Journal of Molecular Liquids 287 (2019) 110960

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Journal of Molecular Liquids

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

Determination of solubilization isotherm in micelles of non-ionic

surfactant L62 for butanol extraction
Atulkumar N. Raut, Abhishek R. Dhobe, Preety S. Gedam, Pradip B. Dhamole ⁎
Department of Chemical Engineering, Visvesvaraya National Institute of Technology, South Ambazari Road, Nagpur, M.S. 440010, India

a r t i c l e i n f o a b s t r a c t

Article history: Earlier studies with extractive butanol fermentation using non-ionic surfactant L62 showed significant increase
Received 25 March 2019 in butanol titer by 50–125%. Butanol was further separated from fermentation broth using L62 in a cloud point
Received in revised form 7 May 2019 extraction system. The present work was undertaken to determine the solubilization of butanol in L62-water sys-
Accepted 10 May 2019
tem. Experiments were conducted to study the effect of different parameters on butanol extraction efficiency.
Available online 11 May 2019
Optimum conditions i.e. 3% L62 (v/v) with 4% (v/v) butanol concentration at 45 °C for 30 min resulted into extrac-
Keywords:
tion efficiency of 40.8% (w/w). The Langmuir isotherm was fitted and isotherm parameters were found to be m
Butanol = 129.87 (mol/mol) and n = 0.308 (L/mol). Langmuir isotherm with estimated parameters was used to predict
Isotherm the surfactant concentration to extract butanol with desired efficiency. Predicted and experimental results were
ATPS in close agreement (96% accuracy). Thus, Langmuir model can be successfully used to design the cloud point ex-
Cloud point tractor and predict the extraction efficiency/surfactant concentration for L62-butanol-water system with great
Non-ionic surfactant accuracy.
© 2019 Published by Elsevier B.V.

1. Introduction
Interest in the production of bio-butanol from renewable resources
has increased during the last decade. Among the alternative biofuels,
biobutanol is considered to be superior and promising as its properties
are similar to gasoline [1]. Besides petroleum route, with the aid of con-
ventional acetone-butanol-ethanol (ABE) fermentation butanol can also
be produced using renewable sources. However, maximum 20-22 g/L
butanol can be obtained in ABE fermentation broth owing to severe
end product toxicity. Due to low butanol titer which leads to high sepa-
ration costs, butanol production is not commercially feasible. Thus, sep-
aration techniques and their applications for butanol separation from
fermentation broth become the important factor for commercial pro-
duction of butanol.
A variety of alternative methods have been explored for separation
and purification of butanol from fermentation broth. This includes ad-
sorption [2], pervaporation [3], perstraction [4], liquid-liquid extraction
[5] and gas stripping [6]. Mostly, these methods target relieving the tox-
icity of butanol by simultaneous separation of butanol. Recently,
Dhamole et al. [7,8] studied a cloud-point extraction (CPE) system for
the butanol extraction from microbial fermentation broth in an extrac-
tive fermentation process. Extractive fermentation system enhances bu-
tanol titer (in terms of production) by reliving butanol toxicity to the
microbes. Other applications of CPE system for extractive microbial
⁎ Corresponding author.
E-mail address: pdhamole@che.vnit.ac.in (P.B. Dhamole).
fermentation as a unique two-phase system has also been described. In-
crease in substrate solubility [9], shifting thermodynamic equilibrium of
bioreaction process [10], recycling of microbial cells as biocatalyst [11],
relatively high polar product extraction [12] and concentration as well
as purification of protein [13], has been reported successfully using
CPE system in extractive microbial fermentation. Numerous advantages
of CPE such as easy to manipulate, reduced process volume, enrichment
of product (butanol) in a small volume, simple, cost-effective as surfac-
tants are required in small quantity and effective to operate makes CPE
very attractive [14,15]. Two phases, an aqueous phase, and a surfactant-
rich phase are obtained at a temperature above cloud point. Dilute
phase consists of the surfactant unimers which has slightly higher con-
centration than that of critical micelle concentration (CMC). Surfactant-
based extractive fermentation reduced butanol toxicity and enhanced
butanol titer by 50–125% [16,17]. Also, the same surfactant was further
used for separation of butanol. Raut et al., have established the phase
separating conditions for L62-butanol-water system [18]. Further, the
extraction of butanol into coacervate phase and back-extraction of buta-
nol from coacervate phase was also investigated using microemulsion
[19].
In order to devise an operative CPE process and to make the process
economical, a suitable model is required to predict the required amount
of surfactant or the extraction efficiency [20]. Further, the mechanism of
solute-surfactant interaction can also be studied using the model.
Purkait et al. reported a collinear relation between different concentra-
tion of solute feed and required surfactant concentrations for a fixed
concentration of solute in dilute phase. [21]. Whereas, change in initial

