Energy Fuels 2010, 24, 66936695

Published on Web 12/02/2010

: DOI:10.1021/ef1012193

Distillation Characteristics of Fatty Acid Ethyl Esters

Sigurd Schober, Melanie Wolf, and Martin Mittelbach*
Institute of Chemistry, University Graz, Heinrichstrasse 28, A-8010 Graz, Austria
Received September 9, 2010. Revised Manuscript Received November 25, 2010

to be slightly higher than for methyl esters.7-9 Sufficient onroad data focusing on ethyl ester behavior have not been
reported. However, it is expected that the higher boiling points
of the (ethyl ester) fuel might have similar impacts on engine
performance comparable to that found from methyl esters.
Fuel droplets of the injection jet, for instance, will be enlarged
and could lead to ignition delays. This will further influence
combustion characteristics, resulting in worse acoustics and
increased soot formation tendencies. Another aspect is the
cold start operability, which is directly linked to distillation
characteristics of the fuel. Fuel viscosity is slightly higher for
ethyl esters, which will reduce the flowability at lower temperatures. However, as already mentioned, further research is
still necessary.
To obtain a broader overview about distillation behavior, a
series of fatty acid ethyl esters (FAEEs) derived from different
feedstocks has been investigated. The background was to take
the different fatty acid profiles of the feedstocks and their
impact on distillation characteristics into consideration. Feedstocks evaluated included two rapeseed oils (fully refined and
degummed), used cooking oil, waste animal fat, and fish oil.
Transesterifications were carried out using high-performance
liquid chromatography (HPLC)-grade ethanol, sodium ethoxide as the catalyst, and glycerol to support phase separation.10
Waste animal fat was pre-esterified before transesterification
because of a higher content of free fatty acids. This was performed by an acid-catalyzed reaction using sulfuric acid
according to an established procedure.11 To ensure the highest
purity of the product, the FAEEs were distilled prior to the
analysis of distillation characteristics. Distilled FAEE from
fish oil was derived from a local company [BioEnergy International AG (BDI)] dealing with fish oil conversion technologies and reflects ethyl ester fractions from continuous distillation. The purpose was to obtain concentrates rich in
(poly)unsaturated FAEEs. Purification was performed by distillation at reduced pressure of less than 1 mbar to remove
glycerol, as well as mono-, di-, and triglycerides, which would
affect the final distillation characteristics. The determination
of the distillation characteristics was carried out using a
Herzog HDV 632 instrument approved for ASTM D1160.
Operating conditions were set as follows: sample, 200 mL;
heating rate, 5 C/min; condenser temperature, 60 C; distillation rate, 6 mL/min; and pressure, 40 mbar.12 The distillation

