1、Designation: D 1552 07An 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 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 an
6、d 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 AssuranceTechniques to Evaluate Analytical Measurement SystemPerformanceD 6792 Practice for Quality System in Petroleum Productsand Lubricants Testing Laboratories3. Summary of Test Method3.1 Iodate Detection SystemThe sample is burned in astream of oxygen at a suff
8、iciently 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 bluecolor is developed in th
9、e 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 sample is weighed in
10、to 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 percent sulfurfrom
11、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 and Use4.1 This tes
12、t 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 sulfur c
13、an 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 higher concentrations. N
14、itrogen 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 not interfere with the IR system. The alkali and1This test method is under the jurisdi
15、ction of ASTM Committee D02 onPetroleum Products and Lubricants and is the direct responsibility of SubcommitteeD02.03 on Elemental Analysis.Current edition approved Dec. 1, 2007. Published January 2008. Originallyapproved in 1958. Last previous edition approved in 2003 as D 155203.2For referenced A
16、STM 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.1*A Summary of Changes section appears at the end of this standard.Copyright A
17、STM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959, United States.Copyright by ASTM Intl (all rights reserved); Wed Jul 30 22:09:32 EDT 2008Downloaded/printed byGuo Dehua (CNIS) pursuant to License Agreement. No further reproductions authorized.alkaline earth met
18、als, 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 types are available, the pri-mary difference being the manner in which the necessary hightemperatures are obtained. These two types are as fol
19、lows: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 temperature of at least1482C (2700F) in the sample combustion zone, under theconditions set forth in 9.1 and shall be equipped with anadditional i
20、nduction 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 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 betw
21、een 350 and450 mA. (WarningThis type of furnace is capable ofinflicting high frequency burns and high-voltage shocks. Inaddition to other precautions, maintain all guards properly.)(WarningDisconnect the furnace from the power line when-ever electrical repairs or adjustments are made.)6.1.1.3 Resist
22、ance 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 either type of furnace is anautomatic titrator, specifically designed for iodometry. This combines thefunctions of absorption and titration t
23、o 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).6.2 Combustion and IR Detection System, comprised ofautomatic balance, oxygen flow controls, drying tubes, com-bustion furnace, infrared d
24、etector and microprocessor. Thefurnace shall be capable of maintaining a nominal operatingtemperature of 1350C (2460F).36.3 Miscellaneous ApparatusSpecific combustion assem-blies require additional equipment such as crucibles, combus-tion boats, crucible lids, boat pushers, separator disks, com-bust
25、ion tubes, sample inserters, oxygen flow indicator, andoxygen drying trains. The additional equipment required isdependent on the type of furnace used and is available from themanufacturer of the specific combustion unit. To attain thelower sulfur concentration given in Section 1, the ceramicsused w
26、ith 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 Materials7.1 Purity of ReagentsReagent grade chemicals shall beused in all tests. Unless otherwise indicated, it is intended thatall reagent
27、s shall conform to the specifications of the Commit-tee on Analytical Reagents of the American Chemical Society,where such specifications are available.4Other grades may beused, provided it is first ascertained that the reagent is ofsufficiently high purity to permit its use without lessening theacc
28、uracy 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 of Specification D 1193.7.3 Alundum (Al2O3)orMagnesium Oxide (Com-Aid).7.4 Anhydrone (Magnesium Perchlorate).(WarningInaddition to other
29、precautions, handle magnesium perchloratewith care. Avoid contacting it with acid and organic materials.Reactions with fuel may be violent.)7.5 Hydrochloric Acid (3 + 197)Dilute 30 mL of concen-trated hydrochloric acid (HCl, relative density 1.19) to 2 L withwater. (WarningPoison. Corrosive. May be
30、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 determi-nation. (WarningOxygen vigorously accelerates combus-tion.)7.7 Phosphorus Pentoxide(P2O5).7.8 Potassium Alum (Aluminum Potassium Sulf
31、ate).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 dried at about180C to constant weight, in water and dilute to 1 L. Thor-oughly mix the solution.7.10 Potassium Iodate, Standard Solution (0.
32、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.3The sole source of supply of Models SC32 or SC132 known to the committeeat this time is LECO Corp., 3800
33、 LakeviewAve., St. Joseph, MI 49085-2396. If youare aware of alternative suppliers, please provide this information to ASTMInternational Headquarters. Your comments will receive careful consideration at ameeting of the responsible technical committee,1which you may attend.4Reagent Chemicals, America
34、n Chemical Society Specifications, AmericanChemical Society, Washington, DC. For suggestions on the testing of reagents notlisted by the American Chemical Society, see Analar Standards for LaboratoryChemicals, BDH Ltd., Poole, Dorset, U.K., and the United States Pharmacopeiaand National Formulary, U
35、.S. Pharmacopeial Convention, Inc. (USPC), Rockville,MD.FIG. 1 Combustion TubeD1552072Copyright by ASTM Intl (all rights reserved); Wed Jul 30 22:09:32 EDT 2008Downloaded/printed byGuo Dehua (CNIS) pursuant to License Agreement. No further reproductions authorized.7.11 Potassium Iodate, Standard Sol
36、ution (0.01248 N), 1mL of this solution 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
37、30-mesh).7.13.2 Iron-Chip Accelerator 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 th
38、e mixture, add 15g of potassium iodide (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-
39、tions of one or more petroleum products 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 i
40、nPractice D 4057.9. Preparation of Apparatus9.1 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 pento
41、xide (P2O5)(Warningsee7.4). Connect a 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,
42、 using gum rubber tubing tomake connections. 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. A
43、dd a sufficient amountof the appropriate 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 Res
44、istanceType 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) Mg(ClO4)2or P2O5(Warningsee 7.4). Connect a rotameter between the purify-ing train and the furnace. Fig
45、. 3 illustrates schematically theassembled 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 dro
46、ps of the appropriatestandard KIO3solution (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
47、 furnace temperature to 1371C(2500F).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 m
48、anu-facturers instructions.10. Standardization10.1 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 dep
49、endent and, in an oxygen atmosphere above1316C, 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 inFIG. 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
