Fuel Processing Technology 142 (2016) 352–360

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Fuel Processing Technology

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fuproc

Purification of biodiesel using a membrane contactor:

Liquid–liquid extraction
A. Amelio a,⁎, L. Loise b, R. Azhandeh a, S. Darvishmanesh a, V. Calabró b, J. Degrève
d
, P. Luis c, B. Van der Bruggen a,e
a
Department of Chemical Engineering, Process Engineering for Sustainable Systems (ProcESS), KU Leuven, W. de Croylaan 46, B-3001 Leuven, Belgium
b
Department of Modeling for Engineering, University of Calabria, Arcavacata Campus, via P. Bucci, 87036 Arcavacata di Rende, Italy
c
Materials & Process Engineering (iMMC-IMAP), Université Catholique de Louvain, Place Sainte Barbe 2, 1348 Louvain-la-Neuve, Belgium
d
Department of Chemical Engineering, Chemical and Biochemical Process Technology and Control Section (BioTec), KU Leuven, W. de Croylaan 46, B-3001, Leuven, Belgium
e
Faculty of Engineering and the Built Environment, Tshwane University of Technology, Private Bag X680, Pretoria 0001, South Africa

a r t i c l e i n f o a b s t r a c t
Article history: The use of biodiesel in engines requires a high purity (99.65 wt.%), which is to be obtained by the removal of a
Received 22 July
2015
large water amount and a large number of distillation steps. Membrane extraction was studied as a more
Received in revised form 22 October efficient and en- vironmentally friendly process to purify a synthetic biodiesel stream composed of methyl
2015 esters from rapeseed oil, methanol and glycerol. The potential of several flat sheet membranes to remove
Accepted 30 October impurities was evaluated. All hydro- phobic membranes showed breakthrough pressure values higher than 0.5
2015
bar. A PTFE membrane from Sterlitech was selected due to its high chemical resistance against biodiesel. The
Available online 8 November
2015 effect of the concentration of solutes and of the flow rate on the flux was investigated. The overall mass
transfer coefficient was calculated and compared
Keywords: with experimentally observed values, which are in the range of 3.5–7 E-03 (cm/min) for methanol. Thus, this
Membrane mem-
extraction Biodiesel brane technique allows purifying biodiesel, suggesting its potential in industrial
purification applications.
Hydrophobic © 2015 Elsevier B.V. All rights reserved.
Flat sheet
membranes

1. Introduction Some drawbacks are related to the additional resistance to mass

Purification of biodiesel is conventionally done via alcohol
removal using vacuum distillation or flash evaporation, and wet or dry
washings to remove triglycerides, catalyst, and soap [1]. Wet washing
is carried out in several ways: it may be washed with distilled
water alone, washed with acids followed by further washing with
distilled water, or it can be washed with an organic solvent, again
followed by further washing with water. The process is known for its
huge water consump- tion, large wastewater discharges, huge
energy consumption, and its high cost of wastewater treatment and
drying of the eventual biodiesel [1]. Thus, wet washing is not favored,
due to its significant negative con- tribution to environmental
pollution and degradation [2].
Membrane contactors are an interesting alternative for selective
extraction compared to the conventional liquid–liquid extraction.
Membrane contactors have some advantages over the conventional
methods to remove contaminants [3–5]: the porous membrane
offers a large surface area to bring the two liquid phases in contact [3];
the sur- face area remains undisturbed at high and low flow rates;
emulsion for- mation does not occur (unlike in traditional
contactors) no density difference is required between fluids; and the
scale-up is more straight- forward than for mechanically agitated
dispersed phase columns [6].
⁎ Corresponding author.
trans- fer, membrane fouling, and the finite lifetime of the membrane
[7].
In the last years, several applications in different fields have been
re- ported in the literature [7–10]. Dupuy et al. [5,11] worked on the
extrac- tion of highly valuable oxygenated terpenes from lemon
essential oil using mixtures of water and ethanol as solvent. They
explored different membrane materials in flat sheet configuration and
using a polymeric hollow fiber membrane contactor. In another
publication [12], phenol extraction from wastewaters was
investigated using various process configurations with hydrophobic
membrane contactors, including gas-
filled membrane extraction, emulsion pertraction and solvent extrac-
tion. The best performance was observed for emulsion pertraction.
Another similar application was investigated by non-dispersive
solvent extraction, using a commercial hollow fiber membrane
contactor: the re- moval of pharmaceutical pollutants such as ibuprofen
and its metabolite
4-isobutylacetophenone from water [10]. The effects of water and
solvent flow rates on the shell and tube side of the hollow fiber,
respectively, were investigated. The hollow fibers were found to be
very efficient in reducing the concentration (10–110 g/ml) of the
pharmaceuticals in water.
The application of a membrane extraction unit in biorefinery pro-
cesses is described by Abels et al. [3]. The application of a membrane
contactor to purify a biodiesel stream is specifically suggested in the
work of He et al. [13]. In a further publication, He et al. [14] compared traditional refining methods. They showed that membrane
biodiesel purification via a membrane contactor with three extraction is a

