1、Designation: D1552 08 (Reapproved 2014)1D1552 15Standard Test Method forSulfur in Petroleum Products (High-Temperature Method)byHigh Temperature Combustion and IR Detection1This standard is issued under the fixed designation D1552; the number immediately following the designation indicates the year
2、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.This standard has been approved for use by agencies of the U.S. Depar
3、tment of Defense.1 NOTEFootnotes were updated editorially in September 2014.1. Scope Scope*1.1 This test method covers three proceduresa procedure for the determination of total sulfur in petroleum products includinglubricating oils containing additives, and in additive concentrates. This test metho
4、d is applicable to samples boiling above 177C(350F)177 C (350 F) and containing a mass fraction of sulfur not less than 0.06 mass % sulfur. Two of the three procedures useiodate detection; one employing an induction furnace for pyrolysis, the other a resistance furnace. The third 0.06 %. This proced
5、ureuses IR detection following pyrolysis in a resistance furnace.1.2 Petroleum coke containing up to 8 mass % sulfur can be analyzed.NOTE 1The D155208 (2014) version of this standard contained two other procedures using iodate titrations. Since these procedures are no longerbeing used in the industr
6、y laboratories based on a survey of D02.SC 3 laboratories conducted in September 2014, they are being deleted. For earlierinformation on the deleted procedures, D155208 (2014) may be perused.1.3 The values stated in SI units are to be regarded as the standard. The values given in parentheses are for
7、 information only.1.4 This standard does not purport to address all of the safety concerns, if any, associated with its use. It is the responsibilityof the user of this standard to establish appropriate safety and health practices and determine the applicability of regulatorylimitations prior to use
8、.2. Referenced Documents2.1 ASTM Standards:2D1193 Specification for Reagent WaterD1266 Test Method for Sulfur in Petroleum Products (Lamp Method)D4057 Practice for Manual Sampling of Petroleum and Petroleum ProductsD6299 Practice for Applying Statistical Quality Assurance and Control Charting Techni
9、ques to Evaluate Analytical Measure-ment System PerformanceD6792 Practice for Quality System in Petroleum Products and Lubricants Testing Laboratories3. Summary of Test Method3.1 Iodate Detection SystemThe sample is burned in a stream of oxygen at a sufficiently high temperature to convert about97 %
10、 of the sulfur to sulfur dioxide. A standardization factor is employed to obtain accurate results. The combustion products arepassed into an absorber containing an acid solution of potassium iodide and starch indicator. A faint blue color is developed in theabsorber solution by the addition of stand
11、ard potassium iodate solution. As combustion proceeds, bleaching the blue color, moreiodate is added. The amount of standard iodate consumed during the combustion is a measure of the sulfur content of the sample.3.1 IR Detection SystemThe sample is weighed into a special ceramic boat which is then p
12、laced into a combustion furnaceat 1371C (2500F)1350 C (2460 F) in an oxygen atmosphere. Most sulfur present is combusted to SO2 which is then measuredwith an infrared detector after moisture and dust are removed by traps. A microprocessor calculates the mass percent sulfur from1 This test method is
13、under the jurisdiction ofASTM Committee D02 on Petroleum Products, Liquid Fuels, and Lubricants and is the direct responsibility of SubcommitteeD02.03 on Elemental Analysis.Current edition approved June 15, 2014April 1, 2015. Published July 2014May 2015. Originally approved in 1958. Last previous ed
14、ition approved in 20082014 asD1552D1552 08 (2014)108 DOI: 10.1520/D1552-08R14E01.10.1520/D1552-15.2 For referencedASTM standards, visit theASTM website, www.astm.org, or contactASTM Customer Service at serviceastm.org. For Annual Book of ASTM Standardsvolume information, refer to the standards Docum
15、ent Summary page on the ASTM website.This document is not an ASTM standard and is intended only to provide the user of an ASTM standard an indication of what changes have been made to the previous version. Becauseit may not be technically possible to adequately depict all changes accurately, ASTM re
16、commends that users consult prior editions as appropriate. In all cases only the current versionof the standard as published by ASTM is to be considered the official document.*A Summary of Changes section appears at the end of this standardCopyright ASTM International, 100 Barr Harbor Drive, PO Box
17、C700, West Conshohocken, PA 19428-2959. United States1the sample weight, the integrated detector signal and a predetermined calibration factor. Both the sample identification number andmass percent sulfur are then printed out. The calibration factor is determined using standards approximating the ma
