Chemical Engineering and Processing 50 (2011) 614622

Contents lists available at ScienceDirect

Chemical Engineering and Processing:

Process Intensication
journal homepage: www.elsevier.com/locate/cep

Estimation of equilibrium parameters using differential evolution in reactive

extraction of propionic acid by tri-n-butyl phosphate
Sushil Kumar, Dipaloy Datta, B.V. Babu
Department of Chemical Engineering, Birla Institute of Technology and Science (BITS), PILA NI333 031 Rajasthan India

a r t i c l e

i n f o

Article history:
Received 21 June 2010
Received in revised form 22 March 2011
Accepted 25 March 2011
Available online 1 April 2011
Keywords:
Differential evolution (DE)
Reactive extraction
Propionic acid
Separation
Equilibrium
Extractant (TBP)
Modier (1-decanol)

a b s t r a c t
The graphical and conventional optimization methods, used for the estimation of equilibrium parameters,
do not guarantee the global optimum values. In this study, the equilibrium parameters are estimated using
a well proven evolutionary based optimization routine [differential evolution (DE)]. For the estimation
of stoichiometry and equilibrium constants, experiments are carried out for the reactive extraction of
propionic acid using tri-n-butyl phosphate (TBP) dissolved in n-decane (inert diluent) and 1-decanol
(modier). The number of TBP molecules (n) in the acid:TBP complex and equilibrium extraction constant
(KE ) using 1:1 volume ratio of 1-decanol and n-decane as a diluent, are determined through proposed
mathematical model using graphical methods as well as the differential evolution algorithm (DE, an
optimization routine) and found that the predicted values of distribution coefcient (KD ) using DE are
closely matching with the experimental values of KD . 1:1 complexes between TBP and acid are formed
in most of the cases. The enthalpy and entropy of reactive extraction of propionic acid using TBP are also
determined and found to be 12.47 kJ mol1 and 32.42 J mol1 K1 , respectively. The results of present
study will be useful to intensify the recovery of propionic acid from fermentation broth (bio-separation)
and aqueous waste stream.
2011 Elsevier B.V. All rights reserved.

1. Introduction
In the recent past, the interest towards propionic acid recovery from fermentation broths and aqueous efuents has increased.
This interest is caused by the growing demand of pure, naturally
produced propionic acid that is used in chemical, pharmaceutical
and food industries [1]. The fermentation process, because of various impurities in the fermentation broth, and recovery of products
from efuent stream require an economic separation method to
compete with the synthetic process. Many separation processes in
chemical industries have been employed to recover the organic
acids from aqueous solution [2,3]. Reactive extraction is developed to intensify separation by solvent extraction and represents
a connection between chemical (solute and extractant reaction)
and physical phenomena (diffusion and solubilization of the system
components). Reactive extraction is found to be an efcient, economical, and environmental friendly method for separation of acids
from waste water streams and fermentation broths [411]. Using
reactive extraction as separating technique, the reactor productivity is found to be increased and reactor pH without the addition

Corresponding author. Tel.: +91 1596 515201; fax: +91 1596 244183.
E-mail addresses: skumar@bits-pilani.ac.in (S. Kumar), dipaloy@bits-pilani.ac.in
(D. Datta), bvbabu@bits-pilani.ac.in (B.V. Babu).
URL: http://discovery.bits-pilani.ac.in/ bvbabu/ (B.V. Babu).
0255-2701/$ see front matter 2011 Elsevier B.V. All rights reserved.
doi:10.1016/j.cep.2011.03.004

of a base is controlled easily. The use of a high-concentration substrate as the process feed reduces process wastes and production
costs. After the extraction of organic acids, solvents are regenerated by stripping the acids for recycle in the extraction process. This
method may reduce the downstream processing load and recovery
costs [7,10].
Organophosphorus compounds and long-chain aliphatic amines
are effective extractants for the separation of carboxylic acids
from dilute aqueous solution [12]. Phosphorus-bonded, oxygencontaining extractants can only co-extract small amounts of water,
and show low solubilities in water. When organophosphorus
extractants are used, the solvation has a higher specicity [12].
Generally, these extractants are dissolved in a diluent such as a
ketone, an alcohol, hydrocarbons, etc. to provide appropriate physical properties for use in the extraction process. For the separation
of organic acids, it is very important to understand the inuence
of different parameters on the overall distribution coefcient of
each organic acid. Since the presence of hydroxyl and carboxylic
groups increases the solubility of acids in the water phase, the
strong interactions of solvent with solutes are necessary to extract
carboxylic acids from dilute aqueous solutions. Polar diluents that
enhance the extraction power of amines are more favorable than
non-polar diluents, as shown in the extraction of citric acid, lactic
acid, and succinic acid [11]. Many factors have been found to inuence the equilibrium extraction characteristics of these systems.
Three important variables are: (1) nature of the acid extracted;

S. Kumar et al. / Chemical Engineering and Processing 50 (2011) 614622

Nomenclature
CHP
C HP
E
[H+ ]
HP
[HP]
KD
KE
Ka
m
n
[P]

[S]
in
[S]
Z

Total concentration of propionic acid in aqueous

phase (kmol m3 )
Total concentration of propionic acid in organic
phase (kmol m3 )
Degree of extraction, extracted acid/initial acid (%)
Hydrogen ion concentration in aqueous solution
(kmol m3 )
Propionic acid
Non-dissociated concentrations of propionic acid
(kmol m3 )
Distribution coefcient
Extraction equilibrium constants (k mol1 m3 )
Dissociation constant
Number of acid molecules involved in complex
Number of extractant molecules involved in complex
Dissociated concentrations of propionic acid
(kmol m3 )
Concentration of extractant, TBP in organic phase
(kmol m3 )
Initial concentration of extractant, TBP in organic
phase (kmol m3 )
Loading ratio, acid extracted/total extractant in
organic phase

(2) concentration of the extractant and (3) type of diluent [1316].

