Chemical Engineering Journal 252 (2014) 185193

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Chemical Engineering Journal

journal homepage: www.elsevier.com/locate/cej

Catalytic wet oxidation of ferulic acid (a lignin model compound)

in the presence of non-noble metal based catalysts at mild conditions
Bholu Ram Yadav, Anurag Garg
Centre for Environmental Science and Engineering, Indian Institute of Technology Bombay, Powai, Mumbai 400076, India

h i g h l i g h t s

 Synthesis and characterization of non-noble metal based supported catalysts.

 Catalytic wet oxidation of ferulic acid (lignin model compound) at mild conditions.
 Theoretical estimation of the mineralization of ferulic acid (in terms of CO2).
 HPLC analysis and determination of reaction kinetics.
 Catalyst thermal regeneration, characterization and reuse in the oxidation process.

a r t i c l e i n f o a b s t r a c t

Article history: The present study investigated the performance of activated carbon and alumina supported non-noble
Received 3 March 2014 metal based catalysts during the catalytic wet oxidation (CWO) of ferulic acid (a lignin model compound).
Received in revised form 28 April 2014 The heterogeneous catalysts, Cu/Ce/AC, Cu/Ce/Al2O3, Cu/Mn/AC and Cu/Mn/Al2O3 (mass ratio = 3:3:4),
Accepted 29 April 2014
were prepared by metal impregnation while Cu/Mn/Ce (mass ratio = 3:3:4) catalyst was synthesized
Available online 9 May 2014
by co-precipitation method. The CWO reaction was performed in a batch reactor at mild conditions (tem-
perature = 120 C and oxygen pressures = 0.5 MPa) with a catalyst concentration of 3 g/l for 3 h duration.
Keywords:
Among all the catalysts, Cu/Ce/AC catalyst showed the maximum chemical oxygen demand (COD) and
Catalytic wet oxidation
Catalyst reusability
total organic carbon (TOC) removals (88% and 82%, respectively) from the wastewater. The ferulic acid
Ferulic acid removal was resulted from a combination of reactions (such as oxidation, hydrolysis, decarboxylation
Heterogeneous catalysts and adsorption). During the CWO reaction, oxalic acid was identied as the major by-product but mean
Reaction kinetics oxidation state of carbon and TOC balance calculation indicated also the presence of other compounds. A
signicant difference in the surface characteristics of the fresh and thermally regenerated catalysts (after
CWO) was observed. The rst time reuse of Cu/Ce/AC catalyst caused 6% lesser reduction in TOC than
the fresh catalyst though no considerable reduction in the catalytic activity could be observed after sec-
ond reuse of the catalyst. The future study should plan for the determination of the change in biodegrad-
ability after the treatment and the effectiveness of CWO on real pulping efuent.
2014 Elsevier B.V. All rights reserved.

1. Introduction which is highly resistant to the conventional biological oxidation.

Catalytic wet oxidation (CWO) is considered a promising
hydrothermal method for the destruction of recalcitrant organic
or inorganic compounds generally found in industrial wastewater.
Typically wet oxidation (WO) process can be performed at
125320 C temperature and 0.520 MPa total pressures by pass-
ing air or molecular oxygen [1]. The operating temperature and
pressure conditions of the reaction can be reduced by introducing
a suitable catalyst. Pulp mill efuents contain compound like lignin
Corresponding author. Tel.: +91 22 25767861; fax: +91 22 25764650.
E-mail address: a.garg@iitb.ac.in (A. Garg).
Therefore, the wastewater needs to be pre-treated by a suitable
physico-chemical process. In the present study, the hetero-
catalytic oxidative degradation of ferulic acid (a lignin model
compound) at mild reaction conditions is explored.
Several ongoing efforts have assessed the performance of the
transition metal based homogeneous and heterogeneous catalysts
for CWO process [27]. The homogeneous catalysts have exhibited
very good activity for the removal of recalcitrant pollutants but
such catalysts are not preferred due to the difcult recovery of
active metal from the treated wastewater. The leached metal con-
centration can enhance toxicity of the treated wastewater. The
noble metal based catalysts have shown comparable performance

