International Journal of Scientific Engineering and Technology (ISSN : 2277-1581)

Volume 2 Issue 4, PP : 211-215 1 April 2013

Recovery of Acetic Acid From Effluent via Freeze Crystallization

Tarak C. Padhiyar, Prof. Suchen B. Thakore

L.D. College of Engineering, Ahmedabad, [email protected], [email protected]

Abstract been used to fractionate solution in specialized applications, the

Freeze crystallization is an efficient separation process that technique has never been adopted on a large scale. In some
can potentially be used in any application. Freeze applications, freezing can perform a separation with 75-90%
crystallization is a high energy efficiency separation process reduction of the energy required by convention distillation
that can be applied to a wide variety of industrial acetic acid and acrylic acid refining are two examples.
requirements. Although the vapor-liquid equilibrium is Freeze crystallization also shows significant energy reduction in
generally employed to separate the components of a solution, many applications for which evaporators are commonly
use of solid-liquid equilibrium should be considered it may employed. Energy consumption of paper-plant black-liquor
be cheaper. This paper describes a case study of recovery of evaporators could be reduced by a half by using freezing. Freeze
acetic acid from effluent via freeze crystallization. Complete separation is not the answer to every separation problem. Under
recovery of acetic acid from acetic acid-water solution by some circumstances, either capital cost or energy consumption
ordinary distillation is nearly impossible, because relative can be excessive.
volatility of this mixture in the range of 1-30% of acetic acid The current paper presents case study of acetic acid recovery
in water is very close to one. But the same separation is from effluent via freeze separation technique. The separation is
possible by freeze separation technique and it is found done in four stages. The paper also presents the loss and
experimentally that large amount of acetic acid (about 71.5%) recovery of acetic acid experimentally and stage wise energy
can be recovered via freeze separation technique. Also it is (heat of sublimation) required for the same.
found that the energy required for recovery of acetic acid is
much lower (about 24 times) than that of distillation. 2. Eutectic Freeze Crystallization (EFC)
In a binary mixture, a point is eventually reached where both
Key words Eutecic freeze crystallization, Solid-liquid components crystallize simultaneously: this is called the eutectic
equilibrium, Recovery of acetic acid, Heat of sublimation point and the crystallization carried out at eutectic point is called
Eutectic Freeze Crystallization (EFC).
Eutectic Freeze Crystallization is an extension of freeze
1. Introduction crystallization where the solution is cooled to the specific EFC
conditions. Ice and salt continue to form at the eutectic
The two major problems currently facing are firstly: the temperature and below until no solid liquid phase is left.
declining availability of sufficient quantities of water, and Eutectic Freeze Crystallization can be applied to solutions of
secondly: the deterioration of the quality of the available water. any concentration but it is best to operate with concentrations
However, with the increasing use of water recycling technology near the eutectic point. Eutectic Freeze Crystallization is a more
such as desalination, ion exchange regeneration, inorganic recently developed technology, where water and salts are
precipitation, biological processes and membrane treatments, the separated by reducing the temperature to the eutectic
result has been an increased generation of inorganic brines and temperature. The big advantage of EFC compared with other
concentrates. separation processes between water and salt is that EFC is more
Handling aqueous saltbearing streams, either for the recovery energy efficient, even up to 90%.
of the salt, or for the reduction of waste streams via a Eutectic freeze crystallization (EFC) is an alternative technology
concentration process, is energy intensive and thus costly. for the separation of highly concentrated aqueous streams.
Because the heat of fusion of ice (6.01 kJ/mol) is six times less Eutectic Freeze Crystallization is a technique that is capable of
than the heat of evaporation of water (40.65 kJ/mol), the energy separating aqueous solutions into pure water and pure-solidified
required to separate the water as ice is significantly less than that solutes and that is highly energy efficient, without the
required to separate it by evaporation, although obviously the introduction of any solvents. In addition, the simultaneous
energy for freezing will be more expensive than that for heating. production of pure ice and pure salt(s) is a major advantage.
Freeze crystallization has been used historically in those The principle of the process is as: when a solution containing
applications where other separation processes are incapable of dissolved contaminants is slowly frozen, water ice crystals form
effecting the separation. Although freeze crystallization has on the surface, and the contaminants are concentrated in the

