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Fuel Processing Technology 90 (2009) 599605

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Fuel Processing Technology


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

A Transesterication Double Step Process TDSP for biodiesel preparation from fatty
acids triglycerides
D. Samios , F. Pedrotti, A. Nicolau, Q.B. Reiznautt, D.D. Martini, F.M. Dalcin
Laboratory of Instrumentation and Molecular Dynamic, Institute of Chemistry, Federal University of Rio Grande do Sul 9500, Bento Gonalves Av., Box 15003, Porto Alegre, RS, Brazil

a r t i c l e

i n f o

Article history:
Received 1 July 2008
Received in revised form 6 October 2008
Accepted 18 December 2008
Keywords:
Transesterication
Acid
Basic
Biodiesel production
Catalysis

a b s t r a c t
This study introduces a two consecutive steps basicacid transesterication process, (denominated
Transesterication Double Step Process TDSP) for biodiesel production from vegetable oils. The process
involves homogeneous consecutive basicacid catalysis steps and is characterized by formation of welldened phases, easy separation procedures, high reaction velocity and high conversion efciency. The
proposed TDSP is different in relation to other traditional two-step procedures which normally include acid
esterication followed by basic transesterication, or enzymatic or even supercritical transesterication
conditions. The biodiesel (fatty acid methyl esters) was analyzed by standard biodiesel techniques in
addition to 1H-NMR, indicating high quality and purity biodiesel products. The transesterication of
sunower and linseed oils resulted in oil conversions higher than 97% corresponding to yields of 85%. A
probable reaction mechanism responsible for the process is presented.
2009 Elsevier B.V. All rights reserved.

1. Introduction

1.1. Transesterication

Approximately 100 years after the initial experiences of Rudolph


Diesel, the international community with new chemical knowledge,
evaluates the possibility to obtain biofuels, similar to the Diesel fuel, as
well as, other products from the chemical treatment of triglycerides
(vegetable or animal fats and oils). This development is based on the
knowledge of catalytic processes as well as the evolution of
instrumental techniques, which permitted the elucidation of the
esterication mechanisms and consequently the study of transesterication. Homogeneous and heterogeneous processes were studied
focusing on basic, acid and enzymatic catalysis [118].
Usually, two-step procedures were used to prepare biodiesel from
different oils, which have high content of free fatty acids [1926]. In
these works the rst step is the acid catalyzed esterication, which
reduces the free fatty acids (FFA) content of the oil and minimizes the
soap formation in the second step (basic catalyzed transesterication). Other papers reported the biodiesel production by two-step
process using supercritical conditions [2731], as well as employment
of enzymes [3234]. The present work presents a new two-step
procedure based on the combination of consecutive basic and acid
catalysis. Therefore, there is no initial acid attack and acid esterication stage for elimination of free fatty acids as proposed by other
papers. Additionally, as it is going to be shown, the second step is not a
simple neutralization, but constitutes a catalytic stage.

The ideal transesterication with a primary alcohol is given by the


overall reaction, Fig. 1. The main feature of this reaction is the
transformation of the triglyceride to glycerol and three ester
molecules. These esters constitute the components of the biodiesel.
The reaction includes at least a catalytic component.
In reality the transesterication process never occurs in the ideal
form. A better approximation is given by the scheme Fig. 2 where the
chemical agents and products are present without consideration of
stoichiometric parameters. So, after nishing the reaction, we must
count with the presence of triglycerides, diglycerides, monoglycerides, biodiesel esters, glycerol, alcohol, and catalytic components and
in the case of basic catalysis, soap moieties. In the literature, there is no
evidence of transesterication with 100% conversion efciency.
Normally the basic catalysis presents conversions of approximately
82%, however the acid catalysis provides higher conversions,
approximately of 98% but the process is extremely slow [13,68].

Corresponding author. Tel.: +55 5133086291; fax: +55 5133087304.


