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Journal of Industrial and Engineering Chemistry 21 (2015) 206211

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Journal of Industrial and Engineering Chemistry


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

Liquidliquid extraction of succinic acid using a hollow ber


membrane contactor
Luciana de Souza Moraes *, Frederico de Araujo Kronemberger,
Helen Conceicao Ferraz, Alberto Claudio Habert
Chemical Engineering Program COPPE, Federal University of Rio de Janeiro, P.O. Box 68502, CEP 21941-972 Rio de Janeiro, RJ, Brazil

A R T I C L E I N F O

Article history:
Received 21 October 2013
Accepted 16 February 2014
Available online 22 February 2014
Keywords:
Succinic acid
Membrane contactor
Hollow ber
Extraction
Amine

A B S T R A C T

Extraction with membrane contactors is an attractive technological alternative for organic acid
separation from fermentation broths. This work aims at studying the recovery process of succinic acid,
integrating both extraction and re-extraction steps. It was proposed to use a non-porous membrane,
which allows more exibility of operation without loss of efciency. For the integrated process, a 5-fold
increase in the recovery of acid from the feed stream was observed when compared to the single
extraction process, leading to an overall recovery close to 50%.
2014 The Korean Society of Industrial and Engineering Chemistry. Published by Elsevier B.V. All rights
reserved.

1. Introduction
The demand for organic acids produced by fermentation has
grown due to their use in the manufacture of biodegradable
polymers, being poly(lactic acid) the most prominent [1].
Separation is still a major cost factor: the main issue in removing
organic acids from aqueous streams as in fermentation broths is
their low concentration and the variety of substances present in
the broth [2]. As an alternative to the highly expensive precipitation method currently used, several processes have been proposed,
such as adsorption, ion exchange, liquidliquid extraction and
membrane separation [36]. Among them, membrane processes
seem to be technically and economically promising. Non-dispersive solvent extraction using hollow ber membrane contactors
(also referred as membrane contactor extraction), liquid membranes and facilitated transport have been extensively studied for
organic acids separation from fermentation broths [710].
Extraction with membrane contactors, using an organic
compound as extraction agent, has many advantages over
conventional liquidliquid extraction. Membrane acts as a barrier
which avoids dispersion of the liquid phases and also enhances

The authors would like to dedicate this paper to Professor Alberto Luiz Coimbra,
in the 50th anniversary of COPPE (19632013), the Graduate School of Engineering
of the Federal University of Rio de Janeiro.
* Corresponding author. Tel.: +55 21 2562 8354.
E-mail address: lmoraes@peq.coppe.ufrj.br (L.d.S. Moraes).

their contact area. Moreover, the process is modular and has low
energy consumption [11]. Despite all potential advantages of this
process, a good extraction also relies on selecting a suitable
extractant. It needs to be highly selective for the component and to
have a good extraction capacity. Also, it is desirable to combine low
cost with low viscosity, a moderate interfacial tension, good
biological degradability and low toxicity [12]. Many works report
the evaluation of hydrocarbons, alcohols, amines and phosphorous
compounds as extractants for organic acids extraction. For the rst
two, the extraction is physical, and the distribution coefcients are
small [13]. Amines form complexes with organic acids, therefore
the extraction is reactive. Phosphorous compounds have been
combined with amines to enhance the distribution coefcients, but
high concentrations are required, increasing costs [14]. To improve
the solubility of the complexes, hydrocarbons and alcohols are
added as diluents to the extractant mixture. They also modify some
properties of the extractants, such as viscosity [15]. Novel
extractants, especially ionic liquids, have been evaluated, although
only a few have presented results as good as trioctylamine (TOA),
the most common extractant for organic acids extraction [1618].
For liquidliquid membrane extraction, porous membranes are
often used, due to the lower mass transfer resistance compared to
dense membranes. However, in this case, a rigorous pressure
control is necessary to avoid disruption of the interface, and
partially soluble extractants (as for example, primary amines)
cannot be used [19]. To overcome eventual limitations of mass
transfer in dense membranes, an appropriate swelling may be

http://dx.doi.org/10.1016/j.jiec.2014.02.026
1226-086X/ 2014 The Korean Society of Industrial and Engineering Chemistry. Published by Elsevier B.V. All rights reserved.

