DIN EN 16761-2-2016 Automotive fuels - Determination of methanol in automotive ethanol (E85) fuel by gas chromatography - Part 2 Method using heart cut technique German version EN .pdf

1、February 2016 English price group 10No 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 75.160.20!%LL8“2414121www.din.d

2、eDIN EN 16761-2Automotive fuels Determination of methanol in automotive ethanol (E85) fuel by gas chromatography Part 2: Method using heart cut technique;English version EN 16761-2:2015,English translation of DIN EN 16761-2:2016-02Kraftstoffe fr Kraftfahrzeuge Bestimmung des Methanolgehalts in Ethan

3、olkraftstoff (E85) mittels Gaschromatographie Teil 2: Verfahren mittels Heart-Cut-Technik;Englische Fassung EN 16761-2:2015,Englische bersetzung von DIN EN 16761-2:2016-02Carburants pour automobiles Dtermination de la teneur en mthanol dans le carburant thanol (E85) pour automobiles par chromatograp

4、hie en phase gazeuse Partie 2: Mthode “heart cutting“;Version anglaise EN 16761-2:2015,Traduction anglaise de DIN EN 16761-2:2016-02www.beuth.deDocument comprises 15 pagesDTranslation by DIN-Sprachendienst.In case of doubt, the German-language original shall be considered authoritative.02.16DIN EN 1

5、6761-2:2016-02 2 A comma is used as the decimal marker. National foreword This document (EN 16761-2:2015) 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

6、responsible German body involved in its preparation was DIN-Normenausschuss Materialprfung (DIN Standards Committee Materials Testing), Working Committee NA 062-06-14 AA Chromatographische Analyse of the Fachausschuss Minerall- und Brennstoffnormung (FAM). EUROPEAN STANDARD NORME EUROPENNE EUROPISCH

7、E NORM EN 16761-2 December 2015 ICS 75.160.20 English Version Automotive fuels - Determination of methanol in automotive ethanol (E85) fuel by gas chromatography - Part 2: Method using heart cut technique Carburants pour automobiles - Dtermination de la teneur en mthanol dans le carburant thanol (E8

8、5) pour automobiles par chromatographie en phase gazeuse - Partie 2: Mthode heart-cutting Kraftstoffe fr Kraftfahrzeuge - Bestimmung des Methanolgehalts in Ethanolkraftstoff (E85) mittels Gaschromatographie - Teil 2: Verfahren mittels Heart-Cut-Technik This European Standard was approved by CEN on 1

9、0 October 2015. 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 standards may

10、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 and notified to

11、 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, Hungary, Iceland,

12、Ireland, Italy, Latvia, Lithuania, Luxembourg, Malta, Netherlands, Norway, Poland, Portugal, Romania, Slovakia, Slovenia, Spain, Sweden, Switzerland, Turkey andUnited Kingdom. EUROPEAN COMMITTEE FOR STANDARDIZATION COMIT EUROPEN DE NORMALISATION EUROPISCHES KOMITEE FR NORMUNG CEN-CENELEC Management

13、Centre: Avenue Marnix 17, B-1000 Brussels 2015 CEN All rights of exploitation in any form and by any means reserved worldwide for CEN national Members. Ref. No. EN 16761-2:2015 EEN 16761-2:2015 (E) 2 Contents Page European foreword 3 1 Scope . 4 2 Normative references . 4 3 Terms and definitions 4 4

14、 Principle 5 5 Reagents and materials 6 6 Apparatus 6 7 Sampling 7 8 Preparation of the apparatus 7 9 Density determination . 8 10 Calibration 9 11 Linearity check . 10 12 Procedure. 10 13 Calculation . 11 14 Expression of results 12 15 Precision . 12 15.1 General 12 15.2 Repeatability, r . 12 15.3

15、Reproducibility, R . 12 16 Test report . 12 Bibliography 13 DIN EN 16761-2:2016-02 EN 16761-2:2015 (E) 3 European foreword This document (EN 16761-2:2015) has been prepared by Technical Committee CEN/TC 19 “Gaseous and liquid fuels, lubricants and related products of petroleum, synthetic and biologi

16、cal 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 or by endorsement, at the latest by June 2016, and conflicting national standards shall be withdrawn at the latest by June 2016. A

