1、Designation: D 5453 06An American National StandardStandard Test Method forDetermination of Total Sulfur in Light Hydrocarbons, SparkIgnition Engine Fuel, Diesel Engine Fuel, and Engine Oil byUltraviolet Fluorescence1This standard is issued under the fixed designation D 5453; the number immediately
2、following the designation indicates the year 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 (e) indicates an editorial change since the last revision or reapproval.1. Scope*1.1 This test
3、method covers the determination of total sulfurin liquid hydrocarbons, boiling in the range from approxi-mately 25 to 400C, with viscosities between approximately0.2 and 20 cSt (mm2/S) at room temperature.1.2 Three separate interlaboratory studies (ILS) on preci-sion, and two other investigations th
4、at resulted in an ASTMresearch report, have determined that this test method isapplicable to naphthas, distillates, engine oil, ethanol, FattyAcid Methyl Ester (FAME), and engine fuel such as gasoline,oxygen enriched gasoline (M-85, RFG), diesel, biodiesel, andjet fuel. Samples containing 1.0 to 800
5、0 mg/kg total sulfur canbe analyzed (Note 1).NOTE 1Estimates of the pooled limit of quantification (PLOQ) foreach of the five precision studies were calculated. Values ranged betweenless than 1.0 and less than 5.0 mg/kg (see Section 8 and 15.1).1.3 This test method is applicable for total sulfur det
6、ermi-nation in liquid hydrocarbons containing less than 0.35 %(m/m) halogen(s).1.4 The values stated in SI units are to be regarded asstandard. No other units of measurement are included in thisstandard.1.5 This standard does not purport to address all of thesafety concerns, if any, associated with
7、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. For warningstatements, see 3.1, 6.3, 6.4, Section 7, and 8.1.2. Referenced Documents2.1 ASTM Standards:2D 1298
8、Test Method for Density, Relative Density (SpecificGravity), or API Gravity of Crude Petroleum and LiquidPetroleum Products by Hydrometer MethodD 4052 Test Method for Density and Relative Density ofLiquids by Digital Density MeterD 4057 Practice for Manual Sampling of Petroleum andPetroleum Products
9、D 4177 Practice for Automatic Sampling of Petroleum andPetroleum ProductsD 6299 Practice for Applying Statistical Quality AssuranceTechniques to Evaluate Analytical Measurement SystemPerformance3. Summary of Test Method3.1 A hydrocarbon sample is either directly injected orplaced in a sample boat. T
10、he sample or boat, or both, is insertedinto a high temperature combustion tube where the sulfur isoxidized to sulfur dioxide (SO2) in an oxygen rich atmosphere.Water produced during the sample combustion is removed andthe sample combustion gases are next exposed to ultraviolet(UV) light. The SO2abso
11、rbs the energy from the UV light andis converted to excited sulfur dioxide (SO2*). The fluorescenceemitted from the excited SO2* as it returns to a stable state,SO2, is detected by a photomultiplier tube and the resultingsignal is a measure of the sulfur contained in the sample.(WarningExposure to e
12、xcessive quantities of ultraviolet(UV) light is injurious to health. The operator must avoidexposing any part of their person, especially their eyes, notonly to direct UV light but also to secondary or scatteredradiation that is present.)4. Significance and Use4.1 Some process catalysts used in petr
13、oleum and chemicalrefining can be poisoned when trace amounts of sulfur bearingmaterials are contained in the feedstocks. This test method canbe used to determine sulfur in process feeds sulfur in finishedproducts, and can also be used for purposes of regulatorycontrol.1This test method is under the
14、 jurisdiction of ASTM Committee D02 onPetroleum Products and Lubricants and is the direct responsibility of SubcommitteeD02.03 on Elemental Analysis.Current edition approved May 1, 2006. Published May 2006. Originallyapproved in 1993. Last previous edition approved in 2005 as D 545305.2For reference
15、d 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 website.1*A Summary of Changes section appears at the end of this standard.Copyrigh
16、t ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959, United States.5. Apparatus5.1 FurnaceAn electric furnace held at a temperature(1075 6 25C) sufficient to pyrolyze all of the sample andoxidize sulfur to SO2.5.2 Combustion TubeA quartz combustion tube con-str
17、ucted to allow the direct injection of the sample into theheated oxidation zone of the furnace or constructed so that theinlet end of the tube is large enough to accommodate a quartzsample boat. The combustion tube must have side arms for theintroduction of oxygen and carrier gas. The oxidation sect
18、ionshall be large enough (see Fig. 1) to ensure complete combus-tion of the sample. Fig. 1 depicts conventional combustiontubes. Other configurations are acceptable if precision is notdegraded.5.3 Flow ControlThe apparatus must be equipped withflow controllers capable of maintaining a constant suppl
