Energy & Fuels 2004, 18, 77-83 77

Optimization of Alkali-Catalyzed Transesterification of

Brassica Carinata Oil for Biodiesel Production
M. Pilar Dorado,*, Evaristo Ballesteros, Francisco J. Lopez, and
Martin Mittelbach#
Department of Mechanics and Mining Engineering, EUP de Linares, Universidad de Jaen,
C/. Alfonso X el Sabio, 28, 23700 Linares (Jaen), Spain, Department of Physical and
Analytical Chemistry, EUP de Linares, Universidad de Jaen, C/. Alfonso X el Sabio,
28, 23700 Linares (Jaen), Spain, Department of Agricultural Engineering, ETSIAM,
Universidad de Cordoba, Avda. Menendez Pidal s/n, 14080 Cordoba, Spain, Institute of
Chemistry, Karl-Franzens-Universitat Graz, Heinrichstrasse 28, A-8010 Graz, Austria

Received May 27, 2003. Revised Manuscript Received October 5, 2003

Environmental concerns are driving industry to develop viable alternative fuels from renewable
resources. On the other hand, to reduce food surplus, the Agricultural Policy of the European
Union (EU) obliges the European farmers to leave a percentage of the arable land as set-aside,
where can be grown, as an exception, vegetables for nonfood purposes, i.e., energetic ones.
Currently, fossil fuels are used in diesel engines and are essential in industrialized places. In
addition, petroleum-based diesel increases environmental pollution. To solve these problems,
transesterified vegetable oil that has been grown in set-aside lands can be considered to be a
renewable energy resource. In this sense, this work describes the optimization of the parameters
involved in the transesterification process of Brassica carinata oil. Gas chromatography was used
to determine the fatty acid composition of Brassica carinata oil and its esters. Results revealed
that the free fatty acid content is a notorious parameter to determine the viability of the vegetable
oil transesterification process. In this sense, it was not possible to perform a basic transesteri-
fication using Brassica carinata oil with a high erucic acid content. The transesterification process
of Brassica carinata without erucic acid required 1.4% KOH and 16% methanol, in the range of
20-45 C, after 30 min of stirring. Our results suggest that the greater the presence of KOH,
the lesser the methanol requirements. However, this is valid only under certain limits. Also, if
the presence of KOH or methanol is lower or higher than the optimal values, the reaction either
does not fully occur or leads to soap production, respectively. Based on this field trial, biodiesel
from Brassica carinata oil could be recommended as a diesel fuel candidate if long-term engine
performance tests provide satisfactory results.

Introduction land. Nevertheless, an exception has been introduced

More than 350 oil-bearing crops have been identified,
among which mainly sunflower, safflower, soybean,
cottonseed, rapeseed, and peanut oils are considered to
be potential alternative fuels for diesel engines.1 Nev-
ertheless, other unknown oleaginous crops, which are
being grown in less-favored countries, could perform
well as an adequate fuel with chemical and physical
properties similar to those of diesel fuel.
In addition, the set-aside rules of the European Union
(EU) Agricultural Policy specify a minimum area of
obligatory set-aside land of the total arable area (10%
in 2001), but also permit up to 50% of the total claimed
area to be put into the voluntary set-aside category.
However, increasing the set-aside area could lead to
erosion problems and may have an impact on arable
* Author to whom correspondence should be addressed. E-mail:
mpdorado@ujaen.es.
Department of Mechanics and Mining Engineering.
Department of Physical and Analytical Chemistry.
Universidad de Cordoba.
# Karl-Franzens-Universitat Graz.
(1) Peterson, C. L. Trans. ASAE 1986, 29, 1413-1422.
into the rules for managing set-aside land, which allows
farmers to cultivate crops for nonfood purposes. In this
sense, Brassica carinata (Ethiopian mustard) is an
adequate oil-bearing crop that is well-adapted to mar-
ginal regions (i.e., Andalusia (Spain), which is one of
the poorest regions of the EU). In fact, this crop, which
is originally from Ethiopia, is drought-resistant and
grown in arid regions such as Andalusia.2,3 Moreover,
nonfood cultures in set-aside lands can significantly
decrease the enormous amount of subsidies spent for
agricultural overproduction in Europe, which leads to
an increase in farmer incomes as well as the creation
of new employment. For these reasons, Brassica cari-
nata constitutes an interesting alternative to diesel fuel
in less-favored regions.