E-mail address: dsamios@iq.ufrgs.br (D. Samios).
0378-3820/$ see front matter 2009 Elsevier B.V. All rights reserved.
doi:10.1016/j.fuproc.2008.12.011

1.2. Catalytic processes


In this part some aspects of the advantages and disadvantages of
acid and basic catalysis are presented. This discussion is important in
order to elucidate the new transesterication procedure and the
mechanism proposed in this work.
1.2.1. Acid catalysis
The acid catalysis transesterication includes the combination of
three reversible reactions (Fig. 3). The high conversion of the acid

600

D. Samios et al. / Fuel Processing Technology 90 (2009) 599605

Fig. 1. Ideal process of transesterication.

Fig. 2. Real transesterication process.

catalyzed transesterication procedure is due to capacity to transesterify


fatty acids and fatty acid salts present in the system. The employed acids
are HCl, H2SO4, BF3 and sulfonic acids [13,14]. However, it is generally
accepted, that the acid catalysis is many times slower than the basic. The
velocity of the biodiesel production reaction with acid catalyst is related
to the conditions of the transesterication reaction. We mention the
alcohol/triglyceride molar ratio, the temperature, the concentration of
catalyst, the purity of reactants which affect velocity and chemical
equilibrium [1,47]. The alcohols used in this process are methanol,
ethanol, propanol, butanol (n, s, and t) and amyl alcohol [1]. The alcohol/
triglyceride molar ratio is essentially large; generally, the best one is
approximately 12 alcohol molecules for 1 triglyceride molecule. The
excess is used in order to shift the reaction equilibrium, to avoid the
reverse reactions and to accelerate the process [1,5,7]. The temperature
inuences the velocity of the electrophilic attack; this way affects the
yields and consequently decreases production cost [1,5,6]. The concentration of catalyst is directly related to the yields; in excess the one
promotes reverse reactions, while a low catalyst concentration results in
a limited process evolution [4,6,8,13]. The impurities promote parallel
reactions, however higher temperature and pressure can eliminate this
inuence, but yields cannot be optimized [4].

1.2.2. Basic catalysis


The basic catalysis is the industrially more used transesterication
process. It presents many advantages as a fast reaction with low
alcohol/triglyceride molar ratio and good yields [5,14]. However the
basic catalysis requires more rigid anhydrous conditions than the acid.
The presence of water leads to irreversible hydrolysis of lipids [36,9].
It can form emulsion or soap if the catalyst concentration is higher
than the necessary one. Essentially the species used in this process are
potassium hydroxide, sodium hydroxide, and generally Lewis bases,
except the oxides that form heterogeneous systems. According to
Fig. 4, it is observed the formation of the active species, with similar
manner to the alkoxides. The active species attack the carbonyl moiety
in triglyceride, originating a tetrahedral intermediate, from which the
alkyl ester and the corresponding anion of the diglyceride are formed
[12,16,17]. Regeneration of the active species occurs after the
liberation of the mono alkyl ester. The formation of the glycerol
occurs in the nishing of the process. Normally a small excess of the
alcohol is necessary in order to dislocate the equilibrium to the
products and to avoid parallel reactions [5]. The reaction time
decreases signicantly by using temperatures near the boiling point
of the alcohol [4,5].

Fig. 3. Mechanism of transesterication according to acid catalysis.

D. Samios et al. / Fuel Processing Technology 90 (2009) 599605

601

Fig. 4. Mechanism of transesterication according to basic catalysis.

1.2.3. The proposed TDSP


The understanding of the basic and acid catalysis mechanisms
permitted to introduce the TDSP. The experimental procedure, as well
as, the suggested chemical mechanism are elucidated next topics of
the paper.
2. Experimental

products and the conversion degrees are discussed using 1H-NMR


spectra. Additionally for the characterization of the biodiesel an
Analysis Protocol was followed which includes the techniques:
specic weight at 20 C (ABNT NBR 14065), ash point (ABNT NBR
14598), cloud point (ASTM D 6371) and kinematic viscosity at 40 C
(ABNT NBR 10441) and FAAS Flame Atomic Absorption Spectroscopy for the determination of sodium and potassium remainder in
the product.

