DIN EN 15779-2013 Petroleum products and fat and oil derivates - Fatty acid methyl esters (FAME) for diesel engines - Determination of polyunsaturated ( 4 double bonds) fatty acid .pdf

1、December 2013 Translation by DIN-Sprachendienst.English price group 8No part of this translation may be reproduced without prior permission ofDIN Deutsches Institut fr Normung e. V., Berlin. Beuth Verlag GmbH, 10772 Berlin, Germany,has the exclusive right of sale for German Standards (DIN-Normen).IC

2、S 75.160.20!%*vT“2078349www.din.deDDIN EN 15779Petroleum products and fat and oil derivates Fatty acid methyl esters (FAME) for diesel engines Determination of polyunsaturated ( 4 double bonds) fatty acidmethyl esters (PUFA) by gas chromatography;English version EN 15779:2009+A1:2013,English transla

3、tion of DIN EN 15779:2013-12Minerallerzeugnisse und Erzeugnisse aus pflanzlichen und tierischen Fetten und len Fettsure-Methylester (FAME) fr Dieselmotoren Bestimmung von mehrfach ungesttigten ( 4 Doppelbindungen)Fettsuremethylestern (PUFA) mittels Gaschromatographie;Englische Fassung EN 15779:2009+

4、A1:2013,Englische bersetzung von DIN EN 15779:2013-12Produits ptroliers et produits drivs des corps gras Esters mthyliques dacides gras (EMAG) pour moteurs diesel (gazole) Dtermination de la teneur en esters mthyliques dacides gras polyinsaturs 4 doubles liaisons) (PUFA) par chromatographie en phase

5、 gazeuse;Version anglaise EN 15779:2009+A1:2013,Traduction anglaise de DIN EN 15779:2013-12SupersedesDIN EN 15779:2010-02www.beuth.deDocument comprises 12 pagesIn case of doubt, the German-language original shall be considered authoritative.11.13“e(DIN EN 15779:2013-12 2 A comma is used as the decim

6、al marker. National foreword This document (EN 15779:2009+A1:2013) has been prepared by Technical Committee CEN/TC 19 “Gaseous and liquid fuels, lubricants and related products of petroleum, synthetic and biological origin” (Secretariat: NEN, Netherlands). The responsible German body involved in its

7、 preparation was the Normenausschuss Materialprfung (Materials Testing Standards Committee), Working Committee NA 062-06-32-0 UA Prfung von FAME. Amendments This standard differs from DIN EN 15779:2010-02 as follows: a) in Clause 5 “Reagents and materials”, the notes have been revised; b) Figure 1 h

8、as been updated. Previous editions DIN EN 15779: 2010-02 EUROPEAN STANDARD NORME EUROPENNE EUROPISCHE NORM EN 15779:2009+A1 September 2013 ICS 75.160.20 Supersedes EN 15779:2009 English Version Petroleum products and fat and oil derivates - Fatty acid methyl esters (FAME) for diesel engines - Determ

9、ination of polyunsaturated ( 4 double bonds) fatty acid methyl esters (PUFA) by gas chromatography Produits ptroliers et produits drivs des corps gras - Esters mthyliques dacides gras (EMAG) pour moteurs diesel (gazole) - Dtermination de la teneur en esters mthyliques dacides gras polyinsaturs ( 4 d

10、oubles liaisons) (PUFA) par chromatographie en phase gazeuse Minerallerzeugnisse und Erzeugnisse aus pflanzlichen und tierischen Fetten und len - Fettsure-Methylester (FAME) fr Dieselmotoren - Bestimmung von mehrfach ungesttigten ( 4 Doppelbindungen) Fettsuremethylestern (PUFA) mittels Gaschromatogr

11、aphie This European Standard was approved by CEN on 22 September 2009 and includes Amendment 1 approved by CEN on 5 August 2013. CEN members are bound to comply with the CEN/CENELEC Internal Regulations which stipulate the conditions for giving this European Standard the status of a national standar

