CEN/TR 15745:2015
(Main)Liquid petroleum products - Determination of hydrocarbon types and oxygenates via multidimensional gas chromatography method - Round Robin research report
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 [2] 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 [3].
This Technical 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. This Technical Report should also support the use of multidimensional chromatography as the method for disputes on oxygenates in EN 228 [1].
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 recherches interlaboratoires
Tekoči naftni proizvodi - Določevanje vrste ogljikovodikov in oksigenatov z multidimenzionalno plinsko kromatografsko metodo - Medlaboratorijsko primerjalno poročilo
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Standards Content (Sample)
SLOVENSKI STANDARD
01-julij-2015
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SIST-TP CEN/TR 15745:2009
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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 composés oxygénés par méthode par chromatrographie multidimensionnelle en
phase gazeuse - Rapport de recherches interlaboratoires
Ta slovenski standard je istoveten z: CEN/TR 15745:2015
ICS:
71.040.50 Fizikalnokemijske analitske Physicochemical methods of
metode analysis
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
April 2015
ICS 75.160.20 Supersedes CEN/TR 15745:2008
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 recherches interlaboratoires gaschromatographischen Verfahren - Round Robin
Forschungsbericht
This Technical Report was approved by CEN on 24 February 2015. It has been drawn up by the Technical Committee CEN/TC 19.
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
© 2015 CEN All rights of exploitation in any form and by any means reserved Ref. No. CEN/TR 15745:2015 E
worldwide for CEN national Members.
Contents Page
Foreword .4
Introduction .5
1 Scope .6
2 Normative references .6
3 Participating laboratories .6
4 Sample set .7
5 Results from the round robin test .8
5.1 Sample 1 .8
5.2 Results sample 2.9
5.3 Results sample 3. 11
5.4 Results sample 4. 13
6 Review of the data . 14
6.1 MTBE . 14
6.2 Methanol . 16
6.3 t-Butanol . 16
6.4 i-Propanol . 17
6.5 i-Butanol . 19
7 Results and conclusions . 20
Annex A (normative) Round Robin Report 2010 - 688 . 22
A.1 General . 22
A.2 Motivation . 22
A.2.1 General . 22
A.2.2 Remarks . 22
A.3 Test Procedure and Protocol . 23
A.3.1 General . 23
A.3.2 Participating Laboratories Method A . 23
A.3.3 Samples . 23
A.3.4 Results and Precision Evaluation . 24
A.4 Essential RRT Details Methods B, C, D . 38
A.4.1 Test Procedure and Protocol . 38
A.4.2 Participating Laboratories Method B, C and D . 38
A.4.3 Samples . 38
Annex B (normative) Round Robin Report 2010 - 689 . 43
B.1 Methods and laboratories used . 43
B.2 Samples . 44
B.3 Results received . 44
B.3.1 General . 44
B.3.2 Conclusions . 44
B.3.3 Overview results received . 45
B.4 Graphs . 52
Bibliography . 56
Foreword
This document (CEN/TR 15475:2015) 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.
This document supersedes CEN/TR 15745:2008.
The second edition of this document includes Round Robin data generated in 2012 that led to revision of
EN ISO 22854.
Introduction
1)
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 [2], 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.
The precision data obtained from this program were used to develop the EN ISO 22854 method which was
published in 2008 [3].
In 2010 another Round Robin was organized to establish a test method to determine the oxygenated
components in ethanol automotive fuel (E85). Components such as ethers, C3-C5 alcohols and ethanol could
be made part of an E85 specification.
Four methods were tested:
A. EN ISO 22854 modified (with sample dilution)
B. EN 1601 modified (with sample dilution)
C. Capillary column method (2 columns in series, UNGDA method)
D. Capillary column method (2 separate columns, Suedzucker method)
Only method A with sample dilution had enough participants to derive a precision statement. The dilution step
was needed to lower the ethanol content in the sample to values below 20 % (V/V).
The Round Robin was carried out by TC 19/WG 9 and the results were evaluated conform EN ISO 4259. As
methods B, C and D did not get enough participants a 2nd ILS was carried out to see if more data could be
obtained for these methods. The details of these Round Robin Tests are added as Appendix A and B to this
Research Report.
1)
Postal address: AC Analytical Controls, Innsbruckweg 35 3047 AG Rotterdam, The Netherlands, E-
mail:sales.netherlands@paclp.com, Web: www.paclp.com.
1 Scope
This Technical Report presents the study on the application of EN 14517 [2] 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 [3].
This Technical 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. This Technical Report
should also support the use of multidimensional chromatography as the method for disputes on oxygenates in
EN 228 [1].
NOTE For the purposes of this document, the term “% (V/V)” is used to represent the volume 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 4259, Petroleum products — Determination and application of precision data in relation to methods of
test (ISO 4259)
3 Participating laboratories
Laboratories that have participated in the 2005 to 2006 Round Robin work are mentioned in Table 1.
