SIST EN ISO 22854:2014
(Main)Liquid petroleum products - Determination of hydrocarbon types and oxygenates in automotivemotor gasoline - Multidimensional gas chromatography method (ISO 22854:2014)
Liquid petroleum products - Determination of hydrocarbon types and oxygenates in automotivemotor gasoline - Multidimensional gas chromatography method (ISO 22854:2014)
EN-ISO 22854 specifies the gas chromatographic (GC) method for the determination of saturated, olefinic and aromatic hydrocarbons in automotive motor gasoline. Additionally, the benzene content, oxygenate compounds and the total oxygen content can be determined. This International Standard defines two procedures, A and B. Procedure A is applicable to automotive motor gasoline with total aromatics of up to 50 % (V/V); total olefins from about 1,5 % (V/V) up to 30 % (V/V); oxygenates from 0,8 % (V/V) up to 15 % (V/V); total oxygen from about 1,5 % (V/V) to about 3,7 % (V/V); and benzene of up to 2 % (V/V). The system may be used for ethers with 5 or more C atoms up to 22 % (V/V) but the precision has not been established up to this level. Although this test method may be used to determine higher-olefin contents of up to 50 % (V/V), the precision for olefins was tested only in the range from about 1,5 % (V/V) to about 30 % (V/V). Although specifically developed for the analysis of automotive motor gasoline that contains oxygenates, this test method may also be applied to other hydrocarbon streams having similar boiling ranges, suchProcedure B describes the procedure for the analysis of oxygenated groups (ethanol, methanol, ethers, C3 - C5 alcohols) in ethanol (E85) automotive fuel containing ethanol between 50 % (V/V) and 85 % (V/V). The gasoline is diluted with an oxygenate-free component to lower the ethanol content to a value below 20 % (V/V) before the analysis by GC. If the ethanol content is unknown, it is advised to use a dilution of 4:1 when analysing the sample. The sample may be fully analysed including hydrocarbons. Precision data for the diluted sample is only available for the oxygenated groups. as naphthas and reformates.
Flüssige Mineralölerzeugnisse - Bestimmung der Kohlenwasserstoffgruppen und der sauerstoffhaltigen Verbindungen in Kraftstoffen für Kraftfahrzeugmotoren - Multidimensionales gaschromatographisches Verfahren (ISO 22854:2014)
Diese Internationale Norm legt ein Verfahren zur gaschromatographischen Bestimmung (GC) der Gehalte an gesättigten, olefinischen und aromatischen Kohlenwasserstoffen in Kraftstoffen für Kraftfahrzeugmotoren und Ethanolkraftstoff (E85) fest. Zusätzlich können die Gehalte an Benzol und sauerstoffhaltigen Verbindungen sowie der Gesamtsauerstoffgehalt bestimmt werden.
ANMERKUNG 1 Für die Zwecke dieses Dokuments werden die Ausdrücke "% (m/m)" und "% (V/V)" verwendet, um den Massenanteil, µ, und den Volumenanteil, φ, auszudrücken.
Dieses Dokument legt zwei Verfahren, A und B, fest.
Verfahren A ist anwendbar für Kraftstoffe für Kraftfahrzeugmotoren mit einem Gesamtanteil bis 50 % (V/V) Aromaten, einem Gesamtanteil an Olefinen von etwa 1,5 % (V/V) bis 30 % (V/V), einem Anteil an sauerstoffhaltigen Verbindungen von 0,8 % (V/V) bis 15 % (V/V), einem Gesamtanteil an Sauerstoff von etwa 1,5 % (V/V) bis etwa 3,7 % (V/V) und einem Anteil an Benzol bis zu 2 % (V/V). Das Verfahren kann auch zur Bestimmung von Ethern mit fünf oder mehr Kohlenstoffatomen bis zu Gehalten von 22 % (V/V) eingesetzt werden, jedoch wurden bis zu diesem Gehalt keine Präzisionsdaten ermittelt.
