1、Liquid petroleum products - Determination of the sulfur content in Ethanol (E85) automotive fuel- Wavelength dispersive X-ray fluorescence spectrometric method BS EN 16997:2017BSI Standards PublicationWB11885_BSI_StandardCovs_2013_AW.indd 1 15/05/2013 15:06EUROPEAN STANDARD NORME EUROPENNE EUROPISCH
2、E NORM EN 16997 August 2017 ICS 75.160.20 English Version Liquid petroleum products - Determination of the sulfur content in Ethanol (E85) automotive fuel- Wavelength dispersive X-ray fluorescence spectrometric method Produits ptroliers liquides - Dtermination de la teneur en soufre dans le carburan
3、t thanol pour automobiles (E85) - Mthode spectromtrique par fluorescence de rayons X dispersive en longueur donde Flssige Minerallerzeugnisse - Bestimmung des Schwefelgehalts in Ethanolkraftstoff (E85) - Wellenlngendispersives Rntgenfluoreszenz-Spektrometrie-Verfahren This European Standard was appr
4、oved by CEN on 12 June 2017. CEN members are bound to comply with the CEN/CENELEC Internal Regulations which stipulate the conditions for giving this European Standard the status of a national standard without any alteration. Up-to-date lists and bibliographical references concerning such national s
5、tandards may be obtained on application to the CEN-CENELEC 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 translation under the responsibility of a CEN member into its own language an
6、d notified to the CEN-CENELEC Management Centre has the same status as the official versions. CEN members are the national standards bodies of Austria, Belgium, Bulgaria, Croatia, Cyprus, Czech Republic, Denmark, Estonia, Finland, Former Yugoslav Republic of Macedonia, France, Germany, Greece, Hunga
7、ry, Iceland, Ireland, Italy, Latvia, Lithuania, Luxembourg, Malta, Netherlands, Norway, Poland, Portugal, Romania, Serbia, Slovakia, Slovenia, Spain, Sweden, Switzerland, Turkey and United Kingdom. EUROPEAN COMMITTEE FOR STANDARDIZATION COMIT EUROPEN DE NORMALISATION EUROPISCHES KOMITEE FR NORMUNG C
8、EN-CENELEC Management Centre: Avenue Marnix 17, B-1000 Brussels 2017 CEN All rights of exploitation in any form and by any means reserved worldwide for CEN national Members. Ref. No. EN 16997:2017 ENational forewordThis British Standard is the UK implementation of EN 16997:2017.The UK participation
9、in its preparation was entrusted to Technical Committee PTI/13, Petroleum Testing and Terminology.A list of organizations represented on this committee can be obtained on request to its secretary.This publication does not purport to include all the necessary provisions of a contract. Users are respo
10、nsible for its correct application. The British Standards Institution 2017 Published by BSI Standards Limited 2017ISBN 978 0 580 93157 4ICS 75.160.20Compliance with a British Standard cannot confer immunity from legal obligations.This British Standard was published under the authority of the Standar
11、ds Policy and Strategy Committee on 31 August 2017.Amendments/corrigenda issued since publicationDate Text affectedBRITISH STANDARDBS EN 16997:2017EUROPEAN STANDARD NORME EUROPENNE EUROPISCHE NORM EN 16997 August 2017 ICS 75.160.20 English Version Liquid petroleum products - Determination of the sul
12、fur content in Ethanol (E85) automotive fuel- Wavelength dispersive X-ray fluorescence spectrometric method Produits ptroliers liquides - Dtermination de la teneur en soufre dans le carburant thanol pour automobiles (E85) - Mthode spectromtrique par fluorescence de rayons X dispersive en longueur do
13、nde Flssige Minerallerzeugnisse - Bestimmung des Schwefelgehalts in Ethanolkraftstoff (E85) - Wellenlngendispersives Rntgenfluoreszenz-Spektrometrie-Verfahren This European Standard was approved by CEN on 12 June 2017. CEN members are bound to comply with the CEN/CENELEC Internal Regulations which s
14、tipulate the conditions for giving this European Standard the status of a national standard without any alteration. Up-to-date lists and bibliographical references concerning such national standards may be obtained on application to the CEN-CENELEC Management Centre or to any CEN member. This Europe
15、an Standard exists in three official versions (English, French, German). A version in any other language made by translation under the responsibility of a CEN member into its own language and notified to the CEN-CENELEC Management Centre has the same status as the official versions. CEN members are
16、the national standards bodies of Austria, Belgium, Bulgaria, Croatia, Cyprus, Czech Republic, Denmark, Estonia, Finland, Former Yugoslav Republic of Macedonia, France, Germany, Greece, Hungary, Iceland, Ireland, Italy, Latvia, Lithuania, Luxembourg, Malta, Netherlands, Norway, Poland, Portugal, Roma
17、nia, Serbia, Slovakia, Slovenia, Spain, Sweden, Switzerland, Turkey and United Kingdom. EUROPEAN COMMITTEE FOR STANDARDIZATION COMIT EUROPEN DE NORMALISATION EUROPISCHES KOMITEE FR NORMUNG CEN-CENELEC Management Centre: Avenue Marnix 17, B-1000 Brussels 2017 CEN All rights of exploitation in any for
