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Applied Catalysis B: Environmental 40 (2003) 9399

A new method to clean industrial water from


acetic acid via esterification
C.L. Bianchi a, , V. Ragaini a , C. Pirola a , G. Carvoli b,1
a

Department of Physical Chemistry and Electrochemistry, University of Milan, Via Golgi 19, I-20133 Milano, Italy
b La Chemial SpA, Cavagli (BI), Italy
Received 7 October 2001; received in revised form 1 June 2002; accepted 1 June 2002

Abstract
The valorisation of very low concentration of acetic acid (6%, w/w) was investigated by reacting with n-butanol and
2-ethyl-1-hexanol taking advantage of the different solubilities of acetic acid and acetic ester in water. The esterification of very
diluted solution of acetic acid with alcohol is a reversible reaction and the conversion is greatly restricted by equilibrium limitation. Therefore, the peculiarity of the present method is to shift the reaction equilibrium towards the ester and not towards the
reagents, thermodynamically favourite, because of the large amount of water. Different acid catalysts were tested in both homogeneous (sulphuric acid) and heterogeneous phase (polymeric resins and sulphated zirconia) to optimise the process efficiency.
2003 Elsevier Science B.V. All rights reserved.
Keywords: Acetic acid recovery; Water purification; Esterification reaction

1. Introduction
Aqueous solutions of acetic acid are produced as
by-products of many important processes, such as
in the production of cellulose esters, terephthalic
acid and dimethyl terephthalate. Moreover, reactions
involving acetic anhydride either as a reagent (e.g.
acetylations) or as a solvent (e.g. nitrations) can produce a large amount of acetic acid containing waste.
Among the industrially relevant examples, the process for the manufacture of cellulose acetate from
acetylation of cellulose by acetic acid, acetic anhydride and sulphuric acid, is typically associated with
Corresponding author. Tel.: +39-2-50314253;
fax: +39-2-50314300.
E-mail address: claudia.bianchi@unimi.it (C.L. Bianchi).
1 Present address: Oxon SpA, Via Sempione 195, 20016 Pero,
Italy.

35% (w/w) aqueous solution of acetic acid as a waste


stream. The process for the synthesis of glyoxal from
acetaldehyde and nitric acid has a relatively dilute
acetic acid stream (1320%, w/w) as a by-product
[1]. Acetic acid is also a product in the destructive
distillation of wood (18%, w/w).
Moreover, it is necessary to remember the importance of such an acid in the food industries: vinegar,
for example is a sour liquid consisting mainly of acetic
acid and water, produced by the action of bacteria on
dilute solutions of ethyl alcohol derived from previous yeast fermentation. In these cases, very dilute acid
streams are produced, due to many rinses of the devices during the production cycles.
Therefore, the recovery of acetic acid is a large problem not always solved because of economical reasons.
In fact, the conventional physical separation methods
such as distillation and extraction suffer from several drawbacks. Distillation is generally uneconomic

0926-3373/03/$ see front matter 2003 Elsevier Science B.V. All rights reserved.
PII: S 0 9 2 6 - 3 3 7 3 ( 0 2 ) 0 0 1 4 4 - 3

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C.L. Bianchi et al. / Applied Catalysis B: Environmental 40 (2003) 9399

because of the high costs involving in vaporising water, that is the most volatile compound and is present in
very large proportion but possesses a large latent heat
of vaporisation. Extraction is limited by phase separation and distribution of the components involved in the
reacting system. These are the reasons why acetic acid
is often very much diluted in water and discharged in
sewer.
In our technology, water containing acetic acid is
simply purified by means of an esterification. Acetic
acid reacts with an alcohol in the presence of an acid
catalyst to give the corresponding ester. The same idea
was exploited by Saha et al. [2] who purified a stream
of contaminated water by an esterification reaction.
However, in that case the reaction was performed using
a more concentrated solution of acetic acid (30%) by
means of a reactive distillation column.
In the present paper, the recovery of very low concentration of acetic acid (6%, w/w) was investigated
by reacting with n-butyl or 2-ethyl-1-hexyl alcohol in
a simple glass reactor taking advantage of the different solubilities of acetic acid and acetic ester in water.
n-Butyl acetate is primarily used as a solvent for
coatings, in the photographic industry, as a reaction
medium for adhesives, as a solvent for leather dressings, as extraction solvent and as process solvent in
various applications and in cosmetic formulations.
2-Ethyl-1-hexyl acetate has a good market value as a
raw material in cosmetic formulations for sunscreen
creams and anti-ageing creams.
The peculiarity of this recovery method is the presence of large amount of water at the beginning of
the reaction, and thus, the ability to shift the reaction
equilibrium towards the ester (to the right) and not towards the reagent (thermodynamically favourite). Different acid catalysts were tested in both homogeneous
(sulphuric acid) and heterogeneous phase (polymeric
resins and sulphated zirconia) to improve the process
rate towards the equilibrium efficiency.

