Influence of Temperature on Reactive Extraction of Propionic Acid using

Tri-n-butyl Phosphate (TBP) dissolved in Inert Diluents and 1-Decanol

Sushil Kumara, B. V. Babub*
a

Lecturer, Chemical Engineering Group, Birla Institute of Technology and Science (BITS),
PILANI 333 031 (Rajasthan) India. Email: skumar@bits-pilani.ac.in
b
Dean- Educational Hardware Division & Professor of Chemical Engineering
Birla Institute of Technology and Science (BITS), PILANI 333 031 (Rajasthan) India
Phone: +91-01596-245073 Ext. 259; Fax: +91-01596-244183
Email: bvbabu@bits-pilani.ac.in
Homepage: http://discovery.bits-pilani.ac.in/~bvbabu
* Corresponding Author

Abstract: This paper deals with propionic acid extraction by tri-n-butylphosphate (TBP), a phosphorusbonded, oxygen-containing extractant dissolved in inert diluent (decane and kerosene) and a modifier (1decanol) at different temperature in the range of 298 K to 333 K. Active diluents (1-decanol) that enhance the
extracting power of amines and phosphorus-bonded, oxygen-containing extractants are more favorable than
inert diluents in the extraction of monocarboxylic acids, hydroxycarboxylic acids and dicarboxylic acids.
Chemical equilibrium experiments have been carried out to investigate the effect of temperature on the
extraction efficiency of tri-n-butylphosphate (TBP) as well as on the equilibrium extraction constant. It was
found that distribution coefficient, KD decreased with increasing the temperature. However, an improved
separation of the phases is observed. The extraction equilibrium constants have been determined using a
mathematical model (mass action law) of recative extraction, taking into account formation of (1:1), acid:amine
complexes. The apparent enthalpy and entropy of the reactive extraction with systems (decane/TBP/1-decanol
and kerosene/TBP/1-decanol) are also determined. These data will be useful in the design of extractive
fermentation processes for production of propionic acid.
Keywords: Propionic acid; Reactive extraction; tri-n-Butylphosphate (TBP); Diluents; Extraction efficiency;
Temperature.

Introduction
The recovery of organic acids from aqueous waste streams released from industries is
important and essential from the points of view of pollution control and recovery of useful
materials. In the recent past, the interest towards propionic acid recovery from fermentation
broths and aqueous effluents has increased. This interest is caused by the growing demand of
pure, naturally produced propionic acid used in chemical, pharmaceutical and food industries
[1]. Many separation processes in chemical industries have been employed to recover the
organic acids from aqueous solution. Reactive extraction is an efficient, economical, and
environmental friendly method for separation of acids from waste water streams and
fermentation broths because of the possibility of high selectivity for desired compounds [24].

Organophosphorus compounds and long-chain aliphatic amines are effective extractants for
the separation of carboxylic acids from dilute aqueous solution [5]. Phosphorus-bonded,
oxygen-containing extractants have a phosphoryl group and a stronger Lewis basicity than
those of carbon-bonded, oxygen-containing extractants. Phosphorus-bonded, oxygencontaining extractants can only coextract small amounts of water, and show low solubilities
in water. When organophosphorus extractants are used, the solvation has a higher specificity
[5]. Generally, organophosphorus-based and amine-based 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 removal and separation of organic acids,
it is very important to understand the influence of different parameters on the overall
distribution coefficient 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 nonpolar
diluents, as shown in the extraction of citric acid, lactic acid, and succinic acid. [6,7]
Such solvating extractants open new avenues in process development and reduce energy and
reagent consumption. Extraction of organic acids has been studied using trioctylphosphine
oxide and tri-n-butyl phosphate. 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. [8]. The
study has been made to examine the use of the organophosphine oxides, (Cyanex@921 and
Cyanex@923) for the extraction of formic, acetic and propionic acids from aqueous solutions
by Wisniewski and Piezchalska [9]. Wang et al. [10] have used Cyanex 923 in kerosene to
extract monocarboxylic acids and found that the distribution ratios increased with an increase
in the trialkylphosphine oxide concentration but decreased with the carboxylic acid
concentration in the aqueous phase.
Active diluents that enhance the extracting power of amines and phosphorus-bonded, oxygencontaining extractants are more favorable than inactive diluents in the extraction of
carboxylic acids. In this equilibrium study, a mixture of inert (n-decane) and active (1decanol) diluents are used to provide the appropriate physical properties of extractant (TBP)
and improved extraction efficiency. 1-decanol as modifier is also useful if a third phase is
formed during the extraction because of low solubility of acidextractant complex in the inert

diluent. The equilibrium experiments are also carried out at different temperatures in the
range of 298 334 K to derive the effect of temperature and to estimate the enthalpy and
entropy of reaction. The results of equilibrium experimental study are useful to design
extraction processes for recovery of propionic acid from aqueous stream using TBP dissolved
in n-decane/1-decanol (1:1 vol%).

