Bioprocess Engineering 5 (1990) 203-216
Bi0processEngineering
Butanol recovery from fermentations by liquid-liquid extraction
and membrane solvent extraction
W. J. Groot, H. S. Soedjak, P. B. Donck, R. G. J. M. van tier Lans, K. Ch. A. M. Luyben, Delft,
J. M. K. Timmer, Ede, The Netherlands
Abstract. Extraction can successfully be used for in-situ alcohol
recovery in butanol fermentations to increase the substrate conver-
sion. An advantage of extraction over other recovery methods may
be the high capacity of the solvent and the high selectivity of the
alcohol/water separation. Extraction, however, is a comprehensive
operation, and the design of an extraction apparatus can be com-
plex. The aim of this study is to assess the practical applicability of
liquid-liquid extraction and membrane solvent extraction in bu-
tanol fermentations. In this view various aspects of extraction pro-
cesses were investigated.
Thirty-six chemicals were tested for the distribution coefficient
for butanol, the selectivity of alcohol/water separation and the tox-
icity towards Clostridia. Convenient extractants were found in the
group of esters with high molar mass.
Liquid-liquid extraction was carried out in a stirred fermenter
and a spray column. The formation of emulsions and the fouling of
the solvent in a fermentation broth causes problems with the oper-
ation of this type of equipment. With membrane solvent extraction,
in which the solvent is separated from the broth by a membrane, a
dispersion-free extraction is possible, leading to an easy operation of
the equipment. In this case the mass transfer in the membrane
becomes important.
With membrane solvent extraction the development of a process
is emphasized in which the extraction characteristics of the solvent
are combined with the property of silicone rubber membranes to
separate butanol from water. In the case of apolar solvents with a
high molar mass, the characteristics of the membrane process are
determined completely by the solvent. In the case of polar solvents
(e.g. ethylene glycol), the permselectivity of the membrane can prof-
itably be used. This concept leads to a novel type of extraction
process in which alcohol is extracted with a water-soluble solvent
via a hydrophobic semipermeable membrane. This extraction pro-
cess has been investigated for the recovery of butanol and ethanol
from water. A major drawback in all processes with membrane
solvent extraction was the permeation of part of the solvent to the
aqueous phase.
The extraction processes were coupled to batch, fed batch and
continuous butanol fermentations to affirm the applicability of the
recovery techniques in the actual process. In the batch and fed batch
fermentations a three-fold increase in the substrate consumption
could be achieved, in the continuous fermentation about 30% in-
crease.
1 Introduction
The in-situ recovery of b u t a n o l from a fermentation has
gained considerable attention in recent years. It is consid-
9 Springer-Verlag 1990
ered that in-situ recovery is one of the m a j o r developments
that m a y attribute to the commercial revival of the b u t a n o l
fermentation [1]. In-situ recovery will reduce the effect of
product inhibition by butanol and will enable the conversion
of a concentrated feed and lead to a high productivity, hence
lowering the production costs. Another aim in research on
in-situ recovery is to develop a separation m e t h o d which
consumes less energy than the conventional distillation.
Research in recent years on in-situ recovery can be sum-
marized as efforts to develop a suitable separation method.
A pre-requisite for such a recovery is that it should not
interfere with the microbial activity in the broth. Secondly,
the selectivity of the separation should be high to reduce
production costs, and the capacity of the recovery should be
high to reduce investment costs. M o r e generally, the recov-
ery process should be robust, reliable and independent of the
quality of the broth, as medium constituents m a y have an
adverse effect on the performance of the combined recovery/
fermentation process (e.g. fouling). In other words the opti-
mization needs to be done on the integrated process. A large
a m o u n t of articles on in-situ butanol recovery deals with
extraction with an organic solvent as the recovery method
[2-9]. This research is justified by the observation that the
selectivity of alcohol/water separation by extraction can be
high and that the capacity of the solvent for alcohol can be
high. F o r use in a fermentation the suitability of a chemical
as a solvent, however, is mainly determined by its toxicity
with respect to the micro-organism. A number of articles has
dealt with this toxicity of chemicals at saturation in water
[2-4, 10-12]. Other properties of a chemical such as the
density, viscosity and surface tension will become i m p o r t a n t
for the design of an extractor. O n lab-scale several types of
extractors have been used: extraction in the stirred fermenter
itself [13], mixer/settler in series [14] and a loop reactor [15].
F o r large scale operation a reciprocating K a r r column has
been p r o p o s e d [16]. A novel a p p r o a c h is the use of a mem-
brane which separates the solvent from the broth (Fig. 1). In
this case no dispersion and subsequent coalescence of the
solvent is needed. F o r ethanol recovery this m e m b r a n e me-
diated extraction can be achieved with non-porous mem-
204 Bioprocess Engineering 5 (1990)

