SIST EN ISO 22854:2016
(Main)Liquid petroleum products - Determination of hydrocarbon types and oxygenates in automotive-motor gasoline and in ethanol (E85) automotive fuel - Multidimensional gas chromatography method (ISO 22854:2016)
Liquid petroleum products - Determination of hydrocarbon types and oxygenates in automotive-motor gasoline and in ethanol (E85) automotive fuel - Multidimensional gas chromatography method (ISO 22854:2016)
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 % (m/m) to about 3,7 % (m/m); and benzene of up to 2 % (V/V). The system can
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 can 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 can 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-amylmethyl
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 advisable
to use a dilution of 4:1 when analysing the sample.
The sample can be fully analysed including hydrocarbons. Precision data for the diluted sample are
only available for the oxygenated groups.
NOTE 3 For Procedure B, the precision can 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 can 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.
Flüssige Mineralölerzeugnisse - Bestimmung der Kohlenwasserstoffgruppen und der sauerstoffhaltigen Verbindungen in Kraftstoffen für Kraftfahrzeugmotoren und in Ethanolkraftstoff (E85) - Multidimensionales gaschromatographisches Verfahren (ISO 22854:2016)
Diese Internationale Norm legt ein Verfahren zur gaschromatographischen Bestimmung (GC) von gesättigten, olefinischen und aromatischen Kohlenwasserstoffen in Ottokraftstoffen 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.
Diese Internationale Norm definiert zwei Verfahren, A und B.
Verfahren A ist anwendbar für Ottokraftstoffe mit einem Gesamtaromatenanteil bis zu 50 % (V/V), einem Gesamtolefinanteil von etwa 1,5 % (V/V) bis zu 30 % (V/V), einem Anteil an sauerstoffhaltigen Verbindungen von 0,8 % (V/V) bis zu 15 % (V/V), einem Gesamtanteil an Sauerstoff von etwa 1,5 % (m/m) bis etwa 3,7 % (m/m) und einem Anteil an Benzol bis zu 2 % (V/V). Das System kann auch für Ether mit fünf oder mehr Kohlenstoffatomen mit Anteilen bis zu 22 % (V/V) eingesetzt werden, jedoch wurden bis zu diesem Niveau keine Präzisionsdaten ermittelt.
Obwohl dieses Prüfverfahren 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, kann es auch auf andere Kohlenwasserstoffe mit ähnlichen Siedebereichen wie z. B. Naphthas und Reformate angewendet werden.
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 (ISO 22854:2016)
ISO 22854:2016 prescrit une méthode pour la détermination par chromatographie en phase gazeuse (GC) des teneurs en hydrocarbures saturés, oléfiniques et aromatiques dans les essences pour moteurs automobile et dans les carburants automobiles à base d'éthanol [carburants pour automobiles éthanol (E85)]. En outre, les teneurs en benzène, en composés oxygénés et en oxygène total peuvent être mesurées par cette méthode.
NOTE 1 Pour les besoins de la présente Norme européenne, les termes % (fraction massique) et % (fraction volumique) sont utilisés pour représenter respectivement la fraction massique, μ, et la fraction volumique, φ, d'un produit.
ISO 22854:2016 définit deux modes opératoires, A et B.
Le mode opératoire A est applicable aux essences pour moteurs automobile dont la teneur en aromatiques totaux est au plus de 50 % (fraction volumique), la teneur en oléfines totales est comprise entre 1,5 % (fraction volumique) environ et 30 % (fraction volumique) au plus, la teneur en composés oxygénés est au moins de 0,8 % (fraction volumique) et au plus de 15 % (fraction volumique), la teneur en oxygène total est comprise entre 1,5 % (fraction massique) environ et 3,7 % (fraction massique) environ, et la teneur en benzène est inférieure à 2 % (fraction volumique). 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 % 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 % (fraction volumique), la fidélité pour les oléfines n'a été établie que pour des teneurs comprises entre 1,5 % (fraction volumique) et 30 % (fraction volumique) 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.
NOTE 2 Pour le mode opératoire A, des valeurs de fidélité ont été établies pour les composés oxygénés dans des échantillons d'essences pour moteurs automobile contenant de l'éthyl tertiobutyl éther (ETBE), du méthyl tertiobutyl éther (MTBE), du tertioamyl méthyl éther (TAME), de l'isopropanol, de l'isobutanol, du tertiobutanol, du méthanol et de l'éthanol. Les données de fidélité dérivées pour le méthanol ne correspondent pas aux calculs de fidélité présentés dans la présente méthode. L'applicabilité de la présente méthode d'essai a, en outre, été vérifiée pour le dosage, du n-propanol, de l'acétone et du di-isopropyl éther (DIPE). Cependant, la fidélité n'a pas été déterminée pour ces composés.
