Indian Journal of Chemical Technology

Vol. 17, November 2010, pp. 441-445

Extraction of acetic acid from aqueous solutions by emulsion type liquid
membranes using Alamine 300 as a carrier
Aynur Manzak* & Melek Sonmezoglu

Department of Chemistry, Faculty of Science, Sakarya University, 54187 Adapazari, Turkey
*Email: manzak@sakarya.edu.tr
Received 4 March 2010; revised 25 August 2010
The extraction of acetic acid from aqueous solutions by an emulsion type liquid membrane process was investigated, using
Alamine 300 as carrier, Span 80 as surfactant, and Na
2
CO
3
solution as stripping agent. A number of significant parameters viz.
mixing speed, surfactant concentration, diluent type, concentration of the carrier Alamine 300, concentration of stripping agent,
pH and concentration of feed solution were investigated. Acetic acid was successfully extracted and concentrated from aqueous
solutions. Approximately 86% extraction of acetic acid was achieved within 10 min in a stirred vessel.
Keywords: Acetic acid extraction, Alamine 300, Emulsion liquid membrane, Surfactant, Diluent
Acetic acid is one of the simplest and most widely
used carboxylic acids, and has many important
chemical and industrial applications. Acetic acid is a
valuable compound for agricultural application
(preservative E280), and substrate for preparing
natural and industrially uncontaminated products
1
.
Until recently, the acid waste containing acetic acid
has been mostly subjected to neutralization without
any proper treatment. However, the conventional
neutralization treatment has problems of formation of
precipitation in a large quantity, cost of alkali, and
sludge disposal, which consequently cause an increase
in the treatment cost
2
. Recovery of carboxylic acids
such as acetic acid is important in a number of
industries. Removal of carboxylic acid from aqueous
waste streams is also important in the petrochemical,
chemical and pulp and paper industries
3
. Classical
methods for recovering low-volatility carboxylic acids
involve formation of the insoluble calcium
carboxylate salt
4
.

Many research groups are working in this field and
some methods
5-10
have been proposed for the
separation and recovery of acetic acid from different
waste sources. Most of these processes are concerned
with an aqueous solution that does not contain high
concentration of inorganic acids. In the absence of
any mature technology, a conventional physical
separation method such as distillation is preferred by
the industries; distillation is not economical because
of the high energy cost involved in the vaporization
process
2-11
. The extraction method has the potential to
replace the existing distillation process used for acetic
acid recovery. Solvent extraction processes have been
proposed by several research groups to separate acetic
acid from mixed acid waste
11
. Acetic acid is generally
recovered by a solvent extraction method
2
. The
recovery of acetic acid from waste streams is also
possible by extractive distillation
10
.

Membrane separation processes have been used for
many applications in the chemical industry, due to the
compactness, simple and efficient operation and low
energy consumption of membrane
12
. Emulsion liquid
membrane (ELM) is a highly sophisticated but an
energy-saving separation technique. Some studies have
been conducted to utilize liquid membrane technology
for the removal of organic acids
13-15
. In this technology,
solutes are not only removed but also concentrated.
The external phase to be treated is contacted with an
emulsion dispersed in globules. Each emulsion globule
consists of droplets of an aqueous internal stripping
phase, encapsulated in an organic membrane phase
containing a surfactant. During this contact, solute
transport occurs through the membrane phase into the
internal stripping phase, where it is concentrated. Since
extraction and stripping are done in a single step, ELM
technology is preferred when treating effluents. The
use of an emulsion liquid membrane in effluent
treatment has received widespread attention, due to its
ease of operation, lower power consumption and
modular design. Odorous distillery effluent was
treated for removal of acetic acid (solute) using ELM
in a batch process
16
. In the present investigation an
INDIAN J. CHEM. TECHNOL., NOVEMBER 2010


442
attempt has been made to use the ELM for removal
and concentration of acetic acid from its solutions.

Experimental Procedure

Materials
The liquid membrane phase (organic phase) is
composed of a surfactant (emulsion stabilizer), carrier
and diluent. Reagent grade surfactant Span 80 (sorbitan
monooleate) was purchased from Fluka and used as
such. The mobile carrier Alamine 300 was obtained
from Cognis Corp. Kerosene, Toluene, Escaid 100 and
Escaid 200 are used as diluents. Kerosene is a complex
mixture of aliphatic origin and also contains aromatics
about 15% w/w.

