Ind. Eng. Chem. Res.

1997, 36, 4809-4814 4809

Kinetics of Wet Oxidation of Formic Acid and Acetic Acid

Rajesh V. Shende and Vijaykumar V. Mahajani*
Department of Chemical Technology, University of Mumbai, Matunga, Mumbai 400 019, India

Oxidation of lower molecular weight carboxylic acids such as formic, acetic, glyoxalic, and oxalic
acids is often the rate-controlling step during wet oxidation (WO) of an aqueous waste stream
exhibiting very high chemical oxygen demand (COD). The kinetics of WO of formic acid was
studied in the absence and presence of a cupric sulfate as catalyst in the temperature range
150-240 °C and oxygen partial pressure range 0.345-1.380 MPa. Wet oxidation of acetic acid
was carried out in the presence of cupric sulfate in the temperature range 215-235 °C.
Homogeneous copper sulfate was found to be a very good catalyst for oxidation of formic acid
and acetic acid.

Introduction to heterogeneous catalyst. Considering both systems,

Wet oxidation (WO) is a very powerful technique for
the treatment of effluent streams exhibiting high chemi-
cal oxygen demand (COD) and biological oxygen demand
(BOD). This technique is gaining popularity among
environmental engineers for treating waste streams to
meet local discharge standards. Organic compounds
present in effluents gradually degrade to low molecular
weight compounds and finally to highly refractory lower
molecular weight carboxylic acids (Mishra et al., 1995)
during wet oxidation. For example, Devlin and Harris
(1984) have studied wet oxidation of phenol and listed
various acids such as formic, acetic, glyoxalic, and oxalic
acids as the products of wet oxidation. The lower
molecular weight carboxylic acids invariably exhibit
resistance to further oxidation. This results in effluent
stream exhibiting finite COD and BOD at the end of
wet oxidation, and at times may not meet local dis-
charge standards. Therefore, more severe oxidation
conditions are required for complete oxidation of lower
molecular weight refractory acids to CO2 and H2O.
Since oxidation of these acids is difficult, their oxidation
to CO2 and H2O often becomes the rate-controlling step
in the overall wet oxidation process. However, severe
oxidation conditions can be reduced by using appropri-
ate catalyst. In order to have a thorough insight into
the process and for better understanding of a reactor
design, knowledge of kinetics of WO of lower molecular
weight carboxylic acids is desired.
Homogeneous and heterogeneous catalysts have been
reported for wet oxidation. The heterogeneous catalytic
system offers (Levec, 1976; Imamura et al., 1982) the
advantage of ease of separation of the catalyst used.
However, if we examine very critically the system, we
foresee a danger of metallic catalyst getting leached into
an aqueous stream by lower molecular weight acids, for
instance, the most stable acetic acid. The aqueous
stream, therefore, needs to be treated to meet discharge
standards with respect to metallic catalyst. As a result,
demetalation of an aqueous stream originating from a
wet oxidation reactor using homogeneous or heteroge-
neous catalyst becomes necessary to meet discharge
standards with respect to metal. However, the load on
the demetalation unit will be lower in the case of
heterogeneous catalytic system than for a homogeneous
catalytic system. On the other hand, a homogeneous
catalyst system is expected to result in a smaller reactor
size due to the higher rate of wet oxidation as compared
* To whom correspondence should be addressed.
S0888-5885(97)00048-1 CCC: $14.00
namely, the main reactor and auxiliary demetalation
system, there would be an economic trade off between
homogeneous and heterogeneous wet oxidation before
arriving at the final decision.
Recently, de Bekker and Heerema (1994) have re-
ported a novel reaction system of a deep shaft reactor
below the Earth’s surface. A homogeneous catalytic
system would definitely then be advantageous for such
a reactor from the process engineering point of view.
Both acids are biodegradable, and it is unlikely that
such a highly capital intensive wet oxidation would be
used in destruction of these acids. As indicated earlier,
these acids are formed during wet oxidation, and since
