DIN EN 1601-2014 Liquid petroleum products - Unleaded petrol - Determination of organic oxygenate compounds and total organically bound oxygen content by gas chromatography (O-FID).pdf

1、July 2014 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).ICS 7

2、5.160.20!%2Y“2159754www.din.deDDIN EN 1601Liquid petroleum products Unleaded petrol Determination of organic oxygenate compounds and total organicallybound oxygen content by gas chromatography (O-FID);English version EN 1601:2014,English translation of DIN EN 1601:2014-07Flssige Minerallerzeugnisse

3、Unverbleite Ottokraftstoffe Bestimmung sauerstoffhaltiger organischer Verbindungen und des Gesamtgehalts anorganisch gebundenem Sauerstoff mittels Gaschromatographie (O-FID);Englische Fassung EN 1601:2014,Englische bersetzung von DIN EN 1601:2014-07Produit ptroliers liquides Essence sans plomb Dterm

4、ination des composs oxygns organiques et de la teneur totale en oxygneorganiquement li par chromatographie en phase gazeuse (O-FID);Version anglaise EN 1601:2014,Traduction anglaise de DIN EN 1601:2014-07SupersedesDIN EN 1601:1997-10www.beuth.deIn case of doubt, the German-language original shall be

5、 considered authoritative.Document comprises 21 pages 05.14 DIN EN 1601:2014-07 2 A comma is used as the decimal marker. National foreword This document (EN 1601:2014) has been prepared by Technical Committee CEN/TC 19 “Gaseous and liquid fuels, lubricants and related products of petroleum, syntheti

6、c and biological origin” (Secretariat: NEN, Netherlands). The 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 Kraft-stoffen und Heizlen of the Fachausschuss Miner

7、all- und Brennstoffnormung. Amendments This standard differs from DIN EN 1601:1997-10 as follows: a) a dilution procedure has been included to measure an oxygenate content higher than 15 % (m/m). In this procedure detailed in Clause 9, the sample is diluted (1:1 or 1:2 mass/mass) with an oxygenate f

8、ree petrol before the addition of the internal standard and the analysis. Precision data have not been evaluated for this procedure; b) the previous precision data for oxygen content covered the range 1,5 % (m/m) to 3,0 % (m/m). The precision data for oxygen content has been updated for the range 2,

9、1 % (m/m) to 3,9 % (m/m), based on data from round robins carried out from 2005 to 2011, available from DIN-FAM, Germany; c) the scope of the test method has been updated to include petrol with higher total oxygen content and with higher oxygenate contents than mentioned in the former edition. The t

10、est method is now applicable for petrol (automotive motor gasoline) with a total oxygen content up to 3,9 % (m/m), and/or with an individual oxygenate compound content higher than 15 % (m/m). Such petrol is specified in EN 228. Precision data have not been evaluated for this procedure and consequent

11、ly the previous precision data for an individual oxygenate compound content within the range of 0,17 % (m/m) to higher than 15 % (m/m) have not been updated or extended above 15 % (m/m) so that automotive ethanol (E85) fuel, for example, can be included in the scope. d) the original Annex A on densi

12、ties of oxygenate compounds has been deleted and some of these compounds are now included in Table 1; e) chromatograms have been updated and the description of gas chromatographic equipment has been improved by including a schematic O-FID instrument configuration in the new Annex A. Previous edition

13、s DIN 51413-7: 1990-05 DIN EN 1601: 1997-10 EUROPEAN STANDARD NORME EUROPENNE EUROPISCHE NORM EN 1601 April 2014 ICS 75.160.20 Supersedes EN 1601:1997English Version Liquid petroleum products - Unleaded petrol - Determination of organic oxygenate compounds and total organically bound oxygen content

14、by gas chromatography (O-FID) Produit ptroliers liquides - Essence sans plomb - Dtermination des composs oxygns organiques et de la teneur totale en oxygne organiquement li par chromatographie en phase gazeuse (O-FID) Flssige Minerallerzeugnisse - Unverbleite Ottokraftstoffe -Bestimmung sauerstoffha

15、ltiger organischer Verbindungen und des Gesamtgehalts an organisch gebundenem Sauerstoff mittels Gaschromatographie (O-FID) This European Standard was approved by CEN on 18 January 2014. CEN members are bound to comply with the CEN/CENELEC Internal Regulations which stipulate the conditions for givi

16、ng 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 European Standard exists in three offi

17、cial 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 the national standards bodies of

