1、Designation: D 1552 03An 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 (e) 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 pro
4、cedures 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 This standard does not purport to ad
5、dress 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:D 1193 Specif
6、ication for Reagent Water2D 1266 Test Method for Sulfur in Petroleum Products(Lamp Method)3D 4057 Practice for Manual Sampling of Petroleum andPetroleum Products4D 6299 Practice for Applying Statistical Quality AssuranceTechniques to Evaluate Analytical Measurement SystemPerformance53. Summary of Te
7、st Method3.1 Iodate Detection SystemThe sample is burned in astream 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 acid
8、solution of potassium iodide and starch indicator. A faint bluecolor 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 mea
9、sureof the sulfur content of the sample.3.2 IR Detection SystemThe 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
10、 and dust are removedby traps. A microprocessor calculates the mass 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
11、 standards approximatingthe material to be analyzed.4. Significance 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
12、of sulfurcompounds is beneficial to the product and monitoring thedepletion 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
13、 mass % does not interfere. The IR system can toleratesomewhat higher concentrations. Nitrogen when present inexcess of 0.1 mass % may interfere with the iodate systems; theextent of such interference may be dependent on the type ofnitrogen compound as well as the combustion conditions.Nitrogen does
14、 not interfere with the IR system. The alkali andalkaline earth metals, as well as zinc, phosphorus, and lead, donot interfere with either system.1This test method is under the jurisdiction of ASTM Committee D02 onPetroleum Products and Lubricants and is the direct responsibility of SubcommitteeD02.
15、03 on Elemental Analysis.Current edition approved March 10, 2003. Published April 2003. Originallyapproved in 1958. Last previous edition approved in 2001 as D 155201.2Annual Book of ASTM Standards, Vol 11.01.3Annual Book of ASTM Standards, Vol 05.01.4Annual Book of ASTM Standards, Vol 05.02.5Annual
16、 Book of ASTM Standards, Vol 05.03.1*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.6. Apparatus6.1 Combustion and Iodate Detection System:6.1.1 FurnacesTwo major types
17、 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 temperatu
18、re 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 minimum in
19、put 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, maintain all
20、 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 eith
21、er 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 1).6
22、.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).66.3 Miscellaneous ApparatusSpecific combust
23、ion 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 avail
24、able 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 and Mat
25、erials7.1 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.7Other grad
26、es 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 III
27、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 Acid (
28、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 dete
29、rmi-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 been dri
30、ed at about180C to constant weight, in water and dilute to 1 L. Thor-oughly mix the solution.7.10 Potassium 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 wa
31、ter. Thoroughlymix the solution.7.11 Potassium Iodate, Standard Solution (0.01248 N), 1mL of this solution is equivalent to 0.2 mg S)Measure6The sole source of supply of Models SC32, or SC132 known to the committeeat this time is LECO Corp., 3800 Lakeview Ave., St. Joseph, MI 49085-2396. If youare a
32、ware of alternative suppliers, please provide this information to ASTMInternational Headquarters. Your comments will receive careful consideration at ameeting of the responsible technical committee1, which you may attend.7Reagent Chemicals, American Chemical Society Specifications, AmericanChemical
33、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., and the United States Pharmacopeiaand National Formulary, U.S. Pharmacopeial Convention, Inc. (USPC), Rockville
34、,MD.FIG. 1 Combustion TubeD1552032exactly 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 h
35、aving 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 adding9gofsoluble starch to 15 mL of water. Add this mixture, withstirring, to 500 mL of boiling water. Cool the mixture, add 15g of potassium iodide (KI
36、), 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 products th
37、at 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 Apparat
38、us9.1 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 rota
39、meter 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 connection
40、s. 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 appropriate s
41、tandard 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 apparatus
42、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 theassembled
43、 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 KIO3solutio
44、n (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).9.3.
45、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. Standardiz
46、ation10.1 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 above
47、1316C, 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 inSectio
48、ns 10 to 14 to determine the alum factor. Use 15 mgFIG. 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
49、 0.01248Over 10 12.1.1 (Note 2)AApproximate.FIG. 3 Schematic Illustration of Resistance-Type FurnaceD1552033weighed 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 ifused for unknowns as recommended in the procedure with theresistance-type furnace.10.1.1.2 Calculate the alum factor as follows:Alum factor AF! 5 SA3 WA!/100Va2 Vb! 3 C1! (1)where:SA= mass perce