Obwohl dieses Verfahren zur Bestimmung höherer Olefingehalte bis zu 50 % (V/V) angewendet werden kann, wurde die Präzision für Olefine nur im Bereich von etwa 1,5 % (V/V) bis etwa 30 % (V/V) ermittelt.
Obwohl dieses Verfahren speziell für die Analyse von Ottokraftstoffen mit sauerstoffhaltigen Verbindungen entwickelt wurde, darf es auch auf andere Kohlenwasserstoffe mit ähnlichen Siedebereichen, wie z. B. Naphthas und Reformate, angewendet werden.
ANMERKUNG 2 Für Verfahren A wurden Präzisionsdaten für sauerstoffhaltige Verbindungen für Proben aus Kraftstoff (für Kraftfahr¬zeuge) ermittelt, die Ethyl-tert-butylether (ETBE), Methyl-tert-butylether (MTBE), tert-Amyl-methyl-ether (TAME), iso-Propanol, iso-Butanol, tert-Butanol, Methanol und Ethanol enthielten. Für Methanol ermittelte Präzisionsangaben erfüllten nicht die in dieser Internationalen Norm dargestellten Anforderungen. Diese Internationale Norm ist auch für die Bestimmung von n-Propanol, Aceton und Diisopropylether (DIPE) geeignet. Jedoch liegen für diese Verbindungen keine Präzisionsdaten vor.
Verfahren B beschreibt das Verfahren zur Analyse von sauerstoffhaltigen Verbindungen (Ethanol, Methanol, Ether, C3 C5 Alkohole) in ethanolhaltigen Ottokraftstoffen mit einem Ethanolgehalt zwischen 50 % (V/V) und 85 % (V/V). Dieser Kraftstoff wird mit einer sauerstofffreien Komponente verdünnt, um den Ethanolgehalt vor der GC-Analyse auf einen Wert unter 20 % (V/V) zu senken. Wenn der Ethanolgehalt unbekannt ist, wird empfohlen, eine Verdünnung von 4 : 1 bei der Analyse zu verwenden.
Für die Probe kann auch eine Vollanalyse einschließlich der Kohlenwasserstoffe erfolgen, jedoch sind Präzisionsdaten für die verdünnte Probe nur für die Gruppe der Sauerstoffverbindungen vorhanden.
ANMERKUNG 3 Für Verfahren B kann die Präzision für einen Ethanolanteil von etwa 50 % (V/V) bis zu 85 % (V/V) verwendet werden. Für den Ethergehalt können die Präzisionsangaben in Tabelle 6 verwendet werden, wenn der Gehalt bei mindestens 11 % (V/V) liegt. Für höhere Alkoholgehalte gab es keine ausreichenden Präzisionswerte für die Angabe einer vollgültigen Präzisionsangabe. In diesem Fall sind die Werte in Tabelle 6 lediglich als informativ anzusehen.
ANMERKUNG 4 Bei der Entwicklung dieses Verfahrens wurde der Siedeendpunkt auf 215 °C begrenzt.
ANMERKUNG 5 Es kann eine Überlappung zwischen C9- und C10-Aromaten auftreten. Das Ergebnis ist jedoch korrekt. Isopropylbenzol wird von C8-Aromaten gelöst und mit den anderen C9-Aromaten erfasst.
Produits pétroliers liquides - Détermination des groupes d'hydrocarbures et de la teneur en composés oxygénés de l'essence automobile pour moteurs - Méthode par chromatographie multidimensionnelle en phase gazeuse (ISO 22854:2014)
L'ISO 22854:2014 spécifie une méthode pour la détermination par chromatographie en phase gazeuse des teneurs en hydrocarbures saturés, oléfiniques et aromatiques dans les essences pour moteurs automobile et dans les carburants automobiles à base d'éthanol (Superéthanol ou E85). En outre, les teneurs en benzène, en composés oxygénés et en oxygène total peuvent être mesurées par cette méthode.
L'ISO 22854:2014 définit deux modes opératoires, A et B.