The extraction constant and the number of reacting molecules of
extractant are estimated from the mass action law but the obtained
values are different according to the composition of the solvent for
the same extractant and the organic acid [17,18].
Such solvating extractants open new avenues in process development and reduce energy and reagent consumption. Extraction
of organic acids has been studied using tri-n-butyl phosphate
[1824]. The study has been carried out to intensify the recovery
of nicotinic acid using reactive extraction with organophosphorus
solvating extractants such as tri-n-octyl phosphine oxide (TOPO)
and tri-n-butyl phosphate (TBP) by Kumar et al. [19]. Extraction
equilibria of the system (tributyl phosphate in dodecane, water,
and monocarboxylic acids) at a temperature (20 1 C) are studied
by Flores-Morales et al. [25]. Reactive extraction study on propionic acid using trioctylamine in various diluents (hexanol, butyl
acetate, and petroleum ether) is performed to show the positive
effect of the different diluents on the extraction by Wasewar et
al. [17]. Uslu et al. [26] studied reactive extraction of propionic
acid using Aliquat 336 (quaternary amine) dissolved in ve pure
solvents and binary solvents under various experimental conditions. However, a study on the same acid with the tertiary amine
(Alamine 336) diluted in toluene at 298.15 K indicated more propionic acid to be transferred to the organic phase than would
be expected from the 1:1 stoichiometry of the reaction, thus 2:1
and 3:1 acid-amine complexes are considered [27]. The effect of
the modier (1-decanol) on the extraction of tartaric acid by the
extractants such as tri-n-octylamine (TOA), Aliquat 336 and their
mixture in the inert diluent (n-dodecane) is studied by Mariya et al.
[28]. Yankov et al. [29] carried out lactic acid extraction by dissolving tri-n-octylamine in decanol and dodecane and reported
a strong inuence of diluent on the values of graphically determined extraction constant and stoichiometry. Poposka et al. [30]
studied equilibrium and kinetics of tartaric acid extraction with
Hostarex A324 (commercial triisooctylamine) dissolved in isodecyl alcohol/kerosene mixtures. An organic solution comprised of
TOA (extractant), 1-decanol (modier) and n-dodecane (inert dilu-

615

ent) was used to recover tartaric acid and lactic acid by Marinova
et al. [31].
Active diluents that enhance the extracting power of amines
and phosphorus-bonded, oxygen-containing extractants are more
favorable than inactive diluents in the extraction of carboxylic
acids. Since earlier equilibrium studies on the reactive extraction of
propionic acid have been carried out using TBP in one diluent only
[18,25]. Also, conventional optimization routines, which have been
used for parameter estimation so far as reported in the literature,
do not guarantee the global optimum. In this equilibrium study, a
mixture of inert (n-decane) and active (1-decanol) diluent is used
to provide the appropriate physical properties of extractant (TBP)
with improved extraction efciency. 1-Decanol (modier) will also
be useful if a third phase is formed during the extraction process due
to the low solubility of acid-extractant complex in an inert diluent
(n-decane). A population-based search algorithm, differential evolution (DE), which has been successfully applied to many industrial
problems [3240], is employed as optimization routine to estimate
the optimum values of KE and n. Application of DE will provide more
accurate estimation of KE and n than that of any other method of
calculations (regression method). The effect of temperature on the
extraction efciency is found by varying the temperature in the
range of 298334 K. The resulting enthalpy and entropy of reactive
extraction are also estimated. The equilibrium results [experimental and theoretical (using DE approach)] of the reactive extraction
of propionic acid using TBP dissolved in n-decane/1-decanol (1:1,
v/v) will be useful to design the extraction process for the intensication of recovery of propionic acid from aqueous waste stream as
well as fermentation broths. TBP is much cheaper than the amine
based extractants such as TOA and Aliquat 336. The propionic acid
can be regenerated from the TBP and diluent system, and solvent
can be recycled to the extraction process to make the recovery
of acid economic viable. The use of reactive extraction with TBP
also will eliminate the environmental problems which arise due to
the recovery of acid by conventional processes (precipitation and
adsorption). In order to be able for applying the process intensication at commercial level, a thorough fundamental understanding at
laboratory level using batch experiments is essential. The present
study is a pointer in this direction.