19、y ofoxygen and carrier gas.5.4 Drier TubeThe apparatus must be equipped with amechanism for the removal of water vapor. The oxidationreaction produces water vapor which must be eliminated priorto measurement by the detector. This can be accomplished witha membrane drying tube, or a permeation dryer,
20、 that utilizes aselective capillary action for water removal.5.5 UV Fluorescence DetectorA qualitative and quantita-tive detector capable of measuring light emitted from thefluorescence of sulfur dioxide by UV light.5.6 Microlitre SyringeA microlitre syringe capable ofaccurately delivering 5 to 20-L
21、 quantities. The needle shall be50 mm (65 mm) long.5.7 Sample Inlet SystemEither of two types of sampleinlet systems can be used.5.7.1 Direct InjectionA direct injection inlet system mustbe capable of allowing the quantitative delivery of the materialto be analyzed into an inlet carrier stream which
22、 directs thesample into the oxidation zone at a controlled and repeatablerate. A syringe drive mechanism which discharges the samplefrom the microlitre syringe at a rate of approximately 1 L/s isrequired. For example, see Fig. 2.5.7.2 Boat Inlet SystemAn extended combustion tubeprovides a seal to th
23、e inlet of the oxidation area and is swept bya carrier gas. The system provides an area to position thesample carrying mechanism (boat) at a retracted positionremoved from the furnace. The boat drive mechanism willfully insert the boat into the hottest section of the furnace inlet.The sample boats a
24、nd combustion tube are constructed ofquartz. The combustion tube provides a cooling jacket for theFIG. 1 Conventional Combustion TubesD5453062area in which the retracted boat rests awaiting sample intro-duction from a microlitre syringe. A drive mechanism whichadvances and withdraws the sample boat
25、into and out of thefurnace at a controlled and repeatable rate is required. Forexample, see Fig. 3.5.8 Refrigerated CirculatorAn adjustable apparatus ca-pable of delivering a coolant material at a constant temperatureas low as 4C could be required when using the boat inletinjection method (optional)
26、.5.9 Strip Chart Recorder, (optional).5.10 Balance, with a precision of 60.01 mg (optional).6. Reagents6.1 Purity of ReagentsReagent grade chemicals shall beused in tests. Unless otherwise indicated, it is intended that allreagents shall conform to the specifications of the Committeeon Analytical Re
27、agents of the American Chemical Society,where such specifications are available.3Other 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.6.2 Inert GasArgon or helium only, high purit
28、y grade(that is, chromatography or zero grade), 99.998 % minimumpurity, moisture 5 ppm w/w maximum.6.3 OxygenHigh purity (that is, chromatography or zerograde), 99.75 % minimum purity, moisture 5 ppm w/w maxi-mum, dried over molecular sieves. (WarningVigorouslyaccelerates combustion.)6.4 Toluene, Xy
29、lenes, Isooctane, reagent grade (other sol-vents similar to those occurring in samples to be analyzed arealso acceptable). Correction for sulfur contribution from sol-vents (solvent blank) used in standard preparation and samplespecimen dilution is required. Alternatively, use of a solventwith nonde
30、tectable level of sulfur contamination relative to thesulphur content in the sample unknown makes the blankcorrection unnecessary. (WarningFlammable solvents.)6.5 Dibenzothiophene, FW184.26, 17.399 % (m/m) S (Note2).6.6 Butyl Sulfide, FW146.29, 21.92 % (m/m) S (Note 2).6.7 Thionaphthene (Benzothioph
31、ene), FW134.20, 23.90 %(m/m) S (Note 2).NOTE 2A correction for chemical impurity can be required.6.8 Quartz Wool.6.9 Sulfur Stock Solution, 1000 g S/mLPrepare a stocksolution by accurately weighing approximately 0.5748 g ofdibenzothiophene or 0.4562 g of butyl sulfide or 0.4184 g ofthionaphthene int
32、o a tared 100 mL volumetric flask. Dilute tovolume with selected solvent. This stock can be further dilutedto desired sulfur concentration (Notes 3-5).3Reagent Chemicals, American Chemical Society Specifications, AmericanChemical Society, Washington, DC. For suggestions on the testing of reagents no
33、tlisted by the American Chemical Society, see Analar 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. 2 Direct Inject Syringe DriveD5453063NOTE 3Working standards
34、should be remixed on a regular basisdepending upon frequency of use and age. Typically, stock solutions havea useful life of about 3 months.NOTE 4Calibration standards can be prepared and diluted on amass/mass basis when result calculations are adjusted to accommodatethem.NOTE 5Calibration standards
35、 from commercial sources can be used ifchecked for accuracy and if precision is not degraded.6.10 Quality Control (QC) Samples, preferably are portionsof one or more liquid petroleum materials that are stable andrepresentative of the samples of interest. These QC samplescan be used to check the vali
36、dity of the testing process asdescribed in Section 14.7. Hazards7.1 High temperature is employed in this test method. Extracare must be exercised when using flammable materials nearthe oxidative pyrolysis furnace.8. Sampling8.1 Obtain a test unit in accordance with Practice D 4057 orPractice D 4177.
