Journal of Membrane Science 496 (2015) 242 –249

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Journal of Membrane Science

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Influence of oil quality on biodiesel purification by ultrafiltration

Maria Carolina Sérgi Gomes a,n, Pedro Augusto Arroyo b, Nehemias Curvelo Pereira b
a
Federal University of Technology of Paraná-UTFPR, Rua Marcílio Dias, 635, CEP 86812-460 Apucarana, PR, Brazil
b
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 ab s t ract

Article history: In the present study, biodiesel was produced by ethylic transesterification of soybean and canola oils
Received 19 May 2015
using sodium hydroxide as a catalyst. It was evaluated the influence of oil quality on the biodiesel and
Received in revised form
glycerol separation by ultrafiltration. The experiments were carried out with tubular a-Al2O3/TiO2
31 July 2015
Accepted 4 September 2015 membranes with average pore diameter of 0.05 mm and 20 kDa, varying the transmembrane pressure
Available online 8 September 2015 and the concentration of the feed mixture. The comparison among the use of degummed soybean oil,
refined soybean oil, crude canola oil, and refined canola oil, demonstrated that free fatty acid presented
Keywords:
in the oils influence the formation of droplets containing glycerol. The separation was efficient when
Ultrafiltration
reaction mixture was produced from degummed soybean oil and crude canola oil, both with a higher
Ceramic membranes
Transesterification
acidity value. The highest free fatty acid content in the crude canola oil, not only favored the formation
Biodiesel of a dispersed phase containing glycerol, which was retained by the membrane, but also resulted in
Glycerol the lowest flux decline rates. The ultrafiltration was efficient in removing glycerol, since the highest
glycerol content in the permeate was 0.013 wt%. This novel refining process of biodiesel showed the
advantage of not requiring previous decantation to separate the two phases obtained after
transesterification and the reduction in the amount of water used in the washing steps. The properties
of the biodiesel produced, which were evaluated, meet the ANP biodiesel standards required for
marketing.
& 2015 Elsevier B.V. All rights reserved.

1. Introduction
Biodiesel is considered a renewable fuel, as vegetable oil and
animal fat are the main raw materials for its production. It has
higher flash point than mineral diesel, ensuring greater safety in
use and also presents appropriate viscosity for burning in diesel
engines. It is biodegradable, non-toxic and has excellent lubricity,
providing longer life to components of engines [1].
The most common method for producing biodiesel is the
transesterification, a reaction between a triacylglycerol, from ve-
getable oils or animal fats, and a short chain alcohol producing
alkyl esters of fatty acids and glycerol as a co-product [2,3]. Bio-
diesel has similar physicochemical properties to that of mineral
diesel and can be used in engines without modification [3].
The potential use of a raw material in biodiesel production
depends on several factors, such as availability, cost, storage
properties and performance as fuel [4]. Given the high biodi-
versity, large territory, climate diversity and soil conditions, Brazil
contains different oil sources for biodiesel production including
soybean, canola, castor, babassu, cotton, palm and sunflower [5].
Since Brazil has a well stablished soybean production, presently
n
Corresponding author.
E-mail address: mariagomes@utfpr.edu.br (M.C.S. Gomes).
most of biodiesel produced in the country used soybean oil [5,6].
Canola presents a high percentage of seed oil, 34–40%, which is
approximately twice the value found in soybeans and correspond
to 84% of all raw materials used in global biodiesel production
[7,8].
Regarding the alcohol used in the process, in Brazil, the use of
ethyl route has a strategic importance, since the availability of raw
materials and technology allows an economically viable produc-
tion of ethanol by fermentation processes, resulting in a cheaper
product than the methanol. In biodiesel production, the use of
vegetable oils and ethanol derived from sugarcane makes the
process completely independent from petroleum, providing en-
vironmental benefits and generating a socio-economic develop-
ment program [9,10].
After transesterification, the final mixture is mainly composed
of alkyl esters of fatty acids, residual alcohol, glycerol, catalyst,
mono-, di- and triglycerides. These and other contaminants in the
biodiesel can cause operational and environmental problems and
must be separated so that esters can be used as fuel [9,11]. The
quality of B100 biodiesel 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 modifications to meet the Brazilian raw material require-
ments [12].
One of the most important parameters for quality control of