2. Experimental
2.1. Reagents and solutions
Tri-n-butyl phosphate (TBP) was used as the extractant supplied by Spectrochem. Pvt. Ltd., India, with purity of 98%. TBP
is a light colorless liquid with the molar mass of 266.32 g mol1
and density of 0.975 g cm3 . n-Decane as an inert diluent [specic gravity = 0.73 g cm3 and viscosity = 0.92 cP (20 C)] with 99%
purity and 1-decanol as an modier [specic gravity = 0.83 g cm3
and viscosity = 11.83 cP (20 C)] with 98% purity were supplied by
Sd. Fine Chem. Ltd., India. Commercial grade kerosene [specic
gravity = 0.80 g cm3 and viscosity = 2.71 cP (20 C)] is also used as a
diluent. Propionic acid (pKa = 4.87), a colorless liquid with a pungent
odor was delivered by SigmaAldrich Co. USA as analytical grade
reagents (98%). Organic solutions were prepared by dissolving TBP
in the active and inert diluents. The initial TBP concentrations were
varied in the range of 0.552.92 kmol m3 . De-ionized water was
used to prepare the aqueous solutions of various concentrations
of propionic acid. Since propionic acid concentration in the fermentation broth and aqueous waste stream is found less than 10%
(w/w), the initial concentration of propionic acid in aqueous solutions was varied in the range of 0.1350.676 kmol m3 . NaOH used
for titration was of analytical grade (98%) and supplied by Merck
Pvt. Ltd., Germany. For the standardization of the NaOH solution,

616

S. Kumar et al. / Chemical Engineering and Processing 50 (2011) 614622

oxalic acid (99.8%) was obtained from Sd. Fine Chem. Ltd., India.
Phenolphthalein solution (pH range 8.210.0) used as an indicator
for titration, was obtained from Ranbaxy, India. All chemicals were
used without any pretreatment.

Due to the strong interactions between acid and extractant (TBP),

the physical extraction of propionic acid, acid dimerization and
water co-extraction are neglected. Extraction equilibrium of propionic acid using TBP as an extractant dissolved in the mixture of
active and inert diluents is represented as:

2.2. Procedure

mHP + nS (S)n (HP)m

The extraction equilibrium experiments were carried out at constant temperature (298 1 K) with equal volumes (16 cm3 of each
phase) of the aqueous and organic solutions shaken at 100 rpm
for 8 h in conical asks of 100 ml on a temperature controlled
reciprocal shaking machine (HS 250 basic REMI labs). Our preliminary studies had shown that 8 h of mixing time is sufcient
to reach equilibrium. After attaining equilibrium, the phases were
brought into contact with each other for separation for 2 h. The
effect of extractant (TBP) composition (0.552.92 kmol m3 ) in
the organic solutions was studied at various acid concentrations
(0.1350.676 kmol m3 ). In the study of effect of temperature, temperature was maintained constant in the shaking machine by a
water thermostat at four different values of 298, 313, 323 and 334 K.
The concentration of propionic acid in temperature study was kept
constant (0.405 kmol m3 ). The initial and equilibrium pH values
of aqueous solutions were measured using a digital pH-meter of
ArmField Instruments (PCT 40, Basic Process Module) which were
varied in the range of 2.452.92 and 2.743.42, respectively. After
settling, organic and aqueous phases were separated. The concentration of acid in the aqueous phase was determined by taking a
sample of 2 cm3 volume and using potentiometric titration with
fresh sodium hydroxide solution of 0.01 N and phenolphthalein as
an indicator. The repeatability in the acid concentration of aqueous
phase is checked for few experiments by taking a larger volume
of aqueous solution (10 mL) and found the results within the error
limit of 2%. The acid concentration in the organic phase was calculated by mass balance. The reproducibility was checked by carrying
out the experiments twice in some selected cases. The results were
found to be reproducible within 5%.
The extraction process is analyzed by means of the degree of
extraction and distribution coefcient. The distribution coefcient,
KD , is calculated using Eq. (1).

The equilibrium constant (KE ) is calculated using Eq. (4)

KD =

Vin CHP

in

VCHP

V CHP

C HP
=
CHP

(1)

KE =

(3)

[(S)n (HP)m ]

(4)

[HP]m [S]n

Propionic acid also dissociates under equilibrium in aqueous

phase as given by Eq. (5):
HP H + + P

(5)

The non-dissociated acid concentration in the aqueous phase [HP]

can be calculated with the relationships as given in Eqs. (68) using
the total (analytical) concentration (CHP ) and the dissociation constant (Ka ).
Ka =

[H + ][P ]
[HP]

(6)

CHP = [HP] + [P ]
[HP] =

(7)

CHP
(1 + Ka /[H + ])

(8)

The distribution coefcient is dened as:

KD =

C HC
[(S)n (HP)m ]
=m
CHC
CHP

(9)

Substituting the values of [HP] and [(S)n (HP)m ] from Eq. (8) and Eq.
(9), respectively in Eq. (4) results Eq. (10).
KE =

KD (1 + Ka /[H + ])

(10)

n m1
m[S] CHP

in the organic phase repreThe free extractant concentration ([S])

sented as:
[S] = [S]in n[(S)n (HP)m ]

(11)

= [S]
in KD nCHP /m
[S]

(12)

where the overbar refers to the organic phase, V is the volume of

the phase, CHP is the total concentration of propionic acid, subscript
in refers the initial condition, and the absence of subscript indicates aqueous solution after reaching equilibrium. The change in
the volume of both the phases was found negligible (maximum
phase volume of organic phase is found to be 16.5 ml after reaching
equilibrium). The values of KD are affected by 1% with assumption of negligible change in volume at equilibrium. It is seen that
mono-carboxylic acids carry less water with them than that of dicarboxylic acids, which may reect the tendency of co-extracted
water molecules to associate with the carboxylate group [41].
The degree of extraction is dened as the ratio of acid concentration in the extracted phase to the initial acid concentration in
aqueous solution by assuming no change in volume at equilibrium
as given by Eq. (2).

