RECOVERY OF ACETIC ACID BY

MEANS OF LIQUID-LIQUID P150e.0

EXTRACTION
GENERAL
Acetic acid is the most widely used aliphatic carbonic acid.
Apart from its use as a reaction partner, e.g. during the
production of acetic-acid esters, it is frequently also
employed as a solvent, for instance, during the production
of cellulose acetate or during the manufacture of
pharmaceutical products. Aqueous acetic acid is obtained
as a rule during the foregoing processes. In most cases its
recovery is of great economic significance.
Separation of the acetic acid and water mixture by simple

 High content of acid in extraction column

 Side stream dispatch for cost reduction
 Drawing off accompanying components

Fig. 1: Acetic-acid recovery unit

rectification or adjustment is ruled out in this respect, since

would necessarily involve high costs for energy and high
this mixture has a very small separating factor. You would
operating costs, if rectification with vapour condensation is
then need towers having a large number of stages, which
not used.
would have to be operated with a high reflux ratio. This
In practice, therefore, azeotropic rectification has
asserted itself and operates either with or without the
1,0 extraction stage, depending on the respective acetic-
0,9 acid concentration. The addition of an auxiliary
substance means that the volatility of the water is
0,8 increased, which in turn means that separation can be
achieved with lower energy consumption. In the case
Y (Kmol/Kmol)

0,7 of acetic-acid concentrations of below 40 wt%, the acetic

0,6 acid is initially extracted from the aqueous solution with a
suitable extraction agent, before pure recovery occurs
0,5 during the rectification of the azeotropic mixture.
The recovery method using extraction must be taken into
0,4
consideration, irrespective of the concentration, if
supplementary impurities in the initial mixture, like salts,
0,3 p=1 bar water/acetic acid
ethyl acetate/; acetic acid would be likely to cause problems during direct recovery by
0,2 distillation.
This technical-information leaflet deals with the recovery of
0,1
acetic acid by means of liquid-liquid extraction and
downstream azeotropic rectification.

0,1 0,2 0,3 0,4 0,5 0,6 0,7 0,8 F . 2: Liquid/vapour equilibrium
i
X (Kmol/Kmol) g
0,9 1,0 LECTION OF THE EXTRACTION AGENT
S Normally, more low boiling extraction agents are used.
E Characteristics like solubility in water, absorption capacity,
distribution coefficient, price, availability and composition of
in the azeotrope. Thus the energy consumption in the case
the azeotrope, and requirements in terms of environmental
of the use of EtAc or MTBE as extraction agents ought to
and health protection must be taken into account for the
be the lowest.
purpose of this selection.
It can be shown that these observations only apply up to
Table 1 shows a selection of extraction agents suitable for
certain feed concentrations of acetic acid, which, for
the recovery of acetic acid, with details on the average
example, amount to approx. 15wt% in the case of ethyl
distribution coefficient between the organic and aqueous
acetate and MTBE. If the feed concentrations are higher,
phase, density of the extraction agent at 20°C; enthalpy of
then the quantity of extraction agent must be increased in
vaporisation and boiling point temperature of the extraction
accordance with the balance and vapour-liquid equilibrium,
agent; and the proportion of water and temperature of the
which consequently causes an increase in the operating
binary azeotrope between extraction agent and water.
costs. A more favourable alternative in terms of energy is
The average distribution coefficients do not differ essentially
the QVF method described below. By means of appropriate
from one another. As a result, all the extraction agents listed
process principle, economic working of the entire procedure
here must be regarded as practically equivalent with regard
can be achieved, even with high inflow concentrations of
to the extraction. The economic viability of the overall
acetic acid.
process greatly depends on the energy requirements of
It can be gathered from the liquid-liquid equilibrium for the
the solvent
two preferred ternary systems (see figs. 3 and 4) that if
ethyl

acetic acid
acetic acid
0,9 0,1
0,9 0,1
0,8 0,2
0,8 0,2
0,7 0,3
0,7 0,3
0,6 0,4
0,6 0,4
0,5 0,5
0,5 0,5
0,4 0,6
0,4 0,6
0,3 0,7
0,3 0,7
0,2 0,8
0,2 0,8
0,1 0,9
0,1 0,9