http://dx.doi.org/10.1016/j.memsci.2015.09.004
0376-7388/& 2015 Elsevier B.V. All rights reserved.
M.C.S. Gomes et al. / Journal of Membrane Science 496 (2015) 242– 243
249
244 M.C.S. Gomes et al. / Journal of Membrane Science 496 (2015) 242–
249
biodiesel is the amount of after transes- terification for ceramic membranes in 2
free glycerin, which has a the separation of phases, separating glycerol from .
maximum allowed limit of without previous decan- biodiesel using different
0.02%. A high concentration tation, was studied in feedstock. To this end, it was E
of free glycerin can result previous works developed by evaluated the influence of oil x
from the separation of our research group. The first quality on ultrafiltration of p
the reaction mixture e
glycerin, causing problems experiments [29] were
r
during storage and in the fuel carried out with micro- produced after ethyl
i
injection system [9,13]. filtration membranes using esterification of vegetable oils m
Thus, besides controlling synthetic mixtures of with different characteristics. e
all the parameters biodiesel, gly- cerol, and The separation of glycerol n
influencing the was performed using t
ethanol. They were evaluated
reaction of biodiesel ultrafiltration membranes, a
the effects of the mem-
production, the stage of l
brane porosity, and the best operating
glycerol separation is very transmembrane pressure, condition was evaluated in
important to achieve a quality terms of permeate flux and s
and the ethanol con- e
product, free of impurities centration in the mixture. The quality of the product. c
and no risk of corrosion to results indicated the influence t
the engine. Conventional of ethanol on behavior of the i
purification pro- cedures use emulsion and the potential of o
a large volume of water, n
applying ceramic membranes
which varies depending on in the separation of glycerol
the impurities present, and 2
and biodiesel.
provides the generation of a .
Afterwards [30], the 1
large amount of effluent that experiments were .
must be properly treated and performed using the
disposed [14]. reactional mixture produced
Studies in the literature P
by ethylic transesterification
[15–19] indicate that r
of de- gummed soybean oil. o
distinct methods Considering the emulsion d
have been applied for behavior of the mixture u
glycerol removal and produced in the c
biodiesel purification. Among transesterification of t
the alternative methods of i
degummed soy- bean oil, it
separation, the process with o
was developed a methodology n
membranes has many of addition of acidified water,
advantages and good aiming to destabilize this
prospects for use in the o
emulsion and improve the f
separation and purification of re- tention of glycerol by the
biodiesel. The use of membrane. The results
membranes can provide high b
showed the key role of both i
quality and purity biodiesel, ethanol and water in the o
and environmental and formation of agglomerates in d
economic advantages for the dispersed phase, since i
reducing the amount of the glycerol retention after e
water used and eliminating s
adding water was significant,
the use of adsorbents. Apart e
with glycerol mass content in l
from the reduction of costs the permeate below 0.02%,
related to effluent treatment, indicating the efficiency of The reaction mixtures
studies indicate that the use the used methodology. needed for the experiments
of membranes in the Continuing the study [31], were pre- pared by alkaline
processing of biodiesel it was evaluated the ethyl transesterification of
provides reduced power influence of the
vegetable oils. They were
consumption, enabling the amount of acidified water used degummed soybean oil
application of this process in added on the separation of and crude canola oil donated
industrial scale [20]. glycerol and biodiesel using by Cocamar (Maringá, Paraná
Regarding the use of micro and ultrafiltration State, Brazil), and commercial
membranes for biodiesel ceramic membranes. The refined soybean and canola
production, the results showed that the oils. The anhydrous ethanol
published studies have amount of acidified water (99.4% purity) was donated by
focused on the use of added influ- ences the Cocafé, Astorga, Paraná State,
membrane reactors to emulsion properties and, Brazil and sodium hy-
improve conversion into consequently, the distribution droxide (NaOH) was
esters [21–23] and the use of of agglomerate size purchased from Biotec.
mem- branes in the containing the glycerol. The previous results of
purification step, after The current work aimed the study of the yield of
separation by decantation at improving knowledge esters as a function of
[18,24–28]. Direct use of on the be- reaction parameters [30]
micro- and ultrafiltration havior of ultrafiltration with indicate that the reaction
 M.C.S. Gomes et al. / Journal of Membrane Science 496 (2015) 242– 245
249
temperature for obtaining a ultrafiltration of the mixture obtained after adding
high ester yield depends on obtained from refined canola acidified water was
the acidity of the oil. In this oil was evaluated. For all tests,
way, when used refined oils, before ultrafiltration of the
the reaction temperature was mixture, the addition of
45 °C, and when used crude acidified water (0.5% HCl)
and degummed oils, the was evaluated in the mass
transesterification was concentrations varying from
carried out at 30 °C. For all 0% to 20% in relation to the
oils, the oil: alcohol molar total mixture mass, under
ratio used was 1:7.5 and the transmembrane pressure of
amount of catalyst was 0.5–2.0 bar. As previously
1% of mass of oil. The reaction discussed [31], addition of
was prepared in a 2 L batch water af- fords the formation
reactor and the reaction time of dispersed phase containing
was 1 h. The reactor contents water, glycerol, catalyst, salts
were mixed using a and other water-soluble
mechanical stirrer. substances, distinct from the
continuous phase rich in
2 ethyl esters and unreacted
. oil.
2 Next, ultrafiltration
. experiments were run with
reaction mix- tures produced
U with refined soybean,
l degummed soybean, refined
t canola and raw canola oils.
r
The experiments were
a
fi performed only with the 0.05
l mm membrane, under
t pressure of 1.0 bar, with prior
r addition of 10% acidified
a water.
t Finally, it was evaluated
i the separation of glycerol
o
from the mixture produced
n
with raw canola oil. In these
experiments were used the
r membranes of 0.05 mm and
u
20 kDa, under pressures of
n
s 1.0, 2.0 and 3.0
bar and water
concentration of
The experimental 10%.
equipment consisted of a Approximately four liters
micro- and ultra- filtration of the mixture were poured
pilot unit UF NETZSCH, into the feed tank of the
Pomerode, Santa Catarina module for each run. After
State, Brazil, model 027.06- heating to 50 °C, the mixture
1C1/07-0005/AI, operating in was pumped into the
cross-flow conditions. A membrane and the pressure
detailed description of the was set to begin the
experimental unit was permeate flux. All the runs
presented in a previous study were undertaken with a flow
[30]. rate of 700 L/h,
The hydrophilic ceramic
corresponding to a
membranes used in the
experiments were made of tangential velocity of about 8
tubular α-Al2O3/TiO2 m/s. The permeate was
(Shumacher GmbHTi 01070), collected and the concentrate
250 mm long, 7 mm in was completely recirculated
2
diameter, and 0.005 m to the feed tank.
filtration area, The performance of the
purchased from Andritz, glycerol separation process by
Pomerode, Santa Catarina ceramic membranes were
State, Brazil. The tests were characterized in terms of
carried out with glycerol rejection, stabilized
ultrafiltration membranes of permeate flux, percentage of
0.05 mm and 20 kDa. All flux decline and flux with
ultrafiltration experiments pure water after membrane
were per- formed at 50 °C. cleaning.
In the first step, The reaction mixture
246 M.C.S. Gomes et al. / Journal of Membrane Science 496 (2015) 242–
249