L.S. Moraes et al. / Journal of Industrial and Engineering Chemistry 21 (2015) 206211

Nomenclature
total amine concentration in the organic phase
(mol/L)
[H2Suc]aq succinic acid concentration in the aqueous phase
(mol/L)
[H2Suc]org succinic acid concentration in the organic phase
(mol/L)
distribution coefcient, dened by Eq. (1)
KD
mH2 Suc succinic acid mass in aqueous phase (kg)
RE
re-extraction efciency (%), dened by Eq. (2)
Recov
succinic acid recovery in membrane contactor (%),
dened by Eq. (3)
Z
loading, dened by Eq. (4)

[Ext]T

Subscripts
eq
equilibrium
ext
extraction
F
feed
o
initial
rext
re-extraction

promoted, in addition to a reduction in the membrane thickness.


Lee et al. [20] already reported that extraction of solutes in liquid
liquid systems using dense membranes is feasible, but the choice of
a solvent with a good interaction with the membrane material is
important.
This work aims at studying the extraction of succinic acid,
investigating both the extraction to the organic phase and the reextraction into a new aqueous phase using a hollow ber dense
membrane module as a contactor. The objective is to obtain a
puried acid, improving extraction efciency. Capacity and
selectivity of mixtures of 1-octanol and several amines were
evaluated and the overall recovery of acid was measured for a
circulating batch feed in a 2-step extraction system.
2. Experimental
To recover succinic acid (Sigma Aldrich, 99%), the extractants
used were 1-octanol (Vetec), Primene JM-T1 (a C16C22 primary
amine, Rohm and Haas, 80%), Primene TOA1 (C8 primary amine,
Rohm and Haas, 99%), n-Butyldiethanolamine (n-BDEA, Sigma
Aldrich, 98.6%) and a trioctylamine (tris(2-ethylhexyl)amine,
TEHA, TCI America, 93%). Because amines are viscous and
corrosive, 1-octanol was used as diluent. The amine concentration
in the organic phase was set in 10% w/w. All products were used as
received from the manufacturers. For the membrane extraction, a
cellulose diacetate membrane module (Dicea 1701, Baxter
Healthcare) was selected. It was packed with dense hollow bers,
with 200 mm of inner diameter, 15 mm of wall thickness and
1.7 m2 of contact area.
Succinic acid solutions were prepared with concentrations
ranging from 0.01 to 0.5 mol/L (160 kg/m3), which include the
typical values found in fermentation broths [21]. Organic acid
concentration in the aqueous phase was determined by HPLC
(Shimadzu, SCR 102H column, H3PO4 as mobile phase, ow rate
0.6 mL/min, 80 8C, RI detector).
2.1. Equilibrium experiments
Equilibrium tests were performed at 25, 40 and 60 8C. Equal
volumes of succinic acid aqueous solution and extractant were

207

charged in 50 mL polypropylene vessels and stirred at 120 rpm for


1 h. The mixture was then centrifuged at 5000  g for 30 min to
allow complete separation of the organic and aqueous phases.
Succinic acid concentration in the aqueous phase was determined
by chromatography and the concentration in the organic phase
was calculated from a mass balance. Distribution coefcients (KD)
were calculated, according to Eq. (1).
KD

H2 Sucorg;eq

(1)