18、 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, Slovakia, Slovenia, Spain,

19、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 2014 CEN All rights of exploitation in any form and by any means reserved worldwide fo

20、r CEN national Members. Ref. No. EN 1601:2014 EEN 1601:2014 (E) 2 Contents Foreword 3 1 Scope 4 2 Normative references 4 3 Principle 4 4 Reagents and materials 5 4.1 Gases 5 4.2 Reagents for the preparation of calibration samples 5 4.3 Internal standards 6 4.4 Oxygenate free petrol 6 5 Apparatus .6

21、5.1 Gas chromatographic assembly 6 5.2 Other equipment 7 6 Sampling .7 7 Procedure .8 7.1 Setting up the apparatus .8 7.2 Calibration 8 7.3 Determination of density of the sample 9 7.4 Preparation of test sample 9 7.5 Introduction of test portion .9 7.6 Examination of chromatogram .9 8 Calculation 9

22、 8.1 Calculation of mass of each component in the test sample .9 8.2 Calculation of each component in the sample as a percentage by mass 10 8.3 Calculation of each component in the sample as a percentage by volume . 10 9 Procedure for the determination of a higher oxygenate compound content . 11 9.1

23、 General . 11 9.2 Dilution of the sample 11 9.3 Preparation of the sample D for analysis . 12 9.4 Analysis of the test sample D 12 9.5 Calculation and expression of results 12 9.5.1 Calculation of the component of interest in the sample D as a percentage by mass . 12 9.5.2 Calculation of the compone

24、nt of interest in the test sample as a percentage by mass . 12 9.5.3 Calculation of the component of interest in the test sample as a percentage by volume 12 10 Total organically bound oxygen content . 12 11 Expression of results . 13 12 Precision 13 12.1 General . 13 12.2 Repeatability, r 13 12.3 R

25、eproducibility, R . 13 13 Test report . 14 Annex A (informative) Guidance on the oxygen selective detection (O-FID) technique . 15 A.1 Description 15 A.2 Summary of the analysis conditions 16 Bibliography . 19 DIN EN 1601:2014-07 EN 1601:2014(E)3 Foreword This document (EN 1601:2014) has been prepar

26、ed 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 publication of an identical text

27、or by endorsement, at the latest by October 2014, and conflicting national standards shall be withdrawn at the latest by October 2014. Attention is drawn to the possibility that some of the elements of this document may be the subject of patent rights. CEN and/or CENELEC shall not be held responsibl

28、e for identifying any or all such patent rights. This document supersedes EN 1601:1997. The major updates towards the former version are: Inclusion of a dilution procedure to measure an oxygenate compound content higher than 15 % (m/m). In this procedure detailed in Clause 9, the sample is diluted (

29、1:1 or 1:2 mass/mass) with an oxygenate free petrol, before the addition of the internal standard and the analysis. Precision data have not been evaluated for this procedure; The previous precision data for oxygen content covered the range 1,5 % (m/m) to 3,0 % (m/m). The data precision for oxygen co

30、ntent has been updated for the range 2,1 % (m/m) to 3,9 % (m/m), based on Round Robins data from 2005 to 2011 available from DIN-FAM, Germany; The scope of the test method has been updated to include petrol with higher total oxygen content and with higher oxygenate contents than mentioned in the for

31、mer edition; the test method is now applicable for petrol (automotive motor gasoline) with a total oxygen content up to 3,9 % (m/m), and/or with an individual oxygenate compound content higher than 15 % (m/m). Such petrol is specified in EN 228 1. Precision data have not been evaluated for this proc

32、edure and consequently the previous precision data for a individual oxygenate compound content in the range of 0,17 % (m/m) higher thanto 15 % (m/m) have not been updated or extended above 15 % (m/m), in order to introduce for instance automotive ethanol (E85) fuel in the scope. Deletion of the orig

33、inal Annex A on densities of oxygenate compounds and inclusion of some of them in Table 1; Updated chromatograms and improved description of the gas chromatographic equipment with inclusion of a schematic instrument O-FID instrument configuration in the new Annex A. According to the CEN-CENELEC Inte

34、rnal Regulations, the national standards organizations of the following countries are bound to implement this European Standard: Austria, Belgium, Bulgaria, Croatia, Cyprus, Czech Republic, Denmark, Estonia, Finland, Former Yugoslav Republic of Macedonia, France, Germany, Greece, Hungary, Iceland, I

