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    ASTM D4294

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    © All Rights Reserved
    Download as PDF or read online from Scribd
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    563 views9 pages

    Astm D4294 - 10

    Uploaded by

    thanhhuyen
    ASTM D4294

    Copyright:

    © All Rights Reserved
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    of 9
    Cong STH tera, ‘Standard 10 attr, es Cocohecen, Fanaa 1928285, rie tates of Anes. Ts copy hs been made by the Cette fr Saar nd Quay (TAME) wes Ks Sulfur In Petroleum and Petroleum Products by Energy Dispersive X-ray Fluorescence Spectrometry* “Tiemann dere Sd designation DID: he smb nm flloing he eit int te yr Tie eae ca ven yur rn mer pens nese ero a apa A ‘Soke taeda Cage sce eat ono PON "hand has Br pred for st by ec oe Deparment of Dee 1. Scope LA This test method covers the determination of total sulfur in petroleum and petroleum products that are single-phase and. either liquid at ambient conditions, liquefiable with moderate heat, or soluble in hydrocarbon solvents. These materials can include diesel fuel, jet fuel, Kerosine, other distillate oi, naphtha residual oi, lubricating base oll, hydraulic oil, crude cil, unleaded gasoline, gusohol, biodiesel (see Note 2), and similar petroleum products. Nove |—Onypenaed ful with ethanol or methanol contents excct- ing tel given fa Tble Len be deat dh ung his west method, bat the precision and bias atements donot apply (see Appedix X3). ‘Nore 2—For samples with high oxygen comets 3 wt ®) sample lion a2 deebed fn 3 or mavix maching ust be performed to ‘eure score re. 1.2 Interlaboratory studies on precision revealed the scope tobe 17 mgfkg to 4.6 mass %. An estimate ofthis test method's ‘pooled limit of quantitation (PLOQ) is 16.0 mg/kg as calcu- lated by the procedures in Practice D6259. However, because instrumentation covered by this test method can’ vary in sensitivity, the applicability of the test method at sulfur ‘concentrations below approximately 20 mg/kg must be deter~ ‘mined on an individual basis. An estimate of the limit of ‘detection i three times the reproducibtity standard deviation, ‘and an estimate of the limit of quanttation® is ten times the reproducibility standard deviation, 1.3 Samples containing more than 4.6 mass % sulfur can be For toca ASTM anda, i th ASTM web, west. zens ASTM Cuter Servo ates mg For Aaa Bok of ATH ‘Sd vole info, lr te wails Dosanet Suma Pe east wee, “+A Summary of Change ston appear tthe ed of hie standard. crores) AST han 18 aH Pt 7S Wt Cachan err 8-28, Ue Sei See AST a aa ree Wet Apa o4st EDT 2010 | Naa ee a ee anenon tra eqns at sy STA Fer St onsen, Pensa 10-2859, SESS ed aes tse is orbs ee mae 1 the ere lr Snares ane Quay (SAME) unde ies ra AS sal 10 Sor Hare Di, 1D6299 Practice for Applying Statistical Quality Assurance ‘and Control Charting Techniques to Evaluate Analytical ‘Measurement System Performance D733 Practice for Optimization, Sample Handling, Cali- ‘bration, and Validation of X-ray Fluorescence Spectrom- ‘etry Methods for Elemental Analysis of Petroleum Prod- ‘ts and Lubricants £29 Practice for Using Significant Digits in Test Data to Determine Conformance with Specifications ‘3, Summary of Test Method 3.1 The sample is placed in the beam emited from an X-ray tube. The resultant excited characteristic X radiation is mea- sured, and the accumulated count is compared with counts i from previously prepared calibration samples to obtain the sulfur concentration in mass % and/or mg/kg. A minimum of three groups of calibration samples are required to span the concentration range: 0.0 to 0.1 mass %, 0.1 t0 1.0 mass % and 110 to 5.0 mass % sulfur. (See Practice D7343.) 4, Significance and Use 41 This test method provides rapid and precise measure- ‘ment of total sulfur in petroleum and petroleum products with minimum of sample preparation. A typical analysis time js 1 105 min per sample. 42 The quality of many petroleam products is related tothe amount of sulfur present. Knowledge of sulfur concentration is necessary for processing purposes. There are also regulations promulgated in federal, state, and local agencies that restrict the amount of sulfur present in some fuels. 