https://doi.org/10.1016/j.molliq.2019.110960
0167-7322/© 2019 Published by Elsevier B.V.
2 A.N. Raut et al. / Journal of Molecular Liquids 287 (2019) 110960
surfactant concentration, as well as initial solute concentration, resulted
in the change in concentration of solute in dilute phase [22]. It is re-
ported that, with increasing concentration of surfactant, the surfactant
partition coefficient remains almost constant beyond particular surfac-
tant concentration [21]. Hence, in this work, a suitable model is used
to fit the experimental data. CPE is anticipated to be an interactive pro-
cess between surfactant micelles and the solute. This type of interactive
process can be considered as a solute (butanol) adsorption on the sur-
face of micelles or within some other destinations of micelles. [23].
Therefore, Langmuir adsorption isotherm was used for data fitting and
estimation of parameters. The intensity of adsorption of micelle is pro-
vided by means of adsorption capacity (m) and adsorption energy (n).
Linear form of Langmuir equation can be used to calculate the values
of m and n. The slope and intercept will provide the values for m and
n respectively [24]. The m and n values significantly differ with respect
to process parameters like time, temperature and concentration of sur-
factant as well as solute. Hence, initial experiments were conducted to
find the butanol extraction efficiency for different surfactant concentra-
tion, butanol concentration, time and temperature. Langmuir adsorp-
tion isotherm equation with estimated values of m and n were used to
calculate the surfactant quantity required to extract the solute to the de-
sired level. Probable mechanism to understand cloud point extraction of
butanol using non-ionic surfactant L62 is also proposed.
2. Experimental
2.1. Chemicals
Analytical grade chemicals were used without further purification
throughout the experimentation. Pluronic L62 (PEO-PPO-PEO) triblock
copolymer was provided by BASF as a gift sample and used without fur-
ther purification. L62 (EO6PO34EO6) has a molecular weight of
2500 g/mol, it contains 20% PEO and has hydrophile-lipophile balance
(HLB) value of 7.0. The CMC of surfactant L62 is 0.0004 M. Butanol
was bought from Hi-media, India. An aqueous solution of all samples
was prepared using distilled water.
2.2. Methods
In a typical cloud point extraction experiment, a precise amount of
butanol and L62 was dissolved in distilled water to get an aqueous solu-
tion of L62 and butanol with different concentrations. The concentra-
tions of L62 and butanol were varied from 3% to 12% (v/v) and 1% to
4% (v/v) respectively. Each experiment was performed in a sealed grad-
uated test tube (15 mL) (borosil). Aqueous solution (10 mL) was then
taken into test tubes and incubated into circulating water bath
(Polyscience Digital Temperature Controller, USA, MX07R-20-A-12E)
at each constant temperature (40 °C to 60 °C) for different time spans
(5 to 30 min). After complete phase separation, samples were collected
from both the phases i.e. upper dilute phase and lower coacervate
phase. Concentration of butanol and L62 in both phases was determined
by gas chromatography (GC) and dry weight method, respectively. Fur-
ther, it was validated by material balance. In order to study the design
parameters, volume of both the phases was noted after complete
phase separation. The calibration curve for butanol was developed for
standard concentrations using GC. For CPE, extraction efficiency and
partition coefficient of butanol as well as fractional coacervate phase
volume were calculated using following equations.
 
