Biomass and Bioenergy 95 (2016) 340e343

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Biomass and Bioenergy

journal homepage: http://www.elsevier.com/locate/biombioe

Research paper

Esterification of oleic acid with ethanol in the presence of Amberlyst

15
Aleksander Hykkerud, Jorge M. Marchetti*
Department of Mathematical Sciences and Technology, Norwegian University of Life Sciences, Drøbakksveien 31, 1430 Ås, Norway

a r t i c l e i n f o a b s t r a c t

Article history: Biodiesel is a promising cleaner burning, less toxic and renewable energy carrier. It is made primarily by
Received 9 February 2016 transesterification of refined vegetable oils, but biodiesel from these sources are becoming more
Received in revised form expensive. Therefore, alternative raw materials are being evaluated, but a major difficulty in the pro-
29 June 2016
duction of biodiesel from these alternative feedstocks is the high concentrations of free fatty acids. This is
Accepted 1 July 2016
Available online 13 July 2016
mainly due to the saponification reaction which occurs with the most commonly used alkali catalysts.
Therefore in this work a parameter screening of the esterification of oleic acid, a free fatty acid, with
ethanol in the presence of the heterogeneous acid catalyst Amberlyst 15 wet ion exchange was con-
Keywords:
Biodiesel
ducted with the intent to produce biodiesel. The parameters screened were reaction temperature,
Esterification catalyst amount and the ratio between moles of alcohol and moles of fatty acid while the reaction time
Oleic acid was set to 6 h. It was found that higher temperature and catalyst amounts increased conversion;
Ethanol however, the ratio between moles of alcohol and moles of fatty acid that gave the highest final con-
Parameter screening version was 1:1. The highest Biodiesel yield obtained was 53%. In addition a reuse test of the catalyst was
Amberlyst 15 in order to test its recyclability; however, the catalyst presented a reduction in its activity after a single
use.
© 2016 Elsevier Ltd. All rights reserved.

1. Introduction
The world is dependent on fossil fuels and its demand is
increasing, but due to their effect on the environment [1] and
because they are finite fossil fuels should eventually be replaced
with renewable energy alternatives. Among the renewables being
evaluated, biodiesel, which is produced from oils from plants and
animals fats have the advantage of being able to directly replace
fossil diesel with none, or few, modifications to existing engines. It
is commonly produced by transesterification where vegetable oil
reacts with an alcohol in the presence of an alkali catalyst [2,3]. In
2013 the global production of biodiesel was 23,806 million liters
[4], but this has started to put pressure on the prices for vegetable
oils due to increased demand on the world market making bio-
diesel from these sources prohibitively expensive [5]. In addition
this price increase is putting a strain on food availability. As such,
alternative feedstock like waste oils, fats and oils from sources not
considered edible need to be evaluated for the production of
biodiesel as they are cheaper and do not compete with food
* Corresponding author.
E-mail address: jorge.mario.marchetti@nmbu.no (J.M. Marchetti).
production. A common issue with waste oils which causes prob-
lems with conventional methods of producing biodiesel is a high
quantity of free fatty acids. As mentioned earlier the conventional
method of producing biodiesel from vegetable oils involves the
use of alkali catalysts, and the alkali catalyst in the presence of FFA
forms soap which is undesirable as it consumes catalyst, makes
separation of products more difficult and reduces the biodiesel
yield. Instead of using an alkali catalyst, an acid catalyst can be
used to convert the FFA into biodiesel through the esterification
reaction as shown in Fig. 1. This can be done as a pre esterification
step before using an alkali catalyst on the resulting free fatty acid
reduced oil for conventional transesterification. For this purpose
the use of homogeneous acid catalysts such as sulfuric acid is
common and has seen much work [6e8], but this requires cor-
rosive resistant equipment due to high acidity, separation and
neutralization steps and the process also produces significant
amounts of contaminated wastewater [2]. Heterogeneous catalysts
avoid these problems as they are trivial to recover, can also be
reused with minimal effort and offer milder operating conditions
in its use [2]. Several heterogeneous catalysts have been tested for
the esterification of free fatty acids. Altiokka et al. [9,10] and Lee
et al. [11] esterified acetic acid with the use of an acidic polymer

