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Fuel Processing Technology 92 (2011) 1225–1229

Contents lists available at ScienceDirect

Fuel Processing Technology

j o u r n a l h o m e p a g e : w w w. e l s ev i e r. c o m / l o c a t e / f u p r o c

Study on the glycerolysis reaction of high free fatty acid oils for use as
biodiesel feedstock
Pedro Felizardo a, João Machado a, Daniel Vergueiro a,c, M. Joana N. Correia a, João Pereira Gomes b,c,⁎,
João Moura Bordado b
a
IST-Instituto Superior Técnico/UTL, Centre for Chemical Process, Av. Rovisco Pais, 1049-001 Lisboa, Portugal
b
Centre for Biological and Chemical Engineering, IBB-Institute for Biotechnology and Bioengineering, IST-Instituto Superior Técnico/UTL-Technical University of Lisbon, Av. Rovisco Pais,
1049-001 Lisboa, Portugal
c
Chemical Engineering Dept., ISEL-Instituto Superior de Engenharia de Lisboa, R. Cons. Emidio Navarro, 1959-007 Lisboa, Portugal

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

Article history: Biodiesel is the main alternative to fossil diesel and it may be produced from different feedstocks such as semi-
Received 6 December 2010 refined vegetable oils, waste frying oils or animal fats. However, these feedstocks usually contain significant
Received in revised form 23 January 2011 amounts of free fatty acids (FFA) that make them inadequate for the direct base catalyzed transesterification
Accepted 25 January 2011
reaction (where the FFA content should be lower than 4%). The present work describes a possible method for the
Available online 1 March 2011
pre-treatment of oils with a high content of FFA (20 to 50%) by esterification with glycerol. In order to reduce the
Keywords:
FFA content, the reaction between these FFA and an esterification agent is carried out before the transesterification
Biodiesel feedstock reaction. The reaction kinetics was studied in terms of its main factors such as temperature, % of glycerin excess, %
Acid oils of catalyst used, stirring velocity and type of catalyst used. The results showed that glycerolysis is a promising pre-
Soap-stocks treatment to acidic oils or fats (N 20%) as they led to the production of an intermediary material with a low content
Glycerolysis of FFA that can be used directly in the transesterification reaction for the production of biodiesel.
© 2011 Elsevier B.V. All rights reserved.

1. Introduction

The current increase of the costs of petroleum based fuels has resulted in a growing interest on alternative fuels, such as biodiesel (fatty acid
methyl esters or FAME), which can be mixed with diesel and fuelled to traditional engines [9].
Biodiesel production by conventional homogeneous catalysis is, actually, a well known process. Regarding biodiesel production the main
interest was put on the transesterification reaction aiming to produce methylic esters, whereas a lipid source (vegetable oils and fats) and an
alcohol (usually methanol) react producing an ester and a by product, which is glycerol as described by reaction 1 [10]. This reaction occurs
stepwise, with mono and diglycerides as intermediate products.

H2C OH O
RCOO CH2

+ 3 ROH HC OH + 3 R O C R (Reaction 1)
RCOO CH

H2C OH
RCOO CH2

Triglyceride Methanol Glycerol Biodiesel

However, the step of recovery and purification of glycerine is also important due to the need to further process the latter compound. Apart
from that, it should be noted that the feedstock represents a significant part of the total cost of biodiesel production. Thus, these costs can be
considerably reduced if biodiesel is produced from low cost materials such as waste frying oils, animal fats and soap-stocks. The problem is that
the transesterification of vegetable oils using alkaline catalysts can only be done if the acidity value of the oil, due to the presence of free fatty acids, is

⁎ Corresponding author at: Chemical Engineering Dept., ISEL-Instituto Superior de Engenharia de Lisboa, R. Cons. Emidio Navarro, 1959–007 Lisboa, Portugal.
E-mail address: jgomes@deq.isel.ipl.pt (J.P. Gomes).