43 This test method provides 2 means of determining whether the sulfur content of petroleum or a petroleum product ‘meets specification or regulatory limits. 444 When this test method is applied to petroleum materials with matzices significantly different from the calibration mate- ‘ial specified in 9.1, the cautions and recommendations in Section 5 should be cbserved when interpreting results. 5. Interferences 5.1 Spectral interferences are cavsed by the closeness ofthe “Xray characteristic ins ofthe elements present ina sample and the Kimited detector ability to completely resolve them. AS 4 result, the lines produce spectral peaks that overlap with each oer. Spectral interferences may arise from samples conain- ing lead alkyl, slicon, phosphorus, calcium, potassium, ha- Tides and eaalyt particles if present st concentrations greater than one tenth ofthe measured concentration of sulfur, or more than afew hundred miligramsfllogram (parts per milli — mass ppm). Follow the manufacturer's operating-guise 10 compensate forthe interferences. ‘5.2 Matrix effects are caused by concentration variations of the elements in a sample. These variations directly influence Xcray abvorption and change the measured intensity of each element. For example, performance enhancing additives, such as oxygenates in gasoline, may affect the appurot sur reading. Other matrix related imterterences may arise fom heavy metal adtives, lead alkys, and elements such as silico, phosphors, calsium, pouasiom, and the halides, ‘erty AST wt teh, We A 2 08:41 EDT2010| 7 See ac rem netsacmnarenecanane TABLE 2 Maire Divents wa ats Dt Riraie a Fait 72 ies Keone Naga Kereare = eran Keroire 200m ewe Uaeot Nome CEetpnee ow tee St own yeu Oe some Ce oF lie ot home Sesatne (vate "SOW = mapa we avy ‘Mom = meara ot wae om especialy if present at concentrations greater than one tenth of| the measured concentration of sulfur, or more than a few hundred milligrams/kilogram (pars per million—ppm). These types of interferences are always present in X-ray Buorescence analysis and are completely unrelated to spectral interferences. ‘53 The interferences mentioned in 5.1 and 5.2 may be ‘compenssted for in contemporary instruments with the use of built-in software for spectra deconvolution or overlap corec- tion and interclement correction by multiple egresson or by ‘other mathematical methods. ‘54 In general, petroleum materials with compositions that vary from oils as specified in 9.1 may be analyzed with standards made from base materials that are of the same, oF similer. composition. Thus, a gasoline may be simulated by mixing isooctane and toluene in a ratio that approximates the ‘uve aromatic content of the samples to be analyzed, Standards ‘made from this simulated gasoline will produce results that are more accurate than results obtained using white oils. Sugges- tions are given in Table 2. [Nora 3—In the case of petroleum marils tat conan suspended ste itis ecommended tt the water be removed before texting or that the sample be thoroughly homogenized and immediately tested. The Inference is retest fhe water rests layer over the transpret fin fit wil atenuate the Xray intensity for sulle One such retbod 10 ‘complih the removal of water sto cestifuge the sample fist under “inbiet sealed conditions, wing care Oat the sample Imegriy is at compromised 6. Apparatas 6.1 Energy-dispersive X-ray Fluorescence Analyzer— nergy dispersive X-ray Borescence anelyzer may be used if lis design incorporates, as 2 minimum, the following features and if test results from it are shown to be equivalent oo the ‘samples of interest. Required design features include: 6.1.1 Source of X-ray Excitation, X-ray tube with excitation energy above 2.5 kev. 6.12 Removable Sample Cup, equipped with replaceable Xray transparent plastic film windows and providing a sample epth of atleast 4 mm and a diameter of atleast 10 men ‘6.1.3 X-ray Detector, wih high sensitivity anda resolution value (Full Width at Half Maximum, FWHM) not to exceed 800 eV at 23 keV. 6.14 Filters or other means of discriminating, between sulfur Ker radiation and other X-rays of higher energy ‘6.1.5 Signal conditioning and data handling electrons that include the functions of X-ray intensity counting, « minimum ‘of two energy regions spectral overap bat sein of tlle Koay ham ts geese concentrason. 