CEN/TR 15160:2005

SLOVENSKI STANDARD
01-oktober-2005
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Petroleum and related products - Applicability of diesel fuel test methods for Fatty Acid
Methyl Esters (FAME) - Information and results on round robin tests
Mineralölerzeugnisse und verwandte Produkte - Anwendbarkeit von Prüfverfahren für
Diesel-Kraftstoffe auf Fettsäure-Methylester (FAME) - Informationen und Ergebnisse aus
Ringversuchen
Produits pétroliers et produits connexes - Applicabilité des méthodes d'essai des
carburants diesel (gazoles) aux esters méthyliques d'acides gras (EMAG) - Information
et résultats relatifs aux essais circulaires
Ta slovenski standard je istoveten z: CEN/TR 15160:2005
ICS:
75.160.20 7HNRþDJRULYD Liquid fuels
2003-01.Slovenski inštitut za standardizacijo. Razmnoževanje celote ali delov tega standarda ni dovoljeno.

TECHNICAL REPORT
CEN/TR 15160
RAPPORT TECHNIQUE
TECHNISCHER BERICHT
August 2005
ICS 75.160.20
English Version
Petroleum and related products - Applicability of diesel fuel test
methods for Fatty Acid Methyl Esters (FAME) - Information and
results on round robin tests
Produits pétroliers et produits relié - Application des Mineralölerzeugnisse und verwandte Produkte -
méthodes d'examination de gazole en Methyl Acides Graz Anwendbarkeit von Prüfverfahren für Diesel-Kraftstoffe auf
(UMAG) - Information ét résultats d'examination inter- Fettsäure-Methylester (FAME) - Informationen und
laboratoir Ergebnisse aus Ringversuchen
This Technical 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, Luxembourg, Malta, Netherlands, Norway, Poland, Portugal, Slovakia,
Slovenia, Spain, Sweden, Switzerland and United Kingdom.
EUROPEAN COMMITTEE FOR STANDARDIZATION
COMITÉ EUROPÉEN DE NORMALISATION
EUROPÄISCHES KOMITEE FÜR NORMUNG
Management Centre: rue de Stassart, 36  B-1050 Brussels
© 2005 CEN All rights of exploitation in any form and by any means reserved Ref. No. CEN/TR 15160:2005: E
worldwide for CEN national Members.

Contents Page
Foreword .3
Introduction.4
1 Summary.5
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 participants 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
products 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 fuel.25
Annex E (informative) Report of the results of the round robin on 'determination of carbon 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 (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

Foreword
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 given to CEN by the European Commission and the European
Free Trade Association.
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 fuels – 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 and all other participants in CEN/TC 19/WG 26 "FAME related fuel test methods" (see Annex A) for their
contribution to this report.
1 Summary
One task under the European Mandate M/245 was to investigate the applicability of existing petroleum test method
standards for fatty acid methyl 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 fossil 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 & reproducibility),
WG 26 has done a major effort to validate all relevant test methods on request of the Task Force of WG 24 and
WG 25 dealing with the specifications.
2 Background
CEN has been asked by the Commission (Mandate M/245) to elaborate standards for fatty acid methyl esters
(FAME) to be used as sole fuel for heating and diesel engines and as an additive to mineral oil based fuels. This
work has been divided amongst two Technical Committees, of which CEN/TC 19 was responsible for determining
the applicability of already existing petroleum type test method standards to both pure FAME and to blends. This
included comparing precision data, generating new reproducibility and repeatability figures and developing new test
method standards if necessary.
For this task CEN/TC 19 has founded a separate working group with the following task: “Verification of applicability
to biodiesel (for use in diesel engines as well as for use as heating oil) of existing test methods (to be validated via
round robins) and development of new test methods, if necessary”. The convenor of this WG 26 was Mrs. Benassy
of Total (former ELF Antar), France. For a list of participants in this WG, see Annex A.
The work of WG 26 was aimed at the drafting of amendments for existing ISO standards (with test methods for
fossil 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 & reproducibility), WG 26 has organised
several round robin studies. Besides that it had several consultations with other WG's responsible for existing or
revising of test methods and with the WG 24 (automotive diesel) and WG 25 (heating fuels) dealing with the
specifications.
Scope of the work was investigating the applicability of each test method towards FAME as 100 % diesel fuel. The
repeatability and reproducibility were determined if the test method was applicable. Furthermore, it was determined
whether the method was also applicable to blends of FAME and diesel fuel.