0378-3820/$ – see front matter © 2011 Elsevier B.V. All rights reserved.
doi:10.1016/j.fuproc.2011.01.020
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1226 P. Felizardo et al. / Fuel Processing Technology 92 (2011) 1225–1229

lower than 4 mg KOH/g of oil, which corresponds to 2% [6]. A higher value would result in a decrease of the yield of the transesterification reaction.
There are several types of vegetable fats having a high free fatty acid (FFA) content which are not consumed at all and, therefore, are used in the
production of low cost soaps, such as the above mentioned soap-stocks. These fats are difficult to undergo transesterification reactions by alkaline
catalysis. A possible way to reduce the acidity content of the fat is to refine it, which will increase significantly the processing costs. It should be noted,
also, that the type and content of free fatty acids in the oil are dependent from the vegetable species used and also its main growing conditions.
The esterification of these type of fats is of interest as a viable process to decrease its acidity and, thus, to reduce the cost of biodiesel
production. This work is focused on obtaining biodiesel from olein of soy beans.
The esterification reaction of fats having a high free fatty acid content was already identified as a way to produce biodiesel [2,3].
This process comprised an esterification pre-treatment to the oil, using an alcohol which could be methanol or glycerine. This reaction,
proceeding with glycerine, is designated by glycerolysis (reaction 2).

OH

OH HO OCOR Mono + H2O

HO OH

Glycerol OH
Esterification
RCOO OCOR Di + H2O

R COOH

Fatty acid OCOR

RCOO OCOR Tri

+ H2O
(Reaction 2)

In order to shift the reaction equilibrium to the left, the product water has to be removed efficiently from the reaction vessel. Several
heterogeneous catalysts have been mentioned in the literature to increase the reaction conversion, such as metallic zinc or zinc chloride [11].
Glycerolysis is used only when the free fatty acid content is high (5–60% of FFA). After this pre-treatment, the glycerides in the oil/ester phase
can be transesterified by basic catalysis.
The main drawback of this process is that it proceeds by a slow reaction, taking place at a high temperature and being limited by equilibrium,
having two liquid phases, where the solubility of glycerine is rather limited in triglycerides. It should also be noted that the use of a glycerine
excess does not necessarily result on higher equilibrium conversion [5].
The fact that the reaction proceeds at high temperature, results in frequent unwanted decomposition and oxidation reactions originating a dark
product, with a strong odour and a low yield of monoglycerides [12]. For this reason, the temperature limit is set at 250 °C (Muniyappa, 1996).
The glycerolysis process, using alkaline catalysis, is not yet fully understood and, therefore, is still subject of research. The kinetics of the reaction is
still not known, which could be due to the multiphase nature of the samples and also to the analysis of samples from the reaction mixture [5].
One of the most important factors on the process is the degree of contact between the olein and the glycerine, which is, of course related with
its relative solubility. Being liquid phases with rather different densities, any temperature increase of the reaction will result in increasing mass
transfer in the phase containing triglycerides to the glycerine phase and increases solubility of both phases. The process can also be improved by
agitation, thus improving a better contact between the two liquid phases.
Monoglycerides are the main product of the reaction, but diglycerides and triglycerides are also present as products. After reaction completion, the
mixture should be cooled in order to prevent any reversion of monoglycerides. Unreacted glycerin can be separated by decantation or by vacuum
distillation, and recycled back to the reactor. After glycerine removal, monoglycerides can be separated by vacuum distillation [7].
To study the influence on glycerolysis of the several experimental variables, a factorial design planning of the experiments was used, with 6
factors (excess % of glycerine, temperature, % of catalyst used, stirring velocity, type of catalyst used and reaction time) and three levels. Factorial
planning of experiments is especially important in the beginning of an experimental study and they reveal high precision with minimum
experimental effort and they enable detection of factor interactions [8].
The present work describes the application of glycerolysis for the pre-treatment of acidulated soap-stocks with a high content of free fatty
acids (20 and 50%). The potential use of these raw materials for biodiesel production can be quite interesting as they are available at low cost and
present a regular quality.

