Ethanol as a blending component for petrol - Determination of higher alcohols, methanol and volatile impurities - Gas chromatographic method

This European 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) from 0,1 % up to 2,5 % (m/m), methanol from 0,1 % up to 3 % (m/m) and other impurities, in the range from 0,1 % up to 2 % (m/m) are determined. Impurities are all the compounds not attributed to the groups of higher alcohols or methanol. Due to possible interferences, the method is not applicable to denatured ethanol samples. 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 in the calculations.

Ethanol zur Verwendung als Blendkomponente in Ottokraftstoff - Bestimmung von höheren Alkoholen, Methanol und flüchtigen Verunreinigungen - Gaschromatographisches Verfahren

Diese Europäische Norm 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) von 0,1 % (m/m) bis 2,5 % (m/m), Methanol von 0,1 % (m/m) bis 3 % (m/m) und andere Verunreinigungen im Konzentrationsbereich von 0,1 % (m/m) bis 2 % (m/m) bestimmt werden.
Verunreinigungen sind alle Verbindungen, welche nicht der Gruppe der höheren Alkohole oder Methanol zugeordnet werden.
ANMERKUNG 1  In der Europäischen Spezifikation (EN 15376) für Ethanol für den Gebrauch als Blendkomponente ist der Grenzwert für den Ethanolgehalt definiert mit Einbezug des Gehalts an höheren Alkoholen definiert. Der Grenzwert beinhaltet also nicht nur den Ethanolgehalt allein.
Das Verfahren ist auf Grund möglicher Störungen nicht für Proben denaturierten (vergällten) Ethanols anwendbar.
Gegebenenfalls in der Probe vorliegendes Wasser wird bei der Analyse nicht berücksichtigt, da das Signal für Wasser im Chromatogramm nicht sichtbar ist. Deswegen muss zur gegebenenfalls erforderlichen Angabe des Alkoholgehalts in einer Anforderungsnorm das Wasser getrennt bestimmt und berücksichtigt werden.
ANMERKUNG 2   Für die Zwecke dieser Europäischen Norm wird zur Angabe des Massenanteils einer Substanz ω der Ausdruck „% (m/m)“ verwendet.

Éthanol 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 européenne 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) de 0,1 à 2,5 % (m/m), de la teneur en méthanol de 0,1 à 3 % (m/m) et de la teneur en autres impuretés de 0,1 à 2 % (m/m).
Les impuretés sont constituées de tous les composés dont les pics ne sont attribués ni au méthanol ni au groupe des alcools supérieurs.
NOTE 1   La Norme de spécification européenne de l’éthanol comme base de mélange fixe une exigence sur la teneur combinée (éthanol + alcools supérieurs) et non sur la teneur en éthanol uniquement.
En raison d’éventuelles interférences, la méthode n'est pas applicable aux échantillons d'éthanol dénaturé.
L'eau, si l'échantillon en contient, n'est pas comprise dans l'analyse car elle ne donne pas de signal visible sur le chromatogramme. Par conséquent, si la "teneur en alcools" est évoquée dans les spécifications, le cas de l'eau nécessitera d’être considéré séparément pour les calculs.
NOTE 2   Pour les besoins de la présente Norme européenne, l’expression « % (m/m) » est utilisée pour désigner la fraction massique (ω).

Etanol kot komponenta za dodajanje motornemu bencinu - Določevanje višjih alkoholov, metanola ter hlapnih nečistoč - Metoda plinske kromatografije

Ta evropski standard določa metodo plinske kromatografije za etanol, s katero se določajo višji alkoholi (propan-1-ol, butan-1-ol, butan-2-ol, 2-metilpropan-1-ol (izobutanol), 2-metilbutan-1-ol in 3-metilbutan-1-ol) od 0,1 % do 2,5 % (m/m), metanol od 0,1 % do 3 % (m/m) in druge nečistoče v razponu od 0,1 % do 2 % (m/m). Nečistoče so vse spojine, ki se ne pripisujejo skupinam višjih alkoholov ali metanolu. Zaradi morebitnih motenj se metoda ne uporablja za vzorce denaturiranega etanola. Če je v vzorcu prisotna voda, ni vključena v to analizo, ker signal za vodo ni viden v kromatogramu. Če se v specifikaciji navaja »vsebnost alkohola«, je treba vodo v izračunih upoštevati ločeno.