This Technical Report gives an overview of the work of WG 26 and of the results in relation to applicability of each
test method and the determined precision data, giving the basic conclusions and data. A full report with all data per
test method has been presented within CEN/TC 19. This report is the basis of two standards:
1. EN 14213:2003, Heating fuels — Fatty acid methyl esters (FAME) — Requirements and test methods
2. EN 14214:2003, Automotive fuels — Fatty acid methyl esters (FAME) for diesel engines — Requirements and
test methods
Moreover, the results of the study by WG 26 have been input in the revision of the automotive diesel fuel
specification standard (EN 590).
NOTE For the purposes of this document, the terms “% (m/m)” and “% (V/V)” are used to represent respectively the mass
fraction and the volume fraction.
3 Basis of the work
The following list of standards has been investigated in the period 1999 until 2002:
 EN 116:1997, Diesel and domestic heating fuels – Determination of cold filter plugging point
 EN 590: 1998, Automotive fuels – Diesel – Requirements and test methods
 EN 12662:1998, Liquid petroleum products – Determination of contamination in middle distillates
 EN 12634:1998, Petroleum products and lubricants – Determination of acid number – Non-aqueous
potentiometric titration method
 prEN 14078:2001, Liquid petroleum products – Determination of fatty acid methyl esters (FAME) in middle
distillates – Infrared spectroscopy method
 EN 22719:1993, Petroleum products and lubricants – Determination of flash point - Pensky-Martens closed
cup method (ISO 2719:1988)
 EN 23015:1994, Petroleum products – Determination of cloud point (ISO 3015:1992)
 EN ISO 2160:1998, Petroleum products – Corrosiveness to copper – Copper strip test (ISO 2160:1998)
 EN ISO 3104:1998/C2:1999, Petroleum products – Transparent and opaque liquids – Determination of
kinematic viscosity and calculation of dynamic viscosity (ISO 3104:1997)
 EN ISO 3405:2000, Petroleum products – Determination of distillation characteristics at atmospheric pressure
(ISO 3405:2000)
 EN ISO 3675:1998, Crude petroleum and liquid petroleum products – Laboratory determination of density –
Hydrometer method (ISO 3675:1998)
2)
 prEN ISO/DIS 3679:2001 , Petroleum products - Determination of flash point - Rapid equilibrium closed cup
method
 EN ISO 4259:1995, Petroleum products – Determination and application of precision data in relation to
methods of test (ISO 4259:1992/Cor.1: 1993)
 EN ISO 5165:1998, Petroleum products – Determination of ignition quality of diesel fuels – Cetane engine
method (ISO 5165:1998)
 EN ISO 10370:1995, Petroleum products – Determination of carbon residue – Micro method (ISO 10370:
1993)
 EN ISO 12185:1996, Crude petroleum and petroleum products – Determination of density – Oscillating U-tube
method (ISO 12185:1996)
 EN ISO 12205:1996, Petroleum products – Determination of the oxidation stability of middle distillate fuels
(ISO 12205:1995)
 EN ISO 12937:2000, Petroleum products – Determination of water – Coulometric Karl Fisher titration method
(ISO 12937:2000)
These standards are referred to in the document as either the EN ISO or the ISO number (given in brackets), but here the
correct reference of the actual, updated standard is given.
2 Succeeded by EN ISO 3679:2004, Petroleum products - Determination of flash point - Rapid equilibrium closed cup method
(ISO 3679:2004)
 EN ISO 13759:1996, Petroleum products – Determination of alkyl nitrate in diesel fuels – Spectrometric
method (ISO 13759:1996)
 EN ISO 14596:1998/C1:1999, Petroleum products – Determination of sulfur content – Wavelength-dispersive
X-ray fluorescence spectrometry (ISO 14596:1998/C1:1999)
 prEN ISO/DIS 20846:2002, Petroleum products – Determination of total sulfur content of liquid petroleum
products – Ultraviolet Fluorescence Method
 ISO 3016:1994, Petroleum products – Determination of pour point
 ISO 3987:1994, Petroleum products – Lubricating oils and additives – Determination of sulfated ash.
