J. Chem. T echnol. Biotechnol.

1998, 73, 127È130

Wet Oxidation of Acetic Acid by H O Catalyzed

by Transition Metal-Exchanged NaY2 Zeolites¤
2
F. Larachi,* S. Le vesque & A. Sayari
Department of Chemical Engineering & CERPIC, Universite Laval, Ste-Foy, Quebec, Canada, G1K 7P4
(Received 3 February 1998 ; revised version received 11 March 1998 ; accepted 29 June 1998)

Abstract : During the wet oxidation of contaminated wastewaters, the destruction

of low molecular weight carboxylic acid intermediates such as acetic, glyoxalic,
and oxalic acids is often the rate-controlling step. Oxidation of acetic acid, a very
recalcitrant intermediate, requires compelling treatment severity. Heterogeneous
catalytic wet oxidation of model acetic acid aqueous solutions was conducted
under mild conditions (below the normal boiling point of water) using hydrogen
peroxide over various transition metal-exchanged NaY zeolites. Treatment of
Cu2`ÈNaY with oxalic acid [OA] led to a catalyst, Cu2`ÈNaY [OA], with sig-
niÐcantly improved properties in terms of total organic carbon (TOC) removal
efficiency and catalyst stability against leaching. This catalyst outperformed
homogeneous Cu2` by a factor of 2È2É5 times. Continuous feeding of H O
2 2
reduced its undesirable decomposition. Improvement of the TOC-degradation
performance by Cu2`ÈNaY [OA] was tentatively attributed to the removal of
sodium and possibly aluminium in the zeolite. ( 1998 Society of Chemical
Industry

J. Chem. T echnol. Biotechnol. 73, 127È130 (1998)

Key words : catalytic wet oxidation ; hydrogen peroxide ; acetic acid ; metal-
exchanged NaY zeolite catalyst