Broth ~//////////////////////////////J > Raffinate

paste. In experiments with immobilized cells the medium
contained glucose, 10kg/m 3 yeast extract powder and
Extract < y, ..-'": < Extractant 5 kg/m 3 CaC12. H20. The medium constituents, in dem-
ineralized water, were autoclaved separately at 110~ The
immobilization of Clostridium beyerinckii, L M D 27.6, in
Membrane calcium alginate, and the start-up procedure of a continuous
Fig. 1. Concept of membrane solvent extraction fermentation with immobilized cells is described elsewhere
[22].
Toxicity experiments with chemicals were carried out in
branes which repel the extractant [17, 18] and porous hydro-
vials in a jar with a GasPack system. Droplets of solvent
phobic membranes which retain the extractant [/9]. These
were added to the medium containing 60 kg/m 3 glucose and
membranes do not show permselectivity, i.e. no separation
10 kg/m 3 yeast extract powder, and a suspension of heat
of alcohol and water takes place due to the different perme-
shocked spores or viable cells was used as an inoculum.
ability of the membrane for these solutes. Permselectivity
The fermenters and membrane equipment were sterilized
has been described for silicone rubber membranes when
by autoclaving at 110~ In batch and fed-batch fermenta-
used in pervaporation. In pervaporation, evaporation via a
tions the inoculum was a 15 cm 3 heat shocked spore suspen-
membrane, butanol can be removed from water, as the per-
sion. All fermentations were carried out by flushing the head
meation of butanol through the membrane is faster than the
space of the fermenters with nitrogen made oxygen free by
permeation of water [20, 21]. In pervaporation, however, a
leading the gas over copper turnings at 300 ~
relatively high consumption of energy exists, as the perme-
The manufacture of membrane modules of silicone rub-
ants must be evaporated. It might be advantageous then to
ber is described elsewhere [20].
use an extractant in combination with the selective mem-
brane. When for example the diffusivity of water in the mem-
brane is low, a high momentary selectivity can be achieved 2.2 Chemicals
when compared to liquid-liquid extraction. It has been de-
Glucose (AVEBE, Stadskanaal, The Netherlands), yeast
scribed for membrane solvent extraction that also extractant
extract paste (Gist-Brocades, Delft, The Netherlands), yeast
can permeate through the membrane to the aqueous phase
extract powder (Difco) and C a C 1 2 . 2 H 2 0 (Merck)were
[17]. When the diffusivity of extractant in the membrane for
used.
a given membrane/solvent combination is low, the technique
Analytical grade: hexane (Aldrich Europe); hexanol,
may also have the advantage that an extractant with favor-
heptanol, octanol, decanol, decane, butyl stearate, tributyl
able separation characteristics, which is otherwise toxic in
citrate, ethylene glycol, diethyleneglycol, triethylene glycol,
liquid-liquid extraction, may be used.
tetraethylene glycol, glycerol, 1,2 butanediol, 1,3 butanediol
In this study several aspects of extraction combined with
(Merck); butanol, dodecanol, heptane, butyl acetate,
fermentation are examined. First experiments with liquid-
dibutyl phtalate (Baker); octane, dodecane, hexyl acetate,
liquid extraction in batch and continuous butanol fermenta-
ethyl oenanthate, methyl laurate, ethyl laurate, isopropyl
tions are described, which demonstrate the advantages and
myristate, methyl oleate, ethyl stearate, dibutyl adipate,
disadvantages of the technique. Secondly, membrane solvent
dibutyl maleate, tributyrin, phtalic acid bis methylglycol-
extraction is investigated with permselective membranes.
ester (PBMG), oleic acid, oleyl alcohol (Fluka); gasoline
This type of extraction has been coupled to batch and fed-
(Shellina, Shell). Vegetable oils were purchased at the gro-
batch butanol fermentations to demonstrate the applicabili-
ceries.
ty of the technique. In this paper the choice of an optimal
Rubber tubing was purchased from Hilversum Rubber
membrane/solvent combination is emphasized, especially
N.V., Hilversum, The Netherlands.
with respect to mass transfer phenomena.

2 Materials and methods
2.i Fermentation
The following microorganisms were used: Clostridium
beyerinckii, L M D 27.6, (fermentation temperature: 37~
and Clostridium species, DSM 2152 (fermentation tempera-
ture: 30 ~ Both organisms were subcultured with heat
shock treatments on a medium containing 60 kg/m 3 glucose,
10 kg/m 3 yeast extract powder and 10 kg/m 3 CaCO3. The
medium for batch fermentations contained next to glucose
10 kg/m 3 yeast extract powder of 13 kg/m 3 yeast extract
2.3 Extraction
For the determination of the distribution coefficient and the
selectivity of a chemical for butanol 0.1 dm 3 of a 20 kg/m 3
aqueous butanol solution was contacted in a shake flask
with enough extractant to end with a 10 kg/m ~ butanol
solution. The flask was shaken at 37 ~ for 24 h. The distri-
bution coefficient was calculated from the decrease in the
butanol concentration in the aqueous phase:
mass fraction in organic phase
distribution coefficient =
mass fraction in aqueous phase "
(1)
 J.
W. Groot et al.: Butanol recovery
The selectivity was calculated from the water content of
the organic phase:
distribution coefficient for butanol
selectivity - distribution coefficient for water
2.4 Membrane solvent extraction
For the determination of the equilibrium and mass transfer
characteristics with membrane solvent extraction two flasks
were used (Fig. 2). One flask contained 0.2 dm 3 of an
20 kg/m 3 aqueous butanol solution, which was pumped
through a tubing immersed in 0.2 dm 3 of the extractant in
the other flask. The flasks were magnetically stirred and
thermostated at 30 ~ The aqueous phase was analyzed for
the butanol concentration. The selectivity was calculated
from the water content of the organic phase (Eq. (2)).
2.5 Analytical methods
Butanol, isopropanol, ethanol, butyric acid and acetic acid
concentrations in aqueous and organic phases were mea-
sured by gaschromatography (Packard Becker Type 43;
FID detector; Chromosorb 106 column, 100-200mesh;
140~ 10~ final hold 170~ In the extraction ex-
periments with dibutyl phtalate, butyl acetate and gasoline
the butanol concentrations were estimated by measuring the
density of the solution with an Anton Paar density meter.
Glucose was measured with the hexokinase method
(Boehringer), or a Yellow Springs YSI 27 glucose analyzer.
The water content of an organic phase was measured by
a coulometric titration with the modified Karl Fischer
reagens (Fluka). The concentration of glycerol, -diols and
-glycols in water were determined by High Performance
Liquid Chromatography (Biorad HP87H column, elution
with 0.01 N H2SO4).
Biomass was centrifuged (10 rain, 4000 rain-1) and mea-
sured as dry weight (24 h, 110~
3 Results and discussion
3.1 Liquid-liquid extraction
3.1.1 Screening of extractants
Thirty-six chemicals were examined for the distribution co-
efficient for butanol, the selectivity of the separation and the
toxicity towards Clostridium beyerinckii, L M D 27.6. Three
chemicals were chosen for use in butanol batch fermenta-
tions, and also extraction was coupled to a continuous fer-
mentation with Clostridium beyerinekii, L M D 27.6, immo-
bilized in calcium alginate.
Several properties of the extractants are given in Table 1.
The distribution coefficients of the extractants for butanol
range from 0.3-12 kg/kg, and are comparable to those re-
ported in other investigations [2-9]. The highest distribu-
tion coefficients were found for the alcohols, the lowest for
205
(2)
Tubing~
ALcohoL
solution Extractant
Fig. 2. Experimental set-up for the measurement of mass transfer
rates in membrane solvent extraction
the alkanes. The selectivities range from 100-4000 and are
comparatively high to those reported in literature [6]. The
higher alcohols and some esters with low molar mass were
found to be toxic. The alkanes, vegetable oils, the derivatives
of these oils and the esters with high molar mass were non-
toxic. These data compare well with literature data [2-4, 10,
11]. It has been described in literature that the toxicity of a
chemical may be predicted on the basis of the molar mass
and the polarity of the compound, represented by the Hilde-
brand solubility parameter. If the molar mass exceeds 200 g/
mol and the Hildebrand solubility parameter is lower than
about 17 MPa ~ then chemicals are usually non-toxic [11].
It can be concluded from Table 1 that this rule is in agree-
ment with our results. Also a concept for predicting the
toxicity has been developed on the basis of the distribution
coefficient of the solvent between water and octanol [23],
which can be seen as a combination of the molar volume and
the solubility parameter [24]. This concept yields additional
information of the degree of toxicity of the solvent. In this
study the toxicity level was not determined.
It has been suggested in literature that a solvent may only
be toxic if it is present in the medium in the form of droplets,
while being non-toxic at saturation in water [12]. This phe-
nomenon may be important with respect to membrane sol-
vent extraction, with which a dispersion-free extraction is
possible. In the present work a toxicity test with droplets of
solvent in broth was used, and care must be taken to reject
these solvents for use in membrane solvent extraction.
Three chemicals were chosen for experimental work in
fermentations in this work: castor oil, oleic acid and iso-
propyl myristate. This choice was based primarily on the
criteria of non-toxicity, a high distribution coefficient and a
high selectivity. Secondly, these chemicals are readily avail-
able at a low price. These demands are important, as large
volumes of solvent may be needed, and, although the chem-
icals are practically insoluble in water, solvent loss will be
inevitable in a process.
3.1.2 The application of liquid-liquid extraction
in butanol fermentations
In short, the experimental set-up for the fermentation/ex-
traction experiments was as follows:
206 Bioprocess Engineering 5 (1990)