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 International Journal of Scientific Engineering and Technology (ISSN : 2277-1581)
Volume 2 Issue 4, PP : 211-215 1 April 2013

remaining solution (the mother liquor). The ice crystals can be

separated from the mother liquor, washed and melted to yield a
nearly pure water stream. The mother liquor will contain a pure
salt, which crystallizes at the eutectic temperature. Theoretically,
a 100% yield can be obtained in a binary system, which is one
of the advantages of EFC technology. Pure water and salt can be
simultaneously recovered from aqueous solutions by EFC at low
energy costs and very high yields. This, however, has never led
to an industrial application for EFC because the process is
currently uneconomical.
The energy reductions under EFC operation are found to be
30% - 65% when compared to conventional multi-step
evaporation. EFC can also in principle achieve a 100 percent
separation of the solution into ice and salt, provided no purge Figure 1. Simple Binary Solid-Liquid Equilibrium Diagram
stream is needed. Corrosion of construction materials is also
subsequently reduced because of the low operating At the initial freezing temperature, only a small amount of
temperatures. The technology can also treat a wide variety of crystal will be formed. As crystals of a component are formed,
feed solutions without the addition or need of adding further the concentration of that component remaining in the solution is
solvents or chemicals. decreased. This causes the crystallization temperature of the
EFC technology has low energy requirements and theoretically remaining liquid to drop minutely, so that a lower operating
the feed can be completely converted to water and solidified temperature is needed to further crystallization. Thus, higher
solutes. The most prominent disadvantages of EFC are conversions to crystal phase require successively lower
investment costs and scale limitations but the current view is temperatures, as shown by the operating line BCD.
that these can be overcome. The current goal is to develop In a binary mixture, a point is eventually reached where both
eutectic freezing equipment for industrial scale. The ice and salt components crystallize simultaneously: this is called the eutectic
crystals need to have a high purity, should be easily separable and is shown as point D. At the eutectic, the concentrations of
and should be economically viable to compete with solid and liquid phase remain constant.
conventional separation techniques.
3.1 Acetic acid-water binary solid liquid equilibrium

3. Solid-Liquid Equilibrium
All freeze separation processes are based on the difference in
component concentrations between solid and liquid phases that
are in equilibrium. This can be most easily understood by
referring to Figure 1. As the solution (say, at point A) is cooled,
there will be some temperature at which a solid crystalline phase
begins to appear in liquid phase (Point B).
Usually only one component in the solution is crystallizes, and
that crystal is pure. This permits operation in a single theoretical
stage. The energy efficiency of the freeze separation process
results both from this single-stage capability and from the lower
latent heats associated with the solid-liquid phase change;
crystallization latent heats are one-half to one-tenth those of Figure 2. Acetic acid-Water SLE Diagram
vaporization.
The Acetic acid-water binary system and the data available in
the literature are summarized in Figure 2. It is noted that the
eutectic point of acetic acid-water system is at 59% acetic acid
and -16 0F (-26.67 0C).

4. Freeze Separation Technology

A general process schematic of the freeze crystallization
separation process is shown in Figure 3.

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 International Journal of Scientific Engineering and Technology (ISSN : 2277-1581)
Volume 2 Issue 4, PP : 211-215 1 April 2013

either melted product or some suitable wash material

that will not dissolve the crystal.
Most of the liquid is recycled to the freezer where more
of the desired constituent is recovered. The washed
crystal is then melted, either directly in contact with the
refrigerant or through a heat exchange surface.
Part of the melted product can be recycled to re-slurry
the washed crystal, as necessary. The net product flow
is pumped through the feed exchanger and out of the
system.
The refrigeration equipment removes heat from the
freezer and transfers it to the melter, with any excess
heat being removed from the system through the heat
Figure 3. Freeze Crystallization Process Diagram rejection compressor.
The Freezer removes sensible heat to cool the feed
4.1 Components of freeze process system down to the freezing point, and then latent heat to
convert liquid to solid.
Freezer (or crystallizer): A freezer, where a portion of
the liquid is changed to the solid phase by removing 5. Experimental Studies
heat. Or where, sufficient heat is removed from the
process fluid to crystallize up to 15% of the mass.
5.1 Experimental Procedure
Separator (Crystal purifier): A crystal purifier, where
the crystal phase is separated from the remaining
The eutectic point of acetic acid from the data is -26 0C. So to
liquid, and the crystals are washed to remove adhering
reach the point the system is divided in four stages (Stage 1: -4
concentrate from the surface. The separated 0
C, Stage 2: -18 0C, Stage 3: -23 0C, Stage 4: -26 0C) as shown
concentrate is recycled to the freezer to provide any
in fig 3.
desired recovery. The Separator can be a centrifugal
device, a filter, a screen, or a vessel called a wash
column.
Refrigeration Cycle (Heat pump): A heat pump that
takes heat out of the freezer and transfers it either to
cooling water or to the melting crystal that is removed
from the purification section.
Feed heat Exchanger: A feed heat-exchanger is
employed to recover the 'cold energy' from the process
streams, for cooling the fresh feed material. In other
word, it is used to pre-cool the feed by using the cold
product and concentrate, thus reducing the load on the
freezer.

