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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.
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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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.
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
95
or
96
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-
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
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
98
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.
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