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1、BS EN 15721:2009 ICS 75.160.20 NO COPYING WITHOUT BSI PERMISSION EXCEPT AS PERMITTED BY COPYRIGHT LAW BRITISH STANDARD Ethanol as a blending component for petrol Determination of higher alcohols, methanol and volatile impurities Gas chromatographic method Licensed CopyChinese University of Hong Kong
2、, 13/06/2009 05:39, Uncontrolled Copy, (c) BSI This British Standard was published under the authority of the Standards Policy and Strategy Committee on 31 May 2009 BSI 2009 ISBN 978 0 580 59849 4 Amendments/corrigenda issued since publication DateComments BS EN 15721:2009 National foreword This Bri
3、tish Standard is the UK implementation of EN 15721:2009. The UK participation in its preparation was entrusted to Technical Committee PTI/13, Petroleum testing and terminology. A list of organizations represented on this committee can be obtained on request to its secretary. This publication does no
4、t purport to include all the necessary provisions of a contract. Users are responsible for its correct application. Compliance with a British Standard cannot confer immunity from legal obligations. Licensed CopyChinese University of Hong Kong, 13/06/2009 05:39, Uncontrolled Copy, (c) BSI BS EN 15721
5、:2009 EUROPEAN STANDARD NORME EUROPENNE EUROPISCHE NORM EN 15721 April 2009 ICS 75.160.20 English Version Ethanol as a blending component for petrol - Determination of higher alcohols, methanol and volatile impurities - Gas chromatographic method Ethanol comme base de mlange lessence - Dtermination
6、de la teneur en alcools suprieurs, mthanol et impurets volatiles - Mthode par chromatographie en phase gazeuse Ethanol zur Verwendung als Blendkomponente in Ottokraftstoff - Bestimmung von hheren Alkoholen, Methanol und flchtigen Verunreinigungen - Gaschromatographisches Verfahren This European Stan
7、dard was approved by CEN on 12 March 2009. 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 s
8、uch national standards may be obtained on application to the CEN 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 langu
9、age and notified to the CEN Management Centre has the same status as the official versions. CEN members are the national standards bodies of Austria, Belgium, Bulgaria, Cyprus, Czech Republic, Denmark, Estonia, Finland, France, Germany, Greece, Hungary, Iceland, Ireland, Italy, Latvia, Lithuania, Lu
10、xembourg, Malta, Netherlands, Norway, Poland, Portugal, Romania, Slovakia, Slovenia, Spain, Sweden, Switzerland and United Kingdom. EUROPEAN COMMITTEE FOR STANDARDIZATION COMIT EUROPEN DE NORMALISATION EUROPISCHES KOMITEE FR NORMUNG Management Centre: Avenue Marnix 17, B-1000 Brussels 2009 CENAll ri
11、ghts of exploitation in any form and by any means reserved worldwide for CEN national Members. Ref. No. EN 15721:2009: E Licensed CopyChinese University of Hong Kong, 13/06/2009 05:39, Uncontrolled Copy, (c) BSI BS EN 15721:2009 EN 15721:2009 (E) 2 Contents Page Foreword 3 Introduction .4 1 Scope 5
12、2 Normative references 5 3 Principle 5 4 Reagents and materials 5 4.1 General 5 4.2 Compounds 6 5 Apparatus .6 5.1 Gas chromatograph .6 5.2 Gas chromatographic column 7 5.3 Analytical balance8 5.4 Vials .8 6 Sampling .8 7 Procedure .8 7.1 General 8 7.2 General considerations for preparation and hand
13、ling of solutions .8 7.3 Preparation of solutions for Procedure A .8 7.4 Preparation of solutions for Procedure B .9 7.5 Determination 11 8 Calculation . 13 8.1 Content of individual compounds . 13 8.2 Calculation of group contents . 13 8.3 Expression of results . 13 9 Precision 14 9.1 General . 14
14、9.2 Repeatability 14 9.3 Reproducibility 14 10 Test report . 14 Annex A (informative) Examples of chromatograms 15 Bibliography . 20 Licensed CopyChinese University of Hong Kong, 13/06/2009 05:39, Uncontrolled Copy, (c) BSI BS EN 15721:2009 EN 15721:2009 (E) 3 Foreword This document (EN 15721:2009)
15、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 status of a national standard, either by publication of an
16、identical text or by endorsement, at the latest by October 2009, and conflicting national standards shall be withdrawn at the latest by October 2009. Attention 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
17、held responsible for identifying any or all such patent rights. 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, Cyprus, Czech Republic, Denmark, Estonia, Finl
18、and, France, Germany, Greece, Hungary, Iceland, Ireland, Italy, Latvia, Lithuania, Luxembourg, Malta, Netherlands, Norway, Poland, Portugal, Romania, Slovakia, Slovenia, Spain, Sweden, Switzerland and the United Kingdom. Licensed CopyChinese University of Hong Kong, 13/06/2009 05:39, Uncontrolled Co
