ICEE2007048-152

Butanol Separation from a Model

Fermented Broth Using Simplified
Pervaporation Process
S. Chuichulcherm1*, S. Tawkeaw1, and P. Asadamongkon2
*Author to correspondence should be addressed via email: sinsupha@swu.ac.th

Theinnovative centre of engineering, energy and environment

1
Department of chemical engineering, Srinakharinwirot University
2
Department of mechanical engineering, Srinakharinwirot University

Abstract:Butanol has superior properties for fuel application when compared to ethanol or other fuels.
These properties include high calorific value (0.687cal g-1 K-1), low freezing point (193.1 K), and low
solubility in water (9.15 part in 100 parts). Butanol can be fermented from sugar, starch and molasses.
Fermented broth comprises of acetone, butanol, ethanol, acetic acid and the unused sugar. Techniques
to separate butanol from the fermented broth including membrane separation and pervaporation are
at the interest. However, there are limitations in these techniques such as fouling which reduces flux in
membrane separation and high energy requirement in pervaporation to evaporate butanol from broth.
The objective of the research was to study the performance of the simplified perveporation
(SPV) process for butanol separation from the model fermented broth. A hydrophobic membrane,
polydimethylsiloxane (PDMS) was used in the SPV process. The experiment was aimed to study the
effects of the feed flow rate, the feed temperature and the inlet feed pH on the overall mass transfer
coeffients (Kov) of butanol. It was found that the Kov of butanol increased when the inlet feed flow rate,
the temperature of the feed increased. However, the optimum pH for the butanol transfer was at the
neutral pH. The maximum butanol obtained from the experiment was 2.90 g h-1 when using the
optimum conditions with the feed flow rate of 1.5 L min-1 and the membrane surface area of 47.8 cm2.

Keyword: pervaporation, mass transfer coefficient, butanol

1. INTRODUCTION
Butanol is a potentially renewable source of energy. It has superior properties for fuel
application when compared to ethanol or other fuels. These properties include high
calorific value (0.687cal g-1 K-1), low freezing point (193.1 K), and solubility in water
(9.15 part in 100 parts) (Perry and Green, 1993).

The production of butanol via fermentation is, however, economically infeasible

compared with the synthetic method based on petroleum feed-stock since butanol
fermentation suffers from severe product induced inhibition (Kawedia et al., 2000).
Furthermore, low butanol concentration in fermentation broth leads to high cost of
butanol recovery. A few techniques have been used to separate butanol from
fermentation broth while fermentation proceeds. There have been a few works
focusing on butanol recovery using membrane techniques. These include
ultrafiltration (Ferras et al., 1986), pervaporation (Qureshi and Blascheck, 1999,
Qureshi et al., 2001), reverse osmosis, and liquid membrane separation.

Pervaporation has been claimed for lower consumed energy comparing with
distillation, adsorption, extraction and perstraction technique. It is estimated to use
energy only 9MJ/kg for butanol recovery (El Zanati ei al., 2006).
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The resistances-in-series model is used to describe mass transfer in membrane system

(Chuichulcherm et al., 2001) and can be applied to simplified pervaporation (SPV)
process. The flux of butanol through the membrane is control by the overall mass
transfer coefficient (OMTC) which consists of the bulk liquid, the membrane and the
vapour resistances. Butanol in aqueous “bulk” solution diffuses from the feed stream
to the membrane interface at the feed side, then, adsorbs into the membrane, diffuses
through the membrane, and consequentially desorbs from the membrane interface at
the permeate side. Finally, the butanol vapour diffuses to the bulk of the vapour phase
where air is used as a carrier gas to minimise the accumulation of butanol vapour at
the membrane surface.
Transport phenomena in each phase can be written in mass transfer equation as
follows:
1) Permeate flux through the boundary layer on the feed side of the membrane;
N i = k L C (X ib − X if* ) (1)
2) Flux through the membrane using solution-diffusion model;
Ni =
KDm
l
( X if* − X ir* ) (2)
3) Flux through the permeate vapour phase;
( )
N i = kV C Pir* − y i γ i PT (3).
Henry’s constant is used as the correlation between gas and liquid phase since dilute
aqueous solution was used in the experiments.
Pir* = H i X ir* (4)
At steady state, the molar flux is constant, and has the same value at any location on
the membrane. The permeate flux can be described by the OMTC as:
⎛ yγ P ⎞
N i = k OV C ⎜⎜ X ib − i i T ⎟⎟ (5)
⎝ Hi ⎠
1 C l 1
where = + + (6)
k OV H i k v KDm k L