http://dx.doi.org/10.1016/j.cej.2014.04.110
1385-8947/ 2014 Elsevier B.V. All rights reserved.
186 B.R. Yadav, A. Garg / Chemical Engineering Journal 252 (2014) 185193
but their use is limited by the high cost of catalysts. Therefore, the
current research emphasizes on the development of less expensive
non-noble metal based heterogeneous catalysts for CWO process.
Among the transition metals, copper has been reported as one of
the active metals for the catalytic oxidation process [3,6,811].
However, only few studies reported the stability and reusability of
WO catalysts. In a study, the several combinations of a heteroge-
neous catalyst comprising Cu and Ce were synthesized and tested
for the oxidative degradation of phenol [3]. 60%CuO/40%CeO2
catalyst (w/w) showed the highest phenol reduction among all com-
binations. Verenich et al. [12] evaluated the performance of different
transition metal based heterogeneous catalysts for CWO of pulp mill
wastewater. The activated carbon (AC) supported copper catalyst
showed promising performance. In another study, AC and ceria sup-
ported transition metals (Cu and Mn) based catalysts were used for
the degradation of pretreated pulping efuent (chemical oxygen
demand (COD) = 2700 mg/l) [10]. The ceria and AC supported cop-
per catalysts exhibited the highest COD removals. In the follow up
study, 60%CuO/40%CeO2 catalyst was also used for the diluted black
liquor (COD = 7000 mg/l) at a lower temperature (=140 C) [13].
In the above studies, the detailed catalyst characterization and
its deactivation were not reported. In addition, the information
on the degradation pattern of lignin (a major persistent compound
in pulping liquor) is lacking. Only few research groups have per-
formed CWO studies for the lignin model compounds (such as
ferulic acid and alkali lignin) [7,1416]. According to the literature,
AC and alumina (Al2O3) supported copper and manganese catalysts
can be effective for the CWO of lignin model compounds. Apart
from this, ceria may promote the oxidation due to its oxygen
carrying capacity. The motivation of the present study was to
investigate the changes in heterogeneous catalysts after regenera-
tion and their performance in CWO after repeated reuse.
In the present study, the catalytic activity of the fresh as well as
spent heterogeneous catalysts was investigated during CWO of the
ferulic acid. The fresh and regenerated catalysts were characterized
before and after the oxidation process. The WO and CWO reaction
kinetics were also studied using a lumped kinetic model.
2. Materials and methods
2.1. Materials
The analytical grade ferulic acid (99% purity) was supplied by
SigmaAldrich Mumbai, India. For the preparation of catalysts,
Cu(NO3)23H2O, CeCl37H2O, MnSO4H2O, and NH4OH (30%) were
purchased from Merck Chemicals, Mumbai, India. Besides, Al2O3
and peat derived AC were supplied by Zeolite and Allied Products,
Mumbai, India and Merck Chemicals, Mumbai, India, respectively.
The synthetic wastewater was prepared by dissolving 1 g of
ferulic acid in 1 L of tap water. The major characteristics of the syn-
thetic wastewater were as follows: pH = 4.13, COD = 1550 mg/l and
total organic carbon (TOC) = 530 mg/l.
2.2. Experimental methods
2.2.1. Catalyst preparation
Out of the ve heterogeneous catalysts used for the CWO study,
Cu/Ce/AC, Cu/Ce/Al2O3, Cu/Mn/AC and Cu/Mn/Al2O3 (mass
ratio = 3:3:4) were prepared by impregnation method as outlined
in earlier research studies [12,1719]. Only Cu/Mn/Ce (mass
ratio = 3:3:4) catalyst was prepared by co-precipitation method
according to the previously reported procedure [6,10,14].
In impregnation method, the stoichiometric amounts of respec-
tive metal salts (Cu(NO3)23H2O, CeCl37H2O and MnSO4H2O) were
dissolved separately in the distilled water and the resulting
solutions were mixed with either of the two supports (AC or