Table 1 — Participating laboratories
Company / lab Country Company / lab Country
Umweltbundesamt Austria MOL Hungary
Total Raffinaderij Belgium ENI Gela Italy
BRC Belgium ENI, Euron Italy
Statoil Kalundborg Denmark ENI Agip Roma Italy
Fortum Finland ENI Agip Italy
ExxonMobil France ENI Agip Sanazzaro Italy
Total CReG France ENI R&M Livorno Italy
Shell Petit-Couronne France SGS Spijkenisse Netherlands
PCK Germany Nerefco Netherlands
BP Gelsenkirchen Germany Total Netherlands
Total Leuna Germany Shell Pernis Netherlands
SGS Speyer Germany Slovnaft Slovak Republic
Bayernoil Germany Repsol Spain
BP Germany BP Castellon Spain
Opel Germany ConocoPhilips UK
Shell Heide Germany Intertek Sunbury UK
Hellenic Petroleum Greece Total UK
MOL RT Hungary Shell Global Solutions UK
Laboratories that have participated in the second RR work are presented in Annex B.
4 Sample set
The sample set as given in Table 2 has been used.
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
t-Butanol 6,8
2 19 8,5 0,54
Methanol 3
i-Propanol 10,3
3 23 14,6 0,70
MTBE 8,4
i-Butanol 10,1
4 22 12,4 0,81
MTBE 0,25
Figure 1 gives an overview of the present oxygenates in the sample.
Key
X min 4 C10 Aromatics
Y pA 5 High boiling aromatics
1 Methanol 6 i-Propanol
2 i-Propanol 7 t-Butanol
3 C9 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
a
Lab Aromatics Olefins Benzene MTBE
1 2 1 2 1 2 1 2
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 results as in Table 4 are determined.
Table 4 — Results
Aromatics Olefins Benzene MTBE
Average 32,23 22,24 0,64 11,53
Stdev 1,36 2,22 0,03 0,30
NOTE 1 Laboratories with chromatographic issues with MTBE – 14, 18, 32 – have been rejected (see 6.1).
NOTE 2 Second analysis of laboratories 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 5. The overall results are given at the
end of the table.
Table 5 — 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 0,53 6,42 6,41 3,82 3,82
4 19,08 19,05 8,51 8,54 0,55 0,55 6,72 6,73 1,50 1,56
5 19,12 19,05 8,83 8,79 0,56 0,56 6,82 6,90 1,66 1,71
6 19,97 19,68 6,40 7,27 0,44 0,44 7,84 7,78 0,00 0,00
7 18,69 18,59 9,04 9,01 0,53 0,53 6,68 6,71 0,93 1,10
8 18,80 18,76 8,15 8,19 0,54 0,54 6,64 6,65 4,36 4,42
9 19,31 19,28 8,87 8,95 0,56 0,56 6,82 6,87 0,38 0,33
10 19,85 20,01 8,23 8,21 0,58 0,57 6,84 6,88 0,87 0,96
12 18,70 18,71 9,15 9,16 0,56 0,57 6,75 6,77 2,48 2,60
a
Lab Aromatics Olefins Benzene t-Butanol Methanol
1 2 1 2 1 2 1 2 1 2
13 18,95 18,92 9,06 9,05 0,55 0,55 6,62 6,63 1,53 1,65
14 18,80 19,13 8,77 8,62 0,55 0,53 6,97 7,14 1,98 2,06
15 20,07 20,11 8,35 8,33 0,56 0,56 6,97 7,00 1,51 1,65
16 18,65 19,15 8,97 9,00 0,53 0,53 6,80 6,73 4,15 4,06
17 18,67 18,61 9,62 9,51 0,55 0,55 6,79 6,77 1,18 1,32
18 18,66 18,81 7,78 7,44 0,52 0,53 0,00 0,00 3,68 3,76
19 20,39 19,71 8,32 8,04 0,54 0,54 7,19 0,00 0,00 0,00
20 18,69 8,33 0,54 6,76 2,71
21 18,81 18,71 8,18 8,35 0,55 0,55 6,76 6,73 2,37 2,48
22 19,67 19,48 8,81 8,85 0,54 0,53 0,00 0,00 0,00 0,00
23 19,22 19,14 8,86 9,01 0,50 0,50 6,83 6,85 1,54 1,36
24 19,74 18,97 7,77 8,37 0,50 0,54 0,00 0,00 0,90 0,89
25 17,40 17,28 8,16 8,06 0,55 0,55 6,75 6,73 2,16 2,37
26 18,78 18,93 7,87 7,38 0,54 0,54 6,62 6,58 4,01 3,98
27 18,65 18,53 8,28 8,25 0,55 0,55 6,76 6,76 2,45 2,53
28 18,76 18,71 7,92 7,88 0,53 0,53 6,36 6,34 3,67 3,72
29 18,74 18,93 8,63 8,56 0,54 0,54 6,59 6,52 3,74 3,72
30 18,41 18,35 8,33 8,23 0,54 0,52 0,00 0,00 1,32 1,33
31 19,09 19,16 9,16 9,15 0,54 0,54 6,63 6,60 1,06 1,16
32 18,27 18,29 8,30 8,29 0,53 0,53 0,00 0,00 3,90 3,91
33 19,47 7,54 0,56 6,71 0,00
34 19,16 19,03 8,74 8,72 0,56 0,55 6,73 6,73 1,67 1,83
35 19,49 19,39 7,80 7,94 0,53 0,54 0,00 0,00 0,00 0,00
44 18,98 18,84 7,92 7,92 0,55 0,55 0,00 0,00 0,00 0,00
Average 19,01 8,44 0,54 5,29 1,85
Stdev 0,55 0,57 0,02 2,85 1,38
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 (greyed cells in Table 5) the results can be determined as in Table 6.