MTBE
water ethyl- water
0,9 0,8 0,7 0,6 0,5 0,4 0,3 0,2 0,1 acetat 0,9 0,8 0,7 0,6 0,5 0,4 0,3 0,2 0,1
azeotrope azeotrope
Fig. 3: Equilibrium diagram of the MTBE/acetic-acid/water
system (information in wt% at 20°C). Fig. 4: Equilibrium diagram of the ethyl-acetate/acetic-acid/water system
(information in wt% at 20°C).

rectification, which in turn depends on the reflux ratio and

acetate is used, there is considerable reciprocal solubility
thus on the performance of condenser and evaporator. The
with water. The space in the immiscibility gap is relatively
difference in boiling temperatures between the pure acetic
small, so that feed concentration of 30 wt% should not be
acid (118°C) and the azeotropic point provides clue on the
exceeded for safe extraction work. On the other hand, the
size of the reflux ratio. According to this, the reflux ratio in
immiscibility gap in the case of the MTBE / acetic-acid /
the case of all the extraction agents listed here ought to be
water system is more pronounced, and the reciprocal solubility
in the same order of magnitude. The energy consumption,
lower. Feed mixtures with acetic-acid concentrations of up to
however, also depends on the vaporisation enthalpy of the
around 40 wt% can, therefore, be reprocessed without problem
azeotropic mixture, which in turn is determined by the
using MTBE as the extraction agent.
proportion of water

Name Average Density Enthalpy Boiling Azeotrope

distribution of point
coefficient vaporisation
kg / kg kg / m³ kJ / kg °C Water T
Wt % °C
Ethyl acetate C4H8O2 EtAc 0,84 900 395 76,7 8,47 70,4
Isopropyl acetate , C5H10O2 iPrAc 0,55 877 361 88,6 10,50 76,5
n-Propyl acetate , C5H10O2 nPrAc 0,50 891 336 101,6 13,20 82,2
Methylpropyl ketone, 2-pentanon, C5H10O 0,97 810 384 102,3 19,50 83,3
MPK
Methylisobutylketon, 4-Methyl-2-Pentanon, 0,50 810 488 115,9 24,30 87,9
C6H12O MIBK
Methyl-tert.-butyl ether , C5H12O MTBE 0,75 740 322 55 4 52,6

Table 1: Extraction agents for the separation of acetic acid from effluent

2
EXTRACTION PROCESS side stream is guided back into the extraction tower. The
Fig. 5 shows the flow chart of a conventional extraction
position of the feeding point depends on the concentration
plant for the recovery of acetic acid. It consists of the
of the acetic acid in the side stream.
extraction tower, the rectification tower for the recovery of
The costs of the whole process are determined by the costs
the extraction agent, and the water-stripping tower. As a
for the
rule, the feed mixture has a greater density than the solvent,
separation of the extraction agent from the acetic acid.
and is fed in at the top end of the extraction tower. Inside
Meticulous care is therefore necessary both in terms of the
the tower it streams towards the bottom and in the process
design and layout of the control system of this process
gives off acetic acid to the extraction agent. Depending on
stage. In the case of the classical process with ethyl acetate
the effort, residual concentrations of 0.1-0.5 wt% can be
or MTBE as extraction agents, separation can occur without
achieved. Since the aqueous phase is simultaneously
problems. Nevertheless it should be taken into account that
saturated with the extraction agent in the extraction tower, it
in the tower a ratio of ethyl acetate to water is set at which
is recovered in a downstream stripping tower. It can in this
the separating factor relative to acetic acid is at its greatest.
respect be performed with live steam.
This is potentially very simple if the inlet concentration of
The extraction agent accumulate at the top end of the
acetic acid in the process water is below 15 wt%.
rectification tower and the acetic acid at the bottom of the
In the case of the QVF process the rectification step is also
tower resulting in acetic-acid concentrations of practically
unproblematic. Nevertheless, the control system of the
100
tower

stripper extractor rectification tower

stripper extractor rectification tower

side stream

steam steam

effluent effluent make up acetic acid

acetic acid process water
make up
process
water

Fig. 5: Flow chart of the classical process Fig. 6: Flow chart of the QVF process