17、ttention 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 responsible for identifying any or all such patent rights. The determination of a significant amount of methanol in ethanol (E85) automotive fuels

18、 was deemed to be necessary to check the product for compliance against EU emission regulations. The CEN/TC 19 Ethanol Fuels Task Force requested the development of such a determination technique. In EN 16761, Automotive fuels Determination of methanol in automotive ethanol (E85) fuel by gas chromat

19、ography, two test methods were developed that comply with this scope: Part 1: Method using single column technique; Part 2: Method using heart cut technique the present document. According to the CEN/CENELEC Internal Regulations, the national standards organizations of the following countries are bo

20、und 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, Norway, Poland, Portug

21、al, Romania, Slovakia, Slovenia, Spain, Sweden, Switzerland, Turkey and the United Kingdom DIN EN 16761-2:2016-02 EN 16761-2:2015 (E) 4 1 Scope This European Standard specifies a determination method of methanol in automotive ethanol (E85) fuel (also designated as ethanol (E85) automotive fuel or sh

22、ortly “E85“) by capillary gas chromatography using heart cutting technique. Fuel quality specifications for this product exist, see Bibliography Entry 1. This standard is applicable to fuels having a methanol content from about 0,5 % (V/V) to about 1,5 % (V/V). Other methanol contents can also be de

23、termined, however no precision data for results outside the specified range is available. NOTE For the purposes of this European Standard, the terms “% (m/m)” and “% (V/V)” are used to represent respectively the mass fraction, , and the volume fraction, . WARNING The use of this standard can involve

24、 hazardous materials, operations and equipment. This standard 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 stand

25、ard, and fulfil statutory and regulatory requirements for 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 refere

26、nces, the latest edition of the referenced document (including any amendments) applies. EN 228, Automotive fuels Unleaded petrol Requirements and test methods EN ISO 3170, Petroleum liquids Manual sampling (ISO 3170) EN ISO 3171, Petroleum liquids Automatic pipeline sampling (ISO 3171) EN ISO 3675,

27、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 Capillary-stoppered pyknometer and graduated bicapillary pyknometer methods

28、(ISO 3838) EN ISO 12185, Crude petroleum and petroleum products Determination of density Oscillating U-tube method (ISO 12185) 3 Terms and definitions For the purposes of this document, the following terms and definitions apply. 3.1 methanol calibration area area of the methanol peak in the calibrat

29、ion chromatogram Note 1 to entry: Figure 4 shows an example of a calibration chromatogram. 3.2 methanol sample area Asarea of methanol peak in the sample chromatogram DIN EN 16761-2:2016-02 EN 16761-2:2015 (E) 5 Note 1 to entry: Figure 6 shows an example of a sample chromatogram. 4 Principle This st

30、andard describes the analysis of methanol content in automotive ethanol (E85) fuels using the heart cut technique. The analyser is based upon the principle described by D.R. Deans 3. This technique controls the pressure between two columns and directs the effluent of a (pre) column to usually two co

31、lumns, an analytical column and a monitor column. By using columns of a very different nature as pre column and analytical column (e.g. a non-polar and a polar column) separations can be achieved that are difficult to obtain using a single column. This allows the analysis of methanol to be independe

32、nt of any impurities or high boiling material that may be present in the sample. The method uses external standard calibration. The sample is injected onto a methyl silicone pre column which elutes the methanol and part of the ethanol plus any light hydrocarbons to the analytical column (Figure 1).

33、After methanol has fully eluted onto the analytical column, the valve and thus a Pressure Control Module (PCM) pressure is switched and the components coming from the pre column are directed to the monitor column (Figure 2). The methanol is now separated from the ethanol and hydrocarbons on the anal

34、ysis column and detected by the Flame Ionization Detector. The detector response, which is proportional to the component concentration, is recorded. The peak areas are measured and the concentration of methanol is calculated using the response factor from the external standard calibration. Key 1 spl

35、it/splitless inlet 3 Pressure Control Module 5 monitor column 2 pre column 4 analytical column 6 Flame Ionization Detector Figure 1 Valve in ON-position DIN EN 16761-2:2016-02 EN 16761-2:2015 (E) 6 Key 1 split/splitless inlet 3 Pressure Control Module 5 monitor column 2 pre column 4 analytical colum

