1、Designation: D 5705 03 (Reapproved 2008)An American National StandardStandard Test Method forMeasurement of Hydrogen Sulfide in the Vapor PhaseAbove Residual Fuel Oils1This standard is issued under the fixed designation D 5705; the number immediately following the designation indicates the year ofor
2、iginal 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. Scope1.1 This test method covers the field determination ofhydrogen su
3、lfide (H2S) in the vapor phase (equilibrium head-space) of a residual fuel oil sample.1.2 The test method is applicable to liquids with a viscosityrange of 5.5 mm2/s at 40C to 50 mm2/s at 100C. The testmethod is applicable to fuels conforming to SpecificationD 396 Grade Nos. 4, 5 (Heavy), and 6.1.3
4、The applicable range is from 5 to 4000 parts per millionby volume (ppm v/v) (micro mole/mole).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, a
5、ssociated 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.2. Referenced Documents2.1 ASTM Standards:2D 396 Specification for Fuel OilsD 4057 Practice for M
6、anual Sampling of Petroleum andPetroleum Products3. Terminology3.1 Definitions:3.1.1 equilibrium headspace, nthe vapor space above theliquid in which all vapor components are in equilibrium withthe liquid components.3.1.2 residual fuel oil, na fuel oil comprising a blend ofviscous long, short, or cr
7、acked residue from a petroleumrefining process and lighter distillates blended to a fuel oilviscosity specification.3.1.2.1 DiscussionUnder the conditions of this test (1:1liquid/vapor ratio, temperature, and agitation) the H2Sinthevapor phase (samples headspace) will be in equilibrium withthe H2S i
8、n the liquid phase.4. Summary of Test Method4.1 A 1-L H2S-inert test container (glass test bottle) is filledto 50 volume % with fuel oil from a filled H2S-inert container(glass sample bottle) just prior to testing. In the test container,the vapor space above the fuel oil sample is purged withnitroge
9、n to displace air. The test container with sample isheated in an oven to 60C, and agitated on an orbital shaker at220 rpm for 3 min.4.2 A length-of-stain detector tube and hand-operated pumpare used to measure the H2S concentration in the vapor phaseof the test container. The length-of-stain detecto
10、r tube shouldbe close to but not in contact with the liquid surface.5. Significance and Use5.1 Excessive levels of hydrogen sulfide in the vapor phaseabove residual fuel oils in storage tanks may result in a healthhazard, OSHA limits violation, and public complaints aboutodors. Control measures to m
11、aintain safe levels of H2Sinthetank atmosphere for those working in the vicinity require aconsistent method for the assessment of potentially hazardouslevels of H2S in fuel oils (WarningH2S is a highly toxicsubstance. Use extreme care in the sampling and handling ofsamples that are suspected of cont
12、aining high levels of H2S.).5.2 This test method has been developed to provide refin-eries, fuel terminals, and independent testing laboratories,which do not have access to analytical instruments such as agas chromatograph, with a simple and consistent field testmethod for the rapid determination of
13、 H2S in the vapor phaseof residual fuel oils.5.3 This test method does not necessarily simulate the vaporphase H2S concentration of a fuel storage tank. It does,however, provide a level of consistency so that the test result isonly a function of the residual fuel oil sample and not the testmethod, o
14、perator, or location. No general correlation can beestablished between this field test and actual vapor phase1This test method is under the jurisdiction of ASTM Committee D02 onPetroleum Products and Lubricants and is the direct responsibility of SubcommitteeD02.E0.01 on Burner Fuels.Current edition
15、 approved Dec. 1, 2008. Published February 2009. Originallyapproved in 1995. Last previous edition approved in 2003 as D 570503.2For referenced ASTM standards, visit the ASTM website, www.astm.org, orcontact ASTM Customer Service at serviceastm.org. For Annual Book of ASTMStandards volume informatio
16、n, refer to the standards Document Summary page onthe ASTM website.1Copyright ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959, United States.concentrations of H2S in residual fuel oil storage or transports.However, a facility that produces fuel oil from the s
17、ame crudesource under essentially constant conditions might be able todevelop a correlation for its individual case.6. Interferences6.1 Typically, sulfur dioxide and mercaptans may causepositive interferences. In some cases, nitrogen dioxide cancause a negative interference. Most detector tubes will
18、 have aprecleanse layer designed to remove certain interferences up tosome maximum interferant level. Consult the manufacturersinstructions for specific interference information.7. Apparatus7.1 Shaker, a bench-top orbital shaker and platformequipped with a four-prong clamp to hold 1-L Boston round-b