(2) Kimber, D. S.; McGregor, D. I. The Species and Their Origin,
Cultivation and World Production; In Brassica Oilseeds: Production
and Utilization; Kimber, D. S., McGregor, D. I., Eds.; CAB Interna-
tional: Wallingford, Oxon, U.K., 1995; pp 1-7.
(3) Mendham, N. J.; Salisbury, P. A. Physiology: Crop Development,
Growth and Yield; In Brassica Oilseeds: Production and Utilization;
Kimber, D. S., McGregor, D. I., Eds.; CAB International: Wallingford,
Oxon, U.K., 1995; pp 11-64.

10.1021/ef0340110 CCC: $27.50 2004 American Chemical Society

Published on Web 11/13/2003
78 Energy & Fuels, Vol. 18, No. 1, 2004 Dorado et al.

Scheme 1. Transesterification Process Table 1. Chemical and Physical Properties of Brassica

Oils
high-erucic Brassica carinata
Brassica carinata oil without
oilb erucic acidb
fatty acids (%)a
palmitic C16:0 5.3 ( 0.1 5.4 ( 0.1
(t 4.118 min)
palmitoleic C16:1
(t 4.545 min)
stearic C18:0 0.20 ( 0.01
(t 5.53 min)
oleic C18:1 10.0 ( 0.2 43.2 ( 0.9
(t 6.167 min)
linoleic C18:2 24.6 ( 0.5 36.0 ( 0.7
(t 7.275 min)
However, vegetable oils are composed primarily of the linolenic C18:3 16.5 ( 0.3 15.2 ( 0.3
(t 8.8 min)
fatty esters of glycerol (triglycerides), with a chemical erucic C22:1 43.6 ( 0.8
structure that differs from diesel fuel. In fact, vegetable (t 13.86 min)
oils used as fuel report several problems that have been Other Propertiesb
identified, i.e., the high viscosity and high molecular free fatty acid (%) 10.81 ( 0.31 2.2 ( 0.2
weight cause poor fuel atomization (which leads to in- peroxide value (meq) 8.9 ( 0.1 22.5 ( 0.4
complete combustion) and low volatility, respectively.4,5 density (kg/m3) 914 ( 1 921 ( 1
In this sense, the transesterification of vegetable oils kinematic viscosity at 118.8 ( 0.9 68.1 ( 0.8
40 C (mm2/s)
constitutes an efficient method to provide a fuel with kinematic viscosity at 48.6 ( 0.9 32.1 ( 0.6
chemical properties that are similar to those of diesel 20 C (mm2/s)
fuel. This chemical reaction resembles the conversion water content (%) 0.25 ( 0.02 0.20 ( 0.01
of an organic acid ester into another ester of the same a Other fatty acids (myristic, margaric, margaroleic, arachidic,
acid (Scheme 1). gadoleic, and behenic) were present in amounts of <1%. b Medium
Although it is a well-known process since, in 1864, value ( standard deviation (n ) 3).
Rochleder described glycol preparation through the
ethanolysis of castor oil,6 the proportion of reagents conventional diesel fuel. In this sense, Ethiopian mus-
affects the process, in terms of conversion efficiency,7 tard presents up to 6% saturated hydrocarbon chains
and this factor differs according to the vegetable oil. (Table 1), whereas sunflower oil, canola oil, and soybean
Several researchers have identified the most important oil methyl esters present up to 4.8%-12.1%, 5%-7%,
variables that influence the transesterification reaction, and 4.7%-17% saturated chains, respectively.
