Journal of Membrane Science 378 (2011) 453–461

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Journal of Membrane Science

journal homepage: www.elsevier.com/locate/memsci

Biodiesel production from degummed soybean oil and glycerol removal using
ceramic membrane
Maria Carolina Sérgi Gomes ∗ , Pedro Augusto Arroyo, Nehemias Curvelo Pereira
Department of Chemical Engineering, State University of Maringá, Av. Colombo 5790, Bloco D90, CEP 87020-900 Maringá, PR, Brazil

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

Article history: In the present study, biodiesel was produced by ethylic transesterification of degummed soybean oil
Received 25 February 2011 using sodium hydroxide as a catalyst. The influence of temperature and oil:alcohol molar ratio was eval-
Received in revised form 11 April 2011 uated using experiment factorial design and response surface methodology. According to the results, the
Accepted 16 May 2011
maximum yields of esters were obtained when the temperature was lower than 40 ◦ C and the oil:alcohol
Available online 24 May 2011
molar ratio was higher than 1:7. A membrane separation process was used to separate glycerol from
biodiesel after transesterification. The reaction mixture was directly microfiltered after the addition of
Keywords:
acidified water without previous settling. Microfiltration runs were performed in batch mode using a
Biodiesel
Transesterification
0.2-␮m ceramic membrane at 1.0, 2.0, and 3.0 bar transmembrane pressures. Membrane performance
Separation was evaluated based on the capacity of glycerol retention and on the permeate flux values. The results
Membrane technology showed that the water concentration added to the mixture plays an important role in glycerol separation,
as well as in the permeate flux, according to the proposed glycerol separation mechanism using ceramic
membrane. The use of filtration with ceramic membrane was efficient to remove glycerol from biodiesel,
and the permeates obtained for all conditions showed free glycerol values lower than 0.02%, which is the
maximum specification limit.
© 2011 Elsevier B.V. All rights reserved.

1. Introduction and decrease the biodiesel yield. Additionally, excess catalyst in

Biodiesel is considered a renewable fuel because vegetable oils
and animal fats are the main raw materials used in its production. It
has a higher flash point than mineral diesel, which ensures greater
safety in its use and also a high cetane number, and consequently,
a high capacity for self-ignition and combustion. Its viscosity is
appropriate for use with diesel engines, it is biodegradable and it
has excellent lubricating properties, which extends the useful life
of diesel engines [1].
In the transesterification reaction, alkaline catalysis is used more
for commercial purposes because of its high yield and selectivity,
shorter reaction time, as compared to acidic catalysis, low cost,
and the possibility of reaction at low temperature and room pres-
sure [2]. Alkaline catalysts are preferable in industrial processes
also because they are less corrosive [3,4]. Studies published in the
literature propose that the concentration of alkaline catalyst con-
centration be 1% in relation to the oil mass, as appropriate for
obtaining high ester yields in the alkaline transesterification of veg-
etable oils. A high amount of alkaline catalyst can result in the
formation of soaps, which increase the viscosity of the reagents
∗ Corresponding author. Tel.: +55 44 33052703.
E-mail address: mcarolinagomes@yahoo.com.br (M.C.S. Gomes).
the reaction mixture raises the cost of the separation step [5–8].
To maximize the yield of the alkaline transesterification, the
alcohol must be free of moisture and the free fatty acid content
of the vegetable oil must be lower than 0.5%. Water in the reac-
tion medium hydrolyzes the synthesized alkyl esters to free fatty
acids. Free fatty acids in the oil and water in the reaction medium
can react with the basic catalyst and form soaps, which reduce the
conversion, increase the viscosity and emulsification, and make the
separation of glycerol more difficult [8,9].
Although reaction with methanol is more commonly employed,
the use of ethanol in the transesterification of oils has been investi-
gated [10–13]. The ethylic route is attractive from an environmental
point of view, since ethanol can be produced from a renewable
source. The use of vegetable oils and ethanol obtained from a fer-
mentative process in the production of biodiesel makes the process
entirely independent of petroleum, thereby providing both envi-
ronmental and economic benefits [14].
One of the most important variables that influence the trans-
esterification reaction is the alcohol to oil molar ratio. The
stoichiometry of the reaction requires 3 mol of alcohol and 1 mol of
triacylglycerol to form 3 mol of fatty acid ester and 1 mol of glycerol.
However, due to the reversible character of the reaction, excess
alcohol is normally used to shift the balance in the direction of
the formation of products and increase the ester conversion [4,9].
The choice of the molar ratio is also associated with the type of