Table 6 — Results
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 Laboratories that failed to identify t-Butanol have been rejected (see 6.3). Laboratory 6 has been rejected for t-
Butanol as Cochran outlier.
5.3 Results sample 3
The results of measurement on sample 3 returned are given in Table 7. The overall results are given at the
end of the table.
Table 7 — Results of sample 3 in % (V/V)
a
Lab Aromatics Olefins Benzene i-Propanol MTBE
1 2 1 2 1 2 1 2 1 2
1 22,67 22,82 14,51 14,40 0,70 0,71 9,74 10,03 8,35 8,44
2 21,69 21,49 13,66 13,81 0,65 0,66 4,83 4,86 8,31 8,33
3 22,64 22,63 15,45 15,46 0,69 0,69 9,96 9,97 8,11 8,09
4 22,21 22,21 14,56 14,62 0,70 0,70 10,41 10,44 8,48 8,48
5 22,42 22,28 14,69 14,79 0,70 0,70 10,55 10,61 8,39 8,42
6 22,39 22,50 13,08 13,07 0,63 0,63 10,82 10,85 8,44 8,47
7 21,96 21,87 15,17 15,24 0,67 0,68 9,71 9,85 8,52 8,38
8 23,00 22,99 14,27 14,54 0,71 0,71 10,61 10,64 8,33 8,32
9 22,53 22,40 15,21 15,00 0,70 0,68 9,51 9,62 8,31 8,35
10 23,50 23,78 13,66 13,72 0,71 0,71 10,17 10,17 8,13 8,10
11 23,11 22,91 13,84 13,92 0,71 0,71 9,25 9,25 8,21 8,30
12 22,26 22,29 15,41 15,60 0,72 0,71 10,07 10,08 8,23 8,19
13 21,90 21,92 15,28 15,36 0,69 0,70 10,40 10,46 8,51 8,38
14 22,61 22,66 19,22 19,40 0,70 0,69 10,66 10,69 3,05 2,94
15 23,49 23,59 14,36 14,30 0,71 0,72 9,85 9,98 8,65 8,65
16 23,38 23,11 15,30 15,60 0,69 0,69 10,47 10,51 8,08 8,20
17 21,47 21,23 16,12 16,14 0,69 0,68 0,00 0,00 8,28 8,20
18 23,08 22,99 13,97 13,95 0,70 0,69 0,00 0,00 5,97 6,14
19 23,44 23,49 13,73 13,89 0,69 0,68 6,57 6,38 10,30 10,71
20 22,77 22,74 14,61 14,58 0,70 0,70 10,34 10,33 8,36 8,37
21 22,26 22,41 14,48 14,55 0,71 0,71 10,23 10,29 8,40 8,46
22 28,62 28,62 16,21 16,24 0,73 0,74 0,00 0,00 8,77 8,68
23 22,17 22,32 15,28 15,36 0,62 0,61 8,95 8,99 8,59 8,43
24 27,50 27,12 14,90 15,28 0,72 0,73 0,00 0,00 10,50 10,44
25 19,04 19,06 4,97 4,88 0,70 0,71 10,45 10,48 8,11 8,11
26 19,74 12,90 0,72 10,14 8,35
27 22,03 22,07 14,10 14,10 0,71 0,70 10,75 10,74 8,28 8,26
28 22,56 22,60 14,30 14,34 0,68 0,68 10,61 10,61 7,99 7,97
29 22,85 22,75 14,80 14,80 0,70 0,70 10,32 10,36 7,99 8,01
30 24,18 23,83 14,69 14,61 0,71 0,70 0,00 0,00 8,39 8,37
31 22,07 22,05 15,29 15,28 0,67 0,67 10,39 10,42 8,43 8,28
a
Lab Aromatics Olefins Benzene i-Propanol MTBE
1 2 1 2 1 2 1 2 1 2
32 22,95 22,88 14,40 14,40 0,70 0,70 0,00 0,00 7,23 7,21
33 25,54 13,44 0,73 0,00 8,68
34 22,28 22,30 14,88 14,85 0,71 0,71 10,52 10,54 8,71 8,49
35 28,60 28,72 14,86 14,91 0,75 0,75 0,00 0,00 9,11 8,99
44 25,01 25,06 14,31 14,22 0,73 0,74 0,00 0,00 8,73 8,76
Average 23,02 14,49 0,70 7,57 8,25
Stdev 1,89 1,94 0,03 4,39 1,13
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 (greyed cells in Table 7) the results can be determined as in Table 8:
Table 8 — Results
Aromatics Olefins Benzene i-Propanol MTBE
Average 22,36 14,42 0,69 10,24 8,32
Stdev 0,91 2,24 0,02 0,47 0,18
NOTE Laboratories that failed to identify i-Propanol or one of the i-Propanol peaks have been rejected (see 6.4).