This work describes an experimental study of the mass transfer phenomena in the
pervaporation membrane process. The OMTC and the membrane resistance to butanol
transferring across the silicone rubber membrane are investigated. The resistances-in-
series model is used to describe the OMTC.

2. EXPERIMENTAL TECHNIQUE
2.1 Analytical method
Butanol, ethanol, butyric acid, and acetic acid in the model fermentation broth and in
the permeate were determined using a GC analysis (a Shimasdzu model GC7AG)
with a recorder integrator (Chomapac CR1A). A carbowax 20M column was used.
Column temperature, injector temperature, and detector temperature were kept
constant at 180oC, 200oC, and 210oC, respectively. Nitrogen gas was used as a carrier
gas at a flow rate of 50dm3 min-1. The coefficient of variation of ten samples at the
concentration of 1g dm-3 was within 10%.

2.2 Model fermentation broth

Four 1dm3 model fermentation broth solutions consisted of 11g acetone, 4g ethanol,
1.5g acetic acid and 1.5g butyric acid. Butanol was added to the solutions at the
 ICEE2007048-154

amount of 50g. The concentrations of each component except butanol were average
means of the fermentation broth reported in literatures (Walton and Martin, 1979).

2.3 Apparatus
The apparatus used to study the OMTC of a silicone rubber membrane for butanol is
shown in Figure 1. The apparatus employed for the test consisted of two 2dm3 glass
reservoirs connected to a membrane separation column via pumps. eight 0.63 metre
30% silica polydimethylsiloxane (PDMS) tubes with 3.02mm. id., Silex, UK, was
used as membrane in a 0.9 metre glass tube, which was used as the separation column.
This non-porous membrane is permeating to butanol and acetone but virtually
impermeable to ionic species such as acetic acid and mineral salts. The total
membrane area was 47.83 cm2. PVC tubing was used as a pump tubing to minimise
butanol loss while circulating via centrifugal pumps. The feed reservoir was placed in
water bath to keep temperatures of the solutions constant. Air was compressed
passing through a humidifier column to minimise moisture content and was used as a
carrier gas in the permeate side. Therefore, the pressure in the permeate side was not
vacuum but slightly above atmospheric pressure. Gas outlet from the membrane
module composing of carrier gas and butanol was condensed at a temperature below
5oC and the liquid obtained was collected in a receiving bottle while the gas part was
vent out.

Figure 1 Schematic diagram of the experimental rig for measuring OMTC

2.4 Experimental procedure

Batch experiments were carried out to investigate the OMTC (kov) and solution-
diffusion resistance (1/KDmem) of butanol across the silicone rubber membrane. Two
litres of chemically-produced model fermentation broth was circulated inside the
membrane tubing at a range of Reynolds number of 550, 1100, and 1650 respectively
to study the effect of flow characteristic on the OMTC. Dehumidified air was used as
a carrier gas and was circulated on the shell side of the membrane module at a
constant Reynolds number of 5052. A range of solution temperatures of 10, 25, and
40oC was controlled via water bath to study the effect of temperature on the OMTC.
 ICEE2007048-155

However, the pH of the feed solutions were not controlled but were measured after
each experiments. Experimental runs were carried out for 8 hours to ensure steady
state.