Using the Eqs. (10) and (12), Eq. (13) results in

KD
E=
100
1 + KD

log KD + log 1 +

(2)

3. Modeling section
Apparent equilibrium extraction constants, expressed in terms
of species concentrations are used. It may be possible that some
amount of acid is extracted by pure diluents (physical extraction).

in KD n
KD = mKE [S]

CHP
m

n

CHP n1
(1 + Ka /[H + ])

(13)

and above equation, in logarithmic form is presented by Eq. (14).

log KD + m log(1 + Ka /[H + ]) = log m + log KE

in KD n
+ n log [S]

CHP
m

+ (m 1) log CHP

(14)

If n molecules of TBP per molecules of acid make complex, the

extraction equilibrium is represented as
HP + nS (S)n HP

(15)

For the case of m = 1, Eq. (14) can be written as:

Ka
[H + ]

in n[HP(S)n ])
= log KE + n log([S]

(16)

Due to apparition of n under logarithm, an optimization procedure

in  n[HP(S)n ], the initial
for estimation of n and KE is applied. If [S]
in can also be used to determine n and
extractant concentration [S]
KE .
The extent to which the organic phase (extractant and diluents)
may be loaded with acid is expressed by the loading ratio, Z (ratio

S. Kumar et al. / Chemical Engineering and Processing 50 (2011) 614622

of total acid concentration in the organic phase to the total TBP

concentration) as given by Eq. (17)
Z=

C HP
in
[S]

(17)

The stoichiometry of the overall extraction equilibrium is dependent on the loading ratio in the organic phase, Z. If the organic phase
is not highly concentrated by acid, i.e., at very low loading ratios
(Z < 0.5), 1:1 complex of acid and TBP is formed. A plot of Z/(1Z)
versus [HP] yields a straight line with a slope of complexation constant (KE1 ) as given by Eq. (18). Eq. (18) is the special case of Eq. (13)
with m = 1 and n = 1 and no dissociation considered, but in terms of
loading ratios.
Z
= KE1 [HP]
1Z

(18)

3.1. Differential evolution approach

During the last two decades there has been a growing interest in algorithms, which are based on the principle of evolution
(survival of the ttest). The best-known algorithms in this class
include Genetic Algorithm, Differential Evolution, Evolutionary
Programming, Evolution Strategies and Genetic Programming. A
brief review of the evolutionary computation techniques is also
presented by Babu [32], and Onwubolu and Babu [33]. Differential
Evolution (DE) is a generic name for a group of algorithms that are
based on the principles of Genetic Algorithm (GA) but have some
inherent advantages over GA. DE algorithms are very robust and
efcient and they are able to nd the global optimum of a function
with ease and accuracy. DE algorithms are faster than GAs. GAs
evaluate the tness of a point to search for the optimum. In other
words, GAs evaluate a vectors suitability. In DE, this vectors suitability is called its cost or prot depending on whether the problem
is a minimization or maximization. In GAs only integers are used
and there is coding in binary format while in DE, there is no coding involved and oating point numbers are directly used. In GAs
when mutation is performed, bits are ipped at random with some
mutation probability. This is essentially an XOR operation. In DE,
direct addition is used.
3.2. DE at a glance
As already stated, DE in principle is similar to GA. So, as in GA,
we use a population of points in our search for the optimum. The
population size is denoted by NP. The dimension of each vector is
denoted by D. The main operation is the NP number of competitions
that are to be carried out to decide the next generation. To start
with, we have a population of NP vectors within the range of the
objective function. We select one of these NP vectors as our target
vector. We then randomly select two vectors from the population
and nd the difference between them (vector subtraction). This difference is multiplied by a factor F (specied at the start) and added
to a third randomly selected vector. The result is called the noisy
random vector. Subsequently, crossover is performed between the
target vector and the noisy random vector to produce the trial vector. Then, a competition between the trial vector and the target
vector is performed and the winner is replaced into the population.
The same procedure is carried out NP times to decide the next generation of vectors. This sequence is continued till some convergence
criterion is met.
However, certain guidelines and heuristics are available for the
choice of these parameters [32,33]. NP should be 510 times the
value of D (dimension of the problem). Initially F = 0.5 is recommended. If this leads to premature convergence, then F needs to be
increased. The range of F is 01.2 but the optimal range is 0.41.0.

