CEN/TR 15745:2008

Liquid petroleum products - Determination of hydrocarbon types and oxygenates via multidimensional gas chromatography method - Round Robin research report

This Technical Report presents the study on the application of EN 14517 to other oxygenates. This report supports an extension of the scope of the method, which has been explicitly requested by ISO/TC 28 at the time of revision of EN 14517 and was agreed to result in the parallel Standard EN ISO 22854.
This report is published as background information to judge the approval of the use of the method for the determination of all oxygenates as mentioned in the European Fuels Directive. Next, this report should support the use of multidimensional chromatography as the method for disputes on oxygenates in EN 228.
NOTE   For the purposes of this document, the term “% (V/V)” is used to represent the volume fraction.

Flüssige Mineralölerzeugnisse - Bestimmung der Kohlenwasserstoffgruppen und sauerstoffhaltigen Verbindungen mit multidimensionalen gaschromatographischen Verfahren - Round Robin Forschungsbericht

Produits pétroliers liquides - Détermination des groupes d'hydrocarbures et de la teneur en composés oxygénés par méthode par chromatrographie multidimensionnelle en phase gazeuse - Rapport de recherche interlaboratoires

Ce Rapport Technique présente l’étude de l’application de l’EN 14517 aux autres composés oxygénés. Ce
rapport constitue un soutien à l’extension du domaine d’application de la méthode, explicitement demandée
par l’ISO/TC 28 au moment de la révision de l’EN 14517. Il a été convenu que la Norme parallèle,
EN ISO 22854, inclue cette extension.
Ce rapport est publié à titre de documentation pour juger de l’agrément de la méthode de détermination de
tous les composés oxygénés, tel que mentionné dans la Directive sur les carburants européens. Par la suite,
ce rapport devrait soutenir l’utilisation de la méthode par chromatographie multidimentionnelle, en cas de litige
portant sur les composés oxygénés de l’EN 228.
NOTE Pour les besoins de la présente Norme européenne, le terme « % (V/V) » est utilisé pour représenter la
fraction volumique.

Tekoči naftni proizvodi - Določevanje vrste ogljikovodikov in oksigenatov z multidimenzionalno plinsko kromatografsko metodo - Medlaboratorijsko primerjalno poročilo

General Information

• Status: Withdrawn
• Publication Date: 18-Nov-2008
• Withdrawal Date: 28-Apr-2015
• ICS: 75.160.20 - Liquid fuels
• Technical Committee: CEN/TC 19 - Petroleum products, lubricants and related products
• Drafting Committee: CEN/TC 19/WG 9 - Chromatographic test methods
• Current Stage: 9960 - Withdrawal effective - Withdrawal
• Completion Date: 29-Apr-2015
• Ref Project: SIST-TP CEN/TR 15745:2009 - Liquid petroleum products - Determination of hydrocarbon types and oxygenates via multidimensional gas chromatography method - Round Robin research report

Relations

• Replaced By: CEN/TR 15745:2015 - Liquid petroleum products - Determination of hydrocarbon types and oxygenates via multidimensional gas chromatography method - Round Robin research report
• Effective Date: 26-Jun-2013

Standards Content (Sample)

SLOVENSKI STANDARD
01-januar-2009
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PXOWLGLPHQ]LRQDOQRSOLQVNRNURPDWRJUDIVNRPHWRGR0HGODERUDWRULMVNR
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Liquid petroleum products - Determination of hydrocarbon types and oxygenates via
multidimensional gas chromatography method - Round Robin research report
Flüssige Mineralölerzeugnisse - Bestimmung der Kohlenwasserstoffgruppen und
sauerstoffhaltigen Verbindungen mit multidimensionalen gaschromatographischen
Verfahren - Round Robin Forschungsbericht
Produits pétroliers liquides - Détermination des groupes d'hydrocarbures et de la teneur
en composé oxygénés par méthode par chromatrographie multidimensionnelle en phase
gazeuse - Rapport de recherche interlaboratoire
Ta slovenski standard je istoveten z: CEN/TR 15745:2008
ICS:
75.160.20 7HNRþDJRULYD Liquid fuels
2003-01.Slovenski inštitut za standardizacijo. Razmnoževanje celote ali delov tega standarda ni dovoljeno.

