1、Designation: D 6667 04An American National StandardStandard Test Method forDetermination of Total Volatile Sulfur in GaseousHydrocarbons and Liquefied Petroleum Gases by UltravioletFluorescence1This standard is issued under the fixed designation D 6667; 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 (e) indicates an editorial change since the last revision or reapproval.1. Scope*1.1 This test method covers the deter
3、mination of totalvolatile sulfur in gaseous hydrocarbons and liquefied petro-leum (LP) gases. It is applicable to analysis of natural,processed, and final product materials containing sulfur in therange of 1 to 100 mg/kg (Note 1).NOTE 1An estimate of pooled limit of quantification (PLOQ), infor-mati
4、on regarding sample stability and other general information derivedfrom the inter-laboratory study on precision can be referenced in theASTM research report.21.2 This test method may not detect sulfur compounds thatdo not vaporize under the conditions of the test.1.3 This test method is applicable f
5、or total volatile sulfurdetermination in LP gases containing less than 0.35 % (mass/mass) halogen(s).1.4 The values stated in SI units are to be regarded asstandard.1.5 This standard does not purport to address all of thesafety concerns, if any, associated with its use. It is theresponsibility of th
6、e user of this standard to establish appro-priate safety and health practices and determine the applica-bility of regulatory limitations prior to use. See 3.1 andSections 6 and 7 for specific warning statements.2. Referenced Documents2.1 ASTM Standards:3D 1070 Test Methods for Relative Density (Spec
7、ific Grav-ity) of Gaseous FuelsD 1265 Practice for Sampling Liquefied Petroleum (LP)Gases (Manual Method)D 3700 Practice for Obtaining LPG Samples Using a Float-ing Piston CylinderD 5287 Practice for the Automatic Sampling of GaseousFuelsD 6299 Practice for Applying Statistical Quality AssuranceTech
8、niques to Evaluate Analytical Measurement SystemPerformanceF 307 Practice for Sampling Pressurized Gas for Gas Analy-sis2.2 Gas Processor Association (GPA) Standards:4GPA 2166 Obtaining Natural Gas Samples for Analysis byGas ChromatographyGPA 2174 Obtaining Liquid Hydrocarbon Samples forAnalysis by
9、Gas Chromatography3. Summary of Test Method3.1 A heated sample valve is used to inject gaseous samples.Liquefied petroleum gas (LPG) samples are injected by asample valve connected to a heated expansion chamber. Thegaseous sample then enters a high temperature combustiontube where sulfur is oxidized
10、 to sulfur dioxide (SO2)inanoxygen rich atmosphere. Water produced during the samplecombustion is removed and the sample combustion gases arenext exposed to ultraviolet (UV) light. The SO2absorbs theenergy from the UV light and is converted to an excited sulfurdioxide (SO2). Fluorescence emitted fro
11、m the excited SO2*asit returns to a stable state SO2*is detected by a photomultipliertube, the resulting signal is a measure of the sulfur contained inthe sample. (WarningExposure to excessive quantities ofultraviolet light is injurious to health. The operator shall avoidexposing their person, espec
12、ially their eyes, not only to directUV light but also to secondary or scattered radiation that ispresent.)4. Significance and Use4.1 The sulfur content of LPG, used for fuel purposes,contributes to SOx emissions and can lead to corrosion in1This test method is under the jurisdiction of ASTM Committe
13、e D02 onPetroleum Products and Lubricants and is the direct responsibility of SubcommitteeD02.03 on Elemental Analysis.Current edition approved Nov. 1, 2004. Published November 2004. Originallyapproved in 2001. Last previous edition approved in 2001 as D 666701.2Supporting data have been filed at AS
14、TM International Headquarters and maybe obtained by requesting Research Report RR: D021506.3For 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 Su
15、mmary page onthe ASTM website.4Available from Gas Processors Association (GPA), 6526 E. 60th St., Tulsa, OK74145.1*A Summary of Changes section appears at the end of this standard.Copyright ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959, United States.engine
16、 and exhaust systems. Some process catalysts used inpetroleum and chemical refining can be poisoned by sulfurbearing materials in the feed stocks. This test method can beused to determine sulfur in process feeds, to measure sulfur infinished products, and can also be used for compliance deter-minati
17、ons when acceptable to a regulatory authority.5. Apparatus5.1 FurnaceAn electric furnace held at a temperature(1075 6 25C) sufficient to pyrolyze the entire sample andoxidize sulfur to SO2.5.2 Combustion TubeA quartz combustion tube con-structed to allow the direct injection of the sample into thehe
18、ated oxidation zone of the furnace. The combustion tubeshall have side arms for the introduction of oxygen and carriergas. The oxidation section shall be large enough (see Fig. 1)toensure complete combustion of the sample (see 11.3). Fig. 1depicts a typical combustion tube. Other configurations area
19、cceptable when precision is not degraded.5.3 Flow ControlThe apparatus shall be equipped withflow controllers capable of maintaining a constant supply ofoxygen and carrier gas at the specified rates.5.4 Drier TubeThe apparatus shall be equipped with amechanism for the removal of water vapor formed d
20、uringsample combustion. This can be accomplished with a mem-brane drying tube, or a permeation dryer that utilizes aselective capillary action for water removal.5.5 UV Fluorescence DetectorA quantitative detector ca-pable of measuring light emitted from the fluorescence ofsulfur dioxide by UV light.