acetic acid is much more stable, its destruction may
become the rate-controlling step. Therefore, a process
design engineer may need to know the kinetics of
destruction of low molecular weight acids to design a
reactor system.
Chang and Lin (1993) have presented some informa-
tion on wet oxidation of acetic acid using homogeneous
CuSO4 as a catalyst in their paper on wet oxidation of
spent caustic. Lin et al. (1996) have also reported
studies on wet air oxidation of a mixture of maleic acid,
fumaric acid, acetic acid, and acrylic acid. They have
studied the catalytic effect of copper sulfate, zinc oxide,
and cobalt oxide on the wet oxidation of a mixture of
acids. Copper sulfate was observed to be the best
catalyst among the above studied catalysts. However,
there is practically no information available on homo-
geneously catalyzed wet oxidation of formic acid and
acetic acid separately. It was, therefore, thought desir-
able to study separately homogeneously catalyzed wet
oxidation of formic and acetic acids.
The inorganic homogeneous catalyst used was in the
form of copper sulfate. Our choice of copper sulfate as
a wet oxidation catalyst was based on the following
rationale of process engineering. The anion, Cl-, is well-
known to cause pitting corrosion and more so in very
hostile conditions, namely, at temperatures above 200
°C and in the presence of oxygen during wet oxidation.
We have experienced in our laboratory severe pitting
corrosion during wet oxidation of organic waste contain-
ing chlorides. Further, NO3- causes stress corrosion
and may lead to explosion. On the other hand, SO42-
is the least hostile of all. Therefore, it was thought
desirable to use a sulfate salt.
Noble metals and metallic elements like Co, Cr, Cu,
and Fe are known for their catalytic activity during
oxidation. Pd and Pt are oxidation catalysts during
oxidation of alkanol to alkanoic acid under alkaline
© 1997 American Chemical Society
4810 Ind. Eng. Chem. Res., Vol. 36, No. 11, 1997
conditions (Mahajani, 1979). Cobalt-based catalytic
formulations (naphthenate, toluate) are well-known
catalysts for oxidation of paraffins to acetic acid, oxida-
tion of p-xylene to terephthalic acid, etc. However,
oxidation of acetic acid to carbon dioxide and water is
more difficult because -CH3 is an electron donor to the
C atom having dO and -OH groups, thereby stabilizing
the whole molecule. It is a well-known fact that copper
interacts well with CO, CO2, and H2 to form CH3OH;
as a result, it is the main ingredient of commercial
methanol catalyst. Further, copper also interacts well
with H2O and CO in a shift reaction. It is the main
element in low-temperature shift (LTS) and recently
introduced medium temperature shift (MTS) conversion
catalyst in ammonia manufacture. This led us to
believe that copper could be the better catalyst in the
oxidation of acetic acid to CO2 and H2O via interaction
with the -COOH group. From the foregoing discus-
sions, the choice of copper sulfate as a catalyst for
oxidation of acetic acid is now obvious.
Shende and Mahajani (1994a) have reported detailed
studies on wet oxidation of glyoxalic acid and oxalic acid
using copper as the homogeneous catalyst. Wet oxida-
tion studies of formic acid and acetic acid have been
recently reviewed by Mishra et al. (1995) in their review
on wet oxidation.
In the present investigation, we have reported kinetic
studies of oxidation of formic acid with and without
catalyst and kinetic studies of oxidation of acetic acid
with the catalyst. A homogeneous catalyst in the form
of CuSO4 was used for obtaining basic kinetic data from
the process engineering point of view. The aqueous
stream can be detoxified with respect to copper by the
well-known ion exchange technique, or precipitation as
a sulfide salt to meet local discharge standards. Since
the entire investigation is from the environmental
engineering point of view, all kinetic results are ex-
pressed in terms of chemical oxygen demand (COD).
Materials and Analytical and Experimental
Procedures
Materials. Formic and acetic acids used were of
analytical reagent grade obtained from s.d. Fine Chemi-
cals, Bombay, India. Cupric sulfate was of analytical
reagent grade, and it was used as a catalyst. Oxygen