General Information

Status
Published
Public Enquiry End Date
04-Jun-2012
Publication Date
03-Oct-2013
Current Stage
6060 - National Implementation/Publication (Adopted Project)
Start Date
12-Sep-2013
Due Date
17-Nov-2013
Completion Date
04-Oct-2013

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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 VerfahrenÉthanol 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 15721:2013SIST EN 15721:2013en,fr,de01-november-2013SIST EN 15721:2013SLOVENSKI

STANDARDSIST EN 15721:20091DGRPHãþD
SIST EN 15721:2013
EUROPEAN STANDARD NORME EUROPÉENNE EUROPÄISCHE NORM
EN 15721
August 2013 ICS 75.160.20 Supersedes EN 15721:2009English Version

Ethanol as a blending component for petrol - Determination of higher alcohols, methanol and other impurities - Gas chromatographic method

Éthanol comme base de mélange à l'essence - Détermination de la teneur en alcools supérieurs, méthanol et autres impuretés - Méthode par chromatographie en phase gazeuse

Ethanol zur Verwendung als Blendkomponente in Ottokraftstoff - Bestimmung von höheren Alkoholen, Methanol und anderen Verunreinigungen - Gaschromatographisches Verfahren This European Standard was approved by CEN on 12 July 2013.

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 such national standards may be obtained on application 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 Management 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, Latvia, Lithuania, Luxembourg, Malta, Netherlands, Norway, Poland, Portugal, Romania, Slovakia, Slovenia, Spain, Sweden, Switzerland, Turkey and United Kingdom.

EUROPEAN COMMITTEE FOR STANDARDIZATION
COMITÉ EUROPÉEN DE NORMALISATION EUROPÄISCHES KOMITEE FÜR NORMUNG
Management Centre:
Avenue Marnix 17,

B-1000 Brussels © 2013 CEN All rights of exploitation in any form and by any means reserved worldwide for CEN national Members. Ref. No. EN 15721:2013: ESIST EN 15721:2013

EN 15721:2013 (E) 2 Contents Page Foreword ..............................................................................................................................................................3 Introduction .........................................................................................................................................................4 1 Scope ......................................................................................................................................................5 2 Normative references ............................................................................................................................5 3 Principle ..................................................................................................................................................5 4 Reagents and materials ........................................................................................................................5 5 Apparatus ...............................................................................................................................................6 6 Sampling .................................................................................................................................................7 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 ...................................................................................................................................... 10 8 Calculation ........................................................................................................................................... 12 8.1 Content of individual compounds ..................................................................................................... 12 8.2 Calculation of group contents ........................................................................................................... 12 8.3 Expression of results ......................................................................................................................... 13 9 Precision .............................................................................................................................................. 13 9.1 General ................................................................................................................................................. 13 9.2 Repeatability ........................................................................................................................................ 13 9.3 Reproducibility .................................................................................................................................... 13 10 Test report ........................................................................................................................................... 14 Annex A (informative)

Examples of chromatograms .................................................................................... 15 Bibliography ..................................................................................................................................................... 21

SIST EN 15721:2013

EN 15721:2013 (E) 3 Foreword This document (EN 15721:2013) 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 February 2014, and conflicting national standards shall be withdrawn at the latest by February 2014. 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. This document supersedes EN 15721:2009. EN 15721:2013 includes the following significant technical changes with respect to EN 15721:2009: the method has been simplified and more tailored towards the determination of the higher alcohols as mentioned in EN 15376 (propan-1-ol, butan-1-ol, butan-2-ol, 2-methylpropan-1-ol (isobutanol), 2-methylbutan-1-ol, 3-methylbutan-1-ol, methanol). All other alcohol compounds are summed as impurities. The response factor check and the listed example response factors have been taken out. According to the CEN-CENELEC Internal Regulations, the national standards organisations of the following countries are bound to implement this European 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, Slovenia, Spain, Sweden, Switzerland, Turkey and the United Kingdom.

