Short Communication

Recovery of acetic acid and propionic

acid from aqueous waste stream
M. N. Ingale and V. V. Mahajani
Chemical Engineering Division, Department of Chemical Technology, University of
Bombay, Matunga, Bombay, India

Keywords:

acetic acid; propionic acid; recovery; waste stream; tributylphosphate

Introduction

Experimental findings

Recovery of low-molecular-weight acids, namely, acetic

acid and propionic acid, is of considerable commercial
interest even from an environmental engineering viewpoint. Tertiary amines (trioctylamine), trioctylphosphine
oxide and tributyl phosphate (TBP) have recently been
found to be superior to conventional solvents such as
ketones, aldehydes, and alcohols.
While using a system for extraction, the process engineer must ensure that the extractant and diluent (if any)
do not contribute to chemical oxygen demand of the
aqueous stream. Amine-base extractant may pose problem for the biological degradation process. By and large,
the waste streams from chemical process plants are likely
to have inorganic salts such as Na,SO, or NaCl, and
therefore it is essential for process design to have a prior
knowledge of how salt affects distribution coefficient.
There exists scant information in the published literature
on recovery of acetic acid and propionic acid at very low
concentrations from the aqueous stream containing salts
such as NaCl and Na$O,. Wardell and King have measured effectiveness
of phosphoryl
compounds as
extracting agents and found that the equilibrium distribution, K,, increases in the order phosphate (TBP) C phosphonate (dibutyl butyl phosphonate) < phosphine oxide
(tributyl phosphine oxide, TBPO). Considering the ease
of availability and the price, TBP may be preferred over
other phosphoryl compounds. Further, TBP has very low
solubility in water (0.039 wt %). It was therefore thought
desirable to study recovery of acetic acid and propionic
acid from aqueous stream with and without Na,SOflaCl
using pure TBP as an extractant.
In the present investigation the effect of concentrations
of acids on KD was studied. Also, the effect of mixed
acids on KD was studied. Further, variation in KD in the
presence of Na2S04 and NaCl was measured.

Reagents

Address reprint requests to Dr. V. V. Mahajani at the Chemical

Engineering Division, Department of Chemical Technology, University
of Bombay, Matunga, Bombay 400 019, India.
Received 9 September 1993; accepted 28 October 1993

0 1994 Butterworth-Heinemann

All the chemicals (acetic acid, propionic acid, NaCl and

Na,SO,) used were of reagent grade. Tributylphosphate,
having purity of 99% was used as an extractant.
To find out the distribution coefficients, 25 mL of an
aqueous solution of acid (acetic acid or propionic acid,
as the case may be) was contacted with 25 mL of solvent
in a 250-mL-capacity stoppered flask using a magnetic
stirrer in a thermostated bath maintained at temperature
30C. The mixture was stirred for 3 h. This time was
sufficient to establish the equilibrium between two
phases. The mixture was then transferred in a separating
funnel and allowed to stand for 2 h. The two phases,
aqueous (rafftnate) and organic, were separated and analyzed for acid content. In general, only the aqueous phase
was analyzed for its acid concentration. The organic phase
acid concentration was obtained from material balance.
However, the organic phase was checked periodically for
its acid content. The distribution coefficients for mixed
acid system, namely, aqueous solution containing known
concentration of acetic acid and propionic acid in 1: 1
proportion was measured. To see the effect of salt present
in aqueous solution of acid, on the distribution coefficient,
separate extraction experiments were carried out. For this
a known amount of salt (Na,SO, or NaCl, as the case
may be) was added to the aqueous acid solution. The
amount of Na,SO, and NaCl was added in such a way
that the ionic strength of resulting solution was the same.
The ionic strength of salt used was varied from 1.05-4.22
kg ion/m3. Concentration of acids in aqueous phase was
determined by using gas chromatograph (GC) technique.
Both internal and external standard techniques were
employed for the analysis of acids. Acetic acid was used
as internal standard for the analysis of propionic acid and
vice versa. For the mixed acid system, only the external
standard method was used for the analysis of acetic acid
and propionic acid. Carbopack BDA 4% carbowax 2 M
@O/100 mesh) column in FID mode of operation was
used to analyze acids on GC.

