CEN TR 15160-2005 Petroleum and related products - Applicability of diesel fuel test methods for Fatty Acid Methyl Esters (FAME) - Information and results on round robin tests《石油及相.pdf

1、PUBLISHED DOCUMENTPD CEN/TR 15160:2005Petroleum and related products Applicability of diesel fuel test methods for Fatty Acid Methyl Esters (FAME) Information and results on round robin testsICS 75.160.20g49g50g3g38g50g51g60g44g49g42g3g58g44g55g43g50g56g55g3g37g54g44g3g51g40g53g48g44g54g54g44g50g49g

2、3g40g59g38g40g51g55g3g36g54g3g51g40g53g48g44g55g55g40g39g3g37g60g3g38g50g51g60g53g44g42g43g55g3g47g36g58PD CEN/TR 15160:2005This Published Document was published under the authority of the Standards Policy and Strategy Committee on 12 December 2005 BSI 12 December 2005ISBN 0 580 47336 8National fore

3、wordThis Published Document is the official English language version of CEN/TR 15160:2005.The UK participation in its preparation was entrusted to Technical Committee PTI/13, Petroleum testing and terminology, which has the responsibility to: aid enquirers to understand the text; present to the resp

4、onsible international/European committee any enquiries on the interpretation, or proposals for change, and keep UK interests informed; monitor related international and European developments and promulgate them in the UK.A list of organizations represented on this committee can be obtained on reques

5、t to its secretary.Cross-referencesThe British Standards which implement international or European publications referred to in this document may be found in the BSI Catalogue under the section entitled “International Standards Correspondence Index”, or by using the “Search” facility of the BSI Elect

6、ronic 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 a Published Document does not of itself confer immunity from legal obligations.Summary of pagesThi

7、s document comprises a front cover, an inside front cover, the CEN/TR title page, pages 2 to 42, an inside back cover and a back cover.The BSI copyright notice displayed in this document indicates when the document was last issued.Amendments issued since publicationAmd. No. Date CommentsTECHNICAL RE

8、PORTRAPPORT TECHNIQUETECHNISCHER BERICHTCEN/TR 15160August 2005ICS 75.160.20English VersionPetroleum and related products - Applicability of diesel fuel testmethods for Fatty Acid Methyl Esters (FAME) - Information andresults on round robin testsProduits ptroliers et produits reli - Application desm

9、thodes dexamination de gazole en Methyl Acides Graz(UMAG) - Information t rsultats dexamination inter-laboratoirMinerallerzeugnisse und verwandte Produkte -Anwendbarkeit von Prfverfahren fr Diesel-Kraftstoffe aufFettsure-Methylester (FAME) - Informationen undErgebnisse aus RingversuchenThis Technica

10、l Report was approved by CEN on 18 June 2005. It has been drawn up by the Technical Committee CEN/TC 19.CEN members are the national standards bodies of Austria, Belgium, Cyprus, Czech Republic, Denmark, Estonia, Finland, France,Germany, Greece, Hungary, Iceland, Ireland, Italy, Latvia, Lithuania, L

11、uxembourg, Malta, Netherlands, Norway, Poland, Portugal, Slovakia,Slovenia, Spain, Sweden, Switzerland and United Kingdom.EUROPEAN COMMITTEE FOR STANDARDIZATIONCOMIT EUROPEN DE NORMALISATIONEUROPISCHES KOMITEE FR NORMUNGManagement Centre: rue de Stassart, 36 B-1050 Brussels 2005 CEN All rights of ex

12、ploitation in any form and by any means reservedworldwide for CEN national Members.Ref. No. CEN/TR 15160:2005: E2 Contents Page Foreword 3 Introduction4 1 Summary5 2 Background.5 3 Basis of the work 6 4 Details of the round robin.7 5 Results.7 6 Conclusion 10 Annex A (informative) List of participan

13、ts in working group 26 activities .11 Annex B (informative) Report of the result of the round robin on determination of flash point using the rapid equilibrium close cup method (prEN ISO/DIS 3679)13 Annex C (informative) Report of the result of the round robin series on distillation of petroleum pro

14、ducts at reduced pressure (ASTM D 1160).20 Annex D (informative) Preliminary study on applicability of distillation of petroleum products at atmospheric pressure (EN ISO 3405) on blends of FAME in diesel fuel25 Annex E (informative) Report of the results of the round robin on determination of carbon

15、 residue via the micro method (EN ISO 10370).29 Annex F (informative) Report of the result of the round robin series on corrosiveness to copper via the copper strip test (EN ISO 2160).33 Annex G (informative) Report of the result of the round robin series on determination of fatty acid methyl esters

16、 (FAME) in middle distillates via infrared spectroscopy (prEN 14078)36 Annex H (informative) Influence of FAME origin on the measure of FAME content in mineral oil using prEN 14078 (Determination of fatty acid methyl esters (FAME) in middle distillates via infrared spectroscopy method).40 CEN/TR 151