Table 1. Distribution coefficient for butanol, selectivity of butanol/water separation and toxicity towards Clostridium beyerinckii of several
chemicals (37 ~

Solvent Toxicity M 6 k S Solvent Toxicity M 6 k S

Hexane N-T 86 15 0.5 2700 Butyl acetate T 116 18 ~3 ND

Heptane N-T 100 15 0.5 3300 Hexyl acetate N-T 144 18 3.6 5
Octane N-T 114 15 0.3 4100 Dibutyl phtalate N-T 278 16 1.4 3
Decane N-T 142 15 0.3 4300 Dibutyl adipate T 258 18 2.5 3
Dodecane N-T 170 16 0.3 2900 Dibutyl maleate T 228 17 2.0 3
Gasoline N T 0.3 ND Tributyl citrate N-T 360 17 2.4 2
Tributyrin N-T 303 17 ND ND
Hexanol T 102 18 12 160 Ethyl oenanthate N-T 158 17 2.0 4
Heptanol T 116 18 11 180 Methyl laurate N-T 214 17 1.8 7
Octanol T 130 18 10 130 Ethyl laurate N-T 228 17 1.7 7
Decanol T 158 16 8 200 Isopropyl myristate N-T 258 17 1.4 7
Dodecanol T 186 15 6 140 Methyl oleate N-T 297 16 1.3 6
Ethyl oleate N-T 311 17 1.3 6
Castor oil N-T 2.6 270 Ethyl stearate N-T 313 18 0.8 7
Soy oil N T 0.7 440 Butyl stearate N-T 341 17 1.2 ND
Corn oil N-T 0.7 440 PBMG T 282 16 2.5 ND
Olive oil N-T 0.7 470
Cocos oil N T 0.8 440 Oleic acid N-T 283 15 3.9 6
Rapeseed oil N-T 0.8 400
Linseed oil N-T 0.7 390
Sesame oil N-T 0.3 220

M [g/mol] Molar mass

6 [MPa ~ [32] Hildebrand solubility parameter
k [kg/kg] distribution coefficient
s [] selectivity
N- T non toxic
T toxic
ND not determined