12、d without any alteration. Up-to-date lists and bibliographical references concerning such national standards may be obtained on application to the CEN-CENELEC Management Centre or to any CEN member. This European Standard exists in three official versions (English, French, German). A version in any

13、other language made by translation under the responsibility of a CEN member into its own language and notified to the CEN-CENELEC Management Centre has the same status as the official versions. CEN members are the national standards bodies of Austria, Belgium, Bulgaria, Croatia, Cyprus, Czech Republ

14、ic, Denmark, Estonia, Finland, Former Yugoslav Republic 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 C

15、OMMITTEE FOR STANDARDIZATION COMIT EUROPEN DE NORMALISATION EUROPISCHES KOMITEE FR NORMUNG CEN-CENELEC Management Centre: Avenue Marnix 17, B-1000 Brussels 2013 CEN All rights of exploitation in any form and by any means reserved worldwide for CEN national Members. Ref. No. EN 15779:2009+A1:2013: E

16、EN 15779:2009+A1:2013 (E) 2 Contents Page Foreword 3 Introduction .4 1 Scope 5 2 Normative references 5 3 Principle 5 4 Apparatus .5 5 Reagents and materials 6 6 Sampling .6 7 Procedure .7 8 Calculation 7 9 Expression of results 8 10 Precision .8 10.1 General 8 10.2 Repeatability, r .8 10.3 Reproduc

17、ibility, R 9 11 Test report 9 Bibliography . 10 DIN EN 15779:2013-12EN 15779:2009+A1:2013 (E) 3 Foreword This document (EN 15779:2009+A1:2013) has been prepared by Technical Committee CEN/TC 19 “Gaseous and liquid fuels, lubricants and related products of petroleum, synthetic and biological origin”,

18、 the secretariat of which is held by NEN. This European Standard shall be given the status of a national standard, either by publication of an identical text or by endorsement, at the latest by March 2014, and conflicting national standards shall be withdrawn at the latest by March 2014. Attention i

19、s 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 rights. This document includes Amendment 1 approved by CEN on 5 August 2013. This document supersedes EN

20、15779:2009. The start and finish of text introduced or altered by amendment is indicated in the text by tags !“. According to the CEN/CENELEC Internal Regulations, the national standards organisations of the following countries are bound to implement this European Standard: Austria, Belgium, Bulgari

21、a, Croatia, Cyprus, Czech Republic, Denmark, Estonia, Finland, Former Yugoslav Republic of Macedonia, France, Germany, Greece, Hungary, Iceland, Ireland, Italy, Latvia, Lithuania, Luxembourg, Malta, Netherlands, Norway, Poland, Portugal, Romania, Slovakia, Slovenia, Spain, Sweden, Switzerland, Turke

22、y and the United Kingdom. DIN EN 15779:2013-12EN 15779:2009+A1:2013 (E) 4 Introduction Polyunsaturated fatty acid methyl esters are considered as a critical component in FAME since they show a low stability against oxidation and polymerization reactions. The specification on polyunsaturated ester co

23、ntent is needed in FAME and biodiesel products to limit the content of polyunsaturated FAME with more than three double bonds. At the time of the first FAME fuel specifications no test method was available for such a complicated determination in terms of identification and quantification, so technic

24、al work has been done in a joint working group with CEN/TC 307 before any standardisation steps could be taken. The method has been prepared by the partners of the project “BIOScopes“ (Lot 1, Task a) funded by the European Commission, DG TREN, with the purpose to execute a Pan-European round robin t

25、est to determine the precision data and the usability of this new and other revised determination methods for FAME. DIN EN 15779:2013-12EN 15779:2009+A1:2013 (E) 5 1 Scope This European Standard specifies a method for the determination of the polyunsaturated ( 4 double bonds) fatty acid (PUFA) methy