 ISO 6245:2001, Petroleum products – Determination of ash
 ISO 12156-1:1997, Diesel fuels – Assessment of lubricity using the high-frequency reproducing rig (HFRR) –
Part 1: Test method (including Cor. 1:1998)
 ASTM D 1160:99, Distillation of Petroleum Products at Reduced Pressure
4 Details of the round robin
After having considered all existing (statistical) data in the standards, WG 26 has decided for which test methods
an inter-laboratory study was necessary. For some methods the data were sufficient, for others the decision on
applicability was made after internal discussions.
For each of the remaining test methods a round robin study was initiated and a project leader from WG 26 was
assigned. The number of participating laboratories changed with each standard, going from 7 to 15. There was a
variety in countries but from France, Italy, Austria and Germany there were always laboratories participating.
Samples from actual FAME products from different feed-stocks were supplied by ITERG, France. Distribution of the
samples, together with the correct protocol, was organised by WG 26. All data received from the labs were
statistically treated according to EN ISO 4259.
For pure FAME, inter-laboratory testing has been completed for the following determination methods : density
(EN ISO 3675 and EN ISO 12185), viscosity (EN ISO 3104), flash point (prEN ISO/DIS 3679), sulfur content
(EN ISO 20846), carbon residue (EN ISO 10370), cetane number (EN ISO 5165), ash content (ISO 3987), water
content (EN ISO 12937), copper corrosion (EN ISO 2160), acid number (EN 12634). For 5 % blends of FAME in
diesel fuel only testing on determination of alkyl nitrate content (EN ISO 13759) has been done by WG 26. For
sulfur content (five methods) and cetane number (one 5 % blend sample tested among four petroleum type
samples) studies have been done by other CEN/TC 19 groups, while they were conducting their round robin
investigations.
5 Results
All results are compiled in Table 1 and Table 2. The conclusions on applicability, repeatability and reproducibility
are given for pure FAME and one for blends of 5 % in diesel. The results of the sulfur study on the blends have
been left out of the table, as this is part of the report of WG 27. However, their results have been incorporated in
the drafting of the two FAME specification standards.
Detailed reports on studies on flash point, distillation, carbon residue, corrosiveness to copper and the FAME
detection method are given in Annex B to Annex H. Other short reports are not available.

In brackets the documents which have been used as a basis for the lab-protocol are given. After the study these standards
might have been updated.
Table 1 - Details of inter-laboratory test programme
Methods for pure FAME
Standard Applicable Precision Repeatability Reproducibility Comments
similar to
a
std
3 3
EN ISO 3675 Yes Yes 0,000 5 g/cm 0,001 2 g/cm Conversion tables
Density at 15 ºC applicable
3 3
EN ISO 12185 Yes Yes 0,2 kg/m 0,5 kg/m Conversion tables not
Density at 15 ºC applicable
EN ISO 3104 Yes Yes 0,11 % 1,8 %
Viscosity at 40 ºC
EN 22719 No
Flash point (Pensky-
Martens)
0,9
prEN ISO/DIS 3679 Yes r: Yes 0,022X °C 15 °C - Electronic detection
Flash point R: No - 2ml test portion
(equilibrium)
EN ISO 20846 Yes Yes 0,028 5 X + 2 0,108 8 X + 2
Sulfur content (X in mg/kg) (X in mg/kg)
2/3 2/3
EN ISO 10370 Yes Yes 0,077 X 0,245 X 10% residue obtained

Carbon residue (X in %) (X in %) by ASTM D1160 run
at 10 mmHg
EN ISO 5165 Yes r: No 2,4 5
Cetane number R: Yes
0,85 0,.85
ISO 3987 Yes Yes 0,06 X 0,142 X
Ash content
(sulphated)
0,5 0,5
EN ISO 12937 Yes Yes 0,0187 4 X 0,0687 7 X

Water content (X in %) (X in %)
EN ISO 2160 Yes No value Not a numerical result
Copper corrosion
EN ISO 3405 No
Distillation
ASTM D 1160 Yes Yes 2 °C 3 °C run at 10mmHg
Distillation (90% distilled) (90% distilled)
ISO 3016 Yes
Pour point
EN 116 Yes  As stated by
CFPP CEN/TC19/WG14
EN 12662   Wait for method
Total contamination revision
EN 12634 Yes r: Yes 0,05 X 0,065+ 0,281 X
(X in mg KOH/g) (X in mg KOH/g)
Acid number R: No
a
if YES: repeatability and reproducibility quoted are the one of the reference standard,
if NO: repeatability and reproducibility quoted are the one obtained during the inter-laboratory testing
Table 2 - Details of inter-laboratory test programme
Methods for blends of FAME, (up to 5 % volume)
Standard Applicable Precision Repeatability Reproducibility Comments
a
similar to std
3 3
EN ISO 3675 Yes Yes 0,000 5 g/cm 0,001 2 g/cm No inter-lab. test
Density at 15 ºC
3 3
EN ISO 12185 Yes Yes 0,2 kg/m 0,5 kg/m No inter-lab. test
Density at 15 ºC
EN ISO 3104 Yes Yes 0,11% 1,8% No inter-lab. test
Viscosity at 40 ºC
EN 22719 Yes Yes 2 °C 3,5 °C Procedure A.
