1、Designation:D602106 Designation: D6021 12Standard Test Method forMeasurement of Total Hydrogen Sulfide in Residual Fuelsby Multiple Headspace Extraction and Sulfur SpecificDetection1This standard is issued under the fixed designation D6021; the number immediately following the designation indicates
2、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 a method suitable for m
3、easuring the total amount of hydrogen sulfide (H2S) in heavy distillates,heavy distillate/residual fuel blends, or residual fuels as defined in Specification D396 Grade 4, 5 (Light), 5 (Heavy), and 6, whenthe H2S concentration in the fuel is in the 0.01 to 100 g/g (ppmw) range.1.2 The values stated
4、in SI units are to be regarded as standard. No other units of measurement are included in this standard.1.3 This standard does not purport 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
5、health practices and determine the applicability of regulatorylimitations prior to use. For specific warning statements, see 5.1, 7.5, 8.2, 9.2, 10.1.4, and 11.1.2. Referenced Documents2.1 ASTM Standards:2D396 Specification for Fuel OilsD1193 Specification for Reagent WaterD2420 Test Method for Hydr
6、ogen Sulfide in Liquefied Petroleum (LP) Gases (Lead Acetate Method)D3609 Practice for Calibration Techniques Using Permeation TubesD4057 Practice for Manual Sampling of Petroleum and Petroleum ProductsD4084 Test Method for Analysis of Hydrogen Sulfide in Gaseous Fuels (Lead Acetate Reaction Rate Me
7、thod)D4323 Test Method for Hydrogen Sulfide in the Atmosphere by Rate of Change of ReflectanceD5504 Test Method for Determination of Sulfur Compounds in Natural Gas and Gaseous Fuels by Gas Chromatography andChemiluminescenceD5705 Test Method for Measurement of Hydrogen Sulfide in the Vapor Phase Ab
8、ove Residual Fuel Oils Test Method forMeasurement of Hydrogen Sulfide in the Vapor Phase Above Residual Fuel OilsD7621 Test Method for Determination of Hydrogen Sulfide in Fuel Oils by Rapid Liquid Phase Extraction3. Terminology3.1 Definitions:3.1.1 heavy distillate, na fuel produced from the distil
9、lation of crude oil which has a kinematic viscosity at 40C between 5.5and 24.0 mm2/s, inclusive.3.1.2 heavy distillate/residual fuel blend, na blend of heavy distillate and residual fuel oil having a viscosity at 40C between5.5 and 24.0 mm2/s, inclusive.3.1.3 multiple headspace extraction, na techni
10、que to determine the total concentration of a gas trapped in a liquid by analysisof successive gas extractions from the vapor space of a closed vessel containing a known amount of the sample.3.1.4 residual fuel oil, nany liquid or liquefiable petroleum product having a kinematic viscosity at 100C be
11、tween 5.0 and50.0 mm2/s, inclusive, burned for the generation of heat in a furnace or firebox or for the generation of power in an engine.1This test method is under the jurisdiction of ASTM Committee D02 on Petroleum Products and Lubricants and is the direct responsibility of Subcommittee D02.E0 onB
12、urner, Diesel, Non-Aviation Gas Turbine, and Marine Fuels.Current edition approved Aug. 1, 2006. Published September 2006. Originally approved in 1996. Last previous edition approved in 2001 as D602196(2001)1. DOI:10.1520/D6021-06.Current edition approved April 15, 2012. Published May 2012. Original
13、ly approved in 1996. Last previous edition approved in 2006 as D602106. DOI:10.1520/D6021-12.2For 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 Su
14、mmary page on the ASTM website.1This 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 recomme
15、nds 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 standard.Copyright ASTM International, 100 Barr Harbor Drive, PO Box C700
16、, West Conshohocken, PA 19428-2959, United States.4. Summary of Test Method4.1 A representative sample of residual fuel oil is obtained in sufficient quantity to completely fill the sample container. Thesample is taken to the laboratory preferably within one to 4 h, within 24 h maximum and placed in
17、 a refrigerator until the hydrogensulfide analysis can be run. At that time, the sample is removed from the refrigerator and allowed to sit at ambient temperatureuntil it flows freely.4.2 A 0.05 to 5.0 g test specimen (aliquot) is placed in a headspace vial and heated in an oven at 60C for more than
18、 five butless than 15 min. The headspace gas is sampled and injected into either of two types of apparatus capable of measuring thehydrogen sulfide concentration in the gaseous sample.3The two types of apparatus are those using the reaction of lead acetate withH2S (see Test Method D4084 or Test Meth