namely, the reaction temperature, the type and amount Based on the fatty acid composition and many other
of catalyst, the ratio of alcohol to vegetable oil, the parameters, the EU is about to approve the fatty acid
stirring rate, the reaction time, etc.8-12 In this sense, it methyl esters requirements and test methods (European
is important to characterize the oil (i.e., fatty acid Standard EN 14214). According to this prenorm, the
composition, water content, and peroxide value (PV)) to maximum amount of linoleic acid methyl ester can be
determine the correlation between them and the feasi- 12%. Also, the iodine value is limited to 120. These
bility to convert the oil into biodiesel.12,13 parameters exclude the use of the biodiesel from sun-
The fatty acid composition of the oils seems to have flower oil, which is one of the main oleaginous crops that
an important role in the performance of biodiesel in are grown in Spain and other southern countries of the
diesel engines. According to Knothe and Dunn,14 satu- EU. In fact, research related to biodiesel from sunflower
rated hydrocarbon chains are especially suitable for oil has been seriously criticized. However, some re-
searchers have found that biodiesel from sunflower oil
(4) Goering, C. E.; Schwab, A. W.; Daugherty, M. J.; Pryde, E. H.; performs adequately in diesel engines.15-17 This obser-
Heaking, A. J. Trans. ASAE 1982, 25, 1472-1483. vation indicates that more research is needed before the
(5) Bagby, M. O. Vegetable Oils for Diesel Fuel: Opportunities for approval of the future EU standard for biodiesel.
Development; American Society of Agricultural Engineers: St. Joseph,
MI, 1987; ASAE Paper No. 87-1588. Because the chemical properties of the esters deter-
(6) Formo, M. W. J. Am. Oil Chem. Soc. 1954, 31, 548-559. mine their feasibility as fuel, the intent of this work is
(7) Freedman, B.; Pryde, E. H.; Mounts, T. L. J. Am. Oil Chem. Soc.
1984, 64, 1638-1643. to investigate and optimize the parameters involved in
(8) Peterson, C. L.; Reece, D. L.; Cruz, R.; Thompson, J. A Com- the transesterification of Brassica carinata oil for fuel
parison of Ethyl and Methyl Esters of Vegetable Oil as Diesel Fuel use, to develop a low-cost chemical process, and to deter-
Substitute: Liquid-Fuels from Renewable Resources; Proceedings of
Alternative Energy Conference; American Society of Agricultural mine the influence of the chemical properties of the oil
Engineers, 1992; pp 99-110. in the transesterification. Transesterification tests were
(9) Isigigur, A.; Karaosmanoglu, F.; Aksoy, H. A. Appl. Biochem.,
Biotechnol. 1994, 45, 103-112.
(10) Muniyappa, P. R.; Brammer, S. C.; Noureddini, H. Bioresour. (14) Knothe, G.; Dunn, R. O. Biofuels Derived from Vegetable Oils
Technol. 1996, 56, 19-24. and Fats. In Oleochemical Manufacture and Applications; Gunstone,
(11) Zheng, D.; Hanna, M. A. Bioresour. Technol. 1996, 57, 137- F. D., Hamilton, R. J., Eds.; Sheffield Academic Press: Sheffield, U.K.,
142. 2001; pp 107-163.
(12) Coteron, A.; Vicente, G.; Martinez, M.; Aracil, J. Recent Res. (15) Fuls, J.; Hawkins, C. S.; Hugo, F. J. C. J. Agric. Eng. Res. 1984,
Dev. Oil Chem. 1997, 1, 109-114. 30, 29-35.
(13) Anggraini, A. A. Wiederverwertung von Gebrauchten Speiseolen/ (16) Kaufman, K. R.; Ziejewski, M. Trans. ASAE 1984, 27, 1626-
-fetten im Energetisch-Technischen Bereich -ein Verfahren und 1633.
Dessen Bewertung; Dep. AgrarTechnik, Universitat Gesamthochschule (17) Harrington, K. J.; DArcy-Evans, C. J. Am. Oil Chem. Soc. 1985,
Kassel: Witzenhausen, Germany, 1999; p 193. 62, 1009-1013.
