1、Licensed Copy: Wang Bin, ISO/EXCHANGE CHINA STANDARDS, 12/12/2007 02:12, Uncontrolled Copy, (c) BSIg49g50g3g38g50g51g60g44g49g42g3g58g44g55g43g50g56g55g3g37g54g44g3g51g40g53g48g44g54g54g44g50g49g3g40g59g38g40g51g55g3g36g54g3g51g40g53g48g44g55g55g40g39g3g37g60g3g38g50g51g60g53g44g42g43g55g3g47g36g58s
2、ulfur content Wavelength dispersive X-ray fluorescence spectrometric methodThe European Standard EN 15485:2007 has the status of a British StandardICS 71.080.60Ethanol as a blending component for petrol Determination of BRITISH STANDARDBS EN 15485:2007 BS 2000-553:2007BS EN 15485:2007Licensed Copy:
3、Wang Bin, ISO/EXCHANGE CHINA STANDARDS, 12/12/2007 02:12, Uncontrolled Copy, (c) BSIThis BritiThe PTArequest to its EnBSThis British Standard was published under the authority of the Standards Policy and Strategy Committee on 31 October 2007 BSI and Energy Institute 2007ISBN 978 0 580 56826 8Complia
4、nce with a British Standard cannot confer immunity from legal obligations. Amendments issued since publicationAmd. No. Date Commentsboth in its annual publication “Standard methods for analysis and testing of petroleum and related products and British Standard 2000 Parts” and individually.Further in
5、formation is available from: Energy Institute, 61 New Cavendish Street, London W1G 7AR. Tel: 020 7467 7100. Fax: 020 7255 1472.This publication does not purport to include all the necessary provisions of a contract. Users are responsible for its correct application.National forewordsh Standard is th
6、e UK implementation of EN 15485:2007.UK participation in its preparation was entrusted to Technical Committee I/13, Petroleum testing and terminology.list of organizations represented on this committee can be obtained on secretary.ergy Institute, under the brand of IP, publishes and sells all Parts
7、of 2000, and all BS EN petroleum test methods that would be Part of BS 2000, EUROPEAN STANDARDNORME EUROPENNEEUROPISCHE NORMEN 15485August 2007ICS 71.080.60English VersionEthanol as a blending component for petrol - Determination ofsulfur content - Wavelength dispersive X-ray fluorescencespectrometr
8、ic methodthanol comme base de mlange lessence - Dosage dusoufre - Mthode par fluorescence X dispersive en longueurdondeEthanol zur Verwendung als Blendkomponente inOttokraftstoff - Bestimmung des Schwefelgehaltes -Wellenlngendispersive Rntgenfluoreszenz-Spektrometrie(wdRFA)This European Standard was
9、 approved by CEN on 30 June 2007.CEN members are bound to comply with the CEN/CENELEC Internal Regulations which stipulate the conditions for giving this EuropeanStandard the status of a national standard without any alteration. Up-to-date lists and bibliographical references concerning such nationa
10、lstandards may be obtained on application to the CEN Management Centre or to any CEN member.This European Standard exists in three official versions (English, French, German). A version in any other language made by translationunder the responsibility of a CEN member into its own language and notifi
11、ed to the CEN Management Centre has the same status as theofficial versions.CEN members are the national standards bodies of Austria, Belgium, Bulgaria, Cyprus, Czech Republic, Denmark, Estonia, Finland,France, Germany, Greece, Hungary, Iceland, Ireland, Italy, Latvia, Lithuania, Luxembourg, Malta,
12、Netherlands, Norway, Poland, Portugal,Romania, Slovakia, Slovenia, Spain, Sweden, Switzerland and United Kingdom.EUROPEAN COMMITTEE FOR STANDARDIZATIONCOMIT EUROPEN DE NORMALISATIONEUROPISCHES KOMITEE FR NORMUNGManagement Centre: rue de Stassart, 36 B-1050 Brussels 2007 CEN All rights of exploitatio
13、n in any form and by any means reservedworldwide for CEN national Members.Ref. No. EN 15485:2007: ELicensed Copy: Wang Bin, ISO/EXCHANGE CHINA STANDARDS, 12/12/2007 02:12, Uncontrolled Copy, (c) BSIEN 15485:2007 (E) 2 Contents Page Foreword3 1 Scope 4 2 Normative references 4 3 Principle4 4 Reagents
14、 and materials 4 5 Apparatus .4 6 Samples and sampling5 7 Preparation of calibration solutions 5 7.1 Blank calibration solution.5 7.2 Stock solution 5 7.3 Calibration solutions .5 7.4 Storage and stability of the calibration solutions 6 8 Settings.6 8.1 Measuring parameters 6 8.2 Optimization .6 8.3
15、 Performance check of the spectrometer.6 9 Calibration 6 9.1 General6 9.2 Calibration solutions .7 9.3 Calibration curves7 9.4 Checking.7 10 Procedure .7 11 Expression of results 8 12 Precision.8 12.1 Repeatability.8 12.2 Reproducibility.8 13 Test report 8 Bibliography 9 Licensed Copy: Wang Bin, ISO
16、/EXCHANGE CHINA STANDARDS, 12/12/2007 02:12, Uncontrolled Copy, (c) BSIEN 15485:2007 (E) 3 Foreword This document (EN 15485:2007) has been prepared by Technical Committee CEN/TC 19 “Gaseous and liquid fuels, lubricants and related products of petroleum, synthetic and biological origin”, the secretar
17、iat of which is held by NEN. This European Standard shall be given the status of a national standard, either by publication of an identical text or by endorsement, at the latest by February 2008, and conflicting national standards shall be withdrawn at the latest by February 2008. The method describ
