1、Designation: D 5705 03An 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 oforiginal adoption or
2、, 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 field determination ofhydrogen sulfide (H2S) in t
3、he 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 The applicable r
4、ange 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 as thestandard. The values given in parentheses are for informationonly.1.5 This standard does not purport to address all of thesafety concerns, if any, associated with
5、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 Manual Sampling
6、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 cracked residue f
7、rom 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 in the liquid ph
8、ase.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 withnitrogen to displace a
9、ir. 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 detector tube shouldbe
10、 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 maintain safe le
11、vels 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 containing high lev
12、els 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 H2S in the vap
13、or 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, operator, or loc
14、ation. 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 on Burner, Diesel, Non-Aviation Gas Turbine, and
15、Marine Fuels.Current edition approved Nov. 1, 2003. Published December 2003. Originallyapproved in 1995. Last previous edition approved in 2000 as D 570595(2000)e1.2For referenced ASTM standards, visit the ASTM website, www.astm.org, orcontact ASTM Customer Service at serviceastm.org. For Annual Boo
16、k of ASTMStandards volume information, refer to the standards Document Summary page onthe ASTM website.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.concentrations o
17、f H2S in residual fuel oil storage or transports.However, a facility that produces fuel oil from the same 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 int
18、erferences. In some cases, nitrogen dioxide cancause a negative interference. Most detector tubes will have aprecleanse layer designed to remove certain interferences up tosome maximum interferant level. Consult the manufacturersinstructions for specific interference information.7. Apparatus7.1 Shak
19、er, a bench-top orbital shaker and platformequipped with a four-prong clamp to hold 1-L Boston round-bottom glass bottles and capable of operation at 220 rpm.37.2 Timer, capable of measuring from1sto30minatsecond intervals.7.3 Stopper with Temperature Measuring Device, a No. 2cork stopper with a tem
20、perature measuring devices insertedthrough it that is capable of accurately measuring the tempera-ture 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 h
21、aving a range of 18 to 82C and a 200mmstem has been found suitable to use.7.4 Oven or Water Bath, capable 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.4It must be specifically design
22、ed for use with detectortubes. (WarningA detector tube and pump together form aunit and must be used as 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
23、is likely to occur.)8. Reagents and Materials8.1 ContainersBoth sample and test containers are com-posed 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. (Warn
24、ingHydrogen sulfide reacts with metalsurfaces and is easily oxidized, which depletes its concentra-tion 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
25、.2 Length-of-Stain Detector Tube and Calibration Scale,asealed glass tube with breakoff tips sized to fit 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 produ
26、ce adistinct color change when exposed to a sample of gascontaining hydrogen sulfide. Any substances known 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
27、) ofhydrogen sulfide content from a separate calibration scaleshould be supplied with the tubes. The calibration 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 d
28、ateof manufacture, when stored according to the manufacturersrecommendations.9. Sampling9.1 The sampling 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
29、the midpoint or belowmidpoint of the fuel oil in a storage tank by first sufficientlypurging sample transfer lines and then taking single sampleswhere each sample comprises one and only one test.3Baxter Scientific Product Models 3518 and 30100, or equivalent, are suitablefor this test.4Direct Readin
30、g Colorimetric Indicator Tubes Manual, First Edition, AmericanIndustrial Hygiene Association, Akron, OH 44311, 1976.FIG. 1 Measurement of H2S in the Vapor Phase of Residual FuelOilD5705032(WarningSamples taken for this test method shall be dedi-cated to a single H2S determination and not used for an
31、y otherpurpose, as any additional handling can lead to loss of H2S andthus low results.)NOTE 1Liquid samples taken well into the fuel oil have had less H2Slost by degassing as compared with a fuel oils surface. Samples takenfrom well within the fuel oil storage provide material that represents thegr
32、eatest potential for H2S exposure during fuel oil movements. Hydrogensulfide is lost by degassing (elevated temperature and mechanical agitationincreases H2S degassing), oxidation, and absorption on water-wet sur-faces.9.2 Fill at least two 1-L size sample containers with fuel oil.Minimize the heads
33、pace 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 important; therefore,sample containers must be composed of inert materials, fillednearly completely with liquid, an
34、d 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 mechanism described in Note 1.10. Procedure10.1 Let each filled sample container sit at room tempera-ture for at least 1 h,
35、 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 with applicable laws. A single test is to beperformed on material from an individual sample container.10.2 Insert a n
36、itrogen 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 time the bottle is open to avoid further lossof sample vapors. Close the test bottle opening (gas tight) witha cor
37、k 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 temperature reaches 606 1C. Keep the sample in the oven or bath for a minimum of30 min, which includes the time fo
38、r 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 obtained for the H2S concentration.10.4 While the sample is heating, place an unbroken length-of-stain detector tub
39、e 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 leak check typically takes 1 min.10.5 Remove the test bottle from the oven and place it in thefour-prong clamp of
40、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 thermometer, and immediately seal the top of thebottle with aluminum foil.10.7 Select a detector tube with a range t
41、hat 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 and insert the tube into thepump, observing the flow direction indication on the tube.Insert the tube through the a
42、luminum 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 liquid, see Fig. 1(b). Use one fullcompression stroke.10.9 Remove the detector tube after complete decompres-sion of the
43、 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 channeling has occurred (non-uniform stain length),read the maximum and minimum stain lengths and average thetwo reading
44、s. (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 results.)10.10 If the calibration scale specifies more than one stroke,correct the reading as below:ppm v/v correct
45、ed!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 thereading as below:ppm v/v corrected!5ppm v/v reading!3 101.325 kPa!/barometric pressure, kPa!(2)10.11 If the detector
46、 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 reuse detector tubes. Continue the testingusing different ranged detector tubes and new samples untileither the readin
47、g 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 raw readings, the readings corrected fornumber of strokes, the readings corrected for barometricpressure, and the
48、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 v/v) for each test along with the testtemperature.12. Precision and Bias512.1 PrecisionThe precision of this test m
49、ethod 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 phase involved four fuels tested byeight participants in four locations. Since samples could not be shipped5Supporting data have been filed at ASTM International Headquarters and maybe obtained by requesting Research Report RR: D02-1358.D5705033too far and could not be kept for different time periods before testing, thefour locations were in a specific geograp
