DIN EN ISO 13032-2012 Petroleum products - Determination of low concentration of sulfur in automotive fuels - Energy-dispersive X-ray fluorescence spectrometric method (ISO 13032 2.pdf

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1、June 2012 Translation by DIN-Sprachendienst.English price group 11No part of this translation may be reproduced without prior permission ofDIN Deutsches Institut fr Normung e. V., Berlin. Beuth Verlag GmbH, 10772 Berlin, Germany,has the exclusive right of sale for German Standards (DIN-Normen).ICS 7

2、5.160.20!$|e“1896688www.din.deDDIN EN ISO 13032Petroleum products Determination of low concentration of sulfur in automotive fuels Energy-dispersive X-ray fluorescence spectrometricmethod (ISO 13032:2012)English translation of DIN EN ISO 13032:2012-06Minerallerzeugnisse Bestimmung niedriger Schwefel

3、gehalte in Kraftstoffen Energiedispersives Rntgenfluoreszenzspektrometrieverfahren (ISO 13032:2012)Englische bersetzung von DIN EN ISO 13032:2012-06Produits ptroliers Dtermination de la teneur en soufre en faible concentration dans les carburantspour automobiles Mthode spectromtrique de fluorescence

4、 de rayons X dispersive en nergie(ISO 13032:2012)Traduction anglaise de DIN EN ISO 13032:2012-06www.beuth.deIn case of doubt, the German-language original shall be considered authoritative.Document comprises 18 pages05.12 DIN EN ISO 13032:2012-06 2 A comma is used as the decimal marker. National for

5、eword This standard has been prepared by Technical Committee CEN/TC 19 “Gaseous and liquid fuels, lubricants and related products of petroleum, synthetic and biological origin” (Secretariat: NEN, Netherlands) in collaboration with Technical Committee ISO/TC 28 “Petroleum products and lubricants”. Th

6、e responsible German body involved in its preparation was the Normenausschuss Materialprfung (Materials Testing Standards Committee), Working Committee NA 062-06-42 AA Prfung von flssigen Kraftstoffen und Heizlen of the Fachausschuss Minerall- und Brennstoffnormung (FAM). Note to Subclause B.3.3: In

7、 the event of a weighted regression it is strongly recommended to document the necessary calculation steps and regression factors. The DIN Standards corresponding to the International Standards referred to in this document are as follows: ISO 3170 DIN EN ISO 3170 ISO 3171 DIN EN ISO 3171 ISO 4259 DI

8、N EN ISO 4259 ISO 20847 DIN EN ISO 20847 National Annex NA (informative) Bibliography DIN EN ISO 3170, Petroleum liquids Manual sampling DIN EN ISO 3171, Petroleum liquids Automatic pipeline sampling DIN EN ISO 4259, Petroleum products Determination and application of precision data in relation to m

9、ethods of test DIN EN ISO 20847, Petroleum products Determination of sulfur content of automotive fuels Energy-dispersive X-ray fluorescence spectrometry EUROPEAN STANDARD NORME EUROPENNE EUROPISCHE NORM EN ISO 13032 March 2012 ICS 75.160.20 English Version Petroleum products - Determination of low

10、concentration of sulfur in automotive fuels - Energy-dispersive X-ray fluorescence spectrometric method (ISO 13032:2012) Produits ptroliers - Dtermination de la teneur en soufre en faible concentration dans les carburants pour automobiles - Mthode spectromtrique de fluorescence de rayons X dispersiv

11、e en nergie (ISO 13032:2012) Minerallerzeugnisse - Bestimmung niedriger Schwefelgehalte in Kraftstoffen - Energiedispersives Rntgenfluoreszenzspektrometrieverfahren (ISO 13032:2012) This European Standard was approved by CEN on 29 February 2012. CEN members are bound to comply with the CEN/CENELEC I

12、nternal 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 standards may be obtained on application to the CEN-CENELEC Management Centre or to

13、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 and notified to the CEN-CENELEC Management Centre has the same status as the official

14、 versions. CEN members are the national standards bodies of Austria, Belgium, Bulgaria, Croatia, Cyprus, Czech Republic, Denmark, Estonia, Finland, France, Germany, Greece, Hungary, Iceland, Ireland, Italy, Latvia, Lithuania, Luxembourg, Malta, Netherlands, Norway, Poland, Portugal, Romania, Slovaki

15、a, Slovenia, Spain, Sweden, Switzerland, Turkey and United Kingdom. EUROPEAN COMMITTEE FOR STANDARDIZATION COMIT EUROPEN DE NORMALISATION EUROPISCHES KOMITEE FR NORMUNG Management Centre: Avenue Marnix 17, B-1000 Brussels 2012 CEN All rights of exploitation in any form and by any means reserved worl