C V
Extraction Efficiency ð%EÞ ¼ 1− Bd d  100
C B0 V 0
C Bc
Partition Coefficient ðK BtOH Þ ¼
C Bd
Vc
Fractional coacervate phase volume ð F c Þ ¼ ð3Þ
V0
where, CB0 represents butanol concentration in initial sample of volume
V0, CBd and CBc represent the concentration of butanol in dilute phase
and coacervate phase of volume Vd and Vc, respectively.
2.3. Analysis
GC was used to analyze the butanol concentration in feed, aqueous
phase, and coacervate phase. Chromatographic analysis was performed
in a Thermo Scientific GC (Series: Trace 1110) with a flame ionization
detector (FID). The GC was equipped with a fused silica capillary col-
umn, BP-20 (Forte), (length: 25 m, id: 0.22 mm). The temperature pro-
gram started with an initial temperature of 60 °C for 2 min, then raised
to 200 °C with a ramp of 10 °C/min, and again held at 200 °C for 5 min.
Split ratio was set to 100 with an injection volume of 1 μL. Nitrogen
(2 mL/min) was employed as a carrier gas. Acetonitrile (ACN) was cho-
sen as an internal standard (IS) to achieve quantitative accuracy. Reten-
tion time and peak area were calculated using Thermoscientific
chrome-card software. Dry weight method was used to determine the
concentration of surfactant in each phase. In this method, 1 mL each of
samples from each phase, standard butanol, L62 surfactant, and distilled
water was taken individually in separate petri plates. Initial weight of
sample was measured. Water and organic solvents were removed by in-
cubating the samples at 37 °C. Weight of samples was taken after every
24 h till the constant weight is observed in the consecutive readings.
3. Results and discussion
This segment is separated into three sub-sections. Section 1 reports
the impact of various process parameters like surfactant concentration,
initial butanol concentration, time and temperature on CPE of butanol.
In Section 2 extraction mechanism has been discussed. Design parame-
ters for cloud point extractor were evaluated using the nature of solubi-
lization isotherm in Section 3.
3.1. Effect of various process parameters on butanol extraction efficiency
3.1.1. Effect of surfactant concentration
Earlier work [16,17] carried out with C. beijerinckii and C. sporogenes
showed enhanced butanol concentration in presence of 3% L62 and 6%
L62, respectively. The effect of Pluronic L62 concentration was esti-
mated in order to maximize butanol extraction, with fixed initial buta-
nol concentration (4% v/v i.e. 32.4 g/L). L62 concentration was studied
up to 12% (v/v) using model fermentation system; as higher L62 con-
centration butanol did not enhance butanol titer during fermentation
[7].
The temperature was fixed above cloud point temperature in order
to assure two-phase formation. Fig. 1 shows the extraction efficiency
of butanol and the fractional coacervate phase volume (Fc) for different
initial L62 concentration. Extraction efficiency of butanol, as well as Fc,
increased with an increase in the surfactant concentration (Fig. 1). How-
ever, the partition coefficient decreased with increase in L62 concentra-
tion (Table 1). Increase in extraction efficiency of butanol with
concentration of surfactant L62 is attributed to greater butanol solubili-
zation as a result of increase in micellar concentration in the solution
[25]. However, the increase in Fc with respect to surfactant concentra-
tion is attributed to concentration of surfactant in the coacervate
phase which remains constant at constant temperature [26,27]. There-
ð1Þ fore, for maintaining material balance, volume of coacervate phase in-
creases. With an increase in surfactant concentration, presence of
surfactant micelles within coacervate phase increases which confirm
an enhancement in butanol solubilization as well as extraction effi-
ciency. The volume of the coacervate phase rises with the increasing
ð2Þ
concentration of surfactant L62, thereby increasing the butanol