19、ottom glass bottles and capable of operation at 220 rpm.7.2 Timer, capable of measuring from1sto30minatsecond intervals.7.3 Stopper with Temperature Measuring Device, a No. 2cork stopper with a temperature measuring devices insertedthrough it that is capable of accurately measuring the tempera-ture
20、of the sample at 60 6 1C as required in the procedure andextending at least 25 mm into the residual fuel but no closerthan 25 mm from the bottom of a test bottle (see Fig. 1(a). Adial thermometer having a range of 18 to 82C and a 200mmstem has been found suitable to use.7.4 Oven or Water Bath, capab
21、le of heating the fuel oilsamples to 60 6 1C.7.5 Detector Tube Pump, a hand-operated piston or bellows-type (Fig. 1(b) pump with a capacity of 100 cm36 5cm3perstroke.3It must be specifically designed for use with detectortubes. (WarningA detector tube and pump together form aunit and must be used as
22、 such. Each manufacturer calibratesdetector tubes to match the flow characteristics of its specificpump. Crossing brands of pumps and tubes is not permitted, asconsiderable loss of system accuracy is likely to occur.)8. Reagents and Materials8.1 ContainersBoth sample and test containers are com-pose
23、d of H2S-inert material such as 1-L size (clear Bostonround-bottom) glass bottles with screw caps. The bottles areclean and dry. Mark test containers at the 50 % volume level byusing a ruler. (WarningHydrogen sulfide reacts with metalsurfaces and is easily oxidized, which depletes its concentra-tion
24、 and gives false low test results. Containers such asepoxy-lacquered cans are suitable for sample collection. Alter-native containers must give equivalent results to those obtainedby using glass.)8.2 Length-of-Stain Detector Tube and Calibration Scale,asealed glass tube with breakoff tips sized to f
25、it the tube holderof the detector tube pump. The reagent layer inside the tube,typically a silica gel substrate coated with the active chemicals,must be specific for hydrogen sulfide and must produce adistinct color change when exposed to a sample of gascontaining hydrogen sulfide. Any substances kn
26、own to inter-fere must be listed in the instructions accompanying the tubes.A calibration scale should be marked directly on the tube, orother markings that provide for easy interpretation (reading) ofhydrogen sulfide content from a separate calibration scaleshould be supplied with the tubes. The ca
27、libration scale shallcorrelate H2S concentration to the length of the color stain.Annex A1 provides additional information. Shelf life of thedetector tubes must be a minimum of two years from the dateof manufacture, when stored according to the manufacturersrecommendations.9. Sampling9.1 The samplin
28、g of residual fuel oils is done according toPractice D 4057 for the sampling of storage tanks, ships, orbarges. Composite sampling or running samples can be taken;spot samples should be taken from the midpoint or belowmidpoint of the fuel oil in a storage tank by first sufficientlypurging sample tra
29、nsfer lines and then taking single sampleswhere each sample comprises one and only one test.(WarningSamples taken for this test method shall be dedi-cated to a single H2S determination and not used for any otherpurpose, as any additional handling can lead to loss of H2S andthus low results.)3Direct
30、Reading Colorimetric Indicator Tubes Manual, First Edition, AmericanIndustrial Hygiene Association, Akron, OH 44311, 1976.FIG. 1 Measurement of H2S in the Vapor Phase of Residual FuelOilD 5705 03 (2008)2NOTE 1Liquid samples taken well into the fuel oil have had less H2Slost by degassing as compared
31、with a fuel oils surface. Samples takenfrom well within the fuel oil storage provide material that represents thegreatest potential for H2S exposure during fuel oil movements. Hydrogensulfide is lost by degassing (elevated temperature and mechanical agitationincreases H2S degassing), oxidation, and
32、absorption on water-wet sur-faces.9.2 Fill at least two 1-L size sample containers with fuel oil.Minimize the headspace of the sample container. Cap imme-diately and deliver to the testing facility. Test each samplewithin one to four hours from the time of sampling.9.3 Sample integrity is extremely
33、important; therefore,sample containers must be composed of inert materials, fillednearly completely with liquid, and capped tightly until tested.Sample handling should be minimized, and rapid testing forH2S is required. Samples can not be stored for later testing asH2S loss may occur by the mechanis
34、m described in Note 1.10. Procedure10.1 Let each filled sample container sit at room tempera-ture for at least 1 h, transfer part of its contents to an empty 1-Ltest bottle such that it is filled 50 % 6 5 volume % with thesample. Discard the remaining contents of the sample containerin compliance wi
