DIN EN 16761-1-2016 Automotive fuels - Determination of methanol in automotive ethanol (E85) fuel by gas chromatography - Part 1 Method using single column technique German version.pdf

1、February 2016 English price group 9No 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!%LL7“2414120www.din.de

2、DIN EN 16761-1Automotive fuels Determination of methanol in automotive ethanol (E85) fuel by gas chromatography Part 1: Method using single column technique;English version EN 16761-1:2015,English translation of DIN EN 16761-1:2016-02Kraftstoffe fr Kraftfahrzeuge Bestimmung des Methanolgehalts in Et

3、hanolkraftstoff (E85) mittels Gaschromatographie Teil 1: Einsulenverfahren;Englische Fassung EN 16761-1:2015,Englische bersetzung von DIN EN 16761-1:2016-02Carburants pour automobiles Dtermination de la teneur en mthanol dans le carburant thanol (E85) pour automobiles par chromatographie en phase ga

4、zeuse Partie 1: Mthode par colonne simple;Version anglaise EN 16761-1:2015,Traduction anglaise de DIN EN 16761-1:2016-02www.beuth.deDocument comprises 14 pagesDTranslation by DIN-Sprachendienst.In case of doubt, the German-language original shall be considered authoritative.02.16DIN EN 16761-1:2016-

5、02 2 A comma is used as the decimal marker. National foreword This document (EN 16761-1:2015) 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 responsible

6、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 EUROPISCHE NORM EN 16

7、761-1 December 2015 ICS 75.160.20 English Version Automotive fuels - Determination of methanol in automotive ethanol (E85) fuel by gas chromatography - Part 1: Method using single column technique Carburants pour automobiles - Dtermination de la teneur en mthanol dans le carburant thanol (E85) pour

8、automobiles par chromatographie en phase gazeuse - Partie 1: Mthode par colonne simple Kraftstoffe fr Kraftfahrzeuge - Bestimmung des Methanolgehalts in Ethanolkraftstoff (E85) mittels Gaschromatographie - Teil 1: Einsulenverfahren This European Standard was approved by CEN on 10 October 2015. CEN m

9、embers 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 be obtained on applic

10、ation 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 the CEN-CENELEC Mana

11、gement 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, Ireland, Italy, Latvi

12、a, 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 Centre: Avenue Marnix

13、 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 16761-1:2015 EEN 16761-1:2015 (E) 2 Contents Page European foreword 3 1 Scope . 4 2 Normative references . 4 3 Terms and definitions 4 4 Principle 6 5 Reagen

14、ts and materials 6 6 Apparatus 7 7 Sampling 8 8 Preparation of the apparatus 8 9 Determination of density 9 10 Calibration 9 11 Linearity check 9 12 Procedure. 10 13 Calculation . 10 14 Expression of results 11 15 Precision . 11 15.1 General 11 15.2 Repeatability, r . 11 15.3 Reproducibility, R . 11

15、 16 Test report . 11 Bibliography 12 DIN EN 16761-1:2016-02 EN 16761-1:2015 (E) 3 European foreword This document (EN 16761-1:2015) has been prepared by Technical Committee CEN/TC 19 “Gaseous and liquid fuels, lubricants and related products of petroleum, synthetic and biological origin”, the secret

16、ariat 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. Attention is drawn to th

17、e 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 was deemed to be neces

18、sary 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 chromatography, two test metho

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

20、uropean 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, Portugal, Romania, Slovakia,

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

22、y capillary gas chromatography using flame ionization detection. Fuel quality specifications for this product exist, see Bibliography Entry 1. The measurement range for the methanol is from about 0,5 % (V/V) to about 1,5 % (V/V). Other methanol contents can also be determined, however no precision d

23、ata 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 hazardous materials, operations

24、 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 standard, and fulfil statutory and re

25、gulatory 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 references, the latest edition of the

26、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, Crude petroleum and liquid petro

27、leum 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 (ISO 3838) EN ISO 12185, Crude p

28、etroleum 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 calibration chromatogram Note 1 to entry

29、: Figure 1 shows an example of a calibration chromatogram. DIN EN 16761-1:2016-02 EN 16761-1:2015 (E) 5 Key 1 methanol X time (min) Y FID signal Figure 1 Example chromatogram of a calibration solution 3.2 methanol sample area Asarea of methanol peak in the sample chromatogram Note 1 to entry: Figure

30、 2 shows an example of a sample chromatogram DIN EN 16761-1:2016-02 EN 16761-1:2015 (E) 6 Key 1 methanol X time (min) Y FID signal Figure 2 Example chromatogram of an automotive ethanol (E85) fuel sample 4 Principle This standard describes the analysis of methanol content in automotive ethanol (E85)