Flash point (P.M.) (at 101°C) (at 101°C) Decision made after
short study
EN ISO 14596 Yes Yes 0,037 X + 1,9 0,063 X + 3,2
Sulfur content (mg/kg) (mg/kg)
2/3 2/3
EN ISO 10370 Yes Yes 0,077 X 0,245 X No inter-lab. test

Carbon residue (X in %) (X in %)
EN ISO 5165 Yes Yes 0,9 4,3
Cetane number at 52 at 52
ISO 6245 Yes Yes  Decision made after
Ash content short study
0,5 0,5
EN ISO 12937 Yes Yes 0,0187 4 X 0,068 77 X No inter-lab. test

Water content (X in %) (X in %)
EN ISO 2160 Yes No value Decision made after
Copper corrosion short study
EN ISO 13759 Yes Yes  Decision made after
Alkyl nitrate short study
ISO 12156-1 Yes
Lubricity
EN ISO 3405 Yes Yes  Decision made after
Distillation short study
EN ISO 12205 Yes Yes  No inter-lab. test
Oxidation stability
ISO 3016 Yes Yes  As advised by
Pour point CEN/TC19/WG14
EN 23015 Yes Yes  As advised by
Cloud point CEN/TC19/WG14
EN 116 Yes Yes  As advised by
CFPP CEN/TC19/WG14
EN 12662   Wait for method
Total contamination revision
EN 14078 Yes r = 2,5 g/l X = 100 g/l
Fame content by IR R = 7,7 g/l
X > 100 g/l
R = 12,7 g/l
a
if YES: repeatability and reproducibility quoted are the one of the reference standard,
if NO: repeatability and reproducibility quoted are the one obtained during the inter-laboratory testing
6 Conclusion
6.1 Pure FAME
Flash point by EN 22719 and distillation by EN ISO 3405 where found to be not applicable to FAME samples after
an internal study.
All other methods were found applicable to FAME samples with similar precision data as for petroleum products,
except for:
- Cetane number: r is significantly higher
- Acid number: R is significantly higher
- Flash point (prEN ISO/DIS 3679): R is significantly higher
No improvement of these methods could be expected in the time given by the Mandate, but information has been
given to the different method working groups for possible future work.
No inter-laboratory test has been conducted on cold properties (EN 116), following advice of CEN/TC19/WG14.
Pour point and cloud point methods where considered to be applicable.
6.2 5 % blends of FAME in diesel fuel
Considering the work done on pure FAME and the known method on diesel fuel, the experts agreed on the fact that
the following methods where applicable with the same precision data than already stated in the standard, without
running an inter-laboratory testing:
 density (EN ISO 3675 and EN ISO 12185),
 viscosity (EN ISO 3104),
 flash point (EN 22719),
 carbon residue (EN ISO 10370),
 cetane number (EN ISO 5165),
 ash content (ISO 6245),
 water content (EN ISO 12937),
 copper corrosion (EN ISO 2160),
 distillation (EN ISO 3405),
 pour point (ISO 3016),
 cloud point (EN 23015),
 lubricity (ISO 12156-1), and
 oxidation stability (EN ISO 12205).
EN ISO 13759 (determination of alkyl nitrate content) was tested and found adequate to be used on products
containing FAME. Cetane number was tested by another WG and found adequate, too.
Annex A
(informative)
List of participants in working group 26 activities
The following people have been active in WG 26 "FAME related fuel test methods" and in the underlying laboratory
work.
Name Company
Mrs. M.F. BENASSY TOTALFINAELF (Convenor)
P. FERRARI EURON
Dr. T. FEUERHELM DIN/FAM
Dr. Ing. J CONNEMANN OELMUEHLE LEER CONNEMANN GmbH Co
Dipl. Ing. B. BLAICH Robert BOSCH GmbH FV/FLA
Dr. J. FISCHER AG QM Biodiesel e.V.