0376-7388/$ – see front matter © 2011 Elsevier B.V. All rights reserved.
doi:10.1016/j.memsci.2011.05.033
454 M.C.S. Gomes et al. / Journal of Membrane Science 378 (2011) 453–461
catalyst used. Freedman et al. [15] studied the transesterification
of soybean oil and demonstrated that the acidic catalysis requires
a higher oil:alcohol molar ratio (1:30) than the alkaline catalysis
(1:6) to obtain high ester conversions. Meher et al. [5] evaluated
oil:alcohol molar ratios ranging from 1:6 to 1:24 in the alkaline
transesterification of vegetable oil. The increase in the oil:alcohol
molar ratio influenced the ester yield positively. A higher excess of
ethanol resulted in a higher conversion in a shorter reaction time.
In contrast, Lin et al. [7] demonstrated that an excess amount of
alcohol in the reaction medium may hinder the glycerol separa-
tion, leading to a drop in yield. Oil:alcohol molar ratios between
1:3 and 1:10 were investigated in the alkaline transesterification
of rice bran oil, and the best conversion ratio was obtained with a
molar ratio of 1:6.
Transesterification can occur at different temperatures depend-
ing on the oil used [4]. According to Van Gerpen et al. [16],
some studies were conducted in the transesterification tempera-
ture range of 25–85 ◦ C. A reaction temperature above 65 ◦ C should
be avoided, since higher temperatures tend to accelerate saponifi-
cation of the glycerides by the alkaline catalyst before completion of
the alcoholysis. Moreover, the reaction temperature must be lower
than the boiling point of alcohol in order to ensure that the alcohol
does not leak out through vaporization [2,7].
After the transesterification, the final mixture is constituted
mainly of alkyl esters of fatty acids, as well as residual alcohol, glyc-
erol, catalyst, and mono-, di- and triacylglycerols. The presence of
these and other contaminants in biodiesel can cause engine oper-
ation and environmental problems and must be separated so that
the esters can be used as a fuel [14,16].
The purity of the final biodiesel product is an important issue
which, in Brazil, is specified by the National Agency of Petroleum,
Natural Gas and Biofuels (ANP), based on the American ASTM
D6751 and European EN14214 standards, with some modifica-
tions to meet the Brazilian raw material requirements. Among the
numerous properties that must be controlled in order to meet
these specifications, the free glycerol content is one of the most
important, since it is related to the effectiveness of the purification
procedure and its maximum limit is 0.02% mass [17].
High free glycerol content in biodiesel may lead to the formation
of two phases, causing storage and fuel injection system problems.
Free glycerol is also associated with deposits on the bottom of
fuel tanks, which attracts other contaminants, like water, increases
engine corrosion, and shortens the engine useful life. The combus-
tion of glycerol together with biodiesel over 180 ◦ C can also cause
the emission of acrolein, a highly toxic substance [14,18].
Thus, one of the critical points of the biodiesel production pro-
cess is the glycerol separation step, mainly when the ethylic route
is used. Methanol and ethanol are not miscible with triacylglyc-
erol at ambient temperature, and the reaction mixtures are usually
mechanically stirred to enhance mass transfer. During the course
of these reactions, emulsions are usually formed. Emulsification
partially results from the formation of the intermediates monoa-
cylglycerol and diacylglycerol, which have both polar hydroxyl
groups and nonpolar hydrocarbon chains [19]. The smaller size of
the methanol molecule relative to that of ethanol facilitates the
simultaneous attack of the methoxy anion in all three chains of
the triacylglycerol, reducing the concentrations of the intermedi-
ates [15]. Thus, in the case of methanolysis, these emulsions quickly
and easily break down to form a lower layer rich in glycerol and an
upper layer rich in methyl ester. In ethanolysis, these emulsions are
much more stable and the separation and purification of the esters
is made much more difficult [19].
Therefore, the resulting esters and glycerol are typically spar-
ingly mutually soluble. The residual alcohol is distributed between
the ester and glycerol phases. The alcohol tends to act as a sol-
ubilizer and may slow separation down [20]. The evaporation of
alcohol before the removal of glycerol is an alternative approach
to make the separation easier; however, due to the reversibility
of the transesterification reaction, some authors do not recom-
mend using this process [20,21]. After the separation of glycerol,
commonly done using decantation or centrifugation, the obtained
biodiesel must be purified, which is normally achieved by neutral-
ization with an acid solution and washing with water to remove the
catalyst, residual glycerol, soaps, and other possible contaminants
[21].
In the face of the diversity of raw materials and processes used
in the production of biodiesel and the difficulties in obtaining a
quality product, it is necessary to research and develop processes
for a more efficient glycerol separation. Some published studies
[5,22–24] indicate the use of a number of methodologies for the
removal of glycerol and the purification of biodiesel.
Studies of the removal of glycerol in the literature use decanta-
tion as the main separation process, which requires long periods
of time and then washing steps that consume large amounts of
water. Çetinkaya and Karaosmanoglu [18] studied the production of
biodiesel from used oil by methylic transesterification with sodium
hydroxide. After the phase separation by decantation, they evalu-
ated the efficiency of the washing of the esters in the removal of
the glycerol. The lowest free glycerol content found in biodiesel by
the titration method after one seven-washing cycle of esters with
distilled water at 50 ◦ C was 0.011%.
Membrane separation technology is largely used in oil emul-
sion processing; however, it is new to the biodiesel purification
process. Some studies [25–29] indicate that the membranes most
used in oil separation are micro and ultrafiltration ceramic mem-
branes, followed by specific polymeric membranes. Regarding the
use of membranes in the production of biodiesel, the literature
has focused on the use of a reactor with membranes to improve
