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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] .

phosphorous. After attaining equilibrium. oxygen containing extractants can only co-extract small amounts of water. To ensure concentration corresponds to time when samples were taken . both the phases are separated in centrifuge at speed 1400 rpm for 30 min.8]. Extractants such as hydrocarbon. The acid concentration in the organic phase is calculated by mass balance.02N NaOH solution and phenolphthalein as an indicator. Phosphorus-bonded. glass . separation of phases was carried out quickly and successively . 30 .2–10. 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. NaOH used for titration and phenolphthalein solution (pH range 8.1-dedocanol and di ethyl ether used as diluents. Reactive extraction is a separation process using the reactions between extractants and the materials extracted. kinetic experiments were performed until equilibrium .6]. used as extractant. 313. repeat the same procedure with 1-dedocanol & di ethyl ether at different temperatures. The concentration of the lactic acid in aqueous phase was determine by titration by using of 0. 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.8 Cm i.Lactic acid is a naturally occurring organic acid that can be produced by chemical synthesis or fermentation [1. 10 .d. which was establish until 120 min . Aqueous solutions of lactic acid are prepared using de-ionized water. Methods Effect of Temperature . oxygen-containing extractants have a phosphoryl group and a stronger Lewis basicity than those of carbon-bonded. Effective interfacial area was 36. The extraction equilibrium experiments are carried out at four different constant temperatures (298. 60 and 120 min . All compounds are used without any pretreatment.2. samples of aqueous phase ( 2 ml each ) were take out at 2 . Experimental Materials Tri-n-butyl phosphate. Kinetic experiment were carried out in 6.317 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 . After separation. Known volumes of organic and aqueous phases ( 20 ml each ) were taken and reactive extraction was carried out for a definite period .02 N of NaOH and . and Methyl iso propyl ketone (MIBK). Phosphorus-bonded. Kinetic Studies . the aqueous phase is analyzed to determine the concentration of acid by titration using fresh 0. and show low solubilities in water [911]. oxygen-containing extractants.0) was used as an indicator for titration. and aliphatic amine extractants are mainly used in the reactive extraction of carboxylic acids [7.

796 0.674 0.335 0.522 0.345 1.584 0.46 0.517 0. Results and Discussion Effect of Temperature .014 50.517 0.1 0.505495 33.4 0.395 0.252 0.504 0.685 0.86 0.9 0.32 0.69 0.35 0.78 dedocanol 0.39 1. The results of the reactive extraction of lactic acid by using tri butyl phosphate dissolved in different diluents such as MIBK.861 46.41 0.014 50. 1-dedocanol and di ethyl ether.685 0.27 41.16 0.950943 48.82 0.254 0. Diluents chosen in the study are MIBK .977011 55.265 0.175 1.257 0.86 0.74 0.36 0.888 47.86 0.517 0.297 56. it is used along with diluents.479 0.335 0.335 0. KE1 Temp.019 50. When TBP was used as an extractant in a mixture with diluent.158 1.35 0.26 0.508 0.435 0.796 0.165 0.45 0.364 0.67 0.462 0.911 47.335 0.34 0.17 1.85 0.63 0.367347 26.861 0.197 0.316 0.45 0.5 0.41 0.37 0.86 0.98 49.7 0.36 0.15 0. Table 1 Equilibrium results for the extraction of the lactic acid by using TBP (0.335 0.699725 41.79 0.245 0.345 1.68 0.8 1- 0.57 0.517 0.223 49.398 0.86 0.425 1.29 0.5 mol/Lit) dissolved in MIBK .18 MIBK Di ethyl ether MIBK 1dedocanol Di ethyl ether Concentration.03 50.413 2. 1-dedocanol & di ethyl ether at different temperatures. it was observed from experiment runs that degree of extraction decreases with increasing the temperature of the system .292 1.483 0.23 0.155 0.117 25 3.058 0.344 57.95 48.34 0. C 2.615 38.98 g cm-3).34 0.093 52.517 0. 1-dedocanol & di ethyl ether is listed in Table 1. which could facilitate good phase separation in the continuous extraction process.86 0. Diluents Initial [HA]aq [HA]org KD E% Z 0. Since TBP has a relatively high viscosity (3.642 2.72 0.006 40 .47 0.84 45.685 0.361 2. So.335 0.56 x 10 -3 Pa s) and density close to unity (0.09 0.86 0.69 0.019355 50.86 0. then the solubility of extracted species increased in the organic phase.261 1.517 0.185 0.514 0.345 0.714 2.985507 49.465 0.685 0.72 46.93 0.238 0.phenolphthalein used as indicator and the concentration of the lactic acid in the organic phase was determine by material balance .398 0.7 0.233 0.394 0.455 0.685 0.16 0.352 0.86 0.685 0.34 0.363 0.462 0.27 0.256 0.225 0.