Le mode opératoire A est applicable aux essences pour moteurs automobile dont la fraction volumique en aromatiques totaux est au plus de 50 % (V/V), la teneur en oléfines est comprise entre 1,5 % (V/V) environ et 30 % (V/V) au plus, la teneur en composés oxygénés est au moins de 0,8 % (V/V) et au plus de 15 % (V/V), la teneur en oxygène total est comprise entre 1,5 % (V/V) environ et 3,7 % (V/V) environ, et la teneur en benzène est inférieure à 2 % (V/V). Le mode opératoire peut être applicable à des produits ayant des éthers avec 5 atomes de carbone ou plus dont la fraction volumique ne dépasse pas 22 % (V/V) mais la fidélité n'a pas été établie à ce niveau.
Bien que cette méthode d'essai puisse être utilisée pour déterminer des teneurs en oléfines plus élevées, jusqu'à 50 % (V/V), la fidélité pour les oléfines n'a été établie que pour des teneurs comprises entre 1,5 % (V/V) et 30 % (V/V) environ.
Bien que cette méthode ait été développée pour l'analyse d'essences pour moteurs automobile qui contiennent des oxygénés, celle-ci peut aussi être appliquée à d'autres bases hydrocarbonées dont l'intervalle d'ébullition est voisin, tels que les naphtas et les réformats.
Le mode opératoire B décrit le mode opératoire pour l'analyse de groupements oxygénés (éthanol, méthanol, éthers et alcools C3-C5) dans des carburants à l'éthanol (E85) (automobile) contenant une fraction volumique d'éthanol comprise entre 50 % (V/V) et 85 % (V/V). L'essence est diluée avec un composant non oxygéné pour abaisser la teneur en éthanol à une valeur inférieure à 20 % (V/V) avant l'analyse GC. Si la teneur en éthanol est inconnue, il est conseillé de diluer l'échantillon à analyser à un taux de 4:1.
L'échantillon peut être analysé en tenant compte des hydrocarbures. Les valeurs de fidélité pour les échantillons dilués ne sont disponibles que pour les groupements oxygénés.
Tekoči naftni proizvodi - Ugotavljanje vrste ogljikovodikov in oksigenatov v bencinih - Metoda multidimenzionalne plinske kromatografije (ISO 22854:2014)
Standard EN-ISO 22854 določa metodo plinske kromatografije (GC) za ugotavljanje nasičenih, olefinskih in aromatskih ogljikovodikov v bencinu za motorna vozila. Prav tako se z njo lahko določi vsebnost benzena in celotna vsebnost kisika. Ta mednarodni standard določa postopka A in B. Postopek A se uporablja za bencin za motorna vozila s skupno vrednostjo aromatov do 50 % (V/V); skupno vrednostjo olefinov od okoli 1,5 % (V/V) do 30 % (V/V); od 0,8 % (V/V) do 15 % (V/V) kisikovih spojin; od okoli 1,5 % (V/V) do okoli 3,7% (V/V) celotnega kisika; in do 2 % (V/V) benzena. Sistem se lahko uporablja za etre s 5 ali več ogljikovimi atomi do 22 % (V/V), vendar natančnost do te vrednosti ni bila dokazana. Čeprav se ta preskusna metoda lahko uporablja za določevanje višje vsebnosti olefinov do 50 % (V/V), je bila natančnost za olefine preskušena le v območju od okoli 1,5 % (V/V) do okoli 30 % (V/V). Čeprav je bila razvita posebej za analizo bencina za motorna vozila, ki vsebuje kisikove spojine, se ta preskusna metoda lahko uporablja tudi za druge vrste ogljikovodikov s podobnimi vrelišči. Postopek B opisuje postopek za analizo kisikovih skupin (etanol, metanol, etri, alkoholi C3–C5) v etanolnem gorivu (E85) za motorna vozila, ki vsebuje med 50 % (V/V) in 85% (V/V) etanola. Bencin je razredčen s komponento brez kisikovih spojin, da se vsebnost etanola pred analizo z metodo plinske kromatografije zmanjša na vrednost pod 20 % (V/V). Če je vsebnost etanola neznana, je priporočeno, da za analizo uporabimo vzorec, razredčen v razmerju 4:1. Vzorec se lahko analizira v celoti, vključno z ogljikovodiki. Podatki o natančnosti za razredčen vzorec so na voljo le za kisikove skupine, kot so naftne frakcije in reformati.