With castor oil the high viscosity of the solvent (0.23 Ns/ Table 2. Liquid-liquid extraction coupled to butanol/isopropanol
m 2 at 40 ~ necessitated the use of a stirrer to disperse the batch fermentations with Clostridium beyerinckii, LMD 27.6,
(37 ~
solvent and to achieve sufficiently high mass transfer rates.
The fermentation and extraction therefore was carried out Extractant Average Fermen- Final Final Glucose
in a stirred 1 dm 3 fermenter coupled to a settler (V = solvent tation butanol iso- consump-
0.25 dm3). Castor oil was added to the fermenter and the flow rate time concen- propanol tion
dispersion was pumped to the settler, where solvent was [cm3/h] [h] tration concen- [kg/m 3]
[kg/m 3] tration
withdrawn by overflow while the broth was returned to the [kg/m 3]
fermenter.
The batch fermentations with extraction by oleic acid and None [20] 47 5.4 3.1 30
isopropyl myristate were carried out in a 1 dm 3 fermenter Castor oil 28 60 4.2 5.5 55
coupled to a spray column (length: 1 m; diameter: 0.028 m) 14 105 4.9 7.8 100
as an extractor. Solvent was injected in the column by a Isopropyl 5 60 3.0 3.0 36
vibrating device producing small droplets of solvent. The myristate 29 160 3.0 8.0 100
solvent was withdrawn from the top of the column by over- Total amount of acetic acid and butyric acid in all fermentations:
flow, where coalescence of the solvent was aided by a screen < 1.1 kg/m 3
of wrapped up stainless steel wire. The broth was circulated
over the column.
The experimental set-up for the continuous fermentation
gas and collected by condensation in a condenser cooled by
with immobilized cells and extraction by isopropyl myristate
tap water.
is shown in Fig. 3. Again, a spray column (length; 1 m;
diameter: 0.019 m) was used, coupled to a 0.4 d m 3 stirred In Table 2 the results of the batch fermentations with
fermenter. Solvent was continuously regenerated by circu- Clostridium beyerinckii, L M D 27.6, are summarized. Com-
lating over a stripper (a I m length packed bed of glass beads pared with a control fermentation, the b u t a n o l concentra-
at 100 ~ The vapours were stripped with 30 dm3/1 nitrogen tion was found to be lowered by simultaneous product re-
W. Z Groot et al.: Butanol recovery
Gasadjustment
Waste~
Medium~
N2 ll,(I
N2
Z_~,~o[--~
Metal screen
Siphon
Overftow
Fermenter SettLer
-@
@
Extraction
c0[umn
covery, resulting in prolonged fermentation time and a
three-fold increase in glucose consumption. The product
yield in the fermentations was similar, as shown by a
gaschromatographic analysis of the alcohol content of the
extract. Similar results with extraction for in-situ butanol
recovery have also been described in other studies [4, 5, 8, 9].
In the fermentation experiments also some problems
were encountered, which may be general for systems with
in-situ product recovery by extraction:
With oleic acid as the extractant the fermentation was
halted when the extraction was started. In the toxicity test,
however, oleic acid was found to be non-toxic. Further ex-
periments showed that oleic acid probably removes essential
nutrients form the broth, as no fermentation took place in
a medium which was first extracted by the solvent.
In practice, the solvent will in general be distilled to re-
cover the alcohol and regenerate the solvent. In this work it
was found that oleic acid regenerated by distillation had
become toxic, and could not be re-used in the fermentation.
With castor oil and oleic acid the formation of emulsions
was severe. These emulsions could not be broken by cen-
trifugation at 4000 min - 1.
All three solvents were fouled by medium components.
Precipitates appeared in the solvents, which were proved to
be proteins with a biuret reaction. Presumably, these precip-
itates also contain water, as more water was collected after
distillation of the solvents, than can be explained from the
selectivity (Table 1).
It may be possible that some of the problems mentioned
above (precipitates, emulsions) are related to the high con-
tent of yeast extract of the medium used in this study. In
other investigations with media containing minerals and less
yeast extract good results were claimed to be obtained with
extraction [5, 9].
In the continuous fermentation with Clostridium beyer-
inckii immobilized in calcium alginate two extraction runs
207
)
I
~
Product
denser
N2
Fig. 3. Experimental set-up for
a continuous fermentation with
.• N2
Stock
extractant
immobilized cells coupled to ex-
traction for in-situ product re-
moval and stripping for regen-
eration of the extractant
Stripper
of 24 h were performed. The removal of butanol, and hence
decrease in inhibition by butanol, resulted in a 30% increase
in productivity. The operation of the total system, however,
was experienced to be tedious. Especially the level control in
the extractor was troublesome. The presence of emulsions
prevented the use of conductivity measurements at the
broth/solvent interphase for the control of feed pumps of the
extractor, and a siphon had to be used for the transport of
raffinate to the fermenter.
The solvent stripper operated satisfactorily. It was again
found that more water was recovered in the distillate than
could be expected on the basis of the selectivity of the extrac-
tion.
In general, it was concluded from the experiments that
liquid-liquid extraction can successfully be used for in-situ
recovery, which is in agreement with literature. However,
the problems encountered in fermentations with direct con-
tact of the extractant and the broth prompted us to investi-
gate membrane solvent extraction with which dispersion-
free extraction is possible.
3.2 Membrane solvent extraction
3.2.1 Introduction
Membrane solvent extraction, also sometimes called per-
straction, is an extraction process in which the aqueous
phase and the solvent are kept apart by a membrane. In
contrast to classical extraction processes, no dispersion and
subsequent coalescence of the two liquid phases takes place.
Consequently, problems with the formation of emulsions
will be avoided, which will be an advantage when a fermen-
tation broth is extracted. The membrane may also form a
barrier to other medium constituents, thus preventing foul-
ing of the extractant.
The combination of a permselective membrane and a
solvent was examined. In such a system alcohol should per-
208
meate preferentially through the membrane, whereas other
medium constituents should be repelled. With membrane
solvent extraction the separation characteristics of the oper-
ation are governed by two factors. In analogy with liquid-
liquid extraction an equilibrium can exist, in which the sep-
aration of alcohol from water is governed by the distribution
coefficient and the selectivity. The membrane phase, how-
ever, may play an active role in the mass transfer phenome-
na in the operation. When, for example, a pervaporation-
type of membrane is used through which alcohol permeates
faster than water, preferential permeation of the alcohol
may be obtained resulting in a higher momentary selectivity
of alcohol/water separation than at equilibrium.
In this work membrane solvent extraction has been inves-
tigated predominantly with silicone rubber membranes,
with which a preferential permeation of butanol over water
is possible. Initial experiments were performed to get an
estimate of the mass transfer with these membranes. The
experimental set-up is shown in Fig. 2. An aqueous butanol
solution is pumped through a tubing immersed in a solvent.
The circulation rate of the aqueous phase is high, and the
liquid phases can be regarded as well-mixed. During the
experiment the butanol concentration in the aqueous phase
will decrease and reach an equilibrium value determined by
the distribution coefficient. The decrease in the butanol con-
centration can be calculated easily, when it is assumed that
the flux of butanol is proportional to the butanol concentra-
tion in the aqueous phase. This proportionality has been
found for pervaporation with silicone rubber [17]. The fol-
lowing differential equation can be derived for the decrease
of the butanol concentration with time in this batch system:
dCBA/dt = -- k" A " (CsA -- CBo/ka), (3)
with the initial condition
t=0, CSA = CBA,O 9 (3a)
In these equations CBA is the butanol concentration in the
aqueous phase, CBA,O the butanol concentration in the
aqueous phase at the beginning of the experiment, CBo the
butanol concentration in the organic phase, k the mass
transfer coefficient, A the membrane area and k d the distribu-
tion coefficient.
The mass balance for this system reads:
V0 9 CBo = V A ' ( C B A , O - - C B A ) , (4)
with VA and Vo being the volume of the aqueous phase and
organic phase, respectively. At equilibrium the following
equation holds:
C~A = Co/kd . (5)
When the mass balance is substituted in the differential
equation, integration of this equation leads to the following
expression for the butanol concentration in the aqueous
phase versus time:
C~A=CBA.O" ~+exp -- VA
Bioprocess Engineering 5 (1990)
The data of the mass transfer experiments were analysed
as follows: first, the distribution coefficient was estimated
with the data at the end of the experiment. Then, the distri-
bution coefficient was introduced in Eq. (6), and the mass
transfer coefficient was calculated by linear regression of the
logarithm of the butanol concentration in the aqueous phase
versus time.
The experiments will now be discussed chronologically.
First, the mass transfer characteristics in membrane solvent
extraction will be described, followed by the application of
this technique in butanol fermentations. The experiments are
divided in two classes: experiments with apolar solvents
such as mentioned in Table 1, and experiments with polar
solvents.
3.3 M e m b r a n e solvent extraction with apolar extractants
3.3.1 Mass transfer phenomena
Experiments were carried out with silicone rubber, neoprene
and natural rubber (latex) as the membrane and seven differ-
ent extractants. Hexane was chosen for experimental work
because of the high selectivity. The lower alcohols are char-
acterised by a high distribution coefficient, but also toxicity
towards Clostridia. It may, however, be possible that the
toxicity is less important in membrane solvent extraction.
Oleylalcohol is non-toxic, and has a distribution coefficient
of about 4 kg/kg [4]. Isopropyl myristate was chosen, as it
had already been used in fermentations with liquid-liquid
extraction.
In Fig. 4 an example is given of an extraction experiment
of butanol with isopropyl myristate and silicone rubber. The
butanol concentration decreases as the alcohol is extracted,
and after about 25 h equilibrium is reached.
In Table 3 the resulting mass transfer coefficients are
given for the different solvent-membrane combinations. The
rate of mass transfer is of the same order of magnitude in all
experiments. (For the cases with a different membrane thick-
ness it must be noted that the mass transfer coefficient will
be inversely proportional to the membrane thickness.) Also
included in Table 3 is the mass transfer coefficient for perva-
potation with silicone rubber as a membrane. It is clear that
the permeability of the membrane for butanol with mem-
brane solvent extraction is significantly improved compared
with pervaporation. In addition, the use of an extractant
greatly enhances the selectivity of the separation.
A qualitative analysis was applied to evaluate the possible
additional separation of butanol and water by the alcohol-
selective membrane in this type of extraction. The permselec-
tivity of membranes is based on the solution-diffusion mech-
anism. A solute permeates through the membrane only when
it dissolves to a certain extent in the membrane. The setectiv-
(6)
W. J. Groot et al.: Butanol recovery 209

