BS PD CEN TR 15745-2015 Liquid petroleum products Determination of hydrocarbon types and oxygenates via multidimensional gas chromatography method Round Robin research rep.pdf

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1、BSI Standards Publication Liquid petroleum products Determination of hydrocarbon types and oxygenates via multidimensional gas chromatography method Round Robin research report PD CEN/TR 15745:2015National foreword This Published Document is the UK implementation of CEN/TR 15745:2015. It supersedes

2、PD CEN/TR 15745:2008 which is withdrawn. The UK participation in its preparation was entrusted to Technical Committee PTI/15, Natural Gas and Gas Analysis. A list of organizations represented on this committee can be obtained on request to its secretary. This publication does not purport to include

3、all the necessary provisions of a contract. Users are responsible for its correct application. The British Standards Institution 2015. Published by BSI Standards Limited 2015 ISBN 978 0 580 88362 0 ICS 75.160.20 Compliance with a British Standard cannot confer immunity from legal obligations. This P

4、ublished Document was published under the authority of the Standards Policy and Strategy Committee on 31 May 2015. Amendments/corrigenda issued since publication Date Text affected PUBLISHED DOCUMENT PD CEN/TR 15745:2015 TECHNICAL REPORT RAPPORT TECHNIQUE TECHNISCHER BERICHT CEN/TR 15745 April 2015

5、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 ptroliers liquides - Dtermination des groupes dhydrocarbures et de la teneur

6、en composs oxygns par mthode par chromatrographie multidimensionnelle en phase gazeuse - Rapport de recherches interlaboratoires Flssige Minerallerzeugnisse - Bestimmung der Kohlenwasserstoffgruppen und sauerstoffhaltigen Verbindungen mit multidimensionalen gaschromatographischen Verfahren - Round R

7、obin 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 Re

8、public 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 COMIT EUROPEN DE NOR

9、MALISATION EUROPISCHES KOMITEE FR 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 worldwide for CEN national Members. Ref. No. CEN/TR 15745:2015 E PD CEN/TR 15745:2015CEN/TR 15745:2015 (E) 2 Contents P

10、age 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 29 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-But

11、anol 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

12、 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 laboratori

13、es used . 43 B.2 Samples . 44 B.3 Results received . 44 B.3.1 General . 44 PD CEN/TR 15745:2015CEN/TR 15745:2015 (E) 3 B.3.2 Conclusions . 44 B.3.3 Overview results received 45 B.4 Graphs 52 Bibliography 56 PD CEN/TR 15745:2015CEN/TR 15745:2015 (E) 4 Foreword This document (CEN/TR 15475:2015) has be

14、en 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 pate

15、nt 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. PD CEN/TR 15745:2015CEN/TR 1574

16、5:2015 (E) 5 Introduction In 2004, the company AC Analytical Controls 1)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 anal

17、ytical 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 wh

18、ere 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

19、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

20、 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 automotiv

21、e 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. Capil

22、lary 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

23、 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: A

24、C Analytical Controls, Innsbruckweg 35 3047 AG Rotterdam, The Netherlands, E- mail:, Web: . PD CEN/TR 15745:2015CEN/TR 15745:2015 (E) 6 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,

25、 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

26、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 re

27、ferences 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

28、. 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

29、 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 Sh

30、ell 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 ConocoPh

31、ilips 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. PD CEN/TR 15745:2015CEN/TR 15745:2015 (E) 7 4 Sample set The sample set as given in Table 2

32、 has been used. Table 2 Sample set of the Round Robin Sample Oxygenate Oxygenate level % (V/V) Aromatics % (V/V) Olefins % (V/V) Benzene % (V/V) 1 MTBE 11 32 24 0,64 2 t-Butanol Methanol 6,8 3 19 8,5 0,54 3 i-Propanol MTBE 10,3 8,4 23 14,6 0,70 4 i-Butanol MTBE 10,1 0,25 22 12,4 0,81 Figure 1 gives

33、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 PD CEN/TR 15745:2015CEN/TR 15745:20

34、15 (E) 8 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 aAromatics Olefins Benzene MTBE 1 2 1 2 1

35、 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,

36、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

37、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 1

38、1,75 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,

39、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 PD CEN/TR 15745:2015CEN/TR 15745:2015 (E) 9 Lab aAromatics Olefins Benzene MTBE 1 2 1 2 1 2 1 2 32 32,63 32,63 20,74 20,94 0,65

40、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 aGreyed cells are classified as an outlier for oxygenates. The results for an entire lab were removed

41、 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

42、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 o

43、f sample 2 in % (V/V) Lab aAromatics 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,

44、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,

45、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 PD CEN/TR 15745:2015CEN/TR 15745:2015 (E) 10 Lab aAromatics 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,

46、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 8,3

47、3 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

48、 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 0,5

49、4 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 aGreyed 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