26、l esters content of fatty acid methyl ester (FAME) as a whole between 0,6 % (m/m) and 1,5 % (m/m). The method covers the predominant four polyunsaturated fatty acid methyl esters of eicosatetraenoic acid (C 20:4 (n-6), eicosapentaenoic acid (C 20:5 (n-3), docosapentaenoic acid (C 22:5 (n-3), and doc

27、osahexaenoic acid (C 22:6 (n-3). Studies have indicated that based on the linearity of results from this European Standard, PUFA methyl esters can be determined in FAME in the range between 0,3 % (m/m) to 3,0 % (m/m). However, the precision was not established in that range, as no samples within the

28、 upper ranges where included in the final interlaboratory test (see 10.1). Although the method is applicable to all uses, it is predominantly for FAME for use in diesel engines. NOTE 1 For the purposes of this document, the term “% (m/m)” is used to represent the mass fraction of a material. NOTE 2

29、This European Standard is based on A.O.C.S Official Method Ce 1b-89 1. 2 Normative references !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 refere

30、nces, the latest edition of the referenced document (including any amendments) applies.“ EN ISO 3170, Petroleum liquids Manual sampling (ISO 3170:2004) EN ISO 3171, Petroleum liquids Automatic pipeline sampling (ISO 3171:1988) 3 Principle Determination of the percentage of polyunsaturated ( 4 double

31、 bonds) fatty acid (PUFA) methyl ester present in FAME is done by gas chromatography/FID detection using internal calibration with C 23:0 methyl ester. The theoretical detector correction factors relative to C 23:0 internal standard for different poly-unsaturated ester types are applied to the analy

32、tical data for optimum accuracy. 4 Apparatus 4.1 Capable gas chromatograph, consisting of a capillary injection system (preferable split mode at a split ratio of 1:50), a flame ionization FID detector and the following: 4.1.1 Injector, temperature 220 C. 4.1.2 Detector, temperature 275 C. 4.1.3 Oven

33、 temperature profile, initial temperature 150 C, initial hold time 1 min; program rate 15 C/min up to 200 C; 2 C/min up to 250 C final temperature. 4.1.4 Capillary column, fused silica; 30 m in length, 0,25 m film thickness and 0,20 mm to 0,32 mm internal diameter. The liquid phase shall be bonded C

34、arbowax or an equivalent polyethylene glycol type. DIN EN 15779:2013-12EN 15779:2009+A1:2013 (E) 6 NOTE HPINNOWax, SUPELCOWAX 10, Carbowax, CP-WAX 52CB and DBwax have been found satisfactory. 4.1.5 Carrier gas, hydrogen or helium of 99,99 % purity or better. 4.1.6 Additional gas, depending on instru

35、mentation (compressed air, oxygen), but of high purity. An oxygen scrubber is mandatory with Wax-type columns. 4.1.7 Data analysis, according to the corresponding instrumentation software. 4.2 Screw-cap vials, of 1,5 ml content, with leak-tight (Teflon) lined caps. 4.3 Volumetric pipette or syringe,

36、 of 1 ml content. 4.4 Pasteur type pipettes. 4.5 Volumetric flask, of 25 ml content. 4.6 Analytical balance, capable to weigh at 0,1 mg. 5 Reagents and materials 5.1 Tricosanoic acid methyl ester (C 23:0), !minimum purity of 99,0 % (m/m)“; internal standard (IS) solution, to be stored at + 4 C and t

37、o be warmed up to room temperature before use. !NOTE 1“ If the storage conditions are maintained carefully, the solution has been found to be stable up to one month without any degradation losses. !NOTE 2 Standards are available from Nu Chek Prep (www.nu-).1)“ 5.2 Heptane, analytical grade. 5.3 Refe