The term biodiesel is typically linked to fatty acid methyl

esters. However, looking into more detail, the American
Society for Testing and Materials (ASTM) specifications
define biodiesel as mono-alkyl esters of long-chain fatty acids
derived from vegetable oils or animal fats.1 This automatically
indicates that, besides methyl esters, also ethyl, propyl, butyl
esters, etc. might be used for either B100 or blending applications. From the analytical point of view, the methods of the
valid standard specifications enable the corresponding analysis of biodiesel, independent from the alcohol used for
transesterification. However, it is not assured that such products, coming from reactions with alcohols different than
methanol, will automatically fulfill quality requirements. In
other words, it has not been sufficiently evaluated yet if all
higher esters from fatty acids are suitable to be used as biofuel.
Such products, of course, will not be competitive compared
to methyl esters from the commercial point of view at the
moment. However, the use of ethanol instead of methanol is
still under investigation, and the first small or experimentalscale production units are already operating. Especially, Latin
American countries, such as Brazil, are highly interested to
replace methanol by ethanol.
Now, with a focus on distillation characteristics of biodiesel, it is well-known that methyl esters have higher boiling
points compared to fossil diesel and the boiling point distribution is very narrow, in the range of 325-350 C.2 Moreover, the required maximum T90 limit of 360 C at which 90%
of the fuel should be distilled according to the ASTM standard
is sometimes almost reached. Especially, if the conversion is
insufficient (and, therefore, the ester content is lower), the T90
limit could hardly be reached.3-6 This is attributed to higher
amounts of tri-, di-, and monoglycerides within the biodiesel,
which partially have much higher boiling points compared to
methyl esters. Data on corresponding ethyl esters are still
limited and not always reproducible. However, reported
values indicate that boiling points of such products are prone
*To whom correspondence should be addressed. Telephone: (43)
316-380-5353. Fax: (43) 316-380-695353. E-mail: martin.mittelbach@
uni-graz.at.
(1) American Society for Testing and Materials (ASTM). ASTM
D6751-09, Standard Specification for Biodiesel Fuel Blend Stock (B100)
for Middle Distillate Fuels; ASTM: West Conshohocken, PA, 2010.
(2) Graboski, M. S.; McCormick, R. L. Prog. Energy Combust. Sci.
1998, 24, 125164.
(3) Encinar, J. M.; Gonzalez, J. F.; Rodr guez, J. J.; Tejedor, A.
Energy Fuels 2002, 16, 443450.
(4) Boz, N.; Kara, M.; Sunal, O.; Alptekin, E.; Degirmenbas-i, N.
Turk. J. Chem. 2009, 33, 433442.
(5) Kumar-Sarma, A.; Konwer, D.; Bordoloi, P. K. Energy Fuels
2005, 19, 656657.
(6) Kinast, J. A. Production of Biodiesels from Multiple Feedstocks and
Properties of Biodiesels and Biodiesel/Diesel Blends; National Renewable
Energy Laboratory (NREL): Golden, CO, 2003; NREL/SR-510-31460.
(7) Encinar, J. M.; Gonzalez, J. F.; Rodr guez-Reinares, A. Fuel
Process. Technol. 2007, 88, 513522.
r 2010 American Chemical Society

(8) Clark, S. J.; Wagner, L.; Schrock, M. D.; Piennaar, P. G. J. Am.

Oil Chem. Soc. 1984, 61, 16321638.
(9) Goodrum, J. W. Biomass Bioenergy 2002, 22, 205211.
(10) Szpiz, R. R.; Jablonka, F. H.; Pereira, D. A.; Araujo Lago, R. C.;
Hartman, L. Braz. Pedido PI 8300429, 1984.
(11) Kawahara, Y.; Ono, T. U.S. Patent 05/884835, 1978.
(12) American Society for Testing and Materials (ASTM). ASTM
D1160-06, Test Method for Distillation of Petroleum Products at Reduced
Pressure; ASTM: West Conshohocken, PA, 2010.

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Energy Fuels 2010, 24, 66936695

: DOI:10.1021/ef1012193
Table 1. Distillation Characteristics of Different FAEEsa

REE 1

REE 2

UCOEE

AFEE

FOEE 1

FOEE 2

FOEE 3

FOEE 4

FOEE 5

volume (%)

T (C)

T (C)

T (C)

T (C)

T (C)

T (C)

T (C)

T (C)

T (C)

DSb
5
10
20
30
40
50
60
70
80
90
95

231.8
354.3
356.7
357.5
358.3
358.6
358.6
359.4
359.6
358.7
360.1
366.5

242.1
355.2
356.8
357.5
358.1
358.9
359.0
359.5
360.3
360.8
361.3
368.2

241.8
352.9
353.6
354.3
355.5
356.1
356.8
358.0
358.6
359.7
360.9
363.6

203.7
346.8
347.3
349.0
350.8
352.4
354.1
355.2
356.7
358.8
360.8
362.3

286.7
336.7
339.2
339.4
342.7
345.6
349.9
353.5
357.5
359.1
362.4
367.9

258.3
332.5
334.5
335.2
338.0
340.5
343.2
345.9
349.8
353.6
359.8
365.7

258.9
338.1
339.6
341.3
342.8
345.2
348.8
351.4
355.7
358.3
360.6
367.1

273.9
333.1
335.3
336.2
338.9
341.9
344.4
347.2
350.9
354.8
361.4
368.4

256.0
337.8
338.9
341.1
341.5
345.8
348.4
351.7
355.7
360.5
364.9
373.8

a
REE, rapeseed oil ethyl ester; UCOEE, used cooking oil ethyl ester; AFEE, waste animal fat ethyl ester; FOEE, fish oil ethyl ester. b DS = distillation
start.