Transesterification of Brassica Carinata Oil
Scheme 2. Process to Obtain Biofuel
conducted in a stirred tank reactor that was equipped
with a temperature controller and a reflux condenser,
to avoid methanol losses.
Materials and Methods
1. Characterization of the Oil. High-erucic and low-erucic
Brassica carinata oilseeds were collected and processed by
mechanical cold-press extraction. At this point, the crude oil
was not refined any further. The fatty acid composition of
the oil was analyzed using gas chromatography (GC)
(Hewlett-Packard, model 5890 GLC). The chromatograph was
equipped with a flame ionization detector (FID) and a 30 m
0.25 mm Supelcolwax-10 glass column that was packed
with poly(ethylene glycol) (film thickness of 0.25 m). Nitrogen
was used as a carrier gas at a flow rate of 1 mL/min. The
injector and detector temperatures were maintained at 250
C. The column temperature was increased from 165 C (2 min)
to 180 C at a rate of 4 C/min (3 min), then to 200 C at a
rate of 5 C/min, and finally to 260 C at a rate of 15 C/min;
this last temperature was maintained for 2 min. ChemStation
software (HP-3365) was used for data acquisition.18 The
chemical and physical properties of Brassica oils are given in
Table 1.
2. Transesterification Process. The reaction vessel was
charged with a given amount of Brassica carinata oil (100 g),
which was stirred at 1100 rpm and preheated at different
temperatures. Meanwhile, the solution of methanol (CH3OH)
and KOH was added. The mixture was stirred and heated.
The time of reaction was varied, to obtain a large range of
methyl ester yields. Heating and stirring were then stopped,
and the product was allowed to settle, to allow the two phases
to be separated. The top phase consisted of biofuel, whereas
the lower phase contained a mixture of impurities. The upper
layer was purified using distilled water and then dried over
anhydrous sodium sulfate (Na2SO4) (see Scheme 2). In this
sense, 0.5 g of anhydrous Na2SO4 were added for every 100
mL of ester, stirred for 15 min, and then was allowed to settle
and be decanted. To remove solid traces from biofuel after the
purification step, a filtration process was needed. This step
was performed with the help of a vacuum pump and a 27-m-
(18) Ballesteros, E.; Cardenas, S.; Gallego, M.; Valcarcel, M. Anal.
Chem. 1994, 6, 628-634.
Energy & Fuels, Vol. 18, No. 1, 2004 79
diameter filter paper (No. 1305, from ALBET (Filtros Anoia
SA, Barcelona, Spain)). For each oil sample, three replications
were performed.
The optimum of each parameter involved in the process was
determined while the rest of them remained constant. After
each optimum was attained, this value was accepted and
considered to be constant during the optimization of the next
parameter. Ester yield results (given as percentages) were
related to the weight of oil at the start (weight of ester/weight
of oil).
Finally, biodiesel fuel properties were determined with the
help of the standard tests and compared to those of diesel fuel,
according to the EN-590 standard and European Standard EN
14214 for biodiesel.
Results and Discussion
1. Oil Properties. According to Table 1, the free fatty
acid (FFA) content was in the range of 2.2% (for
Brassica carinata oil without erucic acid) to 10.8% (for
high-erucic Brassica carinata oil). High-erucic Brassica
carinata oil showed a significantly high FFA value,
compared to samples without erucic acid, probably
because of the presence of the erucic acid. These FFA
contents should make transesterification of the oils
possible; FFA contents of >3% decrease the conversion
efficiency considerably.13 However, Dorado et al.19 found
that transesterification would not occur if oils with an
FFA content of >3% were used. In this work, it was not
possible to perform transesterification of high-erucic
Brassica carinata oil; it led to soap formation. It seems
that the presence of erucic acid was responsible for the
observed high FFA content, and we feel confident that
it was the main obstacle to accomplishing transesteri-
fication of the high-erucic Brassica carinata oil. On the
other hand, it can be noticed that the absence of erucic
acid in the nonerucic Brassica carinata oil has led to
an increase in the presence of oleic and linoleic acids
(see Table 1).