2.1. Materials
3. Results and discussion
The present study uses different types of oils which mainly include
the unsaturated fatty acids: oleic acid (C181), linoleic acid (C182) and
linolenic acid (C183), The alcohol used in this process is methanol
(MeOH) and the catalysts are potassium hydroxide (KOH) and sulfuric
acid (H2SO4). The reactants used were sunower oil Molinos
(Rosario, ARG), linseed oil Farmaqumica, (Porto Alegre, Brazil),
methanol (99.9% P.A.) Synth (So Paulo, Brazil), potassium
hydroxide (98.1% Purity) Nuclear (Diadema, Brazil), H2SO4 (98% P.
A.) Merck (Darmstadt, Germany), CDCl3 (99.8% D with 0.03% (v/v)
TMS) Aldrich Chemical Co. (Milwaukee, WI).
2.1.1. The Procedure of the Transesterication Double Step Process
TDSP
The procedure is a sequence of operations, performed approximately in 4 h. Initially the alkali agent is dissolved in methanol (25 g
KOH in 1 L methanol) in a temperature near 45 C permitting the
formation of the basic catalysis active species. Forty mL of this solution
and 100 mL of vegetable oil, under vigorous and constant agitation, are
introduced in a simple reactor equipped with reux device. The molar
ratio of alcohol/oil is 10 and catalyst/alcohol is 1.78 .10 2. The
temperature is increased until 60 C, near the boiling point of the
alcohol. The system stays in this condition for approximately 1 h. After
this period the system is cooled down to approximately 25 C. The
second main step of the procedure consists of the addition of 60 mL
methanol and 1.5 mL sulfuric acid 18 mol/L in the reactions mixture
followed by soft heating. The reaction mixture is submitted to constant
agitation and the temperature is elevated until 60 C by using the reux
equipment. The heating stabilizes and the system remains in this
condition for 1 h. After this period the system is cooled slowly to
approximately 25 C. In the end of this step the formation of two
phases occurs. The two phases are separated and processed further.
The biodiesel phase is washed with cool water and the residual alcohol
is removed by evaporation under vacuum. The lower phase presents
pH approximately 6 and is used for recuperation of the methanol
excess, the glycerol, as well as, other secondary products.
2.1.2. Characterization
The oils used in this study, as well as, the biodiesel products of the
TDSP procedure were characterized using Nuclear Magnetic Resonance Analysis (Varian - INOVA 300, 300 MHz) in CDCl3 (99.8% D with
0.03% (v/v) TMS) solutions. The chemical characteristics of the

3.1. 1H-NMR and the Analysis Protocol


The 1H-NMR spectra of linseed oil and biodiesel product are shown
in Figs. 5 and 6, respectively. In both gures are presented general
schemes, which include the characteristic NMR shift values of protons
for vegetable oils and methyl esters. In Fig. 5 the methylene and the
methine protons of the glyceride sequence CH2CHCH2 can be
observed in the range between 4.224.42 ppm and 5.37 ppm
respectively [35]. Qualitative analysis of Fig. 6 indicates the conversion
of the triglycerides to methyl esters due to the disappearance of the
resonance signal between 4.22 and 4.42 ppm and the emergence of
the new signal at 3.67 ppm [10]. The same 1H-NMR characteristics are
observed in the transesterication of the sunower oil.
A reliable methodology for 1H-NMR characterization of mono, di
and tri acylglycerides, as well as, fatty acid methyl esters was
established during the last decade [1012,15,18,35]. The mentioned
literature presents fundamentals for the calculation of the conversion
(in %) CME, where ME responds to the methyl ester. According to 1HNMR technique, the normalized integrated intensity of the glyceridic
(4.22 and 4.42 ppm) or the methyl ester hydrogens (3.67 ppm) have
to be considered. The conversion C (in %) of vegetable oil to biodiesel
can be calculated from the evaluation of the general Eq. (1):
1
0
IiQTAG QIf QTAG
A
C = 100x@
IiQTAG

where Ii-TAG and If-TAG are the initial and nal normalized integrated
intensities of the signal in the range between 4.22 and 4.42 ppm.
Considering the integration values of the glyceridic (TAG), the methyl
ester (ME) hydrogens and the methylene groups adjacent (-CH2) to
the ester group NMR signals, the Eqs. (2) and (3) permit the
conversion calculation.


