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Study on the glycerolysis reaction of high free fatty acid oils for use as
biodiesel feedstock
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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
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
Author's personal copy
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
Glycerol OH
Esterification
RCOO OCOR Di + H2O
R COOH
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.
Table 1
Range of variables studied.
2. Experimental
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.
Author's personal copy
Fig. 5. Effect of stirring velocity (in rpm) on the glycerolysis reaction, using metallic zinc
as a catalyst.
Fig. 7. Effect of zinc acetate, as a catalyst, on the glycerolysis reaction.
Fig. 6. Effect of zinc, as a catalyst, on the glycerolysis reaction. Fig. 8. Effect of the type of catalyst on the glycerolysis reaction.
Author's personal copy
4. Conclusions [2] M. Canakci, The potential of restaurant waste lipids as biodiesel feedstocks,
Bioresource Technology 98 (2007) 183–190.
[3] P. Felizardo, M. Correia, I. Raposo, J. Mendes, R. Berkemeier, J. Bordado, Production
The results presented in this work show that glycerolysis may be of biodiesel from waste frying oils, Waste Management 26 (2006) 487–494.
used to reduce the FFA content in acidic and low-cost feedstocks for [4] Felizardo, P., Machado, J., Vergueiro, D., Correia, M., Bordado, J., High free fatty acid
oils for biodiesel production, Chempor 2008, Braga, 2008.
biodiesel production. In fact it was possible to reduce the FFA content [5] P. Ing, Base catalysed glycerolysis of fatty acid methyl esters: investigations
of soap-stocks from 50 to 5% after 3 h of reaction at 200 °C. Also it was towards the development of a continuous process, , 2006.
effective in the reduction of FFA content even without the addition of [6] G. Knothe, Dependence of biodiesel fuel properties on the structure of fatty acid
alkyl esters, Fuel Processing Technology 86 (2005) 1059–1070.
any catalyst. It should be also noted that this process can be combined [7] R. Muniyappa, C. Brammer, H. Noureddini, Improved conversion of plant oils and
with methanolysis [4], as the transesterification of the mono, di and animal fats into biodiesel and co-product, Chemical and Biomolecular Engineering
triglycerides, which is the main goal of the global process, occurs Research Publications, 1996.
[8] M. Otto, Chemometrics: statistics and computer aided application in analytical
simultaneously with the esterification reaction.
chemistry, Wiley-VCH, New York, 1999.
In the most favourable case observed, which corresponds to 0.1% [9] J. Puna, J.F.P. Gomes, J.C. Bordado, J.N. Correia, Development of heterogeneous
catalyst, 94.7% methyl esters and 1.1% of FFA were obtained. catalysts for transesterification of triglycerides, Reaction Kinetics and Catalysis
Letters 95 (2) (2008) 273–279.
[10] J. Puna, J.F.P. Gomes, J. Correia, A. Soares Dias, J. Bordado, Advances on the
Acknowledgements development of novel heterogeneous catalysts for transesterification of triglycerides
in biodiesel, Fuel 89 (11) (2010) 3602–3606.
The authors would like to thank Iberol and Space for supplying [11] B. Shanks, D. Clementes, G. Knothe, J. Van Gerpen, R. Pruszko, Biodiesel Production
Technology, July 2004.
industrial samples for the development of this work, as well as Dr. Pedro [12] M. Blanco, R. Beneyto, M. Castillo, M. Porcel, Analytical control of an esterification
Felizardo for the calculations of the biodiesel properties from its NIR batch reaction between glycerine and fatty acids by near-infrared spectroscopy,
Spectrum, and Prof. Joana Neiva Correia for use of the facilities of the Analytica Chimica Acta 521 (2) (2004) 143–148.
Centre for Chemical Processes of UTL.
References
[1] P. Baptista, P. Felizardo, J. Menezes, M. Correira, Multivariate near infrared
spectroscopy models for predicting the methyl esters content in biodiesel,
Analytica Chimica Acta 607 (2) (2008) 153–159.