6299 Practice for Applying Statistical Quality Assuranceand Control Charting Techniques to Evalu
9、ate AnalyticalMeasurement System PerformanceD6300 Practice for Determination of Precision and BiasData for Use in Test Methods for Petroleum Products andLubricantsD6792 Practice for Quality System in Petroleum Productsand Lubricants Testing Laboratories3. Summary of Test Method3.1 The sample is weig
10、hed and placed into a furnace havingan oxygen atmosphere sufficient to combust the entire sampleand a temperature between 1150 C and 1450 C for ProcedureA or 1150 C for Procedure B. Most sulfur present is com-busted to SO2, which is then measured with a detector aftermoisture and dust are removed by
11、 traps. The instrumentcalculates the mass percent sulfur from the sample mass, theintegrated detector signal, and a predetermined calibrationfactor. The calibration factor is determined using standardsapproximating the material to be analyzed.3.1.1 Procedure AAfter combustion of the sample andsubseq
12、uent moisture/dust removal, SO2is measured usinginfrared (IR) detection.3.1.2 Procedure BAfter combustion of the sample andsubsequent moisture/dust removal, SO2is measured using1This test method is under the jurisdiction of ASTM Committee D02 onPetroleum Products, Liquid Fuels, and Lubricants and is
13、 the direct responsibility ofSubcommittee D02.03 on Elemental Analysis.Current edition approved July 1, 2016. Published August 2016. Originallyapproved in 1958. Last previous edition approved in 2015 as D1552 15. DOI:10.1520/D1552-16E01.2For referenced ASTM standards, visit the ASTM website, www.ast
14、m.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.*A Summary of Changes section appears at the end of this standardCopyright ASTM International, 100 Barr Harbor Drive, PO Box
15、 C700, West Conshohocken, PA 19428-2959. United StatesThis international standard was developed in accordance with internationally recognized principles on standardization established in the Decision on Principles for theDevelopment of International Standards, Guides and Recommendations issued by th
16、e World Trade Organization Technical Barriers to Trade (TBT) Committee.1thermal conductivity detection. An apparatus utilizing TCDmay require the sample gas to pass an oxygen scrubber andadsorption/desorption traps to allow passing of contaminantsprior to measuring SO2.4. Significance and Use4.1 Thi
17、s test method provides a means of monitoring thesulfur level of various petroleum products and additives. Thisknowledge can be used to predict performance, handling, orprocessing properties. In some cases the presence of sulfurcompounds is beneficial to the product and monitoring thedepletion of sul
18、fur can provide useful information. In othercases the presence of sulfur compounds is detrimental to theprocessing or use of the product.5. Apparatus5.1 Combustion Furnace:5.1.1 Procedure AFurnace capable of maintaining a con-stant temperature (between 1150 C minimum and 1450 Cmaximum) sufficient to
19、 ensure quantitative recovery of sulfuras its corresponding gas SO2.5.1.2 Procedure BFurnace capable of maintaining a tem-perature (1150 C) sufficient to ensure quantitative recovery ofsulfur as its corresponding gas SO2.5.2 Combustion and Sulfur Detection System, comprised ofautomatic balance, gas
20、flow controls, drying tubes, oxygenscrubber, adsorption/desorption traps as required, combustionfurnace, combustion boats or tin (Sn) containers as requiredand either an IR (Procedure A) or TCD (Procedure B) SO2detector.5.3 Sieve, 60 mesh (250 m).6. Reagents and Materials6.1 Purity of ReagentsReagen
21、t grade chemicals shall beused in all tests. Unless otherwise indicated, it is intended thatall reagents shall conform to the specifications of the Commit-tee on Analytical Reagents of the American Chemical Society,where such specifications are available.3Other grades may beused, provided it is firs
22、t ascertained that the reagent is ofsufficiently high purity to permit its use without lessening theaccuracy of the determination.6.2 Combustion PromoterMagnesium oxide (MgO), tung-sten trioxode (WO3), or aluminum oxide (Al2O3).Alternatively, COM-CAT, a dual promoter that is both a fixingagent and o
