Ethanol as a blending component for petrol - Determination of higher alcohols, methanol and volatile impurities - Gas chromatographic method
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 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 ethanol samples.
NOTE For the purposes of this document, the term % (m/m) is used to represent the mass fraction of a material.
Ethanol zur Verwendung als Blendkomponente in Ottokraftstoff - Bestimmung von höheren Alkoholen, Methanol und flüchtigen Verunreinigungen - Gaschromatographisches Verfahren
Di eses Dokument legt ein gaschromatographisches Verfahren für Ethanol fest, mit dem höhere Alkohole
(Propan-1-ol, Butan-1-ol, Butan-2-ol, 2-Methylpropan-1-ol (Isobutanol), 2-Methylbutan-1-ol und
3-Methylbutan-1-ol) bis 2,5 % (m/m), Methanol bis 3 % (m/m) und andere flüchtige Verunreinigungen,
insbesondere Ethylethanoat (Ethylacetat), Ethanal (Acetaldehyd) und 1,1-Diethoxyethan (Acetal), im
Konzentrationsbereich bis 2 % (m/m) bestimmt werden.
Das Verfahren ist auf Grund möglicher Störungen nicht für Proben denaturierten (vergällten) Ethanols
ANMERKUNG Für die Zwecke dieses Dokuments wird zur Angabe des Massenanteils einer Substanz der Ausdruck
„% (m/m)“ verwendet.
Ethanol comme base de mélange à l'essence - Détermination de la teneur en alcools supérieurs, méthanol et impuretés volatiles - Méthode par chromatographie en phase gazeuse
La présente norme prescrit une méthode de chromatographie en phase gazeuse applicable à l'éthanol, pour
la détermination de la teneur en alcools supérieurs (propan-1-ol, butan-1-ol, butan-2-ol, 2-méthyl propan-1-ol
(isobutanol), 2-méthyl butan-1-ol, et 3-méthyl butan-1-ol) jusqu'à 2,5 % (m/m), de la teneur en méthanol
jusqu'à 3 % (m/m) et de la teneur en impuretés volatiles, particulièrement celles en éthanoate d’éthyle
(acétate d'éthyle), éthanal (acétaldéhyde) et 1,1-diéthoxyéthane (acétal), jusqu'à 2 % (m/m).
La méthode n'est pas applicable à l'éthanol dénaturé car il peut se produire des interférences.
NOTE Pour les besoins de la présente Norme européenne, l’expression « % (m/m) » est utilisée pour désigner la
Etanol kot komponenta za dodajanje motornemu bencinu - Določevanje višjih alkoholov, metanola ter hlapnih nečistoč - Metoda plinske kromatografije
Standards Content (Sample)
2003-01.Slovenski inštitut za standardizacijo. Razmnoževanje celote ali delov tega standarda ni dovoljeno.JUDILMHEthanol zur Verwendung als Blendkomponente in Ottokraftstoff - Bestimmung von höheren Alkoholen, Methanol und flüchtigen Verunreinigungen - Gaschromatographisches VerfahrenEthanol comme base de mélange à l'essence - Détermination de la teneur en alcools supérieurs, méthanol et impuretés volatiles - Méthode par chromatographie en phase gazeuseEthanol as a blending component for petrol - Determination of higher alcohols, methanol and volatile impurities - Gas chromatographic method75.160.20Liquid fuels71.080.60Alkoholi. EtriAlcohols. EthersICS:Ta slovenski standard je istoveten z:EN 15721:2009SIST EN 15721:2009en,fr,de01-junij-2009SIST EN 15721:2009SLOVENSKI
SIST EN 15721:2009
EUROPEAN STANDARDNORME EUROPÉENNEEUROPÄISCHE NORMEN 15721April 2009ICS 75.160.20 English VersionEthanol as a blending component for petrol - Determination ofhigher alcohols, methanol and volatile impurities - Gaschromatographic methodEthanol comme base de mélange à l'essence -Détermination de la teneur en alcools supérieurs, méthanolet impuretés volatiles - Méthode par chromatographie enphase gazeuseEthanol zur Verwendung als Blendkomponente inOttokraftstoff - Bestimmung von höheren Alkoholen,Methanol und flüchtigen Verunreinigungen -Gaschromatographisches VerfahrenThis European Standard 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 EuropeanStandard the status of a national standard without any alteration. Up-to-date lists and bibliographical references concerning such nationalstandards 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 translationunder the responsibility of a CEN member into its own language and notified to the CEN Management Centre has the same status as theofficial 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, Luxembourg, Malta, Netherlands, Norway, Poland, Portugal,Romania, Slovakia, Slovenia, Spain, Sweden, Switzerland and United Kingdom.EUROPEAN COMMITTEE FOR STANDARDIZATIONCOMITÉ EUROPÉEN DE NORMALISATIONEUROPÄISCHES KOMITEE FÜR NORMUNGManagement Centre:
Avenue Marnix 17,
B-1000 Brussels© 2009 CENAll rights of exploitation in any form and by any means reservedworldwide for CEN national Members.Ref. No. EN 15721:2009: ESIST EN 15721:2009
EN 15721:2009 (E) 2 Contents Page Foreword .3 Introduction .4 1 Scope .5 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 balance.8 5.4 Vials .8 6 Sampling .8 7 Procedure .8 7.1 General .8 7.2 General considerations for preparation and handling 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 9.2 Repeatability . 14 9.3 Reproducibility . 14 10 Test report . 14 Annex A (informative)
Examples of chromatograms . 15 Bibliography . 20
SIST EN 15721:2009
EN 15721:2009 (E) 3 Foreword This document (EN 15721:2009) 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 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 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, Finland, 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. SIST 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 . The test method 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 CEN/TC 19’s Working Group 9 and is based on two methods ( and ) published from a European Regulation on wine and on other internationally published analytical methods on spirits . The method is modified for determinations in ethanol for automotive applications. SIST 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-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 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. For 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 specified 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 programming 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 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 specification, 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 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 sufficient 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. SIST EN 15721:2009
EN 15721:2009 (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 alcohols 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 standard 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 with 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. SIST EN 15721:2009
EN 15721:2009 (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. The 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 (7.4) for the 2-methylbutan-1-ol and 3-methylbutan-1-ol peaks using the following equation: ()()2112699,12WWttR+−= (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 seconds, 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).
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 SIST 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 specified 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, 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 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 the 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 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 mass. Open the vial and fill 80 ml of ethanol in, put the cap on the vial and record the mass of the ethanol added. SIST EN 15721:2009
EN 15721:2009 (E) 9 Successively add 1 ml of each of the following compounds through the septum and record the individual added mass to the nearest 0,1 mg:
a) 3-methylbutan-1-ol, b) 2