Journal of Membrane Science 373 (2011) 121129

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Journal of Membrane Science
j our nal homepage: www. el sevi er . com/ l ocat e/ memsci
Pervaporation performance of PDMS/ceramic composite membrane in acetone
butanol ethanol (ABE) fermentationPV coupled process
Gongping Liu, Wang Wei, Hao Wu, Xueliang Dong, Min Jiang, Wanqin Jin

State Key Laboratory of Materials-Oriented Chemical Engineering, Nanjing University of Technology, 5 Xinmofan Road, Nanjing 210009, PR China
a r t i c l e i n f o
Article history:
Received 18 November 2010
Received in revised form 24 February 2011
Accepted 26 February 2011
Available online 5 March 2011
Keywords:
Acetone butanol ethanol fermentation
PDMS/ceramic composite membrane
Pervaporation
Coupled process
Membrane fouling
a b s t r a c t
Pervaporation (PV) has attracted increasing attention owing to its potential application in biofuel recov-
ery from biomass fermentation process. In this work, PDMS/ceramic composite membrane was directly
coupled with acetone butanol ethanol (ABE) fermentation to in situ remove ABE solvents from the fer-
mentation broth. The membrane PV performances and stability in the spent fermentation broth and
fermentationPV coupled process were systematically investigated. As observed in the ABE fermenta-
tion broth, the inorganic salts favored increasing the membrane selectivity whereas the microbial cells
resulted in a reduced PV performance. Although a uctuation of membrane performance was observed
due to the occurrence of membrane fouling in the fermentationPV coupled process, the PDMS/ceramic
composite membrane exhibited a high ux of 0.670kg/m
2
h and applicable ABE separation factor of 16.7.
The SEM, AFM and FT-IR characterizations conrmed that the membrane fouling originated from the
adsorption of active cells on the membrane surface. Nevertheless, the membrane fouling in the coupled
process was reversible, with easy recovery of PV performance after a simple water rinse.
2011 Elsevier B.V. All rights reserved.
1. Introduction
Because of the shortage of crude oil and the environmental
requirement, the utilization of renewable resources for energy
production, such as using the potential acetone butanol ethanol
(ABE) fermentation process to produce butanol as a biofuel, has
been receiving increased attention in recent years [1]. As an
advanced biofuel, butanol has several advantages over other bio-
fuels, including high energy content, low vapor pressure, less
volatile and more suitable for the existing gasoline supply chan-
nels [2]. However, usually the maximum concentration of total
solvents (ABE) do not exceed 20g/L due to the end-product inhi-
bition [3], resulting in high energy cost to recover ABE from the
dilute fermentation broth by distillation. Therefore, several in situ
product-removal technologies, suchas adsorption[4], gas stripping
[5,6], liquidliquid extraction [7,8], perstraction [9], pervaporation
[1012] andreverseosmosis [13], havebeendeveloped. Thesetech-
nologies couldbe coupledwithABE fermentationprocess to reduce
the effect of product inhibition and improve the sugar utilization
and solvent productivity [1].
Pervaporation (PV) is considered to be the greatest potential
separation technology because of its energy-saving and ef-
ciency, as well as no harmful effects on the microorganisms
[14,15]. Recently, various researches were reported about the PV

Corresponding author. Tel.: +86 25 83172266; fax: +86 25 83172292.