634146 38.8 0.436 0.86 0. the increase in the thermal energy disturbs the interaction in the organic phase between TBP and acid. 313.335 0.498 dedocanol 0.465 0.5 0.638 38.34 0.517 0.335 0.67 40.86 0.5 0.145 0. thus decreasing the extraction.43 0.305 0.335 0.330097 24.6 0.365 0.18 0. For the concentration range of lactic acid.144 0.712 1.335 0.03 0.17 0.054 Di ethyl ether MIBK Di ethyl ether 1.685 0.325 0.286 0. If the enthalpy and the entropy of this reaction assumed to be constant over the temperature range.1906 0.955 0.087 0.231 0.36 0.517 0.13 0.249 0.215 0.86 0.052 0.82 0.MIBK 0.685 0.68 0.302 0.087662 8.05 0.288 0.111828 10.61 0.86 0.32 0.308 0. Thus.152 0.685 0.14 60 1.335 0.685 0.72 41.098361 8.7 0.19 0.27 0.58 0.606 1- 0.525 0.55 dedocanol 0.86 46. acid transfer from the aqueous phase as solvates to the organic phase increases the order and reduces entropy.685 0.41 0. .517 0.25 0.625 0.198 0.29 0.235 0.644359 39.47 0. From a thermodynamic point of view the molecules of acid in the organic phase are more ordered as they appear as a complex.409836 29.517 0.14 0. an improved separation of the phases was observed.55 0.378 27.284 0.408 1.275 0. The temperature is maintained constant at four different values (298.145 0.06 0.487 0.027 0.46 0.77 43.41 0.059 0.205 0.462 0.8 0.9 0.06 0.557 0.16 0.674 0.497 50 1. 1).202326 16.335 0.571101 36.002 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 .357 0.31 0.86 0.376 27.8 44.43 0.303 0.104 0.36 0. However.4 0.186 0.304 0.ΔH Ln KE = ΔS + RT R (1) .337 0.26 0.275 0.155 0.23 0.406571 28.138 1.670732 40. 323 and 333 K). these can be estimated using Van’t Hoff Equation (Eq.755509 43.9 0.86 0.685 0.515 0.543986 35.416438 29.174 0.517 0.396 0.26 0.711921 41.517 0.335 0.03 0.81 0.72 0.67 40.523 0.35 0.67 1- 0. Generally the transfer of compounds from the aqueous phase to the organic phase is accompanied by a decrease in entropy.

4 0.0029 0.0032 0. MIBK 1.3986 R² = 0.8 0. 1-dedocanol & di ethyl ether .985 R² = 0.5 0 0. 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 . .0034 1/T.6 0.5 0.003 0.K 1-dedocanol 1. Determination of apparent enthalpy and entropy of reaction for the extraction of lactic acid with TBP (0.5x .2 0 0.0032 0.0031 0.0033 0.4 0.0032 0.The slope and intercept of a plot of ln KE vs.8 0.3x .10.9173 ln(KE) 1 0.4081 R² = 0.2 y = 1925.003 0.003 0.5.0033 0.0029 0.6 0.588 0.5.K Di Ethyl Ether 1.0034 1/T .0029 -0.0034 1/T .0031 0.2 0 0.9687 ln (KE) 1 0.0033 0.5 y = 3635x .2 ln(KE) 1 y = 1888. K Figure 1 .0031 0.5 kmol m-3) diluted in MIBK . 1/T give the apparent enthalpy and entropy of reactive extraction reaction respectively as shown in Figure 1.

177 ) with respect to TBP ( Figure 5 ). And the rate constant was found from equation (3) as 0. rate of reactive extraction is RA = Kmn ( [HA*]m[S0]n ) (3) Where Kmn is reaction rate constant [ min-1(mol. Regression analysis of the experimental data yielded rate of reaction to be ( n = 1.287 Kinetic studies . [S0] is concentration of TBP in bulk of solution [mol. rate equation and method of describing reaction regime were given .3. mol−1 ) -1. Enthalpy and Entropy at different diluents .737. ii) Slow Reactions .s-1 . Doraiswamy and Sharma (1984) classified mass transfer with reaction into four regime : i) Very Slow Reactions .635 Diluents MIBK 1-dedocanol Di ethyl ether Entropy (J mol−1 K−1 ) .317 Cm2 ) and multiplied by the volume of aqueous phase ( V ) to obtain the specific rate of the reaction V d[HA] A 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. n is reaction order with respect to TBP .0037 (lit/mol)0.1.44.962 .87 . Initial rate was obtained by regression analysis .56 ) with respect to acid ( Figure 4 ) and ( m = 0. m is the reaction order with respect to acid . For slow reaction .91.925 . For each regime .Table 2 . 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. This way divided by total interfacial area ( A = 36. and iv) Instantaneous Reactions .lit -1] . [HA*] is equilibrium concentration of lactic acid in the organic phase (mol.lit -1) .lit -1)1-(m+n)] . Plot of concentration versus time were drawn to obtain initial rate for various concentrations of acid and tri butyl phosphate ( TBP ) respectively .888 .44. With a mass balance about the aqueous phase. iii) Fast Reactions . Enthalpy (kJ.