Table 1
Physicochemical characteristics of the vegetable oils used.

2 3
Vegetable oil Viscosity at 40 °C (mm /s) Density at 20 °C (g/cm ) Moisture (%) Acidity (%)

Degummed soybean 32.55 0.9156 7 0.0007 0.127 7 0.004 0.87 7 0.01

Refined soybean 32.01 0.9122 7 0.0007 0.090 7 0.003 0.43 7 0.05
Crude canola 32.22 0.9105 7 0.0007 0.113 7 0.004 2.40 7 0.06
Refined canola 36.39 0.9134 7 0.0007 0.098 7 0.004 0.24 7 0.03
 M.C.S. Gomes et al. / Journal of Membrane Science 496 (2015) 242– 247
249
directly fed to the micro- and analysis was performed processes are extensively of 1% NaOH and 1% citric acid
ultrafiltration module, with a column temperature employed in the industry, the at 70 °C and then with
substituting the steps of program starting at 140 °C, major disadvantage of their deionized water at the same
settling and washing with heating up to 250 °C at 5 application is the fouling of temperature. It was
water by micro- or ultra- °C/min. The detector the membranes, which evaluated the membrane
filtration. Thus the use of temperature was kept at 220 imposes the need for frequent hydraulic permeability so that
membranes for glycerol °C and that of the injector at cleaning. Therefore, an a cleaning parameter could be
separation en- ables the 260 °C. The internal standard improvement of the cleaning set. After each regeneration
reduction in the number of used was 99% methyl procedure may have a cycle, the permeate flux was
steps in relation to the tricosanoate, pur- chased significant influence on the measured with deionized
conventional treatment, in from Sigma-Aldrich. overall process efficiency water, ensuring the
addition to a lower The free glycerol content [34]. reproducibility of the tests.
consumption of water. of the permeate was Current membrane
determined by volumetric cleaning technologies
2 method based on the official include hydraulic, chemical, 3
. AOCS methodology for the and mechanical methods. .
3 analysis of free glycerol in Ultrasound is an effective
. oils and fats (Ca 14-56) [32]. technique for cleaning a
R
Each sample was analyzed variety of surfaces, which has e
A three times and the averages been used for cleaning fouled s
n are reported. The titration membranes or for increasing u
a method with sodium permeate flux of water l
l through membranes [35]. The t
periodate allows fast and ac-
y basic principle of operation is s
t curate determination of
glycerol in oils and fats at a that ultrasound removes
i
particles from the surface by a
c low cost compared with
causing particle movement in n
a chromatographic methods
or near membrane [36]. d
l [9,32,33]. When gly- cerol
concentration in the permeate In this work, the
membrane cleaning was d
m was too high, i.e., when there
performed in ultra- sonic i
e was permeation of the
bath (Ultra Cleaner 800, s
t dispersed phase through the c
h membrane, titration method UNIQUE) at 40 kHz, with
u
o solutions
could not be applied and it s
d
was only performed a s
s
volumetric quantification of i
the percentage of the o
The viscosity at 40 °C was n
dispersed phase containing
determined with a Brookfield
glycerol.
model DV-III digital 3
rheometer. A 25-mL .
2 1
pycnometer with a coupled
. .
thermometer was used to 4
determine the density at 20 .
°C. The acidity was C
determined according to the h
M a
American Oil Chemical e
Society (AOCS). The moisture r
m a
content was determined by b c
the Karl Fished method r t
using an Analyzer a e
apparatus, model Moisture n r
Control KF-1000. The e i
calorific value was s
determined using a Parr c t
6200 calorimeter. All l i
analyses were e c
performed in triplicate. a s
The fatty acid profile of n
i o
the oil and the
n f
quantification of the ethyl g
esters were done by gas
chromatography with Varian t
p h
model CP-3800 coupled with r e
a flame ionization detector o
(FID) and a c