E-mail address: wqjin@njut.edu.cn (W. Jin).
recovering n-butanol from ABE model solution or fermenta-
tion broth using polydimethylsiloxane (PDMS) membranes with
or without silicalite-1 llers [1619], poly[1-(trimethylsilyl)-1-
propyne] (PTMSP) membranes [20,21], poly(ether block amide)
(PEBA) membranes [22,23], liquid membranes [24,25], other mod-
ied polymer membranes [26], as well as porous polypropylene
(PP) membranes [10,14] and polytetrauoroethylene (PTFE) mem-
branes [27], which are in fact not ABE-selective membranes in PV
separation and the separation process should be classied as the
so-called membrane distillation. Among them, the commonly used
PDMS membranes with good selectivity and stability are regarded
as the most potential PVmembranes for ABE fermentationPVcou-
pled process [15]. Nevertheless, the relative low butanol ux of
PDMS membranes calls for larger membrane area, or demands the
PV process to be operated at higher temperature, which requires
an additional ultraltration process before the PV membrane to
retain the microorganisms [28]. Therefore, the development of
the high ux PDMS membranes and the directly coupled PV
process withABEfermentor aredesired. Our previous workdemon-
strated that the permeate ux of the PDMS membrane could be
greatly improved when it was dip-coated on the porous ceramic
support owing to the thin PDMS layer and negligible transport
resistance of the support [2931]. In addition, for practical applica-
tion, the membrane stability in the ABE fermentationPV coupled
process is another important factor that should be considered.
Comparing withthe ABEwater solution, the real ABE fermentation
broth contains several other components, such as inorganic salts,
glucose, microbial cells and other metabolic compounds, which
0376-7388/$ see front matter 2011 Elsevier B.V. All rights reserved.
doi:10.1016/j.memsci.2011.02.042
122 G. Liu et al. / Journal of Membrane Science 373 (2011) 121129
Fig. 1. Experimental set-up of ABE fermentationPV coupled process.
would affect the membrane PV performance and stability during
the fermentationPV coupled process.
Therefore, in this work, PDMS/ceramic composite membrane
was employedtodirectlycouple withABEfermentation. The effects
of typical impermeable components in ABE fermentation broth on
PV performance were systematically investigated. The membrane
performance and stability were evaluated not only in the spent
ABE fermentation broth but also in the ABE fermentationPV cou-
pled process. The membrane fouling and cleaning behavior were
studied, as well.
2. Experimental
2.1. Materials
PDMS (,-dihydroxypolydimethylsiloxane, M
w
= 60, 000)
was purchased from Shanghai Resin Factory Co., Ltd., China.
Tetraethylorthosilicate (TEOS), n-heptane, dibutyltin dilaurate
and ethanol were obtained as analytical regents from Sinopharm
Chemical Reagent Co., Ltd, China. Deionized water was used in the
all experiments. The ceramic supports were supplied by Mem-
brane Science &Technology Research Center, Nanjing University of
Technology. They are tubular asymmetric ZrO
2
/Al
2
O
3
membranes,
with an average pore size of 0.2m. Their length, outer diameter,
inner diameter were 160mm, 12mm, 8mm, respectively.
2.2. Membrane preparation and characterization
The preparation of PDMS/ceramic composite membrane
followed with our previous work [29]. The PDMS polymer was dis-
solved in n-heptane and then cross-linking agent TEOS and catalyst
dibutyltin dilaurate were added into the PDMS polymer solution
(w
PDMS
:w
n-heptane
:w
TEOS
:w
dibutyltin dilaurate
=1:10:0.1:0.005). The
resulted solution was stirred at 30

C for 10h and then coated on

the outer surface of ceramic support by the dip-coating method for
60s. Subsequently, the composite membrane was dried overnight
at room temperature, and then cured at 120