Al2O3) in the desired proportion. The mixture then was continu-
ously stirred magnetically for 12 h to allow the penetration of
metal precursor into the support. In the next step, the mixture
was oven-dried (at 103105 C temperature) for 24 h. The dried
mass was ground by means of a pestle and mortar before calcining
at high temperature for 2 h in a mufe furnace. The calcination
temperature for AC and Al2O3 supported catalysts was 300 C
and 500 C, respectively.
To synthesize Cu/Mn/Ce catalyst by co-precipitation method,
the stoichiometric amounts of Cu, Mn and Ce metal salts were dis-
solved in distilled water and agitated with a magnetic stirrer to
ensure complete mixing. The solution pH was adjusted around
8.0 with ammonia solution (2 M) to precipitate the respective metal
hydroxides. The suspension was then left undisturbed for 2 h to
allow the settling of the precipitate. Moreover, the solution was l-
tered (lter size = 0.45 lm) to recover the residual suspended sol-
ids. The retained mass at the lter paper was washed ve times
with distilled water to remove excess ammonia. The resulting wet
slurry was oven-dried at a temperature of 103105 C for 24 h.
The dried mass was ground and calcined in a mufe furnace at
500 C temperature for 2 h.
The actual composition of the catalysts was determined using
inductively coupled plasma-atomic emission spectroscopy (ICP-
AES). The synthesized catalysts were characterized to identify the
phase formation by X-ray diffraction (XRD) technique. Brunauer
EmmettTeller (BET) surface area, average particle diameter and
the particle size distribution of the catalysts were also measured.
2.2.2. Wet oxidation (WO) experimentation
WO/CWO batch studies were performed in a 0.7 L capacity high
pressure stainless steel (SS) reactor (material of construction:
SS-316). The instrument was equipped with the provisions for tem-
perature control and mixing speed adjustment. Separate ports for
liquid sampling and air/oxygen injection were also provided on the
reactor cap. A digital display unit was attached with the reactor
assembly to monitor temperature, pressure and stirrer speed during
the reaction. The pressure in the reactor was controlled by two
valves provided at the oxygen cylinder and the reactor cap. For
instantaneous cooling of the liquid samples, a condenser (with water
owing in the outer shell) was also attached to the sample port.
For a typical WO/CWO runs, 250 ml of the synthetic wastewater
was charged into the reactor without or with 3 g/l fresh catalyst (for
CWO runs). The reactor assembly was made leak proof before
raising the reactor temperature to 120 C from the ambient condi-
tion (30 C). The approximate time to achieve the desired temper-
ature was 45 min. A zero time sample (5 ml) was withdrawn just
after attaining the reaction temperature. Then the pure oxygen was
purged into the reactor at an initial oxygen pressure of 0.5 MPa
while the total pressure was maintained at 0.69 MPa. The reactor
contents were mixed vigorously by a mechanical stirrer (rotating
speed = 1000 rpm) continuously during the reaction. All CWO runs
were conducted in triplicate and COD of each sample was deter-
mined thrice. The periodic liquid sampling was done to record
change in pH, TOC and COD with time for the rst run only. No
samples were withdrawn during the remaining two runs so that
the spent catalyst could be quantied and reused.
In addition, an effort was made to quantify the intermediates
and by-products formed during the catalytic run performed with
Cu/Ce/AC catalyst using high performance liquid chromatography
(HPLC).
2.2.3. Catalytic tests at ambient and elevated temperatures in the
absence of oxygen
The removal of ferulic acid from the synthetic wastewater was
also investigated in the absence of oxygen at ambient (30 C) and
 B.R. Yadav, A. Garg / Chemical Engineering Journal 252 (2014) 185193 187