http://dx.doi.org/10.1016/j.fuproc.2015.10.037
0378-3820/© 2015 Elsevier B.V. All rights reserved.
A. Amelio et al. / Fuel Processing Technology 142 (2016) 352– 979
360 7
989 A. Amelio et al. / Fuel Processing Technology 142 (2016) 352–
8 360
promising technology for refining biodiesel. In their work, a hollow
fiber membrane filled with distilled water was immersed into the
reactor at
20 °C, while crude biodiesel is pumped into the hollow fiber
membrane. Subsequently, biodiesel is passed over heated Na2SO4 and
then filtered to remove any remaining water [14].
This approach effectively avoids emulsification during the
washing step and decreases the loss during the refining process. The
purity of the biodiesel obtained and the other properties conform to
the ASTM standards [15]. It is a promising method for purifying
biodiesel [16].
In this paper, hydrophilic and hydrophobic flat sheet commercial
membranes were tested in order to study the purification of
biodiesel using a membrane contactor and water as extractant. A
characterization of these membranes was carried out in order to
select the most suitable membrane. The selected membrane was then
extensively studied to as- sess the possibility of using a membrane
contactor to remove the main impurities (i.e., methanol, glycerol)
from a rough biodiesel stream. A model reported in the literature
was applied to calculate the overall mass transfer coefficient, Kov. In a
later stage a ternary system, biodiesel, methanol and glycerol, was
also investigated, to prove its relevance for industrial applications.
2. Materials and
methods
2.1. Materials
Pure biodiesel was provided by Cargill (Genk, Belgium). The
source of methyl esters is rapeseed oil. Methanol (99.8%) and
glycerol (99%) were provided from Acros Organics (Belgium) and
Milli-Q water was used as extractant.
2.2. Experimental
apparatus
Fig. 1 shows a scheme of the experimental setup used in this
work. The feed (biodiesel stream) and extractant (water) were
pumped by
an air motor gear pump (Micropump A-Mount Air-Driven Pump
Drive) from Metrohm (Belgium). Tubing was made from Teflon with
an inner diameter of 4 mm. In each side 2 manometers (Peleman,
Belgium) were positioned before and after the module, one flow
meter Type KDS S K (Kobold, Belgium) and three regulating valves
(Peleman, Belgium) to vary the pressure and the by-pass stream.
A rectangular (10 ∗ 50 mm) membrane module designed and
real-
ized in our university was used in this study. It was made of two
semi-cells in PTFE material, with a O-ring from Kalrez for each cell. In
the middle, a flat sheet membrane was located. A spacer was used to
avoid flow obstruction due to the pressure (1 barg) of the fluid on
one side of the membrane, entailing a reduction of the active
2
membrane area to 26.6 cm . The spacer, in stainless steel, was
made ad hoc to
avoid the problematic described, covering only and completely the
ex- ternal perimeter of the membrane from both the sides, avoiding
any overestimation of the mass transfer.
2.3. Experimental procedure
The determination of the breakthrough pressure for water in the
case of hydrophobic membranes and for biodiesel in the case of
hydro- philic ones was carried out experimentally. The procedure is
described in Section 2.5.3.
The transmembrane flux was evaluated at 20 °C for 210 min. For
this series of experiments, all the membranes were tested first (see
section below), and afterwards different variables were investigated:
• The volumetric flow rate of the biodiesel was varied between 0.4–
1.5 l/min;
• The volumetric flow rate of water was varied between 0.2–1.8
l/min;
• The concentration of methanol was varied between 1 and 5 wt.
%;
• The presence of glycerol with biodiesel and
methanol.
Concentrations of methanol (l–5 wt.%) and glycerol (0.1 wt.%)
were chosen considering the information available in the literature
[1,17,18]. The extractions were carried out using the module in co-
current configu- ration in order to keep the pressure difference
constant along the module.
The feed tank has a volume of 0.36 L, and the water tank was 2.5 L
to keep the system diluted during the experiments. Both phases
were recycled into their respective reservoirs.
The two phases were sampled each 30 min and the concentration
of the methanol was analyzed by gas chromatography (Perkin
Elmer Autosystem GC) in order to monitor mass transfer. In the case of
the pres- ence of glycerol, an HPLC system, Agilent 1200 series equipped
with Diode Array Detector (UV–VIS) and Refraction Index Detector was
used to mea- sure the solutes only in water. Since the initial amount
of glycerol and methanol was known, a mass balance was used to
determine the flux and recovery. Furthermore, to be consistent with
binary mixture results,
the concentration of methanol was monitored using gas
chromatography analyses.
The mass variation due to the sampling of the two solutions was
considered in the calculation of the mass variation over time.
2.4. Membranes
Table 1 lists hydrophobic and hydrophilic membranes used in this
work. These membranes were selected based on their commercial
avail- ability and compatibility with the solvents.
 A. Amelio et al. / Fuel Processing Technology 142 (2016) 352– 999
360 9
Fig. 1. Schematic view of the experimental setup in the co-current configuration: 1—feed vessel; 2—extractant vessel; 3—membrane cell; 4—by-pass; 5—pumps; 6—regulating
valves; FI—flow indicators; Pin and Pout manometers at inlet and outlet of the membrane cell.
Table 1
selected membrane: trade name, manufacturer, material and pore size as given by the manufacturer.

