2464 Ind. Eng. Chem. Res.

1995,34, 2464-2467

Recovery of Very Dilute Acetic Acid Using Ion Exchange

Frikkie L. D. Cloete* and Amo P. Marais1
Department of Chemical Engineering, University of Stellenbosch, Stellenbosch, 7599 South Africa

Acetic acid can be recovered from 1% solutions using weakly basic ion exchange resins. The
acid is adsorbed by the free-base form of the resin, which can then be eluted using a slurry of
lime to give a solution of calcium acetate. This solution could either be evaporated to crystallize
calcium acetate or reacted with sulfuric acid to form acetic acid and gypsum. Laboratory tests
of the proposed process gave product solutions of 15-20% acetic acid using pure 1% acetic acid
as feed. Some measurements using a typical industrial effluent gave similar recoveries and
showed that there was no initial fouling of the resins.

Introduction ion exchange in a fluidized or agitated bed contactor.

Such techniques have been used in the recovery of
Acetic and related acids occur in many industrial uranium from ore slurries even up to 40% suspended
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wastewaters, often mixed with several other classes of

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solids (Merritt, 1971; Cloete, 1981).

organic compounds (Helsel, 1977; Kohn, 1979; Ricker
et al., 1980). The recovery of very dilute acetic acid and
its higher value homologues could be justified by adding
the savings in effluent treatment to the value of the acid
recovered.
The process proposed in this article incorporates well-
known principles of ion exchange, as are comprehen-
sively described by Helfferich (1962). A very dilute
waste stream from a petrochemical complex containing
0.9% total organic acids was considered as a typical
example. A weakly basic ion exchange resin in the free-
base form could be used to extract acetic and related
acids. The distribution coefficient is extremely high,
since the extraction is based on the neutralization of a
base by an acid. The ion exchanger is totally insoluble:
there is no release of toxic solvents to cause problems
further downstream. This achieves the objectives of
previous workers, summarized by Althouse and Tav-
larides (1992).
The recovery of the acids from the resin is simply
achieved by raising the pH with a suspension of lime
in a fluidized or agitated bed. The time suspension
dissolves as reaction proceeds, forming a solution of the
highly soluble calcium acetate in the range 15-25%. A
similar technique was used by Hendry (1982) in a
partial demineralizing process for effluents.
The logical development of the work of Althouse and
Tavlarides (1992) is to use a solid adsorbent for the
recovery of acetic acid, which is then eluted with lime
slurry. This is the basis of an article by Reisinger and
King (1995), which has been drawn to our attention
(King, 1994). There are considerable similarities be-
tween some of their results and the work reported here.
A typical effluent could contain a mixture of organic
acids as well as non-acids. Any non-acids adsorbed
could be removed from the resin by washing with water.
The acids could then be eluted from the resin by raising
the pH. The subsequent separation of acids could be
carried out using distillations similar to those used in
the manufacture of acetic acid by the oxidation of
hydrocarbons.
Effluent streams containing significant amounts of
suspended solids would be more easily handled using
* Address
correspondence to this author. E-mail:
fcloete@maties.sun.ac.za.
f Present address: Process
Development, SASTECH Ltd.,
P.O. Box 1, Sasolburg, 9570 South Africa.
0888-5885/95/2634-2464$09.00/0
This project consited of preliminary studies of the
behavior of very dilute pure acetic acid when taken up
by various weak base ion exchange resins and eluted
with a slurry of lime. The promising results of this work
were also briefly verified using samples of a typical
effluent from a petrochemical complex.
Experimental Procedures and Results
Standardization of Resins. The ion exchange
resins considered most likely to function were weak base
(Duolite A-368 and Duolite A-378) and intermediate
base (Duolite A-375), from the Rohm and Haas range.
The capacities of the resins were determined by loading
to saturation by passing excess 1 M hydrochloric acid
through a bed of resin in a filter tube of 20 mm
diameter, washing with distilled water, and eluting with
1M sodium hydroxide. The flow rates used were about
4 bed volumes per hour and ambient temperature was
25 °C. Analytical quality reagents were used.
The quantity of chloride eluted was measured by
titration of the total eluate with silver nitrate, after
adjusting the pH to between 7 and 10 with nitric acid.
Potassium chromate was used as indicator. The capac-
ity of each resin waa calculated on the volume of resin
measured in the free-base form under water in a
measuring cylinder.
The results are given in Table 1 and show that the
measured capacities were generally below the nominal
values quoted by the manufacturer. More information
appears in a thesis by Marais (1994).
Preliminary Tests of Resins for Suitability in
the Proposed Process. Samples of 125 mL of resins
in the free-base form were measured under water and
added to measured volumes of 1L of 0.15 M acetic acid
(about 1% weight), made up from analytical quality
glacial acid. The mixtures were tumbled in sealed glass
jars on rollers for 2 h to allow the adsorption reaction
to take place. Experiments had shown that the reaction
was complete after 1 h within the accuracy of the
measurements.
The resin was then filtered off and washed using a
Buchner filter. The combined filtrate and washings
were titrated with standardized sodium hydroxide using
phenolphthalein indicator. A mass balance gave the
amount of acetic acid adsorbed by the resin from the
feed solution.
The washed resin was transferred to another glass
jar followed by a lime sluny, using a 10% stoichiometric
© 1995 American Chemical Society