16、dwide for CEN national Members. Ref. No. EN ISO 13032:2012: E2EN ISO 13032:2012 (E) DIN EN ISO 13032:2012-06 Contents Page Foreword 3 Introduction . 4 1 Scope 5 2 Normative references 5 3 Principle 5 4 Reagents and materials 5 4.1 Diluent oil .5 4.2 Sulfur compounds 6 4.3 Reference materials (CRMs)

17、. 6 4.4 Quality control samples 6 5 Apparatus 6 5.1 Energy-dispersive X-ray fluorescence instrument . 6 6 Sampling and sample handling 7 7 Apparatus preparation 8 7.1 Analyser 8 7.2 Sample cups . 8 8 Calibration 8 8.1 General 8 8.2 Preparation of primary standards 8 8.3 Calibration standards 9 8.4 C

18、alibration procedure 10 9 Procedure . 11 10 Calculation 11 11 Expression of results . 11 12 Precision 12 12.1 General . 12 12.2 Repeatability, r 12 12.3 Reproducibility, R 12 13 Test report . 12 Annex A (informative) Matrix effects 13 Annex B (normative) Guidelines for measuring low sulfur concentra

19、tions 15 Bibliography . 16 EN ISO 13032:2012 (E) 3 Foreword This document (EN ISO 13032:2012) 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 Petroleum products and l

20、ubricants . 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 September 2012, and conflicting national standards shall be withdrawn at the latest by September 2012. Attention is drawn to the possibi

21、lity that some of the elements of this document may be the subject of patent rights. CEN and/or CENELEC shall not be held responsible for identifying any or all such patent rights. According to the CEN/CENELEC Internal Regulations, the national standards organizations of the following countries are

22、bound to implement this European Standard: Austria, Belgium, Bulgaria, Croatia, Cyprus, Czech Republic, Denmark, Estonia, Finland, France, Germany, Greece, Hungary, Iceland, Ireland, Italy, Latvia, Lithuania, Luxembourg, Malta, Netherlands, Norway, Poland, Portugal, Romania, Slovakia, Slovenia, Spai

23、n, Sweden, Switzerland, Turkey and the United Kingdom. DIN EN ISO 13032:2012-06 “ is held by NEN, in collaboration with Technical Committee ISO/TC 28”IntroductionThis International Standard is directed specifically at the lower end of the concentration range covered in ISO 208472. By selecting the i

24、nstrument type, a better signal-to-background ratio for sulfur K-L2,3emission is assured. A knowledge of the general composition of the sample for analysis is advantageous in obtaining the best test result.NOTE IUPAC X-ray line notation (S K-L2,3) is used in this International Standard; the correspo

25、nding Siegbahn X-ray line notation (S-Ka) is being phased out.Where matrix matching is not used and where the C:H mass ratio of the test sample is known or can be determined, accuracy can be improved by the use of Equation (A.1) (see A.2.3) to correct the result to the C:H mass ratio of the calibrat

26、ion standards, i.e. the reference diluent oil (see 4.1).Some instruments include the capability for instrument-based matrix correction; notes on the use of this approach to compensate for matrix effects in the test sample are provided in A.3 for information.This International Standard is based on IP

27、 test method PM DU3developed by the Energy Institute.EN ISO 13032:2012 (E) DIN EN ISO 13032:2012-06 4WARNING The use of this International Standard may involve hazardous materials, operations and equipment. This International Standard does not purport to address all of the safety problems associated

28、 with its use. It is the responsibility of the user of this International Standard to establish appropriate safety and health practices and determine the applicability of regulatory limitations prior to use.1 ScopeThis International Standard specifies an energy dispersive X-ray fluorescence (EDXRF)

29、test method for the determination of sulfur content in automotive gasoline containing up to 3,7 % (m/m) oxygen including those blended with ethanol up to 10 % (V/V), and in diesel fuels including those containing up to about 10 % (V/V) fatty acid methylester (FAME) having sulfur contents in the rang

30、e 8 mg/kg to 50 mg/kg.Other products can be analysed and other sulfur contents can be determined according to this test method; however, no precision data for products other than automotive fuels and for results outside the specified range have been established for this International Standard.For re

31、asons of spectral overlap, this International Standard is not applicable to leaded automotive gasoline, gasoline having a content of greater than 8 mg/kg lead replacement or to product and feedstock containing lead, silicon, phosphorus, calcium, potassium or halides at concentrations greater than on

32、e tenth of the concentration of sulfur measured or more than 10 mg/kg, whichever is the greater.NOTE For the purposes of this International Standard, the terms “% (m/m)” and “% (V/V)” are used to represent the mass fraction, m, and the volume fraction, f, of a material respectively.2 Normative refer