Fig. 1. Process for the production of acidulated soap-stocks.

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P. Felizardo et al. / Fuel Processing Technology 92 (2011) 1225–1229 1227

Table 1
Range of variables studied.

Variable Variation range

Temperature (°C) 180/210/220/230

% of glycerine excess 4 to 65
% of catalyst used 0.1 to 0.4
Stirring velocity 300 and 500 rpm
Type of catalyst Zinc and zinc acetate
Reaction time 90 and 180 min

2. Experimental

Acidulated soap-stocks were produced in a laboratory scale

reactor from industrial soap-stocks produced in the soybean oil
neutralisation process. This material contains soaps, oil and salts,
and yields, after treatment, an oil rich phase with FFA and
triglycerides, which is usually referred to as acidulated soap-stocks.
The procedure used in this work to produce this acidulated soap-
stock consists in adding into the reactor 150 g of soap-stocks plus
150 ml of hydrochloric acid (37%) and 500 ml of water. After 3 h of
reaction at 100 °C, the reaction yields two immiscible phases, one
containing the oil and the FFA and an aqueous phase containing the
acids and salts, as depicted in Fig. 1. The oil-rich phase is then
washed several times with a solution of 120 to 130 mg KOH/g (60–
65% of FFA).
Then, the glycerolysis was carried out using the following
procedure: the acidulated soap-stock and glycerol were added to a
stirred reactor equipped with a condenser. The reaction was carried
out at 200 °C, 350 rpm for 2 h. The glycerol was supplied by a local
biodiesel company and was neutralised with sulphuric acid before
use. The samples withdrawn from the reactor were analysed without
further purification steps.
All chemicals used in this study that were not mentioned
previously were analytical grade and were supplied by Merck. The
acid value of the samples was determined after sample purification
according to EN 14104, whereas EN ISO 12185 was used to determine
the density of samples. Whenever possible, the fatty acid methyl
ester content of the samples was estimated by Near Infrared
Spectroscopy [1], using a NIR BOMEM spectrometer and a SOLVIAS
AG probe.
The experimental conditions were established after a literature
review, as shown in Table 1.
This study was performed considering duplicates for each test. The
results presented thereafter are the arithmetic averaged values.
Fig. 3. Effect of glycerin excess on the glycerolysis reaction.
3. Results and discussion
3.1. Temperature
In order to study the temperature effect on the glycerolysis
reaction tests were performed at temperatures of 180, 220 and 230 °C.
The results are presented in Fig. 2. From this figure we are able to
conclude that the temperature increase favours the reaction, and its
kinetics is considerably faster at 230 °C. However, the more significant
differences seem to occur when the temperature increases from 180
to 220 °C. Apart from other reaction factors, the temperature increase
is bound to provide a better homogenisation of the reactional mixture,
which will result in a decrease of acidity.
3.2. Glycerine excess
Considering this reaction, one mol of glycerine reacts with one mol
of FFA yielding one mol of monoglycerides. Thus, an excess of 4% of
glycerine corresponds to a molar ratio glycerine/FFA of 1.04, and the
percentage of FFA is calculated from the following equation:
%FFAðC18:1 Þ = IAC × ðMFFA = MKOH Þ × ð100 = 1000Þ
where:
MFFA is the molar mass of fatty acid C18:1 (g/mol)
IAC is the acidity index of the sample (mg KOH/g oil)
MKOH is the molar mass of KOH (g/mol)