30 mx0.25 mm capillary e o
column specific for fatty acid s i
separation, BP-X70. The s l
s
carrier gas used was helium,
in a split rate of 1:10. The Although membrane
 248
Table 1 lists the
physicochemical
characteristics of the four
types of oil used in the
experiments: degummed
soybean oil, re- fined soybean
oil, refined canola oil and
crude canola oil.
Vegetable oils exhibited
similar density and viscosity
and in accordance with the
values in the literature [7,37].
The degummed soybean oil
and crude canola oil showed
acidity values of 0.87% and
2.4%, respectively. These
percentages are higher than
the re- commended by
Freedman et al. [38] for
alkaline transesterifica- tion.
Nevertheless, as studies have
shown good results for this
reaction with the use of
vegetable oils with up to 3%
acidity [39] and given the
possibility of reducing the
costs of treating the raw
material, oils were not pre-
treated. For all oils, the
moisture con- tent was
below 0.5%, which is the
maximum value
recommended for the
alkaline transesterification is
not impaired [38].
3.2. Ultrafiltration in the
separation of biodiesel and
glycerol pro- duced by ethyl
transesterification of refined
canola oil
M.C.S. Gomes et al. / Journal of Membrane Science 496 (2015) 242–
249
mixture. Saleh et al. [26]
studied biodiesel purification
using membrane process and
demonstrated that at lower
soap con- centrations, the
increasing amount of water
promotes the gen- eration of
larger glycerol rich particles.
In this present work, soaps
formed in the reaction, when
there are free fatty acids in
the oil, along with salts
from the neutralization with
acidified water, contribute to
the formation of a dispersed
phase containing gly- cerol,
which can be retained by the
membrane.
Fig. 1 illustrates the
samples of permeates in all
conditions evaluated,
indicating the presence of
two phases. The lower phase
is the dispersed phase
containing glycerol, and the
upper phase is formed mainly
by ethyl esters.
Permeate flux curves over
filtration time, produced from
ethyl transesterification of
refined canola oil, using
membranes of
0.05 mm and 20 kDa are
presented in Figs. 2 and 3,
respectively.
It is interesting to observe
a flux increasing in the
beginning of the filtration for
most of the runs. Probably,
until the phase

Ultrafiltration of the
mixture produced from
refined canola oil, whose
acidity was the lowest of all
evaluated oils, was not
efficient in the separation of
glycerol. Considering the
stoichiometry of the reaction,
the amount of glycerol in feed
stream varied from 6% to
7%,
depending
on the
quantity of
water
added.
For all the conditions
evaluated, the dispersed
phase containing glycerol
permeated through the
membrane, and the
percentage of this phase in
the permeate varied from 1%
to 44% (Table 2).
These results are justified
by the absence of acidity in
the oil, which prevented the
agglomeration of the
dispersed phase in the final
M.C.S. Gomes et al. / Journal of Membrane Science 496 (2015) 242– 249
249
 Table 2 450
Concentration of the dispersed phase in the permeate – ultrafiltration of refined
250 M.C.S. Gomes et al. / Journal of Membrane Science 496 (2015) 242–
canola oil. 249 400
1.0 bar - 1%
Sample Membrane Pressure Concentration of Dispersed 350 1.0 bar - 3%
(mm/kDa) (bar) acidified water (% phase (% mass) 1.0 bar - 10%
mass) 300 2.0 bar - 0%
2.0 bar - 5%
1 0.05 0.5 10 1.7 250 2.0 bar - 10%
2 0.05 1.0 1 31

Permeate Flux
3 0.05 1.0 3 8.4 200
4 0.05 1.0 10 12

(kg/h.m2)
5 0.05 2.0 0 34
150
6 0.05 2 5 18
7 0.05 2.0 10 22
100
8 20 0.5 3 4
9 20 0.5 10 5
10 20 1.0 1 3 50
11 20 1.0 10 1
12 20 2.0 0 3 0
13 20 2.0 10 10 0 10 20 30 40 50 60 70 80 90 100
14 20 2.0 20 44 Time (min)
Fig. 2. Permeate flux in the ultrafiltration of biodiesel from refined canola oil for all
conditions evaluated. 0.05 mm membrane, T ¼ 50 °C.