Dr. Ing. K. SCHARMER GET - Gesellschaft Für Entwicklungstechnik
Dr. Ing. TH. GOTTSCHAU FNR
X. MONTAGNE IFP
Mrs. N. DAVIAS RENAULT Technocentre
Ms. U. KIISKI FORTUM Oil and Gas OY, Technology Centre
D. KARNER OMV
Dr. F. van DIEVOET BfB Oil Research
Dott. P. TITTARELLI Stazione Sperimentale Combustibili
Dott. M. VIGO UNIONE PETROLIFERA
M.L. DAANE SHELL Research and Technology Centre
J. WOLDENDORP SHELL Research and Technology Centre
Dr. M. HUTTER IMU
B. DUFRENOY NOVAOL
Ms. F. LACOSTE ITERG
A. FRASER NOVAOL
R.W. HOOKS Shell Research Ltd. / R.W. HOOKS consultancy
F. TORT TOTALFINAELF
Ing. U. JANISCH OELMUEHLE LEER CONNEMANN GmbH Co
W. DORMER ARAL AG
J. PHIPPS INSTITUTE OF PETROLEUM
L. BURMAN SGS SWEDEN AB
U. OSTAN SAYBOLT SWEDEN AB
J. BERG SWEDISH Farmer Supply and Crop Marketing Association
D. MEHLIS PETRO LAB GmbH
T. WILHARM ASG
B. CAHILL PSA CITROEN/PEUGEOT
F. MORDRET ITERG
F. HEGER OMV
A. PHILIPPSEN OELMUEHLE LEER CONNEMANN GmbH Co
J. MUELLER_BELAU Deutsche Shell AG
Dr. J. BOSSE VOLKSWAGEN AG
T.J. BERRYMAN TIM-BER Support
S. PAGLIANTI NOVOAL Srl
M. MARCHI IES Raffineria di Mantova
G. ARALDI TAMOIL
S. CATALANO SGS Redwood
G. LO BAIDO Esso Technical Services
G. PINELLI Stazione Sperimentale Combustibili
F. AVELLA Stazione Sperimentale Combustibili
E. COLOMBO SARPOM
Mrs. C. PUEL ELF ANTAR / TOTALFINAELF

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)
B.1 Scope
In this round robin the applicability of test method EN ISO 3679 "Determination of flash point - Rapid equilibrium
close cup method" towards FAME as 100 % diesel fuel is investigated. The precision, repeatability and
reproducibility, for this product versus the stated precision for petroleum products were also investigated.
NOTE This study has been supervised by Mr. M.L. Daane and Mr. J. Woldendorp.
B.2 Assessed standard documents
EN 22719:1993, Petroleum products and lubricants – Determination of flash point – Pensky-Martens closed cup
method (ISO 2719:1988)
prEN ISO/DIS 3679:2002 – Determination of flash point - Rapid equilibrium closed cup method (ISO/DIS
3679:2002)
EN ISO 4259:1995, Petroleum products – Determination and application of precision data in relation to methods of
test (ISO 4259:1992, including Cor.1: 1993).
B.3 Background
The actual test method at the date of investigation for flash point for EN 590 diesel was EN 22719, the Pensky-
4)
Martens closed cup test method . The applicability of this test method for 100 % FAME has been studied and
found unsuitable for two reasons.
1) the precision of this method for products containing trace amounts of highly flammable material in relatively
high flash point material is very poor;
NOTE The flash point for fatty acid methyl esters is high (> 160 °C). Methanol is used for the manufacturing of 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 for 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, because 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 revision (EN ISO 2719) has been published in November 2002.
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 giving
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 mandatory 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
b
a
166 (134 ) 160 (118 ) 126 116
a a
166 (132 ) 154 (122 ) 126 120
b
b
168 (120 ) 156 (118 ) 124 122
b a
(122 ) 160 (126 ) 128 124
140 130
134 134
a
very weak flash observed, flame blown out, no flame observed
b
flame blown out (sucked into the cup)
B.4 Pre-study for round robin with prEN ISO/DIS 3679
B.4.1 Set-up
The suitability 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, 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 flashpoints 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 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 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, 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 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 when using 4 ml test
portions. For those samples a 2 ml test portion is required according to the test method. However, for samples
containing ca. 0,17 % (m/m) to ca. 0,25 % (m/m), flashpoints > 100 °C will be expected when using a 2 ml test
portion, so a 4 ml test portion is required, etc.