TECHNICAL REPORT
CEN/TR 15745
RAPPORT TECHNIQUE
TECHNISCHER BERICHT
November 2008
ICS 75.160.20
English Version
Liquid petroleum products - Determination of hydrocarbon types
and oxygenates via multidimensional gas chromatography
method - Round Robin research report
Produits pétroliers liquides - Détermination des groupes Flüssige Mineralölerzeugnisse - Bestimmung der
d'hydrocarbures et de la teneur en composés oxygénés par Kohlenwasserstoffgruppen und sauerstoffhaltigen
méthode par chromatrographie multidimensionnelle en Verbindungen mit multidimensionalen
phase gazeuse - Rapport de recherche interlaboratoires gaschromatographischen Verfahren - Round Robin
Forschungsbericht
This Technical Report was approved by CEN on 30 March 2008. It has been drawn up by the Technical Committee CEN/TC 19.
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 STANDARDIZATION
COMITÉ EUROPÉEN DE NORMALISATION
EUROPÄISCHES KOMITEE FÜR NORMUNG
Management Centre: rue de Stassart, 36  B-1050 Brussels
© 2008 CEN All rights of exploitation in any form and by any means reserved Ref. No. CEN/TR 15745:2008: E
worldwide for CEN national Members.

Contents Page
Foreword.3
Introduction .4
1 Scope .5
2 Normative references .5
3 Participating labs.5
4 Sample set .5
5 Results from the round robin test.7
5.1 Sample 1 .7
5.2 Results sample 2.9
5.3 Results sample 3.10
5.4 Results sample 4.12
6 Review of the data .13
6.1 MTBE.13
6.2 Methanol .15
6.3 t-Butanol .15
6.4 i-Propanol .16
6.5 i-Butanol .19
7 Results and conclusions .20
Bibliography .22

Foreword
This document (CEN/TR 15745:2008) 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.
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 announce this Technical Report: 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.
Introduction
In 2004, the company AC Analytical Controls conducted a Performance Monitoring Program on the AC
Reformulyzer™. This is a kind of crosscheck program where customers analyse samples distributed by the
company and then report the analysis results. The company checks the analytical performance of the
instruments, keeping in mind the possible analytical errors that can occur. Because raw data are reported
(chromatogram and data for each carbon number/group), a detailed review can be made. The company
informs a customer when the instrument performance is inadequate and where possible provides information
and instructions to improve the performance.
The intention was to get a precision statement for oxygenates that were not included in EN 14517, but that are
listed in EN 228. Besides this, the performance for other properties (aromatics, olefins, benzene) has been
determined.
More information on the review of the data is available from the monitoring, but this technical report focuses
on oxygenates. Results for other properties (aromatics, olefins, benzene) are listed in the tables but are not
discussed in detail here. Also the evaluation for outliers is done on oxygenates only, not on the other
properties.
Postal address: P.O. Box 10054, 3004 AB Rotterdam, The Netherlands, E-mail: [e-mail], Web:
www.analytical-controls.com.
1 Scope
This Technical Report presents the study on the application of EN 14517 to other oxygenates. This report
supports an extension of the scope of the method, which has been explicitly requested by ISO/TC 28 at the
time of revision of EN 14517 and was agreed to result in the parallel Standard EN ISO 22854.
This report is published as background information to judge the approval of the use of the method for the
determination of all oxygenates as mentioned in the European Fuels Directive. Next, this report should
support the use of multidimensional chromatography as the method for disputes on oxygenates in EN 228.
NOTE For the purposes of this document, the term “% (V/V)” is used to represent the volume fraction.
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 4259, Petroleum products - Determination and application of precision data in relation to methods of
test (ISO 4259:2006)
3 Participating labs
Labs that have participated in the 2005 to 2006 Round Robin work are mentioned in Table 1.
4 Sample set
The sample set as given in Table 2 has been used.
Table 1 — Participating labs
Company / lab Country
Umweltbunderambt Austria
Total Raffinaderij Belgium
BRC Belgium
Statoil Kalundborg Denmark
Fortum Finland
ExxonMobil France
Total CReG France
Shell Petit-Couronne France
PCK Germany
BP Gelsenkirchen Germany
Total Leuna Germany
SGS Speyer Germany
Bayernoil Germany
BP Germany
Opel Germany
Shell Heide Germany
Hellenic Petroleum Greece
MOL RT Hungary
MOL Hungary
ENI Gela Italy
ENI, Euron Italy
ENI Agip Roma Italy
ENI Agip Italy
ENI Agip Sanazzaro Italy
ENI R&M Livorno Italy
SGS Spijkenisse Netherlands
Nerefco Netherlands
Total Netherlands
Shell Pernis Netherlands
Slovnaft Slovak Republic
Repsol Spain
BP Castellon Spain
ConocoPhilips UK
Intertek Sunbury UK
Total UK
Shell Global Solutions UK
Table 2 — Sample set of the Round Robin
Sample Oxygenate Oxygenate Aromatics Olefins Benzene
level
% (V/V) % (V/V) % (V/V) % (V/V)
1 MTBE 11 32 24 0,64
2 t-Butanol 6,8 19 8,5 0,54
Methanol 3
3 i-Propanol 10,3 23 14,6 0,70
MTBE 8,4
4 i-Butanol 10,1 22 12,4 0,81
MTBE 0,25
Figure 1 gives an overview of the present oxygenates in the sample.