31、 fuels using a single high polarity capillary column to separate methanol from the hydrocarbon matrix and other oxygenate components. The method uses external standard calibration. A test portion is introduced into a gas chromatographic column, which separates oxygenated and non-oxygenated hydrocarb

32、ons in the order of increasing polarity and boiling point. The column temperature is raised at a linear reproducible rate and the area under the chromatogram is recorded throughout the analysis. The retention time as well as the calculation of the methanol amount is carried out with reference to cal

33、ibration solution. 5 Reagents and materials Unless otherwise stated, only chemicals of recognized analytical quality shall be used. 5.1 Carrier gases, helium, nitrogen or hydrogen, of at least 99,995 % (V/V) purity, any oxygen present should be removed, e.g. by a chemical resin filter. Follow the sa

34、fety instructions from the filter supplier. 5.2 Hydrogen, grade suitable for flame ionization detectors. 5.3 Compressed air, suitable for flame ionization detectors. DIN EN 16761-1:2016-02 EN 16761-1:2015 (E) 7 5.4 Calibration components, methanol (anhydrous, 99,8 % (m/m) and ethanol (pro-analysis 9

35、9,8 % (m/m) 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 a calibration solution by gravimetrically blending 1,

36、0 % (m/m) methanol (5.4) in an 85:15 (V/V) mixture of ethanol (5.4) and oxygenate-free petrol (5.5). Record the mass to the nearest 0,1 mg when weighing the components. Calculate the % (m/m) of methanol in the mixture and round to the nearest 0,001 % (m/m). The hydrocarbon matrix shall not interfere

37、 with the methanol. 6 Apparatus 6.1 Gas chromatograph, with the following performance characteristics: 6.1.1 Flame ionization detector, 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

38、linear programmed temperature operation over a range from ambient temperature to 150 C. 6.1.3 Sample inlet system, consisting of an injector with variable split flow or similar device. Table 1 contains the typical operating conditions. 6.2 Column, a 50 m capillary column is typically being used, wit

39、h 0,25 mm internal diameter and coated with 1,2,3-tris 2-cyanoethoxypropane (TCEP). See Table 1 for further advised conditions. A different column material is suitable as long as similar separation efficiency is achieved. Precision values are however only available for TCEP material. 6.3 Carrier gas

40、 control, the chromatograph shall be able to deliver a constant carrier gas flow over the whole temperature range of the analysis. DIN EN 16761-1:2016-02 EN 16761-1:2015 (E) 8 Table 1 Typical operating conditions for gas chromatograph Description Value Column length, m 50 Column inner diameter, mm 0

41、,25 Stationary phase 1,2,3-tris2-cyanoethoxypropane (TCEP) Stationary phase thickness, m 0,40 Carrier gas Hydrogen Carrier gas flow rate, ml/min 1,7 Initial column temperature, C 35 Initial column temperature duration, min 7 Final column temperature, C 130 Programming rate, C /min 5 Detector FID Det

42、ector temperature, C 275 Injector temperature, C 200 Sample size, l 0,5 Split ratio 200:1 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 operated either manually or automatically. Plunger in needle

43、 syringes are not recommended due to excessive carryover 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 precision of 0,1 mg. 7 Sampling Samples shall be taken as desc

44、ribed 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 storage shall not be used as evaporation can occur and prolonge

45、d 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 manufacturers instructions. Advised operating conditions are shown in Table 1. 8.2 Chromatog

46、raphic resolution, the column resolution as measured for methanol and benzene eluting from the analytical column shall be at least 3,0. Determine the column resolution, CR, from a mixture of 1 % methanol and 1 % benzene in E85 using the following: DIN EN 16761-1:2016-02 EN 16761-1:2015 (E) 9 ( )( )2

47、1 6992112,ttCRWW=+(1) where t1is the retention time, in seconds, for the methanol peak; t2is the retention time, in seconds, for the benzene peak; W1is the width, in seconds, at half-height of methanol peak; W2is the width, in seconds, at half-height of benzene peak. The separation between methanol

48、and any other peak in the chromatogram should be at least 1,0. 9 Determination of density Determine the density at 15 C of the calibration solution and sample solution in accordance with EN ISO 3675, EN ISO 3838, or EN ISO 12185, and record the result to the nearest 0,1 kg/m. The methanol density is

49、 795,8 kg/m. 10 Calibration 10.1 The application uses an external single point calibration. If there is doubt about the systems linearity, a linearity check can be performed as described in Clause 11. It is strongly advised to perform the calibration procedure in duplicate and use an average response factor in the calculations. An example of a calibration chromatogram is given in Figure 1. When not used, store calibration standards capped in a refrigerator (6.5) at a temperature below 5C. 10.