1、Designation: D 1552 08An American National StandardStandard Test Method forSulfur in Petroleum Products (High-Temperature Method)1This standard is issued under the fixed designation D 1552; the number immediately following the designation indicates the year oforiginal adoption or, in the case of rev
2、ision, 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 Department of Defense.1. Scope*1.1 This test method
3、covers three procedures for the deter-mination of total sulfur in petroleum products includinglubricating oils containing additives, and in additive concen-trates. This test method is applicable to samples boiling above177C (350F) and containing not less than 0.06 mass % sulfur.Two of the three proc
4、edures use iodate detection; one employ-ing an induction furnace for pyrolysis, the other a resistancefurnace. The third procedure uses IR detection followingpyrolysis in a resistance furnace.1.2 Petroleum coke containing up to 8 mass % sulfur can beanalyzed.1.3 The values stated in SI units are to
5、be regarded as thestandard. The values given in parentheses 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
6、 determine the applica-bility of regulatory limitations prior to use.2. Referenced Documents2.1 ASTM Standards:2D 1193 Specification for Reagent WaterD 1266 Test Method for Sulfur in Petroleum Products(Lamp Method)D 4057 Practice for Manual Sampling of Petroleum andPetroleum ProductsD 6299 Practice
7、for Applying Statistical Quality Assuranceand Control Charting Techniques to Evaluate AnalyticalMeasurement System PerformanceD 6792 Practice for Quality System in Petroleum Productsand Lubricants Testing Laboratories3. Summary of Test Method3.1 Iodate Detection SystemThe sample is burned in astream
8、 of oxygen at a sufficiently high temperature to convertabout 97 % of the sulfur to sulfur dioxide. A standardizationfactor is employed to obtain accurate results. The combustionproducts are passed into an absorber containing an acidsolution of potassium iodide and starch indicator. A faint bluecolo
9、r is developed in the absorber solution by the addition ofstandard potassium iodate solution. As combustion proceeds,bleaching the blue color, more iodate is added. The amount ofstandard iodate consumed during the combustion is a measureof the sulfur content of the sample.3.2 IR Detection SystemThe
10、sample is weighed into aspecial ceramic boat which is then placed into a combustionfurnace at 1371C (2500F) in an oxygen atmosphere. Mostsulfur present is combusted to SO2which is then measuredwith an infrared detector after moisture and dust are removedby traps. A microprocessor calculates the mass
11、 percent sulfurfrom the sample weight, the integrated detector signal and apredetermined calibration factor. Both the sample identificationnumber and mass percent sulfur are then printed out. Thecalibration factor is determined using standards approximatingthe material to be analyzed.4. Significance
12、 and Use4.1 This 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 thed
13、epletion of sulfur can provide useful information. In othercases the presence of sulfur compounds is detrimental to theprocessing or use of the product.5. Interferences5.1 For the iodate systems, chlorine in concentrations lessthan 1 mass % does not interfere. The IR system can toleratesomewhat high
14、er concentrations. Nitrogen when present in1This test method is under the jurisdiction of ASTM Committee D02 onPetroleum Products and Lubricants and is the direct responsibility of SubcommitteeD02.03 on Elemental Analysis.Current edition approved Dec. 1, 2008. Published December 2008. Originallyappr
15、oved in 1958. Last previous edition approved in 2007 as D 155207.2For 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 webs
16、ite.1*A Summary of Changes section appears at the end of this standard.Copyright ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959, United States.excess of 0.1 mass % may interfere with the iodate systems; theextent of such interference may be dependent on the
17、type ofnitrogen compound as well as the combustion conditions.Nitrogen does not interfere with the IR system. The alkali andalkaline earth metals, as well as zinc, phosphorus, and lead, donot interfere with either system.6. Apparatus6.1 Combustion and Iodate Detection System:6.1.1 FurnacesTwo major
18、types are available, the pri-mary difference being the manner in which the necessary hightemperatures are obtained. These two types are as follows:6.1.1.1 Induction Type, which depends upon the high-frequency electrical induction method of heating. This assem-bly shall be capable of attaining a temp