CWO reaction temperatures (i.e., 120 C). The aim of these runs
(duration = 3 h) was to assess adsorption potential of the synthe-
sized catalysts. At ambient condition, the runs were performed
with a wastewater sample of 50 ml in a conical ask. The properly
capped conical ask was agitated (shaker speed = 200 rpm) in an
orbital shaker. The reaction at elevated temperature was carried
out in the same high pressure reactor which was used for CWO
experiments. The nally treated wastewater was subjected to the
COD and TOC analyses.
2.2.4. Catalyst reusability studies
The recovered and regenerated catalysts were subjected to the
oxidation reaction under the same temperature and pressure con-
ditions. The treated wastewater sample was ltered through
0.45 lm lter paper to recover the suspended catalyst and the
wet residue retained at the lter paper was oven-dried at 100 C
temperature. The dried mass was then subjected to thermal treat-
ment at a temperature of 300 C or 500 C as done for the fresh cat-
alyst. The regenerated solid mixtures were again characterized for
the physical properties.
During CWO with the regenerated catalysts, no wastewater
sample was withdrawn. Only the treated wastewater obtained
after 3 h reaction was analyzed for pH, TOC and COD.
2.3. Analytical methods
The XRD spectra of the synthesized catalysts were recorded on
Philips diffractometer (PANalytical Xpert Pro, Netherland). Cu Ka
was used as X-ray source and the samples were scanned through
2090 angle (2h). N2 adsorption isotherm were recorded on a
Micrometric ASAP-2020 machine (USA) which were used for deter-
mining BET surface area, pore volume distribution and average
pore diameter.
The actual amount of specic active specie (Cu, Mn or Ce) pres-
ent in a fresh catalyst was determined by dissolving the catalyst in
aqua-regia (HNO3:HCl = 1:3). The highly acidic samples were
appropriately diluted before subjecting for the analysis by
Inductively Coupled Plasma-Atomic Emission Spectroscopy
(ICP-AES) (HORIBA Jobin Yvon-Ultima 2000, France). The metal
leaching after hydrothermal treatment was also measured using
the same procedure.
Particle size distribution and average particle diameter in a cat-
alyst were determined with LS13 320 Laser Diffraction particle size
analyzer (Beckman Coutler, USA). To analyze the sample, a small
amount of the catalyst was suspended in deionized water and son-
icated for 2 min. The laser light wavelength was set at 488 nm.pH
of the untreated and treated wastewater samples was measured
with a digital pH meter (Polmon, LP-139S, India). TOC analyzer
(Shimadzu, TOC-VCSH, Japan) was used to determine TOC of the
wastewater samples, while COD was determined by the standard
closed reux method as per the procedure mentioned in American
Public Health Association (APHA) hand book [20]. For COD
measurement, the wastewater samples were digested in a HACH
COD reactor (DRB200, USA)
Ferulic acid and other compounds (i.e., intermediates and
by-products) present in the wastewater samples were analyzed
by HPLC (Pump: Model PU-2089i, Intelligent HPLC Pump, Jasco,
PDA Detector: MD-2010/2015, Intelligent UV/VIS Multi wavelength
Detector, JASCO). A polar embedded C18 column (Synergi Fusion
RP: 250 mm  4.6 mm, particle size = 4 lm, pore size = 80 )
(Phenomenex, India) was used for the analysis. Phosphate buffer
and acetonitrile (80:20 v/v) were used as mobile phases during
the analysis.
3. Results and discussion
3.1. Catalyst characterization
The actual catalyst composition was determined using the ICP-
AES analysis. The results showed that the stoichiometric amounts
of the respective metal species were signicantly different from
the original values except for Cu/Ce/AC and Cu/Mn/Ce catalysts
(Table 1). XRD analysis was also performed to ascertain the pres-
ence of various constituents in the synthesized catalysts. From
Joint Committee on Powder Diffraction Standards (JCPDS) les,
the peaks for CuO, CeO2 and MnO2 could be identied. Apart from
this, the corresponding peak locations were compared with the
published literature [3,11,17,2123]. XRD patterns of the fresh cat-
alyst are shown in the supporting information as Fig. S1.
The specic surface area of different synthesized materials was
calculated by BET equation. The micropore volume was obtained
using t-plot method while the macro and mesopore volume and
average pore diameter were calculated by Barrett Joyner Halenda
(BJH) method [24]. The results obtained from BET analysis are
shown in Table 1. It can be seen that the untreated activated carbon
has the highest area (576 m2/g) compared to Al2O3 (209 m2/g).
The surface area of Cu/Ce/AC catalyst was found to be the least
compared to the other AC and Al2O3 supported catalysts. Probably
due to the higher macro and mesopore volumes, the surface area of
Cu/Ce/Al2O3 catalyst was almost double to that of Cu/Ce/AC. Apart
from this, the lower Cu content in Al2O3 supported catalyst could
have enhanced the BET surface area. Higher metal impregnation
may cause the blockage of pores resulting in the reduction of sur-
face area of a catalyst. Furthermore, the improved micropore area
enhanced the overall surface area of AC and Al2O3 supported Cu/
Mn catalysts (122 and 61.6 m2/g, respectively) compared to the
other catalysts. The catalyst prepared by co-precipitation method
(i.e. Cu/Mn/Ce) showed the least surface area and porosity. The

