DIN EN 15721-2013 Ethanol as a blending component for petrol - Determination of higher alcohols methanol and other impurities - Gas chromatographic method German version EN 15721 2.pdf

1、December 2013 Translation by DIN-Sprachendienst.English price group 12No 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).I

2、CS 75.160.20!%*z“2078729www.din.deDDIN EN 15721Ethanol as a blending component for petrol Determination of higher alcohols, methanol and other impurities Gas chromatographic method;English version EN 15721:2013,English translation of DIN EN 15721:2013-12Ethanol zur Verwendung als Blendkomponente in

3、Ottokraftstoff Bestimmung von hheren Alkoholen, Methanol und anderen Verunreinigungen Gaschromatographisches Verfahren;Englische Fassung EN 15721:2013,Englische bersetzung von DIN EN 15721:2013-12thanol comme base de mlange lessence Dtermination de la teneur en alcools suprieurs, mthanol et autres i

4、mpurets Mthode par chromatographie en phase gazeuse;Version anglaise EN 15721:2013,Traduction anglaise de DIN EN 15721:2013-12SupersedesDIN EN 15721:2009-07www.beuth.deDocument comprises 23 pagesIn case of doubt, the German-language original shall be considered authoritative.11.13 DIN EN 15721:2013-

5、12 2 A comma is used as the decimal marker. National foreword This document (EN 15721:2013) 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). The responsible Ge

6、rman body involved in its preparation was the Normenausschuss Materialprfung (Materials Testing Standards Committee), Working Committee NA 062-06-32-04 UA, Spiegelausschuss zur CEN/TC 19 TF Analytik und Spezifikation von Ethanol und E85 of the Fachausschuss Minerall- und Brennstoffnormung (FAM). The

7、 DIN Standards corresponding to the International Standards referred to in this document are as follows, whereby EN ISO Standards are only listed below if these have not been published as DIN EN ISO Standards with the same number: EN ISO 3696 DIN ISO 3696 Amendments This standard differs from DIN EN

8、 15721:2009-07 as follows: a) the method has been simplified and more tailored towards the determination of the higher alcohols as mentioned in DIN EN 15376 (propan-1-ol, butan-1-ol, butan-2-ol, 2-methylpropan-1-ol (isobutanol), 2-methylbutan-1-ol, 3-methylbutan-1-ol, methanol). All other alcohol co

9、mpounds are summed as impurities; b) the response factor check and the listed example response factors have been taken out. Previous editions DIN EN 15721: 2009-07 National Annex NA (informative) Bibliography DIN ISO 3696, Water for analytical laboratory use Specification and test methods EUROPEAN S

10、TANDARD NORME EUROPENNE EUROPISCHE NORM EN 15721 August 2013 ICS 75.160.20 Supersedes EN 15721:2009English Version Ethanol as a blending component for petrol - Determination of higher alcohols, methanol and other impurities - Gas chromatographic method thanol comme base de mlange lessence - Dtermina

11、tion de la teneur en alcools suprieurs, mthanol et autres impurets - Mthode par chromatographie en phase gazeuse Ethanol zur Verwendung als Blendkomponente in Ottokraftstoff - Bestimmung von hheren Alkoholen, Methanol und anderen Verunreinigungen - Gaschromatographisches Verfahren This European Stan

12、dard was approved by CEN on 12 July 2013. 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 su

13、ch national standards 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 ow

14、n language and 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,

15、Greece, Hungary, Iceland, Ireland, Italy, Latvia, Lithuania, Luxembourg, Malta, Netherlands, Norway, Poland, Portugal, Romania, Slovakia, Slovenia, Spain, Sweden, Switzerland, Turkey and United Kingdom. EUROPEAN COMMITTEE FOR STANDARDIZATION COMIT EUROPEN DE NORMALISATION EUROPISCHES KOMITEE FR NORM

16、UNG Management Centre: Avenue Marnix 17, B-1000 Brussels 2013 CEN All rights of exploitation in any form and by any means reserved worldwide for CEN national Members. Ref. No. EN 15721:2013: EEN 15721:2013 (E) 2 Contents Page Foreword 3 Introduction .4 1 Scope 5 2 Normative references 5 3 Principle

17、5 4 Reagents and materials 5 5 Apparatus .6 6 Sampling .7 7 Procedure .8 7.1 General 8 7.2 General considerations for preparation and handling of solutions .8 7.3 Preparation of solutions for Procedure A .8 7.4 Preparation of solutions for Procedure B .9 7.5 Determination 10 8 Calculation . 12 8.1 C