Membrane Company Polymer Pore size [μm]

RM MP005 P1060 MICRODYN-NADIR GmbH Polyethersulfone (PES) 0.05

Alfa Laval MFP2 Alfa Laval Fluoro polymer-PP support 0.2
Alfa Laval MFP5 Alfa Laval Fluoro polymer-PP support 0.5
PP022005 Sterlitech Polypropylene(PP) 0.2
GVSP22205 Millipore Polyvinylidene fluoride (PVDF) 0.22
PTU022005 Sterlitech Polytetrafluoroethylene (PTFE) unlaminated 0.2
2.5. Membrane characterization rates were kept similar in the two cases: slightly higher in the
organic phase for the hydrophilic membranes, and higher on the
2.5.1. Contact angle measurements water side for the hydrophobic membranes. This was to keep the
Contact angles with a standard solvent, mostly water, were used as experimental conditions constant to avoid the effect of possible
a measure for the degree of hydrophilicity/hydrophobicity. The perturbances due to the air pump motor that could affect the
contact angle theoretically ranges from 0° to 180°. The higher the measurements. The flux was calculated by a central difference
affinity equation [22]:
between the solvent drop and the membrane surface, the smaller the
con-
tact angle, resulting in a higher degree of surface wetting. In case of 1 dV f ;tot 1 w f ðt
iþ1 Þ−
f w
i ðt −1 Þ
water Jðti Þ ¼ − ≈− 1Þ
ð
as the solvent, hydrophilic surfaces have a small contact angle, A dt Aρsolv tiþ1 −ti−1
whereas hydrophobic surfaces have a large contact angle. Contact angle ti

measure-
2
ments were carried out with a Krüss DSA10 device. For sessile drop in which wf (g) is the weight of the solute at time ti (min), A (m ) is
fitting, the Young–Laplace equation, theoretically the most exact the
method for cal- culating contact angles, was used [19]. membrane area and ρsolv (g/mL) is the density of
biodiesel.
2.5.2. Membrane surface On the other hand, the recovery of the solutes is defined as the
energy ratio of the difference between the initial and final concentration over
If the contact angles of (at least) two different liquids are known, the ini- tial concentration of each solute in the biodiesel phase [10]:
the surface energy of the solid surface can be determined as well
[20]. The surface tension of a solid is a material intrinsic property, c0 −ci i
%Ri ¼0 :
which is a useful measure for the degree of hydrophilicity/hydropho- ð2Þ c
bicity. A high surface tension corresponds to a hydrophilic surface, i
whereas low values for the surface tension are characteristics of hy- 2.6. SEM analysis
drophobic materials.
The calculation of the substrate surface tension was made with
Scanning electron microscopy (SEM) was used to observe the
the
mor- phology of membrane pores. Samples were coated with a gold
Owens, Wendt, Rabel and Kaelble method
[21]. layer with a thickness of approximately 2–4 nm to produce an
electrical con- ductive surface.
For the calculation of the surface energy of a membrane, the
contact angles of de-ionized water and di-iodomethane were
2.7. Mass transfer phenomena
determined experimentally.