Table 1. Ion Exchange Resins Used™
Duolite A-375
pore type macroporous
functional groups tertiary amine
matrix polyacrylic
bead density (free base) 1.07 g/L
nominal capacity 1.6 equiv/L
measured capacity 1.40 equiv/L
a
Manufactured by Rohm and Haas, supplied by ACIX/NCP Ltd., Germiston, South Africa.
Table 2. Recovery of Acetate as Calcium Acetate
Crystals
loading of av overall
acetate on acetate
type of resin resin (equiv/L) recovery (%)
Duolite A-375 1.12 93
Duolite A-368 0.93 75
Duolite A-378 0.90 78
0
Averages from eight cycles of adsorption by and elution from
resin sample.
excess of powdered chemically pure calcium hydroxide,
above the amount of acetic acid taken up by the resin.
The jar was sealed and tumbled on rollers overnight to
achieve complete elution.
The resin was filtered off from the reaction mixture
and washed. The liquid product consisted of a solution
of calcium acetate, which was evaporated to dryness in
an oven at 120 °C and weighed as Ca(CH3COO)2- This
weight was used to calculate the overall recovery of
acetate achieved by the process and the loading of
acetate recovered from the resin.
The samples of resin were each recycled through eight
cycles of absorption and elution to give an average
percentage recovery, as reported in Table 2. The
relative standard deviation in overall recoveries was 1%,
which indicates good repeatability of the experimental
procedures. Full details are given by Marais (1994).
The best recovery was obtained from Duolite-375,
based on tertiary amine functional groups, which is
more strongly basic than the other two resins. The
higher basicity accounts for the superior recovery of
acetic acid on this resin.
Details of Table 2, from Marais (1994), show that
98.5% of the acetic acid was taken up from solution by
Duolite A-375 and 93% of the original acid present in
solution was recovered as calcium acetate crystals.
Comparative values for Duolite A-368 were 82.5% and
78% and for Duolite A-378 were 81% and 75%. Values
for the elution of acetic acid from Amberlite IRA-35 at
60 °C with dolomitic lime slurry were obtained by
Reisinger and King (1995) which correspond to those
obtained here for Duolite A-375.
These recovery values were merely the results of an
arbitrary comparative test of the three resins with a
stoichiometric excess of resin in each case (15% excess
resin for A-375 and A-378 and 30% excess for A-368).
They were not intended as a realistic process simulation
experiment.
Preliminary Tests on an Actual Effluent Using
Duolite A-375 Resin. The effect of a typical effluent
on the total ion exchange capacity of Duolite A-375 was
tested using a sample which contained a mixture of
acetic, propionic, butyric, and valeric acids and their
isomers and other non-acids. The total initial strength
of the acids was 0.21 N, and acetic acid comprized about
70% of the acids.
Ind. Eng. Chem. Res., Vol. 34, No. 7, 1995 2465
type of resin
Duolite A-368 Duolite A-378
macroporous macroporous
90% secondary amines 85% secondary amines
polystyrene—DVB polystyrene DVB
-
1.03 g/L 1.05 g/L
1.7 equiv/L 1.3 equiv/L
1.58 equiv/L 1.39 equiv/L
A sample of 100 mL of Duolite A-375 resin was put
through eight cycles of adsorption of acids from effluent
std dev of and elution with lime, followed by continuous tumbling
recovery in a large excess of effluent for 4 weeks, giving about
values (%) 1000 h of total exposure to effluent. The various acids
1 were recovered in the same proportions as those occur-
1
ring in the effluent. After elution finally with a strong
1
base (NaOH), the capacity of the resin was measured
at 1.36 equiv/L, which was still 97% of the value
measured initially for that resin, 1.4 equiv/L, as given
in Table 1.
Conversion of a Solution of Calcium Acetate to
Acetic Acid. In some applications, where there is no
market for calcium acetate as a deicing salt, the
recovered acetate will have to be processed further at
the cost of at least a stoichiometric amount of sulfuric
acid.
The conversion of the solution of calcium acetate
eluted from the resin with lime to a solution of acetic
acid was simply achieved by mixing with 98% sulfuric
acid. The overall reaction of sulfuric acid with calcium
acetate gives a precipitate of gypsum and a solution of
acetic acid.
The precipitate of white gypsum crystals formed was
readily filtered on a Buchner filter and was washed with
distilled water to recover acetic acid. The moisture
content of the final filter cake was about 38%, and this
accounted for a loss of about 5% of the acetic acid
recovered. The specific resistance of the cake formed
was low (r = 11.4 m-2).
The concentrations of acetic acid solutions finally
produced, incorporating the cake washings, were in the
range 15-25%. The calcium content of this solution was
measured at 300 ppm, while sulfate was estimated at
about 200 ppm from the solubility product.
Equilibrium Data for Acetic Acid on Duolite
A-375 Resin. Quantitative data on equilibria between
dilute solutions of acetic acid and Duolite A-375 ion
exchange resin were obtained for use in design studies.
A solution of 0.15 M acetic acid was made up from
analytical quality glacial acetic acid: various measured
volumes of this feed solution were tumbled for 24 h in
sealed glass jars with samples of 125 mL of resin in the
free-base form. Ambient temperature was 25 °C.
After this process, the contents were filtered and the