C for 12h to remove

the residual solvent.
The morphologies of the fresh and fouled PDMS/ceramic com-
posite membranes were examined by eld emission scanning
electron microscopy (FESEM). Fouled membrane samples after
the fermentationPV coupled process were rinsed with phosphate
buffer (pH=6.5) and xed with 3% glutaraldehyde in phosphate
buffer for more than 4h. Then, the xed samples were rinsed
with deionized water to remove the residual glutaraldehyde on
the membrane surface. Step dehydrations were followed with 25%,
50%, 75% and 100% ethanol for 10min for each of the membrane
samples, respectively to reduce their water contents [32], and then
dried in the air under room temperature overnight. Finally, all
the membrane samples (fresh and fouled) were gold-coated by
a sputter and scanned under FESEM (Hitachi-4800, Japan). The
surface nano-structures of the fresh and fouled PDMS/ceramic
membrane were characterized by atomic force microscopy (AFM)
(AutoCP-Research, Veeco, USA). The images were collected in
contact mode. Fourier transform infrared spectroscopy (FT-IR)
spectra of the foulants removed from the fouled PDMS/ceramic
composite membrane were recorded in a FT-IR spectrophotome-
ter (AVATAR-FT-IR-360, Thermo Nicolet, USA) with the range
of 4000400cm
1
, using the KBr disk technique. Thirty-two
scans were accumulated with a resolution of 4cm
1
for each
spectrum.
2.3. ABE fermentation
2.3.1. Culture and inoculum preparation
Clostridium acetobutylicum XY16 (China Center for Type
CultureCollection, CCTCC NO: M 2010011), was used in all exper-
iments. Cells were grown in 50mL sealed anaerobic bottles
containing 25mL seed medium with the following composition:
soluble starch 10g/L, yeast extract 3g/L, peptone 5g/L, ammo-
nium acetate 2g/L, sodium chloride 2g/L, KH
2
PO
4
1g/L, K
2
HPO
4
1g/L, MgSO
4
3g/L and FeSO
4
7H
2
O0.01g/L. The mediumwas auto-
claved at 121

C for 15min and cooled to 37

C. Anaerobic bottles
were inoculated with 1mL of a 70

C glycerol stock culture and

incubated at 37

C for 2024h as the primary seed culture. Before

inoculation, nitrogenwas bubbledthroughthe mediumfor 1minto
remove oxygen. 7.5mL of the primary seed culture was inoculated
into 250mL sealed anaerobic bottles containing 150mL of seed
medium and incubated at 37

C for 12h as the secondary seed cul-

ture. Beforeinoculation, nitrogenwas bubbledthroughthemedium
for 3min to remove oxygen.
G. Liu et al. / Journal of Membrane Science 373 (2011) 121129 123
2.3.2. Fermentation
Batch fermentation was conducted in a 2-L serumbottle (Boeco,
Germany). The fermentation medium contained: glucose 60g/L,
ammonium acetate 2.2g/L, corn steep liquor (CSL) 1g/L, sodium
chloride 0.01g/L, KH
2
PO
4
0.5g/L, K
2
HPO
4
0.5g/L, MgSO
4
0.2g/L,
MnSO
4
7H
2
O 3g/L and FeSO
4
7H
2
O 0.01g/L. The pH was set at
6.8 using 5N NaOH. The fermentor containing 1.5L fermentation
medium was autoclaved at 121

C for 15min and cooled under

oxygen-free nitrogen gas atmosphere to 37

C for 20min in clean

bench area, then 150mL of the secondary seed culture was inoc-
ulated into fermentor. The fermentation was run at 37

C for 72h.
After that, the resulting fermentation broth designated as spent
ABE fermentation broth.
2.4. Pervaporation and ABE fermentationPV coupled experiment
The pervaporation experiment was conducted on a homemade
apparatus [31], and the ABE fermentationPV coupled process is
shown in Fig. 1. The tubular PDMS/ceramic composite membrane
was sealed in a nylon PV cell, with an effective membrane region
of 48.9cm
2
. When coupled with fermentation, the PV membrane
was sterilized at 110

C for 15min by circulating sterile deion-

ized water. The feed tank with ABE model solution, fermentation
medium or broth, were maintained at 37