General Information
Relations
Standards Content (Sample)
SLOVENSKI STANDARD
SIST EN ISO 22854:2014
01-maj-2014
1DGRPHãþD
SIST EN ISO 22854:2008
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Liquid petroleum products - Determination of hydrocarbon types and oxygenates in
automotivemotor gasoline - Multidimensional gas chromatography method (ISO
22854:2014)
Flüssige Mineralölerzeugnisse - Bestimmung der Kohlenwasserstoffgruppen und der
sauerstoffhaltigen Verbindungen in Kraftstoffen für Kraftfahrzeugmotoren -
Multidimensionales gaschromatographisches Verfahren (ISO 22854:2014)
Produits pétroliers liquides - Détermination des groupes d'hydrocarbures et de la teneur
en composés oxygénés de l'essence automobile pour moteurs - Méthode par
chromatographie multidimensionnelle en phase gazeuse (ISO 22854:2014)
Ta slovenski standard je istoveten z: EN ISO 22854:2014
ICS:
75.160.20 7HNRþDJRULYD Liquid fuels
SIST EN ISO 22854:2014 en
2003-01.Slovenski inštitut za standardizacijo. Razmnoževanje celote ali delov tega standarda ni dovoljeno.
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SIST EN ISO 22854:2014
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SIST EN ISO 22854:2014
EUROPEAN STANDARD
EN ISO 22854
NORME EUROPÉENNE
EUROPÄISCHE NORM
March 2014
ICS 75.080 Supersedes EN ISO 22854:2008
English Version
Liquid petroleum products - Determination of hydrocarbon types
and oxygenates in automotive-motor gasoline and in ethanol
(E85) automotive fuel - Multidimensional gas chromatography
method (ISO 22854:2014)
Produits pétroliers liquides - Détermination des groupes Flüssige Mineralölerzeugnisse - Bestimmung der
d'hydrocarbures et de la teneur en composés oxygénés de Kohlenwasserstoffgruppen und der sauerstoffhaltigen
l'essence automobile pour moteurs et du carburant à Verbindungen in Kraftstoffen für Kraftfahrzeugmotoren -
l'éthanol (E85) - Méthode par chromatographie Multidimensionales gaschromatographisches Verfahren
multidimensionnelle en phase gazeuse (ISO 22854:2014) (ISO 22854:2014)
This European Standard was approved by CEN on 11 January 2014.
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
CEN-CENELEC Management Centre: Avenue Marnix 17, B-1000 Brussels
© 2014 CEN All rights of exploitation in any form and by any means reserved Ref. No. EN ISO 22854:2014 E
worldwide for CEN national Members.
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SIST EN ISO 22854:2014
EN ISO 22854:2014 (E)
Contents Page
Foreword .3
2
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SIST EN ISO 22854:2014
EN ISO 22854:2014 (E)
Foreword
This document (EN ISO 22854:2014) has been prepared by Technical Committee ISO/TC 28 "Petroleum
products and lubricants" in collaboration 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 September 2014 and conflicting national standards shall be withdrawn
at the latest by September 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 ISO 22854:2008.
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
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.
Endorsement notice
The text of ISO 22854:2014 has been approved by CEN as EN ISO 22854:2014 without any modification.