Fig. 2. Effect of reaction temperature on the glycerolysis reaction. Fig. 4. Effect of stirring velocity (in rpm) on the glycerolysis reaction, without a catalyst.
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1228 P. Felizardo et al. / Fuel Processing Technology 92 (2011) 1225–1229
Fig. 5. Effect of stirring velocity (in rpm) on the glycerolysis reaction, using metallic zinc
as a catalyst.
Therefore, in order to study the effect of glycerine excess on the
glycerolysis reaction, tests were performed at 220 °C with a glycerine
excess of 4, 11 and 52%. A temperature of 220 °C was chosen as the
simplest to perform the reaction. Also in spite of somewhat slower
kinetics, the final acidity value is quite similar to the one obtained at a
reaction temperature of 230 °C.
The results are shown in Fig. 3. It can be noticed that the use of a
glycerine excess in this reaction did not lead to any improvements in
the reaction kinetics at a temperature of 220 °C. Therefore, all further
tests were performed using a glycerine excess of 10% (molar ratio
glycerine/FFA = 1.10).
3.3. Stirring velocity
This particular series of tests was intended to evaluate if an
increase on the stirring velocity would result on a faster kinetic of the
glycerolysis. This study was performed with 2 tests without catalyst
and other two tests with a catalyst, on stirring velocities of 300 and
500 rpm. The results are presented on Figs. 4 and 5. These results
showed that no significant improvements were obtained when the
stirring velocity was increased from 300 to 500 rpm. Also, it was
observed that a stirring velocity of 300 rpm is not enough to obtain an
adequate mixture between the olein phase and the glycerine phase in
the tests performed without a catalyst. In the tests with a catalyst it
Fig. 6. Effect of zinc, as a catalyst, on the glycerolysis reaction.
Fig. 7. Effect of zinc acetate, as a catalyst, on the glycerolysis reaction.
seems more appropriate to use a stirring velocity of 500 rpm. It can be
also noticed that, in the tests without a catalyst, more than 2 h are
needed to obtain a final acidity value of 6.8 mg. Fig. 5 shows that, by
that time, using a catalyst, and a stirring velocity of 500 rpm, a final
acidity value of 3.6 mg is obtained.
3.4. Presence and type of catalyst
It was observed previously, that the use of metallic catalysts
favours the reaction kinetics aiming at the production of monoglycer-
ides from oils and fats [11]. Therefore, in this work, two different
catalysts were used: metallic zinc and di-hydrated zinc acetate. In all
tests the added catalyst mass was calculated so that the zinc content
in the mixture was 0.1, 0.2 and 0.3%. The results are presented in
Figs. 6–8. These results show that both catalysts have the same effect
on reaction kinetics, as shown in Fig. 8. Also, it can be noted that an
increase of the mass percentage of catalyst used favours the reaction
kinetic until a reaction time of 60 min, but does not seem to affect the
final acidity value for more 60 min. However, in the tests without
catalyst it was necessary to wait 120 min to achieve the same final
value of acidity.
When using 0.1% catalyst, 94.7% methyl esters and 1.1% of FFA
were determined.
Fig. 8. Effect of the type of catalyst on the glycerolysis reaction.
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P. Felizardo et al. / Fuel Processing Technology 92 (2011) 1225–1229
4. Conclusions
The results presented in this work show that glycerolysis may be
used to reduce the FFA content in acidic and low-cost feedstocks for
biodiesel production. In fact it was possible to reduce the FFA content
of soap-stocks from 50 to 5% after 3 h of reaction at 200 °C. Also it was
effective in the reduction of FFA content even without the addition of
any catalyst. It should be also noted that this process can be combined
with methanolysis [4], as the transesterification of the mono, di and
triglycerides, which is the main goal of the global process, occurs
simultaneously with the esterification reaction.
In the most favourable case observed, which corresponds to 0.1%
catalyst, 94.7% methyl esters and 1.1% of FFA were obtained.
Acknowledgements
The authors would like to thank Iberol and Space for supplying
industrial samples for the development of this work, as well as Dr. Pedro
Felizardo for the calculations of the biodiesel properties from its NIR
Spectrum, and Prof. Joana Neiva Correia for use of the facilities of the
Centre for Chemical Processes of UTL.
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