23、xidizing agent, may be used.46.3 Drying Agent, Magnesium perchlorate: anhydrone(Mg(ClO4)2) or phosphorus pentoxide (P2O5). (WarningInaddition to other precautions, handle magnesium perchloratewith care. Avoid contacting it with acid and organic materials.Reactions with fuel may be violent.)6.4 Oxyge
24、n (Extra Dry)The oxygen shall be at least99.5 % pure and show no detectable sulfur by blank determi-nation. (WarningOxygen vigorously accelerates combus-tion.)6.5 Inert GasHelium or argon, high purity grade,99.995 % minimum purity, as required by manufacturersrecommendations.6.6 Quality Control (QC)
25、 Sample(s), preferably are portionsof one or more petroleum products that are stable and repre-sentative of the samples of interest. These QC samples can beused to check the validity of the testing process and perfor-mance of the instrument as described in Section 11.7. Sampling7.1 Take samples in a
26、ccordance with the instructions inPractice D4057 or D4177.8. Preparation of Apparatus8.1 Assemble and adjust apparatus according to manufac-turers instructions. Initialize instrument, check powersupplies, set gas pressure and flows, and set furnace tempera-ture.8.1.1 Condition the instrument with sa
27、mples that are repre-sentative or typical of the sample types to be analyzed. Duringthe interlaboratory study, laboratories analyzed between oneand five conditioning samples.8.1.2 Calibrate the automatic balance according to manu-facturers instructions.9. Standardization9.1 Determination of Standard
28、ization Factor:9.1.1 Because effects such as sample volatility can alsoaffect the relative recovery as SO2of the sulfur originallypresent in the sample, it is necessary to determine a standard-ization factor. Proceed as described in Sections 9 through 12,using an oil sample of similar type to the un
29、known sample andof accurately known sulfur content.59.1.2 Determine the calibration factor for the particular typeof sample to be analyzed (lubricating oil, petroleum coke,residual fuel) as recommended by the manufacturer.9.2 Quality ControlRun a suitable analytical quality con-trol sample several t
30、imes daily. When the observed value liesbetween acceptable limits on a quality control chart, proceedwith sample determinations.10. Preparation of Coke10.1 It is assumed that a representative sample has beenreceived for analysis. If the sample of coke received is not dry,it is recommended that the s
31、ample be dried prior to grinding.3Reagent Chemicals, American Chemical Society Specifications, AmericanChemical Society, Washington, DC. For Suggestions on the testing of reagents notlisted by the American Chemical Society, see Annual Standards for LaboratoryChemicals, BDH Ltd., Poole, Dorset, U.K.,
32、 and the United States Pharmacopeiaand National Formulary, U.S. Pharmacopeial Convention, Inc. (USPC), Rockville,MD.4The sole source of supply of COM-CAT known to the committee at this timeis LECO Corporation, 3000 Lakeview Ave. St. Joseph, MI 49085 USA. If you areaware of alternative suppliers, ple
33、ase provide this information to ASTM Interna-tional Headquarters. Your comments will receive careful consideration at a meetingof the responsible technical committee,1which you may attend.5Residual fuel oil Standard Reference Materials may be obtained from theNational Institute of Standards and Tech
34、nology or other sources.D1552 161210.2 Grind and sieve the sample received so as to pass a60 mesh (250 m) sieve.10.3 Dry the sieved material to constant weight at 105 C to110 C.11. Analysis of Quality Control Samples11.1 A QC sample shall be analyzed each day samples areanalyzed to verify the testin
35、g procedure and instrument perfor-mance. Additional QC samples may be analyzed. The QCsamples shall be treated as outlined in Section 12, dependingupon the type of furnace set-up used by the lab.11.2 When QC/Quality Assurance (QA) protocols are al-ready established in the testing facility, these may
36、 be used toconfirm the reliability of the test result.11.3 When there is no QC/QA protocol established in thetesting facility, Appendix X1 can be used as the QC/QAsystem.12. Procedures12.1 Procedure ACombustion with Infrared (IR) Detec-tion:12.1.1 Following instrument manufacturerrecommendations, al