18、terial to beanalyzed.4. Significance and Use4.1 This test method provides a means of monitoring the sulfur level of various petroleum products and additives. Thisknowledge can be used to predict performance, handling, or processing properties. In some cases the presence of sulfur compoundsis benefic
19、ial to the product and monitoring the depletion of sulfur can provide useful information. In other cases the presence ofsulfur compounds is detrimental to the processing or use of the product.5. Interferences5.1 For the iodate systems, chlorine in concentrations less than 1 mass % does not interfere
20、. The IR system can toleratesomewhat higher concentrations. Nitrogen when present in excess of 0.1 mass % may interfere with the iodate systems; the extentof such interference may be dependent on the type of nitrogen compound as well as the combustion conditions. Nitrogen does notinterfere with the
21、IR system. The alkali and alkaline earth metals, as well as zinc, phosphorus, and lead, do not interfere with eithersystem.5. Apparatus5.1 Resistance Type Furnace, capable of maintaining a temperature of at least 1350 C (2460 F).5.2 Combustion and Iodate Detection System: Absorber,6.1.1 FurnacesTwo
22、major types are available, the primary 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 assembly shall becapable of attaining a t
23、emperature of at least 1482C (2700F) in the sample combustion zone, under the conditions set forth in9.1 and shall be equipped with an additional induction coil located above the combustion zone, substantially as shown in Fig. 1.6.1.1.2 The furnace work coil should have a minimum output of 500 W; th
24、e minimum input rating of the furnace must be 1000W. With the correct amount of iron chips, weighed to 60.05 g, the maximum plate current will be between 350 and 450 mA.(WarningThis type of furnace is capable of inflicting high frequency burns and high-voltage shocks. In addition to otherprecautions
25、, maintain all guards properly.) (WarningDisconnect the furnace from the power line whenever electrical repairs oradjustments are made.)6.1.1.3 Resistance Type, capable of maintaining a temperature of at least 1371C (2500F). as described in Test Method D1266.6.1.2 Absorber, as described in Test Meth
26、od D1266.NOTE 1Also suitable for use with either type of furnace is an automatic titrator, specifically designed for iodometry. This combines the functions ofabsorption and titration to a predetermined end point.6.1.3 Buret, standard 25-mL or automatic types available from the manufacturers of the s
27、pecific combustion units, are suitable(Note 1).5.3 Combustion and IR Detection System, comprised of automatic balance, oxygen flow controls, drying tubes, combustionfurnace, infrared detector and microprocessor. The furnace shall be capable of maintaining a nominal operating temperature of1350C (246
28、0F).1350 C (2460 F).6.3 Miscellaneous ApparatusSpecific combustion assemblies require additional equipment such as crucibles, combustionboats, crucible lids, boat pushers, separator disks, combustion tubes, sample inserters, oxygen flow indicator, and oxygen dryingtrains. The additional equipment re
29、quired is dependent on the type of furnace used and is available from the manufacturer of thespecific combustion unit. To attain the lower sulfur concentration given in Section 1, the ceramics used with the induction furnaceassembly shall be ignited in a muffle furnace at 1371C (2500F) for at least
30、4 h before use.5.4 Sieve, 60-mesh (250-mm).60 mesh (250 m).6. Reagents and Materials6.1 Purity of ReagentsReagent grade chemicals shall be used in all tests. Unless otherwise indicated, it is intended that allreagents shall conform to the specifications of the Committee on Analytical Reagents of the
31、 American Chemical Society, wheresuch specifications are available.3 Other grades may be used, provided it is first ascertained that the reagent is of sufficiently highpurity to permit its use without lessening the accuracy of the determination.3 Reagent Chemicals, American Chemical Society Specific
32、ations, American Chemical Society, Washington, DC. For Suggestions on the testing of reagents not listed bythe American Chemical Society, see Annual Standards for Laboratory Chemicals, BDH Ltd., Poole, Dorset, U.K., and the United States Pharmacopeia and NationalFormulary, U.S. Pharmacopeial Convent
33、ion, Inc. (USPC), Rockville, MD.D1552 1527.2 Purity of WaterUnless otherwise indicated, references to water shall be understood to mean reagent water as defined byType II or III of Specification D1193.6.2 Alundum Combustion PromoterMagnesium Oxide (Com-Aid) or Alundum (Al2O3) or ).Magnesium Oxide (C
34、om-Aid).6.3 Anhydrone (Magnesium Perchlorate).Magnesium Perchlorate: Anhydrone. (WarningIn addition to other precautions,handle magnesium perchlorate with care.Avoid contacting it with acid and organic materials. Reactions with fuel may be violent.)7.5 Hydrochloric Acid (3 + 197)Dilute 30 mLof conce
