Hussein Salih Hussein a* , S.N.

Shinde b
a

Master Student in Chemical Engineering , Chemical Engineering Department, Bharati Vidyapeeth

Deemed University College of Engineering , Pune ,India
Phone: +91- 9673181787
Email: alali.hsh@gmail.com
b
Professor, Chemical Engineering Department, Bharati Vidyapeeth Deemed University College of
Engineering, Pune ,India
Phone : + 91- 7875089217
Email : snshinde@bvucoep.edu.in
* Corresponding Author

Abstract This paper deals with lactic acid extraction by using tri-n-butyl phosphate (TBP) extractant
dissolved in diluents (Methyl ether di ketone (MIBK) , 1-dedocanol & di ethyl ether ) at different
temperatures range (298 ,313,323,333K) and the kinetic studies for the reactive extraction of lactic acid
with tri butyl phosphate (TBP) dissolved in di ethyl ether to determine the rate of reaction of lactic acid
where the order of reaction with respect to acid is ( m = 1.56 ) and the reaction order with respect to
TBP is ( n = 0.177 ) while the reaction rate constant is ( Kmn = 0.0037 (lit/mol)0.737.s-1) where the
extraction is carried out at 25 0C . Chemical equilibrium experiments have been carried out to
investigate the effect of temperature on the extraction efficiency of tri-n-butyl phosphate (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 of reactive extraction. The
apparent enthalpy and entropy of the reactive extraction with systems (TBP/MIBK , TBP/1-dedocanol
TBP/di ethyl ether) are also determined.
Keywords: Lactic acid; Reactive extraction; tri-n-Butyl phosphate (TBP); Diluents; Extraction
efficiency; Temperature and kinetics .
Introduction
Lactic acid, 2-hydroxypropionic acid, is the simplest hydroxy acid and is predominantly produced by
fermentation in the industry [ 1-3 ] . Lactic acid has a long history of uses for fermentation and
preservation of human foodstuffs [4] It was first discovered in sour milk by Scheele in 1780, who
initially considered it a milk component. In 1789, Lavoisier named this milk component acid lactique,
which became the possible origin of the current terminology for lactic acid. In 1857, however, Pasteur
discovered that it was not a milk component, but a fermentation metabolite generated by certain
microorganisms [5,1,3] .

Lactic acid is a naturally occurring organic acid that can be produced by chemical synthesis or
fermentation [1,2,6]. Reactive extraction is a separation process using the reactions between extractants
and the materials extracted. The extractant in the organic phase reacts with the material in the aqueous
phase and the reaction complexes formed are then solubilized in the organic phase. Extractants such as
hydrocarbon, phosphorous, and aliphatic amine extractants are mainly used in the reactive extraction of
carboxylic acids [7,8].
Phosphorus-bonded, oxygen-containing extractants have a phosphoryl group and a stronger Lewis
basicity than those of carbon-bonded, oxygen-containing extractants. Phosphorus-bonded, oxygen
containing extractants can only co-extract small amounts of water, and show low solubilities in water [911].
Experimental
Materials
Tri-n-butyl phosphate, used as extractant, and Methyl iso propyl ketone (MIBK),1-dedocanol and di
ethyl ether used as diluents. All compounds are used without any pretreatment. Aqueous solutions of
lactic acid are prepared using de-ionized water. NaOH used for titration and phenolphthalein solution
(pH range 8.210.0) was used as an indicator for titration.
Methods
Effect of Temperature . The extraction equilibrium experiments are carried out at four different constant
temperatures (298, 313, 323 and 333 K) with equal volumes (20 cm3 of each phase) of the aqueous and
organic solutions mixed in conical flasks of 100 mL and shake them for 2hrs. After attaining
equilibrium, both the phases are separated in centrifuge at speed 1400 rpm for 30 min. After separation,
the aqueous phase is analyzed to determine the concentration of acid by titration using fresh 0.02N
NaOH solution and phenolphthalein as an indicator. The acid concentration in the organic phase is
calculated by mass balance. repeat the same procedure with 1-dedocanol & di ethyl ether at different
temperatures.
Kinetic Studies . Kinetic experiment were carried out in 6.8 Cm i.d. glass . Effective interfacial area was
36.317 Cm2 and magnetic stirrer is used to stir the solution of aqueous phase and organic phase where
the temperature of the solution is 25 0C . Known volumes of organic and aqueous phases ( 20 ml each )
were taken and reactive extraction was carried out for a definite period . samples of aqueous phase ( 2
ml each ) were take out at 2 , 10 , 30 , 60 and 120 min . kinetic experiments were performed until
equilibrium , which was establish until 120 min . To ensure concentration corresponds to time when
samples were taken , separation of phases was carried out quickly and successively . The concentration
of the lactic acid in aqueous phase was determine by titration by using of 0.02 N of NaOH and

phenolphthalein used as indicator and the concentration of the lactic acid in the organic phase was
determine by material balance .
Results and Discussion

Effect of Temperature . 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 MIBK , 1-dedocanol and di ethyl ether.
When TBP was used as an extractant in a mixture with diluent, then the solubility of extracted species
increased in the organic phase. So, it was observed from experiment runs that degree of extraction
decreases with increasing the temperature of the system . The results of the reactive extraction of lactic
acid by using tri butyl phosphate dissolved in different diluents such as MIBK, 1-dedocanol & di ethyl
ether is listed in

Table 1.