35、reland, Italy, Latvia, Lithuania, Luxembourg, Malta, Netherlands, Norway, Poland, Portugal, Romania, Slovakia, Slovenia, Spain, Sweden, Switzerland, Turkey and the United Kingdom. DINEN 1601:2014-07EN 1601:2014 (E) 4 1 Scope This European Standard specifies a gas chromatographic method for the quant

36、itative determination, in unleaded petrol having a final boiling point not greater than 220 C, of individual organic oxygenate compounds in the range 0,17 % (m/m) to 15 % (m/m) in a direct analysis (without dilution), and total organically bound oxygen up to 3,9 % (m/m). For samples for which one of

37、 the oxygenate compounds content is higher than 15 % (m/m), a procedure with a dilution of the sample before the analysis is given. NOTE 1 Precision data are not available for an oxygenate compound content higher than 15 % (m/m); see Foreword. NOTE 2 For the purposes of this European Standard, the t

38、erms “% (m/m)” and “% (V/V)” are used to represent respectively the mass fraction, , and the volume fraction, . WARNING The use of this European Standard may involve hazardous materials, operations and equipment. This European Standard does not purport to address all of the safety problems associate

39、d with its use. It is the responsibility of the user of this European Standard to establish appropriate safety and health practices and determine the applicability of regulatory limitations prior to use. 2 Normative references The following documents, in whole or in part, are normatively referenced

40、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 (including any amendments) applies. EN ISO 3170, Petroleum liquids - Manual sampling (ISO 3170) EN ISO 3171, Petrole

41、um liquids - Automatic pipeline sampling (ISO 3171) EN ISO 3675, Crude petroleum and liquid petroleum products - Laboratory determination of density - Hydrometer method (ISO 3675) EN ISO 3838, Crude petroleum and liquid or solid petroleum products - Determination of density or relative density - Cap

42、illary-stoppered pyknometer and graduated bicapillary pyknometer methods (ISO 3838) EN ISO 12185, Crude petroleum and petroleum products - Determination of density - Oscillating U-tube method (ISO 12185) 3 Principle After separation using a capillary column, the organic oxygenate compounds are selec

43、tively converted to carbon monoxide, hydrogen and carbon in a pyrolytic cracking reactor. In a hydrogenation reactor, carbon monoxide is then converted to methane and subsequently detected using a flame ionization detector (FID). NOTE Guidance on the oxygen selective detection (O-FID) technique is g

44、iven in Annex A. DIN EN 1601:2014-07 EN 1601:2014 (E) 5 4 Reagents and materials 4.1 Gases 4.1.1 Carrier gas, helium, or nitrogen, free of hydrocarbons and oxygen and water. Few percentages of hydrogen (used as auxiliary gas) shall be mixed to the carrier gas (see Figure A.1). Hydrogen shall not be

45、used as a carrier gas because it will interfere with the cracking reaction. IMPORTANT It is important to minimize oxygen in the carrier gas. To reduce the background signal, it is essential to use oxygen and moisture filters. 4.1.2 Detector gases, hydrogen and air suitable for flame ionization detec

46、tor. WARNING Hydrogen is explosive when mixed with air at concentrations ranging approximately from 4 % (V/V) to 75 % (V/V). All joints and lines carrying hydrogen shall be made gas tight to prevent leakage of hydrogen into a confined space. 4.1.3 Cracking reactor gas, helium or nitrogen, used as pu

47、rge gas to protect the platinum/rhodium element (see Figure A.1). 4.2 Reagents for the preparation of calibration samples Use only reagents of recognized analytical grade. Reagents shall be not less than 99,0 % (m/m) pure. Calibration samples should be combinations of the following reagents: 4.2.1 m

48、ethanol (MeOH); 4.2.2 ethanol (EtOH); 4.2.3 propan-1-ol (NPA); 4.2.4 propan-2-ol (IPA); 4.2.5 butan-1-ol (NBA); 4.2.6 butan-2-ol (SBA); 4.2.7 2-methylpropan-2-ol (TBA); 4.2.8 2-methylpropan-1-ol (IBA); 4.2.9 pentan-2-ol (SAA); 4.2.10 tert-butyl methyl ether (MTBE); 4.2.11 methyl tert-pentyl ether (TAME); 4.2.12 Diisopropyl ether (DIPE); 4.2.13 tert-butyl ethyl ether (ETBE); 4.2.14 butan-2-one (MEK); 4.2.15 acetone. DINEN 1601:2014-07EN 1601:2014 (E) 6 4.3 Internal standards Use one of the reagents listed in 4.2