the conversion of esters [30,31] and the use of membranes in the
purification step, after separation by decanting [32–34].
As an alternative to water washing, Saleh et al. [34] used the
membrane technology. The best result obtained in the ultrafil-
tration of ethyl esters after phase separation by decantation was
the reduction of the glycerol mass content from 0.040% to 0.013%
with the addition of 0.2% water before the separation. Wang et al.
[33] also studied the use of membranes in the purification of
biodiesel after phase separation by decantation. The best results
were obtained with a 0.1-␮m ceramic membrane, which gave a
permeate with a glycerol content of 0.0108 wt%.
Our group studied the use of membranes in the separation
of glycerol without previous decantation in earlier work [35] in
which synthetic mixtures of biodiesel, glycerol, and ethanol were
microfiltered with ceramic membranes to evaluate the effects of
the membrane porosity, transmembrane pressure, and the ethanol
concentration in the mixture. The results indicate the potential of
the application of ceramic membranes in the separation of glycerol
and biodiesel. The best retention of glycerol (99.6%) was obtained
with a 0.2-␮m membrane and 2.0 bar pressure.
Given the variety of methodologies used in the production of
biodiesel and the need to perfect the glycerol separation step, the
present study aimed at the production of biodiesel from degummed
soybean oil by transesterification with ethanol and alkaline catal-
ysis using microfiltration with a ceramic membrane in the phase
separation.
2. Experimental
2.1. Materials
Degummed soybean oil was provided by the cooperative Coop-
erativa Agroindustrial Cocamar (Maringá, Paraná State). Anhydrous
ethanol (99.8 ◦ INPM) was provided by Usina Cocafé (Astorga,
 M.C.S. Gomes et al. / Journal of Membrane Science 378 (2011) 453–461
Fig. 1. Diagram of the micro and ultrafiltration experimental unit.
Paraná State). As a catalyst, we used analytic grade sodium hydrox-
ide in the form of micropearls (Synth, Brazil). All the other reagents
used in the analysis were analytical grade (Synth, Brazil).
2.2. Analytical methods
Oil viscosity at 40 ◦ C was determined with a Brookfield model
DV-III digital rheometer. A 25-mL picnometer with a coupled ther-
mometer was used in the determination of the density at 20 ◦ C.
The acidity and peroxide indexes were determined according to the
methodology recommended by the American Oil Chemical Society
(AOCS). The moisture content was determined by the Karl Fischer
method using an Analyser apparatus, model Moisture Control KF-
1000. All analyses were performed in triplicate.
The fatty acid profile of the oil and the quantification of the
ethyl esters were done by gas chromatography with Varian model
CP-3800 coupled with a flame ionization detector (FID) and a
30 m × 0.25 mm capillary column specific for fatty acid separation,
BP-X70. The carrier gas used was helium, in a split rate of 1:10.
The analysis was performed with a column temperature program
starting at 140 ◦ C, heating up to 250 ◦ C at 5 ◦ C/min. The detector
temperature was kept at 220 ◦ C and that of the injector at 260 ◦ C.
The internal standard used was methyl tricosanoate 99%, purchased
from Sigma–Aldrich.
The free glycerol content of the permeate was determined by
volumetric method based on the official AOCS methodology for the
analysis of free glycerol in oils and fats (Ca 14-56) [36]. Each sam-
ple was analyzed three times and the averages are reported. The
titration method with sodium periodate allows the fast and accu-
rate determination of glycerol in oils and fats at a low cost when
compared with the chromatographic methods [14,36,37].
2.3. Production of biodiesel by ethylic transesterification
The reactions were conducted in a 250-mL three-neck round-
bottom flask fit with a mechanical stirrer, a digital thermometer,
and a reflux condenser to prevent the loss of ethanol. The flask
455
was kept in a thermostatic water bath to maintain the temperature
constant during the entire reaction time.
In each reaction, 100 g of oil was added to the flask and agi-
tated until the desired temperature was reached. Next, a solution
of sodium hydroxide and ethanol, previously mixed until com-
plete dissolution, was added to the reactor. The amount of sodium
hydroxide used in the reactions was 1% in relation to the oil mass.
The reaction time was set at 1 h based on a previous reaction assay,
which showed that this time is sufficient for a maximum ester
yield. After the end of the reaction, the mixture was submitted to
a rotary evaporator under 600-mmHg vacuum at around 65 ◦ C for
30 min for alcohol recovery. After the evaporation of the alcohol, the
mixture was placed in a separating funnel and rested for phase sep-
aration. After decantation and phase separation, the lower phase,
containing ethyl esters, was washed with water at 90 ◦ C to removed
unwanted residues. This procedure was carried out in duplicate
using 50% water in relation to the oil mass in each washing. After
previous decantation, the sample was evaporated again in a rotary
evaporator at 80 ◦ C for 30 min to eliminate the moisture. Finally,
the samples were ready for analysis of the ester content by gas
chromatography.
It has been reported [38] that molar ratio and temperature are
the variables which most affect the synthesis of biodiesel from soy-
bean oil. Thus, these variables were selected for evaluation and the
best reaction conditions for biodiesel production from degummed
soybean oil were determined by random experimental design. Fac-
tor levels were chosen by considering the operational limits of the
experimental setup and preliminary tests. The oil:alcohol molar
ratio levels (XR ) were 1:6 and 1:9 and the temperature levels (XT )
were 30 and 60 ◦ C. A 22 factorial design was used, consisting of
eight assays (−1 and +1) and five center points, for a total of 13
experiments, according to Table 1.
The statistical significance of the experiment data was evaluated
through the SAS software, while Statistica 7.0 was used to gen-
erate the response surface for the method. A given mathematical
model was only considered acceptable when its analysis of vari-
ance (ANOVA) reached high statistical significance, with F-values
456 M.C.S. Gomes et al. / Journal of Membrane Science 378 (2011) 453–461