Table 1
Physical properties of the synthesized heterogeneous catalysts.

Catalyst Actual composition (mass A (m2/ Amicro (m2/ Amacro&meso Vmicro Vmacro&meso dpore dparticle Particle size range
ratio) g) g) (m2/g) (cm3/g) (cm3/g) () (lm) (lm)
Activated 576.08 277.60 158.34 0.2639 0.186 47.08
carbon
Activated 209.09 179.27 0.209 46.54
alumina
Cu/Ce/AC 3:2.1:4 18.48 0.58 12.48 0.0003 0.025 80.89 17.92 1.142.2
Cu/Ce/Al2O3 2.5:1.9:4 37.93 45.81 0.088 76.50 62.58 0.74222.3
Cu/Mn/Ce 3.3:2.9:4 3.71 3.44 0.026 305.31 38.67 0.75138.6
Cu/Mn/Al2O3 1.7:1.8:4 61.62 6.48 55.42 0.0023 0.133 95.88 22.38 1.351.2
Cu/Mn/AC 2.4:1.9:4 122.24 60.16 45.67 0.0274 0.094 81.96 12.91 0.9630.5

ABET = BET surface area (m2/g), Amicro = micropore area (m20 /g), Amacro&meso = macro and mesopore area (m2/g), Vmicro = micropore volume (cm3/g), Vmacro&meso = macro and
mesopore volume (cm3/g), dpore = average pore diameter ( A), dparticle = mean particle diameter (lm).
188 B.R. Yadav, A. Garg / Chemical Engineering Journal 252 (2014) 185193

overall surface area was only 3.71 m2/g mainly comprised of macro
and mesopores. The average pore diameter of the catalyst was
much higher compared to the other catalysts that may be attrib-
uted to the low porosity of the Cu/Mn/Ce catalyst. Similar nding
have been reported in an earlier work [25].
The particle size distribution and average particle size of the
synthesized catalysts were also determined. The results obtained
from the analysis revealed that Cu/Ce/Al2O3 catalyst had the mean
particle size of 62.5 lm with a size range varied from 0.74 to
222.3 lm (Table 1). On the other hand, the activated carbon sup-
ported catalysts have smaller mean particles size. Cu/Ce/AC cata-
lyst had a particle mean size of only 17.92 lm and a narrow
particle size range (1.142.2 lm). The following interpretation
can be made from the above analysis: (i) the presence of metal
content affected the surface area of a supported catalyst, and (ii)
the surface area of a material is inuenced by particle size as well
as the pore size distribution.

3.2. WO/CWO study

3.2.1. Non-catalytic and catalytic WO performance

CWO was performed at moderate operating conditions (i.e.
T = 120 C and Po2 = 0.5 MPa) in the presence of all ve synthesized
heterogeneous catalysts (Cu/Ce/AC, Cu/Ce/Al2O3, Cu/Mn/AC, Cu/
Mn/Al2O3 and Cu/Mn/Ce). The COD and TOC degradation results
from CWO reaction were compared with the non-catalytic WO
conducted under identical temperature and pressure conditions
(Fig. 1). During the non-catalytic WO, only 52% and 50% reductions
in COD and TOC, respectively, could be achieved. After the reaction,
the pH of wastewater was dropped to 3.32 (initial pH = 4.13). The
degradation of ferulic acid was rapid during the rst hour and then
Fig. 1. Ferulic acid degradation patterns during WO/CWO reaction at mild
slowed down for the remaining period.
operating conditions in terms of (a) COD, and (b) TOC (T = 120 C, total
Catalytic oxidation process also followed the similar COD and pressure = 0.69 MPa, Po2 = 0.5 MPa, and catalyst concentration = 3 g/l).
TOC degradation patterns. From the analysis, it was found that
around 3238% COD and 2539% TOC reductions occurred during
the initial heating period of the reactor. This reduction may be
due to the adsorption of reactant species on the catalyst and
hydrolysis of ferulic acid. The COD was further reduced to
7477% after 1 h reaction (corresponding COD = 350400 mg/
l). The degradation rate was very low for the remaining reaction
period. The highest COD and TOC removals of 88% and 82%, respec-
tively were obtained with Cu/Ce/AC catalyst (nal COD = 180 mg/l,
TOC = 93 mg/l). Cu/Mn/Al2O3 catalyst was the least efcient among
all the catalysts with COD and TOC removals of 80% and 72%,
respectively. The variation in the COD values is shown by error bars
in Fig. 2a. In order of increasing catalytic activity, the catalysts can
be arranged as follows:

