1、Designation: D5453 09D5453 12Standard 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 designati
2、on 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 () indicates an editorial change since the last revision or reapproval.1. Scope*1.1 This test method covers the determ
3、ination of total sulfur in liquid hydrocarbons, boiling in the range from approximately25 to 400C, with viscosities between approximately 0.2 and 20 cSt (mm 2/S) at room temperature.1.2 Three separate interlaboratory studies (ILS) on precision, and three other investigations that resulted in an ASTM
4、 researchreport, have determined that this test method is applicable to naphthas, distillates, engine oil, ethanol, Fatty Acid 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. Sa
5、mples containing 1.0 to 8000 mg/kg total sulfur can be analyzed (Note 1).NOTE 1Estimates of the pooled limit of quantification (PLOQ) for the precision 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
6、total sulfur determination in liquid hydrocarbons containing less than 0.35 % (m/m)halogen(s).1.4 The values stated in SI units are to be regarded as standard. No other units of measurement are included in this standard.1.5 This standard does not purport to address all of the safety concerns, if any
7、, 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. For warning statements, see 3.1, 6.3, 6.4, Section 7, and 8.1.2. Referenced Documents2.1 ASTM St
8、andards:2D1298 Test Method for Density, Relative Density, or API Gravity of Crude Petroleum and Liquid Petroleum Products byHydrometer MethodD4052 Test Method for Density, Relative Density, and API Gravity of Liquids by Digital Density MeterD4057 Practice for Manual Sampling of Petroleum and Petrole
9、um ProductsD4177 Practice for Automatic Sampling of Petroleum and Petroleum ProductsD6299 Practice for Applying Statistical Quality Assurance and Control Charting Techniques to Evaluate Analytical Measure-ment System Performance3. Summary of Test Method3.1 A hydrocarbon sample is either directly inj
10、ected or placed in a sample boat. The sample or boat, or both, is inserted intoa high temperature combustion tube where the sulfur is oxidized to sulfur dioxide (SO2) in an oxygen rich atmosphere. Waterproduced during the sample combustion is removed and the sample combustion gases are next exposed
11、to ultraviolet (UV) light.The SO2 absorbs the energy from the UV light and is converted to excited sulfur dioxide (SO2*). The fluorescence emitted fromthe excited SO2* as it returns to a stable state, SO2, is detected by a photomultiplier tube and the resulting signal is a measure ofthe sulfur conta
12、ined in the sample. (WarningExposure to excessive quantities of ultraviolet (UV) light is injurious to health. Theoperator must avoid exposing any part of their person, especially their eyes, not only to direct UV light but also to secondary orscattered radiation that is present.)1 This test method
13、is under the jurisdiction of ASTM Committee D02 on Petroleum Products and Lubricants and is the direct responsibility of Subcommittee D02.03 onElemental Analysis.Current edition approved June 15, 2009Nov. 1, 2012. Published July 2009February 2013. Originally approved in 1993. Last previous edition a
14、pproved in 20082009 asD545308b.09. DOI: 10.1520/D5453-09.10.1520/D5453-12.2 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 Document Summary page on the
15、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 recommends that users cons
16、ult 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 C700, West Conshohocken,
17、 PA 19428-2959. United States14. Significance and Use4.1 Some process catalysts used in petroleum and chemical refining can be poisoned when trace amounts of sulfur bearingmaterials are contained in the feedstocks. This test method can be used to determine sulfur in process feeds sulfur in finishedp
18、roducts, and can also be used for purposes of regulatory control.5. Apparatus5.1 FurnaceAn electric furnace held at a temperature (1075625C) sufficient to pyrolyze all of the sample and oxidize sulfurto SO2.5.2 Combustion TubeA quartz combustion tube constructed to allow the direct injection of the
19、sample into the heatedoxidation zone of the furnace or constructed so that the inlet end of the tube is large enough to accommodate a quartz sample boat.The combustion tube must have side arms for the introduction of oxygen and carrier gas. The oxidation section shall be largeenough (see Fig. 1) to
