1、BSI Standards PublicationBS EN 16761-1:2015Automotive fuels Determination of methanol inautomotive ethanol (E85) fuelby gas chromatographyPart 1: Method using single columntechniqueBS EN 16761-1:2015 BRITISH STANDARDNational forewordThis British Standard is the UK implementation of EN 16761-1:2015.T
2、he UK participation in its preparation was entrusted to TechnicalCommittee PTI/13, Petroleum Testing and Terminology.A list of organizations represented on this committee can beobtained on request to its secretary.This publication does not purport to include all the necessaryprovisions of a contract
3、. Users are responsible for its correctapplication. The British Standards Institution 2015.Published by BSI Standards Limited 2015ISBN 978 0 580 86560 2ICS 75.160.20Compliance with a British Standard cannot confer immunity fromlegal obligations.This British Standard was published under the authority
4、 of theStandards Policy and Strategy Committee on 31 December 2015.Amendments/corrigenda issued since publicationDate T e x t a f f e c t e dBS EN 16761-1:2015EUROPEAN STANDARD NORME EUROPENNE EUROPISCHE NORM EN 16761-1 December 2015 ICS 75.160.20 English Version Automotive fuels - Determination of
5、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 automobiles par chromatographie en phase gazeuse - Partie 1: Mthode par colonne simple
6、 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 members are bound to comply with the CEN/CENELEC Internal Regulations which stipulate t
7、he 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 application to the CEN-CENELEC Management Centre or to any CEN member. This European Standar
8、d 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 Management Centre has the same status as the official versions. CEN members are the nation
9、al 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, Latvia, Lithuania, Luxembourg, Malta, Netherlands, Norway, Poland, Portugal, Romania, Slova
10、kia, 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 17, B-1000 Brussels 2015 CEN All rights of exploitation in any form and by any means
11、reserved worldwide for CEN national Members. Ref. No. EN 16761-1:2015 EBS EN 16761-1:2015EN 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 Reagents and materials 6 6 Apparatus 7 7 Sampling 8 8 Preparation of the a
12、pparatus 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 16 Test report . 11 Bibliography 12 BS EN 16761-1:2015EN 16761-1:20
13、15 (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 secretariat of which is held by NEN. This European Standard shall be given the
14、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 the possibility that some of the elements of this document may be the subje
15、ct 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 necessary to check the product for compliance against EU emission regulations.
16、 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 methods were developed that comply with this scope: Part 1: Method using singl
17、e 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 European Standard: Austria, Belgium, Bulgaria, Croatia, Cyprus, Czech Repu
18、blic, 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, Sweden, Switzerland, Turkey and the United Kingdom. BS E
19、N 16761-1:2015EN 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“) by capillary gas chromatography using flame ionization detection. Fuel quality
20、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 data for results outside the specified range is available. NOTE For the purpose
21、s 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 and equipment. This standard does not purport to address all of the safety pr
22、oblems 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 regulatory requirements for this purpose. 2 Normative references The following d
23、ocuments, 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 228, Automotive fue
24、ls 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 petroleum products Laboratory determination of density Hydrometer method (ISO 3675)
25、 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 petroleum and petroleum products Determination of density Oscillating U-tube me
26、thod (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: Figure 1 shows an example of a calibration chromatogram. BS EN 16761-1:2015E
27、N 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 2 shows an example of a sample chromatogram BS EN 16761-1:2015EN 16761-1:2015 (E)
28、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) fuels using a single high polarity capillary column to separate methanol from the hydro
29、carbon 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 hydrocarbons in the order of increasing polarity and boiling point. The column temperature is rai
30、sed 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 calibration solution. 5 Reagents and materials Unless otherwise stated, only chemicals of r
31、ecognized 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 safety instructions from the filter supplier. 5.2 Hydrogen, grade suitable for flame ioniz
32、ation detectors. 5.3 Compressed air, suitable for flame ionization detectors. BS EN 16761-1:2015EN 16761-1:2015 (E) 7 5.4 Calibration components, methanol (anhydrous, 99,8 % (m/m) and ethanol (pro-analysis 99,8 % (m/m) by GC). It should be ensured that the ethanol contains no methanol detectable by
33、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 1,0 % (m/m) methanol (5.4) in an 85:15 (V/V) mixture of ethanol (5.4) and oxygenate-free petrol
34、 (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 with the methanol. 6 Apparatus 6.1 Gas chromatograph, with the following performance charact
35、eristics: 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 linear programmed temperature operation over a range from ambient temperature to 150 C. 6.1.3
36、 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, with 0,25 mm internal diameter and coated with 1,2,3-tris 2-cyanoethoxypropane (TCEP). See Table
37、 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 control, the chromatograph shall be able to deliver a constant carrier gas flow over the who
38、le temperature range of the analysis. BS EN 16761-1:2015EN 16761-1:2015 (E) 8 Table 1 Typical operating conditions for gas chromatograph Description Value Column length, m 50 Column inner diameter, mm 0,25 Stationary phase 1,2,3-tris2-cyanoethoxypropane (TCEP) Stationary phase thickness, m 0,40 Carr
39、ier 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 Detector temperature, C 275 Injector temperature, C 200 Sample size, l 0,5 Split ratio 200:1 6.4 Micr
40、o-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 syringes are not recommended due to excessive carryover of heavy ends to the following analysis.
41、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 described in EN ISO 3170 or EN ISO 3171 and/or in accordance with the requirements of national standar
42、ds 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 prolonged contact with the sample can cause contamination of the sample due to possible leaching of the pl
43、asticizer. 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 Chromatographic resolution, the column resolution as measured for methanol and benzene eluting from the ana
44、lytical 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: BS EN 16761-1:2015EN 16761-1:2015 (E) 9 ( )( )21 6992112,ttCRWW=+(1) where t1is the retention time, in seconds, for the methanol peak; t2is the retent
45、ion 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 and any other peak in the chromatogram should be at least 1,0. 9 Determination of density Determine the
46、 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 795,8 kg/m. 10 Calibration 10.1 The application uses an external single point calibration. If there is
47、 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 u
48、sed, store calibration standards capped in a refrigerator (6.5) at a temperature below 5C. 10.2 Run the calibration solution (5.6) using the specified procedure described in Clause 12. 10.3 Determine methanol calibration area (3.1) 10.4 The response factors are obtained from the standard chromatogra
49、ms (calibration) and calculated according to: m ss/F MA= (2) where Fmis the response factor of methanol, Asis the peak area of methanol in standard, Msis the concentration of methanol (% (m/m). 11 Linearity check 11.1 The linearity check is only needed in case there is doubt about the systems linearity. For day-to-day analysis a single point calibration can be used. BS EN 16761-1:2015EN 16761-1:2015 (E) 10 11.2 Prepare a stock solution of methanol (10 % (m/m) in E85 by mixing 10 % (m/m) methanol (5.4) in