INTRODUCTION amounts of Cu2`, Mn2` or Co2` enhances the efficacy

Advanced oxidation processes for wastewater treatment
designate a number of aqueous phase oxidation tech-
nologies based primarily on the intermediacy and
immense oxidizing potential of the hydroxyl free radical
(OH~) in the oxidative destruction of organic pollutants.
The hydroxyl free radicals can be generated by various
catalytic (homogeneous and heterogeneous) wet oxida-
tion routes where hydrogen peroxide is used as an oxi-
dizer. In the FentonÏs reaction, the reagent system
(Fe2`/Fe3`ÈH O ) is used to unleash OH~ by the redox
2 2
reaction between H O and Fe2`. Addition of trace
2 2
* To whom correspondence should be addressed.
Email address : Ñarachi=gch.ulaval.ca
¤ Presented at the 47th Canadian Conf. Chem. Eng., Edmon-
ton, AB, Canada, October, 5È8 1997.
Contract/grant sponsor : Natural Sciences and Engineering
Research Council of Canada.
Contract/grant sponsor : Fonds pour la Formation de Cher-
cheurs et lÏAide à la Recherche du Quebec.
127
( 1998 Society of Chemical Industry. J. Chem. T echnol. Biotechnol. 0268-2575/98/$17.50.
of FentonÏs route.1 The major weakness of these
systems is the tight pH control required to prevent pre-
cipitation of Fe(OH) , which occurs at pH [ 5.2
3
Homogeneous catalysts consisting of a mixture of
Cu2`, Mn2`, Fe2` used in conjunction with H O
2 2
showed synergistic e†ects and high destruction levels
under mild conditions.3,4 However, without proper pH
adjustment, precipitation of the catalyst may also occur.
In summary, even though all the Fenton-like catalysts
o†er a cost-e†ective source of hydroxyl radicals and
involve easy-to-handle reagents, additional steps are
required both before and after the oxidation step for pH
adjustment and catalyst precipitation/separation.
To circumvent the above drawbacks, attempts are
being undertaken to explore the feasibility of heter-
ogeneously catalyzed Fenton-like routes for the destruc-
tion of the water-dissolved organic pollutants.5,6 This
strategy combines the advantages of the Fenton-like
systems and those of heterogeneously-catalyzed wet oxi-
dation. This paper is a preliminary account of the wet
Printed in Great Britain
128
oxidation of acetic acid by hydrogen peroxide over new
heterogeneous catalysts based on Cu2`, Fe2`, Fe3`,
Mn2` and Ce3`-exchanged NaY zeolites. There are
two main reasons behind this selection. First, the
destruction of low molecular weight carboxylic acid
intermediates such as acetic acid is often a rate-
controlling step in the overall oxidation process.
Because of their resistance to oxidation, they tend to
build up in the solution. It is thus imperative to develop
a heterogeneous catalyst able to efficiently degrade
acetic acid. Second, some cations (e.g. Cu2`, Fe2`) were
found to be excellent homogeneous catalysts. Since zeo-
lites can play the role of a “solid solventÏ in which the
exchanged cations are stabilized within the pore struc-
ture, while they can move relatively freely as in solution,
it is anticipated that some of these catalysts combine the
efficiency of homogeneous cations and the convenience
of heterogeneous catalysts. In addition, these catalysts
must exhibit marginal leaching of active cations, and
minimal H O parasitic decomposition.
2 2
EXPERIMENTAL
Table 1 lists the various catalysts used in the screening
tests. They were prepared by ion exchange using dilute
solutions of appropriate salts. For multimetallic
systems, the metal cations were exchanged simulta-
neously.
Approximately 100 cm3 of a 2 g dm~3 acetic acid
(AA) aqueous solution (TOC \ 800 ppm) was treated
batchwise at 363 K and 1 atm in a 500 cm3 glass
reactor equipped with a magnetic stirrer and a con-
denser. After the solution was heated up to the preset
temperature, both catalyst and H O (33 wt%) were
2 2
added. No attempt was made to control pH during the
course of the reaction. The relative amount of H O
2 2
used will be referred to as R which represents the ratio
of the actual amount of H O to the amount required
2 2
to oxidize stoichiometrically acetic acid into carbon
dioxide and water. To assess the e†ect of the method of
H O addition on the extent of the parasitic decompo-
2 2
TABLE 1
Tested Catalysts
Catalyst wt.% of active metal
Fe2`ÈNaY 3É3
Fe3`ÈNaY 2É8
Cu2`ÈNaY 2É9
Mn2`ÈNaY 3É3
Ce3`ÈNaY 3É5
Fe2` : Mn2`ÈNaY 2É7, 2É3
Cu2` : Mn2`ÈNaY 2É7, 2É3
Cu2` : Ce3`ÈNaY 2É6, 4É4
Mn2` : Ce3`ÈNaY 3É0, 3É6
Fe2` : Cu2` : Mn2`ÈNaY 2É5, 2É0, 1É3
F. L arachi, S. L e vesque, A. Sayari
sition (leading to inactive molecular oxygen), the peroxi-
de was either injected at once (R \ 2É6) or fed
continuously (R \ 1É5) over a period of 60È120 min
using a syringe pump.
Total organic carbon content of solutions before and
after reaction was analyzed by means of a combustion/
non-dispersive infrared gas analyzer (Shimadzu 5050
instrument). The metal content in fresh (Table 1) and
used catalysts was determined by neutron activation in
a SLOWPOKE nuclear reactor. The metal leaching-o†
was calculated accordingly. Residual H O during wet
2 2
oxidation was titrated iodometrically with Na SO in
2 3
an excess of KI, CH CO H and ammonium molybdate.
3 2
To assess the reproducibility of the oxidation reac-
tions, up to six separate batches were prepared for each
catalyst under the same reaction conditions. The stan-
dard deviation on the measured TOC conversions was
equal to 3%. Similarly, for the residual hydrogen per-
oxide concentrations, the relative standard deviation
was estimated to be 17É7%.
RESULTS AND DISCUSSION
A series of samples was tested with the objective of
Ðnding heterogeneous catalysts with the following
properties : (i) high activity in terms of TOC reduction,
(ii) no leaching of active ingredients to beneÐt from the
advantages of heterogeneously-catalyzed reactions, and
to eliminate the additional pollution caused by the
release of soluble metal compounds, (iii) high H O
2 2
conversion with little or no decomposition.
Only fresh catalysts were employed in the screening
tests. Table 2 shows TOC conversions along with the
concentration of metals that leached into the solution
after 60 min of reaction at 363 K. In these experiments,
H O was added at once, and the initial catalyst
2 2
loading was 5 g dm~3. Only marginal TOC removal
occurred when acetic acid was oxidized either non-
catalytically (Ðrst entry) or over pure NaY zeolite
(second entry). As for the catalysts, they exhibited three
types of behavior : (i) efficient TOC depletion but exces-
sive leaching : Fe2`ÈNaY, Fe3`ÈNaY, Cu2` : Mn2`È
NaY, Cu2` : Ce3`ÈNaY, Fe2` : Cu2` : Mn2`ÈNaY ;
(ii) low TOC reduction regardless of their stability
against leaching : Mn2`ÈNaY, Ce3`ÈNaY,
Mn2` : Ce3`ÈNaY ; and (iii) acceptable TOC conver-
sion and excellent stability to leaching : Cu2`ÈNaY. The
latter catalyst was therefore chosen for further
investigation.
Using equal copper loadings, homogeneous Cu2`
(Table 3, second entry) was found to be slightly better
than fresh Cu2`ÈNaY (Ðfth entry). With the former
catalyst, less residual H O remained, but more H O
2 2 2 2
decomposed. In the absence of organic substrate, both
catalysts fully decomposed H O after 1 h. To split
2 2
converted H O into useful and decomposed (lost) frac-
2 2
Acetic acid oxidation over metal-exchanged NaY zeolite 129