Experimental Section
Reagents and Solutions
Tri-n-butyl phosphate (TBP) is used as the extractant supplied by Spectrochem. Pvt. Ltd.,
India, with purity of 98%. TBP, a phosphorus-bonded oxygen donor, is a light colorless
liquid with the molar mass of 266.32 g mol-1 and density of 0.975 g cm-3.

n-Decane of

analytical reagent grade and kerosene of a commercial grade are utilized as inactive diluent,
and 1-decanol with 98% purity, as modifier (active diluent). These diluents are supplied by
Sd. Fine Chem. Ltd., India. Propionic acid (pKa = 4.87), a colorless liquid with a pungent
odor was delivered by Sigma-Aldrich Co. USA as analytical grade reagents (98%). Organic
solutions are prepared using tri-n-butyl phosphate (TBP) as extractant dissolved in mixture of
active and inert diluents. The initial TBP concentrations were varied in the range of 0.923 and
1.462 kmol m-3. 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 is taken 0.405 kmol m-3. NaOH used for titration is of analytical
grade (98%) and is supplied by Merck Pvt. Ltd., Germany. For the standardization of the
NaOH solution, oxalic acid (99.8 %) was obtained from Sd. Fine Chem. Ltd., India.
Phenolphthalein solution (pH range 8.2 to 10.0) used as an indicator for titration is obtained
from Ranbaxy, India.
Procedure
The extraction equilibrium experiments are carried out at four different constant temperatures
(298, 313, 323 and 333 K) with equal volumes (16 cm3 of each phase) of the aqueous and
organic solutions shaken at 100 rpm for 8 hours in conical flasks of 100 mL on a temperature
controlled reciprocal shaking machine (HS 250 basic REMI labs). After attaining
equilibrium, the phases were brought into contact with each other for separation. The
concentration of propionic acid in temperature study is kept 0.405 kmol m-3. The

concentration of acid in the aqueous phase is determined by taking a sample of 2 cm3 volume
and using potentiometric titration with fresh sodium hydroxide solution of 0.02 N and
phenolphthalein as an indicator. 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 was analyzed by means of the degree of extraction and distribution
coefficient. The distribution coefficient, KD, is calculated using Eq. 1.

KD =

C HP
C HP

(1)

where, C HP is total (analytical) concentration of propionic acid in all its forms (by partition,
dimmers, and as complexes) in organic phase and C HP is total (analytical) concentration of
all its existing forms (dissociated and undissociated) in aqueous phase at equilibrium.
The degree of extraction is defined 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.

E=

KD
100
1+ KD

(2)

Results and Discussion

Since TBP has a relatively high viscosity (3.56 x 10-3 Pa s) and density close to unity (0.98 g
cm-3), it is used along with diluents, which could 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 modifier from active chemical class to examine the
effect of diluent-complex interactions. When TBP is used as an extractant in a mixture with
an inert diluent and an active diluent (modifier) in reactive extraction, then the solubility of
extracted species increases in the organic phase. So, degree of extraction of propionic acid
increases with increasing the concentration of 1-decanol (modifier) in the mixture of TBP and

diluents as shown in Figure 1. The effect of 1-decanol on extraction efficiency is found to be

significant with inert diluents, n-decane and kerosene. Hence the viscosity of modifier, 1decanol is high as compared to inactive diluents such as n-decane and kerosene. The equal
volume mixture of n-decane and 1-decanol is used to estimate the effect of temperature on
equilibrium extraction constant (KE) and degree of extraction.

70

Degree of extraction, %

68
66
64
62
60
58

n-Decane
Kerosene

56
54
10

20

30

40

50

60

% Decanol

Figure 1. Influence of modifier, 1-decanol (10 - 60%) on degree of extraction with 25% TBP
at 0.405 kmol m-3 initial propionic acid concentration.