(19) Dorado, M. P.; Ballesteros, E. A.; de Almeida, J. A.; Schellert,
C.; Lohrlein, H. P.; Krause, R. Trans. ASAE 2002, 45, 525-529.
80 Energy & Fuels, Vol. 18, No. 1, 2004
Figure 1. Percentage yield of ester relative to oil at start (w/w
%), using different amounts of KOH and alcohol over the
stoichiometric amount.
The peroxide value (PV) indicates oil autoxidation,
which is a property that could lead to catalyst inactivity
during the transesterification process. According to
Table 1, the PV ranged from 8.9 meq/kg for high-eruric
Brassica carinata oil to 22.5 meq/kg for nonerucic
Brassica carinata oil. However, Anggraini13 found that,
for transesterification purposes, values up to 30-35
meq/kg could be tolerated. In the present work, the
kinematic viscosity was significantly higher for high-
erucic Brassica carinata oil than that for nonerucic
Brassica carinata oil. Nevertheless, in both cases, the
kinematic viscosity value was too high to allow the use
of straight Brassica carinata oils as fuels. On the other
hand, the water content was very similar in both cases
(<1%), which prevents saponification or the hydrolysis
of glycerides and makes transesterification possible.13
In this field trial study, only Brassica carinata oil
without erucic acid was successfully transesterified,
thus indicating that the FFA content was the more
offensive parameter.
2. Catalyst Optimization. To avoid corrosion prob-
lems in engine components that are due to the presence
of acid traces, basic catalysts instead of acid catalysts
were selected.20 In this sense, two basic catalystssKOH
and NaOHswere tested under the same conditions
(1.26% catalyst and an excess of alcohol, tested at room
temperature). However, no ester formation was ob-
served using NaOH, unless the reaction time was
considerably increased (up to 14 h), compared to KOH
(up to 1 h). For this reason, KOH was selected. The
effect of KOH concentration was studied in the range
of 0%-2.3% (weight of KOH/weight of oil). Results using
KOH (alcohol over the stoichiometric amount) are
shown in Figure 1.
Only nonerucic Brassica carinata oil was successfully
transesterified. As shown in Figure 1, the maximum
yield of ester was obtained by adding 0.8% of KOH.
However, the ester was opaque, which indicated the
presence of unreacted glycerides.21 The optimum was
(20) Ballesteros, E.; Gallego, M.; Valcarcel, M. Anal. Chim. Acta
1993, 282, 581-588.
Dorado et al.
Figure 2. Percentage yield of ester relative to oil at start (w/w
%), using different amounts of methanol and 1.4% KOH.
achieved using 1.4% of KOH, which produced a 91.9%
yield of reddish, crystalline, and transparent ester. This
amount was greater than the amounts of catalyst used
by other researchers.10,22 Ester formation started after
20-40 s of stirring. KOH amounts greater than 1.4%
produced a smaller ester yield, because of the presence
of soaps, which prevents ester layer separation, as found
by Coteron et al.12
3. Alcohol Optimization. Preliminary tests were
conducted using both methanol (50% v/v) and ethanol
(50% v/v). Under the same conditions (1.4% catalyst,
room temperature), it was not possible to achieve ester
formation using ethanol (even using an anhydrous
alcohol, which led to the formation of soap and gelati-
nous layers. Instead, using methanol, both the ester and
glycerol layers were easily separated. Anyway, trans-
esterification using ethanol occurred slower than that
using methanol, as reported by Du Plessis et al.23 In
the present work, methanol was the alcohol selected.
The effect of methanol presence was studied in the
range of 0%-20% (weight of methanol/weight of oil).
Results using methanol are shown in Figure 2.