Extraction efficiency Fc
100
Extraction Efficiency (%)
80
60
40
20
0 0.0
0 3 6 9
L62 Concentration (%)
Fig. 1. Effect of concentration of surfactant L62 on extraction efficiency of butanol and
fractional coacervate phase volume (Reaction conditions: T = 60 °C, time = 30 min,
initial butanol concentration = 32.4 g/L).
solubilization in coacervate phase. However, the amount of butanol, as
well as surfactant in the coacervate phase, also rises with the surfactant
concentration resulted in increment of coacervate phase volume. Incre-
ment in amount of butanol and coacervate phase volume lead to reduc-
tion of butanol concentration in coacervate phase. Thus, partition
coefficient of butanol was decreased with increasing surfactant concen-
tration. Extraction efficiency increased from 29.9% (w/w) to 65.8% (w/
w) and fraction coacervate phase volume increased from 0.1 to 0.4
with increasing concentration of surfactant from 3% to 12% (v/v) L62.
3.1.2. Effect of butanol concentration
The impact of butanol concentration on the extraction efficiency of
butanol was evaluated maintaining constant surfactant concentration
(3% v/v). Singh et al., [16] showed that extractive fermentation in pres-
ence of 3% surfactant L62 enhanced butanol production by 43%. It was
assumed that if a high butanol producing strain (capable of producing
20–22 g/L of butanol) is used, it would produce 31.5 g/L of butanol
which nearly equals to 4% (v/v) (40 mL/L) of butanol. Hence, initial bu-
tanol concentration was varied from 1% (v/v) to 4% (v/v) i.e. 8.1 g/L to
32.4 g/L. The extraction efficiency of butanol, as well as Fc, decreased
with increasing initial butanol concentration at constant L62 concentra-
tion (Fig. 2). Also, partition coefficient increased with increasing butanol
concentration (Table 2). Decrease in extraction efficiency of butanol
with increasing initial concentration of butanol can be attributed to in-
crement of the butanol amount in the aqueous phase at constant L62
concentration and constant temperature [28]. As initial L62 concentra-
tion is constant, the quantity of micelles remains unchanged however
initial concentration of butanol was increasing which results in the pres-
ence of high amount of butanol in the aqueous phase. Also, Fc decreased
with increasing butanol concentration. With increasing initial butanol
concentration volume of coacervate phase decreased whereas amount
of butanol in the coacervate phase was increased. Reduction of coacer-
vate phase volume with simultaneous increase in butanol amount re-
sulted in increasing partition coefficient with respect to the initial
butanol concentration.
Table 1
Partition coefficient of butanol with variation in initial L62 concentration.
Sr no L62 concentration (% v/v)
1 3
2 6
3 9
4 12
A.N. Raut et al. / Journal of Molecular Liquids 287 (2019) 110960 3
Extraction efficiency FC
1.0 100 1.0
Fractional coacevate phase volume
Fractional coacervate phase volume
Extraction Efficiency (%)
0.8 80 0.8
0.6 60 0.6
0.4 40 0.4
0.2 20 0.2
0 0.0
12 15 0 1 2 3 4 5
Butanol concentration (% v/v)
Fig. 2. Effect of initial butanol concentration in feed on extraction efficiency of butanol and
fractional coacervate phase volume (Reaction conditions: T = 60 °C, time = 30 min, L62
concentration = 3% (v/v)).
3.1.3. Effect of temperature
It is noteworthy for any process to have minimum achievable tem-
perature to secure efficient extraction of solute and perfect two-phase
formation. The impact of temperature on butanol extraction was stud-
ied above cloud point temperature in the range of 45 °C to 60 °C. From
Fig. 3, it can be clearly observed that extraction efficiency of butanol de-
creased with increase in temperature. Increase in temperature from 45
°C to 60 °C decreased butanol extraction efficiency from 40.9% (w/w) to
30.1% (w/w). This can be related to Fc, which decreases with the in-
creasing temperature (Fig. 3) At elevated temperature, the CMC of
non-ionic L62 decreases [21,23]. Experiments carried out in the present
work also showed the decrease in CMC from 0.0004 M to 0.0002 M with
increase in temperature from 20 to 37 °C. Thus, concentration of mi-
celles increases at higher temperature because of an equilibrium shift
which favors dehydration of PEO group resulted in increase of hydro-
phobic nature of surfactant. Increase in number of micelles shows in-
crease in solubility of butanol. The interaction between L62 micelles
increases because of dehydration of PEO group at higher temperature
which results in decrease in coacervate phase volume. Therefore, solubi-
lization capacity of the micellar phase increases with temperature, how-
ever volume of coacervate phase decreases. At constant L62
concentration, with increasing temperature, concentration of butanol
in the coacervate phase increases as solubilization capacity increases
but there is decrease in coacervate phase volume leading to decrease
in extraction efficiency of butanol with increasing temperature. At 45
°C, concentration of butanol in coacervate phase was 66.2 g/L which in-
creased to 97.6 g/L at 60 °C, whereas Fc decreased from 0.2 to 0.1 as tem-
perature increased from 45 °C to 60 °C. Thus, the extraction efficiency of
butanol obtained in temperature range between 45 °C and 60 °C de-
creased from 40.8% (w/w) to 30.1% (w/w).
3.1.4. Effect of phase separation time
In CPE process, phase separation time was much shorter than that of
commonly used adsorption process. Hence, the effect of phase separa-
tion time was studied on the extraction efficiency of butanol and Fc
for a shorter time interval of 5 to 30 min and results are presented in
Fig. 4. It was observed that phase separation time had less effect on
Table 2
Partition coefficient of butanol with variation in initial butanol concentration.
Partition coefficient Sr no Initial butanol concentration (%v/v) Partition coefficient
3.85 1 1 1.67
3.66 2 2 1.69
3.00 3 3 3.73
2.90 4 4 3.85
4 A.N. Raut et al. / Journal of Molecular Liquids 287 (2019) 110960