38、rence PUFA methyl esters, C 20:4 (n-6) (eicosatetraenoic acid), C 20:5 (n-3) (eicosapentaenoic acid), C 22:5 (n-3) (docosapentaenoic acid, and C 22:6 (n-3) (docosahexaenoic acid), !with a minimum purity of 99,0 % (m/m)“. !NOTE Standards are available from Nu Chek Prep (www.nu-).1)“ 6 Sampling Unless

39、 otherwise specified in the commodity specification, samples shall be taken as described in EN ISO 3170 or EN ISO 3171 and/or in accordance with the requirements of national standards or regulations for the sampling of the product under test. If it is necessary to determine PUFA methyl esters direct

40、ly out of marine oils, the sample preparation should be in accordance with EN ISO 5509 2. ! 1) Nu Chek Prep(www.nu-) is an example of a suitable product available commercially. This information is given for the convenience of users of this European Standard and does not constitute an endorsement by

41、CEN of these products.“ DIN EN 15779:2013-12EN 15779:2009+A1:2013 (E) 7 7 Procedure 7.1 Weigh approx. 25 mg to the nearest 0,1 mg of internal standard (5.1) into a 25 ml volumetric flask (4.5) and fill up to mark with heptane (5.2). 7.2 Weigh approx. 100 mg to the nearest 0,1 mg of FAME into a 1,5 m

42、l vial (4.2). 7.3 Pipette 1 ml aliquot of the Internal Standard (5.1) into the vial, cap and mix thoroughly. 7.4 Inject 1 l of solution under appropriate gas chromatographic conditions (see 4.1). 8 Calculation The PUFA content, C, expressed in mass percentage, is calculated according: ( )100ISISISPU

43、FAPUFA=mVCCACFA(1) where: AISis the peak area of the internal standard C 23:0; APUFAare the peak areas of the polyunsaturated fatty acid methyl esters (see Figure 1); CISis the concentration in mg/ml of the internal standard; CFPUFAare the theoretical correction factors of the corresponding PUFA met

44、hyl esters (see below); VISis the volume in ml of the internal standard added; m is the mass in mg of the sample (see 7.2). Identification of the polyunsaturated fatty acid methyl esters has to be done by using the reference PUFA methyl esters (5.3). The following theoretical detector correction fac

45、tors (CFPUFA) relative to C 23:0 shall be applied to the calculation for optimum accuracy (see also Figure 1): a) 20:4 n-6: 0,99; b) 20:5 n-3: 0,98; c) 22:5 n-3: 0,98; and d) 22:6 n-3: 0,97. DIN EN 15779:2013-12EN 15779:2009+A1:2013 (E) 8 ! “ Key 1 C 20:4 (n-6) methyl ester 2 C 20:5 (n-3) methyl est

46、er 3 Internal standard C 23:0 methyl ester 4 C 22:5 (n-3) methyl ester 5 C 22:6 (n-3) methyl ester Figure 1 Reference chromatogram based on salmon oil methyl esters 9 Expression of results Report the PUFA content as mass percentage, in % (m/m), rounded to the nearest 0,01. 10 Precision 10.1 General

47、The precision given was derived from statistical analysis by EN ISO 4259 3 of the results of interlaboratory testing of a matrix of biodiesel fuels including 6 types PUFA methyl esters from fish oil blended in FAME in the range of 0,1 % (m/m) to 1,5 % (m/m). NOTE The interlaboratory testing and the

48、statistical evaluation are detailed in 4. 10.2 Repeatability, r The difference between two test results, obtained by the same operator with the same apparatus under constant operating conditions on identical test material would in the long run, in the normal and correct operation of the test method,

49、 exceed the following value in absolute value in only one case in twenty: r = 0,07 % (m/m). DIN EN 15779:2013-12EN 15779:2009+A1:2013 (E) 9 10.3 Reproducibility, R The difference between two single and independent test results, obtained by different operators working in different laboratories on identical test material, would in the long run, in the normal and correct operation of the test method, exceed the following value in only one case in twen