15 0. time with deferent concentration of TBP .25 0. Lactic acid concentration in aqueous phase vs. TBP concentration vs.4 [S]= 0.05 0 0 50 100 150 Time (min) Figure 2 .5 0.min) 0.1 0. .1 0 0 50 100 150 [S].45 [HA] .3 mol/lit 0.335 mol/lit 0.517 mol/lit 0. time with different initial concentration of lactic acid 0.3 [S]= 0.0.86 mol/lit 0.2 [S] = 0.9 mol/lit 0.685 mol/lit 0.7 mol/lit [S] = 0. mol/lit Figure 3 . mol/lit 0.5 0.6 R A mol/(lit.35 0.4 0.2 0.3 0.5 mol/lit 0.

001 y = 0.000136 0.0006 0.00012 0 0.000138 RA .9552 0.1 0.4 0.1.0.4 0.9681 0.0002 R² = 0.888 kJ mol−1 and . mol/(lit.1 0.2 0.00013 0. The enthalpy and entropy of reactive extraction are found to be −1.000122 0.925 kJ mol−1 and −44.000134 0. Conclusion Different parameters like distribution coefficient.mol/lit Figure 5.0001 R² = 0.0008 0.0005 0.962 Jmol−1 K−1 by using 1-dedocanol as diluent and – 3.3 0.3 0.287 Jmol−1 K−1 by using di ethyl ether as diluents respectively where the negative sign of the enthalpy is mean that the .0009 R A . 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 . Effect of TBP concentration on specific rate of extraction for reactive extraction of lactic acid with TBP in Di ethyl ether .2 0.000124 0.0025x .0001 0 0 0.min) 0. The increase in temperature in the range of 298 – 333 K affects the extraction equilibrium significantly.000128 0. .000126 0. mol/lit Figure 4.00014 y = 4E-05x + 0.0002 0.635 kJ mol−1 and – 91.5 [HA*] .6 0.8 [S] .87 Jmol−1 K−1 by using MIBK as diluents . and equilibrium complexation constants are determined.mol/(lit.7 0. degree of extraction.5 0.44.0004 0. As the temperature increases.000132 0. 0.0003 0.0007 0. the percentage amount of acid extracted is found to decrease and degree of extraction decrease and KE1.min) 0.0.

Romanian Biotechnological Letters Vol. n-Butanol as an Extractant for Lactic Acid Recovery. Dordrecht. Engineering and Technology 80 2011. 15. Mathematical modeling of p-aminobenzoic acid reactive extraction without and with phase modifier . Netherlands (1990) pp.Shinde .0037 (lit/mol)0. I would like to express my gratitude to my guide Mrs. Dairy J.E.C. Current research on the genetics of lactic acid production in lactic acid bacteria. Kluwer Academic Publishers. 1–61. for her support throughout my research work.737.J. K.Kailas L Wasewar and Shri Chand . August 2009 . And the rate constant was found from equation (3) as 0.R. Biotechnological Production of Lactic Acid and Its Recent Applications. Hillier. 6: 386-394. Chem. 2001. New extraction techniques on bioseparation . B. [8] Dan Cascaval and Anca-Irina Galaction .. [2] Kanungnit Chawong. 58 (9)375-386 (2004). Hong. Acknowledgement First. [6] Yeon Ki Hong. Babu . Estimation of equilibrium parameters using differential evolution in reactive extraction of propionic acid by tri-n-butyl phosphate . Lett. pp. No. [5] H. S.N. Llanos. [4] B. 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. Her guiding light was the most important source of my accomplishment. and Dong Hoon Han . References [1] Young-Jung Wee. R. 708-713 . [7] Hong.reaction between the lactic acid and the organic phase (extractant and diluents ) is exothermic . Int. Babu . and Panarat Rattanaphanee . Application of Reactive Extraction to Recovery of Carboxylic Acids. W.Reactive extraction of propanoic acid using Aliquate 336 in MIBK : Linear salvation energy relationship (LSER) modeling and kinetics study . Ind. 22: 871-874. . H. Redman. B. Won Hi Hong. M. N. [10] Amit Keshav . Benninga: A History of Lactic Acid Making. and H. Dipaloy Datta. [9] Sushil Kumar. for her patience.56 ) with respect to acid and ( m = 0. Cancilla.177 ) with respect to TBP .V. World Academy of Science. Y. 5 (1995) 763– 784. N. interest and guidance. Biotechnol. ANCA-IRINA GALACTION. V. Influence of Temperature on Reactive Extraction of Propionic Acid using Tri-n-butyl Phosphate (TBP) dissolved in Inert Diluents and 1-Decanol . Chang (2000) Selective extraction of succinic acid from binary mixture of succinic acid and acetic acid.L. Journal of scientific & Industrial Research vol.s-1 . A.2. Davison. Jin-Nam Kim and Hwa-Won Ryu . 2010. Bioprocess Eng. [3] DAN CASCAVAL. Chemical Engineering and Processing 50 (2011) 614– 622. [11] Sushil Kumar. LENUŢA KLOETZER . 68 . Biotechnol.