Preparation of ELM
The emulsion liquid membrane (ELM) used in this
work was a water-oil-water (W/O/W) type of emulsion,
formed by mixing the aqueous phase with the organic
phase. The liquid membrane phase (organic phase) is
composed of a nonionic surfactant, a carrier and
diluent. The external or feed phase is an acetic acid
solution. The surfactant is commercially known as
Span 80. The mobile carrier is Alamine 300
(trioctylamine). Kerosene, Toluene, Escaid 100, Escaid
200 are used as diluents.
The internal phase (V
S
) is a Na
2
CO
3
solution. The
external or feed phase (V
F
) is an acetic acid solution.
The stripping solution (V
S
: 50 mL) was added
dropwise to the membrane solution (V
m
: 50 mL),
stirred at 2000 rpm for 30 min and passed through a
burette in about 20 min. The appropriate liquid
membrane emulsion (V
E
) was added to a feed solution
(V
F
: 250 mL) in a 600 mL beaker with a Teflon-coated
four vertical baffle. The two-phase system was stirred
by a variable speed mixer, equipped with a turbine-type
Teflon impeller. Samples of 1 mL of the feed phase
were taken periodically for analysis. Extraction rates
were measured by analyzing the feed phase acetic acid
concentrations. Analysis of acetic acid samples was
performed by high performance liquid chromatography
(HPLC). At the end of each run, the emulsion was
recovered and subsequently broken into its constituent
organic and aqueous phases using a high-voltage
splitter with niobium electrodes. All the extraction
experiments were carried out batchwise.

Analysis
Acetic acid concentration was determined by
high performance liquid chromatography (HPLC)
(Shim-adzu LC-20AD, Japan), equipped with an
Hypersil C18 ODS column (250 4.6 mm) and
detected with UV detector (Shimadzu SPD-M20A) at
210 nm. All the aqueous solutions were prepared
using deionized water.

Results and Discussion

Effect of mixing speed of feed solution
Figure 1 shows extraction efficiency at mixing
speeds of 250, 300 and 400 rpm (C/C
o
which expresses
the extent of remaining acetic acid in the feed solution).
It was observed that the transfer of acetic acid
increased on increasing the mixing speed from 250 to
400 rpm.
According to Hirato et al.
17
increasing the mixing
speed, reduces the size of the emulsion globules
dispersed in the external phase, leading to greater
surface area for mass transfer, and results in increased
extraction rate. However, at the same time, the higher
mixing speed affects the stability of emulsion globules,
which may lead to breakage. Therefore, the rate of
extraction decreases in the long run, as shown with data
at 400 rpm. Thus, a mixing speed of 300 rpm was
found to be appropriate for conducting the
experiments.

Effect of diluent
Organic diluent influences the performance of many
liquid membrane systems. The role of the diluent is not
only to improve the physical properties of the
extraction system, but also to remove the interaction
product. This needs be taken into account in the choice
of diluent
18
.
In the present study diluents like toluene, kerosene,
Escaid 100 and Escaid 200 were used. The results
shown in Fig. 2 prove that toluene provided the better
performance.

Effect of surfactant concentration
Surfactant concentration has an important bearing
on the stability of the emulsion. Too little surfactant
renders the membrane weak, while an excess of


Fig. 1The effect of mixing speed of feed solution [diluent:
Toluene (91% w/w), extractant: Alamine 300 (5% w/w), surfactant:
Span 80 (4% w/w), external phase concentration: (10% w/v),
stripping phase: 50 mL (10% w/v) Na
2
CO
3,
treatment ratio (V
F
/V
E
)
:

5/2, phase ratio (V
S
/V
m
): 1/1, emulsion mixing speed: 2000 rpm]
MANZAK & SONMEZOGLU: EXTRACTION OF ACETIC ACID FROM AQUEOUS SOLUTIONS


443
surfactant concentration leads to larger diffusional
resistance. Experiments were performed with
surfactant concentrations ranging from 3 to 6%. The
emulsion stability improved with increased surfactant
concentration. Figure 3 shows that increasing the
surfactant concentration from 3 to 6% increased the
stability of the liquid membrane, leading to a decrease
in the break-up rate; hence the degree of extraction of
acetic acid was also increased.

