1、BSI Standards PublicationLiquid petroleum products Determination of hydrocarbontypes and oxygenates via multidimensional gas chromatography method Round Robin research reportPD CEN/TR 15745:2015National forewordThis Published Document is the UK implementation of CEN/TR 15745:2015.It supersedes PD CE
2、N/TR 15745:2008 which is withdrawn.The UK participation in its preparation was entrusted to TechnicalCommittee PTI/15, Natural Gas and Gas Analysis.A list of organizations represented on this committee can be obtained onrequest to its secretary.This publication does not purport to include all the ne
3、cessary provisions ofa contract. Users are responsible for its correct application. The British Standards Institution 2015.Published by BSI Standards Limited 2015ISBN 978 0 580 88362 0ICS 75.160.20Compliance with a British Standard cannot confer immunity fromlegal obligations.This Published Document
4、 was published under the authority of theStandards Policy and Strategy Committee on 31 May 2015.Amendments/corrigenda issued since publicationDate Text affectedPUBLISHED DOCUMENTPD CEN/TR 15745:2015TECHNICAL REPORT RAPPORT TECHNIQUE TECHNISCHER BERICHT CEN/TR 15745 April 2015 ICS 75.160.20 Supersede
5、s CEN/TR 15745:2008English 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 en composs oxygns par mt
6、hode par chromatrographie multidimensionnelle en phase gazeuse - Rapport de recherches interlaboratoires Flssige Minerallerzeugnisse - Bestimmung der Kohlenwasserstoffgruppen und sauerstoffhaltigen Verbindungen mit multidimensionalen gaschromatographischen Verfahren - Round Robin Forschungsbericht T
7、his 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, Fra
8、nce, 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 NORMALISATION EUROPISCHES K
9、OMITEE 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 EPD CEN/TR 15745:2015CEN/TR 15745:2015 (E) 2 Contents Page Foreword 4 Introducti
10、on .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-Butanol 16 6.4 i-Propanol 17
11、 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
12、 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
13、. 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 been prepared by Technical
14、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 CEN
15、ELEC 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 15745:2015 (E) 5 Introduction
16、 In 2004, the company AC Analytical Controls1)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
17、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 info
18、rmation 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 informati
19、on 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 o
20、n 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 s
21、uch 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 sepa
22、rate 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 evaluate
23、d 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, Inn
24、sbruckweg 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, which has been explicitly
25、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 Europea
26、n 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 docu
27、ments, 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 pr
28、oducts 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 Coun
29、try 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 Total ether content; Combined C3 to C5 alcoho
30、ls 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 result
31、s 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. PD CEN/TR 15745:2015CEN/TR 15745:2015 (E) 25 Key X Lab ID S5 Y Ethanol content S6 S1 S7 S2 S8 S3 S9 S4 S10 Figure A.1 Results Method A - Ethanol L
32、ab-Sample Plot PD CEN/TR 15745:2015CEN/TR 15745:2015 (E) 26 Table A.2 Results Method A - Ethanol Laboratory Results 20106881 RRT Ethanol Method A Lab Sample 1 Sample 2 Sample 3 Sample 4 Sample 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 + 5
33、9,13 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 +
34、 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 65,3
35、8 + 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 + 82,9
36、4 83,60 Lab Sample 6 Sample 7 Sample 8 Sample 9 Sample 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、,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
38、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 + 6
39、1,33 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 PD CEN/TR 15745:2015CEN/TR 15745:2015 (E) 27 Table A.3 Results Method A - Ethanol Precision Results Reproducibility R = 3,8461 +
40、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) Valid Laboratories (14) 13 (14) 13 (14) 12 (14) 13 (14) 12 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 R 5,2
41、88 5,350 4,691 3,208 4,499 Degrees of Freedom 13 12 12 13 12 Anderson Darling Criterium 0,898 0,733 0,64 0,201 0,817 Sample 6 Sample 7 Sample 8 Sample 9 Sample 10 (Nr. of Laboratories) Valid Laboratories (14) 13 (14) 13 (14) 13 (14) 12 (14) 11 Mean Value MV 86,30 85,34 79,75 61,89 70,41 Repeatabilit
42、y r 1,200 1,378 1,600 1,270 1,534 Reproducibility R 5,745 5,887 5,537 4,489 3,774 Degrees of Freedom 13 13 13 12 12 Anderson Darling Criterium 0,371 0,468 0,343 0,3 0,222 PD CEN/TR 15745:2015CEN/TR 15745:2015 (E) 28 Key X Mean in % (V/V) Y Repeatability / Reproducibility Reproducibility (R) Repeatab
43、ility (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
44、 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. PD CEN/TR 15745:2015