(both macroreticular-strongly acidic cation exchangers), Amberlist IR120 (a microreticular-strongly acidic


cation exchanger), Nafion NR50 (a super-acidic perfluorinated resin). Sulphated zirconia was prepared as
described in [3].
2.2. Experimental procedure and apparatus
Two kinds of experimental procedures were performed: (a) runs at complete evaporation condensation; (b) runs with distillation and reaction product
removal. In the case (a), all the evaporated species
were condensed and thus directly re-introduced into
the reactor, avoiding the removal of any chemical during the reaction. By working with the procedure (b),
the ester was continuously removed from the reaction
mixture to allow the shift of the reaction equilibrium
towards the right by distillation of the organic phase
(alcohol and ester).
All the tests were performed in a glass reactor provided with breakwater, a mechanical stirrer (300 rpm),
a thermometer and a coil condenser for equipment (a)
(see Fig. 1a) or a Markuson head (distillation column
coupled with an azeotropic head) for equipment (b)
(Fig. 1b).
Standard conditions: 400 ml of bi-distilled water
was contaminated with acetic acid (6%, w/w) and
200 ml of the selected alcohol was added. The reaction was performed at a constant temperature of 99 C
adding the correct amount of catalyst when the stirred
solution reached the right temperature.
All the experimental data reported in the paper are
expressed in terms of process efficiency (E%) calculated as following:


molAcOHin molAcOHfin
E% =
100
molAcOHin
aq
where molAcOH denotes the acetic acid moles
present, in the aqueous phase (aq), at the beginning
(in) and at the end (fin) of reaction.

2. Experimental
2.3. Analysis
2.1. Materials and catalysts
All the chemicals used in the present paper are Fluka
products: acetic acid, n-butanol and 2-ethyl-1-hexanol,
sulphuric acid (96%), Amberlist 200 and Amberlist 15

To follow the reaction product and also to calculate


the efficiency of the process to produce ester, a GC
(ThermoQuest) equipped with a capillary SE52 column ( = 0.53 mm, L = 25 m, T =150 C) was used

C.L. Bianchi et al. / Applied Catalysis B: Environmental 40 (2003) 9399

95

to analyse acetic acid, n-butyl acetate, n-butyl alcohol.


The amount of acetic acid was also cross-checked by
titration with NaOH 0.01 M using phenolphthalein as
indicator.
In the reaction with a large amount of n-butyl
alcohol or 2-ethylhexyl alcohol, two phases were observed inside the reactor. The analyses of the upper
organic phase (n-butyl alcohol, n-butyl acetate and
2-ethylhexyl acetate, 2-ethylhexyl alcohol, respectively) were carried out by gas chromatography. The
amount of water in this organic phase was performed
by KarlFischer instrument.
The presence of acidity in the aqueous phase (lower
phase) was monitored by subsequent titration with
NaOH 0.01 M using phenolphthalein as indicator.

3. Results and discussion


The esterification of acetic acid with an alcohol is a
three-step chemical reaction and all the three steps are
equilibrium limited reactions. The overall reaction is:
CH3 COOH + ROH  CH3 COOR + H2 O
where
R = CH2 CH2 CH2 CH3

or

R = CH2 CH(C2 H5 )CH2 CH2 CH2 CH3

Fig. 1. Scheme of the used equipments. For both configurations:


(1) mechanical stirrer, (3) withdrawal from both phases, (4) thermometer. For procedure (a): (2) coil condenser; for procedure (b):
(2) Markuson head (distillation column coupled with an azeotropic
head).