Sep. Technol., 1994, vol. 4, April

123

Recovery of acetic and propionic acid: M. N. lngale and K K Mahajani

90

concentration), KDincreases from 1.77 to 3.74 when total

acid concentration increases from 250 to 1,000 mg/L and
then falls to average value of 1.72 (Figure 2). This value
agrees well with KD= 1.73 reported by Page1 and McLafferty,6 and Page1 and Schwab at 30C.

70
S

System: Propionic acid-water-TBP

3
z

Like acetic acid in case of propionic acid, KD increases

steadily for acid concentration from 250 mg/L to 2,000
mg/L from 4.55 to 12.33 and then remains steady at
12.78, for total propionic acid concentration > 2,000 mg/
L (Figure 2). This value also agrees well with that
reported by Fahim et al8 (KD = 12.40 at 25C).

50

F
x
2
a
t

30

System: Acids-water-salt-TBP

10

-10

1300

1350

WAVENUMBER

1250
Cd

1200
1

Figure 1 FT i.r. spectra of TBP (---), acetic acid: TBP (---) and
propionic acid: TBP (--).
TBP = tributyl phosphate.

Results and discussions

Tributylphosphate is Lewis base and as a result can form
complex with organic acids (acetic and propionic acid).
The FT i.r. spectra (Bruker IFS-88 model) as indicated
in Figure 1 do substantiate complex formation.
The extraction of monocarboxylic acids by strong solvating extractants such as the organophosphorus compounds, TBP, being a heterogeneous process involves
several ionic reactions. The various steps involved in the
extraction equilibria have been well reviewed by Kertest
and King.
However, for the ease of utility to process environmental engineers we defined the overall distribution coefftcient, K,, as
KD=E]08

Industrial waste stream may contain salts such as Na2S04

or NaCl. Therefore, the effect of salts on KDwas studied.
At acetic acid concentrations of 500 mg/L, KDdecreases
as ionic strength is increased from 1.056 to 4.22 Kg ion/
m3. From Table 1, all along it is seen that NaCl has a
lower effect on KD as compared with Na$O.,.
At 1,000 ppm acid or more, KDvalues are observed to
be higher in the case of NaCl compared with those
obtained with Na$O+ The effect of NaS04 and NaCl on
KDin the case of propionic acid is exhibited in Table 2.
It is seen that for propionic acid concentration 2,000 mg/
L or more, presence of NaCl resulted in considerable
enhancement in KDvalues. Figure 3 shows effect of ionic
strength of Na2S0, and NaCl on distribution coefficient
of acetic acid and propionic acid at concentration of 3,000
mg/L. Mixed acids equilibria have been presented in Figure 4. The presence of propionic acid resulted in higher
KDvalue for acetic acid (almost by a factor of 2). However,
KD value for propionic acid is increased marginally.
Because of the intrinsic higher value of KD,more propi-

(1)

aq

where [HA!, is total (analytical) concentrations of the

acid in all its possible existing forms (dissociated and
undissociated acid) in aqueous phase, and [HA], is the
total concentration of acid in all its possible existing forms
(acid as such, dimer acid and acid-TBP complex) in the
organic phase.
System: Acetic acid-water-TBP
For aqueous phase concentration less than 1,000 mg/L
of acetic acid (total concentration and not equilibrium

124

Sep. Technol.,

1994, vol. 4, April

Figure 2 Effect of acid concentration on distribution

coefficient. AcH = acetic acid; PrH = propionic acid.

Recovery of acetic and propionic acid: M. N. lngale and K K Mahajani

Table 1 Effect of ionic strength of salt on distribution
coefficient of acetic acid at various concentrations

Acid
concentration
(mg/U

Conclusions

Distribution
coefficient, KD
Ionic strength
(kg ion/m3)