61.6 The analyzer shall have the seasitiviy under op ‘mized measurement conditions to measure the concentration of sulfur at the 0.08 % level with « demonstrated eror due to counting sastis with one standard deviation not greater than 5 perent relative atthe 500 mg/kg level. Tis requirement Peruins to sample measurements of less than 1000 mg/kg. ‘61.7 Display or Printer that reads out in mass % sulfur andlor ma/eg slr. ‘62 Analytical Balance, with an accuracy and resolution of| 0.1 mg and capable of weighing up to 100 g. Nore 4—Opeation of euyzer wing Keay be sources i be candice in cordance wih the manfacarer ssf ncn 7, Reagents 71. Purlty of Reagenss—Reagent grade chemicals shall be sed in al tests Unless otherwise indiated, itis intended that all reagents conform tothe specifications ofthe Committee on ‘Analytical Reagents ofthe American Chemical Society (ACS) here soch specifications are available Other grades may be ted, provided it is frst ascerained thatthe reagent is of suficiendy high purty to permit ts use without lessening the accurcy ofthe determination. 12 Diw-BurylSulfde (DBS), a high-purity standard with a cfd analysis for sulfur conten. Use the certified sulfur content and the material purity when calculating the exact concentrations of the calibration standards (see 9.1) (Warning—Di-n-butyl sulfide is arumable and toxic.) Noe Siti eweatal o know the concettton of slr in he em ali tol the psy, ce impure may ab alt conainingcompoxnds 13 Drift Correction Monitors) (Optional)—Severl difer- xt materials have been found to be suitable for use as dit correction monitors. Appropriate dif moniter samples should be permanent materials that are stable with respect to repeated exposure to X-rays, Stable igus lik polysulfide ols, glass or metalic specimens ae recommended. Liguds, pres pow ders, and solid material tht degrade with repeated expostre to X-rays should not be used. Examples of sulfur containing Iaterials that have been found to be suitable include renewable liquid petroleum material, a metal alloy, o a fused ‘ss disk, The monitor's counting rate, in combination with count time, shal be suficient to give a relative counting eror of less than 1%. The counting rate for the monitor sample is Viena ASTM of (al igh eer; We Ape 21 0:14 pumvsot io Llcee Agreement No further eproductosaubarize, Cony ASTH neal, 10 Bar Harr Ori, Cashoeces esas 19025, his copy has been made that are highly stable, the bction factor may not difer signif 714 Polyslfde Oil, generally nony!polysalfides conning |: knowm percentage of sulfur dtd ina hydrocarbon matrix. (Warning—May cause allergic skin reactions) ors 6—Folywle ol ae high moeclar weight ol that contain igh concetsns of ai. x igh 50 weight pct. They exhibit. cele pyc properties sch as wise, lw voli, ead Sable set fe wile being completely mise ia whol. Police ‘ls readily avaiable commer, The sl content of te ply {del cocenoe I eterna va mas dato nurs whi ol followed by «cect compara ease aust NIST referee mae- a 15 Mineral Oil, White (MOW), ACS Reagent Grade con- taining less than 2 mg/kg sulfur or other suitable base material ‘containing less than 2 mk sulfur. When low level (200, mg/kg) measurements are anticipated, thea the sulfur content, ‘if-any, of the base material” needs to be incloded in the calcalation of calibration standard concentration (see 9.1). ‘When the sulfur content ‘of the solvent or reageat Is not certified, verify the absence of sulfur, Use the purest avalable igades for chemicals to be used for preparing calibration apdards, 116 X-ray Transparent Film —Any fm that resists atack by the sample is ee of sulfur, and is suiciently X-ray tanspa ent can be used. Fm types can include polyester, polypropy- lene, polyarbonat, and polyimide. However, samples of high ‘aromatic content can dissolve polypropylene, polycarbonate and polyester films. 17 Helium Purge Gas (optional, Follow manufscrre's segqnmendon fer comeponding specicaos when of helium purge gas is required. 78 Coming Gas, for intruments equpged wih fow 79 Sample Cells, compatible with the sample and the ‘geometry requirements of the spectrometer. Disposable cells ‘are preferred over reusable ones for ultra low (

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