Table 1 After the determination of the best oil:alcohol molar ratio

Experimental matrix for the compound factorial design and the yield values.
and temperature conditions, transesterification was carried out to
Expt. No. Temperature (◦ C) Oil:alcohol molar ratio XT XR Yield (%) obtain sufficient reaction mixture for the microfiltration assays. The
1 30 1:6 −1 −1 88.3 reaction mixture was fed directly into the previously described
2 30 1:6 −1 −1 89.0 membrane module. This step substituted all the conventional
3 30 1:9 −1 1 94.6 purification steps performed in Section 2.3 by microfiltration, as
4 30 1:9 −1 1 98.7 shown in Fig. 2. The use of membranes in the separation of glycerol
5 60 1:6 1 −1 68.5
allows reducing the number of steps in relation to the conventional
6 60 1:6 1 −1 69.8
7 60 1:9 1 1 89.7 treatment, besides consuming less water.
8 60 1:9 1 1 92.9 In the first step, the microfiltration experiments were performed
9 45 1:7.5 0 0 92.5 in batches with a transmembrane pressure of 2.0 bar for compari-
10 45 1:7.5 0 0 91.3
son with the results obtained in the previous work using a mixture
11 45 1:7.5 0 0 90.4
12 45 1:7.5 0 0 91.9 of synthetic biodiesel, glycerol, and ethanol [35].
13 45 1:7.5 0 0 93.6 Next, the influence of the addition of acidified water in the sep-
aration step was evaluated, seeking to maximize the retention of
glycerol by the membrane. For such, acidified water (0.5% HCl) was
within a level of confidence of 95% and p-values <0.05. Based on the added at a concentration of 20% in relation to the total mixture
obtained results it was possible to determine the oil:alcohol molar mass used. The experiments were performed with transmembrane
ratio and temperature for the best ethyl ester yields. pressures of 1.0, 2.0, and 3.0 bar and a temperature of 50 ◦ C.
The module operates by completely recycling the concentrate;
the permeate flux was obtained by determination of the collected
2.4. Assays of microfiltration for the separation of glycerol permeate mass as a function of the time, measured in a semi-
analytical balance (BG 4000-Gehaka). Free glycerol was analyzed
The experimental equipment consisted of a micro- and ultra- in the permeate samples collected after evaporation in vacuum at
filtration pilot unit UF NETZSCH, Pomerode, Santa Catarina State, about 65 ◦ C for 60 min to eliminate the moisture and the ethanol.
Brazil, model 027.06-1C1/07-0005/AI, operating in cross-flow con- The membrane was cleaned in an ultrasound bath with 1%
ditions. A detailed scheme of the experimental unit is given in Fig. 1. sodium hydroxide and 1% citric acid solutions at 70 ◦ C. At the end of
The experimental module feed system consisted of a 5-L two- each cleaning, the membrane flux was measured using deionized
sleeve stainless steel tank and a positive displacement pump with water to ensure the reproducibility of the experiments.
a frequency inverter, which allowed its operation at various flux
rates, that is, with different cross-flow filtration velocities. Two
manometers and a rotameter were used to measure the feed pump 3. Results and discussion
flux. The pump operating pressure was limited by a pressostate, and
a device prevented void operation. The membrane used was set on 3.1. Characteristics of the degummed soybean oil
a stainless steel module fixed to piping with flanges. A Shumacher
GmbH-Ti tubular module ceramic membrane (␣-Al2 O3 /TiO2 ) with The degummed soybean oil had a density of 915.6 kg/m3 at
mean pore diameter of 0.2 ␮m and filtration area of 0.005 m2 was 25 ◦ C and kinematic viscosity of 32.55 mm2 /s at 40 ◦ C. The free
used. fatty acid content, 0.87 wt%, was higher than recommended by

Degummed
soybeanoil
ethanol
glycerol
water
REACTION EVAPORATION SETTLING

biodiesel 1st WASHING

ethanol + NaOH
SETTLING residue

water 2nd WASHING

SETTLING residue

EVAPORATION

purified
biodiesel

glycerol
MICROFILTRATION
purified
biodiesel EVAPORATION
biodiesel

Fig. 2. Biodiesel production and comparison of the traditional process with microfiltration purification.
 M.C.S. Gomes et al. / Journal of Membrane Science 378 (2011) 453–461 457

Fig. 3. Response surface and contour plot for the ester yield as a function of the temperature and the oil:alcohol molar ratio.