wt%. If there is a risk of any higher-boiling components also proportion of acetic acid and, consequently, also water. In
passing into the organic phase during extraction, then it is the downstream rectification stage, separation of the
recommended that the acetic acid should be discharged in extracted phase now occurs in an azeotropic mixture
vapour form. consisting of extraction agent and water, and in acetic acid
Fig. 6 shows the flow chart of the QVF process. Here, of the required concentration. The excess water present in
similar to the conventional method, acetic acid is also the extracted phase is distilled as a liquid side-stream in the
extracted during the extraction stage from the process water rectifying section of the rectification tower. A particularly
with the aid of a suitable extraction agent (MTBE in most favourable choice of the draw off point and reflux ratio can
cases). The extraction tower, however, is operated in such a result in a composition in the side stream, which
way that a high a concentration as possible of acetic acid is approximately corresponds to that of the process water.
achieved during the extraction-sequence phase with After cooling to the operating temperature of the extract
simultaneous fulfilment of the required raffinate purity. phase, the
During this operation the extracted phase contains a high
 is more expensive by comparison with the conventional results from the low extraction agent main stream.
method, i.e. a certain concentration profile must be adjusted As a result, high acetic-acid concentrations develop in the
in the tower with a distinctive concentration maximum for extract, so that the proportion of water in the extract is also
water. In addition the flow rate of the side stream must be higher than in the case of the classical process. However,
controlled. The automatic control-technology concept this excess water is drawn off as a liquid side from the
developed by QVF for this purpose has already proven rectification tower. As a result, it is possible to achieve
outstandingly good in practical applications. azeotropic composition in the distillate, and then only the
quantity of water contained therein has to be condensed in
OPERATING COSTS the top end of the tower.
Greater expenditure in the case of the QVF process is It is not possible to make any generally applicable
justified by the up to 40% lower energy requirement by statements on the operating costs of acetic-acid recovery,
comparison with the classical process. This saving in energy since these
3
depend on the inflow concentration of the acetic acid, run-
off concentrations of the products, type of extraction agent,
choice of method variations, and heat recovery etc. For the
purpose of the assessment two (sets of) reference values
are given below for each method. The figures apply to the
use of MTBE, and assume that 99 wt% liquid boiling acetic
acid is being distilled at the bottom of the rectification (tower).
The duty of the evaporator for the classical process amounts
to the following:
- approx. 280 kW per 100 kg/h of acetic acid with
an acetic-acid concentration of 10 wt%, and
- approx. 260 kW per 100 kg/h of acetic acid with
an acetic-acid concentration of 35 wt%.

The following values have been calculated for the QVF process:
- approx. 260 kW per 100 kg/h of acetic acid with
an acetic-acid concentration of 10 wt%, and
- approx. 180 kW per 100 kg/h of acetic acid with
an acetic-acid concentration of 35 wt%.

DRAWING OFF ACCOMPANYING

COMPONENTS
In many cases the process water contains low boiling
components like ethanol or acetone, which must be
removed along with the acetic acid. Using MTBE as an
extraction agent, this can be performed as follows. During
the steady-state operation the low boiling components pass
the extraction tower without being extracted and reach a
Fig. 8: Extraction Unit
downstream stripper, which is equipped with a rectifying
section (see fig. 7). In the stripper section of the tower the
water is cleared of the extraction agent and accompanying separate MTBE from the accompanying components.
components. On the other hand, the rectifying section of However, during the separation of components, which have
the tower is used to a small boiling-temperature difference to MTBE (e.g.
acetone), MTBE losses can be expected.
In this case it is possible to resort to another variation in the
stripper process. For this purpose a water stripper without rectifying
section is used. Nevertheless, the stripper is operated in
such a way that the accompanying components are driven
to the bottom of the tower and the extraction agent driven to
the top of the tower. In this case, however, it is necessary
back to the ; for the loaded aqueous phase to be purified, for example,
extraction process
by a biological treatment.
concentrated ;
accompanying
; components
7.05. P150e.0. Änderungen vorbehalten.

heating;
steam

supply from the;

extraction process
 effluent

Fig. 7: Stripper with the additional draw off for accompanying components

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