Table 1 Equilibrium results for the extraction of the lactic acid by using TBP (0.5 mol/Lit) dissolved in
MIBK , 1-dedocanol & di ethyl ether at different temperatures.
Diluents

Initial

[HA]aq

[HA]org

KD

E%

0.86

0.45

0.41

0.911

47.674

0.82

0.685

0.34

0.345

1.014

50.364

0.69

0.517

0.256

0.261

1.019

50.483

0.522

0.335

0.16

0.175

1.093

52.238

0.35

0.86

0.45

0.4

0.888

47.058

0.8

1-

0.685

0.29

0.39

1.344

57.352

0.78

dedocanol

0.517

0.225

0.292

1.297

56.479

0.584

0.335
0.86

0.15
0.435

0.185
0.425

1.233
0.977011

55.223
49.41

0.37
0.85

0.685

0.345

0.34

0.985507

49.63

0.68

0.517

0.265

0.252

0.950943

48.74

0.504

0.335

0.155

0.158

1.019355

50.47

0.316

0.86

0.462

0.398

0.861

46.27

0.796

0.685

0.35

0.335

0.95

48.9

0.67

0.517

0.26

0.257

0.98

49.7

0.514

0.335

0.165

0.17

1.03

50.7

0.34

0.86

0.465

0.395

0.84

45.93

0.79

0.685

0.34

0.345

1.014

50.36

0.69

0.517

0.32

0.197

0.615

38.1

0.394

0.86
0.86

0.462

0.398

0.5

0.36

0.861
0.72

46.27
41.86

0.796
0.72

0.685

0.455

0.23

0.505495

33.57

0.46

0.517

0.363

0.254

0.699725

41.16

0.508

0.335

0.245

0.09

0.367347

26.86

0.18

MIBK

Di ethyl
ether

MIBK

1dedocanol

Di ethyl
ether

Concentration.

KE1

Temp.
C

2.714

2.117

25

3.361

2.413

2.642

2.006

40

MIBK

0.86

0.5

0.36

0.72

41.8

0.72

0.685

0.36

0.325

0.77

43.7

0.6

0.517

0.286

0.231

0.8

44.68

0.462

0.335

0.18

0.155

0.86

46.26

0.31

0.86

0.525

0.335

0.638

38.9

0.67

1-

0.685

0.41

0.275

0.67

40.14

0.55

dedocanol

0.517

0.357

0.16

0.378

27.46

0.284

0.335
0.86

0.19

0.145

0.67

40.29

0.27

0.61

0.25

0.409836

29.06

0.5

0.685

0.487

0.198

0.406571

28.9

0.396

0.517

0.43

0.087

0.202326

16.82

0.174

0.335

0.305

0.03

0.098361

8.955

0.06

0.86

0.523

0.337

0.644359

39.186

0.674

0.685

0.41

0.275

0.670732

40.145

0.55

0.517

0.302

0.215

0.711921

41.58

0.43

0.335

0.1906

0.144

0.755509

43.03

0.288

0.86

0.557

0.303

0.543986

35.23

0.606

1-

0.685

0.436

0.249

0.571101

36.35

0.498

dedocanol

0.517

0.365

0.152

0.416438

29.4

0.304

0.335

0.205

0.13

0.634146

38.8

0.26

0.86

0.625

0.235

0.376

27.32

0.47

0.685

0.515

0.17

0.330097

24.81

0.34

0.517

0.465

0.052

0.111828

10.05

0.104

0.335

0.308

0.027

0.087662

8.059

0.054

Di ethyl
ether

MIBK

Di ethyl
ether

1.712

1.497

50

1.138

1.408

1.14

60

1.002

From the results that listed in Table 1 we see that increase in temperature led to decrease in the degree of
extraction and distribution coefficient and KE1 . For the concentration range of lactic 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 was observed. The temperature is
maintained constant at four different values (298, 313, 323 and 333 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. 1).
- H
Ln KE =

S
+

RT

(1)

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 1. Table 2 indicate the results that obtained from
figure 1 for the enthalpy and entropy for reactive extraction of lactic acid by using tri butyl phosphate
dissolved in different diluents .

MIBK
1.2

y = 1925.3x - 5.3986
R = 0.9173

ln(KE)

1
0.8
0.6
0.4
0.2
0
0.0029

0.003

0.0031

0.0032

0.0033

0.0034

1/T,K

1-dedocanol
1.2

ln(KE)

y = 1888.5x - 5.4081
R = 0.588

0.8
0.6
0.4
0.2

0
0.0029

0.003

0.0031

0.0032

0.0033

0.0034

1/T ,K

Di Ethyl Ether
1.5
y = 3635x - 10.985
R = 0.9687

ln (KE)

1
0.5
0
0.0029

-0.5

0.003

0.0031

0.0032

0.0033

0.0034

1/T , K

Figure 1 . Determination of apparent enthalpy and entropy of reaction for the extraction of
lactic acid with TBP (0.5 kmol m-3) diluted in MIBK , 1-dedocanol & di ethyl ether .