Na,SO,

NaCl

500

1.056
2.112
3.168
4.224

1.84
1.48
1.30
0.92

1.31
1.08
0.79
0.66

1,000

1.056
2.112
3.168
4.224

2.04
2.79
2.92
3.18

2.87
3.06
3.38
3.58

1,500

1.056
2.112
3.168
4.224

1.72
2.09
2.65
3.10

2.17
2.48
2.82
3.45

2,000

1.056
2.112
3.168
4.224

1.89
2.22
2.46
2.98

2.13
2.52
2.86
3.22

2,500

1.056
2.112
3.168
4.224

2.03
2.31
2.57
2.88

3.42
3.48
3.91
4.47

1.056
2.112
3.168
4.224

2.47
2.79
2.94
3.26

2.76
3.43
4.15
4.91

3,000

1. FI-IR spectra of the acetic acid-TBP and propionic

acid-TBP phase do indicate acid-TBP complex formation.
2. Ionic strength and nature of the ion have substantial
effect on KD for-both acids.

3750
Acid

concentration.

v/l

Figure 4 Mixed acids equilibrium: distribution coefficient.

AcH = acetic acid; PrH = propionic acid.

Table 2 Effect of ionic strength of salt on distribution

coefficient of propionic acid at various concentrations

.e

;;
u
.

.sf,
t

Acid

concentration,

3000

w/l

coefficient, K.
concentration
(mg/L)

-AcN+Nm
SO,
++mAotl+Na
E1
..m.- Pr N+Nn SO.
AAAAAP~P+N.~~

5.84
5.49
4.15
6.35

5.41
8.61
11.82
9.41

1,000

1.056
2.112
3.168
4.224

852
8.80
6.29

7.13
9.00
9.63
10.11

1,500

1.056
2.112
3.168
4.224

10.11
12.76
19.27
19.00

16.85
21.38
26.77
28.41

2,000

1.056
2.112
3.168
4.224

12.60
13.70
14.03
17.18

14.38
19.83
24.31
23.69

2,500

1.056
2.112
3.168
4.224

15.77
17.38
21.72
18.68

17.24
23.27
23.75
28.09

3,000

1.056
2.112
3.168
4.224

13.27
18.44
18.23
19.98

14.62
18.73
27.30
45.15

OS

21

Ionic

Strength

K&ion/&

Figure 3 Effect of ionic strength on distribution coefficient.

AcH = acetic acid; PrH = propionic acid.

onic acid goes into TBP phase and forms a complex

with TBP the way acetic acid does. Further propionic
acid may also be forming a complex in the TBP phase
via hydrogen bonding with acetic acid. As a result, we
obtain substantial increase in KD for acetic acid in the
presence of propionic acid.

NaCl

1.056
2.112
3.168
4.224

Na,S04

500

Ionic strength
(kg ion/m3)

Sep. Technol., 1994, vol. 4, April

125

Recovery

of acetic and propionic

acid: M. N. lngale and K CcMahajani

3. In the case of mixture of acids, the presence of

propionic acid (higher KD) resulted in considerable
enhancement in KD for acetic acid.

4.
5.
6.

References
1.
2.
3.

126

Wardell, J.M. and King, C.J. Solvent equilibria for extraction of

carboxylic acids from water. J. Chem. Eng. Data 1978,2,144-148
King, C.J. Amine based systems for carboxylic acids recovery.
Chemrech. 1992, 5, 285-291
Ricker, N.L., Pittman, E.F. and King, C.J. Solvent properties of
organic bases for extraction of acetic acid from water. J. Sep.

Sep. Technol., 1994, vol. 4, April

7.

8.

Proc. Technol. 1980, 2, 23-30

Rydberg, J., Musikas, C. and Choppin, G.R. Principles and
Practices ofSolvent Extraction. New York: Marcel Dekker, 1992,
PP. 32
Kertest, A.S. and King, C.J. Extraction chemistry of fermentation
product carboxylic acids. Biotechnol. Bioeng. 1486.28.269-282
Pagel. H.A. and McLaffertv. F.W. Use of tributvlohosohate for
extracting organic acids fromaqueous solution. A&i Chkn. 1948,
3, 272
Pagel, H.A. and Schwab, K.D. Effect of temperature on
tributylphosphate extracting agent for organic acids. Anal. Chem.
1950,9, 1207-1208
Fahim, M.A., Qader, A. and Hughes, M.A. Extraction equilibria
of acetic and propionic acid from dilute aqueous solution by
several solvents. .I. Sep. Sci. Technol. 1992, 13, 1809-1821