Cu=Ce=AC > Cu=Ce=Al2 O3 > Cu=Mn=AC > Cu=Mn=Ce

> Cu=Mn=Al2 O3

From the above results, it can be inferred that the reactant mole-
cules rst occupied the active sites available on a catalyst surface.
During catalytic oxidation, the adsorbed ferulic acid molecules
may have reacted with the oxygen available in molecular form
and the lattice oxygen (particularly for the catalysts containing
CeO2). The presence of copper and manganese is expected to pro-
mote the generation of reactive radicals (HO, ROO, RO, etc. where
R represents alkyl group) in the reaction mixture. As the reaction
proceeds, the resulting intermediates will be desorbed from the
catalyst surface and the vacancies for the other un-reacted mole-
cules is created. In this way, the degradation process continues till
the low molecular weight carboxylic acids are formed which are
not easily degradable under the reaction conditions used in the
present study. It can be noted that Cu/Ce/AC catalyst was the most
Fig. 2. Intermediate/by-products formed during CWO reaction in the presence of
Cu/Ce/AC catalyst.
efcient despite lower surface area. There may be the following
reasons for its high activity: (a) high oxygen storage capacity of
CeO2, (b) catalytic activity of AC [26], and (c) the presence of the
higher copper content in the catalyst.
The comparable COD and TOC removals were achieved with Cu/
Mn/Ce catalyst despite the least surface area and pore volume of
the catalyst. The catalyst contained the highest Cu and Mn (by
mass) compared to the other catalysts. Furthermore, the oxygen
storage capacity of ceria would assist in the improvement of
catalytic activity.
 B.R. Yadav, A. Garg / Chemical Engineering Journal 252 (2014) 185193
The one way ANOVA test veried the signicant difference in
the COD reduction during CWO process with various catalysts
since p value was less than 0.01.
To quantify the adsorbed organics on the catalyst surface, aqua-
regia has been used to dissolve the used oven-dried catalyst [14].
In the present study, the nally treated wastewater was ltered
and the dried spent catalyst (=25 mg) was dissolved in 3 ml
aqua-regia. The resulting solution was diluted to 50 ml and sub-
jected to the TOC determination (after adjusting the pH to 34).
Around 814% of the total TOC was found to be deposited on the
catalyst. The maximum retention of organic substances on Al2O3
supported catalysts suggests the meager interaction among the
adsorbed reactant molecules would have inhibited the oxidation
reaction.
To predict the aqua-regia assisted oxidation of adsorbed carbon
(in the form of COD and TOC) from the catalyst surface, further
runs with ferulic acid and other major possible intermediates (like
oxalic acid) were performed in the absence of oxygen at ambient
temperature. The results are discussed later in Section 3.2.3.
3.2.2. Identication of the reaction intermediates
To identify the intermediates or by-products, the periodically
collected wastewater samples during a CWO run (performed in
the presence of Cu/Ce/AC catalyst) were subjected to HPLC
analysis. The treated wastewater samples were ltered by 0.2 lm
nylon lter and diluted appropriately (20150 times) before
injecting in the HPLC column. Firstly, the retention time of the
various identied compounds (such as ferulic, vanillic and oxalic
acids) were determined by injecting the pure compounds and their
mixture. The chromatograms of untreated and treated wastewater
(obtained after 3 h reaction) are provided in supporting information
as Fig. S3. Vanillic and oxalic acids could only be detected as the
major species formed during and after the reaction (Fig. 2). It was
found that around 98% of ferulic acid was degraded within rst
30 min, out of which 50% was decomposed during the heating
period. Oxalic acid was present in signicant concentration even
in the sample withdrawn at zero time. It can be deduced that
the other reactions like hydrolysis and decarboxylation were also
occurred in addition to adsorption during the heating period. The
concentration of oxalic acid was continuously increased in the reac-
tion mixture and reached to the peak concentration (192 mg/l)
after 120 min reaction. Afterwards, it decreased continuously to a
nal value of 81 mg/l. Vanillic acid was present in very small con-
centration at zero time (2 mg/l) which increased to 6.2 mg/l in
rst 30 min and then decreased to 0.7 mg/l.
The theoretical TOC was calculated using the concentrations of
identied compounds during HPLC analysis which was compared
with that obtained experimentally. The calculated TOC was much
less than that obtained from TOC analyzer (except at zero time).
For instance, the experimental TOC after 15 min and 180 min reac-
tion was 198 and 93 mg/l, respectively whereas the correspond-
ing calculated TOC was only 56 and 21 mg/l. A large difference
between the TOC values clearly indicates the presence of other
organic species which could not be detected by HPLC analysis in
the wastewater.
To get more information pertaining to the other possible
organic compounds, mean oxidaton state of carbon (MOC) with
time was determined using the experimental COD and TOC of
the treated wastewater samples by the following expression [27]:
  
