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

This Technical report is published as background information to judge the approval of the use of the method described in EN ISO 22854 for the determination of all oxygenates as mentioned in the European Fuels Directive. Next, this report supports the use of multidimensional chromatography as the method for disputes on oxygenates in EN 228.
This Technical Report first presents the study on the application of EN 14517 to other oxygenates. It 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.
Next, it shows that the scope of the multidimensional chromatography 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, and that it can also be used for high-ethanol gasoline (also called automotive ethanol (E85) 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.

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

General Information

Status
Published
Publication Date
08-Jun-2015
Current Stage
6060 - National Implementation/Publication (Adopted Project)
Start Date
27-May-2015
Due Date
01-Aug-2015
Completion Date
09-Jun-2015

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SLOVENSKI STANDARD
SIST-TP CEN/TR 15745:2015
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
SIST-TP CEN/TR 15745:2015 en

2003-01.Slovenski inštitut za standardizacijo. Razmnoževanje celote ali delov tega standarda ni dovoljeno.

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SIST-TP CEN/TR 15745:2015
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.
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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

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B.3.2 Conclusions ......................................................................................................................................... 44

B.3.3 Overview results received .................................................................................................................. 45

B.4 Graphs .................................................................................................................................................. 52

Bibliography ...................................................................................................................................................... 56

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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.
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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 [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.

Postal address: AC Analytical Controls, Innsbruckweg 35 3047 AG Rotterdam, The Netherlands, E-

mail:sales.netherlands@paclp.com, Web: www.paclp.com.
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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.

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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

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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)
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
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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

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)
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
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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

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.
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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)
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
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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

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).

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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)
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
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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

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.
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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
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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 thi
...

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