3. RESULTS AND DISCUSSION

3.1 Overall mass transfer coefficient.
The system was operated for 8 hours or until the butanol concentration in the feed
decreased about 50%. Data of the butanol concentrations on the feed varying with
time from a typical operation used to determine the OMTC are shown in Figure 2.
The pH of feed solutions was not significantly changed so they did not affect the
butanol concentration. Ethanol, butyric acid, and acetic acid were not able to be
detected in the receiving solution. The result was confirmed by Huang and Meagher
(2001), which showed that butyric acid and acetic acid did not diffuse through the
thin-film silicalite-filled silicone composite membrane at the concentration of under
0.5 g dm-3. However, concentration of acetone was not measured in the experiments.

60
butanol concentration in feed tank (g/L)

50

40

30

20

10 feed flow rate of 0.5L/min

feed flow rate of 1L/min
feed flow rate of 1.5L/min
0
0 2 4 6 8 10

operating time (hr)

Figure 2 butanol concentration profile in a mass transfer experiment

It can be seen from figure 2 that the butanol concentration decreased linearly with
time. El-Zanati et al. (2006) claimed that the concentration pattern was attributed to
the adsorption and desorption step confirming to Henry’s law (P=HX), which is
recognized by a linear relationship.

The simple flux expression was derived from equation (5) which was related directly
to the feed concentration. In this case, the molar fraction, yi, is very small, “yi~0”,
since the flow of air was enormous compared to the flow of butanol. Equation (5)
becomes:
 ICEE2007048-156

N i = k OV C ( X ib ) = k OV C ib (7)
Flux of butanol occurred due to the concentration gradient. An estimate of the error in
OMTC was obtained by repeating experimental runs twice for each conditions. Data
used in the flux calculation were the average values. The Cib can be estimated as the
mean value between the feed inlet and the outlet of the membrane module which can
be measured at any time interval.

The butanol balance on the pervaporation cell and the feed tank could be express as
equation (8) with the assumption that the volume of the feed and the membrane area
are constant.
dC ib
−V = Ak OV C ib (8)
dt
By integration:
C ib ,o A
ln = k OV t (9)
C ib V
C ib ,o
A plot of ln against t for constant hydrodynamic conditions is shown in Fig 3.
C ib
The slope of the linear line in Figure 3 is kovA/V, and so kov can be obtained. Mean
kov values from two experimental runs for butanol transfer the membrane was
6.64x10-6 ms-1 at the experimental conditions of T=400C, pH6, Re on the shell side
was 536. Overall mass transfer coefficients with a change on tube-side Re were
presented in Table 1.

Table 1. Overall mass transfer coefficients with different Re on the tube side while the
air flow rate on the permeate side was kept constant.

Re on the tube side OMTC (m s-1)

536 6.64x10-6
1072 8.05x10-6
1108 8.33x10-6
 ICEE2007048-157

8.0e-1

y = 0.0693x
6.0e-1 R2 = 0.99
ln (Cibo/Cib)

4.0e-1 y = 0.0572x
R2 = 0.99

2.0e-1

0.0
0 2 4 6 8 10

operating time (hr)

C ib ,o
Figure 3 Plot of ln against time to determine kov, slope of the line is kovA/V
C ib

The OMTCs obtained were independence from initial butanol concentration. Results
from experiments conducted with a change in the initial concentrations of butanol at a
range of 30, 40 and 50 g dm-3 confirmed that the OMTC of each experiments were
constant (data not shown). Also the flux of butanol is shown in figure 4.
 ICEE2007048-158

1.5e-1
feed flow rate of 0.5L/min
1.4e-1 feed flow rate of 1.0L/min
feed flow rate of 1.5L/min

1.3e-1
butanol flux (g/cm2 hr)

1.2e-1

1.1e-1

1.0e-1

9.0e-2

8.0e-2

7.0e-2
0 2 4 6 8 10

operating time (hr)

Figure 4 Flux of butanol with time.