Freedman et al. [9]. However, because of good results found in the model, the contour plots and the response surface were plotted
literature for the alkaline transesterification of vegetable oils with (Fig. 3) for the evaluation of the conditions that gave the highest
acidity of up to 3 wt% [8] and the possibility of reducing the cost ester yields.
of raw material treatment, the degummed oil was not pre-treated. According to the results, the maximum ester yields were
The moisture content of 0.127% was lower than 0.5%, which is the obtained in the region where the temperature is lower than 40 ◦ C
limit recommended so that the alkaline transesterification is not and the oil:alcohol molar ratio is greater than 1:7. Eq. (1) also
hindered [9]. In the analysis of the peroxide index, no peroxides reveals that the effect of the temperature on the ester yield in this
were detected, indicating that the oil was not significantly oxidized. region is negative. This effect can be explained by parallel reaction,
The composition of the degummed soybean oil determined by gas such as triacylglycerol saponification, which is favored at high tem-
chromatography showed a high unsaturated fatty acid content, peratures. Due to the acidity of the degummed soybean oil, 1.74 mg
the main fatty acids being palmitic (11.0%), estearic (4.8%), oleic KOH/g, the neutralization reaction of the free fatty acids also pro-
(26.3%), linoleic (49.0%), and linolenic (5.5%) acids. These values duces soaps, thus further reducing the ester yield. In addition to
agree with those in the literature [39–41]. Based on the chem- these factors, the low yield can be caused by the emulsification of
ical composition of the oil, its calculated molecular weight was the mixture by the presence of mono- and diacylglycerols. Similar
845 g/mol. results were obtained by Bouaid et al. [42] in the ethylic trans-
esterification of mustard (Brassica carinata) oil, with an acidity of
3.2. Production of biodiesel by transesterification 1.69 mg KOH/g. The interaction between temperature and catalyst
had a negative effect on the ester yield and the best results were
The ester yields obtained by experimental design are given in obtained at 35 ◦ C.
Table 1. The data were analyzed using standard statistical tech- It can also be seen that the higher the temperature, the higher
niques (with SAS software), and the following regression model the molar oil:alcohol ratio used must be for obtaining high yields.
was obtained (only statistically significant terms are shown): It is likely that the use of a greater excess of ethanol favored the
formation of esters, minimizing the effect of the temperature on
Y = 88.55 − 6.213 XT + 7.538 XR + 3.538XT XR (1) the formation of undesirable products.
As a result, two molar ratios were selected for the microfiltration
where XT denotes temperature and XR the oil:alcohol molar ratio,
assays – 1:7.5 and 1:9. Ratios greater than 1:9 might affect the reac-
as shown in Table 1.
tion, as the presence of a large amount of ethanol interferes with the
The regression model shown in equation 1 indicates that the
separation of glycerol due to the increased solubility of the phases.
yield of esters was negatively influenced by the temperature and
When glycerol remains in the solution, the reaction balance may
positively influenced by the oil:alcohol molar ratio. The interac-
shift towards the reagents, thus reducing the ester yield [7,8]. The
tion effect of temperature and oil:alcohol molar ratio was positive,
optimum temperature selected for the ethyl transesterification of
probably indicating that increasing the quantity of alcohol used in
the reaction minimizes the negative effects caused by increasing
Table 2
the temperature. The coefficient of determination (R2 ) obtained for ANOVA for the linear model factors.
this model was 0.8837, indicating that 88.37% of the variation in
Source Degrees of Sum of Mean F p-Value
biodiesel yield can be explained by the fitted model. The analysis
freedom squares squares
of variance (ANOVA) table for the surface analysis methodology is
shown in Table 2. XT 1 308.76 308.76 24.46 0.0008
XR 1 454.51 454.51 36.00 0.0002
The F-values obtained in the ANOVA for the significant fac- XT XR 1 100.11 100.11 7.93 0.0202
tors were higher than the listed F-value (3.86), showing that the Regression 3 863.38 287.79 22.79 0.0002
regression curve and analysis were within a 95% confidence level. Error 9 113.63 12.63
Likewise, the p-values are lower than 5%, indicating that the lin- F0.05;3,9 = 3.86
Total corrected 12 977.01
ear terms are statistically significant for the model. Based on this
458
220
biodiesel:glycerol:ethanol mixture (80:10:10% mass)
200 1:9
1:7.5
180
160
Permeate Flux (kg/h.m )
2
140
120
100
80
60
40
20
0 and reducing the size of the glycerol droplets. The oil:alcohol molar
0 20 40 60
Time (min)
Fig. 4. Comparison of the synthetic biodiesel:glycerol:ethanol mixture (80:10:10%
mass) and the reaction mixtures produced with molar ratios of 1:9 and 1:7.5,
P = 2.0 bar, T = 60 ◦ C.
degummed soybean oil is 30 ◦ C, considering that using lower tem-
peratures would require a cooling system, which would increase
the process cost.
3.3. Comparison of microfiltration of the synthetic mixture and
the reaction mixture produced by ethylic transesterification of
soybean oil
According to the results obtained in the determination of the
optimum reaction conditions, transesterification was carried out at
30 ◦ C with oil:alcohol molar ratios of 1:9 and 1:7.5. Fig. 4 presents
the permeate flux curves as a function of the filtration time of the
two studied reaction conditions and also, for the sake of compari-
son, of the synthetic biodiesel, glycerol, and ethanol mixture with
mass percentages of 80, 10, and 10%, respectively, according to pre-
vious work [35]. Both the reaction and the synthetic mixtures were
submitted to microfiltration with a ceramic membrane at 60 ◦ C and
2.0 bar. The approximate total microfiltration time of 2 h was used
so that the flux could be stabilized in all experiments.
For the molar ratio of 1:9, the microfiltered reaction mixture
presented an average stabilized permeate flux of 39.3 kg/h m2 ,
approximately half the value obtained using a synthetic mixture
(78.4 kg/h m2 ). The flux value was even lower, 12.9 kg/h m2 , when
a molar ratio of 1:7.5 was used. This decrease in permeate flux
in relation to the synthetic mixture is due to the presence of an
excess amount of ethanol, as well as of soaps and residual catalyst,
in the reaction mixture, which favors the membrane fouling. It was
also observed that for the oil:alcohol molar ratio of 1:9, there was
a sharp decrease in the permeate flux soon after the first 10 min
of microfiltration. Probably, the larger amount of ethanol used in
this condition makes the passage of glycerol and other substances
present in the aqueous phase through the membrane pores eas-
ier, leading to pore plugging and consequently to flux reduction,
as discussed in previous work [35]. After the evaporation of the
alcohol from the permeate samples in the two conditions eval-
uated, ratios of 1:7.5 and 1:9, two distinct phases were formed,
indicating that glycerol permeated across the membrane during
the microfiltration and that the separation was not satisfactory.
3.4. Separation mechanism
The results obtained by microfiltration of the synthetic mix-
tures of biodiesel, glycerol, and ethanol using ceramic membranes
M.C.S. Gomes et al. / Journal of Membrane Science 378 (2011) 453–461
[35] demonstrated that the ethanol concentration in the emulsion
influences the size of the glycerol agglomerates; the larger the con-
centration of ethanol, the smaller the retention of glycerol. For the
ethanol concentrations used, from 5 to 20%, the glycerol reten-
tion was efficient and the biodiesel obtained had glycerol contents
ranging from 0.04 to 0.1%.
In the reaction mixture obtained after transesterification, the
free glycerol, with the alkali catalyst residue, exists in the form of
droplets suspended in the crude biodiesel. The hydrophilic ends of
soaps bond to the free glycerol droplets, while the hydrophobic end
is immersed in the crude biodiesel [33]. In this biodiesel-glycerol
system, both ethanol and soaps contribute to reduce the interface
tension and increase the contact surface area between the glycerol
and the biodiesel phases, favoring the solubility between the phases
80 100 ratios of 1:7.5 and 1:9 result in an amount of ethanol in the final
reaction mixture around 15 and 20%, respectively, that is, twice
the ethanol used with the synthetic mixture. Thus, the presence
of excess ethanol, together with soaps and salts in the reaction
mixture, not only favored membrane fouling, but also resulted in
permeation of glycerol droplets through the membrane.
It is possible, then, to propose the separation mechanism pre-
sented in Fig. 5, which shows the three distinct conditions that were
studied: (a) biodiesel, glycerol, and ethanol mixture, (b) reaction
mixture obtained by transesterification, and (c) reaction mixture
obtained by transesterification after the addition of acidified water.
Thus, considering the behavior of the emulsified biodiesel, glyc-
erol, and ethanol system, it was necessary to use an alternative
methodology so that the membrane could retain glycerol. There-
fore, in the end of the transesterification reaction, acidified water
(0.5% HCl) was added to the reaction mixture in a total of 20% of
the total mass of the mixture.
The acid neutralizes the residual catalyst and converts the soaps
into water-soluble salts. The addition of water affords the forma-
tion of an aqueous phase containing glycerol, catalyst, salts and
other water-soluble substances, distinct from the phase rich in
ethyl esters and unreacted oil. This means that the presence of
water reduces the solubility of the esters in the glycerol, produc-
ing the agglomeration of glycerol in larger droplets and, thus, its
retention by the membrane [34].
3.5. Microfiltration after the addition of acidified water
To reduce the solubility of glycerol in the esters, the reaction
mixture was produced using only the molar ratio of 1:7.5 and the
microfiltration temperature was reduced to 50 ◦ C. Fig. 6 presents
the results of permeate flux as a function of the microfiltration time
with and without the addition of acidified water.
The curves in Fig. 6 show that the addition of acidified water
afforded a much higher permeate flux than the mixture without it.
However, there occurred a sharp drop in the flux to a mean value
of 6.9 kg/h m2 , which remained constant until the end of the pro-
cedure. The results demonstrate that the retention of glycerol after
the addition of water was significant; the glycerol mass content
lower than 0.02% demonstrates the efficiency of the methodology
used. In addition, the permeates presented a percentage of water
lower than 0.45, which also indicates that the aqueous phase was
retained by the membrane.
Improvement of membrane performance in the separation of
glycerol and biodiesel after the addition of water was also reported
by Saleh et al. [34]. After phase separation by decantation for about
8–12 h, the methyl esters produced were purified using a polymeric
membrane. The addition of water in amounts from 0.06 to 0.2%
mass led to the rejection of glycerol by the formation of an aqueous
phase dispersed in the esters, which was removed by ultrafiltration.
 M.C.S. Gomes et al. / Journal of Membrane Science 378 (2011) 453–461 459

