1、PUBLISHED DOCUMENT PD CEN/TR 15139:2005 Petroleum products and other liquids Applicability of test methods on sulfur determination in petrol and diesel fuel ICS 75.160.20 PD CEN/TR 15139:2005 This Published Document was published under the authority of the Standards Policy and Strategy Committee on
2、30 December 2005 BSI 30 December 2005 ISBN 0 580 46845 3 National foreword This Published Document is the official English language version of CEN/TR 15139:2005. The UK participation in its preparation was entrusted to Technical Committee PTI/13, Petroleum testing and terminology, which has the resp
3、onsibility to: A list of organizations represented on this committee can be obtained on request to its secretary. Cross-references The British Standards which implement international or European publications referred to in this document may be found in the BSI Catalogue under the section entitled “I
4、nternational Standards Correspondence Index”, or by using the “Search” facility of the BSI Electronic Catalogue or of British Standards Online. This publication does not purport to include all the necessary provisions of a contract. Users are responsible for its correct application. Compliance with
5、a Published Document does not of itself confer immunity from legal obligations. aid enquirers to understand the text; present to the responsible international/European committee any enquiries on the interpretation, or proposals for change, and keep UK interests informed; monitor related internationa
6、l and European developments and promulgate them in the UK. Summary of pages This document comprises a front cover, an inside front cover, the CEN/TR title page, pages 2 to 10, an inside back cover and a back cover. The BSI copyright notice displayed in this document indicates when the document was l
7、ast issued. Amendments issued since publication Amd. No. Date CommentsTECHNICALREPORT RAPPORTTECHNIQUE TECHNISCHERBERICHT CEN/TR15139 August2005 ICS75.160.20 EnglishVersion PetroleumproductsandotherliquidsApplicabilityoftest methodsonsulfurdeterminationinpetrolanddieselfuel Produitsptroliersetautres
8、liquidesvaluationde mthodesdessaidedterminationdelateneurensoufre danslessenceetlegazole MinerallerzeugnisseundandereFlssigkeiten AnwendbarkeitvonPrfverfahrenfrdie SchwefelbestimmunginOttokraftstoffenund Dieselkraftstoffen ThisTechnicalReportwasapprovedbyCENon14May2005.IthasbeendrawnupbytheTechnical
9、CommitteeCEN/TC19. CENmembersarethenationalstandardsbodiesofAustria,Belgium,Cyprus,CzechRepublic,Denmark,Estonia,Finland,France, Germany,Greece,Hungary,Iceland,Ireland,Italy,Latvia,Lithuania,Luxembourg,Malta,Netherlands,Norway,Poland,Portugal, Slovakia, Slovenia,Spain,Sweden,SwitzerlandandUnitedKing
10、dom. EUROPEANCOMMITTEEFORSTANDARDIZATION COMITEUROPENDENORMALISATION EUROPISCHESKOMITEEFRNORMUNG ManagementCentre:ruedeStassart,36B1050Brussels 2005CEN Allrightsofexploitationinanyformandbyanymeansreserved worldwideforCENnationalMembers. Ref.No.CEN/TR15139:2005:E2 Contents Page Foreword 3 Introducti
11、on4 1 Scope.5 2 Test methods.5 3 Samples.5 4 Laboratories5 5 Evaluation of round robin results6 6 Statistical analysis6 7 Comparison between methods and accuracy 7 8 Applicability to FAME blends.7 9 Conclusions7 10 Recommendations for updating EN 228 and EN 590 .7 11 Test method publication.8 Acknow
12、ledgements .9 Bibliography.10 CEN/TR 15139:20053 Foreword This Technical Report (CEN/TR 15139:2005) 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. C
13、EN/TR 15139:20054 Introduction During its 8 thmeeting held in London on 25 - 26 October 2000, CEN/TC 19/WG 27 “Elemental analysis of petroleum and related products“ decided to carry out a second round robin, after the first performed in 1998 -1999, to define the precision of new test methods in the
14、range 1 mg/kg to 60 mg/kg sulfur. The range of sulfur content was selected to obtain definite and robust precision statements for future sulfur limits. The round robin was carried out in 2001. The work has formed the basis for sulfur test method standards produced by the following organizations: ISO
15、/TC 28 “Petroleum products“, and CEN/TC 19 “Petroleum products, lubricants and related products“. CEN/TR 15139:20055 1 Scope This Technical Report summarises the activity carried out by CEN/TC 19 to define the precision of new test methods for the determination of low sulfur content in automotive fu