37、 To preserve volatile components which are insome samples, do not uncover samples any longer thannecessary. Samples shall be analyzed as soon as possible aftertaking from bulk supplies to prevent loss of sulfur or contami-nation due to exposure or contact with sample container.(WarningSamples that a
38、re collected at temperatures belowroom temperature can undergo expansion and rupture thecontainer. For such samples, do not fill the container to the top;leave sufficient air space above the sample to allow room forexpansion.)8.2 If the test unit is not used immediately, then thoroughlymix in its co
39、ntainer prior to taking a test specimen.9. Preparation of Apparatus9.1 Assemble and leak check apparatus according to manu-facturers instructions.9.2 Adjust the apparatus, depending upon the method ofsample introduction, to meet conditions described in Table 1.9.3 Adjust the instrument sensitivity a
40、nd baseline stabilityand perform instrument blanking procedures following manu-facturers guidelines.10. Calibration and Standardization10.1 Based on anticipated sulfur concentration, select one ofthe suggested curves outlined in Table 2. Narrower ranges thanthose indicated may be used, if desired. H
41、owever, the testFIG. 3 Boat Inlet SystemTABLE 1 Typical Operating ConditionsSyringe drive (direct inject) drive rate (700750) 1 L/sBoat drive (boat inlet) drive rate (700750) 140160 mm/minFurnace temperature 1075 6 25CFurnace oxygen flowmeter setting (3.84.1) 450500 mL/minInlet oxygen flowmeter sett
42、ing (0.40.8) 1030 mL/minInlet carrier flowmeter setting (3.43.6) 130160 mL/minD5453064method precision using narrower ranges than those indicatedhave not been determined. Ensure the standards used forcalibration bracket the concentrations of the samples beinganalyzed. Carefully prepare a series of c
43、alibration standardsaccordingly. Make other volumetric dilutions of the stocksolution to cover the various ranges of operation within thesecalibration curve guidelines. The number of standards used percurve can vary, if equivalent results are obtained.10.2 Flush the microlitre syringe several times
44、with thesample prior to analysis. If bubbles are present in the liquidcolumn, flush the syringe and withdraw a new sample.10.3 A sample size recommended for the curve selectedfrom Table 2 must be quantitatively measured prior to injectioninto the combustion tube or delivery into the sample boat fora
45、nalysis (Note 6 and Note 7). There are two alternativetechniques available.NOTE 6Injection of a constant or similar sample size for all materialsanalyzed in a selected operating range promotes consistent combustionconditions.NOTE 7Injection of 10 L of the 100 ng/L standard would establisha calibrati
46、on point equal to 1000 ng or 1.0 g.10.3.1 The volumetric measurement of the injected materialcan be obtained by filling the syringe to the selected level.Retract the plunger so that air is aspirated and the lower liquidmeniscus falls on the 10 % scale mark and record the volumeof liquid in the syrin
47、ge. After injection, again retract theplunger so that the lower liquid meniscus falls on the 10 %scale mark and record the volume of liquid in the syringe. Thedifference between the two volume readings is the volume ofsample injected (Note 8).NOTE 8An automatic sampling and injection device can be u
48、sed inplace of the described manual injection procedure.10.3.2 Fill the syringe as described in 10.3.1. Weigh thedevice before and after injection to determine the amount ofsample injected. This procedure can provide greater accuracythan the volume delivery method, provided a balance with aprecision
49、 of 60.01 mg is used.10.4 Once the appropriate sample size has been measuredinto the microlitre syringe, promptly and quantitatively deliverthe sample into the apparatus. Again, there are two alternativetechniques available.10.4.1 For direct injection, carefully insert the syringe intothe inlet of the combustion tube and the syringe drive. Allowtime for sample residues to be burned from the needle (NeedleBlank). Once a stable baseline has reestablished, promptly startthe analysis. Remove syringe once the apparatus has returnedto a stabl
