1、Designation: D5453 12D5453 16Standard 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 approximately2525 C to 400C,400 C, with viscosities between approximately 0.20.2 cSt and 20 cSt 20 cSt (mm2/S) at room temperature.1.2 Three separate interlaboratory studies (ILS) on precision, and three other investigations t
4、hat resulted in an ASTM 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 b
5、lends, and jet fuel. Samples containing 1.01.0 mgkg to 80008000 mg mg/kg 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 than1.01.0 mg kg and less than 5.0 mg/kg (see Section 8
6、and 15.1).1.3 This test method is applicable for total sulfur determination in liquid hydrocarbons containing less than 0.35 % (mm)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 purpo
7、rt 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. For warning statements, see 3.1, 6.3, 6.4, Secti
8、on 7, and 8.1.2. Referenced Documents2.1 ASTM Standards: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 Pract
9、ice for Manual Sampling of Petroleum and Petroleum 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 Metho
10、d3.1 A hydrocarbon sample is either directly injected 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 a
11、nd the sample combustion gases are next exposed 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
12、resulting signal is a measure of1 This test method is 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 Nov. 1, 2012April 15, 2016. Published February 2
13、013April 2016. Originally approved in 1993. Last previous edition approved in 20092012 asD5453D5453 12.09. DOI: 10.1520/D5453-12.10.1520/D5453-16.2 For referencedASTM standards, visit theASTM website, www.astm.org, or contactASTM Customer Service at serviceastm.org. For Annual Book of ASTM Standards
14、volume information, refer to the standards Document 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 a
15、dequately depict all changes accurately, ASTM recommends 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 AS
16、TM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959. United States1the sulfur contained 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 th
17、eir eyes, not only to direct UV light but also to secondary orscattered radiation that is present.)4. 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
18、 can be used to determine sulfur in process feeds sulfur in finishedproducts, and can also be used for purposes of regulatory control.5. Apparatus5.1 FurnaceAn electric furnace held at a temperature (1075 6 25C) (1050 C min to 1150 C max) sufficient to pyrolyzeall of the sample and oxidize sulfur to
19、 SO2. The actual temperature to be recommended by the specific apparatus manufacturer.5.2 Combustion TubeA quartz combustion tube constructed to allow the direct injection of the sample into the heatedoxidation zone of the furnace or constructed so that the inlet end of the tube is large enough to a
20、ccommodate a quartz sample boat.The combustion tube must have shall have one or more side arms for the introduction of oxygen and carrier gas. gas or air. Theoxidation section shall be large enough (see Fig. 1) to ensure complete combustion of the sample. Fig. 1 depicts conventionalcombustion tubes.
21、 Other configurations are acceptable if precision is not degraded.5.3 Flow ControlThe apparatus mustshall be equipped with flow controllers a means of flow control that is capable ofmaintaining a constant supply of oxygen and carrier gas.gas or air.5.4 Drier TubeThe apparatus must be equipped with a
22、 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 action for water removal.5.5 UVFluoresc
23、ence DetectorAqualitative and quantitative detector capable of measuring light emitted from the fluorescenceof sulfur dioxide by UV light.FIG. 1 Conventional Combustion TubesD5453 1625.6 Microlitre SyringeA microlitre syringe capable Capable of accurately delivering 5 to 20-L quantities. The needle
24、shallbe 50 mm (65 mm) long.from 5 L to 90 L of test specimen. Check with the instrument manufacturer for specific test specimenvolume and needle size requirements.5.7 Sample Inlet SystemEither of two types of sample inlet systems can be used.5.7.1 Direct InjectionA direct injection inlet system must
25、 be capable of allowing the quantitative delivery of the material tobe analyzed into an inlet carrier stream 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 approximate
26、ly 1 L/s is required.typical. Check with the instrument manufacturer for specific test specimen injection rates. For example, see Fig. 2.5.7.2 Boat Inlet SystemAn extended combustion tube provides a seal to the inlet of the oxidation area and is swept by a carriergas. The system provides an area to
27、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 sample boats andcombustion tube are constructed of quartz. The combustion tube provides a cooling jack