C by the water-bath.
The ow rate was xed at 15L/h during the pervaporation exper-
iment. The permeate vapor was collected in liquid nitrogen trap.
Permeate pressure was below 400Pa during collections. After a
steady state was obtained, the cold trap was exchanged every
1h with a consecutive permeate collection. The concentrations of
organic compounds (acetone, n-butanol, ethanol, acetic acid and
butyric acid) were determined by gas chromatography (GC-2014,
SHIMADZU, Japan) equipped with a thermal conductivity detector
(TCD) using a Porapak Q packed column and helium (He) as the
carrier gas. Iso-butanol was used as an internal standard. If the per-
meate separated into two phases, the permeate sample was diluted
with deionized water to one phase prior to injection. The concen-
trations of inorganic salts weredeterminedbyICP(Optima 2000DV,
PerkinElmer, USA). Glucose concentration was analyzed by a SBA-
40C biosensor analyzer (Shandong Province Academy of Sciences,
China). Cell concentration in the fermentation broth was evaluated
by optical density (OD
600
) which was measured with a spectropho-
tometer at 600nm. In order to make sure the reproducibility, all
the experiment results were repeated at least three times, and the
errors were less than 10%.
The PV performance of a membrane is usually expressed in
terms of the permeation ux J and separation factor :
J =
W
At
(1)
=
y/(1 y)
x/(1 x)
(2)
where W is the weight of the permeate, A is the effective area of
the membrane, and t is the permeation time interval for the per-
vaporation; y and x are the weight fractions of components in the
permeate and feed, respectively.
3. Results and discussion
3.1. Effects of impermeable components in ABE fermentation
broth on PV performance
The difference between ABE fermentation broth and the model
solution is not only the different density, pH and viscosity, but
also with or without the inorganic salts, glucose, active and inac-
tive microbial cells and several other metabolic compounds. In
Fig. 2. PV performance of PDMS/ceramic composite membrane in three different
ABE systems: (a) total and ABE ux and (b) separation factor of acetone, n-butanol
and ethanol. Feed composition: 0.6wt% acetone, 1.1wt% n-butanol, and 0.2wt%
ethanol.
order to investigate the effects of typical impermeable compo-
nents in the ABE fermentation broth on membrane performance,
the PDMS/ceramic composite membrane was used for pervapo-
ration of ABEwater solution, fermentation medium and spent
fermentation broth, respectively. The ABE feed concentrations in
the three systems were kept the same with0.6wt%acetone, 1.1wt%
n-butanol and 0.2wt% ethanol. The comparison of PV performance
is shown in Fig. 2. There was little difference in total ux, ranging
from1.02 to 1.05kg/m
2
h. The slight ux decrease in the fermenta-
tion mediumand fermentation broth was caused by the suspended
substance such as corn steep liquor or microbial cells, which hin-
dered the transport of the permeates. However, the ABE ux and
separation factor of acetone and n-butanol in the three feed sys-
tems showed obvious differences in the order of fermentation
medium>ABEwater solution>spent fermentation broth. These
results were attributed to the different impermeable components
in three feed systems.
Besides the components in the ABEwater solution, the fermen-
tation medium also contained inorganic salts, glucose, corn steep
liquor, etc. The inorganic salts could increase the ABE activity in the
feedandgenerate a higher ABE ux [33], whereas their effect onthe
water ux was negligible [34]. As a result, the inorganic salts in fer-
mentation medium led to a higher ABE separation factor, and this
phenomenon was called salting out effect [35]. Compared with
above two feed systems, the composition of the spent fermenta-
tion broth is more complex, including inactive microbial cells and
124 G. Liu et al. / Journal of Membrane Science 373 (2011) 121129
Fig. 3. Stability of PDMS/ceramic composite membrane in the spent ABE fermen-
tation broth: (a) total ux and ABE separation factor and (b) separation factor of
acetone, n-butanol and ethanol. Feed composition: 0.64wt% acetone, 1.26wt% n-
butanol and 0.27wt% ethanol.
other metabolic compounds. These components could adsorb on
the membrane surface to form a gel which reduced the membrane
surface hydrophobicity or hindered the adsorption and transport
of ABE molecules. Therefore, the ABE separation factor in the spent
fermentation broth was lower than that of ABEwater solution.
To fully evaluate the separation performance of the
PDMS/ceramic composite membrane, the concentrations of
some other key components, such as acetic acid and butyric
acid, in the fermentation broth and membrane permeates were
detected, respectively. It was found that, the membrane selec-
tivity toward acetic acid and butyric acid were very low, their
separation factors were 1.1 and 1.2, respectively (fermentation
broth: 0.091wt% acetic acid and 0.071wt% butyric acid; permeate:
0.101wt% acetic acid and 0.088wt% butyric acid). This result
favored the conversions of the acetic acid or butyric acid to ABE
solvents, instead of removing them from the fermentation broth.
In addition, the analysis results also showed that neither inorganic
salts nor glucose was detected in the permeates. This is propitious
to avoid the membrane fouling from the inorganic salts and the
losing of glucose during the fermentationPV coupled process.
3.2. Membrane stability in spent ABE fermentation broth
For investigating the ABE fermentationPV coupled process, we
rst studied the stability of PDMS/ceramic membrane in the spent
ABE fermentationbrothat 37