3
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SIST EN ISO 22854:2014
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SIST EN ISO 22854:2014
INTERNATIONAL ISO
STANDARD 22854
Second edition
2014-03-01
Liquid petroleum products —
Determination of hydrocarbon
types and oxygenates in automotive-
motor gasoline and in ethanol (E85)
automotive fuel — Multidimensional
gas chromatography method
Produits pétroliers liquides — Détermination des groupes
d’hydrocarbures et de la teneur en composés oxygénés de l’essence
automobile pour moteurs et du carburant à l’éthanol (E85) —
Méthode par chromatographie multidimensionnelle en phase gazeuse
Reference number
ISO 22854:2014(E)
©
ISO 2014
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SIST EN ISO 22854:2014
ISO 22854:2014(E)
COPYRIGHT PROTECTED DOCUMENT
© ISO 2014
All rights reserved. Unless otherwise specified, no part of this publication may be reproduced or utilized otherwise in any form
or by any means, electronic or mechanical, including photocopying, or posting on the internet or an intranet, without prior
written permission. Permission can be requested from either ISO at the address below or ISO’s member body in the country of
the requester.
ISO copyright office
Case postale 56 • CH-1211 Geneva 20
Tel. + 41 22 749 01 11
Fax + 41 22 749 09 47
E-mail copyright@iso.org
Web www.iso.org
Published in Switzerland
ii © ISO 2014 – All rights reserved
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SIST EN ISO 22854:2014
ISO 22854:2014(E)
Contents Page
Foreword .iv
Introduction .v
1 Scope . 1
2 Normative references . 2
3 Terms and definitions . 2
4 Principle . 3
5 Reagents and materials . 3
6 Apparatus . 4
7 Sampling . 5
8 Procedure. 5
8.1 Conditioning . 5
8.2 Sample preparation . 5
8.3 Test sample injection volume . 5
8.4 Verification of the apparatus and test conditions . 5
8.5 Validation . 5
8.6 Preparation of the test sample . 6
8.7 Preparation of the apparatus and test conditions . 6
9 Calculation . 6
9.1 General . 6
9.2 Calculation as % (m/m) . 6
9.3 Calculation as % (V/V) . 8
9.4 Calculation of total oxygen content in % (m/m) . 9
9.5 Data report according to automotive motor gasoline specification .10
10 Expression of results .10
10.1 Procedure A .10
10.2 Procedure B .10
11 Precision .10
11.1 General .10
11.2 Repeatability, r .10
11.3 Reproducibility, R .11
12 Test report .11
Annex A (informative) Instrument specifications .13
Annex B (informative) Examples of typical chromatograms .15
Bibliography .20
© ISO 2014 – All rights reserved iii
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SIST EN ISO 22854:2014
ISO 22854:2014(E)
Foreword
ISO (the International Organization for Standardization) is a worldwide federation of national standards
bodies (ISO member bodies). The work of preparing International Standards is normally carried out
through ISO technical committees. Each member body interested in a subject for which a technical
committee has been established has the right to be represented on that committee. International
organizations, governmental and non-governmental, in liaison with ISO, also take part in the work.
ISO collaborates closely with the International Electrotechnical Commission (IEC) on all matters of
electrotechnical standardization.
The procedures used to develop this document and those intended for its further maintenance are
described in the ISO/IEC Directives, Part 1. In particular the different approval criteria needed for the
different types of ISO documents should be noted. This document was drafted in accordance with the
editorial rules of the ISO/IEC Directives, Part 2. www.iso.org/directives
Attention is drawn to the possibility that some of the elements of this document may be the subject of
patent rights. ISO shall not be held responsible for identifying any or all such patent rights. Details of any
patent rights identified during the development of the document will be in the Introduction and/or on
the ISO list of patent declarations received. www.iso.org/patents
Any trade name used in this document is information given for the convenience of users and does not
constitute an endorsement.
For an explanation on the meaning of ISO specific terms and expressions related to conformity
assessment, as well as information about ISO’s adherence to the WTO principles in the Technical Barriers
to Trade (TBT) see the following URL: Foreword - Supplementary information
ISO 22854 was prepared by the European Committee for Standardisation (CEN) Technical Committee
CEN/TC 19, Gaseous and liquid fuels, lubricants and related products of petroleum, synthetic and biological
origin, in collaboration with Technical Committee ISO/TC 28, Petroleum and petroleum products, in
accordance with the Agreement on technical cooperation between ISO and CEN (Vienna Agreement).