Table 2. Fatty Acid Composition of FAEEs

fatty acid

REE 1
(wt %)

REE 2
(wt %)

UCOEE
(wt %)

AFEE
(wt %)

FOEE 1
(wt %)

FOEE 2
(wt %)

FOEE 3
(wt %)

FOEE 4
(wt %)

FOEE 5
(wt %)

C12:0
C14:0
C16:0
C16:1
C17:0
C18:0
C18:1
C18:2 (n-6)
C18:3 (n-3)
C18:4 (n-3)
C20:0
C20:1 (n-9)
C20:1 (n-7)
C20:2 (n-6)
C20:4 (n-6)
C20:4 (n-3)
C20:5 (n-3)
C21:5 (n-3)
C22:0
C22:1 (n-9)
C22:4 (n-3)
C22:5 (n-6)
C22:5 (n-3)
C22:6 (n-3)
C24:0
C24:1 (n-9)

<0.01
0.07
4.36
0.25
<0.01
1.87
61.17
19.6
9.63
<0.01
0.65
1.37
<0.01
<0.01
<0.01
<0.01
<0.01
<0.01
0.33
0.33
<0.01
<0.01
<0.01
<0.01
0.28
0.08

<0.01
0.06
4.93
0.21
0.06
1.89
61.89
21.18
7.35
<0.01
0.58
1.08
<0.01
<0.01
<0.01
<0.01
<0.01
<0.01
0.07
0.31
<0.01
<0.01
<0.01
<0.01
0.13
0.25

0.16
0.47
16.94
0.34
0.09
4.07
47.36
25.30
0.14
<0.01
0.43
2.35
<0.01
<0.01
<0.01
<0.01
<0.01
<0.01
0.43
0.50
<0.01
<0.01
<0.01
<0.01
0.52
0.94

2.18
6.28
27.42
0.12
1.58
24.83
30.09
2.94
2.56
<0.01
0.52
0.26
<0.01
<0.01
<0.01
<0.01
<0.01
<0.01
0.13
1.22
<0.01
<0.01
<0.01
<0.01
0.21
0.03

<0.01
0.11
0.21
1.31
0.03
0.06
9.01
1.31
1.12
3.28
0.03
0.64
0.23
2.18
3.14
0.05
45.66
0.03
<0.01
1.91
0.13
0.61
1.40
22.75
<0.01
0.16

<0.01
13.22
26.94
13.13
0.15
5.11
23.20
4.14
1.56
2.69
<0.01
0.69
0.09
0.11
0.43
0.39
6.79
0.13
<0.01
<0.01
<0.01
<0.01
0.18
1.04
<0.01
<0.01

<0.01
8.62
23.42
11.40
0.13
3.36
24.21
5.02
2.89
2.66
<0.01
1.28
0.17
0.21
0.66
<0.01
10.18
0.32
<0.01
0.32
<0.01
0.09
0.68
3.31
<0.01
<0.01

<0.01
0.20
3.49
1.18
0.04
4.52
20.15
3.74
1.59
2.19
0.39
4.27
0.52
0.65
1.63
1.90
25.55
1.11
<0.01
0.44
0.42
0.43
3.08
14.71
<0.01
0.24

<0.01
0.04
0.09
1.22
0.12
0.03
8.32
1.31
1.11
3.50
0.64
0.22
0.38
1.84
2.17
0.07
46.78
<0.01
<0.01
1.85
0.33
0.60
6.18
23.05
<0.01
0.11

temperature at reduced pressure is automatically calculated

into atmospheric pressure temperature equivalents, as given
in ASTM D1160. This calculation is based on an improved
linear correlation for the vapor pressure of pure hydrocarbons
and narrow boiling hydrocarbon admixtures developed by
Maxwell and Bonnell.13 Fatty acid profiles of the ethyl esters
were determined according to a standard procedure.14
The obtained distillation characteristics of the different
ethyl esters are shown in Table 1. The given data represent
mean values of three individual measurements, whereby the
corresponding standard deviations are in the range of 0.120.17 C. As can be seen (values in bold), most of the ethyl
esters exceed the maximum limit of 360 C for T90, as fixed
by the standard specifications.1 The consequence is that such
biodiesel will not fit the given biodiesel quality requirements

and cannot be used for either B100 or blending applications.