The methanol:triglyceride molar ratio that is required
by the stoichiometry should be 3:1. However, as shown
in Figure 2, the maximum yield of ester was obtained
by adding 16% methanol (weight of methanol/weight of
oil), which is equivalent to a molar ratio of 1:4.6 (oil:
methanol). In contrast, other researchers have found it
necessary to increase the molar ratio up to 1:6, or even
to 1:12, to achieve the maximum yield of monoester
product from safflower oil or soybean oil.9,21 Our findings
are probably due to the greater amount of catalyst used
in the present work, compared to that in the work of
other researchers.9,21 Ester formation started after 30
s of stirring. In this work, methanol amounts of >20%
(21) De Filippis, P.; Giavarini, C.; Scarsella, M.; Sorrentino, M. J.
Am. Oil Chem. Soc. 1995, 72, 1399-1404.
(22) Trent, W. R. Process of Treating Fatty Glycerides. U.S. Patent
462,370, 1945.
(23) Du Plessis, L. M.; de Villiers, J. B. M.; Hawkins, C. S. Methods
of Preparing and Purifying Methyl and Ethyl Fatty Acid Esters from
Sunflowerseed Oil; SAE: Pretoria, Republic of South Africa, 1983; p
9.
Transesterification of Brassica Carinata Oil
made glycerol separation difficult, thus decreasing ester
yield formation, which was opaque. In this case, ester
formation started after 80 s of stirring. The addition of
<5% methanol resulted in the creation of a unique and
foamy layer. Methanol amounts up to 10% produced two
layers, although the lower layer was gelatinous and the
upper layer was opaque, because of the presence of
unreacted triglycerides, thus indicating that methanol
was insufficient to perform a complete reaction.
4. Reaction Temperature Optimization. The maxi-
mum yield of ester was obtained at room temperature.
Results revealed that the ester yield slightly decreases
when other reaction temperatures are used, especially
when the temperature is >50 C. However, other
researchers achieved better results using temperatures
above 50 C, up to 70-80 C.9,23 In fact, several
researchers found that the temperature increase influ-
ences the reaction in a positive manner.24
Although a reflux condenser was used to avoid meth-
anol losses, the ester yield significantly decreased at
temperatures of >50 C, probably because of a negative
interaction between temperature and catalyst concen-
tration, due to side reactions, such as soap formation.12
Also, Trent22 found that reaction temperatures of >60
C should be avoided, because they tend to accelerate
the saponification of the glycerides by the alkaline
catalyst before completion of the alcoholysis. Because
of this observation, as well as economic reasons, room
temperature was selected during transesterification.
5. Reaction Time and Stirring Time Optimiza-
tion. To achieve perfect contact between the reagents
and the oil during transesterification, they were mixed
together.21 The ester yield slightly increased as the
reaction time increased. Results revealed that, after 1
min of stirring, a suitable phase separation was achieved.
The maximum yield of ester was reached after 30 min
of stirring, whereas other researchers required up to
4 h.23
6. Settling Time Optimization. After the transes-
terification was finished, the reaction products were
placed in a closed vessel, to be decanted. A successful
reaction produces two liquid phases: ester (upper layer)
and glycerol (lower layer). When room temperature was
>38 C, which is the usual temperature in most places
in Andalusia (Spain) during the summer, separation
between the phases occurred within 1-3 h. However,
when room temperature decreased to 10-15 C, several
days were required for complete settling to occur. To
increase the pouring-off rate, a temperature increase
was requested, i.e., with the help of a double boiler at
40 C. In this case, complete settling could be reached
in <3 h, probably because of the positive influence of
the settling temperature. In fact, it was noticed that,
after a few days of settling, the opaque ester samples
turned crystalline, and a slight glycerol lower phase
appeared. This could be explained by a certain conflict
between glycerol solubility and low temperatures. In
conclusion, this problem could be resolved by increasing
the settling temperature or settling time.
7. Purification Step Optimization. It is important
to remove impurities that are present in the ester layer,
i.e., soaps, KOH traces, methanol traces, and free
(24) Karaosmanoglu, F.; Akdag, A.; Cigizoglu, K. B. Appl. Biochem.,
Biotechnol. 1996, 61, 251-265.