C. The spent fermentationbrothcon-

tained 0.64wt% acetone, 1.26wt% n-butanol and 0.27wt% ethanol.
As showninFig. 3, during the 36hof continuous PVexperiment, the
Fig. 4. PV performance of PDMS/ceramic composite membrane during the ABE
fermentationPV coupled process: (a) total ux and ABE separation factor and (b)
separation factor of acetone, n-butanol and ethanol.
performance of PDMS/ceramic composite membrane was stable,
only with little deviation due to the uctuation of ABE feed concen-
tration. The average total ux was 0.951kg/m
2
h with the average
separation factor of ABE, acetone, n-butanol and ethanol of 20.7,
21.1, 16.2 and 6.8, respectively. This result indicated that, although
the inactive cells in the spent fermentation broth could decrease
the ABE separation factor, their effects on membrane fouling were
not obvious.
3.3. Membrane performance in fermentationPV coupled process
Due to end-product inhibition, the maximum ABE concentra-
tion in a typical ABE fermentation process does not exceed 20g/L
with a general weight ratio of 3:6:1 (acetone:butanol:ethanol) [3].
Butanol is toxic to the culture and inhibition would be noticed as
its concentration up to 510g/L [1]. Therefore, in this work, when
the fermentation lasted for 36h and the n-butanol concentration
reached to ca. 4.5g/L, the sterile PDMS/ceramic composite mem-
brane was coupled to fermentor and the pervaporation in situ ABE
removing process started. The membrane performance during the
fermentationPV coupled process was investigated in details. As
shown in Fig. 4, the average total ux of the PDMS/ceramic com-
posite membrane was 0.670kg/m
2
h, with the average separation
factor of ABE, acetone, n-butanol and ethanol of 16.7, 20.6, 15.1
and 6.7, respectively. It was also found that both the total ux and
separation factor showed a gradually decline from50 to 58h. After
that time they increased again and then remained stable. A pos-
sible explanation was that the membrane fouling occurred during
the fermentationPV coupled process.
G. Liu et al. / Journal of Membrane Science 373 (2011) 121129 125
Fig. 5. Variation of (a) ABE concentration, (b) OD
600
, and glucose concentration in
the fermentation broth during the ABE fermentationPV coupled process.
To further study this phenomenon, the variation of ABE and glu-
cose concentration and OD
600
in the fermentation broth from40 to
72h is displayed in Fig. 5. As pervaporation started to couple with
fermentation, the ABE concentrations were maintained at a low
value (C
n-butanol
<5g/L) during the fermentation time from 36 to
50h, which favored the microbial growth since the butanol inhi-
bition released. From 50 to 58h, it is observed a fast cell growth
in Fig. 5b, which resulted in an obvious raise of ABE concentra-
tion in the fermentation broth and more active microbial cells
accumulated in the broth. Accordingly, more cells absorbed on the
membrane surface, leading to the occurrence and aggravation of
membrane fouling. Therefore, both of the total ux and separation
factor decreased sharply from 50 to 58h. However, as the butanol
concentration in the broth increased to 6.9g/L at 58h, the product
inhibition restarted, accompanying with the exhaustion of glucose
(<5g/L), both resulted in the decrease of ABE concentration and
OD
600
after 58h. Thus, fewer active cells adsorbed on the mem-
brane surface, and the total ux and separation factor began to
increase and then kept stable.
It may be argued that the increase of ABE concentration in the
broth from50 to 58h would also induce the decrease of separation
factor, because most studies found that the increase of feed con-
centration led to the ux increase and separation factor decrease
[23]. In order to distinguish the effect of feed concentration from
membrane fouling on the separation factor, we investigated the
membrane PV performance in the ABEwater solutions whose ABE