Table 3. Mass transfer of butanol and sorption in membrane solvent extraction with different solvents and membranes (30 ~

embrane Silicone Neoprene Latex

k So k So k So
Solvent ~ [10 -7 m/s] [wt%] [10 -v m/s] [wt%] [10-7 m/s] [wt%]

Hexane 0.8" 71 0.5 6 _b 200

Hexanol 5.2 t1 0.4 3.7 0.3 26
Octanol 4.0 8
Decanol 3.4 5
Oleylalcohol 2.2 3
Dibutyl phtalate 3.5 4
Isopropyl myristate 9.9 50 0.6 45 1.9 330

Butanol - 13 1.5 - l0
Water 0.6 - 18 - 28
Pervaporation 1.2

So sorption of solvent by the membrane at equilibrium (g solvent per g total).

Dimensions of the tubings: silicone 0.5 m 1.5 mm ID x 2.1 mm OD, except in
a 0.5 m 1.0 mm ID x 3.0 mm OD; neoprene and latex: 0.5 m 1.0 mm ID x 3.0 mm OD
u Tubing too weak for experimental work

explain the high permeability of the membrane compared to

kg
._g 15
lO
& ZS
o
5 myristate combination is 2.5 9 1 0 - l o m2/s (corrected for the
~, BuLanot
0 1'0 2'0 30' 40
' h
Time t
Fig. 4. The butanol concentration versus time in membrane solvent
extraction in the system silicone/isopropyl myristate
ity of pervaporation is therefore largely governed by the
selectivity of sorption of the solutes by the membrane.
When this sorption is influenced by an extractant in
membrane solvent extraction, then it is to be expected that
the permselectivity of the membrane is affected.
The equilibrium sorption of the extractants by the mem-
branes is also given in Table 3. The sorption of the solvents
by the membrane was found to be higher than the sorption
of water by the membrane. For silicone it was furthermore
found that the sorption of butanol from dilute aqueous solu-
tions is low when compared with the sorption of extractants
(unpublished results). These results suggest that in the pres-
ent solvent/membrane combinations the solvent plays a
dominating role in the permeation of solutes through the
membrane. The property of the membrane to separate bu-
tanol and water by the solution-diffusion mechanism is re-
duced by the sorption by solvent, and the membrane rather
acts as a means to retain the solvent. This concept may also
pervaporation: the permeability of the membrane is deter-
mined by the effective diffusion coefficient of butanol in the
extractant, which is high compared to the diffusion coeffi-
cient in a membrane with a low degree of sorption. It can, for
example, be calculated that the effective diffusion coefficient
of butanol in the membrane in the silicone/isopropyl
swelling of the membrane). This value is of the same order of
magnitude as the value calculated with the Wilke-Chang
50 formulae: 5 - 1 0 - l o m2/s [25]. The effective diffusion coeffi-
cient of butanol in silicone in pervaporation is about 7 times
lower compared to membrane solvent extraction (Table 3).
From this point of view it can also be explained that there
is a tendency that the permeation rate increases when the
degree of sorption of the solvents by the membrane increases.
The mass transfer coefficient in membrane solvent extrac-
tion found in this study are comparable to those found for
other membrane/solvent combinations [17, 26]. For ethanol
extraction with tributyl phosphate via a hydrophilic mem-
brane, and pervaporation of butanol with a membrane of
oleyl alcohol retained in porous polypropylene, the mass
transfer coefficients was 2 9 10-7 m/s (recalculated to mem-
brane thickness of 0.3 mm).
For neoprene and latex rubber no permselectivity of per-
vaporation was observed with butanol/water mixtures. This
appears to be in agreement with the high sorption of water
by the rubbers compared to butanol. In membrane solvent
extraction the sorption of extractant by the membrane leads
to the permeation of butanol. The mass transfer coefficients
with neoprene and latex are lower compared to silicone,
which is partly due to the higher thickness of the membrane.
The sorption of solvent by the membrane also results in
permeation of the solvent. This may mean that toxic solvents
210 Bioprocess Engineering 5 (1990)

can not be used in membrane solvent extraction. This was > Extract
verified experimentally in the system hexanol/silicone: when
a silicone tubing is immersed in a fermentation broth, per-
straction with hexanol leads to toxification of the medium
and fermentation activity ceases.