In the mass transfer phenomena of a species i from one phase to

2.5.3. Breakthrough
pressure
In order to determine the breakthrough pressure for each
hydrophil- ic membrane, the pressure on the biodiesel side was
gradually in- creased (0.05 bar every 10 min) [5]; similarly, the
pressure was increased on the water side for the hydrophobic
membranes. The ex- periments were carried out for both pure
biodiesel and at 5 wt.% meth- anol to evaluate the effect of the
impurities. The experiment began with an overpressure of 0.1 bar on
one of the two sides, which was gradually increased until the
biodiesel (or water) became cloudy, indicating that the
breakthrough pressure had been reached. Breakthrough pressures
were measured at the beginning and at the end of the extraction
when the equilibrium between phases was reached.
2.5.4. Thickness
determination
The thickness of each membrane was measured using a Digital
Mi- crometer (Cole–Parmer; range: 0–25 mm; resolution: 0.001 mm;
accu- racy: 0.002 mm). The measurements were carried out in
different portions of the same sheet and the average value was
calculated and compared with the thickness reported by the
manufacturer.
an- other, the main driving force for mass transfer in membrane
contactor re- moval is the concentration difference. For a flat
membrane [23], in steady state, the flux can be expressed by the
following equation:
Ji ¼ Kov Ci −Ci;e ð3Þ
where Kov is the overall mass transfer coefficient based on one phase
feed concentration, Ci is the concentration in the aqueous phase and
Ci,e is the equilibrium concentration. Typically a concentration profile
develops [10], because of the mass transfer of a solute from organic
phase to the aqueous phase [23]. For this specific technology, the
terms of the right side of Eq. (3) depend on the phase that wets the
pores of the membrane. For a hydrophobic membrane, the terms are
based on the organic phase, on the other hand, for hydrophilic
membranes the aqueous phase wets the membrane, thus Kov and
concentration refer to this phase.
In the experiments in which the organic phase wets the pores of the
hydrophobic membrane, the resistance in series concept is used to
de- scribe the transfer of the organics through the contactor. The
overall mass transfer coefficients can be expressed in terms of
cumulative resis- tances [23]:

2.5.5. Flux and recovery

determination
The determination of the flux of methanol was carried out in two 1 1 1 m i
¼ þ þ ð 4Þ
ways depending on the degree of hydrophobicity. In the case of Kov korg km knorg
hydro- philic membranes, the flux was calculated keeping an
overpressure on the biodiesel side, while for the hydrophobic where korg and knorg are the mass transfer coefficients in the two
membranes the pressure was kept higher in the water phase. For a phases, km is the coefficient inside the membrane and mi is the
fair comparison the flow partition
coefficient. mi is the distribution coefficient, which relates the solvent in the HSPs 3D-energy density space [30,31]:
discontinu- ity of the two concentration phases at the equilibrium:
2 2 2 2
np
c i;e ¼ mi
p
ci;e : ð5Þ ðRa Þ ¼ 4 δd;solv −δd;solu þ δp;solv −δp;solu þ δh;solv −δh;solu : ð13Þ

The estimation of the mass transfer coefficients for this
membrane geometry (flat sheet) is based on the work of Curcio et al.
[24]. They de- veloped a “theoretical” relationship explicating the
local Sherwood number at the membrane surface as a function of a
combination of sig- nificant dimensionless groups. Their relationship
is not based on any empirical consideration, but it is the outcome
from considerations
based only on fundamental principles:
The lower the value of the solubility parameter distance, the
higher the affinity between the substances. The affinity of the two
solutes with the solvent was assessed with this theory.
3. Results and discussion
3.1. Selection of the best membrane

