1、raising standards worldwideNO COPYING WITHOUT BSI PERMISSION EXCEPT AS PERMITTED BY COPYRIGHT LAWBSI Standards PublicationLiquid petroleum products Middle distillates and fatty acidmethyl ester (FAME) fuels andblends Round Robin report on applicability of Rapid SmallScale Oxidation Test methodPD CEN
2、/TR 16366:2012National forewordThis Published Document is the UK implementation of CEN/TR 16366:2012.The UK participation in its preparation was entrusted to Technical CommitteePTI/13, Petroleum Testing and Terminology.A list of organizations represented on this committee can be obtained onrequest t
3、o its secretary.This publication does not purport to include all the necessary provisions of acontract. Users are responsible for its correct application. The British Standards Institution 2012Published by BSI Standards Limited 2012ISBN 978 0 580 76807 1ICS 75.160.20Compliance with a British Standar
4、d cannot confer immunity fromlegal obligations.This Published Document was published under the authority of theStandards Policy and Strategy Committee on 31 May 2012.Amendments issued since publicationAmd. No. Date Text affectedPUBLISHED DOCUMENTPD CEN/TR 16366:2012TECHNICAL REPORT RAPPORT TECHNIQUE
5、 TECHNISCHER BERICHT CEN/TR 16366 March 2012 ICS 75.160.20 English Version Liquid petroleum products - Middle distillates and fatty acid methyl ester (FAME) fuels and blends - Round Robin report on applicability of Rapid Small Scale Oxidation Test method Produits ptroliers liquides - Carburants et m
6、langes des distillats moyens et des esters mthyliques dacides gras (EMAG) - Rport de Round Robin de lapplication de la dtermination methode doxydation acclree petite chelleFlssige Petroleum Produkte - Mitteldestilat und Fettsuremethylester (FAME) Kraftstoffen und Mischungen - Round Robin Rapport der
7、 Applikation des beschleunigten kleinen Mastaben Oxidationstests This Technical Report was approved by CEN on 21 February 2012. 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, Den
8、mark, Estonia, Finland, 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
9、NORMALISATION EUROPISCHES KOMITEE FR NORMUNG Management Centre: Avenue Marnix 17, B-1000 Brussels 2012 CEN All rights of exploitation in any form and by any means reserved worldwide for CEN national Members. Ref. No. CEN/TR 16366:2012: EPD CEN/TR 16366:2012CEN/TR 16366:2012 (E) 2 Contents Page Forew
10、ord 31 Scope 42 Test method background 43 Description of the samples .43.1 RRT 2007-231 .43.2 RRT 2008-231 .53.3 RRT 2010-231 .74 Round Robin Instructions .75 Description of equipment .86 Form of data reports 87 Statistical data summary 8Annex A (informative) Comparative study protocol for oxidation
11、 stability test methods .9Annex B (informative) Precision estimation for PetroOxy test . 12Bibliography . 23PD CEN/TR 16366:2012CEN/TR 16366:2012 (E) 3 Foreword This document (CEN/TR 16366:2012) has been prepared by Technical Committee CEN/TC 19 “Gaseous and Liquid fuels, lubricants and related prod
12、ucts 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
13、rights. This document presents background to EN 16091. PD CEN/TR 16366:2012CEN/TR 16366:2012 (E) 4 1 Scope This Technical Report describes a series of round robin test campaigns for precision estimation of EN 16091. Furthermore, this document includes a summary of the results of the RRTs (see Clause
14、 7 and Annex B). NOTE The identities of the participating laboratories are not displayed in this report. They are, however filed with the original RRT documentation at the CEN/TC 19/JWG1 secretariat. 2 Test method background The Rapid Small Scale Oxidation Test method (RSSOT1, EN 16091, 1) is develo
15、ped as an additional or parallel test method for the determination of oxidation stability (EN 14112 2 and EN 15751 3) in FAMEs according to EN 14214 5 and diesel fuel biodiesel blends 4. Three precision studies (2007-231, 2008-231, 2010-231) have been executed in CEN/TC 19/JWG 1 in order to access t
16、he test method precision in terms of repeatability, r, and reproducibility, R. NOTE In addition, more RR-testing has been executed in order to compare results with those from other tests like EN 14112, EN 15751 or acid number after ageing. These additional test results are not subject of this precis
17、ion report but are reported elsewhere. It shall be noted that the Rancimat2and PetroOXY1results exhibit a good correlation, obviously indicating that both methods provide good estimations of oxidation stability. The three precision studies (2007-231, 2008-231, 2010-231) contained the following: RRT
18、2007-231 pre- study with 10 samples (“B2” “B30”) in 5 laboratories; RRT 2008-231 RRT with 23 samples (“B0” “B100”) in 19 laboratories; RRT 2010-231 RRT with 7 samples testing the influence of EHN in 11 labs (EHN = Cetane improver = 2-ethyl hexyl nitrate). The draft version of EN 16091 was sent to th