35、th applicable laws. A single test is to beperformed on material from an individual sample container.10.2 Insert a nitrogen purge line outlet to within about 13mm above the fuel surface. Nitrogen purge at 2 L/min for 30 sthe headspace above the test sample to displace air and watervapor. Minimize the
36、 time the bottle is open to avoid further lossof sample vapors. Close the test bottle opening (gas tight) witha cork stopper fitted with a dial thermometer (Fig. 1(a)immediately after nitrogen purging.10.3 Place each test bottle with sample in an oven or a waterbath, set at 60 6 1C, until the sample
37、 temperature reaches 606 1C. Keep the sample in the oven or bath for a minimum of30 min, which includes the time for the sample to reach 60C.NOTE 2If the sample temperature does not reach 60C, low resultswill be obtained for the H2S concentration. If the temperature exceeds60C, high results will be
38、obtained for the H2S concentration.10.4 While the sample is heating, place an unbroken length-of-stain detector tube in the hand-operated pump and test thepump for leaks. Consult the manufacturers instructions forleak check procedure details and for maintenance instructionsif leaks are detected. The
39、 leak check typically takes 1 min.10.5 Remove the test bottle from the oven and place it in thefour-prong clamp of the shaker. Shake at 220 rpm for 3 min 61sto achieve H2S equilibrium between the liquid and thevapor phase.10.6 Rest the test bottle on a flat surface, remove the stopperwith the dial t
40、hermometer, and immediately seal the top of thebottle with aluminum foil.10.7 Select a detector tube with a range that best encom-passes the expected H2S concentration. Reading accuracy isimproved when the stain length extends into the upper half ofthe calibration scale.10.8 Break off the tube tips
41、and insert the tube into thepump, observing the flow direction indication on the tube.Insert the tube through the aluminum foil on the test bottle.Rest the pump on top of the test bottle with the detector tubeonly contacting the samples vapor phase. Do not allow thedetector tube to contact the liqui
42、d, see Fig. 1(b). Use one fullcompression stroke.10.9 Remove the detector tube after complete decompres-sion of the pump and immediately read the H2S concentrationfrom the tubes calibration scale or from the charts provided inthe box of tubes. Read the tube at the maximum point of thestain. If chann
43、eling has occurred (non-uniform stain length),read the maximum and minimum stain lengths and average thetwo readings. (WarningIf the calibration scale is not printeddirectly on the detector tube, be certain that any separatecalibration chart is the proper match for the tube in use to avoidincorrect
44、results.)10.10 If the calibration scale specifies more than one stroke,correct the reading as below:ppm v/v corrected!5ppm v/v reading!3specified strokes (1)NOTE 3If the test is being conducted at an altitude above 610 m,corrections for barometric pressure are significant. In this case, correct ther
45、eading as below:ppm v/v corrected!5ppm v/v reading!3 101.325 kPa!/barometric pressure, kPa!(2)10.11 If the detector tube reading is over- or under-ranged,take another detector tube of a different range and test a secondsample of the fuel oil. Do not repeat testing on a previouslytested sample or reu
46、se detector tubes. Continue the testingusing different ranged detector tubes and new samples untileither the reading is on-scale or less than 5 ppm v/v.10.12 After obtaining a satisfactory first result, repeat thetest with another sample of the same fuel oil and a freshdetector tube.10.13 Record the
47、 raw readings, the readings corrected fornumber of strokes, the readings corrected for barometricpressure, and the test temperature.11. Calculation and Report11.1 Determine the average of the readings from the dupli-cate test samples and report the average H2S concentration inparts per million (ppm
48、v/v) for each test along with the testtemperature.12. Precision and Bias412.1 PrecisionThe precision of this test method as deter-mined by statistical examination of interlaboratory test resultsis as follows:NOTE 4The precision data were developed in a 1993 two-phasecooperative testing program. Each
49、 phase involved four fuels tested byeight participants in four locations. Since samples could not be shippedtoo far and could not be kept for different time periods before testing, thefour locations were in a specific geographic area for each phase. Allparticipants tested each sample on the same day. All participants ran eachfuel oil four times using separate samples and fresh detector tubes. Thefirst two results were averaged, and the last two results were averaged. Thetwo average numbers were used to derive the precision statement. Five of