Extraction efficiency Fc core of micelles [29] while remaining butanol might have acted as a co-
surfactant and get oriented in the micelle with hydroxyl group outside
100 1
and carbon chain on the inside as shown in Fig. 5. N-butanol, middle

Fractional coacervate phase volume

Extraction efficiency (%)

chain alcohol which is comparatively smaller, will arrange itself be-

80 0.8
tween the hydrophobic core and the hydrophilic corona. In case of
60 0.6 higher chain alcohol, they will move towards hydrophobic core than hy-
drophilic corona. With increase in temperature, the coalescence of mi-
40 0.4 celles will take place resulting into increase in micelle size and loss of
water [29]. Since water in the hydrophilic core is associated with co-
20 0.2 surfactant butanol, loss of water will also lead to loss of butanol from
the micelle. Therefore, extraction efficiency decreased with increase in
0 0 temperature (Fig. 3) Reduction in Fc with increasing temperature
40 45 50 55 60 65
(Fig. 3) can also be explained with this phenomenon. As swelling of mi-
Temperature (°C)
celles occurred, water present in micelle crust is pushed further due to
lesser hydrogen bonding. Thus, less water gets entrapped in the coacer-
Fig. 3. Effect of temperature on extraction efficiency of butanol and fractional coacervate vate phase which leads to lesser Fc.
phase volume (Reaction conditions: time = 30 min, L62 concentration = 3% (v/v),
initial butanol concentration = 32.4 g/L). 3.3. Solubilization isotherm

the extraction efficiency of butanol as well as fraction coacervate phase At equilibrium, partition of butanol between two phases; coacervate
volume. The complete phase separation was obtained in 5 min with Fc phase and dilute phase can be described by the interaction of solute (bu-
of 0.12 which slightly decreased and remained constant at 0.1 in a tanol) and adsorbent (surfactant L62). It can be acknowledged as ad-
time interval of 10 min to 30 min. However, the extraction efficiency sorption of butanol in the internal or exterior layers of the micelles of
of butanol increased fairly from 22.5% (w/w) in 5 min to 30.1% (w/w) surfactant L62. Thus, assuming homogeneous monolayer adsorption,
in 30 min which was nearly equal to the extraction efficiency in such type of interaction can be conveyed by Langmuir isotherm
20 min (29.6% (w/w)). The maximum extraction efficiency of butanol [21,24,30].
obtained was 30.1% with Fc of 0.1 at time interval of 30 min.
m:n:C Bd
q¼ ð4Þ
3.2. Extraction mechanism 1 þ n:C Bd