from a cylinder with a minimum stated purity of 99.5%
was used for oxidation.
Analytical Procedure. Chemical Oxygen De-
mand. The samples during wet oxidation were ana-
lyzed for COD content using the standard dichromate
reflux method (Snell, 1967).
Infrared (IR) Spectroscopy and Gas Chroma-
tography (GC). In order to detect formic acid formed
as an intermediate, if at all, during wet oxidation of
acetic acid, some typical samples were subjected to GC
and IR analysis (GC instrument used, Chemito-3865,
Toshniwal Instruments India Ltd.; and IR instrument
used, Perkin-Elmer-270-30 spectrophotometer). The
glass column containing Porapak QS packing (length 2
m) was used for GC analysis in the FID mode of
operation.
Experimental Procedure. The wet oxidation was
carried out in a 2-L SS 316 autoclave equipped with a
six-bladed turbine agitator having a variable speed
arrangement. The gas inlet, pressure gauge, release
valve, cooling water feed line, and safety port were
situated on the top of the reaction vessel. The experi-
mental setup is depicted in Figure 1. The sample line
Figure 1. Schematic diagram of the experimental setup for wet
oxidation: CW, cooling water; CY, gas cylinder; δ, sample con-
denser; GS, gas sparger/liquid sampling device; H, electric heater;
PI, pressure indicator; R, reaction vessel/autoclave; RD, rupture
disk; S, sample outlet; SI, speed indicator; T, thermowell; TI,
temperature indicator; TIC, temperature indicator and controller.
and a thermocouple were well immersed in the reaction
mixture.
The autoclave was charged with a known concentra-
tion of formic/acetic acid. In the case of noncatalytic
oxidation, the reaction mixture was heated to the
desired temperature. Once the temperature was at-
tained, the sample was withdrawn. This time was
considered as “zero time” for a reaction. The reaction
temperature was controlled using a temperature indica-
tor controller (TIC). Oxygen was then sparged in the
vessel to a predetermined pressure level. During sam-
pling, the oxygen pressure was maintained in order to
keep the system at constant pressure. Samples were
collected periodically. In the case of catalytic WO a
similar procedure was followed, except that copper
catalyst was first added in the substrate solution and
the reaction mixture was then charged into the auto-
clave.
Results and Discussion
Wet oxidation (WO) is a heterogeneous gas-liquid
reaction and consists of the following steps taking place
in a series at the macroscopic level: transfer of oxygen
from the bulk gas phase to the gas-liquid interface (gas
phase mass transfer); instantaneous saturation of the
interface with respect to the solute gas, O2 in this case;
transfer of the dissolved oxygen from the gas-liquid
interface to the bulk of liquid (liquid phase mass
transfer); chemical reaction in the liquid phase and
desorption of a product like CO2 from the bulk to the
gas phase.
Owing to the high diffusivity of oxygen in the gas
phase and its low solubility in water, the gas phase mass
transfer resistance was estimated to be negligible in the
range of operating temperatures used for oxidation
studies. The liquid phase mass transfer resistance
depends upon the level of turbulence in the liquid phase,
and hence the effect of speed of agitation on the rate of
the reaction may be deemed as the barometer to indicate
the presence of liquid phase mass transfer resistance.
The effect of speed of agitation on the rate of reaction
was studied in the range 6.3-14.5 rps. The liquid side
mass transfer resistance was completely eliminated at
an impeller speed of 14.5 rps. Preliminary calculations
based on oxygen consumption indicated that the reac-
tion was not sufficiently fast enough to take place in
gas-liquid diffusion film (Doraiswamy and Sharma,
1984). Thus it was ensured that the reaction was
kinetically controlled under the experimental conditions
employed.
 Ind. Eng. Chem. Res., Vol. 36, No. 11, 1997 4811
Due to very low concentrations of the substrate used
in the aqueous solutions, the oxygen solubility was
considered to be same as that in water and was
estimated from the data published by Crammer (1980).
By and large, the WO reaction scheme for any organic
compound can be represented as
organic substrate + O2 CO2 + H2O (1)