21、5.6 Sample Inlet SystemThe system provides a heatedgas-sampling valve, or a LP gas-sampling valve, or both, witha heated expansion chamber, connected to the inlet of theoxidation area, Fig. 2. The system is swept by an inert carriergas and shall be capable of allowing the quantitative deliveryof the
22、 material to be analyzed into the oxidation zone at acontrolled and repeatable rate of approximately 30 mL/min.Fig. 3 provides an example.5.7 Strip Chart Recorder, equivalent electronic data logger,integrator or, recorder (optional).6. Reagents6.1 Purity of ReagentsReagent grade chemicals shall beus
23、ed in tests. Unless otherwise indicated, it is intended that allreagents shall conform to the specifications of the Committeeon Analytical Reagents of the American Chemical Society,5where such specifications are available. Other grades may beused, provided it is first ascertained that the reagent is
24、 ofsufficiently high purity to permit its use without lessening theaccuracy of the determination.6.2 Inert GasArgon or helium only, high purity grade(that is, chromatography or zero grade), 99.998 % min purity,moisture 5 mg/kg max. (WarningArgon or helium may be acompressed gas under high pressure (
25、7.1).6.3 OxygenHigh purity (that is chromatography or zerograde), 99.75 % min purity, moisture 5 mg/kg max, dried overmolecular sieves. (WarningOxygen vigorously acceleratescombustion and may be compressed gas under high pressure(7.1).6.4 Calibration StandardsCertified calibration standardsfrom comm
26、ercial sources or calibration gases prepared usingcertified permeation tube devices are required. Table 1 lists thesulfur source material and diluent matrices used during theinter-laboratory study (Notes 2 and 3).5Reagent Chemicals, American Chemical Society Specifications, AmericanChemical Society,
27、 Washington, DC. For suggestions on the testing of reagents notlisted 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.
28、 1 Example of a Typical Direct Inject Quartz Pyrolysis TubeD6667042NOTE 2Other sulfur sources and diluent materials may be used ifprecision and accuracy are not degraded.NOTE 3Calibration standards are typically re-mixed and re-certifiedon a regular basis depending upon frequency of use and age. The
29、secalibration standards may have a useful life of about 6 to 12 months.6.5 Quality Control (QC) Samples, preferably are portionsof one or more gas or LP gas materials that are stable andrepresentative of the samples of interest.7. Hazards7.1 High temperature, flammable hydrocarbons, and gasesunder h
30、igh pressures occur in the test method. Use materialsthat are rated for containing these pressurized hydrocarbons inall sample containers and sample transfer apparatus. Exerciseextra care when using flammable materials near the oxidativefurnace.8. Sampling8.1 Obtain a sample in accordance with Pract
31、ices F 307,D 1265, D 3700, D 5287,orGPA-2174 or GPA-2166. Analyzesamples as soon as possible after taking from bulk supplies toprevent loss of sulfur or contamination due to exposure orcontact with sample containers.8.2 If the sample is not used immediately, then thoroughlymix it in its container pr
32、ior to taking a test specimen. The useof segregated or specially treated sample containers can helpreduce sample cross-contamination and improve sample sta-bility.9. Preparation of Apparatus9.1 Assemble and check the apparatus for leaks according tomanufacturers instructions.9.2 Typical apparatus ad
33、justments and conditions are listedin Table 2.9.3 Adjust instrument sensitivity and baseline stability andperform instrument-blanking procedures following manufac-turers guidelines.10. Calibration and Standardization10.1 Consult Table 3 and select a calibration range based onthe anticipated sulfur c
34、oncentrations present in samples to beanalyzed, preferably using a sulfur compound and a diluenttype representative of the samples to be analyzed (Note 4).Table 3 is representative of typical ranges, but narrower rangesthan those indicated may be used if desired. However, themethod precision using n
35、arrower ranges than those indicatedhas not been determined. Ensure the standards used forcalibration bracket the concentrations of the samples beinganalyzed.NOTE 4The number of standards used per curve may vary.FIG. 2 Example of Orientation of Total Sulfur Analyzer and Gas or Liquid Sampling ValveD6