http://dx.doi.org/10.1016/j.biombioe.2016.07.002
0961-9534/© 2016 Elsevier Ltd. All rights reserved.
 A. Hykkerud, J.M. Marchetti / Biomass and Bioenergy 95 (2016) 340e343
Fig. 1. Esterification reaction.
resin Amberlyst 36 using different alcohols, achieving up to 90%
conversion. Amberlyst 15 is a heterogeneous acid catalyst with
good thermal and chemical resistances [12] has been shown to
work in the esterification of oleic acid in the presence of methanol
by Park et al. [13] where the equilibrium was reached after around
6 h getting a conversion of over 90%. Kusakabe et al. [14] also
esterified oleic acid with methanol under Amberlyst 15 getting
conversions between 69.9% and 84.0% at temperatures ranging
from 80  C to 120  C. No work could, however, be found involving
the use of ethanol as the reacting alcohol with Amberlyst 15 used
as catalyst for the esterification of oleic acid.
Therefore, in this work a parameter screening of Amberlyst 15
for the esterification of oleic acid with ethanol was done as well as a
reuse test of the catalyst used under these conditions. Screening
over reaction temperature, ratio between moles of alcohol and
moles of fatty acid and amount of catalyst was performed using
oleic acid and ethanol as raw materials. The experimental work was
done using Amberlyst 15 as catalyst following preparation tech-
nique of Park et al. [13].
2. Materials and methods
2.1. Materials
Oleic acid (90% purity) was purchased from Sigma Aldrich,
anhydrous ethanol was supplied by a local supplier and Amberlyst
15 wet ion exchange was acquired from the Dow Chemical Com-
pany. For the pretreatment of the catalyst 150 mm Filter paper
circles (597) from Schleicher & Schuell, 96% ethanol from a local
supplier and acetone from Sigma Aldrich were used. KOH from
Sigma Aldrich was utilized for titration purposes to determinate the
acid number in biodiesel while phenolphthalein was used for acid/
base measurements.
2.2. Catalyst pre-treatment
The pretreatment method of the catalyst was adapted from the
data sheet from Dow chemical company and from a method
utilized by Park et al. [13]. 100 g of catalyst was placed in a sieve
funnel covered with 150 mm filter paper. 150 ml of 50% anhy-
drous ethanol/water, 70% anhydrous ethanol/water 96% ethanol,
anhydrous ethanol and acetone was run 5 times each through a
sieve containing the catalyst. The catalyst was then left to dry at
70  C in an oven for 72 h and stored in a closed container ready
for use.
2.3. Esterification of oleic acid
The experiments were conducted in a 500 ml glass batch reactor
from Quark, with a condenser to prevent evaporation of alcohol.
The mixture was stirred by a magnetic stirrer at 200 rpm for all
experiments. Heat was applied by circulating warm water from a
water bath with temperature control with an error of ±0.1  C. Oleic
acid and ethanol was added to the reactor and brought up to the
341
target temperature while being stirred. When the target tempera-
ture was reached a zero sample was taken, catalyst was added and
time started. Each experiment was stopped after 6 h. A mass of
40e60 g of oleic acid was added with alcohol amount varying
dependent of the ratio between moles of alcohol and moles of fatty
acid investigated which were 1:1, 3:1, 6:1, 9:1 and 12:1. The tem-
peratures screened were 45  C, 60  C and 75  C while the catalyst
amounts were 10%, 15% and 20% of the weight of oleic acid. Ex-
periments to test the leaching of the catalyst were also performed.
These studies were carried out by agitating Amberlyst 15 and
ethanol for 2 h at 60  C. The catalyst was then removed and
phenolphthalein was added to determine any change in acidity/
basicity of the ethanol.
2.4. Sample analysis
Samples of 1 ml were withdrawn at specific times and cooled
down in an ice bath for 1 min. These samples were then analyzed
immediately after cooling by titration according to standard EN 14104.
2.5. Reuse of catalyst
The catalyst was collected after use, was rinsed with ethanol and
left to air dry at room temperature for 24 h after which is was used
with the same procedure as the previous esterification experi-
ments. The operating conditions of the reuse experiment were
temperature at 60  C, 20% catalyst amount and a ratio between
moles of alcohol and moles of fatty acid of 6:1.
3. Results
The conversion of oleic acid to fatty acid ethyl esters (FAEE) as a
Fig. 2. Temperature variance results run at 20% catalyst amount and a ratio between
moles of alcohol and moles of fatty acid of 6:1 with temperatures 45  C ( ), 60  C ( )
and 75  C ( ).
342 A. Hykkerud, J.M. Marchetti / Biomass and Bioenergy 95 (2016) 340e343

function of time under different temperatures can be seen in Fig. 2.