H2 Sucaq;eq

where [H2Suc]org,eq and [H2Suc]aq,eq are, respectively, the equilibrium concentration in organic and aqueous phases.
The inuence of the pH of the aqueous phase used for reextraction on the recovery efciency was also evaluated. Equal
volumes of aqueous and organic phases (500 mL each) were
charged in a vessel with controlled stirring (120 rpm) and
temperature (25 8C). Succinic acid concentration in aqueous phase
was 0.17 mol/L (20 kg/m3) and the amine concentration in 1octanol was 10%, w/w. Allowing 3 h for the equilibrium establishment, the phases were then separated by centrifugation (5000  g
for 30 min), and the organic phase was collected and stored.
Samples were taken from the aqueous phase before and after
extraction to determine the percentage of acid extracted. The pH of
the re-extraction was changed by adding 0.1 mol/L hydrochloric
acid or 0.1 mol/L sodium hydroxide solutions. Equal volumes of the
stored organic phase and the re-extraction water were added to
50 mL polypropylene vessels. The procedure was the same as in the
extraction experiments. The re-extraction efciency (RE) was
calculated as the ratio between the concentrations of acid in the
aqueous phase after re-extraction and in the organic phase, as
shown in Eq. (2).
RE %

H2 Sucaq;eq
H2 Sucorg;o

 100

(2)

2.2. Extraction experiments in the 2 ways membrane contactor


system
For membrane contactor extraction (MCE), a system containing
two coupled hollow ber modules was set (Fig. 1), allowing
simultaneously extraction of the acid from an aqueous phase (feed)
to an organic phase (extractant) and re-extraction from this organic
phase into a new aqueous phase (recovery), and therefore, succinic
acid extraction could be achieved. This approach is expected to be
very effective when the acid is extracted from a fermentation broth
(a multicomponent system). In this work, tests were performed with
a solution of pure succinic acid, with the purpose of evaluating the
performance of the selected membrane and extractants, without
interference of other solutes. The system conguration allows its
operation in extraction or coupled (extraction + re-extraction)
modes. Therefore, experiments were performed in both operational
modes, and their results were compared.
For these tests, operation was performed with batches of
succinic acid (0.17 mol/L) and extractant (10%, w/w amine in 1octanol) solutions, and pure water for re-extraction. All solutions
were allowed to recirculate. The extractant ows inside the bers,
at a ow rate of 105 m3/s, corresponding to a Reynolds number
(Re) of 0.4, while the aqueous phases ow externally to the bers
(succinic acid solution ows in the rst module, and pure water in
the second one), at a ow rate of 3  105 m3/s (Re = 19). The
efciency of this process is calculated in terms of the percentage of
recovery, Recov (Eq. (3)):
Recov %

mH2 Suc;rext
 100
mH2 Suc;F

(3)

[(Fig._1)TD$IG]

[(Fig._3)TD$IG]

L.S. Moraes et al. / Journal of Industrial and Engineering Chemistry 21 (2015) 206211

208

Fig. 1. Extraction system representation.

3. Results and discussion


3.1. Liquidliquid extraction (LLE)
Succinic acid concentrations after equilibrium in aqueous and
organic phases were obtained for several initial concentrations in
the aqueous phase. Table 1 shows the percentage of acid extracted
for each mixture used, for a 0.17 mol/L succinic acid solution. For nBDEA and Primene TOA1 extractants, extraction was negligible
due to emulsion formation. The best extractant was Primene JMT1, which extracted 86.0% of the acid.
The temperature effect on equilibrium isotherms was evaluated
for all extractants, despite the observed emulsion formation at
25 8C for Primene TOA1 and n-BDEA amines. Results are presented
in Figs. 24. For 1-octanol, the relationship between succinic acid
concentration in organic and aqueous phases is linear through the

[(Fig._2)TD$IG]

Table 1
Succinic acid removal from aqueous phase by LLE.
Extractant

1-Octanol

Primene JM-T1

Primene TOA1

n-BDEA

TEHA

Removal (%)

15.9

86.0

4.8

3.7

32.0

Amines were diluted in 1-octanol, in a proportion of 10% (w/w). Acid concentration


in aqueous phase: 0.17 mol/L. Temperature: 25 8C.