28、et 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 a controlled and repeatable rate is required. For example, see Fig. 3.5.8 Refrigerated CirculatorAn ad
29、justable apparatus capable of delivering a coolant material at a constant temperature as lowas 4C4 C could be required when using the boat inlet injection method (optional).5.9 Strip Chart Recorder, (optional).5.10 Balance, with a precision of 60.01 mg 60.01 mg (optional).6. Reagents6.1 Purity of Re
30、agentsReagent 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 Chemical Society, wheresuch specifications are available.3 Other grades may be used, provided
31、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 Specifications, American Chemical Society, Washington, DC. For Suggestions on the testing of reagents not listed
32、 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 Convention, Inc. (USPC), Rockville, MD.FIG. 2 Direct Inject Syringe DriveD5453 1636.2 InertCarrier GasArgon or
33、helium only, high purity grade (that is, chromatography or zero grade), 99.998 % minimumpurity, moisture 5 ppm w/w maximum.Inert gas or air. The actual gas to be recommended by the specific apparatus manufacturer.6.2.1 Inert GasArgon or helium only, high purity grade (that is, chromatography or zero
34、 grade), 99.998 % minimum purity,moisture 5 mgkg maximum.6.2.2 AirHigh purity grade (that is, chromatography or zero grade), 99.99 % minimum purity, moisture 5 mgkg maximum.6.3 OxygenOxygen (as required)High purity (that is, chromatography or zero grade), 99.75 % minimum purity, moisture 5ppm w/w ma
35、ximum, dried over molecular sieves. (WarningVigorously accelerates combustion.)6.4 Toluene, Xylenes, Isooctane , Isooctane, reagent grade (other solvents similar to those occurring in samples to be analyzedare also acceptable). Correction for sulfur contribution from solvents (solvent blank) used in
36、 standard preparation and samplespecimen dilution is required.Alternatively, use of a solvent with nondetectable level of sulfur contamination relative to the sulphurcontent in the sample unknown makes the blank correction unnecessary. (WarningFlammable solvents.)6.5 Dibenzothiophene, FW184.26, 17.3
37、99 % (m/m) S (Note 2).6.6 Butyl Sulfide, FW146.29, 21.92 % (m/m) S (Note 2).6.7 Thionaphthene (Benzothiophene) , (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 capa
38、ble of withstanding 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 fur
39、nace. Consult instrument manufacturer recommendations forfurther guidance.6.9 Sulfur Stock Solution, 1000 g 1000 g S/mLPrepare a stock solution by accurately weighing approximately 0.5748 g0.5748 g of dibenzothiophene or 0.4562 g 0.4562 g of butyl sulfide or 0.4184 g 0.4184 g of thionaphthene into a
40、 tared 100 mL100 mL volumetric flask. Dilute to volume with selected solvent. This stock can be further diluted to desired sulfur concentration(Notes 4-7).FIG. 3 Boat Inlet SystemD5453 164NOTE 4Working standards that simulate or match the composition or matrix of the samples analyzed can reduce test
41、 result bias between direct injectand boat sample inlet systems.NOTE 5Working standards should be remixed on a regular basis depending upon frequency of use and age. Typically, stock solutions have a usefullife of about 3three months.NOTE 6Calibration standards can be prepared and diluted on a mass/
42、mass basis when result calculations are adjusted to accommodate them.NOTE 7Calibration standards from commercial sources can be used if checked for accuracy and if precision is not degraded.6.10 Quality Control (QC) Samples, , preferably are portions of one or more liquid petroleum materials that ar
43、e stable andrepresentative of the samples of interest. These QC samples can be used to check the validity of the testing process as describedin 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 H
44、igh 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 accordance with Practice D4057 or Practice D4177. To preserve volatile components which are in somesamples, do not unc
45、over 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 sample container. (WarningSamples that arecollected at temperatures below room temperature can undergo expan
46、sion 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 used immediately, then thoroughly mix in its container prior to taking a test specimen.9. Preparation of Apparat
47、us9.1 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 Table 1.9.3 Adjust the instrument sensitivity and baseline stability and perform instrument blanking procedures
48、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 thanthose indicated may be used, if desired. However, the test method precision using narrower ranges than th
49、ose indicated have notbeen determined. Ensure the standards used for calibration bracket the concentrations of the samples being analyzed. Carefullyprepare a series of calibration standards accordingly. 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 to analysis. If bubbles are present in