Fig. 5. Mechanism of separation of glycerol by microfiltration with a ceramic membrane.

3.6. Influence of transmembrane pressure on the permeate flux 140

and the glycerol retention
120 1.0 bar
To evaluate the influence of the transmembrane pressure on 2.0 bar
the flux behavior and on the retention of glycerol, the experiments 3.0 bar
100
Permeate Flux (kg/h.m )
2

were performed with the addition of acidified water before micro-

filtration at 1.0, 2.0 and 3.0 bar as well. The results are given in
Fig. 7. 80
The concentration factor, which is defined as the ratio between
the initial mixture volume and the concentrate volume, varied from 60
1.02 to 1.11. For all microfiltration experiments, the feed mixture
had an initial composition of 63.1% esters, 6.2% glycerol, 14.0% 40
ethanol, and 16.7% water. Thus, according to the material balance,
the final percent composition of the concentrate was about 57%
20
ester, 7.0% glycerol, 20% water, and 16% ethanol.
The initial permeate flux was lower for the highest transmem-
brane pressure (3.0 bar) than for 2.0 bar; however, the same sharp 0
decrease behavior was observed for the flux. For 1.0 bar, although 0 20 40 60 80 100

the flux was low, it did not drop sharply, and it remained practically Time (min)
level during the entire procedure. As can be observed, in the three
Fig. 7. Permeate flux as a function of time of filtration of the mixture produced with
transmembrane pressures studied, the flux values of the stabilized
molar ratio of 1:7:5 at 1.0, 2.0 and 3.0 bar. Membrane of 0.2 ␮m, T = 50 ◦ C.

140
permeate were close, as shown in Table 3, indicating that proba-
1:7.5 bly in the investigated conditions, microfiltration depends more on
120 1:7.5 - with acidified water addition
the characteristics of the mixture than on the transmembrane pres-
sure applied. The results suggest that the aqueous phase retained
100 on the membrane surface is compact, constituting an additional
Permeate flux (kg/h.m )
2

resistance and reducing the flux sharply. Evidence of this fact is

80 that during the membrane cleaning, a compact layer came off the
internal membrane surface.
One can also observe in Fig. 7 that the increase in transmem-
60
brane pressure resulted in higher microfiltration fluxes for a longer
time, that is, the flux at 3.0 bar lasted 30 min before it decreased,
40 indicating that the highest transmembrane pressure can overcome

20
Table 3
Permeate flux and glycerol retention for the different transmembrane pressures
0 (T = 50 ◦ C).
0 20 40 60 80 100
Transmembrane Stabilized permeate Glycerol in the
Time (min) pressure (bar) flux (kg/h m2 ) permeate (% mass)

1.0 5.7 0.005 ± 0.005

Fig. 6. Permeate flux for the 0.2-␮m membrane as a function of the filtration time,
2.0 6.9 0.006 ± 0.002
oil:alcohol molar ratio of 1:7.5, with and without the addition of acidified water.
3.0 10.3 0.014 ± 0.002
P = 2.0 bar, T = 50 ◦ C.
460 M.C.S. Gomes et al. / Journal of Membrane Science 378 (2011) 453–461

Table 4
Physical chemical characteristics of the permeate obtained by microfiltration
(0.2 ␮m, T = 50 ◦ C, P = 1.0 bar).
Parameter
Specific mass, 20 ◦ C (kg/m3 )
Kinematic viscosity, 40 ◦ C (mm2 /s)
Ester content (%, mass)
Free glycerol (%, mass)
Acidity (mg KOH/g)
mean size larger than the membrane pore diameter, which is
removable with a 0.2-␮m membrane.
This novel refining process of biodiesel showed the advantage
Limit (ANP) Biodiesel produced in of not requiring previous decantation to separate the two phases
this work (permeate)
obtained after transesterification and the reduction in the amount
850–900 876 of water used in the washing steps, thus minimizing the environ-
3.0–6.0 4.4 mental impact of the biodiesel production process. The properties
96.5 min 97.5
of the biodiesel produced from degummed soybean oil and purified
0.02 max 0.005
0.80 max 0.50 by ceramic membrane process are comparable to those of the ANP
biodiesel specifications.