5.4 Results sample 4
The results of measurement on sample 4 returned are given in Table 9. The overall results are given at the
end of the table.
Table 9 — Results of sample 4 in % (V/V)
a
Aromatics Olefins Benzene i-Butanol MTBE
Lab
1 2 1 2 1 2 1 2 1 2
1 22,48 22,88 12,54 12,59 0,83 0,84 10,19 10,34 0,23 0,24
2 22,39 22,26 12,08 12,21 0,79 0,80 10,19 10,03 0,53 0,51
3 22,20 22,24 13,18 13,17 0,81 0,81 9,90 9,91 0,18 0,19
4 22,06 22,05 12,47 12,47 0,82 0,81 9,92 9,94 0,23 0,28
5 22,26 22,11 12,54 12,57 0,82 0,82 10,16 10,09 0,28 0,28
6 21,60 21,80 11,59 11,61 0,81 0,80 10,04 10,09 0,32 0,32
7 21,69 21,54 12,79 12,83 0,78 0,78 9,85 9,84 0,32 0,33
8 22,42 22,38 12,42 12,45 0,82 0,82 10,07 10,09 0,23 0,22
9 22,38 22,54 12,76 12,65 0,83 0,82 10,05 10,15 0,28 0,30
10 24,17 23,83 11,83 11,72 0,83 0,81 9,96 9,87 0,23 0,23
11 23,70 23,73 11,95 11,84 0,86 0,85 0,00 0,00 0,29 0,29
12 21,90 21,92 12,56 12,65 0,83 0,83 9,97 9,97 0,24 0,24
13 22,28 22,15 12,74 12,92 0,82 0,82 10,01 9,96 0,34 0,36
14 22,20 22,32 12,52 12,31 0,82 0,81 10,09 10,23 0,23 0,23
15 23,57 23,62 12,07 12,02 0,84 0,84 10,67 10,73 0,25 0,23
16 21,90 21,93 13,24 13,23 0,80 0,80 0,00 0,00 0,00 0,00
17 20,50 20,56 13,51 13,42 0,78 0,78 0,00 0,00 0,25 0,25
18 23,35 22,89 11,81 11,99 0,82 0,82 0,00 0,00 10,68 10,49
19 23,48 23,55 12,23 12,00 0,80 0,80 10,55 10,62 0,24 0,24
20 22,02 22,06 12,42 12,29 0,80 0,80 9,94 9,96 0,25 0,25
21 21,87 22,03 12,33 12,28 0,82 0,82 9,96 10,02 0,28 0,23
22 21,59 21,73 12,52 12,47 0,78 0,78 0,00 0,00 0,22 0,22
23 22,20 22,31 12,82 12,90 0,74 0,72 10,12 10,51 0,32 0,31
24 24,62 23,49 11,47 12,39 0,77 0,83 0,00 0,00 0,39 0,39
25 19,91 19,90 5,51 5,56 0,80 0,79 0,00 0,01 0,24 0,24
26 22,49 22,54 12,15 12,13 0,81 0,81 10,07 10,20 0,21 0,22
27 21,57 21,58 12,23 12,24 0,82 0,82 10,02 10,01 0,23 0,23
28 22,55 22,63 12,18 12,16 0,80 0,80 9,90 9,93 0,21 0,21
29 22,00 22,20 12,50 12,22 0,80 0,80 0,00 0,00 0,18 0,19
30 22,06 22,09 12,68 12,60 0,81 0,81 0,00 0,00 10,54 10,52
31 21,71 21,76 12,36 12,12 0,78 0,77 0,00 0,00 0,31 0,23
a
Aromatics Olefins Benzene i-Butanol MTBE
Lab
1 2 1 2 1 2 1 2 1 2
32 22,09 22,12 12,37 12,54 0,80 0,80 0,00 0,00 0,00 0,00
33 22,75 11,62 0,83 10,15 0,27
34 22,12 22,22 12,75 12,71 0,82 0,82 9,95 10,00 0,32 0,31
35 22,84 22,90 12,30 12,20 0,82 0,82 0,00 0,00 0,24 0,23
44 22,67 22,41 11,85 11,97 0,83 0,83 0,00 0,00 10,65 10,61
Average 22,31 12,20 0,81 6,40 1,12
Stdev 0,84 1,22 0,02 4,90 2,90
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 (greyed cells) the results can be determined as in Table 10.