617

Values of F < 0.4 and F > 1.0 are seldom effective. CR = 0.9 is a good
rst guess. CR = 0.9 is to be tried rst and then CR = 0.1 to be tried.
Judging by the speed, a value of CR between 01 is to be chosen.
Based on these heuristics, the values of DE key parameters for the
present problem are set as NP = 20, 30; CR = 0.9; F = 0.5.
3.3. Steps in DE
Assume that the objective function, which is to be minimized,
has D dimensions. The weighting constant F and the crossover constant CR are specied. Steps used in DE are given in Fig. 5.
4. Results and discussion
Organophosphorous compounds are effective extractants and
provide higher distribution coefcients than that of carbon bonded
oxygen bearing extractants. The chemical stability of organophosphorous compounds plays an important role in the possibility of its
use as an efcient extractant with good separation efciency. TBP,
an organophosphorous compound, contains a phosphoryl group
(>P = O) which serves as a stronger Lewis base for its high polarity.
This leads to a high degree of extraction. TBP is selected because
of its low water co-extraction (4.67% by weight at 20 C) and very
low solubility in the aqueous phase (0.04% by weight at 20 C).
TBP is soluble in common organic solvents such as aliphatic, aromatic and chlorinated hydrocarbons, alcohols, esters, ketones, and
glycol ethers. Due to the presence of both electron donor and electron acceptor groups in P(O)OH grouping, it undergoes specic
interactions like self-association and molecular complex formation
with diluents or other solutes. Phosphorus-bonded oxygen-bearing
extractants such as TBP and TOPO are used for the extraction of
carboxylic acids by solvation with higher specicity [12]. So, the
higher concentration of TBP will be able to extract more acid in
the organic phase. High concentration of these organophosphorus
extractants are also used by various researchers [18,19,23,25] in
the equilibrium studies of the reactive extraction of acids. Because
of its toxicity and not to be food grade, TBP is not recommended
for the in situ recovery of products in the biological systems. These
equilibrium data can be used to design the extraction system for
the recovery of propionic acid from fermentation broth which may
employ the membranes to have the separation of biomass and the
product. The data obtained in this study are also useful in the extraction of acid from waste water streams.
Since TBP has a relatively high viscosity (3.56 103 Pa s) and
density close to unity (0.975 g cm3 ), it is used along with diluents,
which facilitate good phase separation in the continuous extraction
process. Diluents chosen in the study are n-decane and kerosene
from inactive chemical class, and 1-decanol as modier from active
chemical class to examine the effect of diluent-complex interactions. These interactions are found to affect the stoichiometry of
reaction and magnitude of the corresponding equilibrium constants. When TBP is used as an extractant in a mixture with an
inert diluent and an active diluent (modier) in reactive extraction, then the solubility of extracted species increases in the
organic phase. Hence, the degree of extraction of propionic acid
increases with an increase in the concentration of 1-decanol (modier) in the mixture of TBP and diluents as shown in Fig. 1. The
effect of 1-decanol on extraction efciency is found to be signicant with inert diluents (n-decane and kerosene). Hence, the
viscosity of modier (1-decanol) is higher than that of an inactive diluent, but water co-extraction decreases in the order of
alcohols (1-decanol) > ketones > chlorinated dilunets > inert hydrocarbons (n-decane), which is the same order as the solubility of
water in the diluent alone [41]. In our study, reciprocal shaking
machine with a speed of 100 rpm is used to attain the equilibrium in

618

S. Kumar et al. / Chemical Engineering and Processing 50 (2011) 614622

90

70

66
64
62
60
58
n-Decane
Kerosene

56

Degree of extraction, %

Degree of extraction, %

68

54
10

20

30

40

50

80

70

-3

50

60

0.5

% Decanol

0.6

[HP]org/kmol.m

-3

0.5

0.4

0.3
15% TBP
25% TBP
40% TBP
60% TBP
80% TBP

0.2

0.1
0.10

0.15

0.20

[HP]aq/kmol.m

1.5

2.0

2.5

0.25

0.30

0.35

-3

Fig. 2. Equilibrium isotherms of propionic acid for TBP dissolved in decane/1decanol (1:1 vol.%).

3.0

-3

Fig. 3. Effect of TBP concentration on extraction efciency at various propionic acid

concentration with n-decane/1-decanol (1:1 vol.%).

85

Degree of extraction, %

8 h. It is reported in the literature that equilibrium can be achieved

in less than 2 h using magnetic or mechanical stirrers [27,30]. The
mixture of modier, 1-decanol (higher viscosity), and inert diluent
(n-decane having a lower viscosity) results in a reduced equilibrium time. Since, kerosene and decane are used as inert diluents
with 1-decanol (modier) to see the effect of modier composition,
further equilibrium experiments are carried out using decane as an
inert diluent due to better extractability, lower viscosity and lower
toxicity as compared to kerosene. The equal volume mixture of ndecane and 1-decanol has been used to estimate the equilibrium
extraction constant (KE ) and the stoichiometry of reaction.
The isotherms for propionic acid, determined from six aqueous
solution concentrations and ve concentrations of TBP dissolved in
n-decane and 1-decanol (1:1 vol.%) are shown in Fig. 2. For a low
range of acid concentration, there is a linear relationship between
acid concentration in the two phases, and slightly nonlinear relationship for higher concentrations. It may be noted that for low
concentrations of propionic acid, Henrys law is valid, whereas at
higher concentrations, non-ideal behavior can prevail and causes
this deviation.
The experimental data as presented in Fig. 3 and Table 1 show
that when TBP concentration increases, the degree of extraction
(%) also increases and this increase in the degree of extraction
(%) is more signicant till a composition of 60% TBP. From Fig. 4
and Table 1, initial concentration of propionic acid also affects
the extraction efciency. The degree of extraction signicantly
decreases when the concentration of propionic acid is increased

0.05

1.0

Concentration of TBP/ kmol m

Fig. 1. Inuence of modier, 1-decanol (1060%) on degree of extraction with 25%

TBP at 0.405 kmol m3 initial propionic acid concentration.

