SIST-TP CEN/TR 16366:2012

SLOVENSKI STANDARD
SIST-TP CEN/TR 16366:2012
01-junij-2012
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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
Fettsäure-Metyl-Ester (FAME) als Kraftstoff und als Blendkomponente für Dieselkraftstoff
- Ringversuchsbericht zur Anwendbarkeit des Verfahrens zur Bestimmung der
Oxidationsstabilität mit beschleunigtem Verfahren und kleiner Probenmenge
Produits pétroliers liquides - Distillats moyens, carburants à base d'esters méthyliques
d'acides gras (EMAG) et leurs mélanges - Rapport de l'essai interlaboratoires
concernant l'applicabilité de la méthode d'oxydation accélérée à petite échelle
Ta slovenski standard je istoveten z: CEN/TR 16366:2012
ICS:
75.160.20 7HNRþDJRULYD Liquid fuels
SIST-TP CEN/TR 16366:2012 en
2003-01.Slovenski inštitut za standardizacijo. Razmnoževanje celote ali delov tega standarda ni dovoljeno.

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SIST-TP CEN/TR 16366:2012

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SIST-TP CEN/TR 16366:2012


TECHNICAL REPORT
CEN/TR 16366

RAPPORT TECHNIQUE

TECHNISCHER BERICHT
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 pétroliers liquides - Carburants et mélanges des Flüssige Petroleum Produkte - Mitteldestilat und
distillats moyens et des esters méthyliques d'acides gras Fettsäuremethylester (FAME) Kraftstoffen und Mischungen
(EMAG) - Réport de Round Robin de l'application de la - Round Robin Rapport der Applikation des beschleunigten
détermination methode d'oxydation accéléree petite échelle kleinen Maßstaben 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, Denmark, 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
COMITÉ EUROPÉEN DE NORMALISATION

EUROPÄISCHES KOMITEE FÜR NORMUNG

Management Centre: Avenue Marnix 17, B-1000 Brussels
© 2012 CEN All rights of exploitation in any form and by any means reserved Ref. No. CEN/TR 16366:2012: E
worldwide for CEN national Members.

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Contents Page
Foreword .3
1 Scope .4
2 Test method background .4
3 Description of the samples .4
3.1 RRT 2007-231 .4
3.2 RRT 2008-231 .5
3.3 RRT 2010-231 .7
4 Round Robin Instructions .7
5 Description of equipment .8
6 Form of data reports .8
7 Statistical data summary .8
Annex A (informative) Comparative study protocol for oxidation stability test methods .9
Annex B (informative) Precision estimation for PetroOxy test . 12
Bibliography . 23

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Foreword
This document (CEN/TR 16366:2012) 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.
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 rights.
This document presents background to EN 16091.