This second edition cancels and replaces the first edition (ISO 22854:2008), which has been technically
revised.
iv © ISO 2014 – All rights reserved
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SIST EN ISO 22854:2014
ISO 22854:2014(E)
Introduction
This International Standard is an update of the first edition (ISO 22854:2008). Originally ISO 22854:2008
was used for determination of saturated, olefinic, aromatic and oxygenated hydrocarbons in automotive
motor gasoline according to European fuel specifications. Recent round-robin work has shown that the
scope of the method can be updated without alteration to include petrol with higher oxygen percentages
than mentioned in the first edition and will now be applicable for automotive motor gasoline up to and
including E10.
An interlaboratory study organized by CEN has shown that the method can also be used for high-
ethanol gasoline [also called ethanol (E85) automotive fuel], provided that the sample is diluted with a
component that will not interfere with any of the components or group of components that need to be
analysed. Details of how to perform such analysis are given in 8.2.
The derived precision data for methanol do not comply with the precision calculation as presented in
this International Standard. No precision calculation for methanol has been established as the need for
such data has not been expressed. If methanol is present in the automotive motor gasoline sample, it is
recommended that its contents is verified by the use of an appropriate test method, for instance as given
[1]
in EN 228.
[2]
The test method described in this International Standard is harmonized with ASTM D6839.
© ISO 2014 – All rights reserved v
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SIST EN ISO 22854:2014
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SIST EN ISO 22854:2014
INTERNATIONAL STANDARD ISO 22854:2014(E)
Liquid petroleum products — Determination of
hydrocarbon types and oxygenates in automotive-
motor gasoline and in ethanol (E85) automotive fuel —
Multidimensional gas chromatography method
1 Scope
This International Standard specifies the gas chromatographic (GC) method for the determination
of saturated, olefinic and aromatic hydrocarbons in automotive motor gasoline and ethanol (E85)
automotive fuel. Additionally, the benzene content, oxygenate compounds and the total oxygen content
can be determined.
NOTE 1 For the purposes of this document, the terms % (m/m) and % (V/V) are used to represent respectively
the mass fraction, µ, and the volume fraction, φ.
This International Standard defines two procedures, A and B.
Procedure A is applicable to automotive motor gasoline with total aromatics of up to 50 % (V/V); total
olefins from about 1,5 % (V/V) up to 30 % (V/V); oxygenates from 0,8 % (V/V) up to 15 % (V/V); total
oxygen from about 1,5 % (V/V) to about 3,7 % (V/V); and benzene of up to 2 % (V/V). The system may
be used for ethers with 5 or more C atoms up to 22 % (V/V) but the precision has not been established
up to this level.
Although this test method may be used to determine higher-olefin contents of up to 50 % (V/V), the
precision for olefins was tested only in the range from about 1,5 % (V/V) to about 30 % (V/V).
Although specifically developed for the analysis of automotive motor gasoline that contains oxygenates,
this test method may also be applied to other hydrocarbon streams having similar boiling ranges, such
as naphthas and reformates.
NOTE 2 For Procedure A, precision data have been established for the oxygenate compounds in automotive
motor gasoline samples containing ethyl-tert-butyl ether (ETBE), methyl-tert-butyl ether (MTBE), tert-amyl-
methyl ether (TAME), iso-propanol, iso-butanol, tert-butanol, methanol and ethanol. The derived precision
data for methanol do not comply with the precision calculation as presented in this International Standard.
Applicability of this International Standard has also been verified for the determination of n-propanol, acetone,
and di-isopropyl ether (DIPE). However, no precision data have been determined for these compounds.
Procedure B describes the procedure for the analysis of oxygenated groups (ethanol, methanol, ethers,
C3 – C5 alcohols) in ethanol (E85) automotive fuel containing ethanol between 50 % (V/V) and 85 %
(V/V). The gasoline is diluted with an oxygenate-free component to lower the ethanol content to a value
below 20 % (V/V) before the analysis by GC. If the ethanol content is unknown, it is advised to use a
dilution of 4:1 when analysing the sample.
