EN 1601-2017 en Liquid Petroleum Products - Unleaded Petrol - Determination of Organic Oxygenated Compounds and Total Organically Bound Oxygen Content by Gas Chromatography (O-FID).pdf

1、Liquid petroleum products - Determination of organic oxygenate compounds and total organically bound oxygen content in unleaded petrol - Method by gas chromatography (O-FID)BS EN 1601:2017BSI Standards PublicationWB11885_BSI_StandardCovs_2013_AW.indd 1 15/05/2013 15:06EUROPEAN STANDARD NORME EUROPEN

2、NE EUROPISCHE NORM EN 1601 August 2017 ICS 75.160.20 Supersedes EN 1601:2014English Version Liquid petroleum products - Determination of organic oxygenate compounds and total organically bound oxygen content in unleaded petrol - Method by gas chromatography (O-FID) Produits ptroliers liquides - Dter

3、mination des composs oxygns organiques et de la teneur totale en oxygne organiquement li dans lessence sans plomb - Mthode par chromatographie en phase gazeuse (O-FID) Flssige Minerallerzeugnisse - Bestimmung sauerstoffhaltiger organischer Verbindungen und des Gesamtgehalts an organisch gebundenem S

4、auerstoff in unverbleitem Ottokraftstoff - Methode mittels Gaschromatographie (O-FID) This European Standard was approved by CEN on 19 May 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

5、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 official versions (English, French, German). A

6、 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 Austria, Belgium, Bulgaria, Croatia, Cypr

7、us, 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, Slovenia, Spain, Sweden, Switzerland, Turkey and Un

8、ited 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 form and by any means reserved worldwide for CEN national Members. Ref. No. E

9、N 1601:2017 ENational forewordThis British Standard is the UK implementation of EN 1601:2017. It supersedes BS EN 1601:2014, which is withdrawn.The UK participation in its preparation was entrusted to Technical Committee PTI/13, Petroleum Testing and Terminology.A list of organizations represented o

10、n 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 responsible for its correct application. The British Standards Institution 2017 Published by BSI Standards Limited 2017ISBN 978 0 580 93705

11、7ICS 75.160.20Compliance with a British Standard cannot confer immunity from legal obligations.This British Standard was published under the authority of the Standards Policy and Strategy Committee on 30 September 2017.Amendments/corrigenda issued since publicationDate Text affectedBRITISH STANDARDB

12、S EN 1601:2017EUROPEAN STANDARD NORME EUROPENNE EUROPISCHE NORM EN 1601 August 2017 ICS 75.160.20 Supersedes EN 1601:2014English Version Liquid petroleum products - Determination of organic oxygenate compounds and total organically bound oxygen content in unleaded petrol - Method by gas chromatograp

13、hy (O-FID) Produits ptroliers liquides - Dtermination des composs oxygns organiques et de la teneur totale en oxygne organiquement li dans lessence sans plomb - Mthode par chromatographie en phase gazeuse (O-FID) Flssige Minerallerzeugnisse - Bestimmung sauerstoffhaltiger organischer Verbindungen un

14、d des Gesamtgehalts an organisch gebundenem Sauerstoff in unverbleitem Ottokraftstoff - Methode mittels Gaschromatographie (O-FID) This European Standard was approved by CEN on 19 May 2017. CEN members are bound to comply with the CEN/CENELEC Internal Regulations which stipulate the conditions for g

15、iving 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 o

16、fficial 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

17、 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, Romania, Serbia, Slovakia, Sloven

18、ia, 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 form and by any means reserved w

19、orldwide for CEN national Members. Ref. No. EN 1601:2017 EBS EN 1601:2017EN 1601:2017 (E) 2 Contents Page European foreword . 3 Introduction 4 1 Scope 5 2 Normative references 5 3 Principle . 5 4 Reagents and materials . 6 4.1 Gases 6 4.2 Reagents for the preparation of calibration samples 6 4.3 Int

20、ernal standards 7 4.4 Oxygenate free petrol 7 5 Apparatus . 7 5.1 Gas chromatographic assembly . 7 5.2 Other equipment . 7 6 Sampling . 8 7 Procedure. 8 7.1 Setting up the apparatus. 8 7.2 Calibration . 9 7.3 Determination of density of the sample . 9 7.4 Preparation of the test sample . 9 7.5 Injec

21、tion of the test portion 10 7.6 Examination of the chromatogram 10 8 Calculation 10 8.1 Calculation of mass of each component in the test sample . 10 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 1

22、1 9 Procedure for the determination of a higher oxygenate compound content . 12 9.1 General . 12 9.2 Dilution of the sample 12 9.3 Preparation of the test sample D for analysis 13 9.4 Analysis of the test sample D . 13 9.5 Calculation and expression of results . 13 10 Total organically bound oxygen

23、content . 14 11 Expression of results . 14 12 Precision 14 12.1 General . 14 12.2 Repeatability, r 14 12.3 Reproducibility, R 14 13 Test report 15 Annex A (informative) Guidance on the oxygen selective detection (O-FID) technique . 16 A.1 Description . 16 A.2 Summary of the analysis conditions . 17

24、Bibliography . 20 BS EN 1601:2017EN 1601:2017 (E) 3 European foreword This document (EN 1601:2017) 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. Th