Table 2 . Enthalpy and Entropy at different diluents .

Enthalpy
(kJ. mol1 )
-1.925
- 1.888
- 3.635

Diluents
MIBK
1-dedocanol
Di ethyl ether

Entropy
(J mol1 K1 )
- 44.87
- 44.962
- 91.287

Kinetic studies . Plot of concentration versus time were drawn to obtain initial rate for various
concentrations of acid and tri butyl phosphate ( TBP ) respectively . Initial rate was obtained by
regression analysis . This way divided by total interfacial area ( A = 36.317 Cm2 ) and multiplied by the
volume of aqueous phase ( V ) to obtain the specific rate of the reaction

d[HA]

dt

RA =

( R A, mol cm-2.min-1)

(2)
t=0

Doraiswamy and Sharma (1984) proposed a comprehensive study on the theory of extraction
accompanied with chemical reaction to determine the effect of chemical reaction on the specific rate of
mass transfer. Doraiswamy and Sharma (1984) classified mass transfer with reaction into four regime :
i) Very Slow Reactions ; ii) Slow Reactions ; iii) Fast Reactions ; and iv) Instantaneous Reactions . For
each regime , rate equation and method of describing reaction regime were given . For slow reaction ,
rate of reactive extraction is
RA = Kmn ( [HA*]m[S0]n )

(3)

Where Kmn is reaction rate constant [ min-1(mol.lit -1)1-(m+n)] , [S0] is concentration of TBP in bulk of
solution [mol.lit -1] , [HA*] is equilibrium concentration of lactic acid in the organic phase (mol.lit -1) , m
is the reaction order with respect to acid , n is reaction order with respect to TBP .
With a mass balance about the aqueous phase, the concentration of lactic acid versus time plot (Figure 2)
& ( Figure 3 ) determined the effect of acid concentration and effect of the TBP concentration on rate of
reaction RA. Regression analysis of the experimental data yielded rate of reaction to be ( n = 1.56 ) with
respect to acid ( Figure 4 ) and ( m = 0.177 ) with respect to TBP ( Figure 5 ). And the rate constant was
found from equation (3) as 0.0037 (lit/mol)0.737.s-1

0.5
0.45

[HA] , mol/lit

0.4

0.35
0.3

0.86 mol/lit

0.25

0.685 mol/lit

0.2

0.517 mol/lit

0.15

0.335 mol/lit

0.1
0.05
0
0

50

100

150

Time (min)

Figure 2 . Lactic acid concentration in aqueous phase vs. time with different initial concentration of
lactic acid

0.6

R A mol/(lit.min)

0.5
0.4
[S]= 0.3 mol/lit

0.3

[S]= 0.5 mol/lit

0.2

[S] = 0.7 mol/lit

[S] = 0.9 mol/lit

0.1
0
0

50

100

150

[S], mol/lit

Figure 3 . TBP concentration vs. time with deferent concentration of TBP .

0.001
y = 0.0025x - 0.0002
R = 0.9681

0.0009

R A , mol/(lit.min)

0.0008
0.0007
0.0006

0.0005
0.0004
0.0003
0.0002
0.0001
0
0

0.1

0.2

0.3

0.4

0.5

[HA*] , mol/lit

Figure 4. Effect of lactic acid concentration in organic phase on specific rate of extraction for
reactive extraction of lactic acid with TBP in Di ethyl ether .
0.00014
y = 4E-05x + 0.0001
R = 0.9552

0.000138
RA ,mol/(lit.min)

0.000136
0.000134
0.000132
0.00013
0.000128
0.000126
0.000124
0.000122
0.00012
0

0.1

0.2

0.3

0.4

0.5

0.6

0.7

0.8

[S] ,mol/lit

Figure 5. Effect of TBP concentration on specific rate of extraction for reactive extraction of lactic
acid with TBP in Di ethyl ether .

Conclusion
Different parameters like distribution coefficient, degree of extraction, and equilibrium complexation
constants are determined. 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 and degree of extraction decrease and KE1. The enthalpy and entropy of reactive extraction
are found to be 1.925 kJ mol1 and 44.87 Jmol1 K1 by using MIBK as diluents , - 1.888 kJ mol1
and - 44.962 Jmol1 K1 by using 1-dedocanol as diluent and 3.635 kJ mol1 and 91.287 Jmol1 K1
by using di ethyl ether as diluents respectively where the negative sign of the enthalpy is mean that the

reaction between the lactic acid and the organic phase (extractant and diluents ) is exothermic . and for
the kinetics of reactive extraction of lactic acid with TBP dissolved in di ethyl ether was found that the
rate of reaction to be ( n = 1.56 ) with respect to acid and ( m = 0.177 ) with respect to TBP . And the
rate constant was found from equation (3) as 0.0037 (lit/mol)0.737.s-1 .

Acknowledgement
First, I would like to express my gratitude to my guide Mrs. S.N.Shinde , for her support throughout my
research work, for her patience, interest and guidance. Her guiding light was the most important source
of my accomplishment.
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