The sample may be fully analysed including hydrocarbons. Precision data for the diluted sample is only
available for the oxygenated groups.
NOTE 3 For Procedure B, the precision may be used for an ethanol fraction from about 50 % (V/V) up to
85 % (V/V). For the ether fraction, the precision as specified in Table 6 may be used for samples containing at
least 11 % (V/V) of ethers. For the higher alcohol fraction, too few data were obtained to derive a full precision
statement and the data presented in Table 6 are therefore only indicative.
NOTE 4 While developing this test method, the final boiling point was limited to 215 °C.
NOTE 5 An overlap between C9 and C10 aromatics can occur. However, the total is accurate. Isopropyl benzene
is resolved from the C8 aromatics and is included with the other C9 aromatics.
© ISO 2014 – All rights reserved 1
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SIST EN ISO 22854:2014
ISO 22854:2014(E)
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.
ISO 3170:2004, Petroleum liquids — Manual sampling
ISO 3171:1998, Petroleum liquids — Automatic pipeline sampling
3 Terms and definitions
For the purposes of this document, the following terms and definitions apply.
3.1
hydrocarbon group
family of hydrocarbons such as saturated hydrocarbons, olefinic hydrocarbons, etc
3.1.1
saturated hydrocarbon
saturate
type of hydrocarbon that contains no double bonds with a carbon number of 3 to 12
EXAMPLE n-Paraffins, iso-paraffins, naphthenes and poly-naphthenes.
3.1.2
olefinic hydrocarbon
olefin
type of hydrocarbon that contains double or triple bonds with a carbon number of 3 to 10
EXAMPLE n-Olefins, iso-olefins and cyclic olefins.
3.1.3
aromatic hydrocarbon
aromatic
type of cyclic hydrocarbon with alternating double and single bonds between carbon atoms forming the
rings
EXAMPLE Benzene, toluene and higher homologous series with a carbon number of 6 to 10 and naphthalenes,
with a carbon number of up to 12.
3.2
oxygenate
oxygenated compound
type of hydrocarbon that contains an oxygen group, the addition of which is allowed according to current
petrol specifications
EXAMPLE Alcohols and ethers.
Note 1 to entry: See Clause 1, Note 2.
3.3
partial group
PG
one carbon number in an individual group, being either a single compound like toluene or an isomeric
mixture
EXAMPLE n-Butane and iso-butane.
2 © ISO 2014 – All rights reserved
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SIST EN ISO 22854:2014
ISO 22854:2014(E)
4 Principle
4.1 Procedure A and Procedure B use the same separation technique and analysis procedure, the
difference between the parts is that for Procedure B the sample is diluted. The diluting solvent is not
considered in the integration, this makes it possible to report the results of the undiluted sample after
normalization to 100 %.
4.2 The automotive motor gasoline sample being analysed is separated into hydrocarbon groups by
means of gas chromatographic analysis using special column-coupling and column-switching procedures.
The automotive motor gasoline sample is injected into the gas chromatographic system and, after
vaporization, is separated into the different groups. Detection is always done by a flame ionization
detector (FID).
4.3 The mass concentration of each detected compound or hydrocarbon group is determined by
the application of relative response factors (see 9.2) to the area of the detected peaks, followed by
normalization to 100 %. For automotive motor gasoline samples containing oxygenates that cannot be
determined by this test method, the hydrocarbon results are normalized to 100 % minus the value
of oxygenates as determined by another method. The liquid volume concentration of each detected
compound or hydrocarbon group is determined by the application of density values (see 9.3) to the
calculated mass concentration of the detected peaks followed by normalization to 100 %.
IMPORTANT — It is essential to the correct execution of the method that great care be taken to
ensure that all compounds are correctly identified. This is especially true for the identification of
oxygen - containing compounds because of their wide range of response factors. It is, therefore,
highly recommended for correct identification to verify possibly unknown oxygenates using a
reference mixture that contains these pure compounds.