3.3.2 The application of membrane solvent extraction

with isopropyl myristate in butanol fermentations
The performance of membrane solvent extraction in a fer- []
Isopropyt myristate
mentation was investigated in batch fermentations with
Clostridium, species D S M 2152. A membrane module with Fermentation Extraction
parallel silicone tubings was coupled to a fermenter and Fig. 5. Experimental set-up of a butanol batch fermentation process
extraction was carried out with isopropyl myristate (Fig. 5). coupled to membrane solvent extraction with apolar solvents
The results are shown in Table 4. Figure 6 shows an example
of a fermentation run. The results with membrane solvent
extraction are similar to the results with liquid-liquid extrac-
tion: the in-situ product recovery leads to a reduction in
/, Butanot 9 GLucose conversion
product inhibition, prolongs the fermentation and increases
o lsopropanot
the glucose consumption. Compared to liquid-liquid extrac- 8 125
tion no fouling of the extractant by precipitates was ob- kg kg
served. However, a small amount of solvent permeates
m---f ~ m3
through the membrane and appears as droplets in the broth. _~ 6 l~176
In both fermentations and experiments with synthetic bu-
o~ 75
tanol solutions the selectivity of the extraction was 600, C
.o /,
which is comparable to the selectivity with liquid-liquid ex-
traction (S = 700; Table 1), bearing in mind the difference in ~6 50
'-3 8
temperatures of the experiments. Membrane solvent extrac-
tion was experienced as a simple and reliable technique for 8 2 25
in-situ product recovery. The membrane is not only the
interphase at which the separation takes place, it also forms
a barrier between the fermentation broth and further down- 0 50T 100 150 h 200
stream processing. Fouling of the membrane, which may be
/ Time t
observed as a decrease in permeation rates, did not occur. Fig. 6. Course of a butanol batch fermentation coupled to mem-
brane solvent extraction with isopropyl myristate and silicone mem-
There was no formation of precipitates in the solvent, as branes. Arrow indicates start of extraction
experienced in liquid-liquid extraction.
In Fig. 7a a conceptual flow-sheet is presented of the
downstream side of a isopropanol-butanol fermentation
coupled to membrane solvent extraction with a apolar sol-
vent. In this flow-sheet it is proposed that water can be Table 4. Membrane solvent extraction with isopropyl myristate
distilled from the solvent along with some alcohol. This type coupled to batch fermentations with Clostridium, species DSM
of distillation has been described for ethanol recovery from 2152, (30~
2-ethylhexanol [27]. In a second column the alcohols are
Solvent Average Fermen- Final Final Glucose
stripped from the water, and the resulting concentrated alco- solvent tation butanol iso- consump-
hol/water mixture may again be dehydrated in the first col- flow rate time concen- propanol tion
umn. In a third column the solvent is regenerated, producing [cm3/h] [h] tration concen- [kg/m 3]
the anhydrous alcohol mixture. [kg/m 3] tration
[kg/m31
It can be concluded that membrane solvent extraction
is a promising technique for in-situ alcohol recovery. With None - 79 8.8 4.9 37
the present membrane/solvent combinations, however, the Isopropyl a 70 90 5.5 4.7 62
permselectivity of membranes cannot be used because of the myristate b 70 170 6.7 4.9 62
large degree of sorption of solvent by the membrane. This b 20 187 5.8 5.9 76
degree of sorption is high, as the membrane itself is apolar.
The sorption may be less, and permselectivity may be pre- Total amount of acetic and butyric acid in all fermentations:
<0.6kg/m 3. Biomass concentrations: 2-3kg/m 3. Solvent: iso-
served then, when a membrane and a solvent with very propyl myristate. Membrane: silicone 1.5 mm ID x 2.1 mm OD.
different polarities are combined. In the following the results Fermentation volume: 1.4 dm 3. Membrane area: a 0.059m2; b
obtained with polar solvents will be presented. 0.092 m 2
W. J. Groot et al.: Butanol recovery 211

3.4 Membrane solvent extraction with polar extractants

3.4.1 General
The aim in this study to combine the permselectivity of
Feed
H20"IB
I
silicone rubber membranes with the extraction characteris-
IBE >
tics of solvents necessitated the use of solvents with a polar-
ity approaching that of water. Silicone rubber was chosen as

the permselective membrane, and the following compounds
were therefore tested as extractants: ethylene glycol, glyc-
erol, 2,3 butanediol, 1,4 butanediol, diethyleneglycol, tri-
ethyleneglycol and tetraethyleneglycol. With these extrac-
tants a novel extraction technique is introduced: extraction
of a solute from water with a water-soluble extractant via a
permselective hydrophobic membrane. This technique has
certain aspects which differ from conventional extraction.
When an experimental configuration with membrane sol-
vent extraction, as shown in Fig. 2, is considered, it is obvi-
ous that equilibrium is reached when the concentration of all
the three compounds, solute, water and extractant are equal,
since the compounds are completely miscible and all perme-
ate through the membrane. The rate with which this equilib-
rium is reached depends on the permeability of the three
compounds in the membrane. Since the membrane is hydro-
phobic, the most apolar compound, which is the alcohol, will
diffuse relatively quickly through the membrane, and a
pseudo-equilibrium will occur. This equilibrium can be de-
scribed by a pseudo distribution coefficient for alcohol be-
tween water and solvent, and will be determined by the
activity coefficients of the alcohol in water and extractant. In
this sense a new class of extractants for the recovery of
alcohol from water is defined. The selectivity of the extrac-
tion will also be a pseudo-selectivity governed by the perme-
abilities of the membrane for the different compounds.
In polar extractants the activity coefficient of water may
be less than the activity coefficient of the alcohol. This fea-
ture of polar extractants offers the possibility of an extractive
distillation of alcohol in further downstream processing of
the extract. The product of the process will then be pure
dehydrated alcohol. Extractive distillation processes for
ethanol/water separation with ethylene glycol have been de-
scribed in literature, mainly with the purpose to break the
ethanol/water azeotrope [28, 29]. A conceptual flow-sheet of
a process with fermentation, membrane solvent extraction
and an extractive distillation is shown in Fig. 7 b.
Since the aspects mentioned above are new to extraction
processes and may have perspective for in-situ recovery in
butanol as well as ethanol fermentations, experiments with
membrane solvent extraction with polar compounds were
performed with butanol and ethanol solutions.
3.4.2 Mass transfer phenomena
The experiments were carried out in the experimental config-
uration shown in Fig. 2. The aqueous phase contained ap-
proximately 20 kg/m 3 butanol or 100 kg/m 3 ethanol. The
f
HzO
'BLeed
<
Solvent
Fermentation Membrane DistiLLation
solvent
extraction
Fig. 7a. Conceptual flow sheet of butanol production processes
with in-situ product recovery by membrane solvent extraction with
silicone membranes: apolar solvents
> IBE
Feed
L
> H20
BLeed
SoLvent " 1
Fermentation Membrane Extractive
sol.vent distiLLation
b extraction
Fig. 7b. Conceptual flow sheet of butanol production processes
with in-situ product recovery by membrane solvent extraction with
silicone membranes: polar solvents
concentration-time curve of an experiment with extraction
of butanol or ethanol by ethylene glycol via a silicone mem-
brane is shown in Fig. 8. The alcohol concentration in the
aqueous phase reaches a pseudo-equilibrium after about
100 h. In the case of butanol the alcohol concentration in the
aqueous phase again increases as a result of transport from
the extractant to the aqueous phase, which now also con-
tains a considerable amount of ethylene glycol. For ethanol
it is observed that the alcohol concentration steadily de-
creases, ultimately reaching the point where all concentra-
tions in both compartments are equal. All experiments are
summarized in Table 5 including the time to reach a pseudo-
equilibrium and the value of the pseudo distribution coeffi-
cient. For butanol it is found that the distribution coefficient
with polar compounds is 1 - 8 kg/kg, which is the same order
of magnitude as that for the non-toxic apolar compounds
mentioned in Table 1. The distribution coefficients for
ethanol are found to be between 0.2-0.4 kg/kg. These values
 212 Bioprocess Engineering 5 (1990)

Table 5. Membrane solvent extraction with silicone rubber and polar extractants (30 ~

Solvent Butanol Ethanol

te q a kd b texpc C~ot d te ~ a kd b texv o Csol d

[h] [wt/wt] [h] [kg/m a] [h] [wt/wt] [h] [kg/m a]