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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 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
1
The Rapid Small Scale Oxidation Test method (RSSOT , EN 16091, [1]) is developed 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 the 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 precision report but
1
2
are reported elsewhere. It shall be noted that the Rancimat and PetroOXY results 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 2007-231 Æ pre- study with 10 samples (“B2” . “B30”) in 5 laboratories;
 RRT 2008-231 Æ RRT with 23 samples (“B0” . “B100”) in 19 laboratories;
 RRT 2010-231 Æ 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 the 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 final 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 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 supplied by Petrotest, Instruments GmbH &
Co, Germany. This information is given for the convenience of users of this European Technical Report and does not
constitute an endorsement by CEN of the product named.
2) Rancimat is the trade name of a product, model 743, supplied by Metrohm AG, Switzerland and an example of suitable
equipment available comercially. This information is given for the convenience of users of this European Technical Report
and does not constitute an endorsement by CEN of the product named.
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3.2 RRT 2008-231
There were 23 samples used for the RRT 2008-231. Each sample was randomized, blind coded and
distributed by the coordinator of this RRT.
The following samples were agreed by the CEN/TC 307/WG 1, in addition to 4 B100 Samples 19 Bxx samples
were used: 3 x B00, 6 x B05, 6 x B10 and 4 x B30. The 16 Bxx (B05, B10, B30) fuels have been prepared by
blending of one B00 and one B100 without the addition of other products (additives).
The properties of B0 are given in Table 1.
Table 1 — Diesel Fuel B0 properties for the RRT 2008-231
a b c
Property Unit Method Fuel 1 Fuel 2 Fuel 3
d d
  Swedish
EN 590 fuel EN 590 fuel
d
Class 1
Sulfur Content mg/kg EN 20846 8,6 9,8 < 3
FAME Content % (V/V) EN 14078 0 0,2 0
PAC % (m/m) EN 12916 5,5 2,4 0,1
a
Additised with lubricity- and CFPP improver — no cetane improver
b
EHN (Ethyl – Hexyl – Nitrate) < 100 mg/kg (IR test method)
c
No information
d
The suppliers of these fuels are available from the Secretariat of CEN/TC 19/JWG 1.
The properties of FAME (B100) are given in Table 2.
Table 2 — FAME (B100) properties for RRT 2008-231
a a a a
Parameter Unit Method FAME A FAME B FAME C FAME D
Composition  RME RME SME 75 % RME 60 %
PME 25 %
BHT mg/kg — No 1 000 No No
Oxidation h EN 15751 5,8 13,6 7,2 6,0
stability
a
The supplier of all FAMEs is available from the Secretariat of CEN/TC 19/JWG 1.
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The sample identification is given in Table 3.
Table 3 — Samples identification RRT 2008-231
Sample Fuel Type Sample Code Diesel fuel FAME used FAME content
Number used (% (V/V))
S1 B100 FAME A — — 100
S2 B100 FAME B — — 100
S3 B100 FAME C — — 100
S4 B100 FAME D — — 100
S5 B10 G1A10 1 A 10
S6 B30 G1A30 1 A 30
S7 B5 G1A5 1 A 5
S8 B10 G1B10 1 B 10
S9 B30 G1B30 1 B 30
S10 B5 G1B5 1 B 5
S11 B10 G1C10 1 C 10
S12 B30 G1C30 1 C 30
S13 B5 G1C5 1 C 5
S14 B10 G1D10 1 D 10
S15 B30 G1D30 1 D 30
S16 B5 G1D5 1 D 5
S17 B10 G2B10 2 B 10
S18 B10 G2A10 2 A 5
S19 B5 G2C5 2 C 5
S20 B5 G2D5 2 D 5
S21 B0 Fuel No.1 — — —
S22 B0 Fuel No.2 — — —
S23 B0 Fuel No.3 — — —
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3.3 RRT 2010-231
There were in origin 7 samples in the RRT 2010-231: 5 x B0 samples without Ignition Improver.
The suppliers of these fuels are available from the secretariat of CEN/TC 19/JWG 1. All B0 samples meet the
requirements of EN 590. The properties are given in Table 4.
Table 4 — Diesel fuels B0 properties
a a a a a
Property Unit Method B01 B02 B03 B04 B05
  Swedish Class 1 EN 590 EN 590 EN 590 EN 590
Sulphur mg/kg EN 20884 < 1 N/A 4,7 < 3 12
FAME % (V/V) EN 14078 < 0,05 N/A < 0,1 < 0,1 < 0,5
PAH % (m/m) EN 12916 0,1 N/A 4,8 1,4 2,1
IBP °C ISO 3405 N/A N/A 189 207,9 200,1
T95 °C ISO 3405 284 N/A 363 327,3 352,2
Flashpoint °C EN 2719 72 N/A 80,5 85 81,5
a
The suppliers of these fuels are available from the secretariat of CEN/TC 19/JWG 1.
In addition two B7 samples were used. One from a local station and one based on the B04 EN 590 sample
blended with RME up to a content of 7 % RME.
The B0 and B7 samples were prepared with different concentrations of EHN (EHN = Cetane improver =
2-ethyl hexyl nitrate), and the following sample set was used in eleven labs (see Table 5).
Table 5 — Sample set used
FUEL EHN 0 mg/kg EHN 500 mg/kg EHN 1000 mg/kg
B01 X X X
B02 X X X
B03 X X X
B04 X X X
B05 X X X
B7-1 X X —
B7-2 X X —
In total, there were 19 samples. Each sample was randomized, blind coded and distributed by the coordinator
of this RRT.
For each RRT and laboratory participant a verification fluid from the manufacturer was sent to check if the
used instruments were in the limit of a given oxidation stability value.
4 Round Robin Instructions
The test program instructions were sent to each participating laboratory (see Annex A).
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5 Description of equipment
The apparatus used by each laboratory in this study to develop a precision statement was the Petrotest,
1)
model PetroOXY .
6 Form of data reports
Each laboratory was provided with a data report form for collection of data. The filled out data report forms
were sent by the laboratories to the coordinator of these RRTs.
7 Statistical data summary
All precision values have been calculated following the procedures in EN ISO 4259 [6]. For the final precision
statement in EN 16091, the results from RRT 2008-231 and 2010-231 were combined, resulting in the
following precision formulae:
r = 0,288X + 0,496 5 (1)
R = 0,086 3X + 1,377 2
(2)
where
r is the repeatability (the difference between two test results, obtained by the same operator with the same
apparatus under constant operating conditions on identical test material);
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 nearest 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 Mineralöl- und Brennstoffnormung des NMP (FAM)).
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Annex A
(informative)

Comparative study protocol 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
1)
2)
Stability’ test methods: EN 15751 (Rancimat ) method, JAMA (Delta Acid Number) method and PetroOXY
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 stability
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 additional 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 O–ring seals;
 1 Petrotest verification fluid;
 an instruction manual.
You will be provided with a unique 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 the 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 samples away from direct sunlight and less than +25 °C is recommended.
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A.3 Test conditions for the round robin
3)
Please refer to the attached copy of the short instruction manual (13-3000K.doc ).
Settings for the round robin tests:
 test program: DIESEL;
 test 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 c
...