Figure 4. Acetic acid recovery process diagram

Initially taken feed solution of 2% acetic acid and is frozen up to
-40C. Ice is separated out and the filtrate is taken to the second
4.2 General operating mode stage in which it is frozen to -180C. The same procedure is
repeated for third stage (-23 0C) and fourth stage (-26 0C). The
Feed enters the process through heat exchangers where acetic acid is lost only from the first stage as ice slurry. The ice
the cold is recovered from the product and concentrate slurry from other stages except first stage is proposed to recycle
streams exiting the system. This feed then enters the to the feed solution. After each stage ice is separated out and the
freezer or crystallizer where a portion of it is converted filtrate is analyzed.
to a solid, relatively small (100 to 500 microns)
crystals. 5.2. Results
The crystals are pumped as slurry from the freezer to a
separator which removes the liquid from the slurry, and 5.2.1 Stage wise Results
usually washes the crystals with a small portion of

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 International Journal of Scientific Engineering and Technology (ISSN : 2277-1581)
Volume 2 Issue 4, PP : 211-215 1 April 2013

Stage I
The acetic acid is lost only from first stage as the ice slurry from
second, third and fourth stages are proposed to recycle to the
feed solution.

Stage II

Basis: 1 kg feed

Overall M.B. : F=1=I + M

AA Balance : (0.02)(1) = (I)(WAA) + (M)(0.0673)
Also, from the result of stage I: I/M = 3.7

M= 0.2127, I= 0.7843, WAA= 0.00725

% Loss of AA = 28.43%
Stage III % Recovery of AA = 71.57%

5.2.4 Stage wise heat of sublimation required

Basis: 1000 kg of 2% Acetic acid

Heat of fusion of ice = 6.01 KJ/mol

Table 2. Heat of sublimation for each stage

Stage Heat of Sublimation required (KJ)
I 258.03
II 56.44
Stage IV
III 6.46
IV 1.272
Total 322.20 KJ 350 KJ

For the same separation, energy required by reboiler of

distillation column is approximately 8700 KJ (6).

5.2.2 Trial wise Results

6. Conclusion
Table 1. Concentration of Acetic Acid after each trial and
each stage Wastes have been considered to be a serious worldwide
Concentration of Acetic acid (%) environmental problem in recent years. Because of increasing
Temp.
Stage 1st 2nd 3rd pollution, these wastes should be treated. However, industrial
(0C) Average wastes can contain a number of valuable organic components.
trial trial trial
I -4 6.82 6.51 6.86 6.73% Recovery of these components is important economically.
II - 18 37.94 38.81 38.57 38.44% Using conventional distillation techniques, the separation of
III - 23 52.40 51.90 53.59 52.63% acetic acid and water is both impractical and uneconomical,
IV - 26 58.50 57.85 58.40 58.25% because it often requires large number of trays and a high reflux
ratio.
5.2.3 Loss of Acetic acid In practice special techniques are used depending on the
concentration of acetic acid. Complete recovery of acetic acid

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 International Journal of Scientific Engineering and Technology (ISSN : 2277-1581)
Volume 2 Issue 4, PP : 211-215 1 April 2013

from acetic acid-water solution by ordinary distillation is nearly I. James A. Heist, Freeze crystallization, Chemical
impossible, because relative volatility of this mixture in the Engineering, May 7, 1979, 72-82
range of 1-30% of acetic acid in water is very close to one. For II. James A. Heist, Freeze crystallization: Improving the
this range, either liquid-liquid extraction or azeotropic energy efficiency of a low energy separation process,
distillation is conventionally used. But same require high cost. Third Industrial Energy Technology Conference
Same can be possible economically by using freeze separation Houston, TX, April 26-29, 1981, 97-105
technique. So, for very dilute stream of acetic acid in water III. James A. Heist, Freeze crystallization processes:
(effluent stream), freeze crystallization seems to be more Efficiency by flexibility, Fifth Industrial Energy
economical technique. Also it is found experimentally that about Technology Conference Volume II, Houston, TX,
71.5% of acetic acid can be recovered by using freeze April 17-20, 1983, 837-845
separation technique. It is also found that for recovery of acetic IV. F. van der Ham et al., Eutectic freeze crystallization
acid (1000 kg of 2% acetic acid), the energy (heat of simultaneous formation and separation of two solid
sublimation) required by freeze separation (350 KJ) is much phases, Journal of Crystal Growth 198/199 (1999)
lower (about 24 times) than that of distillation (8700 KJ). Hence 744-748
the recovery of such organic acid becomes important V. B.I. Bhatt and S.B. Thakore, Stochiometry, Tata
environmentally as well as economically. McGraw Hill Education Pvt Ltd, New Delhi
VI. S.B. Thakore and B.I. Bhatt, Introduction to Process
Engineering and Design, Tata McGraw Hill Education
Pvt Ltd, New Delhi,

7. References

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