Le mode opératoire B décrit le mode opératoire pour l'analyse de groupes oxygénés (éthanol, méthanol, éthers et alcools C3-C5) dans des carburants éthanol pour automobiles (E85) contenant de l'éthanol entre 50 % et 85 % (fraction volumique). L'essence est diluée avec un composant non oxygéné pour abaisser la teneur en éthanol à une valeur inférieure à 20 % (fraction volumique) avant l'analyse GC. Si la teneur en éthanol est inconnue, il est conseillé de diluer à 4:1 pour l'analyse de l'échantillon.
L'échantillon peut être totalement analysé y compris les familles d'hydrocarbures. Les valeurs de fidélité pour les échantillons dilués ne sont disponibles que pour les groupes oxygénés.
NOTE 3 Pour le mode opératoire B, les valeurs de fidél
Tekoči naftni proizvodi - Določevanje vrste ogljikovodikov in oksigenatov v motornem bencinu in bencinu na osnovi etanola (E85) - Metoda multidimenzionalne plinske kromatografije (ISO 22854:2016)
Ta mednarodni standard določa metodo plinske kromatografije (GC) za ugotavljanje
nasičenih, olefinskih in aromatskih ogljikovodikov v bencinu in etanolu (E85)
za motorna vozila. Prav tako je mogoče določiti vsebnost benzena in kisikovih spojin ter celotno vsebnost kisika.
OPOMBA 1: V tem dokumentu sta uporabljeni oznaki % (m/m) in % (V/V), ki predstavljata masni delež (µ) oziroma prostornino (φ).
Ta mednarodni standard določa dva postopka, postopek 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 % (m/m) do okoli 3,7% (m/m) 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 lahko ta preskusna metoda uporablja za ugotavljanje višjih vsebnosti olefinov vse do 50 % (V/V),
pa je bila natančnost za olefine preskušena samo v območju od 1,5 % (V/V) do 30 % (V/V).
Čeprav je bila ta preskusna metoda razvita posebej za analizo bencina za motorna vozila, ki vsebuje kisikove spojine, se lahko uporablja tudi za druge vrste ogljikovodikov s podobnimi vrelišči, kot so naftne frakcije in reformati.
OPOMBA 2: Za postopek A so bili podatki o natančnosti določeni za kisikove spojine v vzorcih bencina za motorna vozila, ki vsebujejo etil-tert-butil eter (ETBE), metil-tert-butil eter (MTBE), tert-amilmetil eter (TAME), izo-propanol, izo-butanol, tert-butanol, metanol in etanol. Izpeljani podatki o natančnosti za metanol niso v skladu z izračunom natančnosti, opredeljenim v tem mednarodnem standardu.
Uporabnost tega mednarodnega standarda je bila preverjena tudi za ugotavljanje n-propanola, acetona in di-izopropil etra (DIPE). Vendar podatki o natančnosti za te spojine niso bili določeni. 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.
OPOMBA 3: Pri postopku B se lahko natančnost uporablja za delež etanola od okoli 50 % (V/V) do 85 % (V/V). Za delež etra se lahko natančnost, kot je navedena v tabeli 6, uporablja za vzorce, ki vsebujejo vsaj 11 % (V/V) etrov. Za višji delež alkohola je bilo pridobljenih premalo podatkov, da bi bilo mogoče izpeljati popolno izjavo o natančnosti, zato so podatki v tabeli 6 zgolj okvirni.
OPOMBA 4: Pri razvijanju te preskusne metode je bila zgornja točka vretja omejena na 215 °C.
OPOMBA 5: Med aromati C9 in C10 lahko pride do prekrivanja, vendar je skupna vrednost točna. Izopropilni benzen je izločen iz aromatov C8 in priključen k drugim aromatom C9.
General Information
Relations
Standards Content (Sample)
SLOVENSKI STANDARD
SIST EN ISO 22854:2016
01-junij-2016
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SIST EN ISO 22854:2014
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Liquid petroleum products - Determination of hydrocarbon types and oxygenates in
automotive-motor gasoline and in ethanol (E85) automotive fuel - Multidimensional gas
chromatography method (ISO 22854:2016)
Flüssige Mineralölerzeugnisse - Bestimmung der Kohlenwasserstoffgruppen und der
sauerstoffhaltigen Verbindungen in Kraftstoffen für Kraftfahrzeugmotoren und in
Ethanolkraftstoff (E85) - Multidimensionales gaschromatographisches Verfahren (ISO
22854:2016)
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
(ISO 22854:2016)
Ta slovenski standard je istoveten z: EN ISO 22854:2016
ICS:
71.040.50 Fizikalnokemijske analitske Physicochemical methods of
metode analysis
75.160.20 7HNRþDJRULYD Liquid fuels
SIST EN ISO 22854:2016 en,fr,de
2003-01.Slovenski inštitut za standardizacijo. Razmnoževanje celote ali delov tega standarda ni dovoljeno.