17、60:20053Foreword This document (CEN/TR 15160:2005) 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. This document has been prepared under a mandate gi

18、ven to CEN by the European Commission and the European Free Trade Association. CEN/TR 15160:20054 Introduction This Technical Report gives the results of the round robin series of tests to evaluate different test methods on their compatibility on FAME which are referred to in: EN 14213: Heating fuel

19、s Fatty acid methyl esters (FAME) Requirements and test methods, and EN 14214: Automotive fuels Fatty acid methyl esters (FAME) for diesel engines Requirements and test methods. CEN/TC 19 acknowledges Mrs. M.F. Benassy from Total, all project leaders of each test method as indicated in the annexes a

20、nd all other participants in CEN/TC 19/WG 26 “FAME related fuel test methods“ (see Annex A) for their contribution to this report. CEN/TR 15160:200551 Summary One task under the European Mandate M/245 was to investigate the applicability of existing petroleum test method standards for fatty acid met

21、hyl esters (FAME). For this task CEN/TC 19 has founded a separate working group 26, which has validated 24 methods via round robins, including the development of new test methods. The work of CEN/TC 19/WG 26 was aimed at the drafting of amendments for existing ISO standards (with test methods for fo

22、ssil fuels). These amendments include the extension of the scope of the standards to biodiesel as well as the new precision data for biodiesel. To get these new precision data (repeatability NOTE The flash point for fatty acid methyl esters is high ( 160 C). Methanol is used for the manufacturing of

23、 FAME. Methanol is to a large extent removed from the final product, but remnants may still be present. The current specification for 100 % FAME allows 0,2 % (m/m) methanol max. Methanol as such has a flash point of 11 C. The use of non-equilibrium test methods for the determination of flash point f

24、or products containing trace amounts of highly flammable material (i.e. like FAME containing methanol) give poor repeatable test results due to i) non homogeneous heat transfer conditions, and ii) unfavourable V/L (Vapour/Liquid) conditions in the test cup. 2) optical detection is unsuitable, becaus

25、e methanol burns (and flashes) with a colourless, invisible flame. NOTE The flash point of FAME is caused by methanol, which gives a colourless, invisible flame. Even experienced operators have difficulties to detect this flame using their eyes. 4 At the date of publication of this document a revisi

26、on (EN ISO 2719) has been published in November 2002. CEN/TR 15160:200514 Both procedures A and B of EN 22719 were tested (see Table B.1). Procedure A gave repeatable results for FAME A, giving a greenish flame, caused by the FAME itself, i.e. all methanol is evaporated during the test without givin

27、g a flash. Procedure A gave poorly repeatable results for FAME B. Procedure B gave poorly repeatable results for FAME A and B. These results clearly demonstrated that EN 22719 is not applicable for 100 % FAME. Based on the above, the most suitable test method is an equilibrium test method with a man

28、datory non-optical flash detection. According to state of the art, EN ISO 3679 test method was considered to be most appropriate to run a round robin with. Table B.1 Flash point determinations of 100 % FAME by EN 22719 FAME A FAME B Procedure A Procedure B Procedure A Procedure B 166 (134 a) 160 (11

29、8 b) 126 116 166 (132 a) 154 (122 a) 126 120 168 (120b) 156 (118 b) 124 122 (122b) 160 (126a) 128 124 140 130 34 134 148 avery weak flash observed, flame blown out, no flame observed bflame blown out (sucked into the cup) B.4 Pre-study for round robin with prEN ISO/DIS 3679 B.4.1 Set-up The suitabil

30、ity of prEN ISO/DIS 3679 was initially tested at SRTCA. For this purpose a flash point tester was got on loan. The first tests showed that repeatable flashpoints results for FAME, containing methanol at several concentrations, can be achieved using this apparatus (see Figure B.1, flash point App. 1,

31、 2 ml). Therefore SRTCA decided to get possession of such a flash point tester. The samples, tested on apparatus 1, were also tested on this new apparatus (see Figure B.1, flash point App. 2, 2 ml). It was noted that the flashpoints were somewhat lower on apparatus 2. The curve through the flashpoin

32、ts is S-shaped; the left end site is limited by the flash point of FAME without methanol, the right end site is asymptotically limited by the flash point of methanol, the steep middle of the curve is around the methanol concentration of 0,2 % (m/m) (i.e. the current FAME specification). According to

33、 prEN ISO/DIS 3679, a specified volume is introduced into the test cup, which is maintained at the temperature of the estimated flash point of the material under test. After a specified time, a test flame is applied and the presence or absence of a flash observed. For flashpoints up to and including