Key
1 Methanol   5 High boiling aromatics
2 i-Propanol   6 i-Propanol
3 C9 Aromatics  7 t-Butanol
4 C10 Aromatics  8 i-Butanol
Figure 1 — Overlaid section of chromatogram of samples with identified components
5 Results from the round robin test
5.1 Sample 1
The results of measurement on sample 1 returned are given in Table 3. The overall results (average and
standard deviation) are given at the end of the table.
Table 3 — Results of sample 1 in % (V/V)
a
Lab  Aromatics Olefins Benzene MTBE
1 2 1 2 1 2 1 2
1 32,43 32,18 22,76 23,02 0,66 0,65 11,80 11,56
2 32,29 32,44 21,81 21,69 0,64 0,65 11,87 11,89
3 32,06 32,14 18,91 19,10 0,64 0,64 11,26 11,28
4 31,65 31,59 24,22 24,21 0,65 0,64 11,57 11,60
5 32,01 31,81 24,01 23,40 0,65 0,65 11,37 11,27
6 33,48 34,16 19,99 18,55 0,60 0,62 11,11 12,29
7 30,96  24,94  0,61  11,26
8 32,65 32,46 22,39 22,81 0,66 0,66 11,75 11,74
9 31,46 31,49 20,33 20,27 0,64 0,64 11,43 11,43
10 33,88 34,18 22,83 23,24 0,67 0,66 11,57 11,51
11 35,42 35,46 23,90 24,11 0,70 0,69 11,76 11,69
12 31,10 31,09 19,46 19,82 0,65 0,65 11,26 11,25
13 31,15 30,92 22,45 23,39 0,64 0,64 11,35 11,43
14 32,36 32,58 31,51 31,65 0,67 0,66 3,51 3,46
15 35,44 35,60 23,26 23,70 0,69 0,69 11,86 11,79
16 31,38  25,56  0,63  11,52
17 30,38 30,43 21,00 22,15 0,63 0,63 11,23 11,27
18 33,15 32,91 22,47 22,91 0,67 0,65 9,51 9,02
19 32,90 33,11 21,60 21,97 0,61 0,61 12,01 12,11
20 31,64  23,93  0,65  11,75
21 31,25 31,34 24,42 24,35 0,65 0,65 11,57 11,55
22 30,95 30,98 24,62 24,69 0,63 0,63 11,27 11,23
23 31,58 31,69 25,48 25,49 0,55 0,55 11,51 11,54
24 32,24 34,02 22,72 23,51 0,66 0,63 11,57 11,02
26 28,54  21,67  0,64  11,31
27 32,11 31,59 20,66 21,80 0,66 0,66 11,59 11,72
28 32,86 32,85 24,85 25,55 0,58 0,58 11,07 11,11
29 32,20 32,12 21,13 21,19 0,64 0,64 11,08 11,11
30 31,89 31,92 20,58 20,56 0,65 0,64 11,51 11,45
31 31,20 31,01 15,58 16,20 0,61 0,62 11,24 11,37
32 32,63 32,63 20,74 20,94 0,65 0,65 9,95 9,99
33 34,21 20,89 0,69 12,17
34 32,01 24,36 0,66 11,65
35 31,48 20,42 0,68 12,16
44 32,82 32,80 21,44 21,00 0,67 0,68 11,78 11,94
Average 32,27 22,51 0,64 11,16
Stdev 1,31 2,69 0,03 1,51
a
Greyed cells are classified as an outlier for oxygenates. The results for an entire lab were
removed if an outlier in the oxygenates was found.
After outlier removal (indicated by the grey zones and cells) the following results are determined:
AromaticsOlefinsBenzeneMTBE
Average 32,23 22,24 0,64 11,53
Stdev 1,36 2,22 0,03 0,30
NOTE 1 Labs with chromatographic issues with MTBE – 14, 18, 32 – have been rejected (see Clause 6.1).
NOTE 2 Second analysis of labs 6 and 24 is rejected on Hawkins test for MTBE.
5.2 Results sample 2
The results of measurement on sample 2 returned are given in Table 4. The overall results are given at the
end of the table.
After outlier removal (greyed cells in Table 4) the following can be determined as follows:

Aromatics Olefins Benzene t-Butanol Methanol
Average 18,95 8,60 0,55 6,74 2,12
Stdev 0,51 0,48 0,02 0,17 1,21
NOTE Labs that failed to identify t-Butanol have been rejected (see 6.3). Lab 6 has been rejected for t-Butanol as
Cochran outlier.
Table 4 — Results of sample 2 in % (V/V)
a
Lab  Aromatics Olefins Benzene t-Butanol Methanol
1 2 1 2 1 2 1 2 1 2
1 19,26 19,36 8,77 8,66 0,55 0,56 6,94 7,02 1,32 1,36
2 19,27 19,22 8,29 8,43 0,54 0,55 6,97 6,90 0,60 0,60
3 18,52 18,56 9,01 8,99 0,53 0,5
...