The clouding phenomenon in non-ionic Pluronic surfactant L62 in
presence of n-butanol can be explained using following approaches:
(i) multiple hydrogen bonds between PEO group of surfactants and
water-butanol in the hydrophobic micellar core and (ii) presence of bu-
tanol act as the co-surfactant within the micellar structure. Schematic
representation of the proposed extraction mechanism is shown in Fig. 5.
It is assumed that micellar formation starts with hydrogen bond for-
mation between PEO groups of unimers. Rise in temperature leads to
breaking of hydrogen bond between PEO-water resulting in dehydra-
tion of surfactant [24]. This, in turn, decreases solubility of L62 in
water and hence phase separation takes place leading to the formation
of surfactant-rich phase and aqueous phase.
The hydrophobic core contains PPO block surrounded by hydrophilic
corona which consists of PEO chains, the compound (butanol) may be
attracted towards the core as well as the corona. During the micelliza-
tion in surfactant-water system in presence of butanol, butanol being
hydrophobic in nature some butanol gets entrapped in the hydrophobic
Extraction efficiency
100
Extraction Efficiency (%)
q is the amount of butanol solubilized per mole of surfactant L62. CBd
is the butanol concentration in dilute phase; m and n are Langmuir con-
stants, m represents the solubilization capacity and n signifies the en-
ergy of solubilization.
The isotherm equation can be linearized [24,31,32] and expressed
as:
1 1 þ n:C Bd 1 1
¼ ¼ þ ð5Þ
q m:n:C Bd m m:n:C Bd
According to Eq. (5), a linear plot was obtained with slope 1/mn and
intercept 1/m if 1/q was plotted against 1/CBd. Fig. 6(a) represents the
solubilization isotherm of butanol which is illustrated by plotting 1/q
against 1/CBd. The equilibrium data for butanol adsorption over entire
range of concentrations were fitted to the Langmuir isotherm. Fig. 6
(b) shows a linear plot of 1/q vs. 1/CBd. The Langmuir constants, m and
n, determined from linear form of Langmuir model were 129.87
(mol/mol) and 0.308 (L/mol) for butanol-L62 system.
Fc
1 3.4. Requirement of surfactant for the extraction of butanol
Fractional Coacervate phase volume

80 0.8 The amount of adsorption (q) is defined as:

60 0.6 C Bc
q¼ ð6Þ
C Sc
40 0.4

20 0.2
where CBc and CSc are the concentration of butanol and surfactant L62 in
coacervate phase, respectively. The recovery of solute (E) in CPE process
0 0 can be expressed as:
0 5 10 15 20 25 30 35
Time (min) Amount of butanol in coacervate phase
E¼
Initial amount of butanol in feed

Fig. 4. Effect of phase separation time extraction efficiency of butanol and fractional
C Bc V c
coacervate phase volume (Reaction conditions: T = 60 °C, L62 concentration = 3% (v/ E¼
v), initial butanol concentration = 32.4 g/L). C B0 V 0
 A.N. Raut et al. / Journal of Molecular Liquids 287 (2019) 110960 5

Fig. 5. Schematic representation of proposed extraction mechanism.

Surfactant L62 concentration in coacervate phase (CSc) can be repre-

C Bc ðV 0 −V d Þ sented as:
E¼ ð7Þ
C B0 V 0
Amount of L62 in coacervate phase
C Sc ¼
Volume of coacervate phase
where, CB0 is the initial butanol concentration, V0, Vc and Vd are initial
C S0 V 0 −C Sd V d
volume of system, volume of coacervate phase and volume of dilute C Sc ¼ ð8Þ
phase respectively. V 0 −V d

where, CS0 and CSd are initial concentration of L62 and concentration of
L62 in dilute phase respectively.
Rearranging Eqs. (6)–(8) leads to:
14
(a)
1 C S0 V 0 −C Sd V d
R² = 0.9613 ¼ ð9Þ
Moles of butanol solublized per

12 q EC B0 V 0
mole of L62, q (mol/mol)