19、py, (c) BSI BS EN 15721:2009 EN 15721:2009 (E) 4 Introduction This document specifies a GC test method for the determination of a number of compounds present in ethanol for use as a blending component in petrol according to the CEN ethanol blending component specification EN 15376 1. The test method
20、 comprises of GC identification and analysis of a number of molecules, which are then attributed to several classes (“impurities“, “methanol“, “higher alcohols“), which are needed for calculation of the specified values as required in EN 15376. The method described in this document was prepared by C
21、EN/TC 19s Working Group 9 and is based on two methods (2 and 3) published from a European Regulation on wine and on other internationally published analytical methods on spirits 4. The method is modified for determinations in ethanol for automotive applications. Licensed CopyChinese University of Ho
22、ng Kong, 13/06/2009 05:39, Uncontrolled Copy, (c) BSI BS EN 15721:2009 EN 15721:2009 (E) 5 1 Scope This standard specifies a gas chromatographic method for ethanol, in which higher alcohols (propan-1-ol, butan-1-ol, butan-2-ol, 2-methylpropan-1-ol (isobutanol), 2-methylbutan-1-ol, and 3-methylbutan-
23、1-ol) up to 2,5 % (m/m), methanol up to 3 % (m/m) and other volatile impurities, especially ethyl-ethanoate (ethyl acetate), ethanal (acetic aldehyde) and 1,1-diethoxyethane (acetal) in the range up to 2 % (m/m) are determined. Due to possible interferences the method is not applicable to denatured
24、ethanol samples. NOTE For the purposes of this document, the term “% (m/m)” is used to represent the mass fraction of a material. 2 Normative references The following referenced documents are indispensable for the application of this document. For dated references, only the edition cited applies. Fo
25、r undated references, the latest edition of the referenced document (including any amendments) applies. EN ISO 3170, Petroleum liquids Manual sampling (ISO 3170:2004) EN ISO 3696:1995, Water for analytical laboratory use Specification and test methods (ISO 3696:1987) 3 Principle The compounds specif
26、ied in the scope are determined by direct injection of a test portion into a gas chromatograph (GC) system. An internal standard is added to the sample prior to the injection. The compounds are separated with suitable GC equipment using temperature programming with the option to also use flow progra
27、mming on a suitable column. They are detected using a flame ionization detector (FID). The concentration of each compound is determined from response factors with respect to the internal standard. The response factors are obtained during calibration using the same chromatographic conditions as those
28、 for the analysis of the ethanol samples. A procedure is also given for the additional estimation of unknowns. Water, if present in the sample, is not included in this analysis, because a signal for water is not visible in the chromatogram. Therefore, if “alcohol content“ is called up in a specifica
29、tion, water needs to be considered separately. Two procedures (“Procedure A“ and “Procedure B“) are specified which differ mainly in the optional use of a water dilution step prior to the analysis. Both variants have been validated to produce identical results and precision in extensive RR tests. 4
30、Reagents and materials 4.1 General All reagents shall be of recognized analytical grade (minimum 99 %) or of higher purity, if commercially available. They shall be stored in closed dark glass bottles and can be used for some long time. Other internal standards may also be used when there is suffici
31、ent proof that their GC signal does not interfere with the other signals in the chromatogram. Water, for analytical laboratory use, shall conform to grade 2 of EN ISO 3696:1995. Licensed CopyChinese University of Hong Kong, 13/06/2009 05:39, Uncontrolled Copy, (c) BSI BS EN 15721:2009 EN 15721:2009
32、(E) 6 4.2 Compounds The compounds used for calibration and peak identification are listed in Table 1. Table 1 Compounds for calibration, used as solvents and other related information Compound Attributed to group Calibration compounds: Methanol Methanol Higher alcohols Higher alcohols Higher alcohol
33、s Higher alcohols Higher alcohols Higher alcohols Impurity Impurity Impurity Propan-1-ol Butan-1-ol Butan-2-ol 2-Methylpropanol 2-Methylbutan-1-ol 3-Methylbutan-1-ol Ethanal (acetic aldehyde) Ethyl-ethanoate (ethyl acetate) 1,1-diethoxy ethane (acetal) Internal standards: Pentan-3-ol Internal standa
34、rd for Procedure A 4-Mehylpentan-2-ol Internal standard for Procedure B Solvent: Ethanola Solvent a Ethanol is needed in Method “A“ and “B“ as a solvent for the calibration solutions. Therefore, this shall be extra pure (“UV quality“). 5 Apparatus 5.1 Gas chromatograph Gas chromatograph equipped wit