Table 10 — Results
Aromatics Olefins Benzene i-Butanol MTBE
Average 22,38 12,39 0,81 10,09 0,26
Stdev 0,61 0,39 0,02 0,22 0,04
NOTE 1 Laboratories that failed to identify i-Butanol have been rejected.
NOTE 2 Lab 2 is Cochran outlier on MTBE.
6 Review of the data
6.1 MTBE
The results are given in Figure 2 and Figure 3.
Key
X Expected Normal Value
Y MTBE content, % (V/V)
1 Lab 14 – EthAlc trap separation too high, Break through to C4 Olefins
2 Laboratories 18, 32 – Precolumn too low. Elution in first and second aromatics fraction. Second
fraction identified as propanol / t-butanol
Figure 2 — sample 1, n-Probability of MTBE - all data
Key
X Expected Normal Value
Y MTBE content, % (V/V)
Figure 3 — Sample 1, n-Probability of MTBE - laboratories 14, 18, 32 removed
6.2 Methanol
Methanol results have been found to vary from near zero to the expected level of the sample. The high
response factor of methanol is a contributing factor. The high variance may be due to the pre-column not
being able to retain methanol. This component is not routinely analysed since it does not occur in production
samples at high levels. When found it is usually a remainder of the MTBE production process. The instrument
should be tuned for this component with a gravimetric standard.
The results are plotted in Figure 4. No results have been omitted from the calculation other than the results
where no methanol was found at all.
Key
X Expected Normal Value
Y Methanol content, % (V/V)
Figure 4 — Sample 2, n-Probability of Methanol
6.3 t-Butanol
The most common error has been that t-Butanol was not identified properly. It has been identified as one of
the oxygenated components that could elute in this part of the chromatogram such as n-Butanol.
Key
X Expected Normal Value
Y t-Butanol content, % (V/V)
Figure 5 — Sample 2, n-Probability t-Butanol all data
Key
X Expected Normal Value
Y t-Butanol content, % (V/V)
Figure 6 — Sample 2, n-Probability t-Butanol - unidentified removed
6.4 i-Propanol
On many instruments, i-Propanol has been cut into two peaks (see Figure 7). In this case, it often happens
that at least one of the peaks is misidentified. With a normal probability plot it becomes clear that a normal
distribution is not followed.
Key
X min
Y PA
1 i-Propanol peak cut in two
Figure 7 — Example of an i-propanol plot
Key
X Expected Normal Value
Y i-Propanol content, % (V/V)
Figure 8 — Sample 3, n-Probability i -Propanol - all data
Key
X Expected Normal Value
i-Propanol content, % (V/V)
Y
Figure 9 — Sample 3, i-Propanol - most partially identified data removed
6.5 i-Butanol
i-Butanol has little chance to be cut into several peaks (see Figure 10). However, the peak has been identified
as MTBE, Ethanol, n-Propanol, t-Butanol and s-Butanol.
Key
X min
Y pA
1 i-Butanol
Figure 10 — Example of an i-butanol plot
Key
X Expected Normal Value
Y i-Butanol content, % (V/V)
Figure 11 — Sample 4, n-Probability i-Butanol – all data
Key
X Expected Normal Value
i-Butanol content, % (V/V)
Y
Figure 12 — Sample 4, n-Probability i-Butanol - unidentified removed
7 Results and conclusions
From the returned data an estimate of the precision is calculated (see Table 11). Laboratories that reported a
value of zero were excluded from the calculations. Reprocessing with correct identification may have given a
correct result.
Precision estimates have been calculated according to EN ISO 4259. These figures have been incorporated in
EN ISO 22854.
Table 11 — Estimated precision data for oxygenates
Concentration Valid
Component Repeatability Reproducibility
% (V/V) laboratories
Methanol 3 0,24 3,8 35 (*)
t-Butanol 6,7 0,13 0,48 26
i-Propanol 10 0,19 1,35 26
i-Butanol 10,1 0,24 0,65 23
MTBE 0,25 0,05 0,13 22
MTBE 8,3 0,17 0,52 25
MTBE 11,5 0,2 0,8 32
Methanol: no data removed.
t-Butanol: laboratories removed = 6, 18, 19, 22, 24, 30, 32, 35 and 44.
i-Propanol: laboratories removed = 2, 17, 18, 19, 22, 24, 30, 32, 33, 35 and 44.
i-Butanol: laboratories removed = 11, 16, 17, 18, 22, 24, 25, 29, 30, 31, 32, 35 and 44.