19、erature of at least1482C (2700F) in the sample combustion zone, under theconditions set forth in 9.1 and shall be equipped with anadditional induction coil located above the combustion zone,substantially as shown in Fig. 1.6.1.1.2 The furnace work coil should have a minimumoutput of 500 W; the minim
20、um input rating of the furnace mustbe 1000 W. With the correct amount of iron chips, weighed to60.05 g, the maximum plate current will be between 350 and450 mA. (WarningThis type of furnace is capable ofinflicting high frequency burns and high-voltage shocks. Inaddition to other precautions, maintai
21、n all guards properly.)(WarningDisconnect the furnace from the power line when-ever electrical repairs or adjustments are made.)6.1.1.3 Resistance Type, capable of maintaining a tempera-ture of at least 1371C (2500F).6.1.2 Absorber, as described in Test Method D 1266.NOTE 1Also suitable for use with
22、 either type of furnace is anautomatic titrator, specifically designed for iodometry. This combines thefunctions of absorption and titration to a predetermined end point.6.1.3 Buret, standard 25-mL or automatic types availablefrom the manufacturers of the specific combustion units, aresuitable (Note
23、 1).6.2 Combustion and IR Detection System, comprised ofautomatic balance, oxygen flow controls, drying tubes, com-bustion furnace, infrared detector and microprocessor. Thefurnace shall be capable of maintaining a nominal operatingtemperature of 1350C (2460F).36.3 Miscellaneous ApparatusSpecific co
24、mbustion assem-blies require additional equipment such as crucibles, combus-tion boats, crucible lids, boat pushers, separator disks, com-bustion tubes, sample inserters, oxygen flow indicator, andoxygen drying trains. The additional equipment required isdependent on the type of furnace used and is
25、available from themanufacturer of the specific combustion unit. To attain thelower sulfur concentration given in Section 1, the ceramicsused with the induction furnace assembly shall be ignited in amuffle furnace at 1371C (2500F) for at least 4 h before use.6.4 Sieve, 60-mesh (250-mm).7. Reagents an
26、d Materials7.1 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 Commit-tee on Analytical Reagents of the American Chemical Society,where such specifications are available.4Other
27、 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.7.2 Purity of WaterUnless otherwise indicated, referencesto water shall be understood to mean reagent water as definedby Type II or
28、 III of Specification D 1193.7.3 Alundum (Al2O3)orMagnesium Oxide (Com-Aid).7.4 Anhydrone (Magnesium Perchlorate).(WarningInaddition to other precautions, handle magnesium perchloratewith care. Avoid contacting it with acid and organic materials.Reactions with fuel may be violent.)7.5 Hydrochloric A
29、cid (3 + 197)Dilute 30 mL of concen-trated hydrochloric acid (HCl, relative density 1.19) to 2 L withwater. (WarningPoison. Corrosive. May be fatal if swal-lowed. Liquid and vapor cause severe burns.)7.6 Oxygen (Extra Dry)The oxygen shall be at least99.5 % pure and show no detectable sulfur by blank
30、 determi-nation. (WarningOxygen vigorously accelerates combus-tion.)7.7 Phosphorus Pentoxide(P2O5).7.8 Potassium Alum (Aluminum Potassium Sulfate).7.9 Potassium Iodate, Standard Solution (0.06238 N), 1mL of this solution is equivalent to 1 mg S)Dissolve 2.225g of potassium iodate (KIO3) that has bee
31、n dried at about180C to constant weight, in water and dilute to 1 L. Thor-oughly mix the solution.3The sole source of supply of Models SC32 or SC132 known to the committeeat this time is LECO Corp., 3800 LakeviewAve., St. Joseph, MI 49085-2396. If youare aware of alternative suppliers, please provid
32、e this information to ASTMInternational Headquarters. Your comments will receive careful consideration at ameeting of the responsible technical committee,1which you may attend.4Reagent Chemicals, American Chemical Society Specifications, AmericanChemical Society, Washington, DC. For Suggestions on t
33、he 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.FIG. 1 Combustion TubeD15520827.10 Potass
34、ium Iodate, Standard Solution (0.006238 N), 1mL of this solution is equivalent to 0.1 mg S)Measureexactly 100 mL of KIO3solution (0.06238 N) into a 1Lvolumetric flask, and dilute to volume with water. Thoroughlymix the solution.7.11 Potassium Iodate, Standard Solution (0.01248 N), 1mL of this soluti
35、on is equivalent to 0.2 mg S)Measureexactly 200 mL of KIO3solution (0.06238 N) into a 1-Lvolumetric flask and dilute to volume with water. Thoroughlymix the solution.7.12 Ascarite, 8 to 20 mesh.7.13 Special Materials for Induction-Type Furnaces:7.13.1 Tin (20 to 30-mesh).7.13.2 Iron-Chip Accelerator