Effect of Alamine 300 concentration
The effect of carrier concentration is shown in
Fig. 4. The efficiency of tertiary amines in the
recovery of various organic acids has been
demonstrated in some previous studies
19-21
. The initial
extraction rate of acetic acid is slightly higher for 3 and
5% (w/w) Alamine 300 than for 8%, as shown in
Fig. 4. A very high content of extractant in the
membrane does not result in a benefit, due to the
respective increase in viscosity, which leads to larger
globules
22
. The increasing concentration of extractant
also promotes permeation swelling, which dilutes the
aqueous receiving phase and reduces the efficiency of
the ELM process.

Effect of feed solution pH
The pH strongly affects the ionization of
carboxylic acids. Acetic acid is a weak acid (HA) that
partially ionizes in aqueous solutions. The
concentrations of dissociated and undissociated acids
(HA) are affected by the hydrogen ion (H
+
)
concentration or pH. At extremely low pH values, the
acid is mainly in undissociated form. Most aliphatic
amines extract undissociated acids from the aqueous
phase by forming an acid-base complex. The effect of
hydrogen ion concentration was examined by varying
the initial pH of the external phase between 1 and 4,
as shown in Fig. 5. The acetic acid solution had a pH
of 1.8. The extraction rate and ultimate yield of acetic
acid decreased with increasing pH. As the pH


Fig. 2The effect of diluent on the extraction of acetic acid [diluent:
(91% w/w), extractant: Alamine 300 (5% w/w), surfactant: Span 80
(4% w/w), feed solution concentration: (10% w/v), stripping phase: 50
mL (10% w/v) Na
2
CO
3
, pH of feed solution: 1.8, treatment ratio
(V
F
/V
E
): 5/2, phase ratio (V
S
/V
m
): 1/1, emulsion mixing speed: 2000
rpm]



Fig. 3The effect of surfactant on the extraction of acetic acid
[diluent: Toluene (89-92% w/w), extractant: Alamine 300 (5% w/w),
surfactant: Span 80 (3-6% w/w), feed solution concentration: (10%
w/v), stripping phase: 50 mL (10% w/v) Na
2
CO
3
, pH of feed solution:
1.8, treatment ratio (V
F
/V
E
) : 5/2, phase ratio (V
S
/V
m
): 1/1, emulsion
mixing speed: 2000 rpm]


Fig. 4The effect of extractant on the extraction of acetic acid
[diluent: Toluene (88-93% w/w), extractant: Alamine 300 (38%
w/w), surfactant: Span 80 (4% w/w), feed solution concentration:
(10% w/v), stripping phase: 50 mL (10% w/v) Na
2
CO
3
, pH of
feed solution: 1.8, treatment ratio (V
F
/V
E
): 5/2, phase ratio
(V
S
/V
m
): 1/1, emulsion mixing speed: 2000 rpm]



Fig. 5The effect of feed phase pH on the extraction of acetic
acid [diluent: Toluene (91% w/w), extractant: Alamine 300 (5%
w/w), surfactant: Span 80 (4% w/w), feed solution concentration:
(10% w/v), stripping phase: 50 mL (10% w/v) Na
2
CO
3,
pH of feed
solution: 1-4, treatment ratio (V
F
/V
E
) : 5/2, phase ratio (V
S
/V
m
):
1/1, emulsion mixing speed: 2000 rpm]
INDIAN J. CHEM. TECHNOL., NOVEMBER 2010


444
increased, the resulting decrease in the external phase
hydrogen ion concentration reduces the extent to
which the amine can couple with the acetic acid, and
thus the rate of extraction decreases. The data for a
pH level of 1 show that further decrease in pH results
in reduced extraction efficiency
23
. This process is
further accelerated by the stripping action of Na
2
CO
3
.