The reproducibility of i-propanol is higher than for the other components, mainly because it can appear as a
double peak and then both peaks have to be identified properly. The repeatability indicates that a better
precision can be obtained when comparing the ratio reproducibility / repeatability with the ratio for i-butanol.
The reproducibility of Methanol is far greater than anticipated from the repeatability. The main cause is that
Methanol is a fairly active component. When analysing this component one has to be careful with the proper
operation of the precolumn.
The reproducibility of MTBE agrees with the precision stated in EN 14517.
There are more issues with oxygenated components that are not commonly found in production gasoline. The
main issue is failing to identify a component properly, which causes 20 % to 30 % rejects. With identification
issues removed the precision of the components is acceptable. When unknown oxygenates are found in a
sample, the identification should be verified using a reference mixture or a mixture with added pure
component.
Annex A
(normative)
Round Robin Report 2010 - 688
A.1 General
The Round Robin that this Annex addresses was organized by CEN/TC 19/WG 9 and held for the
determination of Oxygenates in E85 Fuels.
A specific request was made by the E85 Task Force to look at the possibilities to establish a test method to
determine oxygenated components in E85. The responsible working group CEN/TC 19/WG 9 selected four
methods for evaluation:
— a modified EN ISO 22854 method with sample dilution,
— a modified EN 1601 method (O-FID) with sample dilution,
— a capillary column method with two columns in series (UNGDA method), and
— a capillary column method with two separate columns (Suedzucker method).
The results of this RR are given in this Annex.
A.2 Motivation
A.2.1 General
Target was to find out test method applicability in E85 and precision for the GC determination of oxygenates
for the ethanol test methods A, B, C, D listed below.
— Method A EN ISO 22854 with dilution
— Method B EN 1601 with dilution
— Method C UNGDA Method (2 capillary columns in series)
— Method D Suedzucker Method (2 capillary columns, separated analysis)
For each of these test methods, results were sought for the following analyte groups
— Ethanol (RRT 2010 – 688 part 1)
— Benzene (RRT 2010 – 688 part 2)
— C3 to C5 alcohols (RRT 2010 – 688 part 3)
— Ethers (RRT 2010 – 688 part 4)
A.2.2 Remarks
Except for method A, test methods were not executed with a satisfactory number of laboratories. This means
that a full RRT precision evaluation for methods B, C, D was not possible with the necessary significance. For
these methods it was tried to conduct another RRT (2010-689), however again with not enough laboratories.
Therefore, results for methods B, C, and D are not conclusive, and only some statistical summary is given for
these methods.
In addition, levels for the different analytes were not separately designed to keep the overall effort in control.
This results in a somewhat uneven spacing of content level for some analytes. Therefore, transformations as
described in EN ISO 4259 have not been applied.
A.3 Test Procedure and Protocol
A.3.1 General
Test method was EN ISO 22854 using a sample pre‐dilution step (1 part sample with 4 parts dilutant).
A.3.2 Participating Laboratories Method A
14 Laboratories reported results for method A (Laboratories listed in alphabetical order)
— AC Analytical Controls BV
— Adam Opel GmbH
— ASG Analytik Service GmbH
— BP Gelsenkirchen
— CEPSA Research
— Conoco Phillips
— GMA mbH
— OMV Refining & Marketing GmbH
— Petroplus Raffinerie Ingolstadt
— PSA Peugeot‐Citroen
— Repsol
— SGS Germany GmbH
— SGS Nederland BV
— Total CReG
A.3.3 Samples
10 samples with Ethanol content ranging from approximately 50 % to 85 % (V/V) have been used (see
Figure A.1). For preparing the blends two different Ethanol samples and two petrol samples (without
oxygenates) were used and blend in the order shown in Table A.1.
NOTE Samples were prepared by Petrolab.
Table A.1 — Sample Blending in % (V/V)
Ethanol 1 Ethanol 2 BOB 1 BOB 2
S1 50 0 50 0
S2 55 0 0 45
S3 0 60 40 0
S4 0 65 0 35
S5 90 0 10 0
S6 0 87 0 13
S7 0 85 15 0
S8 83 0 0 17
S9 63 0 37 0
S10 0 70 0 30
The samples were analysed for the following groups:
— Ethanol content;
— Total ether content;
— Combined C3 to C5 alcohols content;
— Benzene content.
The results of the laboratory analyses and the precision evaluation for each group are given in A.3.4.
A.3.4 Results and Precision Evaluation
A.3.4.1 Results Method A – Ethanol
The Ethanol content in the samples ranged from approx. 50 % to 85 % (V/V). The laboratory results for
Ethanol are shown in Table A.2 where only the raw data is shown.
Table A.3 contains the precision evaluation results which are shown in Figure A.2.