18、ontent of individual compounds . 12 8.2 Calculation of group contents . 12 8.3 Expression of results . 13 9 Precision 13 9.1 General . 13 9.2 Repeatability 13 9.3 Reproducibility 13 10 Test report . 14 Annex A (informative) Examples of chromatograms 15 Bibliography . 21 DIN EN 15721:2013-12 EN 15721

19、:2013 (E) 3 Foreword This document (EN 15721:2013) 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 o

20、f a national standard, either by publication of an identical text or by endorsement, at the latest by February 2014, and conflicting national standards shall be withdrawn at the latest by February 2014. Attention is drawn to the possibility that some of the elements of this document may be the subje

21、ct of patent rights. CEN and/or CENELEC shall not be held responsible for identifying any or all such patent rights. This document supersedes EN 15721:2009. EN 15721:2013 includes the following significant technical changes with respect to EN 15721:2009: the method has been simplified and more tailo

22、red towards the determination of the higher alcohols as mentioned in EN 15376 (propan-1-ol, butan-1-ol, butan-2-ol, 2-methylpropan-1-ol (isobutanol), 2-methylbutan-1-ol, 3-methylbutan-1-ol, methanol). All other alcohol compounds are summed as impurities. The response factor check and the listed exam

23、ple response factors have been taken out. According to the CEN-CENELEC Internal Regulations, the national standards organisations of the following countries are bound to implement this European Standard: Austria, Belgium, Bulgaria, Croatia, Cyprus, Czech Republic, Denmark, Estonia, Finland, Former Y

24、ugoslav Republic of Macedonia, France, Germany, Greece, Hungary, Iceland, Ireland, Italy, Latvia, Lithuania, Luxembourg, Malta, Netherlands, Norway, Poland, Portugal, Romania, Slovakia, Slovenia, Spain, Sweden, Switzerland, Turkey and the United Kingdom. DIN EN 15721:2013-12 EN 15721:2013 (E) 4 Intr

25、oduction This document specifies a gas chromatographic (GC) test method for the determination of a number of compounds present in ethanol for use as a blending component in petrol according to the CEN ethanol blending component specification EN 15376 1. The test method comprises of GC identification

26、 and analysis of a number of molecules, which are then attributed to several classes (“impurities“, “methanol“, “higher alcohols“), which are needed for calculation of the specified values as required in EN 15376. The method described in this document was prepared by CEN/TC 19s Working Group 9 and i

27、s based on two methods (2and 3) published from a European Regulation on wine and on other internationally published analytical methods on spirits 4. The method is modified for determinations in ethanol for automotive applications. DIN EN 15721:2013-12 EN 15721:2013 (E) 5 1 Scope This European Standa

28、rd specifies a gas chromatographic method for ethanol, in which higher alcohols (propan-1-ol, butan-1-ol, butan-2-ol, 2-methylpropan-1-ol (isobutanol), 2-methylbutan-1-ol, and 3-methylbutan-1-ol) from 0,1 % up to 2,5 % (m/m), methanol from 0,1 % up to 3 % (m/m) and other impurities, in the range fro

29、m 0,1 % up to 2 % (m/m) are determined. Impurities are all the compounds not attributed to the groups of higher alcohols or methanol. NOTE 1 The European ethanol blending component specification1sets a limit for the combined result of ethanol + higher alcohols, not the ethanol content itself. Due to

30、 possible interferences, the method is not applicable to denatured ethanol samples. Water, if present in the sample, is not included in this analysis, because a signal for water is not visible in the chromatogram. Therefore, if “alcohol content“ is called up in a specification, water needs to be con

31、sidered separately in the calculations. NOTE 2 For the purposes of this European Standard, the term “% (m/m)” is used to represent the mass fraction (). 2 Normative references The following documents, in whole or in part, are normatively referenced in this document and are indispensable for its appl

32、ication. For dated references, only the edition cited applies. For undated references, the latest edition of the referenced document (including any amendments) applies. EN ISO 3170, Petroleum liquids Manual sampling (ISO 3170) EN ISO 3696, Water for analytical laboratory use Specification and test m

33、ethods (ISO 3696) 3 Principle The compounds specified in the scope are determined by direct injection of a test portion into a gas chromatograph (GC) system. An internal standard is added to the sample prior to the injection. The compounds are separated with suitable GC equipment using temperature p

34、rogramming with the option to also use flow programming on a suitable column. They are detected using a flame ionisation detector (FID). The concentration of each compound is determined from response factors with respect to the internal standard. The response factors are obtained during calibration