Therefore, the esterification of 6% aqueous solution


of acetic acid with alcohol is obviously a reversible
reaction and the conversion is greatly restricted by
equilibrium limitation.
Just to confirm this limitation, a first run with
n-butanol was performed taking advantage of the solubility of this alcohol in water (Table 1). The reactor
was filled with 400 ml water, acetic acid (6%, w/w),
n-butanol (6%, w/w) and Amberlist 200 as an heterogeneous catalyst and temperature raised to 99 C
(procedure (a)). A single phase was present inside
the reactor. The process efficiency after 6 h was only
3.4%.
By increasing the amount of n-butanol present in the
reactor, a double phase was immediately generated.
Therefore, a second run was performed at the same
temperature as above with the same amount of water
and catalyst, but 200 ml of alcohol was loaded. The
process efficiency after 6 h was 67.9%.

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C.L. Bianchi et al. / Applied Catalysis B: Environmental 40 (2003) 9399

Table 1
Solubility data
Compound

Formula

T ( C)

Sa (mass%)

n-Butanol
Butyl acetate
2-Ethyl-1-hexanol
2-Ethylhexyl acetate

C4 H10 O
C6 H12 O2
C8 H18 O
C10 H20 O2

25
25
25
25

6.4 [4]
0.68 [4]
0.01 [4]
0.55 [5]

Sb (mass%)
1.2 [5]
<0.03 [5]

Solubility in water.
b Solubility of water.

The presence of a double phase leads to a great different result of the process efficiency that increased
nearly 20 times. The thermodynamic equilibrium was
shifted towards right thanks to the co-presence of two
immiscible phases (an aqueous heavy phase and an organic lighter phase) and thus the possibility of acetic
acid to move from one phase to the other. The alcohol, immiscible in water, is present in the upper
phase where acetic acid is able to migrate and react
with alcohol to give 1 mol of ester and 1 mol of water. The acetic acid solved in water is in the lower
phase and here the water moles, produced in the upper
phase during the esterification reaction, continuously
migrate.
After having confirmed the effectiveness of our procedure, all the measurements were performed using
2-ethyl-1-hexyl alcohol as esterification agent.
Using H2 SO4 as an acid catalyst the process efficiency was 69.2% after 6 h (always performing the
reaction at standard conditions with procedure (a),
Fig. 2a. A typical trend of the disappearance of both
the reagents (acid in the aqueous phase and alcohol
in the organic one) and of the formation of the product (ester) is shown in Fig. 2b. The initial drop in the
acetic acid concentration is a consequence of its different partition in the two phases.
It was also interesting to observe that E% increased
by a small amount reaching 75.0% decreasing the
amount of acetic acid into the water from 6 to 1.2%
(w/w) (Fig. 2a).
These experimental results show the good performance of sulphuric acid as an esterification catalyst in
our condition. However, all the side effects of the use
of this kind of acid are well known: first of all corrosion problem and also the residual contamination of
the purified water by means of the SO4 2 ions. For
these reasons, the use of solid acid catalysts is prefer-

able. However, their performances are dramatically


lower than the homogeneous catalysts. In fact, the process efficiency falls down much under 50% (Table 2).
Nafion NR 50 shows better result with an efficiency
of 45% but it undergoes a rapid deactivation right
after the first run. The same deactivation was observed for sulphated zirconia: a leakage of sulphated
ions was observed into the water. On the contrary, all
Amberlist samples show very stable catalytic performance from one run to another. For example, Amberlist 15 still shows its unchanged acid property after
1000 runs.
It was demonstrated by the tests performed with butanol that the esterification reaction does not take place
in the aqueous phase but in the organic one or perhaps
at the interface between the two phases. Therefore, a
sure explanation of the decrease of the efficiency of
all the heterogeneous catalysts in comparison to sulphuric acid is clearly due to the difficulty to maintain
the catalyst particles close to the alcohol.
To increase the reaction performance, several runs
were performed by coupling the above described reaction to the distillation of the evaporated phase in order
to remove the esterification product from the reaction
mixture and, therefore, to shift the reaction equilibrium
Table 2
Process efficiency (E%)
Catalyst

E%

H2 SO4
Amberlist 200
Amberlist 15
Amberlist IR 120
Nafion NR 50
SO4 -zirconia

69.2
43.6
44.7
42.6
45.6
31.9

Reaction performed with 2-ethylhexyl alcohol, standard conditions,


procedure (a).