TABLE 2
Removal of Acetic Acid by Various Heterogeneous Catalysts and Leaching-o†
of Active Metal Species (initial TOC (AA) \ 800 ppm, catalyst
loading \ 5 g dm~3, R \ 2É6, reaction time \ 60 min, temperature \ 363 K,
atmospheric pressure)

Catalyst % T OC removal [Metal] in solution (ppm)

No catalyst 10 È
NaY 5 È
Fe2`ÈNaY 31É5 (28)
Fe3`ÈNaY 33 (15)
Cu2`ÈNaY 18 (\3)
Mn2`ÈNaY 6 (35)
Ce3`ÈNaY 6 È
Fe2` : Mn2`ÈNaY 15É5 (24), (32)
Cu2` : Mn2`ÈNaY 34 (27), (20)
Cu2` : Ce3`ÈNaY 26 (41), (È)
Mn2` : Ce3`ÈNaY 5 (35), (33)
Fe2` : Cu2` : Mn2`ÈNaY 38 (9), (32), (20)

tions, we made the assumption that the converted TOC The strong enhancement of catalyst performance is
was transformed into CO , and the useful H O frac- most intriguing. At Ðrst, oxalic acid (OA) which is a
2 2 2
tion was computed accordingly. possible reaction intermediate, was thought to a†ect the
The stability of Cu2`ÈNaY was evaluated by running catalyst via dealumination.7 To support this contention,
three wet oxidation cycles using the same catalyst under a fresh catalyst was treated in a 4 g dm~3 OA solution
identical conditions (catalyst loading \ 5 g dm~3, at the reaction temperature (373 K) for 1 h, and tested
363 K, R \ 2É6, initial TOC \ 800 ppm). When the for wet oxidation of acetic acid. Table 3 shows that,
catalyst was reused directly, Cu2`ÈNaY [U] activity under otherwise identical conditions, a remarkable
remained almost constant within measurement uncer- improvement of the TOC removal performance was
tainties, and as conÐrmed by the atomic ratios of the attained until Cu2`-exchanged ions did not leach. It is
zeolite cations (Table 3) almost no leaching took place. also seen that during treatment with OA, the Na : Si
Interestingly, the catalyst activity was boosted signiÐ- ratio decreased more than the Al : Si. In light of all
cantly by calcination at 673 K in air for 6 h (Cu2`È these data, it may be tentatively concluded that the
NaY [UC]) and the TOC conversion was superior to improvement in TOC abatement is related to the
that obtained over homogeneous Cu2`. Recalcination removal of Na`. Additional work is under way to
and reuse of the catalyst in the third cycle (Cu2`ÈNaY unravel this problem. In particular, new catalysts using
[UCUC]) did not a†ect its performance. The Al : Si 4HNY instead of NaY are being prepared. They will be
atomic ratio remained constant, while the Na : Si ratio used to discriminate between the possible e†ect of
decreased steadily indicating that Na` cations were sodium and that of aluminium content in the zeolite.
gradually exchanged. After the third cycle, Cu2` began To evaluate the e†ect of the method of H O addi-
2 2
to leach as inferred from decreasing Cu : Si ratio. tion on the TOC conversion and H O decomposition,
2 2
TABLE 3
Oxidation of Acetic Acid by Cu2` and Leaching-o† of Na, Cu, Al from NaY zeolite (initial TOC (AA) \ 800 ppm,
catalyst loading \ 5 g dm~3, R \ 2É6, reaction time \ 60 min, temperature \ 363 K, atmospheric pressure)