Energy & Fuels, Vol. 18, No. 1, 2004 81
glycerol. Otherwise, a high content of free glycerol can
result in separation of the glycerol, causing problems
during storage, in the fuel system or produce higher
aldehyde emissions.25 In the present work, washing with
distilled water, gentle stirring for 4 min, and settling
in a vessel (to allow decanting) was applied to remove
mineral contaminants in the ester. After this step, two
layers were formed. The upper layer was made of
biofuel, and the lower layer was made of water and
impurities. This process was repeated until the lower
phase had a pH value that was similar to that of
distilled water, thus indicating that only water was
present and that the impurities were removed in the
former washing. Preliminary tests were conducted by
adding 2, 4, or 15 mL of distilled water to the ester (2.27,
4.55, or 17.01 wt % of ester, respectively) and allowing
the mixture to settle in a vessel, to be poured off. After
the settling was completed, the ester layer appeared
opaque, and a second washing process was performed
to achieve a more suitable and crystalline sample of
ester (Figure 3). However, by adding 10 mL (11.36%)
or 15 mL (17.01%) of distilled water, no more washes
were needed. For economic reasons, washing one time
using 11.36% of distilled water at 25 C was considered
to be the best choice. Also, washing more than one time
above room temperature is not economically sound,
because of the additional cost, although other research-
ers found it necessary to wash several times or use wash
water at temperatures up to 90 C.23,24,26,27 In Figure 3,
on the x-axis, the first addend of each sum indicates the
percentage of distilled water used during the first step
of the washing process. The second addend indicates the
percentage of distilled water used during the second step
of the washing process, which is needed to achieve a
pH value of the lower layer that is similar to the
pH value of the distilled water, thus indicating that
no impurities were present in the ester layer after
the previous washing step. As in Du Plessis et al.,23
losses of esters during the washing process were<6%
(2%-3%).
8. Fuel Specifications. The fuel properties of the
biodiesel from Brassica carinata oil without erucic acid
were determined with the aid of standard tests. The
biodiesel properties were determined to be similar to
those of diesel fuel (according to standard EN-590) and
were especially similar to those of the EN 14214
standard, thus indicating that methyl esters from
Brassica carinata oil without erucic acid have adequate
values, compared to diesel fuel (Table 2). The iodine
value does not meet the EN 14214 standard. However,
this parameter (which is related to biofuel storage
performance) has not been accepted by the Spanish
government, because it excludes sunflower oil (which
is one of the main Spanish oleaginous crops) from being
used as biodiesel. In this sense, to determine the
implications of this parameter, research concerning the
performance of diesel engines is needed.
The cold filter plugging point (CFPP), pour point (PP),
and cloud point (CP) are three important parameters
that are associated with the engine behavior in cold-
weather operating conditions. However, instead of the
(25) Mittelbach, M. Bioresour. Technol. 1996, 56, 7-11.
(26) Purcell, D. L.; McClure, B. T.; McDonald, J.; Basu, H. N. J.
Am. Oil Chem. Soc. 1996, 73, 381-388.
(27) Canakci, M.; Van Gerpen, J. Trans. ASAE 1999, 42, 1203-1210.
82 Energy & Fuels, Vol. 18, No. 1, 2004 Dorado et al.

Figure 3. Ester pH after washing one and two times with distilled water (percentage of ester weight).