19、e laboratories as the requested test procedure along with the Round Robin instructions. The same test method procedure was used is the three different RRTs. Since no significant modifications had been made which could be precision-relevant, this test procedure remained the same as specified in the f
20、inal standard (EN 16091:2011). 3 Description of the samples 3.1 RRT 2007-231 There were 10 samples used for the pre-study in 2007. Each sample was randomized, blind coded and distributed by the coordinator of this RRT. The following samples had been agreed by the CEN/TC 307/WG 1, 10 Bx samples: 1 x
21、B2, 1 x B4, 1 x B5, 1 x B7, 1 x B8, 1 x B12, 1 x B15, 1 x B20, 1 x B30, 1 x B100. The samples have been prepared by blending of one B0 and one B100 (RME/SME (90/10). Information of the fuel properties are not provided. 1) Also known as the PetroOXY test. PetroOXY is the trade name of a product suppl
22、ied by Petrotest, Instruments GmbH R is the reproducibility (the difference between two single and independent test results, obtained by different operators working in different laboratories on identical test material); X represents the mean of the two results expressed in min, rounded to the neares
23、t 0,01 min. Some more statistical detail and data is given in Annex B. The statistical review was provided by several precision experts of DIN FAM (Fachausschuss Minerall- und Brennstoffnormung des NMP (FAM). PD CEN/TR 16366:2012CEN/TR 16366:2012 (E) 9 Annex A (informative) Comparative study protoco
24、l for oxidation stability test methods IMPORTANT Before starting sample measurements, read this protocol carefully and follow the instructions. A.1 Scope and overview The main purpose of this CEN Round Robin is to determine the precision of three proposed Oxidation Stability test methods: EN 15751 (
25、Rancimat2) method, JAMA (Delta Acid Number) method and PetroOXY1)method. A second objective is to determine if any correlations exist between any of the measured properties of the methods. The specific consideration of this study is to find a useful method which is able to predict the oxidation stab
26、ility for pure mineral oil diesel (B0) and different bio-diesel blends (B5, B10, B30). The Rancimat and PetroOXY methods will also make measurements on pure FAME (B100) materials. Precision will be determined in accordance with EN ISO 4259. The correlations between methods will be determined by addi
27、tional statistical means. A.2 Round Robin sample reception Along with the PetroOXY test method protocol (dated XX/XX/XX) you will receive: a set of 23 samples with unique codes; 50 plastic pipettes; 100 Oring seals; 1 Petrotest verification fluid; an instruction manual. You will be provided with a u
28、nique laboratory code to preserve confidentiality. The laboratory code and the designated sample number and its origin are known only to the round robin programme coordinator. A computer programme has randomly generated the testing order and no two laboratories have the same order. Upon receipt of t
29、he samples, please do the following: unpack the samples from the box; check the samples containers for any signs of damage or leakage; if there is any, please contact the programme manager and add all information indicated on the label glued to the sample container; as soon as possible, store the sa
30、mples away from direct sunlight and less than +25 C is recommended. PD CEN/TR 16366:2012CEN/TR 16366:2012 (E) 10 A.3 Test conditions for the round robin Please refer to the attached copy of the short instruction manual (13-3000K.doc 3). Settings for the round robin tests: test program: DIESEL; test
31、temperature: 140 C; filling pressure: 700 kPa (Oxygen); sample amount: 5 ml; remove the previous sample by means of a pipette or similar device; remove the used “O-ring” seal after each test and discard. NOTE To avoid contamination of the new test, it is necessary to discard the used “Oring” seal, b
32、ecause it might be soaked with oxidation products from the previous test. IMPORTANT Only the O-ring seals delivered together with the test samples shall be used for the test. As a solvent for the removal of oxidation residues from the test vessel ethanol of approx. 95 % (V/V) commercial available ha
33、s been found to be suitable and shall be used. The solvent shall be of suitable purity to leave no residue on the apparatus. Wipe the test sample cup, the seal groove and the cover of the test vessel with lint-free cleaning tissue soaked with solvent until free of gum or other oxidation residues. Al