compositions were in accordance with that of fermentation broth
during 5058h, and the result is shown in Fig. 6. It could be seen
that, with the increase of ABE concentration in the feed, the total
ux increased linearly and separation factor just kept constant in
Fig. 6. PV performance of PDMS/ceramic composite membrane in the ABEwater
solution and ABE fermentationPV coupled process with the same ABE concentra-
tion in the feed.
the ABEwater solution, whereas in the fermentation broth dur-
ing 5058h, both the total ux and separation factor decreased
gradually as described in Fig. 4a. This result demonstrated that the
variation of membrane performance during the fermentationPV
coupled process was not caused by the changes of ABE concentra-
tion in the broth but attributed to the membrane fouling.
3.4. Membrane fouling and cleaning behavior
Several investigations have reported the PV membrane fouling
in fermentationPVcoupled process [12,19,20,24,28,36]. However,
little attention has been paid on the micro-structures of the fouled
membrane and chemical nature of the membrane foulants [20],
which are indeed instructive to understand the nature of mem-
brane fouling behavior. Therefore, inthis work, SEM, AFMandFT-IR
were used to investigate the fouled membrane morphologies and
chemical properties inorder tofurther study the membrane fouling
behavior during the fermentationPV coupled process.
The SEMimages of the surface and cross-sectionof the freshand
fouledPDMS/ceramic composite membrane after fermentationPV
coupled process are shown in Fig. 7. The fresh PDMS membrane
surface was clean and smooth (displayed in Fig. 7a); the PDMS
layer and ceramic support could be clearly observed fromits cross-
section image (shown in Fig. 7c). However, the fouled membrane
surface was covered with a fouling layer (see Fig. 7b), the microbial
cells aggregated with each other and absorbed on the membrane
surface by some extracellular polymeric substances (EPS), which
was an indication of biofouling occurring on the membrane sur-
face [37]. From Fig. 7d, some biopolymers-like substances were
observed on the ceramic support layer, indicating that besides ABE,
acetic acid and butyric acid, some other organic matter such as EPS
and soluble microbial products (SMP) maybe permeate through
the PDMS separation layer during the fermentationPV coupled
process. Furthermore, the surface nano-structures of the fresh and
fouled PDMS/ceramic membrane were characterized by AFMtech-
nique, as shown in Fig. 8. We could clearly nd that, the surface
of the fresh membrane was ultra smooth (mean-square surface
roughness R
ms
=9.1nm), while that of the fouled membrane was
very rough (R
ms
=43.5nm). According to the SEM characterization,
the roughness of the fouled membrane surface could be attributed
to the adsorption of foulants.
In order to analyze the functional groups of the foulants, the
fouling layer and biopolymers-like substances were removed from
the fouled membrane and characterized by FT-IR. As shown in
Fig. 9, the FT-IR spectra of the foulants on the membrane sur-
face and cross-section were similar with each other. The broad
126 G. Liu et al. / Journal of Membrane Science 373 (2011) 121129
Fig. 7. SEMimages of the fresh and fouled PDMS/ceramic composite membrane: (a) fresh membrane surface, (b) fouled membrane surface, (c) fresh membrane cross-section
and (d) fouled membrane cross-section.
peak present at 10001200cm
1
was assigned to the symmetric
and asymmetric C O stretch in carbohydrates [38]; the absorption
band near 1400cm
1
was attributed to symmetrical stretches of
COO

associated with amino acids [39]; two vibrational bands

located at around 1660 and 1540cm
1
were assigned to the
protein secondary structure, amido-I and amido-II bands, respec-
tively [38]. Additionally, it should be noticed that the amido-II
and COO

