1、BSI Standards PublicationBS EN 16761-2:2015Automotive fuels Determination of methanol inautomotive ethanol (E85) fuelby gas chromatographyPart 2: Method using heart cut techniqueBS EN 16761-2:2015 BRITISH STANDARDNational forewordThis British Standard is the UK implementation of EN 16761-2:2015.The
2、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. U
3、sers are responsible for its correctapplication. The British Standards Institution 2015.Published by BSI Standards Limited 2015ISBN 978 0 580 86561 9ICS 75.160.20Compliance with a British Standard cannot confer immunity fromlegal obligations.This British Standard was published under the authority of
4、 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 16761-2:2015EUROPEAN STANDARD NORME EUROPENNE EUROPISCHE NORM EN 16761-2 December 2015 ICS 75.160.20 English Version Automotive fuels - Determination of met
5、hanol 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 (E85) pour automobiles par chromatographie en phase gazeuse - Partie 2: Mthode heart-cutting Kraftstoffe
6、 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 10 October 2015. CEN members are bound to comply with the CEN/CENELEC Internal Regulations which stipu
7、late 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 application to the CEN-CENELEC Management Centre or to any CEN member. This European S
8、tandard 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
9、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, Latvia, Lithuania, Luxembourg, Malta, Netherlands, Norway, Poland, Portugal, Romania,
10、 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 17, B-1000 Brussels 2015 CEN All rights of exploitation in any form and by any
11、means reserved worldwide for CEN national Members. Ref. No. EN 16761-2:2015 EBS EN 16761-2:2015EN 16761-2:2015 (E) 2 Contents Page European foreword 3 1 Scope . 4 2 Normative references . 4 3 Terms and definitions 4 4 Principle 5 5 Reagents and materials 6 6 Apparatus 6 7 Sampling 7 8 Preparation of
12、 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 Reproducibility, R . 12 16 Test report . 12 Bibliography 13 BS EN 16761-2:2015EN 16
13、761-2:2015 (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 biological origin”, the secretariat of which is held by NEN. This European Standard shall be gi
14、ven 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 the possibility that some of the elements of this document may be t
15、he 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 necessary to check the product for compliance against EU emission regu
16、lations. 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 usi
17、ng 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 bound to implement this European Standard: Austria, Belgium, Bulgaria, Croatia, Cyprus, Cz
18、ech 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, Sweden, Switzerland, Turkey and the United Kingd
19、om BS EN 16761-2:2015EN 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 shortly “E85“) by capillary gas chromatography using heart cutting technique. Fuel quality spec
20、ifications 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 determined, however no precision data for results outside the specified range is available. NOT
21、E 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 and equipment. This standard does not purport to address all
22、 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 regulatory requirements for this purpose. 2 Normative reference
23、s 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 referenced document (including any amendments) applies. EN 22
24、8, 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 petroleum products Laboratory determination of density Hydrometer
25、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 petroleum and petroleum products Determination of density Osci
26、llating 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: Figure 4 shows an example of a calibration chromatogram. 3.
27、2 methanol sample area Asarea of methanol peak in the sample chromatogram BS EN 16761-2:2015EN 16761-2:2015 (E) 5 Note 1 to entry: Figure 6 shows an example of a sample chromatogram. 4 Principle This standard describes the analysis of methanol content in automotive ethanol (E85) fuels using the hear
28、t 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 columns, an analytical column and a monitor column. By using columns of a very different nature as p
29、re 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 independent of any impurities or high boiling material that may be present in the sample. The method uses e
30、xternal 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). After methanol has fully eluted onto the analytical column, the valve and thus a Pressure Control
31、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 analysis column and detected by the Flame Ionization Detector. The detector response, which is proport
32、ional 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 split/splitless inlet 3 Pressure Control Module 5 monitor column 2 pre column 4 analytical column 6 F
33、lame Ionization Detector Figure 1 Valve in ON-position BS EN 16761-2:2015EN 16761-2:2015 (E) 6 Key 1 split/splitless inlet 3 Pressure Control Module 5 monitor column 2 pre column 4 analytical column 6 Flame Ionization Detector Figure 2 Valve in OFF-position 5 Reagents and materials Unless otherwise
34、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 chemical resin filter. Follow the safety instructions from the filter supplier. 5.2 Hydrogen, grade suitabl
35、e 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) by GC). It should be ensured that the ethanol contains no methanol detectable by this test method in a
36、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 oxygenates free petrol (5.5) with 85 % (V/V) ethanol (5.4). Prepare a calibration solution (C1) of methanol (5.
37、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: 6.1.1 Flame ionization detector, FID, capable of operating at a temperature at least equivalent to the max
38、imum 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. BS EN 16761-2:2015EN 16761-2:2015 (E) 7 6.1.3 Sample inlet system, consisting of an injector with variable split flo
39、w 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 mm (diameter) 0,88 m (film thickness) Polydimethylsiloxane (PDMS); analytical column: Polar column, typical
40、ly 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. 6.3 Carrier gas control: the chromatograph shall be able to deliver a constant carrier gas pressure over th
41、e 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 operated either manually or automatically. Plunger in needle syringes are not recommended due to excessive
42、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 precision of 0,1 mg 7 Sampling Samples shall be taken as described in EN ISO 3170 or EN ISO 3171 and/or in a
43、ccordance 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 of parts of the sample can occur and prolonged contact with the sampl
44、e 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 below: Oven Temp Program: 100 C for 5 min then 25
45、 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 commercially available products. This information is given for the convenience of users of this European Standard and
46、 does not constitute an endorsement by CEN of these products. BS EN 16761-2:2015EN 16761-2:2015 (E) 8 Detector temperature: 250 C Switching Valve: Off After 1,8 min the valve shall be switched on, whereas after 2,02 min the valve shall be switched off. The valve switching time shall be fine-tuned. 8
47、.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 re
48、tention time, in seconds, for the methanol peak; t2is the retention time, in seconds, for the ethanol peak; W1is the width, in seconds, at half-height of methanol peak; W2is the width, in seconds, at half-height of ethanol peak. 8.3 Skewness, determine the skew of the methanol peak by measuring the
49、width of the leading part of the peak at 5 % peak height (A) and the width of the following part of the peak at 5 % peak height (B), see Figure 3. The ratio (B)/(A) shall be not less than 1 or more than 4. Figure 3 Calculation of peak skewness 9 Density determination 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 795,8 kg/
