1、Designation: D5453 161Standard 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 D5453; the number immediately following the designation indi
2、cates 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.1NOTESubsection 1.1 was corrected editorially in June
3、2016.1. Scope*1.1 This test method covers the determination of total sulfurin liquid hydrocarbons, boiling in the range from approxi-mately 25 C to 400 C, with viscosities between approxi-mately 0.2 cSt and 20 cSt (mm2/s) at room temperature.1.2 Three separate interlaboratory studies (ILS) onprecisi
4、on, and three other investigations that resulted in anASTM research 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),die
5、sel, biodiesel, diesel/biodiesel blends, and jet fuel. Samplescontaining 1.0 mgkg to 8000 mgkg total sulfur can beanalyzed (Note 1).NOTE 1Estimates of the pooled limit of quantification (PLOQ) for theprecision studies were calculated. Values ranged between less than1.0 mg kg and less than 5.0 mg/kg
6、(see Section 8 and 15.1).1.3 This test method is applicable for total sulfur determi-nation in liquid hydrocarbons containing less than 0.35 %(mm) 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
7、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 and determine the applica-bility of regulatory limitations prior to use. For warningstatements, see 3.1,
8、6.3, 6.4, Section 7, and 8.1.2. Referenced Documents2.1 ASTM Standards:2D1298 Test Method for Density, Relative Density, or APIGravity of Crude Petroleum and Liquid Petroleum Prod-ucts by Hydrometer MethodD4052 Test Method for Density, Relative Density, and APIGravity of Liquids by Digital Density M
9、eterD4057 Practice for Manual Sampling of Petroleum andPetroleum ProductsD4177 Practice for Automatic Sampling of Petroleum andPetroleum ProductsD6299 Practice for Applying Statistical Quality Assuranceand Control Charting Techniques to Evaluate AnalyticalMeasurement System Performance3. Summary of
10、Test Method3.1 A hydrocarbon sample is either directly injected orplaced 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 re
11、moved andthe sample combustion gases are next exposed to ultraviolet(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 t
12、he resultingsignal is a measure of the sulfur contained in the sample.(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 scatter
13、edradiation that is present.)1This test method is under the jurisdiction of ASTM Committee D02 onPetroleum Products, Liquid Fuels, and Lubricants and is the direct responsibility ofSubcommittee D02.03 on Elemental Analysis.Current edition approved April 15, 2016. Published April 2016. Originallyappr
14、oved in 1993. Last previous edition approved in 2012 as D5453 12. DOI:10.1520/D5453-16E01.2For referenced 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 Sum
15、mary page onthe ASTM website.*A Summary of Changes section appears at the end of this standardCopyright ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959. United States14. Significance and Use4.1 Some process catalysts used in petroleum and chemicalrefining can
16、 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.5. Apparatus5.1 FurnaceAn electric furnace held at a tempera
17、ture(1050 C min to 1150 C max) sufficient to pyrolyze all of thesample and oxidize sulfur to SO2. The actual temperature to berecommended by the specific apparatus manufacturer.5.2 Combustion TubeA quartz combustion tube con-structed to allow the direct injection of the sample into theheated oxidati
18、on zone of the furnace or constructed so that theinlet end of the tube is large enough to accommodate a quartzsample boat. The combustion tube shall have one or more sidearms for the introduction of oxygen and carrier gas or air. Theoxidation section shall be large enough (see Fig. 1) to ensurecompl
19、ete combustion of the sample. Fig. 1 depicts conven-tional combustion tubes. Other configurations are acceptable ifprecision is not degraded.5.3 Flow ControlThe apparatus shall be equipped with ameans of flow control that is capable of maintaining a constantsupply of oxygen and carrier gas or air.5.