25、is 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 2018, and conflicting national standards shall be withdrawn at the latest by February 2018. Attention is drawn to the possibility that some o

26、f the elements of this document may be the subject of patent rights. CEN shall not be held responsible for identifying any or all such patent rights. This document supersedes EN 1601:2014. Significant changes between this document and EN 1601:2014 include: Improved description of the carrier gases,

27、equipment and procedure for cooling the samples; Expansion of Table 1 on the oxygenate compounds data, a.o. the addition of ETBE and TAEE; Editorial changes in order to clarify the test procedure. According to the CEN-CENELEC Internal Regulations, the national standards organisations of the followin

28、g 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, Ireland, Italy, Latvia, Lithuania, Luxembourg, Malta, Netherlands, Norw

29、ay, Poland, Portugal, Romania, Serbia, Slovakia, Slovenia, Spain, Sweden, Switzerland, Turkey and the United Kingdom. BS EN 1601:2017EN 1601:2017 (E) 4 Introduction This European Standard is an update of the first edition (EN 1601:1997). The scope of the test method has been updated to include petro

30、l with higher total oxygen content and with higher oxygenate contents than mentioned in the former 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

31、/m). Such petrol is specified in EN 228 1. The previous precision data for an individual oxygenate compound content in the range of 0,17 % (V/V) to 15 % (V/V) has not been updated or extended above 15 % (V/V). A dilution procedure to measure an oxygenate compound content higher than 15 % (m/m) is in

32、cluded in the standard. 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 content has been updated for the range 2,1 % (m/m) to 3,9 % (m/m), based on Round Robins data

33、from 2005 to 2011 available from DIN-FAM, Germany. BS EN 1601:2017EN 1601:2017 (E) 5 1 Scope This European Standard specifies a gas chromatographic method for the quantitative determination, in unleaded petrol having a final boiling point not greater than 220 C, of individual organic oxygenate compo

34、unds 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 the oxygenate compounds content is higher than 15 % (m/m), a procedure with a dilution of the sample before the analysis is given.

35、NOTE 1 The conversion from percent mass to percent volume is done using the calculation mentioned in 8.3 and 9.5.3. NOTE 2 Precision data are not available for an oxygenate compound content higher than 15 % (m/m); see Introduction. NOTE 3 For the purposes of this European Standard, the terms “% (m/m

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

37、ith its use. It is the responsibility of users of this European 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 for this purpose. 2 Normative references The following documents,

38、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 (including any amendments) applies. EN ISO 3170, Petroleum liquids M

39、anual sampling (ISO 3170) EN ISO 3171, Petroleum 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 Determinatio

40、n of density or relative density Capillary-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 organ

41、ic oxygenate compounds are selectively 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

42、detection (O-FID) technique is given in Annex A. BS EN 1601:2017EN 1601:2017 (E) 6 4 Reagents and materials 4.1 Gases 4.1.1 Carrier gas, helium, or nitrogen, free of hydrocarbons and oxygen and water. Hydrogen shall be dosed exactly and mixed properly to the carrier gas to ensure a stable operation

43、of the cracking reactor (see Figure A.1 and the recommendation in A.2). It is important to minimize the oxygen content of 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 detector

44、 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 purge

45、 gas to protect the platinum/rhodium element (see Figure A.1). 4.2 Reagents for the preparation of calibration samples 4.2.1 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.

46、2 methanol (MeOH); 4.2.3 ethanol (EtOH); 4.2.4 propan-1-ol n-propyl alcohol (NPA); 4.2.5 propan-2-ol iso-propyl alcohol (IPA); 4.2.6 butan-1-ol n-butyl alcohol (NBA); 4.2.7 butan-2-ol s-butyl alcohol (SBA); 4.2.8 2-methylpropan-2-ol tert-butyl alcohol (TBA); 4.2.9 2-methylpropan-1-ol iso-butyl alcoh

47、ol (IBA); 4.2.10 2-pentanol (SAA); 4.2.11 2-methoxy-2-methylpropane Methyl tert-butyl ether (MTBE); 4.2.12 2-methoxy-2-methylbutane tert-Amyl methyl ether (TAME); 4.2.13 2-Isopropoxypropane Diisopropyl ether (DIPE); 4.2.14 2-Ethoxy-2-methyl-propane Ethyl tert-butyl ether (ETBE); 4.2.15 2-Ethoxy-2-me

48、thylbutane tert-Amyl ethyl ether (TAEE); 4.2.16 butan-2-one methyl-ethyl ketone (MEK); BS EN 1601:2017EN 1601:2017 (E) 7 4.2.17 acetone dimethyl ketone (DMK). 4.3 Internal standards Use one of the reagents listed in 4.2. If all of these reagents are likely to be present in the sample under test, use

49、 a different organic oxygenate compound of the same purity. The internal standard of choice shall elute at a different retention time as components present in the test sample. 4.4 Oxygenate free petrol Petrol examined to ensure that it contains no oxygenate compounds detectable by this test method. Cool the oxygenate free petrol to between 0 C and 5 C before the preparation of the calibration samples and test samples. 5 Apparatus 5.1 Gas chromatographic assembly 5.1.1 Gas chromatograph, equipped w