compaction for a longer time before the permeation falls to a min-

imum.
The mean percent values of glycerol in the permeate and the
standard deviation of each condition are presented in Table 3, as
are the values of the stabilized permeate flux.
One can see that in all assays, the percentage of glycerol in
the permeate was below the maximum value specified for com-
mercialization of 0.02%. Considering the permeate flux practically
constant during processing and the lowest glycerol content in the
permeate, the lowest transmembrane pressure that was evaluated
afforded the best result. Thus, the permeate obtained at 1.0 bar
was then evaporated in a rotary evaporator at 90 ◦ C under vacuum
(630 mmHg) for 30 min to ensure that neither ethanol nor water
was present in the final permeate.
Table 4 compares the characteristics of the permeate obtained
with the Brazilian biodiesel B100 specification values [17].
The obtained permeate was clear, had a specific mass of
876 kg/m3 at 20 ◦ C, viscosity of 4.4 mm2 /s at 40 ◦ C, ester content
of 97.5% in % mass, acidity of 0.50 mg KOH/g, and free glycerol con-
tent of 0.005%; that is, all the evaluated properties of the permeate
are within the required specifications.
It was demonstrated that the glycerol content in all assays with
the reaction mixture directly microfiltered was below the ANP free
glycerol standard specification of 0.02% mass. In comparison to the
studies in the literature that used membrane technology to purify
biodiesel [32–34], the methodology used has the advantages of
eliminating the step of separation by decantation and of producing
a biodiesel with much low glycerol content after a single processing
step.
Considering that the commonly used decantation and wash-
ing steps can be replaced with membrane filtration and that this
process affords lower glycerol contents than those reported in the
literature, the present work points to the promising improvement
of the biodiesel separation and purification step.
4. Conclusion
The overall results obtained in this study demonstrate that
degummed soybean oil can be used to obtain biodiesel by transes-
terification with ethanol and a basic catalyst (NaOH 1%, w/w). Due
to the free fatty acids of degummed soybean oil used in the exper-
iments (0.87%), it was found that a temperature lower than 40 ◦ C
and an oil:alcohol molar ratio higher than 1:7 give the maximum
ester yield.
Free glycerol can be removed from biodiesel using a mem-
brane separation process. The ceramic membrane with pore size
of 0.2 ␮m was suitable for this separation process due to the good
quality of the permeate, which presented a glycerol content lower
than 0.02 wt%, the specification limit of free glycerol in biodiesel.
Our results indicate that the addition of acidified water to the
reaction mixture prior to microfiltration has a great effect in remov-
ing glycerol from the biodiesel phase. According to the mechanism
proposed for the glycerol separation using ceramic membrane,
the addition of water promotes the formation of a disperse aque-
ous phase including glycerol, soap, and ethanol, with agglomerate
References
[1] A. Demirbas, Biodiesel: A Realistic Fuel Alternative for Diesel Engines, Springer-
Verlag London Ltd, London, 2008.
[2] D.Y.C. Leung, X. Wu, M.K.H. Leung, A review on biodiesel production using
catalyzed transesterification, Applied Energy 87 (2010) 1083–1095.
[3] R.A. Ferrari, V.S. Oliveira, A. Scabio, Biodiesel de soja – Taxa de conversão em
ésteres etílicos, caracterização físico-química e consumo em gerador de ener-
gia, Química Nova 28 (2005) 19–23.
[4] F. Ma, M.A. Hanna, Biodiesel production: a review, Bioresource Technology 70
(1999) 1–15.
[5] L.C. Meher, V.S.S. Dharmagadda, S.N. Naik, Optimization of alkali-catalyzed
transesterification of Pongamia pinnata oil for production of biodiesel, Biore-
source Technology 97 (2006) 1392–1397.
[6] K.G. Georgogianni, M.G. Kontominas, E. Tegou, D. Avlonitis, V. Gergis, Biodiesel
production: reaction and process parameters of alkali-catalyzed transesterifi-
cation of waste frying oils, Energy & Fuels 21 (2007) 3023–3027.
[7] L. Lin, D. Ying, S. Chaitep, S. Vittayapadung, Biodiesel production from crude
rice bran oil and properties as fuel, Applied Energy 86 (2009) 681–688.
[8] A. Murugesan, C. Umarani, T.R. Chinnusamy, M. Krishnan, R. Subramaniam, N.
Neduzchezhain, Production and analysis of biodiesel from non edible oils – a
review, Renewable & Sustainable Energy Reviews 13 (2009) 825–834.
[9] B. Freedman, E.H. Pryde, T.L. Mounts, Variables affecting the yields of fatty
esters from transesterified vegetable oils, Journal of the American Oil Chemists’
Society 61 (1984) 1638–1643.
[10] K.S.R. Brandão, F.C. SILVA, U.M. Nascimento, M.C. Sousa, A.M.C. Mouz-
inho, A.G. Souza, M.M. Conceição, K.R.M. Moura, Produção de biodiesel por
transesterificação do óleo de soja com misturas de metanol-etanol, 2006. Avail-
able at http://www.biodiesel.gov.br/rede.html in January 2011.
[11] A.B.R. Moreira, V.H. Pérez, G.M. Zanin, H.F. Castro, Biodiesel synthesis by
enzymatic transesterification of palm oil with ethanol using lipases from sev-
eral sources immobilized on silica-PVA composite, Energy & Fuels 21 (2007)
3689–3694.
[12] O.J. Alamu, M.A. Waheed, S.O. Jekayinfa, Effect of ethanol-palm kernel oil ratio
on alkali-catalyzed biodiesel yield, Fuel 87 (2008) 1529–1533.
[13] G.A. Albuquerque, Obtenção e caracterização físico-química do biodiesel