36、66704310.2 With the sample valve in the load position, connect thepressurized sample container to the sample valve of the sampleinlet system.10.3 Obtain a quantitative measurement of the injectedmaterial by filling the sample loop of the sample valve systemfor the matrix being analyzed (see Table 2)
37、 (Notes 5 and 6).NOTE 5Injection of a constant or similar sample size for all materialsanalyzed in a selected operating range promotes consistent combustionconditions and may simplify result calculations.NOTE 6An automatic sample transfer and injection device may beused.10.3.1 Flush the sample loop
38、with sufficient calibrant toassure that the material to be injected is representative.10.3.2 For LPG samples, if bubbles are present in theviewable portion of the liquid column, flush the sample loop tointroduce a new liquid-full sample portion.10.4 Start the analyzer and inject the calibration mate
39、rialaccording to the manufacturers instructions.10.5 Calibrate the instrument using one of the followingtechniques.10.5.1 Multi-point Calibration:10.5.1.1 When the apparatus features an internal self-calibration routine, analyze the calibration standards and blankthree times using the procedures des
40、cribed in 10.2-10.4.10.5.1.2 Calibrate the analyzer according to the manufac-turers instructions to yield sulfur concentration (see Section13). This curve is typically linear and system performance shallbe checked at least once per day, each day of use. (Note 7).NOTE 7Other calibration curve techniq
41、ues may be used when accu-racy and precision are not degraded. The frequency of calibration may bedetermined by the use of quality control charts or other quality assurance/quality control techniques.FIG. 3 Sample Inlet System Flow PathTABLE 1 Typical Standard MaterialsSulfur Source DiluentDimethyl
42、sulfide n, butaneiso-butanepropylenepropaneTABLE 2 Typical Operating ConditionsSample inlet system temperature 85 6 20CSample injection system carrier gas 2530 mL/minFurnace temperature 1075 6 25CFurnace oxygen flow meter setting 375450 mL/minInlet oxygen flow meter setting 1030 mL/minInlet carrier
43、flow meter setting 130160 mL/minGas sample size 1020 mLLPG sample size 15 LTABLE 3 Typical Sulfur Calibration Ranges and StandardConcentrationsCurve ISulfur mg/kgCurve IISulfur mg/kgBlank Blank5.00 10.0010.00 50.00100.00TABLE 4 Repeatability (r) and Reproducibility (R)Concentration(mg/kg S)rR1 0.1 0
44、.35 0.6 1.610 1.2 3.125 2.9 7.850 5.8 15.6100 11.5 31.3D666704410.5.2 One-point Calibration:10.5.2.1 Utilize a calibration standard (6.4) with a sulfurcontent close to that of the samples to be analyzed (625 %max.).10.5.2.2 Follow the instrument manufacturers instructionsto establish an instrument z
45、ero (instrument blank) by conduct-ing an analysis run without injection of the calibration stan-dard.10.5.2.3 Perform measurements of the calibration standard aminimum of three times.10.5.2.4 Calculate a calibration factor K, in counts pernanogram of sulfur (counts/ng S) as described in 12.2.11. Pro
46、cedure11.1 Obtain a test specimen using the procedure describedin Section 8. Typically the sulfur concentration in the testspecimen is less than the concentration of the highest standardand greater than the concentration of the lowest standard usedin the calibration.11.2 Measure the response for the
47、 test specimen using oneof the procedures described in 10.2-10.4.11.3 Inspect the combustion tube and other flow pathcomponents to verify complete oxidation of the test specimen.11.3.1 Reduce the rate of injection or the sample size, orboth, of the specimen into the furnace when coke or sooting isob
48、served.11.4 Cleaning and Re-calibrationClean any coked orsooted parts according to the manufacturers instructions. Afterany cleaning or adjustment, assemble and check the apparatusfor leaks. Repeat instrument calibration prior to reanalysis ofthe test specimen.11.5 To obtain one result, measure each
49、 test specimen threetimes and calculate the average detector response.11.6 Density values needed for calculations are to bemeasured using Test Methods D 1070 or equivalent, at thetemperature at which the sample was tested (Note 8).NOTE 8When sample matrix compositions are known, other tech-niques may be used to derive sample density, provided accuracy andprecision are not degraded.12. Calculation12.1 For analyzers calibrated using an internal self-calibration, calculate the sulfur content in the test specimen asfollows:Sulfur, mg/kg 5G 3 ds(1)w
