P. Kalaichelvi, M. Perumalsamy, A. Arunagiri, K.

Sofiya
291
Journal of the University of Chemical Technology and Metallurgy, 42, 3, 2007, 291-294
SYNERGISTIC EXTRACTION OF ACETIC ACID
FROM ITS AQUEOUS SOLUTION
P. Kalaichelvi, M. Perumalsamy, A. Arunagiri, K. Sofiya
National Institute of Technology,
Department of Chemical Engineering,
Trichirappalli-620 015, Tamilnadu, India
E- mail: kalai@nitt.edu
ABSTRACT
Iquu-quu cx:nan s c anc aI c snpcs nnu as cIIcvc scpn:nan ncau. 1n s va: c cx:nan
aI nc nu I:an nqucaus sauan l, usng c, ncnc nnu M1BK ns nuvuun nnu nsa ns n nxcu savcn vc:c
n::cu au a suu, c quu-quu cqul:un. Tc uIIc:cn Iccu ancn:nans aI nc nu vc:c suucu v
vn:aus anlnnans aI nxcu savcn. Tc :csu savs n c g s,nc:gsns vc:c alnncu Ia: nxcu savcn nnu
gc: ancn:nan aI Iccu gvcs c lcs :csu. CCFOS nnu PRSV naucs nvnnlc n HYS1S snunan saIvn:c vc:c
uscu a nunc c K
u
vnucs nnu csc vnucs vc:c anpn:cu v cxpc:ncn :csus a scc c lcs nauc.
Kc,va:us: quu-quu cx:nan, nc nu, savcn, c:nn:, ung:nn, HYS1S, snunan.
Received 19 March 2007
Accepted 25 July 2007
INTRODUCTION
!n separation ano purilication teclnology tle liq-
uio-liquio extraction plays an important role. Tle liq-
uio-liquio extraction is useo to separate two miscible
liquios using a solvent tlat prelerentially oissolves one
ol tlem [1]. Tle tlree brancles ol solvent extraction
are tle traoitional applieo lielo, tle nuclear material
lielo ano tle tleoretical lielo [2]. Tlis is a low tempera-
ture ano a low cost process. Metals are also purilieo by
tlis process. Close boiling mixtures or substances can
also be separateo by tlis metloo [3]. Tle equilibrium
relationslip ol tle components involveo is ol prime
importance in solvent extraction. Tle equilibrium rela-
tionslip in liquio extraction are generally more com-
plicateo tlan lor otler separations, because tlere are
tlree or more components present in eacl plase. So,
tle equilibrium relationslips are presenteo on a trian-
gular oiagram [3]. Tle ellect ol oual solvent was louno
to bring synergism, wlen compareo to tle single sol-
vent, tle reciprocal property also satislieo witl tle oual
solvent extraction. !n simulation metloos tle \!IAC,
\!Q\AC mooels are usually stuoieo, but tlese are
baseo on temperature parameter [3]. Ior lyorocarbon
leeo tle PRSV, GCIOS mooels are prelerreo.
Acetic acio is one ol tle most wioely useo car-
boxylic acios. !t is useo in many reactions, lor example,
tle syntlesis ol acetic ester or it can be useo as a sol-
vent. Tle separation ol acetic acio lrom its aqueous so-
lution by simple rectilication is very oillicult, requiring a
column witl many stages ano a ligl rellux ratio, tlus
incurring ligl running costs [4]. !n practice otler pro-
cesses are also useo oepenoing on tle concentration ol
acetic acio present in tle leeo. Between 5 % ano 7 %
wfw acetic acio, extractive oistillation is useo. By aooing
a tliro component, tle volatility ol water is increaseo
Journal of the University of Chemical Technology and Metallurgy, 42, 3, 2007
292
ano tle separation can be aclieveo witl less energy [4].
Below 4 % acetic acio, liquio-liquio extraction witl
single solvent is tle most appropriate. Acetic acio is
extracteo lrom water by a suitable solvent in oroer to
obtain substantially pure acetic acio [4].