low molecular weight acids

(formic, acetic, etc.)

The destruction of organics via the wet oxidation

technique is known to be combination of various free
radical reactions (Li et al., 1991; Tufano, 1993):

O2 f O• + O• (2)

O• + H2O f HO• + HO• (3)

Figure 2. Effect of temperature and oxygen partial pressure on
RH + HO• f R• + H2O (4) COD reduction during noncatalytic WO of formic acid: (g) 150
°C, 0.69 MPa; (0) 200 °C, 0.69 MPa; (4) 210 °C, 0.69 MPa; (×)
225 °C, 0.35 MPa; (9) 225 °C, 0.69 MPa; (2) 225 °C, 1.38 MPa;
R• + O2 f ROO• (5) (]) 240 °C, 0.69 MPa.

ROO• + RH f R• + ROOH (6) The variation in k with respect to temperature and

oxygen concentration can then yield the energy of
RH + O2 f R• + HO2• (7) activation and nthe order with respect to oxygen.
The data in the case of catalytic oxidation can also
RH + HO2• f RO• + H2O (8) be analyzed in a similar manner using the following
expression:
where RH ) organic substrate resulting in COD.
The destruction of acid (COD) to CO2 and H2O could d(COD)
) r ) k0 exp[-E/RT][COD][O2]n[CuSO4]p
be a combination of the various above reactions. How- dt
-
ever, for the ease of design, we consider lumped or global (14)
kinetics of COD destruction to CO2 and H2O. The order
Kinetics of Wet Oxidation of Formic Acid
with respect to oxygen could vary between 0 and 1
depending upon the rate-determining reactions in the The reaction for oxidation of formic acid can be
case of the free radical mechanism as mentioned before. represented as
The reaction continues until CO2 and H2O are formed.
Since we are interested from an environmental point HCOOH + 1/2O2 f H2O + CO2 (15)
of view, the results are presented in terms of COD of
the final stream. The results can be interpreted as In the present investigation, oxidation was carried out
follows: from an environmental engineering point of view, and
therefore, results are given in terms of COD.
d(COD)
) r ) k0 exp[-E/RT][COD]m[O2]n (9) The kinetics of noncatalytic oxidation was carried out
dt
-
in the temperature range 150-240 °C and oxygen
partial pressure range 0.345-1.380 MPa. In order to
For a given temperature and oxygen partial pressure
ascertain the absence of a mass transfer resistances (kGa
we have a pseudo mth order expression as
and kLa), it was decided to study the destruction of COD
d(COD) as a function of speed of agitation by varying the
) k[COD]m (10) impeller speed in the range 6.3-14.5 rps. It was
dt
-
observed that the rate of oxidation was independent of
where impeller speed, indicating the absence of liquid phase
mass transfer resistance. The high oxygen partial
pressures employed and the low solubility of oxygen
k ) k0 exp[-E/RT][O2]n (11) meant the absence of gas phase mass transfer resis-
tance. All subsequent measurements were carried out
The data can be well fitted to m ) 1, for given at an impeller speed of 14.5 rps.
temperature and time. Thus we have The effect of temperature and oxygen partial pressure
d(COD) on COD reduction during noncatalytic wet oxidation is