Key
X Lab ID S5
Y Ethanol content S6
S1 S7
S2 S8
S3 S9
S4 S10
Figure A.1 — Results Method A - Ethanol – Lab-Sample Plot
Table A.2 — Results Method A - Ethanol – Laboratory Results
2010–688–1 RRT Ethanol Method A
Sample Sample Sample Sample Sample
Lab
1 2 3 4 5
1 + 50,21 50,30 + 55,06 54,92 + 61,75 62,10 + 67,01 66,83 + 87,24 87,33
2 + 48,42 47,83 + 52,40 52,39 + 59,13 59,14 + 63,87 64,13 + 87,03 87,01
3 + 49,04 48,91 + 54,87 54,48 + 60,80 60,89 + 65,69 65,76 + 86,86 86,94
4 + 47,90 48,01 + 51,66 51,72 + 59,21 59,37 + 63,61 63,42 + 84,57 84,48
5 + 49,42 49,28 + 54,30 53,78 + 60,86 60,06 + 65,08 64,35 + 85,34 84,50
6 + 44,57 45,06 + 55,03 54,56 C 66,97 63,63 + 66,17 67,29 H 77,58 76,69
7 + 49,39 49,41 + 53,47 53,52 + 61,02 61,04 + 65,48 65,40 + 87,35 87,50
8 H 47,05 47,07 H 51,43 51,22 H 55,81 56,25 H 60,24 57,38 H 79,28 83,56
9 + 49,32 49,55 + 54,40 54,41 + 61,37 61,26 + 66,03 65,96 + 87,44 87,28
10 + 46,26 44,10 + 48,97 49,11 + 57,05 55,21 + 65,76 65,38 + 83,49 84,84
11 + 47,44 47,85 + 51,82 52,20 + 59,30 59,87 + 64,03 64,29 + 86,32 86,57
12 + 48,95 48,95 + 52,86 52,75 + 60,68 60,83 + 65,32 65,33 + 86,35 86,42
13 + 49,04 49,42 + 54,72 54,67 + 60,07 60,31 + 65,74 65,88 + 86,86 86,99
14 + 49,86 50,29 + 54,55 54,72 + 60,16 60,28 + 64,38 64,81 + 82,94 83,60
Sample Sample Sample Sample Sample
Lab
6 7 8 9 10
1 + 88,01 88,03 + 86,65 86,74 + 81,03 80,89 + 62,27 61,98 + 72,11 72,21
2 + 85,98 85,31 + 85,99 85,10 + 79,85 79,55 + 61,33 60,70 + 69,05 69,35
3 + 86,15 86,16 + 84,24 84,54 + 79,53 79,49 + 61,99 61,66 + 70,74 70,77
4 + 84,00 83,88 + 82,00 81,37 + 75,80 76,25 + 58,54 58,90 + 68,50 68,70
5 + 85,06 84,40 + 83,97 83,17 + 78,35 77,79 + 62,15 61,58 + 69,48 68,67
6 + 91,55 90,24 + 90,35 89,49 + 84,43 82,43 C 66,33 62,40 C 78,01 73,87
7 + 87,43 87,07 + 86,43 86,40 + 81,31 80,94 + 63,33 62,64 + 72,49 71,27
8 H 74,95 70,26 H 72,88 70,14 H 78,24 79,79 H 59,10 58,17 H 69,37 67,54
9 + 87,14 87,21 + 85,87 85,88 + 81,00 80,86 + 62,90 62,77 + 71,31 71,29
10 + 83,91 83,94 + 85,10 86,29 + 79,32 80,44 + 65,16 63,85 + 70,19 71,85
11 + 85,97 86,39 + 84,66 85,55 + 78,69 79,45 + 60,47 60,77 + 69,29 69,84
12 + 86,43 86,64 + 85,42 85,29 + 79,75 79,60 + 61,33 61,30 + 70,58 70,58
13 + 86,19 86,51 + 85,02 85,03 + 80,03 80,04 + 62,76 62,30 + 70,40 70,43
14 + 84,56 85,53 + 83,85 84,48 + 77,93 78,63 + 62,01 62,73 C 70,37 62,52
Table A.3 — Results Method A - Ethanol – Precision Results
Reproducibility R = 3,8461 + 0,0144 × MV [% (V/V)]
Repeatability r = 0,8488 + 0,0056 × MV [% (V/V)]
Sample 1 Sample 2 Sample 3 Sample 4 Sample 5
(Nr. of
Laboratories)
(14) 13 (14) 13 (14) 12 (14) 13 (14) 12
Valid
Laboratories
Mean Value MV 48,42 53,36 60,07 65,27 86,05
Repeatability r 1,450 0,561 1,352 0,920 1,111
Reproducibility
5,288 5,350 4,691 3,208 4,499
R
Degrees of
13 12 12 13 12
Freedom
Anderson
Darling 0,898 0,733 0,64 0,201 0,817
Criterium
Sample 6 Sample 7 Sample 8 Sample 9 Sample 10
(Nr. of
Laboratories)
(14) 13 (14) 13 (14) 13 (14) 12 (14) 11
Valid
Laboratories
Mean Value MV 86,30 85,34 79,75 61,89 70,41
Repeatability r
1,200 1,378 1,600 1,270 1,534
Reproducibility
5,745 5,887 5,537 4,489 3,774
R
Degrees of
13 13 13 12 12
Freedom
Anderson
Darling 0,371 0,468 0,343 0,3 0,222
Criterium
Key
X Mean in % (V/V)
Y Repeatability / Reproducibility
Reproducibility (R)
Repeatability (r)
Figure A.2 — Repeatability and Reproducibility Plot
The round robin test result fulfils the “2R”–rule for the E85 Specification for ethanol. Constant precision values
instead of formulas can be used due to the very small slopes of both repeatability and reproducibility.