Table 2. Fuel Specifications of Nonerucic Brassica Carinata Oil Methyl Esters, Diesel Fuel (EN-590), and Biodiesel
European Standard (EN 14214)
Value
biodiesel, European diesel fuel, nonerucic Brassica carinata
parameter test method Standard EN 14214 EN-590 oil methyl esters
Distillate Properties
distillate content at 250 C (vol %) ASTM-D-86 <65 0
distillate content at 350 C (vol %) ASTM-D-86 >85 83.60
temperature, 95 vol % (C) ASTM-D-86 360 357.2
Other Properties
density at 15 C (kg/m3) EN ISO 3675 860-900 820-860 888.8
kinematic viscosity at 40 C (mm2/s) ASTM D445*IP-71*BS188 3.5-5.0 2-4.5 4.83
iodine value UNE 55.013 <120 138
flash point (C) ASTM-D-2709 >120 >55 163
cetane number, CNa ASTM-D-613 >46
cetane index, CIa ASTM-D-4737/96a >51.0 56.9
water content (mg/kg) ASTM-D-1744 <500 <50
cold filter plugging point, CFPP (C) IP-309/96 depends on the climate -9
cloud point, CP (C) ASTM-D-2500 -9
pour point, PP (C) ASTM-D-97 -6
Conradson carbon residue (wt %) ASTM-D-4530 0.15 1.73
copper corrosion (3 h, 50 C), degrees ASTM-D-130 Class 1 1 1a
gross heating value (MJ/kg) ISO 1928 39.55
acid value (mg KOH/g) EN 12634 <0.5 0.1
free glycerol (wt %) NF-T-60-704 0.0008 <0.02
a The equations for predicting the cetane number (CN) are not applicable to biodiesel. As an alternative method, the cetane index (CI)
is used for biodiesel.

CP and PP, the European Standard EN 14214 only
includes the CFPP determination. In this sense, non-
erucic Brassica carinata oil methyl ester provides a
suitable fuel for cold-weather use. The CP and PP values
for nonerucic Brassica carinata oil methyl ester are also
more appropriate than those for cottonseed methyl ester
(PP ) -4 C), soybean methyl ester (CP ) +2 C, PP )
-1 C), sunflower methyl ester (CP ) 0 C, PP ) -4
C), or rapeseed methyl ester (CP ) -2 C, with an also
appropriate PP value of -9 C).14
According to the Conradson carbon residue (CCR)
content, which represents the carbon-forming tendency
of fuels, the biodiesel from Brassica carinata oil exhib-
ited a value over the No. 2 diesel fuel specification (EN
590). This could lead to the formation of deposits at the
injector and combustion problems. For this reason, a
long-term performance test should be performed to
verify the formation of abnormal carbon deposits or any
problems related to incomplete combustion that could
require a more frequent cleaning.
Finally, regarding to the low presence of free glycerol,
it can be seen that the glycerol removal was successfully
performed (see Table 2), thus indicating that the
purification step was adequate.
Conclusions
A low-cost transesterification process of Brassica
carinata oil has been described. An oil:methanol molar
ratio of 1:4.6, the addition of 1.4% of KOH, a reaction
Transesterification of Brassica Carinata Oil
temperature in the range of 20-45 C, and 30 min of
stirring are considered to be the best conditions to
develop a low-cost method to produce biodiesel from
Brassica carinata oil. The impurities, including glycerol
traces, are removed after the biofuel is washed with
11.36% of distilled water at 25 C. Results show that
the presence of erucic acid increases the free fatty acid
(FFA) content and prevents the conversion of Brassica
carinata oil in its methyl ester. Also, our results suggest
that there is a correlation between the amount of
methanol required to perform the transesterification of
the oil and the amount of KOH. In this sense, the
greater the presence of KOH, the lesser the methanol
requirements. However, this is valid only under certain
limits. In fact, if the presence of KOH or methanol is
less than the optimal values, the reaction does not fully
occur. Similarly, amounts of KOH or methanol that are
Energy & Fuels, Vol. 18, No. 1, 2004 83
greater than the optimal values lead to soap production,
which prevents separation of the ester layer. Also, a
certain conflict between glycerol solubility and low
temperatures was observed. This is an important factor
to consider while promoting the separation of biodiesel
and glycerol. Finally, based on this field trial, biodiesel
from Brassica carinata oil could be recommended as a
diesel fuel candidate, if long-term engine performance
tests provide satisfactory results.
Acknowledgment. The authors thank KOIPESOL
(Spain), which provided Brassica carinata oil sam-
ples for testing, and REPSOL-YPF, which performed
analytical analysis to determine the biofuel specifica-
tions.
EF0340110