) k[COD] (12) shown in Figure 2. The COD reduction was 12.92% at
dt
-
150 °C and 0.69 MPa oxygen partial pressure. However,
and therefore, about 95% COD reduction was observed at 240 °C. Over
the entire temperature range studied, the reaction was
(COD)0 found to obey first-order kinetics with respect to COD
ln ) kt (13) (m ) 1) though other orders were also tried. The
(COD)f reaction kinetics could be well explained by having m
4812 Ind. Eng. Chem. Res., Vol. 36, No. 11, 1997
Figure 3. First-order kinetics plot for wet oxidation of formic
acid: (0) 210 °C, 0.69 MPa; (4) 218 °C, 0.69 MPa; ()) 225 °C, 0.69
MPa; (g) 225 °C, 0.345 MPa; (+) 225 °C, 1.38 MPa.
Figure 4. Energy of activation for noncatalytic wet oxidation of
formic acid.
) 1, i.e., order with respect to substrate (formic acid
(COD)) as 1. The first-order kinetics plot is shown in
Figure 3.
The effect of oxygen partial pressure on COD reduc-
tion was studied over the range of oxygen partial
pressures 0.345-1.380 MPa at 225 °C. The order with
respect to oxygen was found to be 0.86. This may be
due to combination of reactions 2, 3, 5, and 7. This,
therefore, indirectly presents evidence for a free radical
mechanism.
The Arrhenius plot showing ln k vs 1/T is exhibited
in Figure 4. The energy of activation was found to be
28.94 kcal/(g mol), confirming the absence of diffusional
resistance.
Based on experimental findings, the global rate equa-
tion for noncatalytic wet oxidation of formic acid is given
by
r1 ) 4.712 × 1010 exp[-14565/T][COD]1[O2]0.86 (16)
Catalytic oxidation of formic acid using cupric sulfate
(CuSO4) was studied in the temperature range 150-
Figure 5. Effect of temperature, oxygen partial pressure and
catalyst loading on COD reduction of formic acid solution: (0) 150
°C, 0.690 MPa, 6.888 × 10-4 kmol/m3; (4) 165 °C, 0.345 MPa, 6.888
× 10-4 kmol/m3; ()) 165 °C, 0.690 MPa, 6.888 × 10-4 kmol/m3;
(g) 165 °C, 1.380 MPa, 6.888 × 10-4 kmol/m3; (+) 180 °C, 0.690
MPa, 6.888 × 10-4 kmol/m3; (×) 165 °C, 0.690 MPa, 1.252 × 10-4
kmol/m3; (9) 165 °C, 0.690 MPa, 3.131 × 10-4 kmol/m3.
Figure 6. Energy of activation for catalytic wet oxidation of formic
acid.
180 °C and oxygen partial pressure range 0.345-1.035
MPa.
The effect of temperature, oxygen partial pressure,
and catalyst loading on COD reduction is shown in
Figure 5. For the catalyst loading of 6.888 × 10-4 kmol/
m3, a maximum COD reduction of 97% was achieved at
180 °C in 1.5 h.
In this interesting case, we have observed that the
order with respect to COD is 1.5 and first order with
respect to O2. The higher order with respect to COD
(formic acid) may be due to a formic acid-Cu complex
forming during oxidation.
The Arrhenius plot for catalytic WO of formic acid is
shown in Figure 6. The energy of activation was found
to be 22.5 kcal/(g mol). This value confirms the absence
of mass transfer resistance.
Kinetic data for the catalytic wet oxidation of formic
acid within the range of above variables could be