Tle cloice ol a suitable extracting solvent lor
any liquio extraction outy mainly oepenos on its ex-
tractive capacity ano equilibrium claracteristics apart
lrom its stability, lavorable oensity, viscosity ano inter-
lacial tension properties ano sullicient oillerence in
boiling point between tle solute ano tle solvent [5].
Ior tle leeo containing 5 % ol acetic acio, M!BK is
tle most wioely useo solvent [4].
Tle solubility is less lor M!BK wlen compareo
to etlyl acetate. On tle otler lano tle boiling point ol
tle M!BK is close to tle boiling point ol tle acetic
acio. So tle separation is oillicult. Tle combineo ac-
tion can bring out synergism, oue to tle increaseo solu-
bility ol tle solute in tle mixeo solvent.
EXPERIMENTAL
Tle simple mixer settler oescribeo elsewlere [6]
is useo to stuoy tle equilibrium ano 5 %, 4 %, 3 % ano
2 % (%
mass
) ol acetic acio samples were prepareo by aoo-
ing tle acio in tle water ano tlese samples were useo to
carry out liquio - liquio extraction stuoies using etlyl
acetate, M!BK ano tle combination ol tlese two sol-
vents. Tle leeo ano solvent mixture were mixeo lor 15
min ano alloweo to settle lor 15 min ano tlese timings
were lixeo by trial runs. Tle extract (bottom) plase was
analyzeo by acio-base titration metloo ano tle rallinate
(top) plase was analyzeo by spectroplotometer. Tle ex-
periments were carrieo out at room temperature ano
pressure.
RESULTS AND DISCUSSION
Ior tle leeo containing 2 % ol acetic acio, tle
separation lrom aqueous solution witl various solvents
las been revieweo using reporteo oistribution coelli-
cient values ano oistribution coellicients obtaineo in
tle present experimental work. Analysis ol oistribution
coellicient values lor various solvents ano leeo contain-
ing 2 % acetic acio slows tlat etlyl acetate gives bet-
ter extraction result tlan M!BK ano tleir combination
wlicl is also observeo lrom Table 1. Analysis ol tle
experimental oistribution coellicients obtaineo lor vari-
ous leeo concentrations (2 %, 3 %, 4 % ano 5 %)
ano oillerent solvent ratios in Table 2 slows tlat lor
leeo containing lower concentration ol acetic acio, etlyl
acetate alone is suitable. !t is also observeo lrom tle K
o
values tlat lor tle leeo containing ligler concentra-
tions ol etlyl acetate (5 %) is not able to give any
result ano tlis oue to tle co-extract, tle water lrom tle
solvent [6]. Wlereas lor tle leeo containing ligler con-
centration (4 %, 5 %) ol acetic acio, combination ol
tlese solvents exlibits synergism. !ncrease in tle value
ol oistribution coellicient in tlis case is oue to tle
lavoureo conoitions arising lrom tle combineo action.
Tle increase in oistribution coellicient lor tle case ol
mixeo solvent (Itlyl Acetate M!BK) is being explaineo
using ternary oiagram orawn below.
1ornry ouIlIhrIum JIgrm lor sInglo solvont
Irom tle literature tle equilibrium oiagram lor
tle ternary systems etlyl acetatefacetic aciofwater ano
M!BKfacetic aciofwater were taken [4], ano slown in
Iig. 1a, 1b. Tle two plase region is quite small lor
etlyl acetatefacetic aciofwater slown in Iig. 1a, limit-
ing tle maximum leeo concentration lor tle liquio-liq-
uio extraction. However, tle two plase region lor tle
ternary system M!BKfacetic aciofwater is larger (Iig.


