1、Designation: D 5453 09Standard 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 following the designation ind
2、icates 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 () indicates an editorial change since the last revision or reapproval.1. Scope*1.1 This test method covers the determinatio
3、n 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 three other investigations that resulted in an ASTMresear
4、ch 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 (ethanol blends, E-85, M-85, RFG),diesel, biodiesel, diesel/biodiesel blends, and jet fuel. Samplescon
5、taining 1.0 to 8000 mg/kg total sulfur can be analyzed(Note 1).NOTE 1Estimates of the pooled limit of quantification (PLOQ) for theprecision studies were calculated. Values ranged between less than 1.0 andless than 5.0 mg/kg (see Section 8 and 15.1).1.3 This test method is applicable for total sulfu
6、r determi-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
7、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. For warningstatements, see 3.1, 6.3, 6.4, Section 7, and 8.1.2. Referenced Documents2.1 ASTM Standards:2D
8、1298 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 Pro
9、ductsD 4177 Practice for Automatic Sampling of Petroleum andPetroleum ProductsD 6299 Practice for Applying Statistical Quality Assuranceand Control Charting Techniques to Evaluate AnalyticalMeasurement System Performance3. Summary of Test Method3.1 A hydrocarbon sample is either directly injected or
10、placed in a sample boat. The 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 ultravio
11、let(UV) light. The SO2absorbs 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 sa
12、mple.(WarningExposure to excessive 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.)1This test method is under the juris
13、diction of ASTM Committee D02 onPetroleum Products and Lubricants and is the direct responsibility of SubcommitteeD02.03 on Elemental Analysis.Current edition approved June 15, 2009. Published July 2009. Originallyapproved in 1993. Last previous edition approved in 2008 as D 545308b.2For referenced
14、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.Copyright
15、ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959, United States.4. Significance and Use4.1 Some process catalysts used in petroleum and chemicalrefining can be poisoned when trace amounts of sulfur bearingmaterials are contained in the feedstocks. This test me
16、thod canbe used to determine sulfur in process feeds sulfur in finishedproducts, and can also be used for purposes of regulatorycontrol.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
17、quartz combustion tube con-structed 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 c
18、arrier gas. The oxidation sectionshall 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 o
19、f maintaining a constant supply 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 dryin
20、g tube, or a permeation dryer, 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 ofa
21、ccurately delivering 5 to 20-L 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
22、 an inlet carrier stream which 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 combus
23、tion tubeprovides a seal to the 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 positionFIG. 1 Conventional Combustion TubesD5453092removed from the furnace. The boat drive mechanism willfully insert
24、 the boat into the hottest section of the furnace inlet.The sample boats and combustion tube are constructed ofquartz. The combustion tube provides a cooling jacket for thearea in which the retracted boat rests awaiting sample intro-duction from a microlitre syringe. A drive mechanism whichadvances
25、and withdraws the sample boat 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 in
26、letinjection method (optional).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
27、 the Committeeon Analytical Reagents 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 GasAr
28、gon or helium only, high purity 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. (WarningVigorouslyaccelerat
29、es combustion.)6.4 Toluene, Xylenes, 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. Alternative
30、ly, use of a solventwith nondetectable 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).
31、6.7 Thionaphthene (Benzothiophene), FW134.20, 23.90 %(m/m) S (Note 2).NOTE 2A correction for chemical impurity can be required.6.8 Quartz Wool, or other suitable absorbent material that isstable and capable of withstanding temperatures inside thefurnace (see Note 3).NOTE 3Materials meeting the requi
32、rements in 6.8 provide a moreuniform injection of the sample into the boat by wicking any remaining3Reagent Chemicals, American Chemical Society Specifications, AmericanChemical Society, Washington, DC. For Suggestions on the testing of reagents notlisted by the American Chemical Society, see Annual
33、 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 DriveD5453093drops of the sample from the tip of the syringe needle prior to introduction
34、of the sample into the furnace. Consult instrument manufacturer recom-mendations for further guidance.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 into a tared 1
35、00 mL volumetric flask. Dilute tovolume with selected solvent. This stock can be further dilutedto desired sulfur concentration (Notes 4-7).NOTE 4Working standards that simulate or match the composition ormatrix of the samples analyzed can reduce test result bias between directinject and boat sample
36、 inlet systems.NOTE 5Working standards should be remixed on a regular basisdepending upon frequency of use and age. Typically, stock solutions havea useful life of about 3 months.NOTE 6Calibration standards can be prepared and diluted on amass/mass basis when result calculations are adjusted to acco
37、mmodatethem.NOTE 7Calibration standards 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
38、QC samplescan be used to check the validity 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
39、with Practice D 4057 orPractice D 4177. 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
40、sample container.(WarningSamples that are 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 im
41、mediately, then thoroughlymix in its container prior to taking a test specimen.9. Preparation of Apparatus9.1 Assemble and leak check apparatus according to manu-facturers instructions.FIG. 3 Boat Inlet SystemD54530949.2 Adjust the apparatus, depending upon the method ofsample introduction, to meet
42、conditions described in Table 1.9.3 Adjust the instrument sensitivity and 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
43、Table 2. Narrower ranges thanthose indicated may be used, if desired. However, the testmethod 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
44、calibration 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
45、 with thesample prior to analysis. If bubbles are present in the liquidcolumn, flush the syringe and withdraw a new sample.10.3 A sample injection size recommended for the curveselected from Table 2 shall be quantitatively measured prior toinjection into the combustion tube or delivery into the samp
46、leboat for analysis (Notes 8-10). There are two alternativetechniques available.NOTE 8Injection of a constant or similar sample size for all materialsanalyzed in a selected operating range promotes consistent combustionconditions.NOTE 9Injection of 10 L of the 100 ng/L standard would establisha cali
47、bration point equal to 1000 ng or 1.0 g.NOTE 10Other injection sizes can be used when complete samplecombustion is not compromised and accuracy/precision are not degraded.10.3.1 The volumetric measurement of the injected materialcan be obtained by filling the syringe to the selected level.Retract th
48、e plunger so that air is aspirated and the lower liquidmeniscus falls on the 10 % scale mark and record the volumeof liquid in the syringe. 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. Thediffe
49、rence between the two volume readings is the volume ofsample injected (Note 11).NOTE 11An automatic sampling and injection device can be used 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 of 60.01 mg is used.10.4 Once the appropriate sample size has been measuredinto the microlitre syringe, prompt