0.5 bar - 3%
240 0.5 bar - 10%
1.0 bar - 1%
210 1.0 bar - 10%
2.0 bar - 0%
180 2.0 bar - 10%
Permeate Flux (kg/h.m )
2

2.0 bar - 20%

150

120

90

60

30

0
0 10 20 30 40 50 60 70 80 90 100
Time (min)
8 9 10 11 12
13 14 Fig. 3. Permeate flux in the ultrafiltration of biodiesel from refined canola oil for all
conditions evaluated. 20 kDa membrane, T ¼ 50 °C.

According to Fig. 2, the 0.05 mm membrane showed very high

Fig. 1. Samples of ultrafiltration permeates of the refined canola oil.
initially retained on the membrane surface is removed by the
convective flux and a concentration profile is established, which is
the transient period, there is an increase in the flux. After this
initial period, due to the size of glycerol agglomerates and the
pressure used, permeation occurs through the membrane pores,
and consequently the fouling, which reduces the flux.
flux rates, so that, in some tests, the minimum volume required in
the feed tank was achieved before the default time of 95 min. The
use of 2.0 bar pressure promoted a sharp decline in flux for all
concentrations of water, as well as a high glycerol content in the
permeate (Table 1). Although the lower pressure, 1.0 bar, has
caused a reduction of membrane fouling, there was glycerol per-
meation for the three concentrations of water evaluated, and the
lowest value of glycerol phase in the permeate was 8.4%, with
acidified water concentration of 3%.
Given the same concentration of water, 10%, increased
pressure of 1.0 to 2.0 bar provided increased glycerol content
in the permeate from 12 to 22% in the 0.05 mm membrane and 1
to 10% in the 20 kDa membrane.
On the other hand, at constant pressure, it is observed that in
0.05 mm membrane, there was an increased retention of glycerol
with higher concentration of water compared to the lowest con-
centration studied. As for the 20 kDa membrane, increased re-
tention of glycerol with increasing concentration of water was
only verified at 1.0 bar pressure. At 2.0 bar pressure, increasing the
concentration of water promoted a reduction of glycerol retention,
and with the maximum time are presented in Fig. 4. T degummed soybean oil.
a
concentration of water According to the results, an b Samples of the permeates
evaluated, it was obtained increase is observed in the l obtained from the
the highest content of flux for e ultrafiltration of
glycerol phase in the refined oils in the 10 initial mixtures produced from
minutes, followed by a 3
permeate, vegetable oils are shown in
Comparison of the permeate flux and
44%. Compared to other constant de- cline over time. Fig. 5. As these samples
glycerol concentration of the
results, it is observed that the As already discussed ultrafiltration with different passed through the refining
addition of previously, glycerol per- vegetable oils studied.
process that removed
20% water caused a great meation provides fouling
Raw material Permeate substances providing color to
increase in permeation of increasing.
the oil, the permeates
glycerol, probably indicating The curve for degummed 2
flux (kg/h m ) Glycerol in the
soybean oil shows a obtained from the mixtures
inversion of the emulsion.
typical behavior produced from refined oils
From these results, it was permeate (%) Degummed soybean
concluded that for the of membrane separation exhibited a lighter color
two mem- processes, with concentration 69.7 0.018 7 compared to permeates of
branes at the same polariza- tion and fouling. degummed soybean and
0.001
concentration of water, the The fouling is caused by Refined soybean 166.1 crude canola oils. In addition,
increased pressure favors the external clogging of pores, 12
it is possible to identify the
Crude canola 101.1
permeation of glycerol. The but without glycerol 0.013 7 0.003 dispersed phase in the
0.05 mm membrane showed permeation, according to the Refined canola 121.4 permeate of refined oils, in
an average value of percen- tage of glycerol in 12
which the separation was not
glycerol phase in permeate the permeate listed in Table
efficient.
greater than 3.
20 kDa membrane, In turn, for the crude agglomerates containing
suggesting that glycerol canola oil, the decline of glycerol and water-soluble Degummed Refined soybean Crude c
agglomerates have sizes near flux over time is substances. Such soybean
the pore diameter of the 0.05 minimum, indicating that agglomerates are likely
mm membrane. the retained phase does much larger than the