Obviously 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, irrespective of flashpoint. The
fixation of the test portion to either 2 ml or 4 ml was up for debate.

p
Effect of methanol content, apparatus and sample intake on FP
Flash point
App.1, 2ml
Flash point
App.2, 2ml
Apparatus 1
Flash point
App.2, 4ml
Flash point
Apparatus 2
App.1, 2ml
P.M.- check
ISO 3679
ISO 2719
0 0,05 0,1 0,15 0,2 0,25 0,3 0,35 0,4 0,45 0,5 0,55
Methanol, %m/m
Figure B.1 — EN ISO 3679 at 100 % FAME
Flash point, °C
B.4.2 2 ml test portion
pro: the flashpoint limit for transportation regulation is around 65 °C, which is based 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 samples containing ca. >0,17 % (m/m) methanol, flashpoint will be <100 °C, so original test
method is not performed accordingly, and
2) there is no comparison with other fuels, for which generally 2 ml sample volume is required.
After advice from ISO/TC 28 and ISO/TC 35, it was decided to specify a 2 ml test portion for the flashpoint
round robin.
B.5 Details of the round robin
A total of 11 laboratories in 4 countries (i.e. United Kingdom, Germany, France and The Netherlands) took
part in the round robin. 10 laboratories used the Seta Flash apparatus and 1 laboratory used the Normalab
NPV 210 apparatus. The sample set comprised two types of FAME, i.e. rapeseed (EMC, samples 1-5) and
sunflower (EMT, samples 6-10). These FAME’s were first purged with nitrogen to remove any methanol and
were successively spiked with 0 % (m/m), 0,05 % (m/m), 0,1 % (m/m), 0,2 % (m/m) and 0,5 % (m/m)
methanol. The FAME batches were sampled into 250 ml flasks. All participants received a test protocol and
prEN ISO/DIS 3679 (see B.6). The round robin results were statistically treated by EN ISO 4259.
B.6 Round robin protocol specific measurement instructions
In addition to the requirements of prEN ISO/DIS 3679, the following measurement instructions apply:
 2 ml test portions are used for all flash points tests, even those carried out at temperatures greater than
100 °C.
 The occurrence of a flash is to be detected by the flash point tester’s automatic detector only.
 Determine the flash point to the nearest 0,5 °C.
 Perform duplicate flash point determinations. Also report the atmospheric pressure at each test. Fill the
duplicate results and the atmospheric pressures in the reporting table.
 For indicative purposes only, the samples’ flashpoints are in the neighbourhood of:
Samples 1 and 6: 180 °C
Samples 2 and 7: 170 °C
Samples 3 and 8: 150 °C
Samples 4 and 9: 110 °C
Samples 5 and 10: 60 °C
B.7 Results
The results are displayed in Table B.2. Lab No. 6 was not able to test all samples due to instrument failure.
Lab No. 10 used an apparatus suitable for flashpoint testing up to 110 °C, so it was not able to test all the
samples. The results from lab No. 4 were clearly outliers; on inquiry, this lab ignored the protocol and applied
a 4 ml test portion instead of the required 2 ml test portion.