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SIST EN ISO 22854:2016
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SIST EN ISO 22854:2016
EN ISO 22854
EUROPEAN STANDARD
NORME EUROPÉENNE
April 2016
EUROPÄISCHE NORM
ICS 75.080 Supersedes EN ISO 22854:2014
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
22854:2016)
Produits pétroliers liquides - Détermination des Flüssige Mineralölerzeugnisse - Bestimmung der
groupes d'hydrocarbures et des composés oxygénés de Kohlenwasserstoffgruppen und der sauerstoffhaltigen
l'essence pour moteurs automobiles et du carburant Verbindungen in Kraftstoffen für
pour automobiles éthanol (E85) - Méthode par Kraftfahrzeugmotoren und in Ethanolkraftstoff (E85) -
chromatographie multidimensionelle en phase gazeuse Multidimensionales gaschromatographisches
(ISO 22854:2016) Verfahren (ISO 22854:2016)
This European Standard was approved by CEN on 20 February 2016.
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
© 2016 CEN All rights of exploitation in any form and by any means reserved Ref. No. EN ISO 22854:2016 E
worldwide for CEN national Members.
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SIST EN ISO 22854:2016
EN ISO 22854:2016 (E)
Contents Page
European foreword . 3
2
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SIST EN ISO 22854:2016
EN ISO 22854:2016 (E)
European foreword
This document (EN ISO 22854:2016) 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 October 2016, and conflicting national standards shall
be withdrawn at the latest by October 2016.
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 22854:2014.
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 22854:2016 has been approved by CEN as EN ISO 22854:2016 without any modification.
3
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SIST EN ISO 22854:2016
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SIST EN ISO 22854:2016
INTERNATIONAL ISO
STANDARD 22854
Third edition
2016-03-15
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 des composés oxygénés de l’essence pour moteurs
automobiles et du carburant pour automobiles éthanol (E85) —
Méthode par chromatographie multidimensionelle en phase gazeuse
Reference number
ISO 22854:2016(E)
©
ISO 2016
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SIST EN ISO 22854:2016
ISO 22854:2016(E)
COPYRIGHT PROTECTED DOCUMENT
© ISO 2016, Published in Switzerland
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
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Tel. +41 22 749 01 11
Fax +41 22 749 09 47
copyright@iso.org
www.iso.org
ii © ISO 2016 – All rights reserved
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SIST EN ISO 22854:2016
ISO 22854:2016(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
8.2.1 Procedure B only − Sample dilution . 5
8.2.2 Procedure A and B − Sample cooling . 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) . 7
9.4 Calculation of total oxygen content in % (m/m) . 9
9.5 Data report according to automotive motor gasoline specification . 9
10 Expression of results . 9
10.1 Procedure A . 9
10.2 Procedure B .10
11 Precision .10
11.1 General .10
11.2 Repeatability, r .10
11.3 Reproducibility, R .10
12 Test report .11
Annex A (informative) Instrument specifications .12
Annex B (informative) Examples of typical chromatograms .14
Bibliography .19
© ISO 2016 – All rights reserved iii
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SIST EN ISO 22854:2016
ISO 22854:2016(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
The committee responsible for this document is ISO/TC 28, Petroleum products and related products of
synthetic or biological origin.
This third edition cancels and replaces the second edition (ISO 22854:2014), which contained a serious
mistake in the scope regarding the levels of oxygen content.
iv © ISO 2016 – All rights reserved
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SIST EN ISO 22854:2016
ISO 22854:2016(E)
Introduction
This International Standard is a small update of the second edition (ISO 22854:2014), which in turn
was a revision to extend the scope of the first edition. Originally ISO 22854:2008 (and its predecessor
EN 14517:2004) 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
[1]
given in EN 228 .
[2]
The test method described in this International Standard is harmonized with ASTM D6839 .
© ISO 2016 – All rights reserved v
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SIST EN ISO 22854:2016
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SIST EN ISO 22854:2016
INTERNATIONAL STANDARD ISO 22854:2016(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 % (m/m) to about 3,7 % (m/m); and benzene of up to 2 % (V/V). The system can
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 can 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 can 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 advisable
to use a dilution of 4:1 when analysing the sample.
The sample can be fully analysed including hydrocarbons. Precision data for the diluted sample are
only available for the oxygenated groups.
NOTE 3 For Procedure B, the precision can 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 can 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.
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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, Petroleum liquids — Manual sampling
ISO 3171, Petroleum liquids — Automatic pipeline sampling
ISO 4259, Petroleum products — Determination and application of precision data in relation to
methods of test
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.
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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 GC analysis using special column-coupling and column-switching procedures.
The automotive motor gasoline sample is injected into the GC 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
Installation of suitable moisture filters is recommended for hydrogen, helium and nitrogen 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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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:
— 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.
— 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
...
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