Ethylene glycol 90 2.0 310 92 310 0.55 310 88

Diethylene glycol 93 4.1 231 26 138 0.59 232 27
Triethylene glycol 92 2.0 307 55 162 0.43 307 36
Tetraethylene glycol 90 2.3 256 8 256 0.41 256 25
Glycerol 186 0.7 262 14 262 0.15 262 10
1,2 Butanediol 237 4.6 237 17 237 0.70 237 17
1,3 Butanediol 175 8 239 31 239 0.74 239 34

Experiments were carried through with 0.1 dm 3 of solvent and 0.1 dm 3 of the aqueous solution and a silicone tubing of 1 m length and
dimensions 1.5 mm ID x 2.1 mm OD.
a Approximate time at which the equilibrium is reached
b Distribution coefficient at the pseudo equilibrium
Duration of the experiment
d Concentration of solvent in the aqueous phase at the end of the experiment

20 100 Table 6. Comparison of mass transfer coefficients in membrane sol-

kg kg vent extraction with silicone rubber and ethylene glycol (30 ~
m 3 m 3

15 75 Permeant Mass transfer coefficient

[10- 7 m/s]
-5 c~
Butanol 3.1
50
co (pervaporation: butanol) 1.2
Ethanol 1.3
25 (pervaporation: ethanol) 0.6
,'. Butanol Water 0.052
o E. glycol (pervaporation: water) 0.021
i ] I
0 i 0 Ethyleneglycol 0.007
Ioo4k 100
k~ Dimensions of silicone tubing: 1.5 mm ID x 2.1 mm OD
m 3

75 75 F o r one of the experiments with butanol extraction by

A
ethylene glycol also the concentration of water in the extrac-
tant was measured, from which the permeability of the mem-
50 5O o~ brane for water was calculated. This permeability expressed
,tl,
as a mass transfer coefficient, together with the mass transfer
W
coefficients for butanol and ethanol as calculated with (6),
25 hanol 25 are summarized in Table 6. It shows that the permeability of
o E. glycol the m e m b r a n e for alcohol is increased with m e m b r a n e sol-
I I i i I
vent extraction by ethylene glycol when c o m p a r e d with
' 0
0 50 100 150 200 250 300 h 350 pervaporation. This is also the case for water, and a pseudo-
b Time t selectivity results which is the same as for p e r v a p o r a t i o n
Fig. 8a and b. The alcohol concentration versus time in membrane (S = 60). The enhancement in the mass transfer rate is less
solvent extraction in the system silicone/ethylene glycol, a butanol, than with the a p o l a r extractants (Table 3), which is in agree-
b ethanol ment with the observation that the sorption of ethylene
glycol by silicone rubber is low ( < 1 wt%). F o r the other
polar extractants the sorption was also found to be low
are relatively high c o m p a r e d with the values reported for ( < l w t % ) , and the mass transfer rates of butanol and
non-toxic apolar extractants [30, 31]. ethanol with these polar solvents are comparable to the rates
Table 5 also includes the concentration of extractant in obtained with ethylene glycol. A detailed description of
the aqueous phase at the end of the experiment. This value membrane solvent extraction of butanol from water with
gives an indication of the permeability of the membrane for ethylene glycol and silicone rubber, and a comparison with
extractant. p e r v a p o r a t i o n will be published separately.
W.J. Groot et al.: Butanol recovery
The value of the pseudo distribution coefficient for bu-
tanol extraction with ethylene glycol, recalculated to activity
coefficients at infinite solution, is in agreement with the
values calculated from literature data on the vapor-liquid
equilibrium in the system butanol/ethylene glycol (activity
coefficients: butanol in water 53 [32], butanol in ethylene
glycol 6.6 and water in ethylene glycol 2.3 [33]). From these
activity coefficients and the volatility of water and butanol it
can also be calculated that extractive distillation of butanol
from ethylene glycol should be possible (relative volatility of
butanol/water in ethylene glycol is 1.5). Literature data on
the activity coefficient of butanol in solvents less polar than
ethylene glycol suggest that an extractive distillation of bu-
tanol with these solvents is not possible [33]. For ethanol,
however, it has been verified experimentally that an extrac-
tive distillation is possible with all the solvents used [28].
With these measurements it was established that butanol
can be extracted from water with polar solvents and a sili-
cone rubber membrane, and fermentations were performed
to use this technique for in-situ butanol recovery. Ethylene
glycol was chosen as the solvent because of the low price, the
relative low viscosity and the possibility of an extractive
distillation of butanol.
3.4.3 The application of membrane solvent extraction
with ethylene glycol in butanol fermentations
Membrane solvent extraction with the system silicone/
ethylene glycol was coupled to batch and fed batch fermen-
tations with Clostridium, species DSM 2152. Since the mass
transfer experiments revealed that ethylene glycol will also
permeate to the aqueous phase, first fermentations were per-
formed to investigate the toxic effects of ethylene glycol on
Clostridia. These fermentation tests were carried out in anal-
ogy to the toxicity test for water-insoluble extractants, with
different concentrations of ethylene glycol. It was found that
the fermentation was not influenced up to about 80 kg/m 3
ethylene glycol. Then experiments were carried out in a fer-
menter coupled to an external membrane module of silicone
tubings. It was found that maldistribution of extractant in
the module occurred, probably due to the viscosity of
ethylene glycol. To solve this problem the fermenter was
equipped with an internal membrane (15 m 1.5 ID x 2.1 mm
O D silicone tubing in a coil; Fig. 9). Since water is removed
from the fermentation, a level-controlled addition of sterile
water was applied. In two cases a glucose solution was used
for this addition, resulting in a fed-batch butanol fermenta-
tion with in-situ product recovery.
The results from the fermentations are summarized in
Table 7. The course of a fed-batch fermentation is shown in
Fig. 10. In the fed-batch part of the experiment the sugar
concentration in the fermentation increases as the glucose
feed rate exceeds the glucose consumption rate. The total
glucose consumption can be approximated from the concen-
trations in the broth and the feed rate. In the fed batch
fermentations then a glucose consumption of about 80 kg/
213
> Extract
Ethyleneglycol
GLucose Fermentationand
feed extraction
Fig. 9. Experimental set-up of a butanol fed batch fermentation
process with membrane solvent extraction with silicone/ethylene
glycol
A Butanol 9 GLucose
o IsoproponoL + EthyLenegtycoL
kg4 - ~ kg i
100
7
8O -~
60 "
20
0 h /,000 o
I Timet
Fig. 10. Course of a fed-batch butanol fermentation with product
recovery by membrane solvent extraction with silicone/ethylene gly-
col. Arrow indicates start of extraction
m 3 can be calculated, similar to the former batch experi-
ments (Tables 2 and 4). During the fermentation the concen-
tration of ethylene glycol increases to about 60 kg/m a, due to
permeation through the membrane.
With these experiments it was established that membrane
solvent extraction with the system silicone/ethylene glycol
can be used for in-situ product recovery in fermentations.
Again, when compared with liquid-liquid extraction, this
membrane technique was found to be simple and reliable, as
it has been found with membrane solvent extraction with
apolar solvents. In the concluding paragraph the different
recovery techniques will now be evaluated.
4 Conclusions
Extraction is a suitable technique for the recovery of butanol
during fermentation. The advantage of extraction compared
to other recovery techniques can be the high capacity of the
extractant (= high distribution coefficient) and the high se-
lectivity of butanol/water separation. A disadvantage of ex-
traction in practice may be the complications resulting from
the addition of a new liquid phase to the fermentation broth.
214 Bioprocess Engineering 5 (1990)