This is an interesting point because, if biodiesel is blended into
fossil diesel at common ratios (B5-B20), the resulting blend
would surely fulfill the T90 temperature limit. However, it
should be noted that distillation characteristics of blends with
higher biodiesel proportions (greater than B10) have not been
reported thus far. A further remarkable aspect is that, by
prolonging distillation up to 95% recovery, a massive increase
in boiling points is observed. Although T95 is not part of the
ASTM D6751 standard, it is specified, e.g., within European
diesel fuel specifications.14 More important is the fact that,
during distillation, thermally induced degradation reactions
are taking place in the flask, leading to the formation of polymerized ethyl esters and, therefore, a shift in boiling points.
The problem occurs especially on feedstocks rich in polyunsaturated fatty acids. This is also underlined by the data given
in Table 1, where generally all feedstocks with high amounts of
unsaturated ethyl esters (rapeseed and fish oil) show a significant increase in distillation temperatures from T90 to T95.
On the other hand, feedstocks with high amounts of saturated

(13) Maxwell, J. B.; Bonnell, L. S. Ind. Eng. Chem. 1957, 49, 1187
1196.
(14) American Oil Chemists Society (AOCS). Ce 1i-07, Official
Methods and Recommended Practices, 6th ed.; AOCS: Champaign, IL,
2009.

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Energy Fuels 2010, 24, 66936695

: DOI:10.1021/ef1012193

fatty acids, such as used cooking oil and waste animal fat, are
characterized by moderate increases in temperatures from
T90 to T95. However, it has to be mentioned that all FAEEs
investigated have been pre-purified by distillation, whereby
polymerized material was already removed. This, of course,
positively impacts the distillation characteristics of used cooking oil ethyl esters. Such waste oils naturally contain significant amounts of polymerized triglycerides, respectively esters,
if converted into biodiesel.
By a comparison of the individual FAEEs, it is worth
mentioning further observations. However, to explain them,
it is necessary to take the fatty acid distribution of the different
ethyl esters into consideration (Table 2). The two rapeseed oil
ethyl esters exhibit very similar fatty acid compositions. The
slight differences are because REE 1 and REE 2 came from
different sources but represent overall fatty acid compositions
typically found in rapeseed oils. Looking at the distillation
characteristics, even their boiling behavior is very similar. In
particular, the very narrow boiling point range from 354 C at
T5 to 360 C at T90 is remarkable.
Comparable results can be observed on UCOEE and
AFEE. Differences (lower temperatures) during the distillation on AFEE compared to REE and UCOEE are based on
higher amounts of short-chain fatty acids, which have lower boiling points. However, associated T90 temperatures are nearly the
same. Increasing the distillation recovery to T95 resulted in
temperature drifts explainable by differences in saturated versus
unsaturated fatty acid composition, as already mentioned above.

Looking at the boiling behavior of the different FOEEs,

roughly two groups can be identified with respect to their fatty
acid distribution. As with all of the esters derived from varied
distillation experiments, two FOEEs are enriched in shortchain fatty acid esters (FOEE 2 and FOEE 3), whereas three of
them (FOEE 1, FOEE 4, and FOEE 5) are enriched in longchain (mostly polyunsaturated) fatty acid esters. As expected,
these differences in fatty acid distribution also induced changes
in distillation characteristics. FOEEs with higher amounts of
long-chain esters also show higher T90 temperatures. However, even FOEEs rich in short-chain fatty acids showed T90
temperatures close to the ASTM limit. Higher proportions of
unsaturated species lead to significant increases in temperatures from T90 to T95 because of accelerated polymer formation. Fish oil is not the mostly preferred feedstock for biodiesel
production, but the intention of this work is to highlight that,
independent from the feedstock (with low or high iodine
values), the corresponding FAEEs exceed the mandatory
temperature limit for distillation characteristics. Therefore, it
can be estimated that other ethyl esters (or generally higher
esters), e.g., from soybean, sunflower, and palm oil, will show
similar behavior. This might be helpful for further discussion
on the standardization of biofuels. Indeed, European standardization groups are working on a separate standard
specific for ethyl esters.
Acknowledgment. The authors thank BioEnergy International
AG (BDI) for allocation of the different fish oil ethyl esters.

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