10
The surfactant concentration in the dilute phase nearly equals to the
8 CMC of surfactant and is very less compared to that in coacervate phase.
Thus, assuming initial concentration of surfactant much more than CMC
6
of surfactant, the amount of surfactant in the dilute phase can be
4 neglected in mass balance. Therefore, CS0V0 − CSdVd can be replaced
with CS0V0 in Eq. (9) and the expression of Eq. (9) can be rewritten as:
2
1 C S0
0 ¼ ð10Þ
0.00 0.05 0.10 0.15 0.20 0.25 0.30 0.35 0.40 q EC B0
Concentration of butanol in dilute phase, CBd (mol/L)
Concentration of butanol in dilute phase (CBd) can be written as:

Amount of butanol in dilute phase

0.30 C Bd ¼
(b) y = 0.025x + 0.0077 Volume of dilute phase
0.25 R² = 0.9939
According to material balance, it can be rearranged as:
0.20
C B0 V 0 −C Bc V c
C Bd ¼
1/q

0.15 Vd

0.10 C B0 V 0 −C Bc ðV 0 −V d Þ
C Bd ¼ ð11Þ
Vd
0.05

0.00 Rearranging Eqs. (7) and (11), leads to:

0 2 4 6 8 10 12
C B0 V 0 −EC B0 V 0
1/CBd C Bd ¼ ð12Þ
Vd

Fig. 6. (a) Solubilization Isotherm of the butanol over surfactant L62; (b) Langmuir Plot of The volume of dilute phase is much higher compared to that of coac-
butanol for calculation of Langmuir constants m and n. ervate phase and approximately equals to the initial volume of system.
6 A.N. Raut et al. / Journal of Molecular Liquids 287 (2019) 110960

Thus, dilute phase volume (Vd) can be approximated to the initial vol-
ume of system (V0) and Eq. (12) can be rewritten as;
C Bd ¼ C B0 ð1−EÞ
Combining and rearranging Eqs. (5), (10) and (13), leads to;
E EC B0
C S0 ¼ þ ð14Þ
m:n:ð1−EÞ m point extractor to attain maximum extraction efficiency. The required
If initial butanol concentration CB0 and the Langmuir constants m
and n are known, the initial surfactant concentration in feed required
to extract butanol to the desired efficiency can be calculated using
Eq. (14). The experiments were performed with variable concentration
of surfactant in feed to analyze the effect of surfactant concentration in
Section 3.1.1. The extraction efficiency obtained experimentally was
used to calculate required initial surfactant concentration using
Eq. (14). A plot of calculated initial surfactant concentration against
those experimentally used provides a good regression as shown in
Fig. 7a. The difference between the calculated and experimental value
is below 5% suggesting that required initial surfactant concentration is
well described by Eq. (14). Further, solving Eq. (14), by using the desired
extraction efficiency of butanol as 90%, the surfactant L62 concentration
required for different initial butanol concentration are evaluated and
plotted in Fig. 7b.
4. Conclusions
Cloud point extraction (CPE) was effectively used to extract butanol
from aqueous solution of surfactant L62. The effect of surfactant concen-
tration, initial butanol concentration, temperature and time on butanol
extraction was studied in detail. It was perceived that extraction
0.06
Predicted value for feed L62 (mol)
efficiency increased with concentration of surfactant and phase separa-
tion time, whereas decreased with initial butanol concentration and
temperature. Butanol adsorption within the micelles of L62 followed
ð13Þ Langmuir isotherm. Langmuir constants, m and n, determined from a
linear form of Langmuir model were 129.87 (mol/mol) and 0.308 (L/
mol) for butanol-L62 system. The relationship between the initial buta-
nol concentration and required concentration of surfactant L62 was
established. The developed relationship can be used to design a cloud
concentration of surfactant L62 increased with rise in initial butanol
concentration. The experimental and predicted results were compared
and found in close agreement with regression of coefficient of 0.96.
Acknowledgment
Dr. Pradip B. Dhamole would like to thank Department of Biotech-
nology (Govt. of India) for funding this work (vide Sanction order No.
BT/PR5886/PBD/26/304/2012 dated 26.12.2013). Authors would also
like to thank BASF for providing the free samples of surfactant.
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