de canola, MSc Thesis, Departamento de Química/Universidade Fed-
eral da Paraíba, 2005. Available at http://www.biodiesel.gov.br/
docs/defesageuzacompleto.pdf in January 2010.
[14] M.R. Monteiro, A.R.P. Ambrozin, L.M. Lião, A.G. Ferreira, Critical review on ana-
lytical methods for biodiesel characterization, Talanta 77 (2008) 593–605.
[15] B. Freedman, R.O. Butterfield, E. Pryde, Transesterification kinetics of soybean
oil, Journal of the American Oil Chemists’ Society 63 (1986) 1375–1380.
[16] J. Van Gerpen, B. Shanks, R. Pruszko, D. Clements, G. Knothe, Biodiesel Pro-
duction Technology, Nacional. Midwest Research Institute, 1st ed., Renewable
Energy Laboratory, Colorado, 2004.
[17] ANP, 2008. National Petroleum Agency. ANP Resolution Number 7, March 19,
2008. Available at http://www.anp.gov.br/petro/biodiesel.asp in January 2011.
[18] M. Çetinkaya, F. Karaosmanoglu, Optimization of base-catalyzed transesterifi-
cation reaction of used cooking oil, Energy & Fuels 18 (2004) 1888–1895.
[19] W. Zhou, S.K. Konar, D.G.B. Boocock, Ethyl esters from the single-phase base
catalyzed ethanolysis of vegetable oils, Journal of the American Oil Chemists’
Society 80 (2003) 367–371.
[20] J. Van Gerpen, Biodiesel processing and production, Fuel Processing Technology
86 (2005) 1097–1107.
[21] G. Knothe, J. Van Gerpen, J. Krahl (Eds.), The Biodiesel Handbook, AOCS Press,
Champaing, IL, 2005.
[22] I.M. Atadashi, M.K. Aroua, A.A. Aziz, Biodiesel separation and purification: a
review, Renewable Energy 36 (2011) 437–443.
[23] F. Karaosmanoglu, B. Cigizoglu, M. Tüter, S. Ertekin, Investigation of the refining
step of biodiesel production, Energy & Fuels 10 (1996) 890–895.
[24] J. Van Gerpen, E.G. Hammond, L.A. Johnson, S.J. Marley, L. Yu, I. Lee, A. Monyem,
Determining the Influence of Contaminants on Biodiesel Properties, The Iowa
Soybean Promotion Board, Iowa State University, 1996.
[25] A.B. Koltuniewicz, R.W. Field, Process factors during removal of oil-in-
water emulsions with cross-flow microfiltration, Desalination 105 (1996)
79–89.
[26] P. Wang, N. Xu, J. Shi, A pilot study of the treatment of waste rolling emulsion
using zirconia microfiltration membranes, Journal of Membrane Science 173
(2000) 159–166.
 M.C.S. Gomes et al. / Journal of Membrane Science 378 (2011) 453–461
[27] F.L. Hua, Y.F. Tsang, Y.J. Wang, S.Y. Chan, H. Chua, S.N. Sin, Performance study
of ceramic microfiltration membrane for oily wastewater treatment, Chemical
Engineering Journal 128 (2007) 169–175.
[28] R. Del Colle, E. Longo, S.R. Fontes, Demulsification of water/sunflower oil emul-
sions by a tangential filtration process using chemically impregnated ceramic
tubes, Journal of Membrane Science 289 (2007) 58–66.
[29] Y. Pan, W. Wang, T. Wang, P. Yao, Fabrication of carbon membrane and micro-
filtration of oil-in-water emulsion: an investigation on fouling mechanisms,
Separation and Purification Technology 57 (2007) 388–393.
[30] M.A. Dubé, A.Y. Tremblay, J. Liu, Biodiesel production using a membrane reactor,
Bioresource Technology 98 (2007) 639–647.
[31] P. Cao, A.Y. Tremblay, M.A. Dubé, K. Morse, Effect of membrane pore size on the
performance of a membrane reactor for biodiesel production, Industrial and
Engineering Chemistry Research 46 (2007) 52–58.
[32] H.Y. He, X. Guo, S.L. Zhu, Comparison of membrane extraction with tradi-
tional extraction methods for biodiesel production, Journal of the American
Oil Chemists’ Society 83 (2006) 457–460.
[33] Y. Wang, X. Wang, Y. Liu, S. Ou, Y. Tan, S. Tang, Refining of biodiesel by ceramic
membrane separation, Fuel Processing Technology 90 (2009) 422–427.
[34] J. Saleh, A.Y. Tremblay, M.A. Dubé, Glycerol removal from biodiesel using mem-
brane separation technology, Fuel 89 (2010) 2260–2266.
[35] M.C.S. Gomes, N.C. Pereira, S.T.D. Barros, Separation of biodiesel and glycerol
using ceramic membranes, Journal of Membrane Science 352 (2010) 271–276.
461
[36] M.L. Pisarello, B.O. Dalla Costa, N.S. Veizaga, C.A. Querini, Volumetric method for
free and total glycerin determination in biodiesel, Industrial and Engineering
Chemistry Research 49 (2010) 8935–8941.
[37] D. Naviglio, R. Romano, F. Pizzolongo, A. Santini, A. De Vito, L. Schiavo, G. Nota,
S.S. Musso, Rapid determination of esterified glycerol and glycerides in triglyc-
eride fats and oils by means of periodate method after transesterification, Food
Chemistry 102 (2007) 399–405.
[38] G.F. Silva, M.S. Castro, J.S. Silva, J.S. Mendes, A.L.O. Ferreira, Simulation and
optimization of biodiesel production by soybean oil transesterification in non-
ideal continuous stirred-tank reactor, International Journal of Chemical Reactor
Engineering 8 (2010) A34, Available at http://www.bepress.com/ijcre/vol8/A34
in March 2011.
[39] S.P. Sing, D. Sing, Biodiesel production through the use of different sources and
characterization of oils and their esters as the substitute of diesel: a review,
Renewable and Sustainable Energy Reviews 14 (2010) 200–216.
[40] A. Demirbas, Biofuels sources, biofuel policy, biofuel economy and global
biofuel projections, Energy Conversion and Management 49 (2008)
2106–2116.
[41] W Cao, H. Han, J. Zhang, Preparation of biodiesel from soybean oil using super-
critical methanol and co-solvent, Fuel 84 (2005) 347–351.
[42] A. Bouaid, M. Martinez, J. Aracil, Production of biodiesel from bioethanol and
Brassica carinata oil: oxidation stability study, Bioresource Technology 100
(2009) 2234–2239.