Solvents
Distribution
coeIIicient
(Kd)

ReIerence

Ethyl acetate

MIBK

n-Butanol

Ethyl ether

Cyclohexyl acetate


Cyclohexanol


1-Hexanol


Cyclohexanol
Cyclohexyl acetate


Hexane

Tri-n-octylamine

24.2

7.235

16.37

6.179

3.880

11.48

6.29

8.125


6.29

2.34

Present work

Present work

Present work & Eahim |3|

Present work & Judson |5|

Tamura |8|

Matsumoto |9|

Eahim |3|

Cehreli |9|


Present work

Michiaki |10|
Table 1. Distribution coellicients lor leeo containing
2 % ol acetic acio.
P. Kalaichelvi, M. Perumalsamy, A. Arunagiri, K. Sofiya
293
Distribution coeIIicient(K
d
) Sample
No
Solventt
ratio (s) 20 % 30 % 40 % 50 %
1

2
3
4
5
6
7
8
9
10
11
0(Ethyl
acetate)
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1
24.2

16.1
-
-
19.3
12.7
14.0
-
8.81
2.53
7.23
2.35

1.23
1.49
-
1.52
12.4
-
1.72
2.6
4.23
6.52
-

4.81
2.18
9.27
4.94
-
56.4
3.07
3.42
-
4.53
-

54.2
3.73
9.272
58.89
-
-
-
5.516
7.89
3.63

Table 2. Comparison ol oistribution coellicients lor vari-
ous leeo concentrations.
Distribution CoeIIicients (Kd ) Solvent
ratio (s) Experiment
results
GCEOS
model
PR
model
0 (Ethyl
acetate)
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1(MIBK)
-

3.63
-
4.56
5.516
-
-
58.89
9.272
3.73
54.2

-

1.6
12.74
2.53
8.816
15.54
14.05
19.37
22.25
-
16.11

-

1.021
1.6
1.013
1.017
1.036
1.017
1.021
1.046
1.718
1.148


Table 3. Comparison ol estimateo oistribution coellicients
witl experimental values (lor leeo concentration ol 5 %).
1b) ano tlerelore can be useo lor ligler leeo concen-
trations. Similar binooal curve lor tle ternary system ol
acetic aciofwaterfetlyl acetate M!BK lave been orawn
using tle calculateo tie line oata lrom tle present ex-
perimental work [11] ano slown in Iig. 2. !t is ob-
serveo tlat tle two plase region is ligler tlan tlat lor
tle single solvent system (etlyl acetate as well as M!BK).
MoJol proJIctIons nJ comprIson
GCIOS ano PRSV mooels in HYS!S simula-
tion soltware were useo to lino tle oistribution coelli-
cients (K
o
) lor tle leeo concentration ol 5 % ano mixeo
solvents. Tle calculateo K
o
values were compareo witl
experimental results in Table 3 ano tle % RMSD (Root
Mean Square Deviation) are 26 % ano 9 % lor GCIOS
ano PRSV mooels, respectively. Tlis slows tlat GCIOS
can preoict tle results wlicl are in gooo comparison
witl tle experimental results.
CONCLUSIONS
Illect ol oual solvent on liquio-liquio equilib-
rium las been analyzeo in terms ol oistribution coelli-
cients ano ternary oiagram ano tle suitable mooels lor
estimating tle oistribution coellicients oiscusseo. Tle
oistribution coellicients lor various acetic acio leeo con-
centrations were stuoieo using oillerent combination ol
solvent. Tle liquio-liquio equilibrium was orawn in tle
Fig. 1. Ternary equilibrium diagram for single solvent: 1a. Ternary equilibrium diagram for ethyl acetate/acetic acid/water; 1b. Ternary
equilibrium diagram for MIBK/acetic acid/water.
=
>
Journal of the University of Chemical Technology and Metallurgy, 42, 3, 2007
294
lorm ol ternary grapl lor tle leeo containing 5 % ace-
tic acio. Tle oistribution coellicient oata were obtaineo
using mooels available in HYS!S soltware ano GCIOS
mooel coulo preoict tle values witl less RMSD wlen
compareo witl PRSV mooel. Tlougl it coulo appreci-
ate tle ellect ol oual solvent on improving tle extrac-
tion elliciency, as an extension ol tlis work, lurtler in-
vestigations can be oone because tle ellect ol property
clange ano temperature on mixing lave not been taken
into consioeration. However, tlis stuoy woulo oelinitely
give a lirst lano knowleoge about tle problem ano pro-
Fig. 2. Ternary equilibrium diagram for a system of acetic acid/
water/ethyl acetate + MIBK.
vioe a gooo insiglt into tle complex ano conllicting ol
tle parameters governing tle process.
REFERENCES
1. W.L.McCabe, 1.C.Smitl, Harriott, \nit operations ol
clemical engineering, 5tl eo., 1993.
2. G.M.Ritcey, A.W. Aslbrook, Solvent extraction,
Ilsevier scientilic publisling company, 1979.
3. I.M.Ialim, S.A.Multaseb, !.M.aslel, 1. Clem.
Ingg. Data, " 1, 1997, 183.
4. De Dietricl Process System, Tle recovery ol acetic
acio by liquio-liquio extraction process.
(www.oeoietricl.com).
5. C.1uoson King, Acetic acio water leeo contain-
ing 2 % ol acetic acio, www.stevens-tecl.eou, 1883.
6. P.Kalaiclelvi, Hungarian 1ournal ol !noustrial Clem-
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1.Sep.Proc., #, 22, 537.
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