As the best retention of not cause clogging of pores. membrane pores, thus
glycerol in the permeate The presence of fatty acids in
retained more easily.
was obtained the oil and hence, soaps and
Comparing the refined
with the 20 kDa membrane salts formed in the reaction, soybean oil with degummed
at 1.0 bar pressure and 10% favor the formation of soybean oil
water, additional tests were and refined canola oil with
performed by reducing the crude canola oil, it can be
pressure to concluded that the formation
0.5 bar. However, even with of the dispersed phase is
the reduction of pressure, for favored by the pre- sence of
the two water concentrations fatty acids in the oil, allowing
tested, there was no glycerol
retention by the membrane.
retention by the membrane.
However, the agglomeration
of this phase forms a layer
3.3. Influence of
on the membrane surface
the type of oil
used in the that provides an additional
separation resistance to the flux and
thus a lower value of the
To evaluate the influence stabilized permeate flux
Fig. 5. Permeate obtained in the
of the type of oil used in com- pared to the ultrafiltration of mixtures of the
membrane separation, corresponding refined oil. vegetable oils studied.
ultrafiltration tests were run Importantly, as shown in
with reaction mixtures Table 3, the percentage of
obtained from refined and glycerol in
degummed soybean oils and the permeate was the same,
Fig. 4. Permeate flux in the
from crude and refined ultrafiltration of biodiesel from 12%, both for refined soybean
canola oils. Thus, it was soybean and biodiesel from canola. oil and refined canola oil.
possible to compare the Membrane of 0.05 mm, P ¼ 1.0 bar, These results indicate that
10% acidified water.
characteristics of probably the se- paration of
ultrafiltration of the biodiesel glycerol by ultrafiltration
produced from oil with a depends more on the acidity
higher acidity (degummed of the oil used in the reaction
soybean and crude canola) than on its origin.
and biodiesel produced from
Furthermore, the higher
refined oil, which has low
acidity of the crude canola oil
acidity. Tests were performed
provided the best retention of
at 50 °C at a pressure of 1.0
the dispersed phase and,
bar with prior addi- tion of
10% acidified water, and the consequently, of glycerol
curves of permeate flux over when com- pared to the
160 Table 4
Permeate flux and glycerol concentration in the permeate in the ultrafiltration of
the mixture produced from crude canola oil.
140
2
Membrane (mm) Pressure (bar) Permeate flux (kg/h m ) Glycerol (%)
120
0.05 1.0 101.1 0.013 7
100 0.05 2.0 108.4 0.003 7
0.012
0.05 3.0 97.8 0.005
0.013 7
80 20 kDa 1.0 89.4 0.007
0.011 7
20 kDa 2.0 96.4 0.008 7
0.011
60 1.0 bar 20 kDa 3.0 90.5 0.004 7
0.013
0.008
2.0 bar
40 3.0 bar
 rates of flux decline were permeate flux solution. The authors
20
observed at this pressure, i.e. in relation to explained that under acidic
0 24% for the 0.05 mm the pressure of conditions, there is a
0 10 20 30 40 membrane
50 60 70and 26%
80 for
90 the100
20 2.0 bar. reduction of the electrostatic
T kDa membrane. The increase In accordance with repulsive forces between the
i in pressure from 1.0 to 2.0 bar Chakrabarty et al. [40] and Yi clusters, causing them to
Permeate Flux (kg/h.m

m caused an increase in the et al. [41], the increased flux bind to each other, forming
e permeate flux. However, the with increasing pressure is
( larger agglomerates and thus
pressure of 3.0 bar showed a due to driving force across re- ducing membrane fouling.
m
lower stabilized the membrane. Nevertheless, Similar results of fouling
in
) this increase is not linear, reduction, given the
since the appearance of formation of larger clusters,
140
)

Fig. 6. Permeate flux over time additional resistances, such as

2

under different pressures in the were also obtained by

the com- paction of the Hesampour et al. [42] when
ultrafiltration of the mixture
120 phase retained on the
produced from crude canola oil. treated oily emulsions by
0.05 mm membrane, T ¼ 50 °C, 10% membrane surface, which ultrafiltration.
acidified water. 100 reduce the flux. Also, this formation of
The ultrafiltration of the larger clusters when used the
3.4. Ultrafiltration of 80 crude canola oil, with
mixture produced from crude
biodiesel produced from membranes of
Permeate Flux

crude canola oil: in- canola oil provided not only

0.05 mm and 20 kDa, was
fluence of membrane pore 60 a greater re- tention of
(kg/h.m2)