Effect of stripping solution concentration
Strip phase concentration was varied from 5 to
20%, as shown in Fig. 6. The difference in hydrogen
ion chemical potentials between the two aqueous
phases is the main driving force in the emulsion liquid
membrane process. It can be noted from Fig. 6 that,
when Na
2
CO
3
concentration is increased from 5 to
10%, extraction efficiency increases, but decreases
when Na
2
CO
3
concentration is further increased from
10 to 20%. At 20% Na
2
CO
3
concentration, the
emulsion swells up, and the extraction efficiency of
acetic acid is decreased.

Effect of feed concentration
The acetic acid concentration in the feed or
external phase was varied from 2 to 10%. The rate of
acetic acid extraction increased as the feed
concentration decreased, as shown in Fig. 7.

Extraction mechanism
The transport mechanism of acetic acid in ELM
can be explained via the following steps, as shown in
Fig. 8.

(i) The acetic acid dissociates into H
+
and acetate
ions as shown in Eq. (1).
HA H
+
+ A
-
... (1)


Fig. 6The effect of stripping phase concentration on the
extraction of acetic acid [diluent: Toluene (91% w/w), extractant:
Alamine 300 (5% w/w), surfactant: Span 80 (4% w/w), feed
solution concentration: (10% w/v), stripping phase: 50 mL (5-20%
w/v) Na
2
CO
3,
pH of feed solution: 1.8, treatment ratio (V
F
/V
E
):
5/2, phase ratio (V
S
/V
m
): 1/1, emulsion mixing speed: 2000 rpm]



Fig. 7The effect of feed phase concentration on the extraction
of acetic acid [diluent: Toluene (91% w/w), extractant: Alamine
300 (5% w/w), surfactant: Span 80 (4% w/w), feed solution
concentration: (2,10% w/v), stripping phase: 50 mL (10% w/v)
Na
2
CO
3
, pH of feed solution: 1.8, treatment ratio (V
F
/V
E
): 5/2,
phase ratio (V
S
/V
m
): 1/1, emulsion mixing speed: 2000 rpm]


Fig. 8Schematic mechanism of acetic acid extraction and stripping by tertiary amine (Alamine 300) and sodium carbonate
15
.
MANZAK & SONMEZOGLU: EXTRACTION OF ACETIC ACID FROM AQUEOUS SOLUTIONS


445
(ii) The tertiary amine reacts with the acetic acid to
form amine salt at the interface between the
external and membrane phases in the extraction
step, as given in Eq. (2).

H
+
(aq)
+ A
-
(aq)
+ R
3
N
(org)
R
3
N

H
+
A
-
(org)
(2)

(iii) Transport of the amine salt followed by stripping
at the interface between the membrane and
internal phase, after the amine salt had diffused
across the membrane, the complex reacts with the
stripping solution (Na
2
CO
3
) at the membrane-
stripping phase interface, as indicated in Eq. (3).

2R
3
NH
+
A
-
(org)
+ 2Na
+
(aq)
+ CO
2-
3(aq)
(R
3
NH
+
)
2
CO
2-
3(org)
+ 2Na
+
(aq)
+ 2A
-
(aq)
(3)

(iv) Finally, the amine carbonate formed in the
stripping reaction diffuses back to the external
phase interface where it dissociates into carbon
dioxide and water, and thus regenerates the free
amine as given by Eq. (4).

(R
3
NH
+
)
2
CO
2-
3(org)
2R
3
N
(org)
+ CO
2
+ H
2
O (4)

Conclusions
The proposed ELM can be successfully employed to
achieve acetic acid extraction from aqueous solutions.
The concentration of the carrier, Alamine 300, affects
the extraction rate. The highest acetic acid extraction
rate was obtained with 5% concentration of alamine
300. The optimum conditions obtained from the
experimets were: membrane phase with surfactant
Span 80 (4% w/w), the carrier alamine 300 (5% w/w),
and the diluent toluene (91% w/w), Na
2
CO
3

concentration in the feed solution (10% w/v). The
optimal feed phase pH was 1.8, and the mixing speed
of feed solution was 300 rpm. The use of toluene as a
diluent achieved 86% extraction of acetic acid.

Acknowledgements
The authors wish to express their sincere gratitude
to the State Planning Organization of Turkey which
supported this work, and Mehmet Yilmaz, coordinator
of BAPK in Sakarya University. Special thanks to
Assist. Prof. Osman Kola, Department of Food
Engineering, Sakarya University, for analyzing HPLC
data.

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