Fig. 2. Effect of temperature on succinic acid LLE with 1-octanol.

Fig. 3. Effect of temperature on succinic acid LLE with the primary amines Primene
JM-T1 (a) and Primene TOA1 (b). Amine concentration in 1-octanol: 10% (w/w).

entire concentration range, and extraction is not inuenced by


temperature, since it is a physical extraction. For reactive
extraction with amines, the relation between concentrations in
aqueous and organic phases, at equilibrium, is not linear,
particularly at high concentrations. This is clearly a deviation
from a Henrys law type isotherm (typical for physical extraction),
as described by Wasewar et al. [22]. Moreover, these results appear
to indicate that at higher temperatures, the reaction mechanism
may be different, and that another type of complex between
succinic acid and amine could be formed, as also suggested by
Tamada et al. [15] and Tamada and King [3]. Increasing the
temperature from 25 to 40 8C did not improve extraction efciency
when primary amines (Fig. 3) were used as extractants. Also, for
diluted succinic acid aqueous solutions extracted by Primene JMT1, temperature did not affect extraction at all (Fig. 4).
In the case of extraction with tertiary amines, the effect of
temperature on extraction is more pronounced. For n-BDEA,
extraction was signicant only at the highest temperature
investigated (60 8C). At this temperature, the relationship between
the equilibrium concentrations in aqueous and organic phases was
linear, and the distribution coefcient obtained is close to 1. For all
other conditions, the behavior is very close to that obtained for 1octanol, an indication that the acid in the organic phase was
extracted by the diluent, being the exception the highest
concentration, at 40 8C. The TEHA isotherms did not show a

[(Fig._4)TD$IG]

[(Fig._5)TD$IG]

L.S. Moraes et al. / Journal of Industrial and Engineering Chemistry 21 (2015) 206211

209

Fig. 5. Temperature dependence on distribution coefcient for succinic acid LLE for
all extractants evaluated. Amine concentration in 1-octanol: 10% (w/w).

shown in Eq. (4), in which [H2Suc]org is the succinic acid molar


concentration in organic phase after extraction and [Ext]T is the
total amine concentration (kmol/m3). Loading curves for Primene
JM-T1 and TEHA are shown in Fig. 7.

Fig. 4. Effect of temperature on succinic acid LLE with the tertiary amines n-BDEA
(a) and TEHA (b). Amine concentration in 1-octanol: 10% (w/w).

particular behavior, which may be interpreted as a change in the


complexes stoichiometry, and this hypothesis should be further
investigated.
Values of distribution coefcients (KD) obtained for the
extractants are summarized in Fig. 5. For comparison, a xed
initial concentration (0.17 mol/L) was assumed for calculations. It
can be clearly seen that Primene JM-T1 was the best extractant for
succinic acid LLE. Its KD value was more than ve times higher than
the second best extractant, TEHA, at 25 8C. It is also possible to
check that at the highest temperature, the efciency of all amines
increased considerably. For the case of Primene TOA1 and n-BDEA
amines, this behavior may be due to the fact that reaction
mechanism changes with increasing temperature. The KD values
for 1-octanol and TEHA amines are similar to those found in the
literature. Li et al. [13] obtained a distribution of 0.26 when 1octanol was used for succinic acid extraction, at 25 8C, and Huh
et al. [21] and Song et al. [23] reported a KD of 0.3 with a mixture of
6.5% (w/w) of tri-n-octylamine in octanol.
Fig. 6 shows the dependence of KD on the succinic acid
concentration in aqueous phase and temperature for the two more
suitable extractants evaluated: Primene JM-T1 and TEHA. For the
primary amine, KD value decreases with increasing acid concentration in the aqueous phase. Additionally, the results for 25 and
40 8C seem to indicate that its extraction capacity approaches a
limit. One way to identify this behavior is to obtain the loading
curves. According to Wasewar et al. [22], loading (Z) is dened as