The temperature range studied varied from 45  C to 75  C which is
below the boiling point of ethanol. This is to assure that the alcohol
will be in the liquid phase at all times and to avoid pressure
buildup.
As can be seen in Fig. 2, the lower temperatures give a reduced
conversion in comparison with higher temperature values. Also, as
expected, the effect of temperature can be observed to affect the
reaction rate. Where for 75  C the reaction is faster at the initial
times than for the other two batch runs at lower temperatures.
These results are in agreement with those presented by Park et al.
[13]. It is, however, important to notice that in this work the
equilibrium has not yet been reached. The reason why the reaction
has been stopped after 6 h is in order to have a more substantial
comparison with earlier mentioned work. It is expected that if the
reaction would have been allowed to continued, the higher tem-
peratures would have provided a higher final equilibrium conver-
sion, as presented by Park et al. [13]. This is also supported by work
carried on by other researchers such as that by Marchetti et al. [15]
Fig. 4. Molar ratio experiments run at 60  C and catalyst amount of 20% with the final
where the esterification reaction using Dow resins has shown to be conversion shown for each separate experiment with ratios between moles of alcohol
an endothermic reaction. and moles of fatty acid of 1:1( ), 3:1( ), 6:1( ), 9:1( ) and 12:1( ).
In Fig. 2, in times below 30 min it can be seen an unusual behavior
where the middle temperature seems to have a higher conversion
than the highest temperature tested. This could be due to the The ratio between moles of alcohol and moles of fatty acid was
measurement error in the technique and methods. The temperature varied from 1:1 to 12:1, while catalyst amount and temperature
dependence batch runs were performed with a ratio between moles were fixed at 20 wt % and 60  C respectively.
of alcohol and moles of fatty acid of 6:1 and 20 wt % of catalyst. In this case a lower ratio between moles of alcohol and moles of
The conversion of oleic acid to FAEE as a function of time with fatty acid appears to give higher final conversion. As the esterifi-
different catalyst wt. % can be seen in Fig. 3. The catalyst amount cation is an equilibrium reaction this is counter intuitive and does
was varied from 10 wt % to 20 wt %, while ratio between moles of not fit with earlier mentioned literature, but as the reaction did not
alcohol and moles of fatty acid and temperature were fixed at 6:1 reach the equilibrium it can be said to be in initial stage and the
and 60  C respectively. final equilibrium state does not apply. An experiment with a time
It is clear from Fig. 3 that higher catalyst amounts give higher frame of 50 h was carried out which is 8.3 times bigger than the
conversion and faster reaction rates. The faster reaction rates are as reaction time utilized in the experiments, it can be observed in
expected and in line with literature, but regarding the final con- Fig. 5 that the equilibrium has not yet been reached, based on this
version, catalyst amount should not affect the final conversion. As the previous results are for a reaction that is taking place in its
mentioned earlier the equilibrium has not been reached and this is transit state not close to equilibrium; therefore, the effect pre-
the reason for the apparent higher final conversion. It is expected sented in Fig. 4 is in accordance to Marchetti [16] where a ratio
that if the equilibrium was allowed to be reached the final con- between moles of alcohol and moles of fatty acid of 1:1 gives the
version would be equal in each run. highest initial reaction rate which is what is believed to be observed
Fig. 4 shows the final conversion of oleic acid to FAEE as a in the results. If the reaction would have been allowed to continue
function of ratio between moles of alcohol and moles of fatty acid. to equilibrium the final conversions would likely be in the order of

Fig. 3. Catalyst amount experiments run at 60  C and a ratio between moles of alcohol Fig. 5. Conversion of oleic acid at 6:1 ratio between moles of alcohol and moles of fatty
and moles of fatty acid of 6:1 with catalyst amount at 10% ( ) 15% ( ) and 20% ( ). acid, 60 C, 20% catalyst amount and 200 rpm for 50 h.
 A. Hykkerud, J.M. Marchetti / Biomass and Bioenergy 95 (2016) 340e343
higher conversion with higher ratio between moles of alcohol and
moles of fatty acid.
The catalyst showed reduced activity after a single reuse. This is
most likely due to water blocking the active sites of the catalyst
which was reported by Kusakabe et al. [14].
4. Discussion & conclusion
The reaction under consideration was studied under different
operational variables. The reaction equilibrium was not reached in
any of the tested conditions, and therefore, the process can be
considered on its transit state.
As presented in Fig. 2, the effect of temperature follows an
endothermic behavior. This behavior was in agreement with those
previously established by other researchers [13,15]. The appliance
of temperature was limited by the boiling point of the alcohol
(ethanol) and the lower temperature that could allow a kinetics
process to develop.
The impact of catalyst amount on the reaction kinetics is shown
in Fig. 3. Higher concentration of catalyst gives a higher reaction
rate. The effects of amount of alcohol on the reaction rate is shown
in Fig. 4. The obtained results suggested that the small amount of
alcohol (equal or higher than the stoichiometric value) leads to a
higher reaction rate, whereas, higher alcohol concentration resul-
ted in slower reaction rate but superior final conversion. This effect
was also presented by Marchetti [16].
It is clear from Figs. 2, 3 and 5 that the equilibrium of the re-
action was not reached. As such the results do not reflect the final
conversion relations that might be achieved at longer reaction
times. Therefore the catalyst amount appears to give increased
conversion even though according to literature and theory should
not affect the final conversion. The same goes for the ratio between
moles of alcohol and moles of fatty acid which generally gives
higher conversion at higher ratio between moles of alcohol and
moles of fatty acid. The trend for the obtained results with the ratio
between moles of alcohol and moles of fatty acid was in agreement
with the work reported by Marchetti [16], wherein the initial re-
action rate of the esterification reaction with oleic acid and ethanol
was determined to be the highest at a ratio between moles of
alcohol and moles of fatty acid of around 1:1.
343
Acknowledgements
The support of the Norwegian University of Life Sciences is
greatly appreciated.
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