0.00

0.135 kmol m
-3
0.270 kmol m
-3
0.405 kmol m
-3
0.540 kmol m
-3
0.676 kmol m

60

80

75

70
-3

2.923 kmol m
-3
2.192 kmol m
-3
1.462 kmol m
-3
0.913 kmol m

65

60
0.2

0.4

0.6

0.8

Initial acid concentration/ kmol m

1.0

-3

Fig. 4. Effect of initial acid concentration on extraction efciency with variable TBP
concentration in n-decane/1-decanol (1:1 vol.%).

from 0.135 to 0.676 kmol m3 . Different concentrations of TBP

have been used to derive the effect of initial acid concentration
on extraction efciency. The experimental values of equilibrium
concentrations of propionic acid in aqueous phase are in agreement with the results obtained by Keshav et al. [18]. They studied
extraction of propionic acid with TBP in the diluents (not used the
mixture of inert and active diluent). For the estimation of equilibrium extraction constant (KE ) and the stoichiometry [number of
extractant molecules (m) and acid molecule (n)], the theoretical
study has been performed in the modeling section [12] (Fig. 5).
Keshav et al. [18] have reported that the solvation number of the
aliphatic carboxylic acids is the same as the numbers of carboxyl
groups on each acid. This indicates a stoichiometric association
between the individual phosphoryl group and individual acid group
and displays the effect of acid concentration on the experimentally determined distribution ratio. A plot of Eq. (16) by taking,
in on x-axis yields a
log KD + log(1 + Ka /[H+ ]) on y-axis and log [S]
straight line with a slope of n and an intercept of log KE as shown
in Fig. 6. For the extraction equilibrium with TBP, the slopes of
the straight lines suggest the formation of solvates between one
molecule each of both the reactants. The slope (n) and the value of
equilibrium constant (KE ) for different initial acid concentrations
are given in Table 2.
An evolutionary optimization routine is also used to solve the
model Eq. (16) for the estimation of extraction equilibrium constants (KE ) and the number of reacting extractant molecules (n).

S. Kumar et al. / Chemical Engineering and Processing 50 (2011) 614622

619

Table 1
Equilibrium results for the extraction of propionic acid using TBP dissolved in n-decane/1-decanol (1:1, v/v) at 298 K with various concentrations of TBP and acid.
Cin (kmol m3 )

in (kmol m3 )
[S]

CHP (kmol m3 )

C HP (kmol m3 )

KD, exp

KD, pred using DE

KD, pred using graphical method

0.135

0.913
1.462
2.192
2.923

0.046
0.036
0.027
0.021

0.089
0.099
0.108
0.114

65.57
73.52
79.87
84.64

1.9
2.78
3.97
5.51

1.87
2.85
4.06
5.18

1.69
2.7
3.99
5.23

0.270

0.913
1.462
2.192
2.923

0.096
0.073
0.055
0.043

0.174
0.197
0.215
0.227

64.51
72.99
79.61
84.24

1.82
2.7
3.9
5.35

1.81
2.76
3.94
5.02

1.54
2.53
3.83
5.1

0.405

0.913
1.462
2.192
2.923

0.148
0.116
0.084
0.064

0.257
0.289
0.321
0.341

63.46
71.4
79.17
84.11

1.74
2.5
3.8
5.29

1.71
2.66
3.81
4.89

1.4
2.39
3.67
4.93

0.540

0.913
1.462
2.192
2.923

0.201
0.159
0.116
0.088

0.339
0.381
0.424
0.452

62.73
70.61
78.55
83.78

1.68
2.4
3.66
5.17

1.65
2.57
3.66
4.66

1.25
2.23
3.5
4.76

0.676

0.913
1.462
2.192
2.923

0.256
0.202
0.147
0.114

0.42
0.474
0.529
0.561

62.11
70.1
78.24
83.07

1.64
2.34
3.6
4.91

1.62
2.51
3.54
4.48

1.11
2.07
3.33
4.59

Fig. 5. Steps used in DE.

A population based search algorithm called differential evolution

(DE), which is simple and robust and has a proven successful record
for various engineering applications in both single- and multiobjective optimization [3240], is employed. An objective function
based on least square error between experimental and predicted
value of log KD + log(1 + Ka /[H+ ]) has been minimized. Similarly Eq.
(14) is solved to determine the stoichiometry [values of number of
acid molecule (m) and number of extractant molecule (n) in the formation of acid:TBP complexes] and equilibrium extraction constant
(KE ) as given in Table 3.
Table 2 presents the calculated values of KE and n, the modeling
results of equilibrium experiments carried out with different initial

Table 3
Values of Equilibrium extraction constant (KE ) and the number of reacting extractant molecules (m and n) with TBP as an extractant with different concentration of
propionic acid using DE (optimization procedure).
Diluents

in (kmol m
[S]

nDecane/1decanol
(1:1 vol.%)