effective in retaining glycerol,

diameter and 1.0 bar glycerol by the membrane,
once the values of glycerol in
transmembrane pressure 2.0 bar but also the stabilization of
the permeate varied from
40 fluxes at higher values (Fig. 7
0.011% to 0.013% under the
In order to examine the 3.0 bar and Table 4).
conditions evaluated (Table
influence of acidity on the Therefore, regarding the
4). Besides that, the flux
separation of glycerol, 20 lowest rate of flux decline
curves versus time showed a
ultrafiltration tests were over time and the quality of
high initial flux, which
performed with the mixture permeate achieved, the
0 remained almost constant
produced from the 0 10 20 30 pressure of 1.0 bar is the most
throughout the operation,
transesterification of crude 40 50 60 70 recommended for separation
that is, the decline in flux
canola oil, whose acidity is 80 90 100 of glycerol and biodiesel pro-
over time was small and
2.4%, that is ten-fold higher T duced by ethyl
ranged from 14% to 26%.
than the acidity of the re- i transesterification of the
These results indicate that the
fined canola oil. For the m crude canola oil through
retained phase did not cause
production of the reaction e ultrafiltration. Wang et al.
membrane fouling. Probably,
mixture, transesterification ( [25] employed ultrafiltration
this reduction of fouling is
m with
was carried out at 30 °C and due to the larger size of
i 0.1 mm ceramic membrane for
1:7.5, which was the best glycerol agglomerates, which
n biodiesel purification after
condition when using an oil are formed in the presence
) separa- tion of the phases by
with high acidity [30]. of free fatty acids in the oil
settling, and concluded that
The variation of permeate Fig. 7. Permeate flux over time used. This retention of the
flux along time for the the smaller re- duction of flux
under different pressures in the dispersed phase was
membranes of ultrafiltration of the mixture along time (16.7%) was
confirmed by glycerol
0.05 mm and 20 kDa are produced from crude canola oil. 20 obtained at a pressure of 1
analysis (Table 4), since its
presented in Figs. 6 and 7, kDa membrane, T ¼ 50 °C, 10% 5 bar with a
acidified water. highest concentration in the
stabilized
respectively. For all permeate was 0.013%. permeate flux of
conditions evaluated, the Comparing the results of 300 L/h m2.
concentration factor ranged ultrafiltration of crude
from canola bio- diesel with the 3
1 results of degummed soybean .
. biodiesel presented in a 5
3 previous study [31], it was .
observed that the largest
t amount of free fatty acids in M
o the crude canola oil favors e
the formation of the m
1 b
dispersed phase containing
. r
glycerol and thus the a
4 removal by the membrane.
. n
Yi et al. [41] investigated e
For both membranes at the influence of acidity on
the three pressures the ultra- filtration of oil-in-
examined, the stabilized c
water emulsions and l
permeate fluxes were close, concluded that the clusters of e
ranging from 89 to 108 kg/h oil retained when used an a
m2. Furthermore, the highest acidic solution had a larger n
stabilized permeate flux was size compared to i
obtained under the pressure ultrafiltration of an alkaline n
of 2.0 bar. Meantime, higher g
Before starting the
experiments, the
membranes were
characterized with deionized water at pressures of 1.0, 2.0 and treatment to reduce its acidity to around 0.8%, which was the
3.0 bar. The hydraulic permeability values of the membranes of acidity of the degummed soybean oil. As discussed earlier, it is
2
0.05 mm and 20 kDa were respectively 893 and 474 kg/h.m bar. important to have a certain acidity in the oil so that the metho-
The average values of permeate flux at 25 °C and 1.0 bar used to dology developed in this work is adequate to separate glycerol
assess the cleaning of the membranes after each cleaning cycle, using membranes.
for the membranes of 0.05 mm and 20 kDa, were 867 and 450 kg/h The calorific value of all biodiesel samples was above the
m2, respectively. minimum required by the specification, 35,000 kJ/kg. The average
The methodology for membrane cleaning was efficient, and calorific values of the vegetable oil and of the biodiesel produced
after each washing cycle, the initial flux of the membranes was from it were similar. The calorific value of degummed soybean oil
restored with deionized water. Additionally, the cleaning in ul- was 39,230 kJ/kg and of the degummed soybean biodiesel was
trasonic bath reduced the water consumption compared to 38,154 kJ/kg. The calorific value of crude canola oil was 39,381 kJ/
washing the membrane in the module. Considering a complete kg and increased to 39,575 kJ/kg in the crude canola biodiesel.
washing cycle, corresponding to 6 washes with sodium hydroxide These values, as well as variations between oil and biodiesel were
solution, 6 washes with citric acid and 6 rinses with deionized similar to values reported by Lee et al. [7] in the transesterification
water, the total volume of water used is approximately 4.5 l. If of soybean and canola oils.
the same washing was performed in the micro-and The ester content of both soybean biodiesel and canola bio-
ultrafiltration module, the minimum water consumption would diesel was higher than 97.0% in all samples, indicating that