20、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, that utilizes aselective cap
21、illary 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 SyringeCapable of accurately deliveringfrom 5 Lto 90 Lof test specimen. Check with the instrumentm
22、anufacturer for specific test specimen volume and needle sizerequirements.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 inl
23、et carrier stream which directs thesample into the oxidation zone at a controlled and repeatablerate. A syringe drive mechanism which discharges the sampleFIG. 1 Conventional Combustion TubesD5453 1612from the microlitre syringe at a rate of approximately 1 L/s istypical. Check with the instrument m
24、anufacturer for specifictest specimen injection rates. For example, see Fig. 2.5.7.2 Boat Inlet SystemAn extended combustion 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
25、 positionremoved from the furnace. The boat drive mechanism willfully insert 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 samp
26、le intro-duction from a microlitre syringe. A drive mechanism whichadvances 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
27、 a constant temperatureas low as 4 C could be required when using the boat inletinjection 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 indi
28、cated, it is intended that allreagents shall conform to the specifications of 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 perm
29、it its use without lessening theaccuracy of the determination.6.2 Carrier GasInert gas or air. The actual gas to berecommended by the specific apparatus manufacturer.6.2.1 Inert GasArgon or helium only, high purity grade(that is, chromatography or zero grade), 99.998 % minimumpurity, moisture 5 mgkg
30、 maximum.6.2.2 AirHigh purity grade (that is, chromatography orzero grade), 99.99 % minimum purity, moisture 5 mgkgmaximum.6.3 Oxygen (as required)High purity (that is, chromatog-raphy or zero grade), 99.75 % minimum purity, moisture 5 ppmw/w maximum, dried over molecular sieves. (WarningVigorously
31、accelerates 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. Al
32、ternatively, use of a solvent3Reagent Chemicals, American Chemical Society Specifications, AmericanChemical 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
33、 the United States Pharmacopeiaand National Formulary, U.S. Pharmacopeial Convention, Inc. (USPC), Rockville,MD.FIG. 2 Direct Inject Syringe DriveD5453 1613with nondetectable level of sulfur contamination relative to thesulphur content in the sample unknown makes the blankcorrection unnecessary. (Wa
34、rningFlammable 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 (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 ab
35、sorbent material that isstable and capable of withstanding temperatures inside thefurnace (see Note 3).NOTE 3Materials meeting the requirements in 6.8 provide a moreuniform injection of the sample into the boat by wicking any remainingdrops of the sample from the tip of the syringe needle prior to i
36、ntroductionof 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 int
37、o a tared 100 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
38、boat sample 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 three months.NOTE 6Calibration standards can be prepared and diluted on amass/mass basis when result calculations are a
39、djusted to accommodatethem.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 i
40、nterest. These QC samplescan be used to check the validity of the testing process asdescribed in Section 14.6.11 Oxidation Reagent (as required)Tungsten trioxide(WO3), granular (typical particle size 2.0 mm), high purity,99.75 % minimum.7. Hazards7.1 High temperature is employed in this test method.
41、 Extracare must be exercised when using flammable materials nearthe oxidative pyrolysis furnace.8. Sampling8.1 Obtain a test unit in accordance with Practice D4057 orPractice D4177. To preserve volatile components which are insome samples, do not uncover samples any longer thannecessary. Samples sha
42、ll be analyzed as soon as possible afterFIG. 3 Boat Inlet SystemD5453 1614taking from bulk supplies to prevent loss of sulfur or contami-nation due to exposure or contact with sample container.(WarningSamples that are collected at temperatures belowroom temperature can undergo expansion and rupture
43、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 container prior to taking a test specimen.9. Preparation of Apparatus9.1 Assemble and l
44、eak 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 and baseline stabilityand perform instrument blanking procedures following manu-factur
45、ers 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. However, the testmethod precision using narrower ranges than those indicatedhave not b
46、een determined. Ensure the standards used forcalibration bracket the concentrations of the samples beinganalyzed. Carefully prepare a series of calibration standardsaccordingly. Make other volumetric dilutions of the stocksolution to cover the various ranges of operation within thesecalibration curv
47、e guidelines. The number of standards used percurve can vary, if equivalent results are obtained.10.2 Flush the microlitre syringe several times 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 reco
48、mmended for the curveselected from Table 2 shall be quantitatively measured prior toinjection into the combustion tube or delivery into the sampleboat for analysis (Notes 8-10). There are two alternativetechniques available.NOTE 8Injection of a constant or similar sample size for all materialsanalyz
49、ed in a selected operating range promotes consistent combustionconditions.NOTE 9Injection of 10 L of the 100 ng L standard would establisha calibration 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 the plunger so that air is aspirated and the lower liquidmeniscus falls on the 10 % s