36、n 6 Flame Ionization Detector Figure 2 Valve in OFF-position 5 Reagents and materials Unless otherwise stated, only chemicals of recognized analytical quality shall be used. 5.1 Carrier gases, helium or nitrogen, of at least 99,995 % (V/V) purity, any oxygen present should be removed, e.g. by a chem

37、ical resin filter. Follow the safety instructions from the filter supplier. 5.2 Hydrogen, grade suitable for flame ionization detectors. 5.3 Compressed air, regulated for flame ionization detectors. 5.4 Calibration components, methanol (anhydrous, 99,8 % (m/m) and ethanol (pro-analysis 99,8 % (m/m)

38、by GC). It should be ensured that the ethanol contains no methanol detectable by this test method in a mixture (85/15 % (V/V) of ethanol and petrol (5.5). 5.5 Oxygenate-free petrol (EN 228-compliant). 5.6 Calibration solution: Prepare an E85 stock solution by (S1) by mixing 15 % (V/V) of an oxygenat

39、es free petrol (5.5) with 85 % (V/V) ethanol (5.4). Prepare a calibration solution (C1) of methanol (5.4) in E85 by accurately weighing 0,1 g of methanol with 9,9 g of stock solution S1 with an accuracy of 0,1 mg. 6 Apparatus 6.1 Gas chromatograph, with the following performance characteristics: 6.1

40、.1 Flame ionization detector, FID, capable of operating at a temperature at least equivalent to the maximum column temperature employed in the method. 6.1.2 Column temperature programmer, capable of linear programmed temperature operation over a range from ambient temperature to 250 C. DIN EN 16761-

41、2:2016-02 EN 16761-2:2015 (E) 7 6.1.3 Sample inlet system, consisting of an injector with variable split flow or similar device. 6.2 Columns, the following set of columns are recommended, other columns may be used as long as a similar separation efficiency is achieved: pre-column: 30 m (length) 0,53

42、 mm (diameter) 0,88 m (film thickness) Polydimethylsiloxane (PDMS); analytical column: Polar column, typically a 10 m x 0,53 mm x 10 m OxyPlot or Lowox1column has been proven to work satisfactorily; monitor column: empty fused silica, typically 0,7 m x 0,25 mm. Length shall be tuned for each system.

43、 6.3 Carrier gas control: the chromatograph shall be able to deliver a constant carrier gas pressure over the whole temperature range of the analysis. 6.4 Micro-syringe, of appropriate volume, e.g. 5 l, for introduction of 0,5 l of the calibration solution and test portions. The micro-syringe may be

44、 operated either manually or automatically. Plunger in needle syringes are not recommended due to excessive carry-over of heavy ends to the following analysis. 6.5 Refrigerator, It is recommended that the refrigerator be of an explosion-protected design. 6.6 Analytical balance, able to weigh with a

45、precision of 0,1 mg 7 Sampling Samples shall be taken as described in EN ISO 3170 or EN ISO 3171 and/or in accordance with the requirements of national standards or regulations for the sampling of petroleum products. Store samples in either glass or metal containers. Plastic containers for sample st

46、orage shall not be used as evaporation of parts of the sample can occur and prolonged contact with the sample can cause contamination of the sample due to possible leaching of the plasticizer. 8 Preparation of the apparatus 8.1 Set up and operate the gas chromatograph in accordance with the manufact

47、urers instructions. Advised operating conditions are shown below: Oven Temp Program: 100 C for 5 min then 25 C/min to 250 C for 4 min Run Time: 15 min Injector temperature: 200 C Inlet pressure: 38 kPa Injection volume: 0,5 L Split ratio: 100:1 1) Both column types are examples of suitable commercia

48、lly available products. This information is given for the convenience of users of this European Standard and does not constitute an endorsement by CEN of these products. DIN EN 16761-2:2016-02 EN 16761-2:2015 (E) 8 Detector temperature: 250 C Switching Valve: Off After 1,8 min the valve shall be swi

49、tched on, whereas after 2,02 min the valve shall be switched off. The valve switching time shall be fine-tuned. 8.2 Chromatographic resolution: the column resolution as measured for methanol and ethanol eluting from the analytical column shall be at least 3,0. Determine the column resolution, CR, with the calibration solution (5.6) using the following Formula (1): ( )( )21 6992112,ttCRWW=+(1) where t1is the retention time, in seconds, for the methanol peak; t2is the retent