Catalyst % T OC H O % H O % Al : Si Na : Si Cu : Si Na ] 2Cu : Si
2 2 2 2
removal residual decomposition

Cu2` (homo.) No AA 0 100 È È È È

Cu2` (homo.) 26 6 84 È È È È
Cu2`ÈNaY No AA 0 100 È È È È
NaY È È È 0É41 0É41 0É00 0É41
Cu2`ÈNaY 18 19 74 0É41 0É29 0É06 0É41
Cu2`ÈNaY [U] 16 29 66 0É42 0É14 0É06 0É26
Cu2`ÈNaY [UC] 40 9 74 È È È È
Cu2`ÈNaY [UCUC] 40 15 70 0É40 0É08 0É03 0É15
Cu2`ÈNaY [OA] 56 0 79 0É30 0É12 0É06 0É24
130
Fig. 1. Oxidation of acetic acid over Cu2`ÈNaY [OA] (a) and
% cumulative decomposition of hydrogen peroxide (b) for the
continuous (R \ 1É5) and the impulse R \ 2É6) modes. Initial
TOC (AA) \ 800 ppm, catalyst loading \ 5 g dm~3,
temperature \ 363 K, atmospheric pressure.
the oxidant was fed continuously over 1 or 2 h. Data
are shown in Fig. 1 as a function of the number of
moles of H O added in the continuous mode (R \ 1É5)
2 2
and the pulse injection mode (R \ 2É6). As seen, less
decomposition (51 versus 80%) occurred when the con-
tinuous mode was used. Moreover, although less H O
2 2
was used, for a 2 h injection duration, the TOC conver-
sion reached 63%, corresponding to an improvement of
2É5 times over the homogeneous Cu2`.
CONCLUSION
Wet oxidation of acetic acid with hydrogen peroxide
heterogeneously catalyzed by copper-exchanged NaY
zeolite proved to be a potential means to destroy recal-
citrant carboxylic acids at very mild conditions (90¡C,
F. L arachi, S. L e vesque, A. Sayari
1 atm). Postsynthetic treatment of Cu2`ÈNaY with
oxalic acid and continuous injection of nearly stoichio-
metric amounts of hydrogen peroxide led to a catalyst
with signiÐcantly improved TOC abatement efficiency,
catalyst stability to leaching, and less hydrogen peroxi-
de parasitic decomposition. Enhancement in TOC-
degradation performance with this heterogeneous
catalyst was tentatively ascribed to the extraction of
sodium and possibly framework aluminium from the
zeolite. To conÐrm this interpretation, current work is
being conducted on the oxidation of acetic acid using
sodium-free Cu2`ÈHY zeolites.
ACKNOWLEDGEMENTS
Funds for this research were provided by the Natural
Sciences and Engineering Research Council of Canada
and the Fonds pour la Formation de Chercheurs et
lÏAide à la Recherche du Quebec. The authors are grate-
ful to Dr G. Kennedy for the neutron activation ele-
mentary analysis of the catalyst.
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