18、m and by any means reserved worldwide for CEN national Members. Ref. No. EN 16997:2017 EBS EN 16997:2017EN 16997:2017 (E) 2 Contents Page European foreword . 3 1 Scope 4 2 Normative references 4 3 Principle . 4 4 Reagents and materials . 4 5 Apparatus . 5 6 Sampling . 5 7 Preparation of calibration
19、solutions 6 7.1 Interferences 6 7.1.1 Background . 6 7.1.2 FP-Method 7 7.1.3 Correction table . 7 7.2 Blank calibration solution . 7 7.3 Stock solution . 7 7.4 Calibration solutions 7 7.5 Storage and stability of the calibration solutions . 7 8 Settings 8 8.1 Measuring parameters 8 8.2 Optimization
20、. 8 8.2.1 Monochromatic excitation . 8 8.2.2 Polychromatic excitation . 8 8.3 Performance check of the spectrometer 8 9 Calibration . 8 9.1 General 8 9.2 Calibration solutions 8 9.3 Calibration curves . 9 9.3.1 Calibration without matrix correction 9 9.3.2 Calibration with matrix correction . 9 9.4
21、Checking 10 10 Procedure 10 11 Expression of results . 11 12 Precision 11 12.1 Repeatability 11 12.2 Reproducibility . 11 13 Test report 12 Annex A (informative) Fundamental parameters method background . 13 Bibliography . 14 BS EN 16997:2017EN 16997:2017 (E) 3 European foreword This document (EN 16
22、997:2017) has been prepared by Technical Committee CEN/TC 19 “Gaseous and liquid fuels, lubricants and related products of petroleum, synthetic and biological origin”, the secretariat of which is held by NEN. This European Standard shall be given the status of a national standard, either by publicat
23、ion of an identical text or by endorsement, at the latest by February 2018, and conflicting national standards shall be withdrawn at the latest by February 2018. Attention is drawn to the possibility that some of the elements of this document may be the subject of patent rights. CEN shall not be hel
24、d responsible for identifying any or all such patent rights. The methodology described in this document is based on EN ISO 20884 1 and EN 15485 2. According to the CEN-CENELEC Internal Regulations, the national standards organisations of the following countries are bound to implement this European S
25、tandard: Austria, Belgium, Bulgaria, Croatia, Cyprus, Czech Republic, Denmark, Estonia, Finland, Former Yugoslav Republic of Macedonia, France, Germany, Greece, Hungary, Iceland, Ireland, Italy, Latvia, Lithuania, Luxembourg, Malta, Netherlands, Norway, Poland, Portugal, Romania, Serbia, Slovakia, S
26、lovenia, Spain, Sweden, Switzerland, Turkey and the United Kingdom. BS EN 16997:2017EN 16997:2017 (E) 4 1 Scope This European Standard specifies a wavelength-dispersive X-ray fluorescence (WDXRF) test method for the determination of the sulfur content in ethanol (E85) automotive fuel 3, containing e
27、thanol between 50 % (V/V) and 85 % (V/V), from 5 mg/kg to 20 mg/kg, using instruments with either monochromatic or polychromatic excitation. NOTE 1 Sulfur contents higher than 20 mg/kg can be determined after sample dilution with an appropriate solvent. However, the precision was not established for
28、 diluted samples. NOTE 2 For the purposes of this European Standard, the terms “% (m/m)” and “% (V/V)” are used to represent the mass fraction () and the volume fraction () of a material respectively. WARNING The use of this Standard can involve hazardous materials, operations and equipment. This St
29、andard does not purport to address all of the safety problems associated with its use. It is the responsibility of users of this standard to take appropriate measures to ensure the safety and health of personnel prior to application of the standard, and fulfil statutory and regulatory requirements f
30、or this purpose. 2 Normative references The following documents, in whole or in part, are normatively referenced in this document and are indispensable for its application. For dated references, only the edition cited applies. For undated references, the latest edition of the referenced document (in
31、cluding any amendments) applies. EN ISO 3170, Petroleum liquids - Manual sampling (ISO 3170) EN ISO 3171, Petroleum liquids - Automatic pipeline sampling (ISO 3171) EN ISO 22854, Liquid petroleum products - Determination of hydrocarbon types and oxygenates in automotive-motor gasoline and in ethanol
32、 (E85) automotive fuel - Multidimensional gas chromatography method (ISO 22854) 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-L2,3. X-ray fluorescence and the count rate of the background radiation are measured
33、. The correlation between the pulse rate and the concentration is calculated by software. The matrix effects are compensated either on the basis of fundamental parameters or using a correction table. The sulfur content is then determined using this calibration. 4 Reagents and materials 4.1 General C