20、ensure complete combustion of the sample. Fig. 1 depicts conventional combustion tubes. Otherconfigurations are acceptable if precision is not degraded.5.3 Flow ControlThe apparatus must be equipped with flow controllers capable of maintaining a constant supply of oxygenand carrier gas.5.4 Drier Tub
21、eThe apparatus must be equipped with a mechanism for the removal of water vapor. The oxidation reactionproduces water vapor which must be eliminated prior to measurement by the detector. This can be accomplished with a membranedrying tube, or a permeation dryer, that utilizes a selective capillary a
22、ction for water removal.5.5 UVFluorescence DetectorAqualitative and quantitative detector capable of measuring light emitted from the fluorescenceof sulfur dioxide by UV light.5.6 Microlitre SyringeA microlitre syringe capable of accurately delivering 5 to 20-L quantities. The needle shall be 50 mm(
23、65 mm) long.FIG. 1 Conventional Combustion TubesD5453 1225.7 Sample Inlet SystemEither of two types of sample inlet systems can be used.5.7.1 Direct InjectionA direct injection inlet system must be capable of allowing the quantitative delivery of the material tobe analyzed into an inlet carrier stre
24、am which directs the sample into the oxidation zone at a controlled and repeatable rate. Asyringe drive mechanism which discharges the sample from the microlitre syringe at a rate of approximately 1 L/s is required.For example, see Fig. 2.5.7.2 Boat Inlet SystemAn extended combustion tube provides a
25、 seal to the inlet of the oxidation area and is swept by a carriergas. The system provides an area to position the sample carrying mechanism (boat) at a retracted position removed from thefurnace. The boat drive mechanism will fully insert the boat into the hottest section of the furnace inlet. The
26、sample boats andcombustion tube are constructed of quartz. The combustion tube provides a cooling jacket for the area in which the retracted boatrests awaiting sample introduction from a microlitre syringe. A drive mechanism which advances and withdraws the sample boatinto and out of the furnace at
27、a controlled and repeatable rate is required. For example, see Fig. 3.5.8 Refrigerated CirculatorAn adjustable apparatus capable of delivering a coolant material at a constant temperature as lowas 4C could be required when using the boat inlet injection method (optional).5.9 Strip Chart Recorder, (o
28、ptional).5.10 Balance, with a precision of 60.01 mg (optional).6. Reagents6.1 Purity of ReagentsReagent grade chemicals shall be used in tests. Unless otherwise indicated, it is intended that allreagents shall conform to the specifications of the Committee on Analytical Reagents of the American Chem
29、ical 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.6.2 Inert GasArgon or helium only, high purity grade (that is, chroma
30、tography or zero grade), 99.998 % minimum purity,moisture 5 ppm w/w maximum.3 Reagent Chemicals, American Chemical Society Specifications, American Chemical Society, Washington, DC. For Suggestions on the testing of reagents not listed bythe American Chemical Society, see Annual Standards for Labora
31、tory Chemicals, BDH Ltd., Poole, Dorset, U.K., and the United States Pharmacopeia and NationalFormulary, U.S. Pharmacopeial Convention, Inc. (USPC), Rockville, MD.FIG. 2 Direct Inject Syringe DriveD5453 1236.3 OxygenHigh purity (that is, chromatography or zero grade), 99.75 % minimum purity, moistur
32、e 5 ppm w/w maximum,dried over molecular sieves. (WarningVigorously accelerates combustion.)6.4 Toluene, Xylenes, Isooctane , reagent grade (other solvents similar to those occurring in samples to be analyzed are alsoacceptable). Correction for sulfur contribution from solvents (solvent blank) used
33、in standard preparation and sample specimendilution is required. Alternatively, use of a solvent with nondetectable level of sulfur contamination relative to the sulphur contentin the sample unknown makes the blank correction unnecessary. (WarningFlammable solvents.)6.5 Dibenzothiophene, FW184.26, 1
34、7.399 % (m/m) S (Note 2).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 absorbent material that is stable and capable of withstan
35、ding temperatures inside the furnace(see Note 3).NOTE 3Materials meeting the requirements in 6.8 provide a more uniform injection of the sample into the boat by wicking any remaining drops ofthe sample from the tip of the syringe needle prior to introduction of the sample into the furnace. Consult i
