1、Designation: D4045 04 (Reapproved 2010)Standard Test Method forSulfur in Petroleum Products by Hydrogenolysis andRateometric Colorimetry1This standard is issued under the fixed designation D4045; the number immediately following the designation indicates the year oforiginal adoption or, in the case
2、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 determination of sulfur inpetroleum products in the range from 0.
3、02 to 10.00 mg/kg.1.2 This test method may be extended to higher concentra-tion by dilution.1.3 This test method is applicable to liquids whose boilingpoints are between 30 and 371C (86 and 700F). Materialsthat can be analyzed include naphtha, kerosine, alcohol, steamcondensate, various distillates,
4、 jet fuel, benzene, and toluene.1.4 The values stated in SI units are to be regarded asstandard. The values given in parentheses are for informationonly.1.4.1 Certain specifications for the recorder (see 5.5) areexcepted.1.5 This standard does not purport to address all of thesafety concerns, if any
5、, associated 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:2D1193 Specification for Reagent WaterD6299 Practice
6、 for Applying Statistical Quality Assuranceand Control Charting Techniques to Evaluate AnalyticalMeasurement System Performance3. Summary of Test Method3.1 The sample is injected at a constant rate into a flowinghydrogen stream in a hydrogenolysis apparatus. The sampleand hydrogen are pyrolyzed at a
7、 temperature of 1300C, orabove, to convert sulfur compounds to hydrogen sulfide (H2S).Readout is by the rateometric detection of the colorimetricreaction of H2S with lead acetate. Condensable components areconverted to gaseous products, such as methane, during hydro-genolysis.4. Significance and Use
8、4.1 In many petroleum refining processes, low levels ofsulfur in feed stocks may poison expensive catalysts. This testmethod can be used to monitor the amount of sulfur in suchpetroleum fractions.4.2 This test method may also be used as a quality-controltool for sulfur determination in finished prod
9、ucts.5. Apparatus3,45.1 Pyrolysis FurnaceA furnace that can provide anadjustable temperature from 900 to 1400C in a 5-mm insidediameter or larger tube is required to pyrolyze the sample. Thefurnace entry temperature shall allow insertion of the hypoder-mic tip to a depth at which the temperature is
10、550C to providesample vaporization at the injection syringe tip. This tempera-ture shall be above the boiling point of the sample and of thesulfur compounds in the sample (see Fig. 1). The pyrolyzertube may be of quartz; however, the lifetime is limited above1250C. Ceramic may be used at any tempera
11、ture.5.2 Rateometric H2S Readout Hydrogenolysis productscontain H2S in proportion to sulfur in the sample. The H2Sismeasured by measuring rate of change of reflectance caused bydarkening when lead sulfide is formed. Rateometric electron-ics, adapted to provide a first derivative output, allows suffi
12、-cient sensitivity to measure below 0.1 mg/L (see Fig. 2).5.3 Hypodermic SyringeA hypodermic having a needlelong enough to reach the 550C zone is required. A side port isconvenient for vacuum filling and for flushing the syringe. A100-L syringe is satisfactory for injection rates down to 3L/min and
13、a 25-L syringe for lower rates. (WarningExercise caution as hypodermics can cause accidental injury.)1This test method is under the jurisdiction of ASTM Committee D02 onPetroleum Products and Lubricants and is the direct responsibility of SubcommitteeD02.03 on Elemental Analysis.Current edition appr
14、oved May 1, 2010. Published May 2010. Originallyapproved in 1987. Last previous edition approved in 2004 as D4045 04. DOI:10.1520/D4045-04R10.2For referenced ASTM standards, visit the ASTM website, www.astm.org, orcontact ASTM Customer Service at serviceastm.org. For Annual Book of ASTMStandards vol
15、ume information, refer to the standards Document Summary page onthe ASTM website.3The apparatus described in 5.1-5.4 inclusive is similar in specification to theequipment available from Houston Atlas, Inc., 22001 North Park Dr., Kingswood,TX 77339-3804. For further information see Drushel, H. V., “T
16、race SulfurDetermination Petroleum Fractions,” Analytical Chemistry, Vol 50, 1978, p. 76.4The sole source of supply of the apparatus known to the committee at this timeis Houston Atlas, Inc. If you are aware of alternative suppliers, please provide thisinformation to ASTM International Headquarters.