be about 15 l, considering an alkaline wash, an acid wash and the reaction conditions used were appropriate for the
three rinses with deionized water, since the volume necessary for transesterifica- tion of each oil. In other words, the permeates
the recirculation in the module is 3 l. showed mass percentage of esters greater than the minimum
required for marketing as biodiesel, 96.5%.
3.6. Characteristics of the biodiesel produced Likewise, in all tests with the reaction mixture directly ultra-
filtered, the percentage of glycerol was below the value specified
The permeate of the mixture obtained from crude canola oil by the ANP for free glycerol, which is 0.02% in mass. Compared to
using the 20 kDa membrane, at a pressure of 1.0 bar and 10% the works in the literature using membrane technology in the
acidified water was subjected to evaporation under reduced purification of biodiesel [18,24–28], the methodology used herein
pressure in a rotary evaporator at 70 °C and 600 mmHg for has the advantage of eliminating the step of separation by settling
30 min and then characterized for specific mass, kinematic visc- and provide a biodiesel with a very low content of glycerol after a
osity, ester content, acidity, moisture, free glycerol content and single processing step.
calorific value. These results were compared to those obtained Taking into account that steps usually employed of settling and
using degummed soybean oil [31] and are listed in Table 5 to- washing can be replaced by membrane filtration and that this
gether with the values specified for the B100 biodiesel in Brazil process has provided lower content of glycerol than those pre-
[12]. sented in the literature, this study demonstrates a great prospect
The permeates showed viscosities within the specified range. for improving the separation and purification of biodiesel.
The canola biodiesel had a higher average viscosity than the soy-
bean biodiesel, which is a characteristic related to the fatty acid
profile of the oil. 4. Conclusions
Although ultrafiltration has removed most of the moisture,
since the initial concentration of water was 9.1% and the Ceramic ultrafiltration membranes are used for the purification
permeate before being evaporated showed an average moisture of biodiesel produced from ethyl transesterification of vegetable
content of oils with different characteristics, and enable to evaluate the in-
0.45%, the vacuum evaporation treatment was not sufficient to fluence of the acidity of the oil used on the membrane separation
reduce the moisture in the final product to less than 0.05%. It is step.
possible that using a lower evaporating pressure for more than The ultrafiltration separation of glycerol from the reaction
30 min is adequate to reach the specified moisture value. The mixture obtained from refined canola oil is not effective in any
temperature should not exceed 70 °C, given the possibility of condition evaluated. The comparison between the mixtures ob-
polymerization of the esters. tained by transesterification of degummed soybean oil, refined
In the case of canola biodiesel, the high acidity can be reduced soybean oil, crude canola oil and refined canola oil demonstrate
if the crude oil, which had an acidity of 2.4%, receives a pre- that the efficiency of membrane separation of glycerol depends on
the acidity present in the oil. The highest percentage of acid in the
Table 5
oil contributes to the agglomeration of the glycerol after addition
Characteristics of the biodiesel produced from degummed soybean oil and crude of acidified water in the final reaction mixture. Accordingly, the
canola oil using ultrafiltration to remove glycerol. ultrafiltration of reaction mixtures produced from degummed
Characteristic Unit Limit Soybean biodiesel Canola biodie-
(Permeate) sel (Permeate)
soybean oil and crude canola oil is efficient in the removal of
GOMES et al. [31] glycerol. On the other hand, when used refined oils, the agglom-
erates in the emulsion show a diameter smaller than the mem-
3
Specific mass at kg/m 850–900 874 866 brane pore size, so that the glycerol permeates through the
20 °C
2 membrane.
Kinematic visc- mm /s 3.0–6.0 4.38 4.85
osity at 40 °C The efficiency of the ultrafiltration of the mixture obtained
Ester content, % massa 96.5 97.2 97.5 from crude canola oil, which has the highest acidity, indicates that
mín the formation of dispersed phase clusters not only causes a
Free glycerol, % massa 0.02 0.014 0.011 greater retention of glycerol by the membrane, but also the
max
stabilization of
Moisture, max mg/kg 500 976 1670
fluxes at higher rates.
Acidity, max mg KOH/g 0.5 0.48 1.26 This process of biodiesel purification by ultrafiltration has the
Calorific value kJ/kg 35000 38154 39575 advantage of eliminating the step of separation by settling and
results in a biodiesel with very low content of glycerol after a
single processing step, and
reduce the amount of water
used for washing.
Biodiesel produced using
the methodology developed,
both from degummed
soybean oil and crude canola
oil, showed values of ester
content, glycerol content,
viscosity, density and
calorific value within the
range specified by the ANP
for marketing.
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