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Article history:
Received 21 May 2012
Accepted 26 February 2013
Available online 30 March 2013
Biodiesel is an environmental-friendly fuel that can replace petroleum diesel. However, after transesterication reaction of vegetable oils, the obtained crude biodiesel must be puried. The commonly
applied purication step is water washing. This step is a concern in biodiesel production, since large
quantities of clean water are used, generating a wastewater stream to be further treated. Here we propose the application of micro and ultraltration processes to purify crude biodiesel. Crude biodiesel was
ltrated in a dead-end process at different transmembrane pressures and using membranes of different
pore sizes. Flux results showed that greater transmembrane pressures, as well as greater pore sizes,
enable greater uxes. Density, viscosity and acid values of puried biodiesel (washed and ltrated) are in
accordance to the international legislation for biodiesel quality. Both processes (water washing and
membrane separation) were able to reduce the amount of soap detected in crude biodiesel. However, the
proposed microltration membranes were not efcient as the washing method to reduce the free
glycerol content. The ultraltration membrane of 30 kDa was also not able to produce a puried biodiesel
according to the international legislation for free glycerol content. Between the analyzed membranes, the
glycerol content limit (less than 0.02 wt%) was achieved only with the ultraltration membrane of
10 kDa. Water addition in the crude biodiesel improved the glycerol removal by membrane ltration. The
obtained results showed that the membrane separation process is a suitable alternative for biodiesel
purication.
2013 Elsevier Ltd. All rights reserved.
Keywords:
Biodiesel
Purication
Membrane
1. Introduction
Energetic and environmental issues have encouraged the
development of alternative fuel sources. Biodiesel is a potential fuel
for diesel engines since it is obtained of renewable sources and
combustion emissions for biodiesel are lower than for petroleum
diesel [1]. Biodiesel can be derived from vegetable oils, animal fats
or recycled greases. Choice of the raw material to be used in biodiesel production is both a process chemistry decision and an
economic decision [1]. In Brazil, soybean oil is largely applied for
biodiesel production [2].
Biodiesel is commonly produced by the transesterication reaction. In this reaction, a triglyceride reacts with an alcohol of short
chain (methanol or ethanol) in the presence of a catalyst to produce
a mixture of fatty esters (biodiesel) and glycerol. Although the 3:1
mole ratio between methanol and oil is required, extra alcohol is
added to the reactor in order to drive the reaction closer to higher
yields. Using vegetable oils as a feedstock, base catalyst systems are
* Corresponding author.
E-mail addresses: miria@feq.ufu.br, miriareis@hotmail.com (M. Reis).
0960-1481/$ e see front matter 2013 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.renene.2013.02.035
mainly used. The most commonly used catalyst materials for converting triglycerides to biodiesel are sodium hydroxide, potassium
hydroxide, and sodium methoxide [3]. Typical catalyst loadings
range from 0.3% to about 1.5% [1]. The operating reactor temperature is usually about 60 C, although temperatures from 25 C to
85 C have been reported [1]. After the reaction, the reaction
mixture is allowed to settle in a decanter to give a separation of
ester and glycerol phases. Alcohol is removed from both the glycerol and ester stream using an evaporator or a ash unit. After these
steps, the ester phase still contains impurities such as free
dispersed glycerol particles, soap, and trace amounts of residual
catalyst and mono, di, and triglycerides. This crude biodiesel must
be treated in order to attempt standard specications that dene
the quality of biodiesel (e.g., ASTM D6751 [4] and EN 14214 [5]).
The conventional purication process of the ester phase is water
washing, being applied to remove the residual glycerol, base catalyst, and any soap formed during the reaction [6]. However, this
process generates a large amount of highly polluting wastewater,
causing environmental disposal problems.
Membrane technology can be applied for biodiesel purication
in order to avoid the water washing step. Atadashi et al. [6] stated
16
Fig. 1. Scheme for biodiesel (FAME) purication by the membrane separation process.