clear filtrate was titrated with standardized NaOH
solution as described above. The loading of acetic acid
on the resin was calculated from the fall in concentra-
tion of the acetic acid. This loading was then taken as
being in equilibrium with the final concentration of
acetic acid in solution. A range of values was obtained
by varying the quantities of acid initially used in the
reaction.
The data in Figure 1 show a sharp step function,
indicative of strong adsorption of acetic acid, until a
2466 Ind. Eng. Chem. Res., Vol. 34, No. 7,1995
Concentration of acetic acid in solution (eq/L)
Figure 1. Equilibrium distribution of acetic add between Duolite
A-375 and dilute solution.
Time (minutes)
Figure 2. Kinetics for adsorption of acetic acid with Duolite A-375
from dilute solution.
plateau is reached at a loading of about 1.2 equiv/L
resin, after which the loading is not affected by fiirther
increases in concentration of acid.
Kinetics of Adsorption of Acetic Acid on Duolite
A-375 Resin. Preliminary kinetic studies were done
on the adsorption of acetic acid as a guide for sizing the
reactor, which was anticipated to be of a continuous
fluidized bed design for large-scale applications (Cloete
and Streat, 1970).
Samples of 50 mL of resin in the free-base form were
tumbled in a sealed glass jar with 500 mL of 0.15 M
acetic acid, as carried out previously, but the reaction
was stopped at various times and the resin filtered off.
The filtrate was titrated to determine the loading of acid
on the resin at the time of stoppage. The resin was then
eluted and used again for fiirther measurement. The
reactions took place at 25 °C.
The loading is shown as a function of reaction time
in Figure 2. The batch reaction appears to be sensibly
complete complete after 1 h, but the contact time in a
continuous countercurrent process will be considerably
shorter, as mentioned by Marais (1994).
Kinetics of Elution of Acetic Acid from Duolite
A-375 Resin with Lime Slurry. Experiments similar
to the studies of adsorption were carried out using 35
mL samples of resin fully loaded with acetic add. These
were added to glass jars together with 500 mL of
distilled water and an excess of powdered lime. The jars
were sealed and tumbled at 25 °C for various times,
after which the solution was filtered off and titrated for
acetic acid, as described above.
Time (minutes)
Figure 3. Kinetics for elution of acetic acid from Duolite A-375
with calcium hydroxide slurry.
It is clear from Figure 3 that most add is removed
after 20 min, but that about 5% does not appear to come
off. This has not affected the performance of the resin,
so no cumulative effects are apparent within the limited
scope of this work.
Discussion
It is clear from Tables 1 and 2 that not all ion
exchange sites on the resins are fully loaded with acetic
acid. Resin A-375, containing mostly tertiary amine
active sites, has nearly 80% of its capadty utilized,
whereas the other two contain mainly secondary amines
and use 60% or less. This result would be expected from
the findings of many other writers cited above that
tertiary amines dissolved in an organic diluent are very
effective in extracting acetic acid.
The reactions with the resin are essentially protona-
tion and deprotonation reactions rather than ion ex-
change reactions. The extreme form of the equilibrium
curve in Figure 1 is what would be expected for such a
process. Similar curves are obtained when the acid or
hydroxide forms of strongly acidic or basic ion exchang-
ers are neutralized, which are a well-known class of ion
exchange reactions.
Preliminary measurements of the adsorption of acids
from a petrochemical effluent and their elution with
lime, followed by 1 month of continual exposure to the
effluent showed no serious effects on the capacity of the
resin. This shows that the process can work with a
complex effluent solution within the limits of the
restricted test period. All the homologues of acetic acid
were eluted together using lime. Subsequent separation
of specific acids using distillation should prove straight-
forward.
The kinetics of both the adsorption and elution
reactions are relatively fast. There should be no prob-
lem in designing continuous countercurrent processes
to handle both these parts of the recovery process.
Conclusions
Ion exchange, based on weakly basic resins, has been
demonstrated as a potentially useful technique for
recovering acetic acid and its homologues from dilute
aqueous solutions ranging down to 1%.
There are also potential advantages over alternative
processes based on solvent extraction. These include
the ability to handle feeds with high loadings of sus-

pended solids and the absence of any traces of toxic
solvents added to effluent streams.
Acknowledgment
The authors wish to thank Sastech Ltd., a member
of the Sasol group of companies, for financial support
of this project.
Literature Cited
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Cloete, F. L. D.; Streat, M. Solid/fluid contacting. U.S. Patent
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Helfferich, F. Ion Exchange·, McGraw-Hill: New York, 1962;
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Received for review July 12, 1994
Revised manuscript received April 12, 1995
Accepted April 26, 1995®
IE9404386
®
Abstract published in Advance ACS Abstracts, June 1,
1995.