19、od D4323) and those based on chemiluminescence (see Test Method D5504).4.3 The remaining contents of the headspace vial are cooled for 5 min, then again heated in the oven. The headspace contentsare again transferred to the hydrogen sulfide measuring instrument. The procedure is repeated for a third
20、 time. This is known asmultiple headspace extraction procedure (MHE).4.4 A linear plot of the natural logarithm of the area or peak height difference of the instrument reading against the number ofinjections is indicative of the correctness of the extraction procedure.The difference in area or peak
21、height of the first two injectionsis used to calculate a total area or total peak height difference. The total area or total peak height difference is multiplied by aresponse factor determined from a direct gas calibration mixture and divided by the weight of the test specimen to determine theconcen
22、tration of H2S in the residual fuel in g/g (ppmw).5. Significance and Use5.1 Excessive levels of hydrogen sulfide in the vapor phase above residual fuel oils in storage tanks may result in health hazard,OSHA limits violation, and public complaint. An additional concern is corrosion that can be cause
23、d by the presence of HResidualfuel oils can contain H2S during refining and other production activities. Control measures to maintain safe levels of HS in the liquid phase,and this can result in hazardous vapor phase levels of H2S require a consistent method for the assessment of potentially hazardo
24、us levels of HSin storage tank headspaces. The vapor phase levels can vary significantly according to the headspace volume, fuel temperature, and agitation. Measurement of H2Sinfueloils. (WarningHS levels in the liquid phase provides a useful indication of the residual fuel oils propensity to form h
25、igh vapor phase levels, and lower levels inthe residual fuel oil will directly reduce risk of H2S is a highly toxic substance. Extreme care must be used in the sampling and handling ofsamplesthataresuspectedofcontaininghighlevelsofHS exposure. It is critical, however, that anyone involved in handlin
26、g fuel oil, such as vessel ownersand operators, continue to maintain appropriate safety practices designed to protect the crew, tank farm operators and others who can be exposed to H2S. )5.2A concentration of 0.1 g/g (ppmw) of HS.5.1.1 The measurement of H2S in the liquid phase of a No. 4, 5, or 6 r
27、esidual fuel oil can generate an actual gas concentrationof 10 to 100 L/L(ppmv) of HS in the liquid phase is appropriate for product quality control, while the measurement of H2S in the vapor phase; thereforean accurate analytical method is required to determine the total HS in the vapor phase is ap
28、propriate for health and safety purposes.5.2 This test method was developed so refiners, fuel terminal operators and independent testing laboratory personnel cananalytically measure the amount of H2S concentration of these residual fuel oils. This test method was developed so refiners, fuelterminal
29、operators, and independent testing laboratory personnel can analytically measure the amount of HS in the liquid phase of residualfuel oils.NOTE 1Test Method D6021 is one of three test methods for quantitatively measuring H2S in residual fuel oils.5.3Test Method S in residual fuels:1) Test Method D57
30、05 provides a simple and consistent field test method for the rapid determination of His a simple field test methodfor determining H2S in the residual fuel oils storage tank vapor phase. However, it does not necessarily simulate the vapor phase HSlevels in the vapor phase.2) Test Method D7621 is a r
31、apid test method to determine H2S concentration of a fuel storage tank nor does it provide any indication of the liquidphase HS levels in the liquid phase.5.3 H2S concentration. This test method provides a quantitative measure of a residual fuel oils liquid phase HS concentrations in theliquid and v
32、apor phase attempt to reach equilibrium in a static system. However, this equilibrium and the related liquid and vapor concentrations can vary greatly dependingon temperature and the chemical composition of the liquid phase. A concentration of 1 mg/kg (g/g) (ppmw) of H2S concentration. It requires a
33、 laboratory anda skilled operator to perform the test but gives a more quantitative indication of potential HS in the liquid phase of a residual fuel can typicallygenerate an actual gas concentration of 50 to 100 L/L(ppmv) of H2S exposure thanTest Method D5705. S in the vapor phase, but the equilibr
34、iumof the vapor phase is disrupted the moment a vent or access point is opened to collect a sample.NOTE 12Because of the reactivity, absorptivity, and volatility of H2S any measurement method only provides an H2S concentration at a givenmoment in time.6. Apparatus6.1 A schematic of the headspace sam