Effect of Temperature
The effect of temperature on the extraction of propionic acid with 25% and 40% of TBP in ndecane/1-decanol (1:1 vol%) and in kerosene/1-decanol (1:1 vol%) are presented in Figures 2
and 3. 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 as a complex. Thus, 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 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. 3).

ln K E =

H S
+
RT
R

(3)

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 Figure 4. The results from Figure 4
indicate that the reactive extraction of propionic acid is exothermic as H is found to be
negative (5.65 kJ mol1). Similarly, the entropy for the acid is found to be 12.37 Jmol1
K1. Based on the Equation (5.1), the more exothermic reaction, the more sensitive
equilibrium is to change with temperature. Since the diluent system, n-decane/1-decanol (1:1
vol%) is found better than that of kerosene/1-decanol (1:1 vol%) based on equilibrium
results, apparent enthalpy and entropy of reactive extraction reaction are calculated only for
n-decane/1-decanol (1:1 vol%).

-1

1.462 mol L
-1
0.913 mol L

Distribution coefficient, KD

2.50

2.25

2.00

1.75

1.50

1.25

1.00
290

300

310

320

330

340

T/ K

Figure 2. Influence of temperature on extraction of propionic acid with TBP (0.913 and 1.462
kmol m-3) diluted in n-decane/1-decanol (1:1 vol%).

Degree of Extraction (%)

72

68

64

60

-1

1.462 mol.L
-1
0.913 mol.L

56
290

300

310

320

330

340

T, K

Figure 3. Influence of temperature on extraction of propionic acid with TBP (0.913 and 1.462
kmol m-3) diluted in kerosene/1-decanol (1:1 vol%).
1.1

1.0

ln KE

0.9

0.8

0.7

0.6
-1

0.913 mol.L
-1
1.462 mol.L

0.5
3.0

3.1

3.2
3

3.3

3.4

-1

1/T 10 [K ]

Figure 4. Determination of apparent enthalpy and entropy of reaction for the extraction of
propionic acid with TBP (0.913 and 1.462 kmol m-3) diluted in n-decane/1-decanol (1:1
vol%).

Conclusions
The extraction efficiency of TBP increases with the concentration of active diluent, 1-decanol
in the mixture of inert and active diluents. Different parameters like distribution coefficient,
degree of extraction, and equilibrium complexation constants are determined. Equilibrium
extraction constant (KE1) for 1:1 complex of propionic acid and TBP at 298 K is found to be

2.61. The increase in temperature in the range of 298 333 K affects the extraction
equilibrium significantly. As the temperature increases, the percentage amount of acid
extracted is found to decrease. The enthalpy and entropy of reactive extraction are found to
be 5.65 kJ mol1 and 12.37 Jmol1 K1 respectively.

References

1. Playne MJ, Propionic and butyric acids. in Comprehensive biotechnology, ed by MooYoung M, Pergamon, Oxford, New York, 3 (1985).
2. Wasewar KL, Separation of lactic acid: recent advances. Chem. Biochem. Eng. Q. 19: 159172 (2005).
3. Schugeri K, Solvent extraction in biotechnology. Springer-Verlag, Berlin (1994).
4. Kumar S and Babu BV, Process intensification for separation of carboxylic acids from
fermentation broths using reactive extraction. J. Fut. Eng. Technol. 3: 19-26 (2008).
5. Kertes AS and King C, Extraction Chemistry of fermentation product carboxylic acids.
Biotechnol. Bioeng. 28: 269-282 (1986).
6. Wasewar KL, Heesink ABM, Versteeg GF and Pangarkar VG, Equilibria and kinetics for
reactive extraction of lactic acid using Alamine 336 in 1-decanol. J. Chem. Technol.
Biotechnol. 77: 1068-1075 (2002).
7. King CJ, Advances in separation techniques: recovery of polar organics from aqueous
solution. 11th International Congress of Chemical Engineers Chisa, Prague, 2(1): 10621067 (1993).
8. Kumar S, Wasewar KL and Babu BV, Intensification of nicotinic acid separation using
organophosphorous solvating extractants: reactive extraction. Chem. Eng. Technol. 31:
1584-1590 (2008).
9. Wisniewski M and Pierzchalska M, Recovery of carboxylic acids C1C3 with
organophosphine oxide solvating extractants. J. Chem. Technol. Biotechnol. 80: 14251430 (2005).
10. Wang Y, Li Y, Wang J, Li Z and Dai Y, Extraction equilibria of monocarboxylic acids
with trialkylphosphineoxide. J. Chem. Eng. Data. 46: 831-837 (2001).