Table B.2 — Round robin results
Sample 1 2 3 4 5 6 7 8 9 10
L1 Result 1 180 169,5 159,5 115 61,5 179,5 169,5 159 114 62
Result 2 179 169,5 157,5 113,5 60 179 170 157,5 114 63
L2 Result 1 177,5 172 166,5 117,6 64,2 176,5 173,5 162 120,6 63,2
Result 2 177,5 172,5 166 118,6 64,7 177 174 162 121,1 63,7
L3 Result 1 181 173 156 105 59 181 171 190 109 57
Result 2 182 174 156 105 59 182 173 193 109 58
L4 Result 1 164 151 140 80 57 175 152 107 42 50
Result 2 164 153 142 78 56 174 150 106 41 50
L5 Result 1 184 177 166,5 126 63 184 175 165 122 61,5
Result 2 184 177,5 167 127 63 183,5 175,5 165,5 123 62
L6 Result 1 173,5 164  174 159,5
Result 2 175 165  172,5 159
L7 Result 1 181 173 160 116,5 64,5 180 171 158 114 63
Result 2 180,5 174 159 116,5 64 179,5 171,5 157 113,5 63,5
L8 Result 1 179,7 176,3 169,8 141,3 65,9 183,4 175,8 168,9 143,9 65,4
Result 2 184,2 176,3 169,3 149,3 64,4 183,4 179,4 168,4 139,4 61,3
L9 Result 1 179,5 177 173 153 89 178,5 174 171,5 164 81,5
Result 2 179,5 177,5 173 152,5 90 178 174,5 171 164,5 81
L10 Result 1   85   85
Result 2   85   85
L11 Result 1 176,5 166,5 161,5 112 71,5 177,5 170,5 161 116,5 65
Result 2 176,5 168 161 111,5 71,5 178 171 161,5 116 65
Samples 1-5: EMC (rapeseed) Samples 1 and 6: 0 % (m/m) methanol
Samples 6-10: EMT (sunflower) Samples 2 and 7: 0,05 % (m/m) methanol
Sample 3 and 8: 0,1 % (m/m) methanol
Sample 4 and 9: 0,2 % (m/m) methanol
Sample 5 and 10: 0,5 % (m/m) methanol

Since labs No. 4 and 10 were not using the right protocol or the right apparatus, they were excluded from the
statistical analysis. The statistical evaluation was performed using EN ISO 4259.
Lab No. 3 was detected as an outlier in the results of sample 8. Lab No.8 was detected as an outlier in the
results of samples 1, 4, 7, 9 and 10. Lab No. 9 was detected as an outlier in the results of samples 4, 5, 9 and
10. The statistical analysis is summarised in Table B.3.
Table B.3 — Statistical analysis of flashpoint round robin
Sample
1 2 3 4 5 6 7 8 9 10
Average
179,2 172,4 163,9 115,4 64 179,3 172,4 163,5 116,1 62,2
r 1,8 1,9 2 2,2 2,1 1,7 2,2 1,9 1,4 1,7
r %
1,0 1,1 1,2 1,9 3,3 0,9 1,3 1,2 1,2 2,7
R
10,3 14,7 19,9 26 13,8 10,9 7,2 17,9 18,1 9,4
R %
5,7 8,5 12,1 22,5 21,6 6,1 4,2 10,9 15,6 15,1
n
8 9 8 6 7 9 7 7 6 6
Ex. Lab V
L8  L8  L8 L8 L8
Ex. Lab M
L9 L9 L6 L3 L9 L9
The repeatability can be considered as constant over the interval 62°C - 179°C. The global repeatability is
estimated at 1,9 °C, which is somewhat higher than the repeatability stated in prEN ISO/DIS 3679 for
0,9
petroleum and related products (i.e. 0,022 X for flashpoint > 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 high-flyer at 26 °C. The reproducibilities found for this round robin are significantly higher than
0,9
the reproducibilities stated in prEN ISO/DIS 3679 (i.e. 0,083 X for flashpoints > 70 °C). The R is maximal
around the 0,2 % (m/m) methanol concentration (samples 4 and 9) and decreases (significantly) going 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 reproducibility 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 exceptional 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 addressed 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 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 method’s repeatability. The
derived reproducibility, however, was significantly higher than the method’s reproducibility.
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
Reduced 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 Pressure
C.3 Details of the round robin
A total of 5 laboratories in 4 countries took part in the round robin. They are labelled 1 to 5.
4 laboratories used automatic instrument and 1 laboratory used a manual instrument (laboratory N°3).
5 FAME samples were supplied by Elf. Their composition is given in Table C.1.
Table C.1 — Composition of FAME samples
Sample Sample Sample Sample Sample Sample
WI 18-1 WI 18-2 WI 18-3 WI 18-4 WI 18-5
Type of 100 % FAME 100 % FAME 100 % FAME 100 % FAME 100 % FAME
FAME from Rape from Sun Flower from Soya from animal from used oil
(Tallow)
Country Europe Europe United Stated United States United States

In addition to the requirements of ASTM D 1160 the following measurement instructions were applied:
- Test carried out at a pressure of 10 mm Hg and at a uniform rate of 6 ml/min to 8 ml/min.
- For each sample, the test has been carried out in duplicate.
- Results reported rounded at 0,1°C.
These recommendations came out from an applicability study done by Mr. M.L. Daane and Mr. M. Hutter.
Handling of the samples was done according to EN ISO 3170.
The statistical treatment of this round robin was performed according to EN ISO 4259.