bands were not obvious existence in the spectra (b),

suggesting that the components of the foulants adsorbed on mem-
brane surface and permeated through the membrane had some
differences. This FT-IR result demonstrated that the membrane
foulants were consisted of the carbohydrates, amino acids and
protein, which are exactly the main components of microbial
cell.
It was noted that the microbial cells were present in both
spent and live (fermentationPV coupled process) ABE fermenta-
tion broth, however, membrane fouling only occurred in the live
fermentation broth. Similar result was also found by Qureshi and
Blaschek [12,36]. The major discrepancy between the spent and
live fermentation broth is the status of microbial cells, the former
is inactive whereas the latter is active. It can be inferred from the
results in Sections 3.1 and 3.2 that, the adsorption of inactive cells
on membrane surface was limited because most of the microbial
cells autolyzed in the spent fermentation broth. Thus, they could
not form a fouling layer on the membrane surface, resulting in the
stable membrane performance during the continuous PV of spent
fermentation broth. In contrast, the adsorption of active cells on
membrane surface could be accelerated by two factors in the live
Fig. 8. AFM image of (a) fresh and (b) fouled PDMS/ceramic composite membrane surface.
G. Liu et al. / Journal of Membrane Science 373 (2011) 121129 127
Fig. 9. FT-IR spectra of the foulants on the (a) surface and (b) cross-section of the
fouled PDMS/ceramic composite membrane.
fermentationbroth: multipolar divisionof cells inducing more cells
adsorbed on membrane surface and metabolism of cells adsorbed
on membrane surface improving the surface adhesion between
cells and membrane surface. Therefore, a fouling layer can be easily
formed by the adsorption and aggregation of active cells on mem-
brane surface and then membrane fouling occurred during the live
fermentationPV coupled process.
After ABE fermentationPV coupled process, the fouled
PDMS/ceramic composite membrane was washed with deionized
water for several times and then its PV performance was tested
in ABEwater solution (0.6wt% acetone, 1.1wt% n-butanol and
0.2wt% ethanol). As shown in Fig. 10, the total ux and separation
factor of the water-washed membrane was nearly the same as that
of the fresh membrane. Qureshi et al. used silicalite lled PDMS
membrane for PV of cells-free ABE fermentation broth for 120h
and then washed the membrane with water and measured its ux
inABE water solution. They also foundthat, the membrane couldbe
restored after water cleaning, indicating that the effect of foulant
deposition on membrane surface on ux decline was reversible
Fig. 10. PV performance of fresh and water-washed PDMS/ceramic composite
membrane in ABEwater solution. Feed composition: 0.6wt% acetone, 1.1wt% n-
butanol, and 0.2wt% ethanol.
[28]. After the PV experiments, the micro-structures of the water-
washed PDMS/ceramic composite membrane were characterized
by SEM. The results showed that the micro-structures of the water-
washedmembrane have not beenchanged. This result showedthat,
the PV performance of the fouled membrane could be recovered
by a simple water rinse. It means that this PDMS/ceramic com-
posite membrane should be suitable for the ABE fermentationPV
coupled process, and the membrane fouling problem could
be easily resolved by intermittent water cleaning in practical
applications.
3.5. Comparison of pervaporation performance with literature
Table 1 lists PV performance of various membranes in different
feedsystems. As for ABEwater solutioninthefeed, althoughalower
separation factor was shown comparing with the silicalite lled
PDMS membrane and liquid membrane, the PDMS/ceramic com-
posite membrane exhibited much higher permeate ux at 37

C
(both total and ABE individual uxes) than that of the reported
membranes, except the porous PTFE membrane with very low
butanol-selectivity and the silicalite lled PDMS membrane oper-
Table 1
Pervaporation performances of different PV membranes in ABE water solution, fermentation broth and coupled process.
Membrane type Temp. (