4.4 After this analysis, the automotive motor gasoline is separated into hydrocarbon groups and
then by carbon number. By the use of the corresponding relative response factors, the mass distributions
of the groups in the automotive motor gasoline sample can be calculated.
5 Reagents and materials
5.1 Gases
NOTE Installation of suitable moisture filters is recommended for helium, nitrogen and hydrogen lines.
5.1.1 Hydrogen, 99,995 % pure.
DANGER — Hydrogen is explosive when mixed with air at concentration between 4 % (V/V) and
75 % (V/V). See the equipment manufacturers’ manuals concerning leaks in the system.
5.1.2 Helium or nitrogen, 99,995 % pure.
The system’s operating parameters such as column and trap temperatures, carrier gas flows and valve
switching times are depending on the type of carrier gas used. The use of nitrogen as carrier gas is
not possible on all configurations. Contact the equipment manufacturer for specific information or
instructions on the use of nitrogen.
5.1.3 Compressed air.
5.2 Vials, airtight and inert, e.g. with rubber-membrane caps covered with self-sealing polytetra-
fluoroethylene (PTFE).
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SIST EN ISO 22854:2014
ISO 22854:2014(E)
5.3 Reference solutions, finished automotive motor gasoline(s) used as reference and which contain
components and concentration levels comparable to those of the test sample.
The composition of the reference solution should have been determined in a round robin or by other
methods.
DANGER — Flammable. Harmful if inhaled.
5.4 Diluting solvent, used in Procedure B, shall not interfere with any other component in gasoline
being analysed. Dodecane (C H ) or tridecane (C H ) are recommended solvents.
12 26 13 28
6 Apparatus
6.1 Gas chromatograph, computer-controlled, multidimensional GC equipment, injector, FID,
suitable columns, traps and hydrogenation catalysts, of which an example is given in Annex A.
6.2 Switching valves, suitable switching valves that are used for the transfer of compounds from one
column to the other in the gas chromatograph.
They shall have a chemically inactive surface and a small dead volume.
6.3 Traps, suitable short columns (see Annex A for an example) used for retaining certain selected
chemical groups of the automotive motor gasoline using temperature control.
The absorption of the trapped compounds shall be reversible.
EXAMPLE A typical sequence is the following:
— First, the alcohols and higher-boiling aromatics are absorbed in a trap (sulfate column I). The remaining
aromatics are separated from the other components by means of a polar column (for example, OV 275).
— The ethers are separated from the remaining fraction by means of another trap (sulfate column II).
— The olefins are separated from the saturates by the olefin trap (for example, silver salt) in two steps. This is
necessary due to the limited capacity of such traps to retain high amounts of butene or total olefins. If the
trap capacity is sufficient for the olefin concentration, the separation may be performed in one step.
— Next, the remaining saturated hydrocarbons are separated into paraffins and naphthenes according to their
carbon number using a 13X molecular sieve column.
— The ethers are then eluted from the trap (sulfate column II) and separated and detected according to boiling
point.
— The olefins are desorbed from the olefin trap and hydrogenated in the Pt-column. They are separated and
detected as the corresponding saturated compounds using a 13X molecular sieve .
— The alcohols and higher-boiling aromatics are eluted from the polar column and the trap (sulfate column I),
separated using a non-polar column (for example, OV 101 methyl silicone) and detected according to boiling
point.
Examples of typical chromatograms with this order of elution of the hydrocarbon fractions are shown in
Figures B.1 and B.2. Specifically for Procedure B, a typical chromatogram is shown in Figure B.6.
IMPORTANT — Sulfur-containing compounds are irreversibly adsorbed in the olefins trap and
can reduce its capacity to retain olefins. Sulfur can also be adsorbed in the alcohol and ether-
alcohol-aromatic traps. Although the effect of low amounts of sulfur components on the various
traps or colu
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