34、 100 C, the specified test portion is 2 ml and the specified time is 1 minute; for flashpoints above 100 C the specified test portion is 4 ml and the specified time is 2 min. When 4 ml FAME is introduced instead of 2 ml, then much lower flashpoints are achieved (see Figure B.1, flash point, App. 2,

35、4 ml). Clearly the two curves through the flashpoints derived by 2 ml and 4 ml do not overlap, which is partly accounted for by differences in V/L (Vapour/Liquid) ratios: V/L for 2 ml and 4 ml test portions are 9/1 and 8/2 respectively. It was noted that the flashpoint results for 100 % FAME without

36、 methanol and 100 % FAME with methanol 0,5 % (m/m) were less sensitive to sample volume. Generally the flashpoints for 100 % FAME will be above 100 C, so a test portion of 4 ml is required. However, for samples containing more than ca. 0,17 % (m/m) methanol, the flashpoint will be 100 C will be expe

37、cted when using a 2 ml test portion, so a 4 ml test portion is required, etc. CEN/TR 15160:200515Obviously the test method cannot be used for FAME samples regarding the specified test portion. Hereto the test method had to be modified, i.e. specifying a single test portion for FAME samples, irrespec

38、tive of flashpoint. The fixation of the test portion to either 2 ml or 4 ml was up for debate. CEN/TR 15160:2005pEffect ofmethanol content,apparatus andsample intake on FP5055606570758085909510010511011512012513013514014515015516016517017518018500,050,10,150,20,250,30,350,40,450,50,55Methanol, %m/mF

39、lash point, CFlash pointApp.1,2mlFlash pointApp.2,2mlFlash pointApp.2,4mlFlash pointApp.1,2mlP.M.-checkISO3679ISO2719Apparatus1Apparatus2Figure B.1 EN ISO3679 at 100 %FAMECEN/TR 15160:200516 17 B.4.2 2 ml test portion pro: the flashpoint limit for transportation regulation is around 65 C, which is b

40、ased on 2 ml sample intake contra: flashpoint for 100 % FAME will generally be 110 C, so test method is not performed accordingly B.4.3 4 ml test portion pro: flashpoint for 100 % FAME will generally be 100 C, so the original test method is performed accordingly most of the time. contra: 1) for samp

41、les containing ca. 0,17 % (m/m) methanol, flashpoint will be 70 C) for flashpoints up to 150 C but is similar to the repeatability stated in prEN ISO/DIS 3679 at higher flashpoints. The reproducibility (R), however, cannot be considered as constant: it varies between 10 C and 20 C, except for one hi

42、gh-flyer at 26 C. The reproducibilities found for this round robin are significantly higher than the reproducibilities stated in prEN ISO/DIS 3679 (i.e. 0,083 X0,9 for flashpoints 70 C). The R is maximal around the 0,2 % (m/m) methanol concentration (samples 4 and 9) and decreases (significantly) go

43、ing to higher and lower concentrations. So there clearly is a relationship of R and the methanol (flashpoint) concentration. However, the standard software is not able to linearise this (Gaussian) relationship and consequently estimates the global reproducibility to 15,8 C. This implies that the rep

44、roducibility is significantly underestimated at the flash point specification (i.e. flashpoint at 0,2 % (m/m) methanol) and is significantly overestimated at higher or lower methanol concentrations. Based on the physics involved one might expect that this type of error distribution is not that excep

45、tional and will occur more frequently, certainly for any flash point caused by “trace contamination“ (mixing a high flash point material with trace amounts of low flash material). And it is exactly this situation, which has the most potential hazard in terms of flammability. This issue has been addr

46、essed to the standardization bodies (i.e. ASTM and ISO TC 28 / TC 35). B.8 Conclusion prEN ISO/DIS 3679 and its later successor, the test method for the determination of flashpoint, is applicable for 100 % FAME, when the following modifications are implemented: 1) For FAME samples, 2 ml test portion

47、 and 1 min stabilisation time are dictated. 2) The use of the flash point detector is mandatory for testing FAME samples. The repeatability derived for the round robin can be regarded as similar to the methods repeatability. The derived reproducibility, however, was significantly higher than the met

48、hods reproducibility. CEN/TR 15160:200520 Annex C (informative) Report of the result of the round robin series on distillation of petroleum products at reduced pressure (ASTM D 1160) C.1 Scope In this round robin the applicability of test method ASTM D 1160 “Distillation of Petroleum Products at Red

49、uced Pressure“ towards FAME as 100 % diesel fuel is investigated. The repeatability and reproducibility are determined if the test method was applicable. NOTE This study has been supervised by Mr. M.L. Daane. C.2 Assessed standard documents EN ISO 3170:1998, Petroleum liquids Manual sampling (ISO 3170:1988) EN ISO 4259:1995, Petroleum products Determination and application of precision data in relation to methods of test (ISO 4259:1992/Cor.1:1993) ASTM D1160 :95, Distillation of Petroleum Products at Reduced Press