r = 1, 238 % (V/V), to be rounded to adequate No of significant digits.
R = 4, 847 % (V/V), to be rounded to adequate No of significant digits.
A.3.4.2 Results Method A – Ethers
The Ethers content in the samples ranged from approx. 0,25 to 1,6 % (V/V). The laboratory results for Ethers
are shown in Table A.4 where only the raw data is shown.
Table A.5 contains the precision evaluation results.
Key
X Lab ID S5
Y Ether content S6
S1 S7
S2 S8
S3 S9
S4 S10
Figure A.3 — Results Method A - Ethers – Lab-Sample Plot
Table A.4 — Results Method A - Ethers – Laboratory Results
Sample Sample Sample Sample Sample
LAB
1 2 3 4 5
1 + 1,57 1,58 + 0 0 + 1,23 1,22 + 0,12 0,12 + 0,28 0,28
2 + 1,62 1,62 + 0,65 0,64 + 1,31 1,31 + 0,50 0,50 + 0,37 0,36
3 + 1,56 1,56 + 0,59 0,59 + 1,22 1,22 + 0,45 0,45 + 0,33 0,32
4 H 0,41 0,46 + 0 0 H 0,40 0,42 + 0 0 + 0,20 0,21
5 + 1,63 1,63 + 0,60 0,59 + 1,28 1,27 + 0,48 0,48 C 0,47 0,58
6 C 1,68 1,77 C 0,85 1,08 C 1,36 1,7 H 1,20 1,16 C 1,43 1,59
7 + 1,53 1,54 + 0,60 0,59 + 1,21 1,21 + 0,45 0,45 + 0,33 0,33
8 + 1,58 1,62 + 0,62 0,61 + 1,29 1,3 + 0,47 0,45 + 0,49 0,52
9 + 1,66 1,65 + 0,78 0,79 + 1,28 1,29 + 0,61 0,61 + 0,61 0,66
10 H 0,11 0,12 + 0 0 H 0,11 0,1 + 0 0 + 0 0
11 + 1,78 1,75 + 0,64 0,64 + 1,34 1,33 + 0,49 0,49 + 0,48 0,48
12 + 1,66 1,66 + 0,67 0,67 + 1,28 1,28 + 0,47 0,47 + 0,39 0,39
13 + 1,63 1,61 + 0,49 0,49 + 1,31 1,3 + 0,46 0,47 + 0,37 0,36
14 + 1,49 1,51 + 0,57 0,56 + 1,14 1,14 + 0 0 + 0 0
Sample Sample Sample Sample Sample
LAB
6 7 8 9 10
1 + 0 0 + 0,38 0,38 + 0 0 + 1,16 1,17 + 0 0
2 + 0,19 0,20 + 0,49 0,49 + 0,26 0,27 + 1,21 1,23 + 0,43 0,42
3 + 0,16 0,16 + 0,48 0,48 + 0,23 0,23 + 1,11 1,11 + 0,38 0,38
4 + 0 0 + 0 0 + 0 0 H 0 0 + 0 0
5 + 0,42 0,42 + 0,81 0,77 C 0,70 0,79 + 1,58 1,57 + 0,63 0,62
6 H 1,03 1,03 C 1,33 1,51 C 1,81 1,94 C 2,94 2,75 C 1,54 1,95
7 + 0 0 + 0,44 0,44 + 0 0 + 1,16 1,14 + 0,37 0,38
8 + 0,18 0,17 + 0,48 0,46 + 0,36 0,32 C 1,28 1,19 + 0,41 0,44
9 C 0,17 0,34 + 0,68 0,70 C 0,61 0,5 + 1,54 1,5 + 0,58 0,59
10 + 0 0 + 0 0 + 0 0 H 0 0 + 0 0
11 + 0,31 0,31 + 0,66 0,65 + 0,43 0,43 + 1,53 1,52 + 0,55 0,56
12 + 0,26 0,26 + 0,49 0,55 + 0,38 0,38 + 1,25 1,25 + 0,40 0,41
13 + 0,19 0,20 + 0,81 0,84 + 0
...
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