k 1 0:13 The results of the experiments for the characterization of the mem-
L L μb
3
Sh ¼ ¼ 6:43 Re Sc : ð6Þ
DAB x μw branes used are summarized in Table 2.
In the first three columns the contact angles for water and di-
This correlation is based on the local Sherwood number and its iodomethane followed by the surface energy are reported. PES, MFP2
inte- gration for the entire length of the cell L gives: and MFP5 membranes have a low contact angle and higher values of
surface energy, and are thus hydrophilic membranes. The last three
k L 3 3
1
membranes, PP, PVDF and PTFE, are
hydrophobic.
Sh ¼ ¼ 6:43 ðRe ScÞ : ð7Þ
DAB 2 The values of breakthrough pressure are consistent with the
degree of hydrophobicity. Indeed the membranes classified as
hydrophilic have
With the following expressions of the very low values for the breakthrough pressure, around 0.2 bar, while
Reynolds the hydrophobic membranes have a value above 0.5 bar. A high
break-
ρvL through pressure is desirable to facilitate process control for industrial
Re ¼ ð8Þ
μ application, and the value of 0.5 bar seems to be a minimally
acceptable target [5]. Thus, all three membranes, PP, PVDF and PTFE,
are suitable in
and Schmidt number this respect.
For the measurements of the flux, the MFP5 membrane was not
μ
Sc ¼ ð9Þ con- sidered because of its low breakthrough pressure, which made it
ρ DAB diffi- cult to control the system. Excluding this membrane, all the
others
showed a flux value of the same order of magnitude, with the highest
The diffusion coefficient of methanol in water is known in the for the PVDF membrane.
liter-
Considering that this membrane had also the highest
ature [25].
breakthrough pressure, it was selected as the best for this
The Wilke–Chang correlation [26] was used to calculate the diffu-
application. Nevertheless, during the experiments to investigate the
sivity (Dorg) of methanol in biodiesel:
effect of the main parameters,
T the breakthrough pressure with the PVDF membrane reduced with
−16 1=2
DAB ¼ 1:173 10 ðφMB Þ ð10Þ time. In particular, after 1 h, water passed through the membrane.
μ B VA0:6
This shift of properties was also observed for the contact angle.
Indeed
the used membranes were first dried, and then the contact angle was
where MB is the molecular weight of the solvent B (biodiesel), μB is
again measured. This resulted in a reduction of the contact angles
the viscosity of B, V A is the solute molar volume at boiling point
caused by the lack of material compatibility and to the high solvation
and φ is an “association parameter” of the solvent, equal to 1 for power of biodiesel, causing a degradation of the structure [32]. A
biodiesel.
further investigation was done by comparing the SEM results. In Fig. 2,
The membrane pore resistance can be estimated by the diffusivity
the cross sections for this membrane are reported before and after its
of the solute into the phase that fills the pores and its geometrical
use. A clear phenomenon of fouling on the membrane can be noticed,
proper- ties [27]:
which is relat- ed to a reduction of the hydrophobicity of the
D AB ε membrane [34].
This phenomena can be expected for microfiltration and ultrafiltra-
km ¼ ð11Þ tion membranes [33].
τδ
As reported by Haseeb et al. [35], fluorocarbons (e.g., PTFE), acetal
where ε is the porosity of the membrane, τ the tortuosity and δ the etc., are compatible for use in biodiesel. Thus, the most suitable mem-
thickness. brane for this application is rather the PTFE membrane of Sterlitech
The value of Kov calculated by Eq. (4) can be compared with that (Fig. 3). This membrane also showed a high breakthrough pressure
ex- perimentally determined by the following expression [10,28,29]: with a flow comparable to that of the other membranes.

Vfeed c0feed Table 2

K ov ¼ ln ð12Þ
Am t cfeed Results of the membrane selected for the characterization.
t the time of experiment cfeed the tion of
0
Vfeed is the volume of the feed solution, Am is the membrane area, the , c feed and are concentra the solute
at the time
0 and t, respectively.
Membrane Contact Contact angle Surface Breakthrough Methanol
angle di-iodomethane energy pressure flux [g/min
water (Owens) [bar] 2
∗ cm ]
−
PES 53.8 41.7 51.04 0.25 5.50 ∗ 10 4
−
MFP2 78.2 44.525 39.13 0.2 7.22 ∗ 10 4
2.8. Solvent–solute assessment via HSPs theory MFP5 42.6 52.325 55.88 b 0.2 –
−
PP 135.3 106.5 6.95 0.8 2.82 ∗ 10 4
−
PVDF 154.8 141.92 0.6 1.85 9.74 ∗ 10 4
The solubility parameter distance (Ra, Eq. (13)) developed by
PTFE 139.1 126.6 2.16 1.78 3.20 ∗
Skaaru 10
− 4