4xIME
2
CME = 100x
4xIME + 9xITAG

CME

!
6xIME
= 100x
:
9xIaQCH2

602

D. Samios et al. / Fuel Processing Technology 90 (2009) 599605

Fig. 5. 1H NMR spectrum of linseed oil and a general scheme, which includes the NMR shift values of protons for a vegetable oil.

IME is the integration value of the methyl ester peak and ITAG is the
integration value of the glyceridic peaks in the triacylglycerides (TAG)
of the vegetable oil. The factors 9 and 6 result from the fact that the
three methyl ester moieties resulting from one triglyceride molecule
have nine hydrogens (3.67 ppm) and the three methylene groups
adjacent to the ester group in both vegetable oil and biodiesel have six
hydrogens (2.31 ppm) [10]. With respect to Eq. (2), many authors
have erroneously used the factor 5, considering that the glycerol
moiety of a triglyceride has ve protons contributing at (4.22
4.42 ppm), however according to literature [35] the methine
hydrogens present signal at 5.37 ppm and the correct factor must be

4. Note that mono and diacylglycerides, which are formed as


intermediates in the transesterication reaction, exhibit signals of
their glyceridic hydrogens in the same region as glyceridic hydrogens
of the triacylglycerides in the feedstock.
The normalization factor NF can be obtained by using one or the
sum of some peaks that do not suffer change after reaction. For this
reason we choose the signal at 2.31 ppm which corresponds to the
methylene hydrogens adjacent to the ester group in both vegetable oil
and biodiesel. The terminal methyl group might also be used.
According to Vigli et al. [35] and Gelbard et al. [12], it appears as a
superposition of triplets in the range between 1.1 and 0.88 ppm as

Fig. 6. 1H NMR spectrum of biodiesel from linseed oil and a general scheme, which includes the NMR shift values of protons for a methyl ester.

D. Samios et al. / Fuel Processing Technology 90 (2009) 599605

603

Fig. 7. A suggested mechanism for the Transesterication Double Step Process TDSP.

indicated in Fig. 5. More specically the end methyl triplet of


triunsaturated fatty acids and esters is centered at 0.95 ppm while
all the other appears at 0.88 ppm. The evaluation of the 1H-NMR data
of the sunower and linseed oils and the corresponding biodiesel
products indicate conversion degrees of vegetable oil to fatty acid
methyl ester higher than 97%. As it can be seen in Fig. 6 the 1HNMR
spectrum indicates only the presence of pure fatty acid methyl ester.

There is no presence of triglyceride (4.224.42 ppm), di or monoglycerol (small peaks at 3.44.1 ppm) evidenced. In other words the
proposed procedure results to high purity fatty acid methyl ester and
this is coherent with the nal elevated value of methanol/triglyceride
ratio used for this purpose.
The yields (w/w %), by using the TDSP procedure, were
calculated by Eq. (4) taking into account the initial volume of the

Table 1
Results of the Analysis Protocol for the biodiesel from linseed and sunower oils
Physicochemical property

Linseed oil biodiesel

Sunower oil biodiesel

Technique

Biodiesel specication according to American (AM),


European (EN) and Brazilian (BR) norms

Specic weight at 20 C (g/mL)


Flash point, minimum C

0.88
163 4

0.88
140 4

ABNT NBR 14065a


ABNT NBR 14598a

Kinematic viscosity at 40 C mm2/s

3.9

4.3

ABNT NBR 10441a

K, mg/kg
Na, mg/kg

b 0.015
b 0.013

b 0.015
b 0.013

EN 14109b
EN 14108b

0.86 to 0.90 (BR)


100 (BR)
120 (EN)
130 (AM)
3.55.0 (EN)
1.96.0 (AM)
10 (BR) (K + Na) maximum limit
5 (EN) (K + Na) maximum limit

a
b

Brazilian Association of Norms and Techniques.