0.548
0.913
1.462
2.192
2.923

KE

1.24
1.31
1.30
1.39
1.49

1
1
1
1
1

3.83
3.75
3.29
3.34
3.38

Table 2
Values of equilibrium extraction constant (KE ) and the number of reacting extractant molecules, TBP (n) with different concentrations of propionic acid.
Diluents

Cin (kmol m3 )

nDecane/1decanol
(1:1 vol.%)

0.135
0.270
0.405
0.540
0.676

Using graphical method (Fig. 6)

Using DE

KE

R2

SD

KE

SD

2.05
1.99
1.83
1.77
1.74

0.93
0.93
0.97
0.97
0.95

0.998
0.999
0.993
0.993
0.946

0.21
0.24
0.30
0.37
0.42

2.21
2.27
2.28
2.30
2.33

0.85
0.81
0.80
0.76
0.72

0.20
0.20
0.25
0.31
0.27

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S. Kumar et al. / Chemical Engineering and Processing 50 (2011) 614622

1.5

1.0

0.8

1.2

0.6

0.9

Z/(1-Z)

log KD + log (1 + Ka/[H ])

-1

0.548 mol.L
-1
0.913 mol.L
-1
1.462 mol.L
-1
2.192 mol.L
-1
2.923 mol.L

0.4

0.6

-3

0.135 kmol m
-3
0.27 kmol m
-3
0.405 kmol m
-3
0.54 kmol m
-3
0.676 kmol m

0.2

0.0
-0.1

0.0

0.1

0.2

0.3

0.4

0.5

0.3

0.0
0.00

0.6

0.05

0.10

log [S]in

concentration of propionic acid. With higher initial acid concentration, the loading of acid on TBP molecule is increased. The obtained
results of KE and n, for TBP extractant using computational procedure are showing the better trend than that obtained by graphical
method using assumption of [S]in  n[HP(S)n ]. The assumption of
in  n[HP(S)n ] is not completely valid at higher concentrations
[S]
of propionic acid due to increased concentration of extractant (TBP)
in complex form. Therefore, the values of KE using graphical method
are found to be decreased with an increase in the concentration of
acid (Table 2). Using optimization approach (DE), the values of KE
are found to be almost constant with an increase in the concentration of acid (0.1350.676 kmol m3 ) due to higher concentration
range of TBP (0.5482.923). The KE values for the acid concentration range of 0.1350.676 kmol m3 are found to be decreased with
an increase in the concentration of TBP (Table 3). At higher concentration of TBP, free TBP concentration is increased more than that
of complex. It can be seen from Table 1, the predicted values of KD
using DE are closely matching with the experimental values of KD .
Active diluents, having higher dielectric constant also contribute
in the extraction of organic acid and result in a value of less than
one for stoichiometry coefcients (n). The dielectric constant may
be considered as an indicator of solventsolute local interactions,
inducing the limitation of solute solvation by solvent or extractant, due to the presence of ionizable groups in the solute chemical
structure. Therefore, the solvent polarity controls the extraction
constant through its inuence on separation efciency and mechanism.
Since propionic acid is used in the concentration range
of 0.1350.676 kmol m3 and TBP is diluted in the range of
0.5482.923 kmol m3 , the loading ratios are found to be low,
(Z < 0.5) except few values at low concentration of TBP. 1:1 complexes between acid and TBP are formed and Z/(1Z) versus [HP]
for the respective TBP concentrations are plotted to obtain the values of equilibrium complexation constant (KE1 ) as shown in Fig. 7.
Equilibrium extraction constant (KE1 ) for 1:1 complex of acid and
TBP at 298 K for the extraction of propionic acid with different concentrations of TBP dissolved in n-decane/1-decanol (1:1 vol.%) are
given in Table 4. For TBP concentration of 0.548 kmol m3 , the loading ratios are found to be slightly greater than 0.5 (0.55 and 0.68
for acid concentrations of 0.54 and 0.676 kmol m3 , respectively),
2:1 complexes between acid and TBP may also formed. Equilibrium
extraction constant (KE1 ) for 1:1 complex of propionic acid and TBP
at 298 K for the extraction of acid in the entire concentration ranges
of TBP (0.9132.923 kmol m3 ) and acid (0.1350.676 kmol m3 ) is
found to be 2.61 with coefcient of determination (R2 = 0.97) and
standard deviation (SD = 0.06) (refer Fig. 8).

0.20

0.25

0.30

0.35

-3

[HP]aq, kmol.m

Fig. 7. Plot of Z/(1Z) versus [HP] for the estimation of (1:1) propionic acid-TBP
equilibrium complexation constant (KE1 ) in n-decane/1-decanol (1:1 vol.%) with
different TBP concentration.
Table 4
Equilibrium extraction constant (KE1 ) for the extraction of propionic acid with various concentrations of TBP dissolved in n-decane/1-decanol (1:1 vol.%) from Fig. 8.
Diluents

in (kmol m
[S]

nDecane/1decanol
(1:1 vol.%)

0.548
0.913
1.462
2.192
2.923

KE1
4.38
3.03
2.29
2.11
2.10

0.36
0.13
0.04
0.02
0.01

SD ()

R2

0.122
0.050
0.010
0.005
0.002

0.985
0.991
0.998
0.999
0.999

1.0

0.8

Z/(1-Z)

Fig. 6. Graphical representation of Eq. (11) for determination of extraction constants (KE ) and apparent number of reacting molecule (n) using TBP dissolved in
n-decane/1-decanol (1:1 vol.%) with different initial acid concentration.