35、using the same chromatographic conditions as those for the analysis of the ethanol samples. Two procedures (“Procedure A“ and “Procedure B“) are specified which differ mainly in the optional use of a water dilution step prior to the analysis. Both variants have been validated to produce identical re

36、sults and precision in extensive RR tests. 4 Reagents and materials All reagents shall be of recognised analytical grade (minimum 99 %) or of higher purity, if commercially available. They shall be stored in closed dark glass bottles and can be used for some long time. Other internal standards may a

37、lso be used when there is sufficient proof that their GC signal does not interfere with the other signals in the chromatogram. 4.1 Water which, for analytical laboratory use, shall conform to grade 2 of EN ISO 3696. DIN EN 15721:2013-12 EN 15721:2013 (E) 6 4.2 Compounds The compounds used for calibr

38、ation and peak identification are listed in Table 1. Table 1 Compounds for calibration, used as solvents and other related information Compound Attributed to group Calibration compounds Methanol Methanol Propan-1-ol Higher Alcohols Butan-1-ol Higher Alcohols Butan-2-ol Higher Alcohols 2-Methylpropan

39、-1-ol Higher Alcohols 2-Methylbutan-1-ol Higher Alcohols 3-Methylbutan-1-ol Higher Alcohols Internal standards Pentan-3-ol Internal standard for Procedure A 4-Methylpentan-2-ol Internal standard for Procedure B Solvent Ethanol aSolvent aEthanol is needed in Procedure “A“ and “B“ as a solvent for the

40、 calibration solutions. The purity of the ethanol should be taken into account when preparing the mixtures. It should not contain any impurities that may interfere with the analysis and the results shall be corrected for the purity of the ethanol 5 Apparatus 5.1 Gas chromatograph, equipped with a Fl

41、ame Ionisation Detector (FID), a split injector and connected to a PC or other system permitting the recording of chromatograms and execution of quantitative calculations. 5.2 Gas chromatographic column 5.2.1 General Bonded capillary column with a suited phase, permitting the complete separation of

42、all requested compounds for the analysis, except for 2-methylbutan-1-ol and 3-methylbutan-1-ol, for which a minimum peak resolution of 1,0 (see 5.2.2) is required. The internal standard shall be perfectly separated from all other compounds. Additional detail, including sample chromatograms, is given

43、 in Annex A. 5.2.2 Chromatographic resolution The column resolution (as measured for 2-methylbutan-1-ol and 3-methylbutan-1-ol) shall be at least 1,0. Determine the column resolution, CR, with the calibration solutions (7.3) or (7.4) for the 2-methylbutan-1-ol and 3-methylbutan-1-ol peaks using the

44、following Formula (1): ( )( )211269912WWttCR+=,(1) DIN EN 15721:2013-12 EN 15721:2013 (E) 7 where t1is the retention time, in seconds, for the 2-methylbutan-1-ol peak; t2is the retention time, in seconds, for the 3-methylbutan-1-ol peak; W1is the width, in seconds, at half-height of 2-methylbutan-1-

45、ol peak; W2is the width, in seconds, at half-height of 3-methylbutan-1-ol peak. Figure 1 presents further clarification on the calculation of column resolution, CR, of 2-methylbutan-1-ol and 3-methylbutan-1-ol according to procedure “B” (example: CR = 1,30). Key 1 Pentan-3-ol (retention time 12,292

46、min) X retention time (min) 2 2-methylbutan-1-ol (retention time 13,741 min) Y FID signal 3 3-methylbutan-1-ol (retention time 13,820 min) Figure 1 Typical chromatogram for calculation of column resolution 5.3 Analytical balance, capable of weighing to the nearest 0,1 mg. 5.4 Vials, having seals and

47、 used for test portions and calibration solutions. 6 Sampling Unless otherwise specified, laboratory samples shall be obtained by the procedures specified in EN ISO 3170. Glass bottles shall be used for taking samples. The glass bottles shall be meticulously cleaned and rinsed at least twice with th

48、e product to be sampled. Special care shall be taken during all further manipulations with the samples to avoid any risk of further contamination, e.g. with water. DIN EN 15721:2013-12 EN 15721:2013 (E) 8 7 Procedure 7.1 General Two method variants are defined in this document: a) “Procedure A“, using direct injection of a test portion; b) “Procedure B“, using injection after one additional preparation step, i.e. dilution of the sample with water. Which of the two method variants is used is subject to decis