Manometer
Filtration
module
Permeate
collection
Magnetic stirrer
N 2 gas tank
Digital balance
Yield%
Fig. 2. Schematic diagram of ltration module.
MWCO (GE Osmonics, USA) were evaluated in this work. Only new
membranes were used in the experiments.
The microltration experiments were carried out at two
different transmembrane pressures, 1 and 2 bar. The ultraltration
tests were performed at 4 bar of transmembrane pressure for both
evaluated ultraltration membranes. These pressures were chosen
based on preliminary tests in which suitable biodiesel uxes were
observed.
The ltrations were carried out in a semi-batch module (Fig. 2)
using membranes with ltration radius of 45 mm. A volume of
500 mL of biodiesel was fed into the membrane module for each
experiment. The pressure was adjusted with N2 gas and monitored
in a manometer. The permeate ux was monitored through the
ltration time. Micro and ultraltrations were carried out during 10
and 60 min, respectively. These times were xed based on the
volume of crude biodiesel fed in the ltration module.
Besides crude biodiesel ltrations, additional tests were carried
out by the adding of low quantities of water to the crude biodiesel
before the ltration. Deionized water was added to the biodiesel
sample at concentrations of 0.1 and 0.2 wt%, as suggested by Saleh
et al. [16]. Deionized water was mixed with the crude biodiesel
using a magnetic stirrer for 1 h at ambient temperature prior to the
ltration run.
2.3. Chemical analysis
Soybean oil and crude, washed and ltrated biodiesel samples
were analyzed for free glycerol content, density at 20 C, kinematic
viscosity at 40 C, acid value, saponication value, amount of soap
and water content.
Kinematic viscosity, density, and acid value, were determined
according to ASTM D445 [17], D1298 [18], and D664 [19], respectively. The acid number is a direct measure of free fatty acids in
biodiesel. It is measured in terms of the quantity of KOH required to
neutralize the sample.
Amount of soap was measured following a modied version of
AOCS method Cc 17e79 [20], soap in oil. Saponication value was
17
mbiodiesel
100
mraw oil
(1)
Biodiesel sample
Crude
Washed
880
5.0
525.4
0.08
191.5
2.6 103
0.029
880
5.0
1026.2
0.14
179.2
n. d.
0.007
n. d. not detected.
a
As potassium oleate.
18
19
Table 2
Final ux throughout micro and ultraltration membranes.
Membrane pore size
0.22 mm
Pressure (bar)
Final ux (kg h1 m2)
1
109
0.30 mm
2
253
1
536
2
923
10 kDa
30 kDa
4
55
4
120
0.22 mm (1 bar)
0.22 mm (2 bar)
0.3 mm (1 bar)
0.3 mm (2 bar)
10 kDa (4 bar)
30 kDa (4 bar)
30 kDa (3 bar)
a
Parameter
Amount of soap
(103 gsoap g1sample)a
Free glycerol
(%, wt/wt)
1.3
1.3
1.6
1.6
1.0
2.7
2.4
0.022
0.025
0.026
0.026
0.020
0.031
0.029
Fig. 5. Reductions for amount of soap and free glycerol content in puried biodiesel
samples.
Biodiesel sample
Crude
Washed
0.049
0.011
0.019
20
References
Fig. 6. Permeate uxes throughout the ultraltration membrane of 10 kDa with water
addition to the crude biodiesel.
Table 5
Free glycerol and water contents in biodiesel permeate samples with water addition
for the 10 kDa membrane at 4 bar.
Filtration
time (min)
10
40
60
Free glycerol
(%, wt/wt)
Water
(ppm)
Free glycerol
(%, wt/wt)
Water
(ppm)
0.002
0.006
0.010
1577.17
1362.36
987.90
0.007
0.007
0.009
1001.08
937.76
910.28
Acknowledgments
The research work was funded by VALE S.A. and Conselho
Nacional de Desenvolvimento Cientco e Tecnolgico (CNPQ).
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