34、low the test sample cup and cover to dry in air and visually inspect for cleanliness. Compressed air is generally unsuitable to speed up evaporation of solvent because it can contain traces of oil that could contaminate the next test. IMPORTANT Insert a new “O-ring” seal for every new test. Using a
35、new pipette which you have received together with the round robin samples for every new test, place 5 ml 0,5 ml of the sample into the test sample cup. Proceed further according the short instruction manual3). A.4 Testing Please ensure that test methods and manufacturers instructions are carefully f
36、ollowed. Make sure that the sample temperature is approximately ambient temperature prior opening the sample container. Before starting the testing of RR samples, run a test with the Petrotest verification fluid which is enclosed with the sample set. IMPORTANT This verification fluid shall be tested
37、 prior starting the tests with the RR samples. Make sure that the obtained result is within 1 h and 57 min 6 min. 3)The short instruction manual is available from the secretariat of CEN/TC 19/JWG 1 or Petrotest ().PD CEN/TR 16366:2012CEN/TR 16366:2012 (E) 11 If the result is outside the limits, then
38、 repeat the test with a fresh portion of the verification fluid. Report the value of the verification fluid in the RR protocol. If the result is still out of limits contact Petrotest at . NOTE Only one bottle of Petrotest verification fluid is supplied. The main point is to ensure the equipment is i
39、n quality control. A.5 Running the samples Only two tests shall be carried out on each sample and both results shall be included on the test results sheet. using fresh sample each time; same Operator; same equipment; new O-ring; new pipette for sample filling. On each sample container you will find
40、the Sample ID Code. Run the samples in the testing order as stated by the Programme Manager. It is quite important to run all tests on the same instrument with the same operator and as soon as possible after the first test (repeatable conditions). In any case report the results of two consecutive ru
41、ns on each sample. The induction period shall be reported for each test in: hours:minutes:seconds TIME FRAME: 4 weeks maximum after receipt of the sample set. After completion of the Round Robin send the report form to: Thank you for your participation in this Round Robin. PD CEN/TR 16366:2012CEN/TR
42、 16366:2012 (E) 12 Annex B (informative) Precision estimation for PetroOxy test B.1 General This annex includes the evaluations on RRT 2007-231, RRT 2008-231 and RRT 2010-231. Responsible for the RRTs was CEN/TC 19/JWG 1. NOTE CEN/TC 19/JWG 1 was established in 2010. Responsible for the RRT in 2007
43、and 2008 was CEN/TC 19-CEN/TC 307 JWG, the predecessor of CEN/TC 19/JWG 1. B.2 Methods and calculation used All calculations were executed separately for each of the three exercises following the procedures, calculations and outlier tests from EN ISO 4259 6. Transformations were not executed because
44、 an evenly spaced set of test results over the measurement range could not be accomplished. For the final precision estimation, the results from RRT 2008-231 and RRT 2010-231 were combined into one precision statement. Since the block matrix resulting from the combination of the two separate RRTs ha
45、s only very little overlap, the precision functions r = f(x) and R = f(x) were calculated from the combined triplets (mean, r, R) as described below. Since no simple recipe was found to do outlier tests on the block matrix described above, alternative outlier criteria had to be agreed, which were: a
46、ccept (exclude) outliers as indicated in the two segregated RRT exercises; exclude samples with test results outside the agreed measurement range; exclude samples for which the reproducibility, R, is much higher than the reproducibility from the (sorted) neighbour samples. Separate and combined resu
47、lts are described and discussed on the following pages. B.3 RRT 2007-231 pre-study This clause gives an overview over the results of the pre-study RRT 2007-231. For this pre-study 10 samples in the range from “B2” to “B100” were used. Table B1 gives an overview over the oxidation stability of the sa
48、mples tested and the corresponding values for r, R and R%. (“R%” is the relative Reproducibility as percentage from the test result, calculated as 100 * R / X). PD CEN/TR 16366:2012CEN/TR 16366:2012 (E) 13 Table B.1 Results of the pre study RRT 2007-231 Sample Oxidation stabilitymin r R R % 1 25,90
49、1,299 8,184 31,6 2 37,57 3,582 3,386 9,0 3 38,03 1,246 7,108 18,7 4 64,44 1,642 18,193 28,2 5 52,09 2,109 1,556 3,0 6 48,14 1,366 1,669 3,5 7 68,43 2,623 11,152 16,3 8 48,50 1,578 9,291 19,2 9 14,19 0,347 3,796 26,8 10 80,44 1,339 15,982 19,9 Figure B.1 displays a good relationship between the accelerated oxidation method according to the modified Rancimat, EN 15751 (X-axis,