33、encesThe 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.ISO 3170:2004, Petroleum liquids Manual sampl

34、ingISO 3171:1988, Petroleum liquids Automatic pipeline sampling3 PrincipleThe test portion, in a cup fitted with an X-ray transparent window, is placed in a beam of exciting radiation from an X-ray tube. The intensity of the sulfur K-L2,3characteristic X-radiation is measured and the accumulated cou

35、nt is compared with a calibration curve constructed from sulfur standards covering the range of sulfur contents under examination.NOTE The exciting radiation can be either direct or indirect via a polarizing or secondary target.4 Reagents and materials4.1 Diluent oilThe reference diluent oil is whit

36、e oil (light paraffin oil) of high purity grade, with a maximum sulfur content of 0,5 mg/kg. However, if only one type of matrix is to be analysed (e.g. motor gasoline), the accuracy of results EN ISO 13032:2012 (E) DIN EN ISO 13032:2012-06 5may be improved by using a matrix-matched diluent. These s

37、hould match, approximately, the aromatic and oxygen contents of the material to be analysed and should consist of high-purity components of less than 0,5 mg/kg sulfur content.NOTE 1 Suitable components for the matched matrix diluent include n-heptane, 2,2,4-trimethylpentane, toluene, xylenes, ethano

38、l, methyl tertiary butyl ether (MTBE), ethyl tertiary butyl ether (ETBE) and tertiary amyl methyl ether (TAME).NOTE 2 For the analysis of diesel fuels containing FAME, the accuracy of results can be improved by use of a matched matrix diluent oil of the white oil with FAME.4.2 Sulfur compounds4.2.1

39、GeneralSulfur compounds of known sulfur content shall be used for the preparation of the primary standards. The compounds given in 4.2.2 to 4.2.5 are suitable and their nominal sulfur contents are given. Where the purity of these compounds is less than 99 % (m/m), either the concentrations and natur

40、e of all impurities are to be known or certified reference materials (CRMs) shall be used instead.4.2.2 Dibenzothiophene (DBT), with a nominal sulfur content of 17,399 % (m/m), or4.2.3 Dibutylsulfide (DBS), with a nominal sulfur content of 21,915 % (m/m), or4.2.4 Thionaphthene (Benzothiophene) (TNA)

41、, with a nominal sulfur content of 23,890 % (m/m), or4.2.5 Dibutyldisulfide (DBDS), with a nominal sulfur content of 35,950 % (m/m).4.3 Reference materials (CRMs)CRMs from accredited suppliers, containing a range of sulfur concentrations, are suitable alternatives to the compounds listed in 4.2.2 to

42、 4.2.5 for use as calibration standards.4.4 Quality control samplesStable samples representative of the materials being analysed, which have a sulfur content that is known by this test method over a substantial period of time, or are supplied commercially with a certified value. Ensure, before use,

43、that the material is within its shelf-life.5 Apparatus5.1 Energy-dispersive X-ray fluorescence instrument5.1.1 Performance characteristics.For a 10 mg/kg sulfur standard (see 8.3), the instrument shall be capable of meeting the following performance characteristics:RR Rsb b1,3() (1)andCRV()s5% (2)wh

44、ereEN ISO 13032:2012 (E) DIN EN ISO 13032:2012-06 6Rsis the gross count rate (counts per second) for the sulfur region of interest for a 10 mg/kg sulfur standard;Rbis the gross count rate (counts per second) for the same region of interest for a blank sample diluent oil (4.1);CVis the coefficient of

45、 variation (relative standard deviation) based on 10 individual measurements of the calibration standard.The 10 mg/kg sulfur standard shall be a CRM (4.3) or shall be prepared from one of the compounds given in 4.2.2 to 4.2.5 following the procedures described in Clause 8.5.1.2 Source of X-ray excit

46、ation, with significant flux at X-ray energies above 2,5 keV.For X-ray detectors with a resolution greater than 200 eV at 2,3 keV, all characteristic X-ray lines originating from the X-ray tube anode shall have an energy above 3,3 keV to ensure minimal background variation due to scatter from the X-

47、ray tube anode lines.5.1.3 Removable sample cup, providing a sample depth of at least 5 mm and equipped with replaceable X-ray transparent film.NOTE The transparent film is normally polyester or polycarbonate film with a thickness of between 2 m and 6 m. Polyester film is the preferred choice as sam

48、ples of very high aromatic content can dissolve polycarbonate film. There are possibly trace amounts of silicon, calcium and sulfur in some types of film. However, the effects are normally cancelled out where 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.5.1.4 X-ray detector, with a resolution not exceeding 800 eV at 2,3 keV.5.1.5 Means of discriminating between s