37、low the system to warm up and thefurnace to reach an operating temperature between 1150 Cminimum and 1450 C maximum.12.1.2 Mix or swirl the test sample thoroughly to ensurehomogeneity. Select the appropriate test specimen size asrecommended by the instrument manufacturer. As an example,for liquid sa
38、mples, take up to 0.13 g for analysis and for solidsamples, take up to 0.4 g for analysis.12.1.3 Determine and store the system blank value.12.1.4 Weigh solid samples into combustion boats or con-tainers and record the net masses. For liquid samples, follow12.1.4.1 to 12.1.4.4.12.1.4.1 Following man
39、ufacturer recommendations; addcombustion promoter, if used, to combustion boat or containerusing scoop or spatula. Fill the combustion boat to one-thirdcapacity with evenly spread MgO powder.12.1.4.2 Place combustion boat or container on the balanceand tare.12.1.4.3 Weigh an appropriate amount of th
40、e sample ontothe combustion promoter. Record and enter the mass of sample.If using combustion container, seal before recording samplemass.12.1.4.4 Remove the combustion boat or container from thebalance.Additional combustion promoter can be added to opencombustion boat after weighing, if recommended
41、 by manufac-turers guidance.12.1.5 Initiate gas flow and load sample into furnace.12.1.6 When the analysis is complete, read the result fromthe instrument.12.1.7 Prepare furnace and instrument for next run accord-ing to manufacturers recommendation. Remove the expendedcombustion boat from the furnac
42、e, if used.12.1.8 Perform a second determination and average the twovalues for a single result.12.2 Procedure BCombustion with Thermal ConductivityDetection (TCD):12.2.1 Following instrument manufacturerrecommendations, allow the system to warm up and thefurnace to reach an 1150 C operating temperat
43、ure.12.2.2 Mix or swirl the test sample thoroughly to ensurehomogeneity. Select the appropriate test specimen size asrecommended by the instrumentmanufacturer. As an example,for liquid samples, take up to 0.13 g for analysis and for solidsamples, take up to 0.4 g for analysis.12.2.3 Determine and st
44、ore the system blank value.12.2.4 Weigh solid samples into combustion containers andrecord the net masses. For liquid samples, follow 12.2.4.1 to12.2.4.3.12.2.4.1 Add combustion promoter, if used, to combustioncontainer using scoop or spatula.12.2.4.2 Place combustion container on the balance andtar
45、e.12.2.4.3 Weigh an appropriate amount of the sample ontothe combustion promoter. Seal tin combustion container beforerecording mass. Record and enter the mass of sample.12.2.5 Initiate gas flow and load sample into furnace.12.2.6 When the analysis is complete, read the result fromthe instrument.12.
46、2.7 Prepare furnace and instrument for next run accord-ing to manufacturers recommendation.12.2.8 Perform a second determination and average the twovalues for a single result.12.3 In cases of dispute between procedures, Procedure Ashall be considered the referee procedure.13. Calculation13.1 Report
47、all results using the microprocessor.13.2 Report the average of two results.14. Report14.1 In the range from mass fraction sulfur 0.05 to 5.00,report to the nearest mass fraction of 0.01 %. In the range ofmass fraction sulfur 5 to 30 mass % sulfur, report to the nearest0.1 %.14.2 Report the followin
48、g information: Results were ob-tained according to Test Method D1552, Procedure A orProcedure B.15. Quality Control15.1 Confirm the performance of the test procedure byanalyzing a quality control sample that is stable and represen-tative of the sample of interest.15.1.1 When the quality control/qual
49、ity assurance protocolsare already established in the testing facility, these may be usedto confirm the reliability of the test result.15.1.2 When there is no quality control/quality assuranceprotocol established in the testing facility, Appendix X1 can beused for this purpose.D1552 161316. Precision and Bias616.1 For Petroleum Products and Coke by IR Detection,Procedure AEach test result is the average of two S deter-minations (see Section 12).16.1.1 Repeatability (r)The difference between two testresults obtained by the same operator w