17、 Your comments will receivecareful consideration at a meeting of the responsible technical committee,1whichyou may attend.1Copyright ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959, United States.5.4 Syringe Injection DriveThe drive shall provide uni-form, co
18、ntinuous sample injections. Variation in drive injectionrate caused by mechanical irregularities of gears will causenoise. The adjustable drive shall be capable of injection from 6L/min to 0.06 L/min over a 6-min interval.5.5 RecorderA chart recorder with 10-V full scale and10 000-V input or greater
19、 and having a chart speed of 0.2 to 1in./min (approximately 0.5 to 3 cm/min) is required. Anattenuator can be used for more sensitive recorders. Newerinstruments that display the results are acceptable in lieu of achart recorder.5.6 ThermocoupleA thermocouple suitable for use at 500to 1400C, 250-mm
20、long with readout is required. Type K,116-in. (1.6-mm) diameter, Type 316 stainless steel sheath issuitable.6. Reagents and Materials6.1 Purity of ReagentsReagent grade chemicals shall beused in all tests. Unless otherwise indicated, it is intended thatall reagents conform to the specifications of t
21、he Committee onAnalytical Reagents of the American Chemical Society wheresuch specifications are available.5Other grades may be used,provided it is first ascertained that the reagent is of sufficientlyhigh purity to permit its use without lessening the accuracy ofthe determination.6.2 Purity of Wate
22、rUnless otherwise indicated, referencesto water shall be understood to mean Type II reagent gradewater conforming to Specification D1193.6.3 Sensing TapeLead acetate impregnated paper of chro-matographic quality shall be used. (WarningLead is acumulative poison.)6.4 HydrogenAs no commercial grade of
23、 hydrogen has asulfur specification sufficiently low, each new source of supplymust be tested. A change in the zero base line of 5 % of fullscale from no flow to full flow indicates impure hydrogen.(WarningExtremely flammable gas under pressure. Hydro-gen is a flammable gas. Test all flow systems fo
24、r leaks andpurge with inert gas before introducing hydrogen and afterremoving hydrogen. Keep all flow systems as small in volumeas practical and provide protective screening for containersother than sample flow lines. Dispose of exhaust gases in afume hood or by vacuuming to a safe area. If gas cyli
25、nders areused handle carefully as rupture of the valve or cylinder isdangerous.)6.5 Reference Standards:5Reagent Chemicals, American Chemical Society Specifications, AmericanChemical Society, Washington, DC. For Suggestions on the testing of reagents notlisted by the American Chemical Society, see A
26、nnual Standards for LaboratoryChemicals, BDH Ltd., Poole, Dorset, U.K., and the United States Pharmacopeiaand National Formulary, U.S. Pharmacopeial Convention, Inc. (USPC), Rockville,MD.NOTEThe humidifier gas wash bottle is optional.FIG. 1 Hydrogenolysis Flow DiagramFIG. 2 Photorateometry H2S Reado
27、utD4045 04 (2010)26.5.1 2,2,4 Trimethyl Pentane (Isooctane)(WarningExtremely flammable.)6.5.1.1 ASTM Knock Test Reference Fuel6may be used asthe solvent. However, when this material is used, each new lotshall be tested for sulfur by this procedure because thespecifications are not rigorous enough fo
28、r this application.NOTE 1Heptane or equivalent material may also be used but precisiondata is based on the use of isooctane.6.6 Acetic Acid SolutionMix glacial acetic acid 1 part byvolume into 19 parts water (see 6.2). (WarningCorrosive.)6.7 Di-n-Butyl Sulfide(CH3CH2CH2CH2)2S) is used toprepare stan
29、dards. Equivalent sulfur compound may be used ifcare is exercised to prevent more volatile compounds fromevaporating during preparation or use of standards.6.8 Helium or Nitrogen Purge Gas.(WarningCompressed gas under high pressure.)7. Preparation of Apparatus7.1 Turn on the furnace with temperature
30、 controls at mini-mum. Gradually increase furnace control over a 3-h period toapproximately 1300C to minimize thermal shock. Reverse theprocedure when preparing for long-term storage. For shutdownat night and over weekends, reduce temperature to about 900Cbut do not turn off the furnace. Furnace and
31、 quartz tubing lifeare extended by not cooling to room temperature.7.2 Connect all tubing and fill prehumidifier outside thecabinet with water if this apparatus is being used, and finalhumidifier inside the cabinet with 5 % by volume acetic acidsolution. Purge with inert gas, then close valve. Check
32、 allconnections and repair any leaks that are found.(WarningOn instruments where electronics are in closeproximity with the flow systems, exercise care if leak checkingwith a soap solution. A suitable method is to block the line thatgoes to the final humidifier and observe the flow meter. If theflow
33、 drops to zero, the flow systems are adequately leak-free.)Set hydrogen flow at 200 mL/min, and allow temperature tostabilize. (WarningExtremely flammable gas under pres-sure.) Make final temperature adjustment to 1315 6 15C. Usea standard thermocouple to verify temperature by insertingthrough a sep
34、tum with hydrogen flowing at the rate notedabove. Determine depth of insertion required, and always insertthe hypodermic tip to the 550C point (see 7.6). (WarningThe use of a humidifier gas wash bottle filled with approxi-mately 250 mL of water is a potential safety hazard ashydrogen pressure may bu
35、ild up inside the container. The userof this test method should take appropriate safety measures toprevent an accidental injury, if the humidifier gas wash bottleis used in the analysis.)7.3 Prepare the sample injection drive. Check to be suredesired injection rate is obtained at various settings. V
36、erify thaterratic pulses of fast drive do not occur when the drive rangeis switched. Pulses of high sample flow above 15 L/min willcause carboning and spurious readings.7.4 Install sensing tape, and turn H2S readout analyzer on.7.5 Connect the recorder and adjust the zero to desiredposition with hyd
37、rogen flowing.7.6 Fill syringe with blank reference standard solution,typically isooctane, insert the needle through the septum to the550C temperature zone, and clamp to the syringe drive. Athigh temperature the hot needle may absorb sulfur and at lowertemperature heavy compounds may not evaporate.