Figure 7. Effect of temperature, oxygen partial pressure and
catalyst loading on COD reduction during catalytic WO of acetic
acid: (g) 215 °C, 0.69 MPa, 3.13 × 10-3 kmol/m3; (0) 225 °C, 0.69
MPa, 3.13 × 10-3 kmol/m3; (4) 235 °C, 0.35 MPa, 3.13 × 10-3 kmol/
m3; ()) 235 °C, 0.69 MPa, 3.13 × 10-3 kmol/m3; (g) 235 °C, 1.04
MPa, 3.13 × 10-3 kmol/m3; (×) 235 °C, 0.69 MPa, 1.88 × 10-3 kmol/
m3; (9) 235 °C, 0.69 MPa, 6.262 × 10-3 kmol/m3.
correlated by the expression
r2 ) 1.752 × 1012 exp[-11302/T][COD]1.5[O2]1 ×
[CuSO4]0.44 (17)
It was possible to achieve complete oxidation of formic
acid (in terms of COD) within 3 h using 6.888 × 10-4
kmol/m3 catalyst loading at 180 °C. Thus the homoge-
neous copper catalyst was found to be effective at lower
temperatures.
Kinetics of Wet Oxidation of Acetic Acid
Acetic acid is the most refractory acid among low
molecular weight carboxylic acids (C1-C6 carboxylic
acids) toward wet oxidation. Recently, Merchant (1992)
has studied the kinetics of noncatalytic wet oxidation
of acetic acid. He has reported only a 7% reduction in
COD during WO of acetic acid at 275 °C in 5 h. In fact,
it is the key refractory component that provides resis-
tance for further oxidation, and therefore, the effluent
stream exhibits finite COD after wet oxidation.
Kinetics of catalytic wet oxidation using copper sulfate
were studied in the temperature range 215-235 °C and
oxygen partial pressure range 0.345-1.04 MPa. The
effect of temperature, oxygen partial pressure, and
catalyst loading on COD reduction is shown in Figure
7. It can be seen that as temperature, oxygen partial
pressure, and catalyst loading increases, reduction in
COD also increases. About 80% COD reduction was
achieved after 5 h at 235 °C.
The wet oxidation of acetic acid in the presence of
catalyst was found to obey first-order kinetics with
respect to substrate COD.
A plot of ln k vs 1/T is shown in Figure 8. The energy
of activation was found to be 22.77 kcal/(g mol). This
value indicates that the reaction is free of mass transfer
resistance.
The effect of oxygen partial pressure was studied in
the range 0.345-1.04 MPa using the catalyst loading
3.131 × 10-3 kmol/m3 at 235 °C. Also, the effect of
Ind. Eng. Chem. Res., Vol. 36, No. 11, 1997 4813
Figure 8. Energy of activation for catalytic wet oxidation of acetic
acid.
catalyst loading was studied in the range 6.262 × 10-4
to 6.262 × 10-3 kmol/m3 using 0.69 MPa oxygen partial
pressure at 235 °C.
The final expression for the kinetics of catalytic WO
of acetic acid based on COD reduction is as follows
r3 ) 8.479 × 109 exp[-11459.2/T][COD]1[O2]0.92 ×
[CuSO4]1 (18)
The order with respect to O2 is 0.92, which means attack
by O• via OH• and by O2 both may be contributing
simultaneously.
During WO of acetic acid catalyzed by “CuSO4”, formic
and oxalic acids were not observed as decomposition
products in infrared and gas chromatographic analyses.
Formic acid (present study) and oxalic acid (Shende and
Mahajani, 1994a) in the presence of “CuSO4” under WO
conditions were found to be highly reactive, and there-
fore, even if produced during catalytic WO of acetic acid,
they might have disappeared instantaneously under the
reaction conditions. Since acetic acid is more stable as
compared to formic acid, severe reaction conditions were
required. However in the presence of “CuSO4” wet
oxidation of acetic acid was found to proceed even at a
temperature of 215 °C.
The waste stream can be easily detoxified with respect
to copper by the ion exchange technique. Alternately,
it can be precipitated as a CuS salt by adding Na2S/
FeS or a hydroxide under alkaline conditions.
We, therefore, postulate that since homogeneous
“CuSO4” can destroy acetic acid, it could be a very
effective catalyst in wet oxidation of any organic sub-
strate. Almost complete destruction of phenol (COD)
was possible during catalytic wet oxidation in the