36、 having a sulfur content of notmore than 0.005 mass %.7.14 Standard SamplePotassium alum (AlK(SO4)212H2O).7.15 Starch-Iodide SolutionMake a paste by adding 9 g ofsoluble starch to 15 mL of water. Add this mixture, withstirring, to 500 mL of boiling water. Cool the mixture, add 15g of potassium iodid
37、e (KI), and dilute to 1 L with water.7.16 Sulfuric Acid (relative density 1.84)Concentratedsulfuric acid (H2SO4). (WarningPoison. Corrosive. Strongoxidizer.)7.17 Vanadium Pentoxide, anhydrous, powdered V2O5.7.18 Quality Control (QC) Sample(s), preferably are por-tions of one or more petroleum produc
38、ts that are stable andrepresentative of the samples of interest. These QC samplescan be used to check the validity of the testing process andperformance of the instrument as described in Section 12.8. Sampling8.1 Take samples in accordance with the instructions inPractice D 4057.9. Preparation of Ap
39、paratus9.1 Induction-Type FurnaceAssemble the apparatus ac-cording to the instructions furnished by the manufacturer.Purify the oxygen by passing it through (1)H2SO4(relativedensity 1.84), (2) Ascarite, and (3) magnesium perchlorate(Mg(ClO4)2) or phosphorus pentoxide (P2O5)(Warningsee7.4). Connect a
40、 rotameter between the purifying train and thefurnace. Insert a small glass-wool plug in the upper end of theglass tubing connecting the furnace with the absorber to catchoxides of tin. Connect the exit end of the combustion tube tothe absorber with glass tubing, using gum rubber tubing tomake conne
41、ctions. Position the absorber so as to make thisdelivery line as short as possible. Fig. 2 illustrates schemati-cally the assembled apparatus. Adjust the oxygen flow to 1 60.05 L/min. Add 65 mL of HCl (3 + 197) and 2 mL ofstarch-iodide solution to the absorber. Add a sufficient amountof the appropri
42、ate standard KIO3solution (Table 1) to producea faint blue color. This color will serve as the end point for thetitration. Adjust the buret to zero. Turn on the furnace filamentswitch and allow at least 1 min warm-up before runningsamples (Warningsee 7.4).9.2 ResistanceType FurnaceAssemble the appar
43、atus ac-cording to the instructions furnished by the manufacturer.Purify the oxygen by passing it through (1)H2SO4(relativedensity 1.84), (2) Ascarite, and (3) Mg(ClO4)2or P2O5(Warningsee 7.4). Connect a rotameter between the purify-ing train and the furnace. Fig. 3 illustrates schematically theasse
44、mbled apparatus. Turn on the current and adjust thefurnace control to maintain a constant temperature of 1316614C (2400 6 25F). Adjust the oxygen flow rate to 2 6 0.1L/min.Add 65 mL of HCl (3 6 197) and 2 mL of starch-iodidesolution to the absorber. Add a few drops of the appropriatestandard KIO3sol
45、ution (Table 2) to produce a faint blue color.Adjust the buret to zero.9.3 ResistanceType FurnaceIR DetectionAssemble andadjust apparatus according to manufacturers instructions.Initialize microprocessor, check power supplies, set oxygenpressure and flows and set furnace temperature to 1371C(2500F).
46、9.3.1 Condition a fresh anhydrone scrubber with four coalsamples when analyzing petroleum coke samples, or with fourpetroleum product samples that are representative or typical ofthe sample types to be analyzed.9.3.2 Calibrate the automatic balance according to manu-facturers instructions.10. Standa
47、rdization10.1 For Iodate Methods:10.1.1 Determination of Alum Factor:10.1.1.1 Because these rapid combustion methods involvethe reversible reaction 2SO2+O2= 2SO3, it is not possible toevolve all the sulfur as SO2. The equilibrium of the reaction istemperature dependent and, in an oxygen atmosphere a
48、bove1316C, about 97 % of the sulfur is present as SO2. To assurethat the furnace is in proper adjustment and that its operationproduces acceptably high temperature, potassium alum isemployed for standardizing the apparatus. Depending on thetype of combustion equipment used, proceed as described inSe
49、ctions 10 to 14 to determine the alum factor. Use 15 mgweighed to 60.1 mg of potassium alum for this determination.Use the same materials in the determination of the alum andstandardization factors as for the unknown samples. Forexample, V2O5has a definite effect and should be included ifFIG. 2 Schematic Illustration of Induction-Type FurnaceTABLE 1 Sample Weight for Induction FurnaceSulfur Content, %Weight of Sampleto be Taken, mgNormality of StandardKIO3solution for Titration0to2 90A0.0062382 to 4 50 to 90 0.0062384 to 10 50 to 90