18、ed in this document is based on EN ISO 20884 1. According to the CEN/CENELEC Internal Regulations, the national standards organizations of the following countries are bound to implement this European Standard: Austria, Belgium, Bulgaria, Cyprus, Czech Republic, Denmark, Estonia, Finland, France, Ger
19、many, Greece, Hungary, Iceland, Ireland, Italy, Latvia, Lithuania, Luxembourg, Malta, Netherlands, Norway, Poland, Portugal, Romania, Slovakia, Slovenia, Spain, Sweden, Switzerland and United Kingdom. Licensed Copy: Wang Bin, ISO/EXCHANGE CHINA STANDARDS, 12/12/2007 02:12, Uncontrolled Copy, (c) BSI
20、EN 15485:2007 (E) 4 1 Scope This document specifies a wavelength-dispersive X-ray fluorescence (WDXRF) test method for the determination of the sulfur content of ethanol from 7 mg/kg to 20 mg/kg. NOTE For the purposes of this European Standard, the term “% (m/m)“ is used to represent the mass fracti
21、on of a material. 2 Normative references The following referenced documents are indispensable for the application of this document. For dated references, only the edition cited applies. For undated references, the latest edition of the referenced document (including any amendments) applies. EN ISO 3
22、170, Petroleum liquids Manual sampling (ISO 3170:2004) 3 Principle The sample under analysis is exposed in a sample cell to the primary radiation of an X-ray tube. The count rates of the S-K X-ray fluorescence and the count rate of the background radiation are measured. The sulfur content of the sam
23、ple is determined from a calibration curve defined for the relevant measuring range. NOTE Whilst the Siegbahn X-ray line notation (S-K) is used in this document, the corresponding IUPAC X-ray line notation is S K-L2,3. 4 Reagents and materials 4.1 Dibutylsulfide, of nominal sulfur content 21,92 % (m
24、/m), or 4.2 Dibutyldisulfide, of nominal sulfur content 35,95 % (m/m), used as a calibrating substance for sulfur. 4.3 Ethanol absolute, where the purity is not less than 99 %, for use as a blank solution, high purity grade, with a sulfur content 1 mg/kg. Check the blank solution prior to use with t
25、he spectrometer (5.1). A signal for sulfur shall not be detectable. 5 Apparatus 5.1 Wavelength dispersive X-ray fluorescence spectrometer, with the capability for measuring the count rates of the S-K X-ray fluorescence radiation and the background radiation. The minimum requirements for the spectrom
26、eter are given in Table 1. Licensed Copy: Wang Bin, ISO/EXCHANGE CHINA STANDARDS, 12/12/2007 02:12, Uncontrolled Copy, (c) BSIEN 15485:2007 (E) 5 Table 1 Spectrometer requirements Component Requirement Recommendations Anode Rhodium, scandium or chromium Voltagea)No less than 30 kV 30 kV Currenta) No
27、 less than 50 mA 100 mA Collimator Coarse Analysing crystal Germanium, pentaerythrite, or graphite Germanium Optical path Helium Sample cup windowb)Polyester film, sulfur-free, 4 m maximum Polyester film 3,5 m Detector Proportional counter with pulse-height analyser aLower power systems may be used,
28、 provided that these have been validated to meet the precision requirements specified in Clause 12. bOther sample window materials with the same or better transparency, purity and stability, can also be used.5.2 Analytical balance, capable of weighing to the nearest 0,1 mg. 6 Samples and sampling Un
29、less otherwise specified, laboratory samples shall be obtained by the procedures described in EN ISO 3170. High density polyethylene containers shall be used. The containers should be carefully cleaned and rinsed with pure water to avoid contamination. Samples should be analysed as soon as possible
30、after removal from bulk supplies to prevent loss of sulfur. Thoroughly mix samples in their containers immediately prior to withdrawal of the test portions. NOTE Particular attention should be paid to avoid contamination of sampling bottles from phosphorus containing detergents. 7 Preparation of cal
31、ibration solutions 7.1 Blank calibration solution Use ethanol (4.3) as a blank solution. 7.2 Stock solution Weigh a quantity of the required calibrating substance (4.1 or 4.2) to the nearest 0,1 mg, and dilute with blank solution (7.1) at room temperature so that a stock solution with an accurately
32、known sulfur content (to the nearest 1 mg/kg) of approximately 1 000 mg/kg is obtained. NOTE Care should be taken due to volatility of the calibrating substance. 7.3 Calibration solutions Weigh the stock solution (7.2) to the nearest 0,1 mg into bottles and dilute with blank solution (7.1) so that s
33、tandard solutions with sulfur contents in accordance with Table 2 are provided by stirring at room Licensed Copy: Wang Bin, ISO/EXCHANGE CHINA STANDARDS, 12/12/2007 02:12, Uncontrolled Copy, (c) BSIEN 15485:2007 (E) 6 temperature. The sulfur contents in the calibration solutions are indicated in mil