C.L. Bianchi et al. / Applied Catalysis B: Environmental 40 (2003) 9399

97

Fig. 2. (a) Process efficiency vs. reaction time for reaction performed with procedure (a) (2-ethyl-1-hexanol as upper phase, 6% AcOH ()
or 1.2% AcOH (), H2 SO4 as acid catalyst). (b) () Ester, () acetic acid (6% at the beginning of the run) and () 2-ethyl-1-hexanol
trend vs. reaction time.

towards the right with even greater efficacy (procedure (b)). All these kinds of runs were performed using 2-ethyl-1-hexanol and sulphuric acid as an acid
catalyst to avoid all the problem due to the decrease
of the process efficiency using a solid catalyst.
The acetic acid removal is complete after 55 h
of reaction as shown in Fig. 3. The main disadvantage of this method is due to the co-presence of two
azeotropic mixtures (alcohol/water, water/ester) with
a boiling point lower than both the pure alcohol and
ester (Table 3). This fact causes the removal not only
of the reaction product (the ester), but also of the
alcohol and of the water. For this reason, the distillation column was coupled with an azeotropic head

to separate the organic phase from the aqueous one


(Fig. 1b). The removal of the organic phase and not
of the aqueous one was decided for two main reasons:
first of all the water acts as an azeotropic mixture
agent to the ester and therefore its removal would
prevent the distillation of this component; secondly,
the presence of the only alcoholic phase into the
reactor may cause a bad dispersion of the catalyst,
especially when it is solid, due to the alcohol high
viscosity.
Therefore, the quantity of alcohol into the reaction
mixture tends to decrease and for the future it would
be necessary to plan the possibility of its continuous
addition through the whole reaction.

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C.L. Bianchi et al. / Applied Catalysis B: Environmental 40 (2003) 9399

Fig. 3. Process efficiency vs. reaction time coupling the classical reaction to the distillation of the evaporated phase (procedure (b), H2 SO4
as acid catalyst, 2-ethylhexyl alcohol as upper phase).

Table 3
Thermodynamic data
Compound

bp ( C)

A (wt.%)

B (wt.%)

C (wt.%)

BuOH
2-Et-esOH
BuOAc
2-Et-esOAc
H2 O/BuOH [6]
H2 O/BuOAc [6]
H2 O/BuOH/BuOAc [6]
H2 O/2-Et-esOH [6]
H2 O/2-Et-esAc [6]
H2 O/2-EtesOH/2-Et-esAc [6]

117.7
183.5
126.2
198.6
92.7
90.2
90.7
99.1
99.0
99.0

100
100
100
100
42.5
28.7
29.0
80.0
73.5
74.0

57.5
71.3
8.0
20.0
26.5
10.0

63.0

16.0

4. Conclusions
The valorisation of very low concentration of acetic
acid (6%, w/w) was investigated by reacting with
n-butanol or 2-ethyl-1-hexanol taking advantage of
the different solubilities of water with the acetic acid
and with the acetic ester.
The reaction is equilibrium limited. The peculiarity of the method is the presence of large amount of
water at the beginning of the reaction, and thus, the
ability to shift the reaction equilibrium towards the ester and not towards the reagent (thermodynamically
favourite).

Two kind of experimental procedures were performed: (a) runs at complete evaporation condensation; (b) runs with distillation and reaction product
removal. In this latter configuration, a complete removal of acetic acid was achieved.

References
[1] I. Kroschwitz (Ed.), Kirk-Othmer Encyclopedia of Chemical
Technology, 4th Edition, Wiley, New York, 1991, pp. 124
178.
[2] B. Saha, S.P. Chopade, S.M. Mahajani, Catal. Today 60 (2000)
147.

C.L. Bianchi et al. / Applied Catalysis B: Environmental 40 (2003) 9399


[3] S. Ardizzone, C.L. Bianchi, M. Signoretto, Appl. Surf. Sci.
136 (1998) 213.
[4] D.R. Lide, H.P.R. Frederiske (Eds.), Handbook of Chemistry
and Physics, 78th Edition, CRC Press, New York, 1997,
p. B-260.

99

[5] H. Stephen, T. Stephen (Eds.), Solubilities of Inorganic and


Organic Compounds, Pergamon Press, Oxford, 1963, p. 1799.
[6] L.H. Horsley, in: R.F. Gould (Ed.), Azeotropic Data III,
Advances in Chemistry Series 116, ACS, Washington, 1973,
pp. 1339, p. 469.

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