38、Set thesyringe drive rate desired, normally 6 L/min, maximum with200 mL/min hydrogen flow. Drive rate may be increased forincreased sensitivity up to the point at which carbon is formed.(Hydrogen flow at 500 mL/min allows injection of 15 L/min;however, dibenzothiophene conversion will be low.)8. Cal
39、ibration Standard8.1 Prepare a reference standard-solution or solutions ofstrength near that expected in the unknown. Measurements canbe made by weight or by volume for carrier liquid.8.2 Units of sulfur in milligrams per litre of sample arepreferred as this is independent of the density of the carr
40、ierliquid. The following equation is used to calculate the volumeof solvent required to dissolve a precise weight of sulfurcompound, of known composition and purity to prepare aliquid standard:z 5Sbc3 d 3 e 3 106D/a! or alternatively : (1)a 5Sbc3 d 3 e 3 106D/z! (2)where:a = desired concentration of
41、 sulfur, mg/L, of the standardsolution of z millilitre of volume,b = molecular weight of sulfur: 32.06,c = molecular weight of the sulfur compound to be used toprepare the standard.d = mass of the sulfur compound used to prepare thestandard, g,e = purity of sulfur compound expressed as a decimal, an
42、dz = millilitres of standard solution required to give thedesired concentration a.Example:Calculate the volume of sulfur free isooctane with volume ofsulfur compound necessary to dissolve 0.5013 g of 98 % byweight di-n-butyl sulfide to obtain a standard containing 1000mg/L of sulfur in a solution.a
43、= 1000 mg/Lb = 32.06c = 146.29 di-n-butyl sulfide (CH3CH2CH2CH2)2Sd = 0.5013 ge = 0.98z =32.06/146.29 3 0.5013 3 0.98 3 10610005 107.66 mLIsooctane is added to bring the solution to a total volume of107.66 mL. When results are to be reported in mass of parts permillion mg/kg, the conversion from mil
44、ligrams per litre shouldbe done as the last step in the calculations.8.3 To prepare a sulfur standard with a sulfur concentrationof 1000 mg/L, as previously described, obtain a clean 125-mL6Available from Phillips Petroleum Co., P.O. Drawer O, Borger, TX 79071.D4045 04 (2010)3glass container, a 100-
45、mL flask, and a 20-mL graduated glasspipet. Rinse each thoroughly with 2,2,4-trimethyl pentane(isooctane). (WarningExtremely flammable.) Pour approxi-mately 90 mL of isooctane into the 100-mL flask. Weighapproximately 0.5 g of di-n-butyl sulfide directly into the flaskand record the mass added, to 6
46、50 g. Add additionalisooctane to the flask to 100 mL. Transfer the mixture to the125-mL container and add isooctane equal to the difference ofz minus 100 mL. Keep containers closed as much as possible.Do not open containers of pure sulfur compound in the vicinityof sulfur free stocks or low-level st
47、andards. Evaporation fromcontainers of pure sulfur compounds can contaminate othernearby liquids. This is particularly troublesome when workingbelow 1 mg/L near volatile sulfur compounds. Volumetricallydilute stock to prepare low-level standards.9. Calibration and Standardization9.1 With hydrogen fl
48、ow at 200 mL/min, advance new tapeand note baseline. Adjust the offset up scale about 5 % to beclear of the recorder stops. Record the stable reading averagevalue as the zero sulfur reference and record as Rbin 11.1.There will be essentially no difference in reading with orwithout hydrogen flow and
49、with or without blank injection, ifblank and hydrogen have no sulfur.9.2 Advance the tape and inject a reference material with asulfur concentration near that expected in the unknown. Afterabout 4 min injection time, adjust the recorder span forapproximately 90 % of scale. Record the average reading asRstdin 10.1.10. Procedure10.1 Advance the tape and inject the unknown sample.Aftera stable reading is obtained record this average value as Rsin11.1.10.2 Proceed with additional samples. Every 2 h, or asneeded, verify blank and span v