C) Flux (g/m
2
h) Separation factor Reference
Total Acetone n-Butanol Ethanol Acetone n-Butanol Ethanol
Feed: ABE solution
PERVAP-1060 40 340 14.4 18 14.5 18.9 [18]
PERVAP-1070 40 100 12.8 16 16.7 21.7 [18]
Silicalite lled PDMS 70 907 79.8 414 3.9 13.7 49 4.3 [19]
Liquid membrane 54 17 54 5 215
a
245
a
100
a
[25]
PEBA 23 34 1.05 6.6 0.73 5.1 12.4 3.5 [22]
PTFE 40 980 98 9.5 [27]
PDMS/ceramic 37 1065 165 181 11.7 30.3 18.4 5.4 This work
Feed: Cells-free or spent ABE fermentation broth
Silicalite lled PDMS 78 89 17 48 0 38.1 97.3 0 [28]
Liquid membrane 54 9 31 4 111
a
197
a
54
a
[25]
PDMS/ceramic 37 951 114 163 17 21.1 16.2 6.8 This work
Feed: ABE fermentationPV coupled process
PDMS 37 4.411.5
b
11 [16]
PDMS 35 2531 8.410.2 9.318.8 3.110.2 [12]
PP 35 1.210.7
c
0.58.1 2.86
d
[14]
Liquid membrane 30 3.3 66 [24]
PDMS/ceramic 37 626741 (670)
e
14.342.7 (27.1)
e
34.166.1 (48.2)
e
3.16.1 (4.6)
e
11.329.2 (20.6)
e
8.321.4 (15.1)
e
4.89.6 (6.7)
e
This work
a

solvent/water
, calculated by the following equation:
solvent/water
=(y
solvent
/ywater)/(x
solvent
/xwater) (y and x are the weight fractions of components in the permeate and feed,
respectively).
b
Evaluated in water solution.
c
ABE ux.
d
ABE separation factor.
e
Average.
128 G. Liu et al. / Journal of Membrane Science 373 (2011) 121129
ated at almost twice higher temperature (70

C). Additionally, in
the cells-free or spent ABE fermentation broth, the permeate ux
of PDMS/ceramic membrane just under the fermentation temper-
ature (37

C) had a big advantage over that of the silicalite lled

PDMS membrane operated at even more than twice higher tem-
perature (78

C). Furthermore, during the ABE fermentationPV

coupled process, our PDMS/ceramic composite membrane also
showed much better PV performance than the other membranes.
Especially, the highmembrane uxfacilitatedthis composite mem-
brane to be directly coupled with ABE fermentor just under its
fermentation temperature (37

C). Moreover, it was found that, in

most of the ABE fermentationPV coupled process, the PV perfor-
mance was lower than that in the ABE water solution and there
was a uctuation of PV performance during the coupled process.
As discussed above, this could be attributed to the occurrence of
membrane fouling.
4. Conclusions
PDMS/ceramic composite membrane was applied in the ABE
fermentationPV coupled process to in situ recover ABE prod-
ucts from their fermentation broth. In the ABE fermentation
broth, the inorganic salts increased the ABE activity and improved
the membrane selectivity, while the microbial cells adsorbed on
membrane surface decreased the PV performance. During the
fermentationPV coupled process, the PDMS/ceramic composite
membrane showed a high ux of 0.670kg/m
2
h and applicable ABE
separation factor of 16.7, though a periodical uctuation existed
due to the membrane fouling. The membrane fouling was relatedto
the adsorptionof active cells onthe membrane surface, and it could
be accelerated by microbial growth and metabolism in the live
fermentation broth. Fortunately, the membrane fouling could be
easily removed by a simple water rinse method and the membrane
PV performance could be restored, as well. Our work demon-
stratedthat the ABE fermentationPVcoupledprocess basedonthe
PDMS/ceramic composite membrane is a promising technology for
the biobutanol production.
Acknowledgements
This work was supported by the National Basic Research Pro-
gram of China (No. 2009CB623406); National Natural Science
Foundation of China (No. 20990222); Six kinds of important tal-
ents program of Jiang Su (2007007); China Postdoctoral Science
Foundation funded project (Nos. 20090461105 and 201003581).
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