35、ntrated hydrochloric acid (HCl, relative density 1.19) to 2 Lwith water.(WarningPoison. Corrosive. May be fatal if swallowed. Liquid and vapor cause severe burns.)6.4 Oxygen (Extra Dry)The oxygen shall be at least 99.5 % pure and show no detectable sulfur by blank determination.(WarningOxygen vigoro
36、usly accelerates combustion.)6.5 Phosphorus Pentoxide(P2O5).7.8 Potassium Alum (Aluminum Potassium Sulfate).7.9 Potassium Iodate, Standard Solution (0.06238 N), 1 mL of this solution is equivalent to 1 mg S)Dissolve 2.225 g ofpotassium iodate (KIO3) that has been dried at about 180C to constant weig
37、ht, in water and dilute to 1 L. Thoroughly mix thesolution.7.10 Potassium Iodate, Standard Solution (0.006238 N), 1 mL of this solution is equivalent to 0.1 mg S)Measure exactly 100mL of KIO3 solution (0.06238 N) into a 1L volumetric flask, and dilute to volume with water. Thoroughly mix the solutio
38、n.7.11 Potassium Iodate, Standard Solution (0.01248 N), 1 mL of this solution is equivalent to 0.2 mg S)Measure exactly 200mL of KIO3 solution (0.06238 N) into a 1-L volumetric flask and dilute to volume with water. Thoroughly mix the solution.6.6 Ascarite, 88 mesh to 20 mesh.20 mesh.7.13 Special Ma
39、terials for Induction-Type Furnaces:7.13.1 Tin (20 to 30-mesh).7.13.2 Iron-Chip Accelerator having a sulfur content of not more than 0.005 mass %.7.14 Standard SamplePotassium alum (AlK(SO4)2 12H2O).7.15 Starch-Iodide SolutionMake a paste by adding 9 g of soluble starch to 15 mL of water. Add this m
40、ixture, with stirring,to 500 mL of boiling water. Cool the mixture, add 15 g of potassium iodide (KI), and dilute to 1 L with water.7.16 Sulfuric Acid (relative density 1.84)Concentrated sulfuric acid (H2SO4). (WarningPoison. Corrosive. Strongoxidizer.)6.7 Vanadium Pentoxide, anhydrous, powdered V2O
41、5.6.8 Quality Control (QC) Sample(s) , Sample(s), preferably are portions of one or more petroleum products that are stable andrepresentative of the samples of interest. These QC samples can be used to check the validity of the testing process andperformance of the instrument as described in Section
42、 1211.7. Sampling7.1 Take samples in accordance with the instructions in Practice D4057.8. Preparation of Apparatus9.1 Induction-Type FurnaceAssemble the apparatus according to the instructions furnished by the manufacturer. Purify theoxygen by passing it through (1) H2SO4 (relative density 1.84), (
43、 2) Ascarite, and (3) magnesium perchlorate (Mg(ClO4)2) orphosphorus pentoxide (P2O5) (Warningsee 7.4). Connect a rotameter between the purifying train and the furnace. Insert a smallglass-wool plug in the upper end of the glass tubing connecting the furnace with the absorber to catch oxides of tin.
44、 Connect theexit end of the combustion tube to the absorber with glass tubing, using gum rubber tubing to make connections. Position theabsorber so as to make this delivery line as short as possible. Fig. 2 illustrates schematically the assembled apparatus. Adjust theoxygen flow to 1 6 0.05 L/min. A
45、dd 65 mL of HCl (3 + 197) and 2 mL of starch-iodide solution to the absorber. Add a sufficientamount of the appropriate standard KIO3 solution (Table 1) to produce a faint blue color. This color will serve as the end pointfor the titration. Adjust the buret to zero. Turn on the furnace filament swit
46、ch and allow at least 1 min warm-up before runningsamples (Warningsee 7.4).9.2 ResistanceType FurnaceAssemble the apparatus according to the instructions furnished by the manufacturer. Purify theoxygen by passing it through (1) H2SO4 (relative density 1.84), (2) Ascarite, and (3) Mg(ClO4)2 or P2O5 (
47、Warningsee 7.4).Connect a rotameter between the purifying train and the furnace. Fig. 3 illustrates schematically the assembled apparatus. Turn onthe current and adjust the furnace control to maintain a constant temperature of 1316 6 14C (2400 6 25F). Adjust the oxygenflow rate to 2 6 0.1 L/min. Add
48、 65 mL of HCl (3 6 197) and 2 mL of starch-iodide solution to the absorber. Add a few drops ofthe appropriate standard KIO3 solution (Table 2) to produce a faint blue color. Adjust the buret to zero.D1552 1538.1 ResistanceType FurnaceIR DetectionAssemble and adjust apparatus according to manufacture
49、rs instructions. Initializemicroprocessor, check power supplies, set oxygen pressure and flows and set furnace temperature to 1371C (2500F).1350 C(2460 F).8.1.1 Condition a fresh anhydrone scrubber with four coal samples when analyzing petroleum coke samples, or with fourpetroleum product samples that are representative or typical of the sample types to be analyzed.8.1.2 Calibrate the automatic balance according to manufacturers instructions.9. Standardization9.1 For Iodate Methods: Determination of Standard