34、ligrams per kilogram rounded to the nearest 0,1 mg/kg. Table 2 Calibration solutions Number Sulfur content mg/kg 0 (blank solution) 0,0 1 5,0 2 10,0 3 20,0 7.4 Storage and stability of the calibration solutions Calibration solutions prepared in accordance with Table 2 have a limited stability and sh
35、all be used on the same day they are prepared. NOTE While stock solutions may be stable for a longer time, calibration solutions may not. 8 Settings 8.1 Measuring parameters For optimum measuring parameters, refer to Table 1. 8.2 Optimization The spectrometer shall be optimized in accordance with th
36、e manufacturers specifications in order to achieve the optimum signal-to-noise ratio. The calibration solution with 20 mg/kg sulfur is recommended for optimization. The counting time shall be adjusted such that, for the 20 mg/kg calibration solutions, an optimal signal-to-noise ratio and signal area
37、, for example resulting from 15 000 net counts, is obtained. This optimized counting time shall be used for both calibration (see 9) and measurement (see 10). 8.3 Performance check of the spectrometer Prior to a measurement series (calibration and/or measurement), but in any case at least once daily
38、, the manufacturers specifications shall be used to check that the spectrometer is operating correctly, so that an optimum performance and a consistent standard of highest possible quality is ensured. NOTE 1 Many modern WDXRF systems use drift monitoring and correction to ensure that systems produce
39、 accurate data over long periods of time without the need to recalibrate. NOTE 2 Performance checks should be performed on a regular basis, since such checks will give valuable information about the status and stability of the spectrometer. 9 Calibration 9.1 General Take care to ensure that the spec
40、trometer is in an optimized condition after having executed all provisions given in Clause 8 and operating optimally before calibration (see 8.3). Licensed Copy: Wang Bin, ISO/EXCHANGE CHINA STANDARDS, 12/12/2007 02:12, Uncontrolled Copy, (c) BSIEN 15485:2007 (E) 7 9.2 Calibration solutions Transfer
41、 the calibration solutions (7.3) into suitable sample cups and fill them half full (see the note below). Depending on the concentration range, all calibration solutions prepared in accordance with Table 2 shall be measured consecutively in ascending order. The count rate, Is, of the S-K X-ray fluore
42、scence radiation at 0,537 3 nm, and the count rate, IB, of the background radiation at 0,545 nm, shall be measured consecutively. NOTE Too small sample quantities will give a low result or relatively more evaporation/concentration effects when measuring volatile samples, whilst too much quantity of
43、sample will give more sagging of the cell window especially when light aromatic samples are measured. 9.3 Calibration curves The net count rate, I0, is calculated according to equation (1). To determine the calibration curve, the relevant net count rate, I0, is plotted against the corresponding sulf
44、ur content of the calibration solution; the calibration curve shall then be calculated and stored using the linear model according to equation (2). The regression calculation may be carried out either separately or using the spectrometer calculator. I0BSII = (1) where I0is the net count rate for the
45、 relevant determination; Isis the count rate of the S-K X-ray fluorescence radiation at 0,537 3 nm; IBis the count rate of the background radiation at 0,545 nm; () bxaxI +=0(2) where x is the sulfur content of the relevant calibration solution, expressed in milligrams per kilogram (mg/kg); a, b are
46、the parameters from the regression calculation; I0(x) is the net count rate computed from the regression calculation for the content, x. 9.4 Checking Check the WDXRF system daily or before a measurement series by using quality control samples with known sulfur contents. Check immediately when using
47、a new batch of films. If the check result differs by more than the 0,71 R, where R is the reproducibility of this test method (see 12.2), execute a recalibration. NOTE It is recommended to execute a control chart analysis. 10 Procedure Fill a sample cup with a sufficient quantity of the sample under
48、 analysis so that an approximate medium height level is achieved (see the note to 9.2). Expose the sample to the radiation of the X-ray tube. Measure consecutively the count rate, Is, of the S-K X-ray fluorescence radiation at 0,537 3 nm and the count rate, IB,of the background radiation at 0,545 nm
49、. Calculate the net count rate, I0, according to equation (1). Read the sulfur content in milligrams per kilogram from the calibration curve (see 9.3) for the measuring range of 7 mg/kg to 20 mg/kg sulfur. If the sulfur content Licensed Copy: Wang Bin, ISO/EXCHANGE CHINA STANDARDS, 12/12/2007 02:12, Uncontrolled Copy, (c) BSIEN 15485:2007 (E) 8 is higher than 20 mg/kg, then a new sample in a new cup shall be measured using a sample obtained by appropriate dilution with the blank solution (7.1). 11 Expression of results Report the sulfur content of the s