presence of homogeneous cupric sulfate (Shende and
Mahajani, 1994b).
Conclusions
The wet oxidation of formic and acetic acids catalyzed
by cupric sulfate was proved to be an effective technique
to meet the discharge standards with respect to COD
and concentration of individual acids as well. The
noncatalytic wet oxidation of formic acid was found to
obey first-order kinetics with respect to substrate COD,
whereas, in the case of catalytic oxidation the data could
be well fitted to m ) 1.5. Wet oxidation of acetic acid
was found to obey first-order kinetics with respect to
4814 Ind. Eng. Chem. Res., Vol. 36, No. 11, 1997
substrate COD and it was found to be oxidized directly
into carbon dioxide and water. The use of homogeneous
CuSO4 catalyst may be very effective in destroying
organic molecules via wet oxidation because it is effec-
tive in destroying formic and acetic acids that are
formed in wet oxidation.
Acknowledgment
R.V.S. is grateful to University Grants Commission,
India, for the financial support.
Nomenclature
CA0 ) initial substrate concentration, mg/L
COD ) chemical oxygen demand, mg/L
BOD ) biochemical oxygen demand, mg/L
[O2] ) oxygen concentration, kmol/m3
E ) energy of activation, kcal/(g mol)
m ) order with respect to COD
n ) order with respect to oxygen
p ) order with respect to catalyst
r ) rate of oxidation reaction with respect to COD reduc-
tion, mg/L s
R ) gas constant, kcal/(g mol K)
k0 ) preexponential factor (unit dependent on n and p)
k ) rate constant
T ) temperature, K
[COD]0 ) initial COD, mg/L
[COD]t ) COD (mg/L) at time “t” (s)
t ) time, s
Literature Cited
Chang, C. J.; Lin, J. E. Effect of Temperature and Cu+2 Catalyst
on Liquid-Phase Oxidation of Industrial Wastewaters. J. Chem.
Technol. Biotechnol. 1993, 57, 355.
Crammer, S. D. The Solubility of Oxygen in Brines from O to 300
°C. Ind. Eng. Chem. Process Des. Des. 1980, 19, 300.
de Bekker, P.; Heerena, K. Dutch Deept Shaft Takes the Pressure
off Wet Oxidation. Water Quality Int. 1994, 3, 28.
Devlin, H. R.; Harris, I. J. Mechanism of the Oxidation of Aqueous
Phenol with Dissolved Oxygen. Ind. Eng. Chem. Fundam. 1984,
23, 387.
Doraiswamy, L. K.; Sharma, M. M. Heterogeneous Reactions.
Analysis, Examples and Reactor Design; John Wiley and Sons:
New York, 1984; Vol. 2.
Imamura, S.; Hirano, A.; Kawabat, N. Wet Oxidation of Acetic Acid
Catalyzed by Co-Bi complex oxides. Ind. Eng. Chem. Prod. Res.
Dev. 1982, 21, 570.
Levec, J.; Herskowitz, M.; Smith, J. M. An Active Catalyst for the
Oxidation of Acetic Acid Solutions. AIChE J. 1976, 22, 919.
Li, L.; Chen, P.; Gloyna, E. F. Generalized Kinetic Model for Wet
Oxidation of Organic Compounds. AIChE J. 1991, 37, 1687.
Lin, S. H.; Ho, S. J.; Wu, C. L. Kinetic and Performance
Characteristics of Wet Air Oxidation of High-Concentration
Wastewater. Ind. Eng. Chem. Res. 1996, 35, 307
Mahajani, V. V. Noble Metal Catalyzed Liquid Phase Oxidation
of Alkanol to Alkanoic acid. Ind. Chem. Eng. 1979, 21, 741.
Merchant, K. P. Studies in Heterogeneous Reactions. Ph.D. Thesis,
University of Bombay, India, 1992.
Mishra, V. S.; Mahajani V. V.; Joshi, J. B. Wet Air Oxidation. Ind.
Eng. Chem. Res. 1995, 34, 2.
Shende, R. V.; Mahajani, V. V. Kinetics of Wet Air Oxidation of
Glyoxalic Acid and Oxalic Acid. Ind. Eng. Chem. Res. 1994a,
33, 3125.
Shende, R. V.; Mahajani, V. V. Detoxification of Phenolic Stream
by Catalytic Wet Air Oxidation. A paper presented at the
National Seminar on Clean Environment-Strategies, Planning
and Management. Lucknow, Feb 1994b, India.
Snell, F. D.; Ettre, L. S. Encyclopedia of Industrial Chemical
Analysis; John Wiley and Sons: New York, 1967; Vol. 17.
Tufano, V. A. Multi-Step Kinetic Model for Phenol Oxidation in
High Pressure Water. Chem. Eng. Technol. 1993, 16, 186.
Received for review January 21, 1997
Revised manuscript received May 6, 1997
Accepted May 12, 1997X
IE970048U
X
Abstract published in Advance ACS Abstracts, September
1, 1997.