Table 7. Membrane solvent extraction with silicone rubber and ethylene glycol coupled to batch and fed batch butanol fermentations with
Clostridium species DSM 2152 (30~

Average solvent Fermentation Fermentation Final concentrations Glucose

flow rate time volume [kg/m 3] consumption
[cm3/h] [h] [dm3] [kg/m 3]
Butanol Isopropanol Ethylene glycol
Batch
15.3 190 1.4 5.5 5.3 60 68
18.5 138 1.5 3.2 2.7 18 60
23.5 210 1.1 2.3 2.3 26 74
F ed-batch
26.8" 290 1.2 0 0.5 70 58
28.8 b 340 1.2 0 0 80 100

Average glucose feed rate 3.2 cm3/h. Glucose solution 24 wt%

b Average glucose feed rate 2.6 g/h. Glucose solution 14 wt%
Total amount of acetic and butyric acid in all fermentations: <0.6 kg/m 3. Biomass concentrations: 2-3 kg/m 3. Membrane: 15 m silicone
1,5 mm ID x 2.1 mm OD

Table 8. Evaluation of extraction techniques for in-situ recovery

Liquid-liquid extraction Membrane solvent extraction Membrane solvent extraction

Apolar solvents Polar solvents

Distribution coefficient [kg/kg] 1-4 1-4 1-8

Selectivity 200 600 200-600 60
Mass transfer rates Relatively high Relatively low Relatively low
Performance in a fermentation Fouling of extractant No fouling No fouling
Emulsions No emulsions No emulsions
Advantages Simple and cheap equipment Easy operation Easy operation
Disadvantages Operation relatively difficult Leakage and loss of Leakage and loss of
insoluble solvent soluble solvent

These complications can be avoided by separating the two
liquids by a membrane. The different aspects of liquid-liquid
extraction and membrane solvent extraction are summa-
rized in Table 8.
The major drawback of using direct extraction in a fer-
mentation is the formation of emulsions and fouling of the
extractant. The major advantage is the use of simple equip-
ment and, in principle, the high mass transfer rates when the
formation of emulsions does not obstruct a high level of
dispersion of the extractant. The major advantage of mem-
brane solvent extraction is that no dispersion of the extrac-
tant is needed. The method, however, requires the installa-
tion of membrane area, which will bring additional costs. On
a large scale a difficulty with membrane solvent extraction
may arise from the relatively high viscosity of extractants
resulting in pressure losses and, possibly, mass transfer lim-
itation in the solvent phase.
In the separation of alcohol from water by membrane
solvent extraction it is possible to combine the permselective
properties of a membrane with the capacity of an extractant.
This is the case with a pervaporation-type membrane like
silicone rubber, and polar extractants like ethylene glycol. A
drawback of this method is the permeation of the water-sol-
uble extractant to the aqueous phase. This means loss of the
solvent and may cause problems with the toxicity of the
extractant. It is to be expected on the basis of the solution-
diffusion mechanism of permselective membranes that the
permeation of polar extractants will be reduced with the
development of membranes with a high selectivity for alco-
hol/water separation, since a decrease of the permeation of
water will also probably mean a decrease in the permeation
of an extractant with a polarity close to that of water.
F r o m this study it follows that at present the highest
selectivities for butanol/water separation can be achieved
with extraction with apolar solvents. When these solvents
are used in membrane solvent extraction the permselective
properties of the membrane are overruled by the extraction
characteristics of the solvents, as the sorption of the solvent
by the membrane is high. This technique then becomes
analogous to membrane solvent extraction with hydropho-
bic porous membranes like porous teflon or polypropylene.
With these membranes the extractant is retained in the pores
of the membrane by capillary forces. It may be possible with
porous hydrophobic membranes, however, that fouling of
W. J. Groot et al.: Butanol recovery
the extractant by medium constituents of a fermentation
b r o t h occurs, which will likely not be the case with, for
example, swollen silicone membranes. The swelling of mem-
branes however m a y cause problems with the mechanical
stability of m e m b r a n e modules.
W h e n m e m b r a n e solvent extraction is c o m p a r e d with
pervaporation, it is likely that on the basis of transmem~
brane fluxes p e r v a p o r a t i o n is more advantageous than
m e m b r a n e solvent extraction. Thin p e r v a p o r a t i o n mem-
branes have already been developed with high fluxes (thick-
ness 1 - 5 gin). Although it is found in this study that in
m e m b r a n e solvent extraction the flux can be higher than
with pervaporation, it can be estimated that with m e m b r a n e
solvent extraction on a large scale high fluxes cannot be
obtained due the high mass transfer resistance in the solvent
phase. The advantage of the extraction process will be that
the selectivity is higher c o m p a r e d with pervaporation. This
will lead to a selectivity of the extraction process higher than
the selectivity of pervaporation. New developments in mem-
brane technology, however, m a y lead to an increase in the
permselectivity of p e r v a p o r a t i o n membranes.
The economical feasibility of butanol production process-
es with integrated product recovery is favorable, as it has
been calculated for extraction [16] and p e r v a p o r a t i o n [34].
F r o m the present study it m a y be concluded that for the
actual implementation of liquid-liquid extraction, mem-
brane solvent extraction or p e r v a p o r a t i o n in alcohol fer-
mentations it is necessary to apply these techniques on pilot
plant scale. These investigations must prove the operational
simplicity of the processes, and will supply the engineering
d a t a to assess the technical feasibility of in-situ p r o d u c t re-
covery on a large scale.
Acknowledgements
The authors would like to thank N. W. E Kossen and G. H. Schou-
tens for the extensive discussions and P.N. van Beelen and G.H.
Schoutens for assistance in some of the experiments.
This work was supported (in part) by the Netherlands Founda-
tion for Chemical Research (SON), with financial aid from the
Netherlands Organization for the Advancement of Pure Research
(ZWO).
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