[30], which takes into account the distance between the solute and
the
Fig. 2. SEM pictures of the cross section surface of the GVSP22205 (PVDF): left, in dry condition; right, after the use.
3.2. Experimental results
Once the membrane was
selected, a further investigation
was carried out to evaluate the
effect of the main parameters on
the transmembrane flux and to
calculate the mass transfer
coefficients. In Fig. 4 the
variation of the flux over time is
reported for three different
concentrations.
In Fig. 4athe experimental
values of the flux are reported.
These were calculated as
described by Luis et al. [22]. The
variation of weight over time
allows the calculation of the
transmembrane flux J (Eq. (1)),
which indicates the rate of
solvent extraction. After the
first 30 min, the points at the
same concentration oscillate
around the same value. Because
of the oscillation of the flux, its
value was calculated by the
slope of the mass in the feed
(or water) of methanol over
time, divided by the effective
membrane area. The dashed line
indicates the constant value of
the flux over time. It is also
clear that the values of the flux
in- crease with initial
concentration of methanol in
the feed (Fig. 4b).
Using Eq. (11) the values of
the overall mass transfer
coefficient Kov over time were
determined at the three
investigated concentrations.
The values of the overall mass
transfer coefficient are very
similar at dif- ferent
concentrations, showing a slight
dependence of the concentra-
tion on the mass transfer
coefficient. Constant values
of Kov are observed at the
studied concentrations.
3.3. Dependence of flow rates
In Fig. 5a the effect of the
flow rate on the overall mass
transfer coef-
ficient determined
experimentally over time is
reported.
It is clear that when the flow
rate increases, the Kov values
increase as well, because the
Reynolds number is increased.
The increase of the
Reynolds number reduces the
effect on the mass transfer
resistance on the bulk side; as a
consequence, the mass transfer
becomes faster. This
consistent with Eq. (7): when
the Reynolds number increases
and the other terms remain
constant, the Sherwood number
increases, L is con- stant, and the
diffusivity is also constant since
it is independent of velocity, so
Kov increases.
It can be also seen that the
recovery of methanol (Fig.
5b) depends
Fig. 3. SEM picture of the on the flow rate. A higher flow
surface of the
PTU022005 (PTFE). rate corresponds to a higher
recovery of the solute.
Nevertheless, the data points
seem to reach a plateau, thus
the increase of the recovery is
not directly proportional to the
in- crease of the flow rate.
However, higher feed flow
rates are beneficial for the
separation.
Fig. 5 shows the flux and
overall mass transfer coefficient
as a func- tion of the flow rate
at the water side, allowing a
comparison with the variation
of the flow rate at the biodiesel
side.
Fig. 6a indicates that both
sides have an influence on the
metha- nol flux. In the case of a
variation of the biodiesel flow
rate (circles), the flux increases
by 44% when the flow rate is
increased three times, showing
a clear effect of the flow rate on
the flux. When the flow rate of
water is increased by a factor
nine, the flux is less than a
fifth higher than the initial
values. Although the flux
values have a lower slope
when the flow rate of water is
investigated, this effect is
more evidenced because in the
case of the variation of the
biodie- sel flow rate the water
flow was constant at a
Reynolds number of
24,000. On the other hand, the
Reynolds number in biodiesel
was kept constant at 1100
when the water flow rate was
changed. A similar conclusion
can be drawn for K ov (Fig. 6b),
even though the effect at the
biodiesel side is more
pronounced than the effect
on the flux (Fig. 6a).
overall
mass
transf
er
is
The experimental values
were finally compared with
those found using the model of
Curcio et al. [24], Eq. (7).
The values of k at the water
side and at the biodiesel side
and in the membrane were
determined as explained in
Section 2.7. Nevertheless, for the
calculation of Kov the value of
the partition coefficients is also
needed (Eq. (4)). This value was
not available from the
literature, thus it was
determined using the
experimental flux that allowed
calculating the concentration at
the equilibrium interface then
consequently the partition
coefficient was found (Eq. (5)).
In Fig. 7 the comparison of
this approach with the
experiments is reported.
The overall mass transfer
values obtained in this
investigation are coherent with
what has been reported in the
literature. The calculated mass
transfer coefficients agree with
the experimentally observed,
giv- ing the same order of
magnitude as the experiments,
although the values calculated
were always higher than the
experiments. The