C.4 Results
Table C.2 — Results of test method ASTM D1160 for different laboratories and samples
Labs Sample Sample Sample Sample Sample
WI 18.1 WI 18.2 WI18.3 WI 18.4 WI 18.5
1 Initial 317,9 280,5 305 304,4 295,3
5 % 348 346 345,5 336,1 338,2
10 % 348,7 347,7 345,7 338,8 341
20 % 349 348,1 346,8 341,9 342
30 % 349,3 348,8 347,9 343,9 340,4
40 % 350,1 349,6 348,2 345,2 342,1
50 % 350,1 349,3 349 346,7 344,4
60 % 351 350,3 349,8 348 345,6
70 % 351,5 350,7 350,4 350 347,9
80 % 351,9 351,4 351 351,6 350
90 % 353,3 352,3 352,4 353,7 352,6
95 % 358,5 354,5 353,8 356,4 354,4
Final 436,6 398,6 416 404,6 393,9
1 Initial 316,9 279 313,1 306,3 290,2
5 % 348,5 345,9 345,5 337,1 337,7
10 % 349 347,4 345,8 338,9 340,1
20 % 349,1 348,4 344,8 341,8 338,7
30 % 350,1 348,8 345,4 343,5 340,7
40 % 350,6 349,1 347,3 345 342,1
50 % 350,9 349,1 348,3 346,1 344,3
60 % 351,6 350,1 348,7 347,4 345,9
70 % 351,9 351 349,9 349,4 347,8
80 % 352,6 351,6 350,6 351,1 350,2
90 % 354,4 352,3 351,5 353,8 352,6
95 % 359,2 355,2 352,7 356,4 354,4
Final 450,1 401,6 411,7 404,4 395,7
2 Point Initial 136,2 144,5 336,7 316,2 312,2
5 % 347,8 346,3 345,5 339,4 337,9
10 % 348,7 347 345,7 340,4 339,7
20 % 348,6 348,1 347 341,9 342,5
30 % 349,5 348,7 347,4 343,5 343,2
40 % 349,9 349 348,1 345 344,9
50 % 390,2 349,4 348,7 346,4 346,5
60 % 350,6 349,9 349,5 348 348
Labs Sample Sample Sample Sample Sample
WI 18.1 WI 18.2 WI18.3 WI 18.4 WI 18.5
70 % 351,2 350,3 350 349,8 349,5
80 % 352 350,8 350,7 351,4 351,2
90 % 353,3 351,9 351,8 353,7 353,5
Final 437,4 406,5 416,7 408,3 398,9
2 Initial 140,7 143,4 326,6 311,3 303,8
5 % 347,9 346,4 344,7 338,3 338
10 % 348,7 347,6 345,5 339,8 339,2
20 % 349,1 348 347,1 342,1 342
30 % 349,4 348,4 347,6 343,4 343,4
40 % 350 348,9 348,2 344,8 344,8
50 % 350,3 349,5 348,7 346,4 346,2
60 % 350,6 349,4 349,4 348 347,9
70 % 351,2 350,8 350,1 349,8 349,5
80 % 351,7 350,9 350,8 351,4 351,4
90 % 353,1 352 351,7 353,4 353,9
Final 437,4 406,3 419,9 408,6 420,4
3 Initial 328,2 291,1 292,3 287,5 315,1
5 % 350,7 347,2 347,2 341,2 335,3
10 % 350,7 348,3 348,3 344,8 341,2
20 % 351,9 349,5 348,3 346 344,8
30 % 351,9 350,7 349,5 347,2 347,2
40 % 353,1 350,7 350,7 348,3 347,2
50 % 353,1 350,7 350,7 349,5 348,3
60 % 353,1 350,7 350,7 350,7 348,3
70 % 354,2 351,9 350,7 353,1 350,7
80 % 354,2 351,9 351,9 353,1 353,1
90 % 356,6 353,1 353,1 355,4 355,4
Final 381,2 357,8 362,5 368,3 364,8
3 Initial 319,9 294,7 295,9 286,3 304,3
5 % 350,7 349,5 348,3 341,2 341,2
10 % 351,9 349,5 349,5 343,6 342,4
20 % 351,9 350,7 349,5 344,8 343,6
30 % 351,9 350,7 350,7 346 344,8
40 % 351,9 351,9 350,7 348,3 344,8
50 % 353,1 351,9 350,7 349,5 346
60 % 353,1 351,9 350,7 350
...