36、nstrument manufacturer recommendations forfurther guidance.6.9 Sulfur Stock Solution, 1000 g S/mLPrepare a stock solution by accurately weighing approximately 0.5748 g ofdibenzothiophene or 0.4562 g of butyl sulfide or 0.4184 g of thionaphthene into a tared 100 mL volumetric flask. Dilute to volumew
37、ith selected solvent. This stock can be further diluted to desired sulfur concentration (Notes 4-7).NOTE 4Working standards that simulate or match the composition or matrix of the samples analyzed can reduce test result bias between direct injectand boat sample inlet systems.NOTE 5Working standards
38、should be remixed on a regular basis depending upon frequency of use and age. Typically, stock solutions have a usefullife of about 3 months.NOTE 6Calibration standards can be prepared and diluted on a mass/mass basis when result calculations are adjusted to accommodate them.NOTE 7Calibration standa
39、rds from commercial sources can be used if checked for accuracy and if precision is not degraded.FIG. 3 Boat Inlet SystemD5453 1246.10 Quality Control (QC) Samples , preferably are portions of one or more liquid petroleum materials that are stable andrepresentative of the samples of interest. These
40、QC samples can be used to check the validity of the testing process as describedin Section 14.7. Hazards7.1 High temperature is employed in this test method. Extra care must be exercised when using flammable materials near theoxidative pyrolysis furnace.8. Sampling8.1 Obtain a test unit in accordanc
41、e with Practice D4057 or Practice D4177. To preserve volatile components which are in somesamples, do not uncover samples any longer than necessary. Samples shall be analyzed as soon as possible after taking from bulksupplies to prevent loss of sulfur or contamination due to exposure or contact with
42、 sample container. (WarningSamples that arecollected at temperatures below room temperature can undergo expansion and rupture the container. For such samples, do not fillthe container to the top; leave sufficient air space above the sample to allow room for expansion.)8.2 If the test unit is not use
43、d immediately, then thoroughly mix in its container prior to taking a test specimen.9. Preparation of Apparatus9.1 Assemble and leak check apparatus according to manufacturers instructions.9.2 Adjust the apparatus, depending upon the method of sample introduction, to meet conditions described in Tab
44、le 1.9.3 Adjust the instrument sensitivity and baseline stability and perform instrument blanking procedures following manufac-turers guidelines.10. Calibration and Standardization10.1 Based on anticipated sulfur concentration, select one of the suggested curves outlined in Table 2. Narrower ranges
45、thanthose indicated may be used, if desired. However, the test method precision using narrower ranges than those indicated have notbeen determined. Ensure the standards used for calibration bracket the concentrations of the samples being analyzed. Carefullyprepare a series of calibration standards a
46、ccordingly. Make other volumetric dilutions of the stock solution to cover the variousranges of operation within these calibration curve guidelines.The number of standards used per curve can vary, if equivalent resultsare obtained.10.2 Flush the microlitre syringe several times with the sample prior
47、 to analysis. If bubbles are present in the liquid column,flush the syringe and withdraw a new sample.10.3 A sample injection size recommended for the curve selected from Table 2 shall be quantitatively measured prior toinjection into the combustion tube or delivery into the sample boat for analysis
48、 (Notes 8-10). There are two alternative techniquesavailable.NOTE 8Injection of a constant or similar sample size for all materials analyzed in a selected operating range promotes consistent combustionconditions.NOTE 9Injection of 10 L of the 100 ng/L standard would establish a calibration point equ
49、al to 1000 ng or 1.0 g.NOTE 10Other injection sizes can be used when complete sample combustion is not compromised and accuracy/precision are not degraded.10.3.1 The volumetric measurement of the injected material can be obtained by filling the syringe to the selected level. Retractthe plunger so that air is aspirated and the lower liquid meniscus falls on the 10 % scale mark and record the volume of liquid inthe syringe. After injection, again retract the plunger so that the lower liquid meniscus falls on the 10 % scale mark and recordth