34、ompounds with a minimum purity of 99 % (m/m) as in 4.2 to 4.4. Where the purity of these compounds is less than 99 % (m/m), the concentrations and nature of all impurities shall be established. A correction for chemical impurity may be applied when the sulfur content is known with accuracy. Certifie
35、d reference materials (CRMs) from accredited suppliers are suitable alternatives to the compounds listed in 4.2 to 4.4. 4.2 Dibutylsulfide, of nominal sulfur content 21,92 % (m/m), or dibutyldisulfide, of nominal sulfur content 35,95 % (m/m), used as a calibrating substance for sulfur. BS EN 16997:2
36、017EN 16997:2017 (E) 5 4.3 Ethanol absolute, of a purity not less than 99 %, for use as a compound of the blank solution (7.2), high purity grade, with a sulfur content 1 mg/kg. Check the blank solution (7.2) prior to use with the spectrometer (5.1). A signal for sulfur shall not be detectable. 4.4
37、n-Heptane, of a purity not less than 99 %, for use as a compound of the blank solution (7.2), high purity grade, with a sulfur content 1 mg/kg. Check the blank solution (7.2) prior to use with the spectrometer (5.2). A signal for sulfur shall not be detectable. 5 Apparatus 5.1 Software to set up a c
38、alibration and for the application to the fundamental parameter method of calculating the corresponding correction factor for the varying ethanol content in the sample in the calibration and the in use of such a calibration during the evaluation of samples. The software can be part of the device sof
39、tware, separate software is also possible. If software for the application of the fundamental parameter method isnt available, the correction table (Table 3) may be used. The correction factors of Table 3 are only applicable for monochromatic excitation. 5.2 Wavelength-dispersive X-ray fluorescence
40、spectrometer, with the capability for measuring the count rates of the S K-L2,3X-ray fluorescence radiation and the background radiation. Due to the inherently low background radiation produced by instruments utilizing monochromatic radiation for excitation, it is not mandatory to measure the backgr
41、ound radiation when this type of instrument is used. The minimum requirements for the spectrometer are given in Table 1. 5.3 Analytical balance, capable of weighing to the nearest 0,1 mg. 6 Sampling Unless otherwise specified, laboratory samples shall be obtained by the procedures described in EN IS
42、O 3170 or EN ISO 3171. Samples should be analysed as soon as possible after removal from bulk supplies to prevent loss of sulfur. Thoroughly mix samples in their containers prior to withdrawal of the test portions. IMPORTANT Particular attention should be paid to avoid contamination of sampling bott
43、les from phosphorus containing detergents and thus to prevent the risk of interference with sulfur. BS EN 16997:2017EN 16997:2017 (E) 6 Table 1 Spectrometer requirements Component Polychromatic excitation Monochromatic excitation Anode Rhodium, scandium or chromium Rhodium, scandium, chromium or tit
44、anium VoltageaNo less than 30 kV (S) No less than 50 kV (Compton) No less than 30 kV CurrentaNo less than 33 mA (S) No less than 20 mA (Compton) No less than 0,1 mA Collimator or optic Coarse collimator Monochromator Analysing crystal Germanium, pentaerythrite or graphite LIF200 for Rh (Compton) Ger
45、manium, pentaerythrite or graphite Optical pathbVacuum or helium Vacuum or helium Sample cup windowcPolyester film, 4 m maximum Polyester film, 4 m maximum Detector Proportional counter with pulse-height analyser (S) Scintillation counter with pulse-height analyser (Compton) Proportional counter wit
46、h single channel analyser Wavelengths S K-L2,3at 0,537 3 nm Background radiation at 0,545 nm Tube anode elements Compton signal dS K-L2,3at 0,537 3 nm aLower-power systems may be used, provided they have been validated to meet the precision requirements specified in Clause 12. bIn instruments using
47、vacuum, the sample is not exposed directly to the vacuum of the optical path, but is separated by a secondary window. Helium, minimum purity 99,9 %. cPolyester film is the preferred choice as samples of very high aromatic content may dissolve polycarbonate film. There are possibly trace amounts of s
48、ilicon, calcium and sulfur in some types of film. However, the effects should be cancelled out when samples and standards are analysed using the same batch of film. It is important that samples, standards and blanks be measured using the same batch of film to avoid bias. Other sample window material
49、s with the same or better absorptivity, purity and stability can also be used. dAs the peak position of the tube lines Compton peak also depends on the spectrometer geometry it is not possible to present the absolute position / wavelength. The peak positon can be set with the blank standard 0. The Compton peak is a broad peak on the low energy / high 2 theta angle side of the tube anodes normal (Rayleigh) signal. 7 Preparation of calibration solutions 7.1 Interferences 7.1.1 Background Differences between the elemental composition of t