When analysed each term of the mass transfer coefficient in the OMTC, the mass
transfer coefficient in vapour phase is usually much higher than the mass transfer
coefficient in liquid phase and membrane phase (approximately in 2-3 order of
magnitude). It is easier to neglect the term of mass transfer coefficient in vapour
phase in equation (6), then the OMTC can be rewritten as:
1 l 1
= + (10)
k OV KDm k L
The kL depends on the feed flow rate while the term of membrane resistance should
be constant. Since the flow characteristics used in the experiment were in laminar
regime, equation described kL follows Cusler et al., (1992).
D
k L = i 1.62Gr 0.33 (11)
d
d 2v
Where Gr = (12)
Di L
When the values kL of were calculated (1.032x10-5 ,1.29x10-5, and 1.48x10-5 ms-1
when using feed flow rate of 500, 1000, and 1500 ml min-1 respectively) and
substituted in equation (10), the term of membrane coefficient was calculated to get
the mean value of 2.01x10-5 ms-1. It can be seen that the resistances in the SPV
process, the membrane resistance and the hydrodynamic resistances, were nearly
equal. In order to get higher OMTC, an increase in feed flow rate can be performed
easier than a change in membrane thickness.

3.2 Effect of temperature on the OMTC

 ICEE2007048-159

The OMTCs increased when the temperature increased. Seader and Henley (1998)
stated that the effect of temperature over a modest range of about 50oC was able to be
represented for diffusivity by Arrhenius equation:
−E D
Dmem = Dmem ,o e RT

An increase in temperature can cause a substantial increase in diffusivity and,

therefore, a corresponding increase in permeability and mass transfer coefficient. This
phenomenon was supported by Huang and Meagher (2001). Their results showed that
the n-butanol flux increased nearly 10 folds when the operating temperature increased
from 30oC to 70oC. Their results of the effect of the temperature on the butanol flux
were also fitted well with the Arrhenius-type manner. However, results from this
experiment showed that The OMTC increased only 20% when the temperature
increased from 10oC to 40oC.

4. CONCLUSIONS
A silicone rubber membrane successfully recovered n-butanol from the model
fermentation broth. Ethanol, butyric acid, and acetic acid did not diffused through the
membrane at the concentration of < 4g dm-3, which was the concentration used in the
experiments. Butanol transferred through the membrane from the ABE fermentation
broth into a carrier gas. The overall mass transfer coefficient of a silicone rubber
membrane for the butanol, which included hydrodynamic mass transfer coefficients in
the feed solution and a membrane mass transfer coefficient, was 8.33x10-6 m s-1 at an
operating temperature of 40 oC. The solution-diffusion coefficient of the membrane
was calculated to be 2.02 x 10-5 cm s-1. Separation of butanol from the model
fermentation broth at the first step is beneficial to the overall process. It permitted the
process operating without suffering from severe butanol inhibition to the micro-
organism.

Nomenclature
A average membrane area, cm2
Cib,t concentration of butanol in feed solutionat time t=t, g dm-3
Cif* concentration of butanol in membrane interface at time t=t, g dm-3
Cib,0 initial concentration of butanol in feed solution, g dm-3
Dmem diffusivity of butanol in the membrane, s-1
Dmem,0 diffusivity of butanol in the membrane at the reference datum, s-1
ED activation energy of diffusion in polymer, kJ mol-1
H Henry’s constant
K thermodynamic equilibrium partition coefficient, -
kov overall mass transfer coefficient of butanol transferred through the membrane,
m s-1
kL, kV liquid and gas mass transfer coefficients due to hydrodynamic behaviours
respectively, m s-1
l membrane thickness, m
PT total pressure at the permeate side
R gas constant, J mol-1 K-1
T temperature, K
t time, s
V volume of the feed solution, dm3
X,y molar fraction of butanol in liquid and gas phase respectively
γi activity coefficient
 ICEE2007048-160

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