H2 Sucorg
ExtT

(4)

For the primary amine (Fig. 7a), loading curves for 25 and 40 8C
tend to reach a plateau at Z = 1, conrming that the amine achieves
its limit (saturation). The same behavior was not observed at 60 8C,
when loading exceeds 1 at [H2Suc]aq,o = 0.5 mol/L. This is an
indicative that complexes with more than one acid molecule per
amine molecule are formed. Wasewar et al. [22] states that for
concentrated acid solutions, when loading is higher than 0.5, it is
possible an acid/amine ratio different from 1. Therefore, it could be
inferred from this study that n:1 (with n > 1) stoichiometries, in
which n is the number of acid molecules in the complex, are
formed
in the extraction with Primene JM-T1 amine, while for
[(Fig._6)TD$IG]

Fig. 6. Temperature dependence on distribution coefcient for succinic acid LLE.


Amine concentration in 1-octanol: 10% (w/w). Succinic acid initial concentration in
aqueous phase varies from 0.01 to 0.5 mol/L.

[(Fig._7)TD$IG]

210

[(Fig._8)TD$IG]

L.S. Moraes et al. / Journal of Industrial and Engineering Chemistry 21 (2015) 206211

Fig. 8. Effect of the pH of the aqueous re-extraction phase on the efciency of


succinic acid recovery from an organic phase consisting of 10% (w/w) Primene JMT1 in 1-octanol.

Fig. 7. Loading curve for succinic acid LLE with (a) Primene JM-T1 and (b) TEHA,
both diluted in 1-octanol, in a proportion of 10% in mass.

tertiary amine TEHA (Fig. 7b) this is improbable, although this


possibility could not be entirely ruled out.
For Primene JM-T1 diluted in 1-octanol, re-extraction was
evaluated as a function of the pH of the aqueous phase. As a rst
step, the liquidliquid extraction resulted in an efciency of 86.3%.
The organic phase loaded with succinic acid was then used in the
re-extraction experiments. Results are presented in Fig. 8.
Observing the pH of the aqueous phase after extraction, it was
possible to identify a buffering region in which the recovery
efciency was extremely low. When the initial pH was very basic
(above 13), it was observed a signicant increase in recovery of the
acid, with an efciency of about 60%. Some authors, such Lee et al.
[24], Keshav and Wasewar [25], have obtained similar results
studying the effect of the addition of sodium ions for the reextraction of succinic and propionic acids, respectively, from an
organic phase containing trioctylamine (TOA) in alcohols. The
former pointed out that in a basic environment, when the pH is
higher than pKa1 and pKa2 of succinic acid, it is possible to back
extract the acid by destroying the complex and forming a sodium
succinate salt. The high solubility of this salt in the aqueous phase
explains the increase in the efciency of recovery.

liquid phases, and consequently, emulsion formation. Thus, a


variety of extractants can be evaluated. Fig. 9 shows the efciency
of acid recovery with the membrane contactor for the investigated
extractants. This recovery is dened as the ratio between succinic
acid mass in the aqueous re-extraction phase and the mass in the
initial aqueous phase (feed), as shown in Eq. (3). For n-BDEA amine,
the presence of succinic acid in aqueous re-extraction phase was
observed only after 6 h, which makes n-BDEA not suitable for
succinic acid extraction, even when a non-dispersive method, such
as the extraction with a membrane contactor, is adopted.
It is possible to observe that equilibrium was reached in
approximately 2 h, the only exception being Primene TOA1 amine.
The initial permeate uxes obtained for succinic acid are close to
3  106 kg/(m2 s). Water passage to the organic phase was only
perceived after long-term extraction. Although the membrane
employed in this study is hydrophilic, its swelling degree in the
aqueous phase is low (about 8% in mass). This swelling resulted in
insignicant water content in organic phase at the end of the
experiments, and for this reason, it was not quantied. Organic
phase by-passing through the membrane was not observed.