16、els. The full description of the activity can be found in the Working Group Report completed in August 2002, which is an internal CEN/TC 19 document. 2 Test methods WG 27 identified the most suitable instrumental methods to include in the round robin, also according to the experience gained in the r
17、ound robin carried out in 1999. The methods available at that time and used in the assessment are listed below (see also Clause 12). - EN ISO 14596 WDXRF (with internal standard) 1; - ISO/CD 20846 UVF 2; - ISO/CD 20847 EDXRF 3; - ISO/CD 20884 WDXRF (without internal standard) 4; - prEN ISO/DIS 16591
18、 Oxidative microcoulometry 5. 3 Samples Eight petrol and ten diesel samples with sulfur content from 1 mg/kg to 55 mg/kg were included in the round robin. Two samples were blends of FAME in diesel (5 % (V/V) FAME) and were included in the round robin to examine the applicability of the methods to FA
19、ME blends according to EN 590 specification 6. Two samples (one petrol and one diesel) were considered as “quality control” samples, to check for accuracy of results, as sulfur content had been determined using Isotope Dilution Mass Spectrometry (ID-MS), the technique employed for the certification
20、of element content in reference materials. 4 Laboratories European laboratories were contacted to obtain a satisfactory participation for the methods listed above. A total of 102 applications from 11 countries were received. Table 1 shows the distribution of the techniques employed by the laboratori
21、es that effectively participated in the round robin. Table 1 Final list of participants WDXRF a EDXRF UVF Microcoulometry High Power Lower Power Polarised Non-polarised Laboratories 40 15 6 17 39 20 aHigh power instruments 3kW, lower power instruments 1 kW. CEN/TR 15139:20056 5 Evaluation of round r
22、obin results The results received by the participants were firstly examined by the project leaders of each method for possible non compliance to the test methods (analytical outliers). The experts looked at the technical issues on the basis of the information submitted by the participants. They did
23、not make judgement on the basis of the values submitted or on a statistical basis. 6 Statistical analysis The statistical process used for the examination of the round robin was the methodology indicated in EN ISO 4259 7. Only linear models were chosen for the evaluation of repeatability and reprodu
24、cibility. Global precision for all fuel samples or specific precision for each fuel was calculated according to the provisions already given in the precision clauses of the methods. The following results were obtained (X is the mean of two results expressed in mg/kg): EN ISO 14596 1: All fuels (high
25、 power) r = 0,039 9X + 1,59 R = 0,067 2X + 2,69 All fuels (lower power) r = 0,026 9X + 2,69 R = 0,042 7X + 4,27 ISO/CD 20846 2: Petrol r = 0,063 1X + 0,35 R = 0,174 9X + 0,96 Diesel r = 0,055 3X + 0,55 R = 0,112 0X + 1,12 ISO/CD 20847 3: Petrol r = 0,031 2X + 9 R = 0,111 6X + 11 Diesel r = 0,018 8X
26、+ 8 R = 0,016 9X + 12 The precision data of ISO/CD 20847 were obtained by combining the results of the first and second round robin, to cover the complete sulfur range for the scope of the method. ISO/CD 20884 4: All fuels (high power) r = 0,024 8X + 1,7 R = 0,120 1X + 1,9 All fuels (lower power) r
27、= 0,040 8X + 2,0 R = 0,088 9X + 4,5 prEN ISO/DIS 16591 5: All fuels r = 0,045 6X + 1,14 R = 0,101 8X + 2,55 CEN/TR 15139:20057 7 Comparison between methods and accuracy The comparison, using EN ISO 14596 as the reference method, showed statistically significant differences between the methods, but t
28、hese differences were certainly very small and could be ignored from a practical point of view. The accuracy of the methods was verified using the “quality control samples”. The results obtained for each test method for these samples were within the limits of the repeatability. 8 Applicability to FA
29、ME blends The maximum difference observed between the sulfur content of the pure diesel fuel and that of the corresponding 5 % (V/V) FAME blends was in any case lower than the repeatability of each method. 9 Conclusions 9.1 EN ISO 14596: The precision found in the round robin for both high and lower
30、 power systems was better than that stated in the method, that refers to high power systems only. 9.2 ISO/CD 20846: The precision was better for diesel fuel than for petrol, as observed for other methods. The test method was found suitable for the determination of sulfur content 3 mg/kg (according t