3.4.
Deter
minati
on of
the
Fig. 4. a) Flux of methanol vs. time: diamonds 5 wt.%, circles 3 wt.% and triangles 1 wt.% of methanol in the feed; dashed line shows the constant value of the flux over time for each
concentration
5,3,1 wt.%. b) Average value of flux vs. initial mass fraction of methanol. c) Kov of methanol vs. time, squares 5 wt.%, diamonds 3 wt.% and triangles 1 wt.% of methanol in the feed. QBio =
0.4 l/min
(Reynolds_Bio = 1100), QH2O = 1.8 l/min (Reynolds_H2O = 24,000), temperature at 20 °C.
difference in calculated and −
5.7 ∗ 10 3. Since Ra is lower for
observed Kov values is probably
glycerol, it suggests a higher
due to the estimation of the
affinity than between methanol
properties of biodiesel and
and water, thus even glycerol is
methanol. Indeed the use of a
expected in water phase.
generic correlation can affect
Furthermore, to avoid
the final result.
problems related to the
The correlation used was the
detection of glyc- erol in low
most suitable from those found
concentrations, the quantity of
for the system described here,
water, used as extractant
in terms of geometry and
during the experiments, was
phases. Nevertheless, it is
reduced by a factor 6.The
absolutely general and focuses
experimental removal was
on the determination of a local
2.5%, confirming that the
Sher- wood number and not
contactor is also able to sepa-
specific for this kind of
rate glycerol from biodiesel.
application. This suggests a
The effect of dilution
need for further investigation.
(reduction of water quantity)
and the presence of a third
3
component do not affect the
.
5 separation of methanol: the
. recovery remains the same at
3.5%. It is evident that the
glycerol removal is slightly
T
e lower than that of methanol.
r This difference becomes more
n evident when the values
a of the fluxes for the two
r components were determined:
−
y 2.33 ∗ 10 4
−7
and 7.51 ∗ 10
2
g/min cm for
s methanol and glycerol,
y respectively. The initial
s amount of methanol was 50
t times more than that of glyc-
e
erol, even though in terms of
m
fluxes the difference becomes
larger, suggesting that for
Along with methanol, traces
designing the system, glycerol
of glycerol are present in the
should be consid- ered as
biodiesel system, and must be
target compound.
removed. For this reason, a
ternary system with
5% and 0.1% methanol and
glycerol was also studied. Since
the detection of glycerol was
complicated and was only
possible at the highest con-
centration, the affinity of
glycerol and methanol with
water was deter- mined in
terms of Hansen Solubility
Parameters. The value of Ra
between water–methanol
−
is
1.25 ∗ 10
2
, while for
glycerol–water it is
Fig. 5. a) Kov vs. QBio (l/min): triangles 1.5, squares 1, circles 0.7, diamonds 0.4; b) R% vs. QBio (l/min). At 5 wt.% of methanol, QH2O = 1.8 l/min (Reynolds_H2O = 2400), Reynols_Bio
=
1100–4200 and temperature at 20 °C.
 However, the results are strongly dependent on the initial further investigation on the glycerol quantity, requiring even the real
quantity of the components. This is confirmed in Fig. 4; the flux values of initial concentration to calculate the effective membrane
decreases pro- portionally with the reduction of the initial area needed.
concentration. It suggests a

Fig. 6. Comparison of the effect of water and biodiesel flow rate on the fluxes a) and Kov b) at 5 wt,% of methanol and temperature at 20 °C: triangles QH2O = 0.2–1.8 l/min,
(Reynolds_H2O = 2700–24,000) at QBio = 0.4 l/min (Reynolds_Bio = 1100); circles QBio = 0.4–1.5 l/min, (Reynolds_Bio = 1100–4200) at QH2O = 1.8 l/min (Reynolds_H2O =
24,000). QBio = 0.4 l/min (Reynolds_Bio = 1100).
Fig. 7. Comparison theoretical (squares) vs. observed (diamonds) data for Kov at 5 wt.% of methanol and QH2O = 1.8 l/min (Reynolds_H2O = 24,000) and temperature at 20 °C.
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