SIST EN 15721:2013

EN 15721:2013 (E) 4 Introduction This document specifies a gas chromatographic (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 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 ([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. SIST EN 15721:2013

EN 15721:2013 (E) 5 1 Scope This European 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) from 0,1 % up to 2,5 % (m/m), methanol from 0,1 % up to 3 % (m/m) and other impurities, in the range from 0,1 % up to 2 % (m/m) are determined. Impurities are all the compounds not attributed to the groups of higher alcohols or methanol. NOTE 1 The European ethanol blending component specification[1] sets a limit for the combined result of ethanol + higher alcohols, not the ethanol content itself. Due to possible interferences, the method is not applicable to denatured ethanol samples. 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 in the calculations. NOTE 2 For the purposes of this European Standard, the term “% (m/m)” is used to represent the mass fraction (). 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 referenced document (including any amendments) applies. EN ISO 3170, Petroleum liquids — Manual sampling (ISO 3170) EN ISO 3696, Water for analytical laboratory use — Specification and test methods (ISO 3696) 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 ionisation 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.

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 All reagents shall be of recognised 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. 4.1 Water which, for analytical laboratory use, shall conform to grade 2 of EN ISO 3696. SIST EN 15721:2013

EN 15721:2013 (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 Propan-1-ol Higher Alcohols Butan-1-ol Higher Alcohols Butan-2-ol Higher Alcohols 2-Methylpropan-1-ol Higher Alcohols 2-Methylbutan-1-ol Higher Alcohols 3-Methylbutan-1-ol Higher Alcohols Internal standards Pentan-3-ol Internal standard for Procedure A 4-Methylpentan-2-ol Internal standard for Procedure B Solvent Ethanol a Solvent a Ethanol is needed in Procedure "A" and "B" as a solvent for the calibration solutions. The purity of the ethanol should be taken into account when preparing the mixtures. It should not contain any impurities that may interfere with the analysis and the results shall be corrected for the purity of the ethanol

5 Apparatus

5.1 Gas chromatograph, equipped with a Flame Ionisation Detector (FID), a split injector and connected to a PC or other system permitting the recording of chromatograms and execution of quantitative calculations. 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 shall 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 (as measured for 2-methylbutan-1-ol and 3-methylbutan-1-ol) shall be at least 1,0. Determine the column resolution, CR, with the calibration solutions (7.3) or (7.4) for the 2-methylbutan-1-ol and 3-methylbutan-1-ol peaks using the following Formula (1): ()()211269912WWttCR+−=, (1) SIST EN 15721:2013

EN 15721:2013 (E) 7 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. Figure 1 presents further clarification on the calculation of column resolution, CR, of 2-methylbutan-1-ol and 3-methylbutan-1-ol according to procedure “B” (example: CR = 1,30).

Key 1 Pentan-3-ol (retention time 12,292 min) X retention time (min) 2 2-methylbutan-1-ol (retention time 13,741 min) Y FID signal 3 3-methylbutan-1-ol (retention time 13,820 min)

Figure 1 — Typical chromatogram for calculation of column resolution 5.3 Analytical balance, capable of weighing to the nearest 0,1 mg. 5.4 Vials, having seals and 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. SIST EN 15721:2013

EN 15721:2013 (E) 8 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 may also depend on a particular request for solution to a specific problem. See the examples of 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 solu

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