31、o 2R rule of EN ISO 4259). 9.3 ISO/CD 20847: A substantial improvement was achieved with ISO/CD 20847 compared to EN ISO 8754 8, and also compared to the results obtained in the 1998-1999 round robin. The current precision showed that the method is suitable for sulfur contents down to around 30 mg/k
32、g. The results indicated that a new generation of EDXRF instruments (polarised source) has the potential to be used at lower sulfur content ( 10 mg/kg). 9.4 ISO/CD 20884: The results confirmed the precision stated in the method for low sulfur content, and showed that the new method is suitable for t
33、he determination of sulfur content 5 mg/kg (according to 2R rule of EN ISO 4259), when using high power instruments. On the other hand, the results showed that lower power instrumentation might not achieve adequate precision for sulfur contents of 10 mg/kg and below. 9.5 prEN ISO/DIS 16591: The prec
34、ision found is quite close that stated in current ISO/CD 16591. 10 Recommendations for updating EN 228 and EN 590 According to the results obtained in the round robin, WG 27 recommended the following actions for the 2004 versions of the European specifications on petrol (EN 228 9 ) and diesel (EN 59
35、0 6 ): EN ISO 14596 to be replaced by ISO/DIS 20884. The new method does not require the addition of the internal standard and shows satisfactory precision at 50 mg/kg and 10 mg/kg; EN 24260 10 to be replaced by ISO/DIS 20846. UVF method, also based on sample combustion, shows satisfactory precision
36、 at 50 mg/kg and 10 mg/kg; EN ISO 8754 to be replaced by ISO/DIS 20847. EN ISO 8754 cannot be used at 350 mg/kg and 150 mg/kg (2R rule of EN ISO 4259 is not fulfilled), while ISO/DIS 20847 can determine down to 30 mg/kg sulfur. CEN/TR 15139:20058 11 Test method publication The new precision statemen
37、ts of ISO/CD 20846, ISO/CD 20847 and ISO/CD 20884 were incorporated in the test methods, and the revised versions were forwarded to ISO TC/28 for ballot as ISO/DIS. The three test methods developed by WG 27 were published by ISO and CEN in March 2004 2 4, without technical changes from the prEN ISO/
38、DIS text that could have impacted the precision, nor the conclusions as indicated in this document. CEN/TR 15139:20059 Acknowledgements CEN/TC 19 acknowledges the following people and organizations for their contribution to this guide: a) P. Tittarelli, Stazione Sperimentali Combustibili, Italy, as
39、author of this guide, b) C. Do Marco, Total France, as project leader for the UV Fluorescence method, c) R. Hensel, Shell Deutschland, project leader for the Wavelength Dispersive XRF method, d) J. Crighton, BP UK, project leader for the Energy Dispersive XRF method, e) H. Read, BP UK, project leade
40、r of the actual interlaboratory study and former WG convenor, and f) the CEN/TC 19/WG 27 “Elemental analysis of petroleum and related products“ experts, for guidance and assistance. CEN/TR 15139:200510 Bibliography 1 EN ISO 14596:1998, Petroleum products - Determination of sulfur content Wavelength
41、dispersive X- ray fluorescence spectrometry (ISO 14596:1998, incl. Cor. 1:1999) 2 EN ISO 20846:2004, Petroleum products Determination of sulfur content of automotive fuels Ultraviolet fluorescence method (ISO 20846:2004) 3 EN ISO 20847:2004, Petroleum products Determination of sulfur content of auto
42、motive fuels Energy-dispersive X-ray fluorescence spectrometry (ISO 20847:2004) 4 EN ISO 20884:2004 Petroleum products Determination of sulfur content of automotive fuels Wavelength-dispersive X-ray fluorescence spectrometry (ISO 20884:2004) 5 prEN ISO 16591:2000, Petroleum products Determination of
43、 the sulfur content Oxidative microcoulometry method (ISO/DIS 16591:2000) 6 EN 590:2004, Automotive fuels Diesel Requirements and test methods 7 EN ISO 4259, Petroleum products Determination and application of precision data in relation to methods of test (ISO 4259:1992, including Cor. 1: 1993) 8 EN
44、 ISO 8754:1995, Petroleum products Determination of sulfur content Energy-dispersive X-ray fluorescence spectrometry (ISO 8754:1995) 1)9 EN 228:2004, Automotive fuels Unleaded petrol Requirements and test methods 10 EN 24260:1994, Petroleum products and hydrocarbons Determination of sulfur content W
45、ickbold combustion method (ISO 4260:1987) 1) Meanwhile replaced by EN ISO 8754:2003. CEN/TR 15139:2005blankPD CEN/TR 15139:2005 BSI 389 Chiswick High Road London W4 4AL BSI British Standards Institution BSI is the independent national body responsible for preparing British Standards. It presents the
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