European Norms.

604

D. Samios et al. / Fuel Processing Technology 90 (2009) 599605

used oil (Voil), the volume of the biodiesel (VBD), the corresponding
densities (Oil, BD) and the conversion degrees XME obtained by 1HNMR technique.

= 100x



VBD xBD xXME
:
Voil xoil

Eq. (4) permits a good approximation of the yield with a small


error, lower than 0.4%. In spite of very high conversions values the
yields were lower than 90% (the average values for six experiments
are: sunower 86 5% and linseed 85 4%). This result is related to the
purity of the starting materials, the non-anhydrous conditions and the
losses of material inherent to procedure handling. However these
values are signicantly higher than the basic catalysis industrial yields
and lower than the acid catalysis, which is difcultly applicable for
industrial purposes.
As we already mentioned before, the biodiesel was characterized
by standard techniques, permitting the evaluation of the product
quality (Table 1). These results are in good agreement with American,
European and Brazilian biodiesel specications.
3.2. A suggested mechanism for the Transesterication Double Step
Process TDSP
As mentioned before the mechanism related to this process (Fig. 7)
can be described as a basicacid consecutive transesterication
mechanism incorporating the main characteristics and principles of
the basic and acid catalysis. The rst two reactions (r1 and r2)
constitute the rst step and describe the typical basic catalysis
process. The reaction r1 is related to the alkoxide preparation while
the second one corresponds to the basic transesterication. The two
rst reactions of the mechanism do not need any additional
explanation or elucidation. The basic catalysis principles were
described before. The second operational step occurs with the
addition of sulfuric acid and more alcohol when still the reactions
mixture presents pH between 12 and 14, in other words approximately total absence of H+. The reactions r3 and r4 occur after the
addition of the acid catalyst and alcohol. As it is described in the
reaction r3, the H+ active species produced by the addition of the acid
would be responsible for the neutralization and simultaneously the
production of the R+
1 species, which attack directly the carbonylic
groups. It is to expect that the difference between this acid catalysis
step and the classical acid one, is that the acid is added in to the
reaction mixture, which includes alkoxide and presents very high pH
value. In the classical acid catalysis, as described before, the acid/
alcohol solution is added in to the neutral triglyceride. The very active
species R+
1 reacts immediately according to reaction r4, with mono, di
and residual triglycerides, as well as, soap, already present in the
reaction mixture, resulting to fast process and very high conversion
degree, which is evidenced by the purity of the nal product. It is
important to observe that according to this suggested mechanism the
fatty acid methyl esters produced by the basic catalysis process, do not
suffer any degeneration by the acid catalysis.
4. Conclusions
This study demonstrated that the use of the Transesterication
Double Step Process surpasses various difculties of the conventional
basic or acid catalytic procedures, permitting a much faster procedure
than the acid catalysis, easy and clear separation of phases and high
purity biodiesel. The operational conditions of the proposed TDSP are
relatively low temperature and easy separation of phases. The TDSP
surpasses the necessity of employment of anhydrous materials, low
acidity vegetable oil, eliminates any soap or emulsion formation
problem (frequently present in basic catalysis transesterication),

requires extremely shorter times than the acid catalysis transesterication and results to high conversion degrees. From the other side,
the TDSP compared to the single step basic catalysis, needs the
employment of two catalysts and approximately double quantity of
methanol, which makes the process more expensive. This preliminary
evaluation of the TDSP is evidencing a capability to obtain biodiesel
with higher conversions than the basic one in operational times
sufciently smaller than the acid catalysis. It seems to be a new way
for biodiesel production. This initial study must be continued in order
to create a new opportunity for technological and/or industrial
purposes.
Acknowledgments
The authors acknowledge the Conselho Nacional de Desenvolvimento Cientco e Tecnolgico (CNPq) and Coordenao de Aperfeioamento de Pessoal de Nvel Superior (CAPES) for nancial support.
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