[(Fig._9)TD$IG]

3.2. Extraction experiments with the membrane contactor


In this work, a non-porous membrane was selected since the
membrane provides a barrier which prevents contact between

Fig. 9. Succinic acid recovery in MCE. Amine concentration in organic phase: 10%
(w/w). Succinic acid initial concentration in aqueous phase: 0.17 mol/L.

[(Fig._10)TD$IG]

[(Fig._1)TD$IG]

L.S. Moraes et al. / Journal of Industrial and Engineering Chemistry 21 (2015) 206211

Fig. 10. Efciency in succinic acid extraction in a membrane contactor. Amine


concentration in organic phase: 10% (w/w). Succinic acid initial concentration in
aqueous phase: 0.17 mol/L.

Three extractants presented a recovery of about 45%: 1-octanol,


Primene TOA1 and TEHA. To better understand this result, the
extraction was analyzed separately, and the result is shown in
Fig. 10. Primene JM-T1 extracted 77% of the total acid in the feed.
For the other amines chosen, the results are similar to that
obtained for the 1-octanol. This could be explained by the fact that,
as there is no chemical reaction, the step of re-extraction is more
effective for 1-octanol. In the case of the amines, as acid
accumulation in the organic phase occurs, the reaction equilibrium
is reached, and consequently the amount of acid removed from the
feed is lower. To improve the re-extraction efciency for amines, it
would be necessary to add sodium ions to the aqueous reextraction phase, as shown in the experiments using direct contact
(Fig. 8). However, this would lead to the production of succinate
salts, which is not desired in most applications, since an additional
process would be necessary to recover the acid. Another way to
improve the recovery is exploring the variation of temperature
(either in extraction or re-extraction), for example.
At the experimental conditions of these tests, TEHA performance was similar to that exhibited by 1-octanol. However, it is
important to emphasize that the alcohol alone is not selective
toward organic acids. The use of amines is justied by the
possibility of extracting the organic acid directly from fermentation broths. For this reason, this extractant was chosen to evaluate
the gain in efciency when both extraction and re-extraction steps
are coupled, comparing results with the efciency of the extraction
itself. The advantage of coupling extraction and re-extraction steps
is to shift the extraction equilibrium, increasing the total amount of
acid recovered from the feed. Results in Fig. 11 shown that, when
re-extraction is coupled, the total acid removed from the feed is
almost 5 times higher than the single extraction.
4. Conclusions
Extraction of succinic acid with ve different extractants was
successfully accomplished using a non-porous cellulose diacetate
membrane as a contactor. Liquidliquid extraction tests indicated
that the inuence of temperature on the distribution coefcients
leads to different behaviors when 1-octanol and amines are
compared. Primene JM-T1 amine was the best succinic acid
extractant among those evaluated, removing 86.0% of the succinic
acid in a 0.17 mol/L aqueous solution. For membrane contactor
extraction, 45% of acid recovery was achieved, using water as re-

211

Fig. 11. Comparison between extraction and coupled process in a membrane


contactor, for TEHA/1-octanol extractant. Amine concentration in organic phase:
10% (w/w). Succinic acid initial concentration in aqueous phase: 0.17 mol/L.

extraction agent. This value can be improved, especially for


Primene JM-T1 amine, by using a sodium solution in re-extraction
or by changing the temperature. Results presented in this work
indicate that extraction with non-porous membrane contactor for
succinic acid extraction is feasible and advantageous since there
are fewer restrictions in the extractant choice.
Acknowledgments
The authors would like to thank to Rohm and Haas, who kindly
donated Primene JM-T1 and Primene TOA1 amines, and to the
Brazilian Council for Scientic Development, CNPq (Conselho
Nacional de Desenvolvimento Cientco e Tecnologico), for
nancial and research support.
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