35、h a Flame Ionization Detector (FID), a split injector and connected to a PC or other system permitting the recording of chromatograms and execution of quantitative calculations. Licensed CopyChinese University of Hong Kong, 13/06/2009 05:39, Uncontrolled Copy, (c) BSI BS EN 15721:2009 EN 15721:2009
36、(E) 7 5.2 Gas chromatographic column 5.2.1 General Bonded capillary column with a suited phase, permitting the complete separation of all requested compounds for the analysis, except for 2-methylbutan-1-ol and 3-methylbutan-1-ol, for which a minimum peak resolution of 1,0 (see 5.2.2) is required. Th
37、e internal standard must be perfectly separated from all other compounds. Additional detail, including sample chromatograms, is given in Annex A. 5.2.2 Chromatographic resolution The column resolution shall be at least 1,0. Determine the column resolution, R, with the calibration solutions (7.3) or
38、(7.4) for the 2-methylbutan-1-ol and 3-methylbutan-1-ol peaks using the following equation: () () 21 12 699, 1 2 WW tt R + = (1) where t1 is the retention time, in seconds, for the 2-methylbutan-1-ol peak; t2 is the retention time, in seconds, for the 3-methylbutan-1-ol peak; W1 is the width, in sec
39、onds, at half-height of 2-methylbutan-1-ol peak; W2 is the width, in seconds, at half-height of 3-methylbutan-1-ol peak. NOTE See Figure 1 for further clarification on the calculation of column resolution, R, of 2methylbutan-1-ol and 3methylbutan-1-ol according to procedure “B” (example: R = 1,08).
40、Key 1 4-methylpentan-2-ol (retention time 16,996 min) 2 2-methylbutan-1-ol (retention time 18,255 min) 3 3-methylbutan-1-ol (retention time 18,346 min) Figure 1 Typical chromatogram for calculation of column resolution Licensed CopyChinese University of Hong Kong, 13/06/2009 05:39, Uncontrolled Copy
41、, (c) BSI BS EN 15721:2009 EN 15721:2009 (E) 8 5.3 Analytical balance Capable of weighing to the nearest 0,1 mg. 5.4 Vials Vials shall have seals and are used for test portions and calibration solutions. 6 Sampling Unless otherwise specified, laboratory samples shall be obtained by the procedures sp
42、ecified in EN ISO 3170. Glass bottles shall be used for taking samples. The glass bottles shall be meticulously cleaned and rinsed at least twice with the product to be sampled. Special care shall be taken during all further manipulations with the samples to avoid any risk of further contamination,
43、e.g. with water. 7 Procedure 7.1 General Two method variants are defined in this document: a) “Procedure A“, using direct injection of a test portion; b) “Procedure B“, using injection after one additional preparation step, i.e. dilution of the sample with water. Which of the two method variants is
44、used is subject to decision in the laboratory. It can also depend on a particular request for solution to a specific problem. See the sample chromatograms in Annex A for additional detail. 7.2 General considerations for preparation and handling of solutions Several precautions shall be observed in t
45、he preparation and handling of stock solutions and calibration solutions to avoid loss of material due to the high volatility of all used compounds. Therefore, preparations should always be done starting with the least volatile compound. All solutions are prepared gravimetrically. Septum caps shall
46、only be removed immediately before adding the next component and replaced immediately after. 7.3 Preparation of solutions for Procedure A 7.3.1 Calibration stock solution (E) for Procedure A Put a 100 ml septum vial (5.4) on the analytical balance (5.3), close the vial with a cap, and record the mas
47、s. Open the vial and fill 80 ml of ethanol in, put the cap on the vial and record the mass of the ethanol added. Licensed CopyChinese University of Hong Kong, 13/06/2009 05:39, Uncontrolled Copy, (c) BSI BS EN 15721:2009 EN 15721:2009 (E) 9 Successively add 1 ml of each of the following compounds th
48、rough the septum and record the individual added mass to the nearest 0,1 mg: a) 3-methylbutan-1-ol, b) 2-methylbutan-1-ol, c) butan-1-ol, d) 2-methylpropan-1-ol (isobutanol), e) propan-1-ol, f) butan-2-ol, g) methanol, h) 1.1-diethoxyethan (acetal), i) ethanal (acetic aldehyde), and j) ethyl-ethanoa
49、te (ethyl acetate). CAUTION Care shall be taken to avoid loss of volatile components during preparation of the standard. NOTE It is strongly recommended to replace a used cap by a new one. This change should be done after cooling the sample to about 4 C. The glass vial containing the prepared calibration stock solution (E) shall be stored at 4 C and may be used for 6 months at maximum. 7.3.2 Internal standard stock solution (ES) for Procedure A In a 10 ml vial add about 8 ml of ethanol and weigh to the nearest 0,1 mg. Add 80 l of the inter