35、pling system required for this analysis is shown in Fig. 1. It consists of:3 Determination of H2S in Residual Fuel Oils by Multiple Headspace Extraction: A Critical Evaluation of Available AnalyticalMethods. Silva, B., Carvajal, N., Gonzalez, A., Eastern Analytical Symposium, sponsored by American C
36、hemical Society and theAmerican Microchemical Society, November 1620, 1992, Somerset, N.J.D6021 1226.1.1 Sampling On/Off Valve, with 3.2 mm o.d. connector (Valve 1).6.1.2 Six-Port External Loop Injection Valve, made with 316 stainless steel, resistant to attack by sulfur compounds and having3.2 mm o
37、.d. tubing from each port (Valve 2).6.1.3 Polytetrafluoroethylene (PTFE) Sample Loops, of 0.5, 2.5, and 10 mL are used for H2S content of 1 to 100, 0.1 to 50, and0.01 to 10 ppmw, respectively.6.1.4 Pressure/Vacuum Gage, 6.3 mm diameter dial type with range of 100 to 200 kPag, 5 kPa divisions from 10
38、0 to 0 and10 kPa divisions from 0 to 200 kPag.6.1.5 Vacuum On/Off Valve, 3.2 mm o.d. connector (Valve 3).6.1.6 Sulfur Selective Detector, any H2S specific detector capable of measuring H2S in the gas from 1 to 10 000 ppmv with arepeatability of 62 % of full scale.NOTE2Good 3Good performance has been
39、 obtained with a lead acetate tape detector and a sulfur chemiluminescence detector.6.1.7 Fluorocarbon Tubing, 0.6 m long by 3.2 mm o.d. to connect components together.6.2 Vacuum pump, 3.2 mm o.d. outlet, capable of achieving a 0.2 kPa vacuum and with a capacity of 100 mL/min.6.3 Headspace Oven, cap
40、able of operating at 60 6 0.5C with internal dimensions of 30 by 30 by 30 cm.An optional vent lineis recommended in case a vial leaks.6.4 Analytical Balance, sensitivity of 0.01 mg, maximum weight of 250 g.6.5 Data Handling System, such as electronic integrator or any computer unit that can work wit
41、h a chromatographic signal.6.6 If sulfur specific detectors are used instead of an H2S analyzer then a chromatographic system equipped with a suitablecolumn and oven is required to separate H2S from other sulfur compounds (see Test Method D5504).6.7 Hand Crimper, to crimp 20 mm diameter aluminum sea
42、ls.7. Reagents and Materials7.1 Purity of ReagentsReagent grade chemicals shall be used in all tests. Unless otherwise indicated, it is intended that allreagents conform to the specifications of the Committee on Analytical Reagents of the American Chemical Society where suchspecifications are availa
43、ble.4Other grades may be used, provided it is first ascertained that the reagent is of sufficiently high purityto permit its use without lessening the accuracy of the determination.4Reagent Chemicals, American Chemical Society Specifications, American Chemical Society, Washington, DC. For suggestion
44、s on the testing of reagents not listed bythe American Chemical Society, see Analar 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. 1 Schematic of Headspace Ana
45、lysis SystemD6021 1237.2 Acetic Acid SolutionAdd 50 mLof glacial acetic acid (CH3COOH) to a 1-Lvolumetric flask and then add Type II distilledwater, as specified in Specification D1193, to the 1-L mark to make a 5 % acetic acid solution.7.3 Aluminum Seals, 20 mm diameter to seal septas to headspace
46、sample vials.7.4 Headspace Vials, 30-, 60-, or 120-mL borosilicate glass vials with 20 mm mouth diameter.7.5 Hydrogen Sulfide Gas Calibration Standard, 1, 10, and 100 L/L H2S in helium or nitrogen high pressure cylinders (obtainfrom gas supply company). (WarningHydrogen sulfide is an extremely toxic
47、 gas.)7.6 Gases, helium or nitrogen (H2S free), chemically pure grade or purified, as carrier gas to sweep sample into the detector.7.7 Lead Acetate Sensing PaperPrepare in accordance with Test Method D2420, using appropriate size strips and drying inan H2S-free environment. Commercially available t
48、est paper has been found satisfactory.NOTE3Reagents from 4Reagents from 7.2 and 7.7 are only needed if using an H2S lead acetate tape detector.7.8 Nuts and Ferrules, Polytetrafluoroethylene (PTFE) and stainless steel (3.2 mm).7.9 Septas, 20 mm diameter PTFE silicone/fluorocarbon to seal headspace sa
49、mple vials.7.10 Side Port Needles, for pressure lock, A-gas series (with reduction union 3.2 mm to 1.6 mm).7.11 Syringe Needles, common dischargeable (dosing needle).8. Sampling8.1 Using a suitable H2S inert container of 250 to 500 mL, collect a representative sample by Practice D4057. Suitablecontainers can be made of borosilicate glass or aluminum. If the sample temperature is below 60C then a high densitypolyethylene bottle can be used.8.2 Fill the container completely to the top so that there is no headspace in the container. Cap immediately.