0.15

0.6

0.4

0.2

0.0
0.00

0.05

0.10

0.15

0.20

[HP]aq/kmol m

0.25

0.30

-3

Fig. 8. Plot of Z/(1Z) versus [HP] for the estimation of (1:1) propionic acid-TBP
equilibrium complexation constant (KE1 ) in the entire range of TBP concentrations.

4.1. Effect of temperature

The effect of temperature on the extraction of propionic acid
with 25% and 40% of TBP in n-decane/1-decanol (1:1 vol.%) is presented in Fig. 9. As the temperature increases, the percentage
amount of acid extracted decreases. In this concentration range
of propionic acid, the increase in the thermal energy disturbs
the interaction in the organic phase between TBP and acid, thus
decreasing the extraction. However, an improved separation of the
phases is observed. The temperature is maintained constant at four
different values (298, 313, 323 and 334 K).
From a thermodynamic point of view, the molecules of acid in
the organic phase are more ordered as they appear in the form of
complexes. Therefore, acid transfer from the aqueous phase as solvates to the organic phase increases the order and reduces entropy.
Generally the transfer of compounds from the aqueous phase to

S. Kumar et al. / Chemical Engineering and Processing 50 (2011) 614622

621

5. Conclusions
-3

1.462 kmol m
-3
0.913 kmol m

Distribution coefficient, K D

2.50
2.25
2.00
1.75
1.50
1.25
1.00
290

300

310

320

330

340

T/ K
Fig. 9. Inuence of temperature on extraction of propionic acid with TBP (0.913 and
1.462 kmol m3 ) diluted in n-decane/1-decanol (1:1 vol.%).
Table 5
Equilibrium extraction constant (KE ) and the number of reacting extractant
molecules, TBP (n) with different temperatures using DE.
Cin (kmol m3 )

Temperature
298
313
323
334

in (kmol m
[S]

0.405

0.5480.913

KE

2.93
2.59
2.30
1.62

1.10
1.06
1.08
0.80

the organic phase is accompanied by a decrease in entropy. If the

enthalpy and the entropy of this reaction assumed to be constant
over the temperature range, these can be estimated using Vant
Hoff Equation [(Eq. (19)]. DE approach is used to estimate the equilibrium extraction constant (KE ) and the number of reacting TBP
molecules (n) with the results of effect of temperature. The values
of KE and n are presented in Table 5. These KE values are used to
determine the H and S for the reaction.
ln KE =

H
S
+
RT
R

(19)

The slope and intercept of a plot of ln KE vs 1/T give the apparent

enthalpy and entropy of reactive extraction reaction respectively as
shown in Fig. 10 [41,42]. The results from Fig. 10 indicate that the
reactive extraction of propionic acid is exothermic as H is found
to be negative (12.47 kJ mol1 ). Similarly, the entropy for the acid
is found to be 32.42 J mol1 K1 . Based on the Eq. (19), the more
exothermic reaction, the more sensitive equilibrium is to change
with temperature.

1.2

1.0

ln KE

0.8

0.6

0.4
2.9

3.0

3.1

3.2

3.3
3

3.4

3.5

-1

1/T x 10 , K

Fig. 10. Determination of apparent enthalpy and entropy of reaction for the extraction of propionic acid with TBP diluted in n-decane/1-decanol (1:1 vol.%).

A population based search algorithm (Differential evolution) has

been successfully applied for the estimation of equilibrium constants and stoichiometric coefcients in the reactive extraction of
propionic acid with TBP dissolved in inert and active diluents. The
results also indicate that the reactive extraction occurs by means
of the formation of complexes between acid and extractant. The
extraction efciency of TBP increases with an increase in the concentration of active diluent (1-decanol). Different parameters such
as distribution coefcient, degree of extraction, loading ratio, and
equilibrium complexation constant are determined. With constant
concentrations of extractant in the organic phase, the obtained
values of degree of extraction depend on the initial aqueous acid
concentration. The overall distribution coefcient (KD ) and degree
of extraction (%) increases with increasing TBP concentration more
signicantly till 60% of TBP. More exact values of KE and n have been
obtained when an evolutionary optimization routine (differential
evolution algorithm) is used to solve the model equations. Since
the loading ratios are found to be less than 0.5 in most of the cases,
no overloading is obtained and only 1:1 complexes of acid and TBP
are formed. However, in a few systems, in low concentration of TBP
and Z > 0.5, 2:1 complexes of acid and TBP may also form. Overall
equilibrium extraction constant (KE1 ) for 1:1 complex of propionic
acid and TBP at 298 1 K is found to be 2.61. The increase in temperature in the range of 298334 K affects the extraction equilibrium
signicantly. The enthalpy and entropy of reactive extraction are
found to be 12.47 kJ mol1 and 32.42 J mol1 K1 , respectively.
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