COD
MOC 4  1:5
TOC
The theoretical MOC of ferulic, vanillic, oxalic and acetic acid is
0.38, +0.05, +3 and 0, respectively. The positive MOC of the nally
treated sample (=+1.11) predicts the accumulation of acetic acid.
189
The MOC of the intermediate wastewater samples was negative
indicating the presence of non-acidic ferulic acid degradation
products.
MOC of the nally treated wastewater (obtained after 3 h run)
by WO or CWO was also calculated (Fig. 3). After CWO process,
the MOC was above zero in the range of +0.8 to +1.3. In contrast,
MOC of the wastewater obtained after the non-catalytic treatment
was negative (nal MOC = 0.2). Thus, it can be deduced that
ferulic acid was degraded into short chain compounds after
catalytic treatment.
The change in pH during WO/CWO process was also recorded.
The addition of various catalysts to the wastewater enhanced the
solution pH from initial pH (i.e., 4.13) to 4.75.45. After 3 h CWO
treatment, pH of the treated wastewater samples was reduced to
3.984.73. The maximum difference in pH (0.92 units) was
observed during Cu/Ce/AC catalyzed reaction (initial reaction
pH = 5.45, nal pH = 4.53). A pH drop of 0.7 unit was noted after
the reaction in the presence of Cu/Mn/Ce catalyst. The drop in pH
after the reaction can also be attributed to the formation and
accumulation of the acidic compounds.
3.2.3. Activity of the catalysts in the absence of oxygen and estimation
of CO2 yield during CWO process
The synthetic wastewater sample was also treated in the
absence of oxygen with the synthesized catalysts. The reaction
was conducted at room (30 C) and WO reaction temperatures
(i.e. 120 C) for 3 h duration. The degradation of ferulic acid in terms
of COD and TOC is shown in Fig. 4. The maximum COD and TOC
reductions were 30% and 27%, respectively for the reaction at room
temperature with Cu/Ce/AC catalyst. At 120 C temperature, the
highest reduction in COD and TOC was around 60% obtained with
Cu/Ce/Al2O3 catalyst. Hence it can be deduced that all these cata-
lysts were capable of removing a signicant amount of COD and
TOC even without addition of oxygen externally. Cu/Mn/Ce catalyst
showed the comparable removal of ferulic acid under the tested
temperature conditions despite the lowest surface area. Generally,
the efciency of physical adsorption reduces with increase in tem-
perature which is in contrast to the present results. The enhance-
ment in ferulic acid removal at elevated temperature clearly
indicates the occurrence of a combination of adsorption and other
chemical degradation processes. In addition, the oxidation of
organics may also have happened due to the presence of O2 in the
reactor head space and catalyst lattice. The elevated temperature
could have assisted in the generation of active radical species to
initiate the reaction. These free radicals will react with the adsorbed
1
Fig. 3. MOC of the wastewater samples obtained after WO and CWO treatment.
190 B.R. Yadav, A. Garg / Chemical Engineering Journal 252 (2014) 185193

CO2 + H2O (complete)

k1

Fig. 4. TOC and COD reductions after catalytic reactions performed in the absence
of oxygen.
compounds which may be converted into the other compounds.
During CWO, the addition of oxygen is expected to promote the
degradation of adsorbed parent and intermediate compounds thus
reducing the contribution of adsorption in overall TOC removal.
To predict the contribution of adsorption of organics on the cat-
alyst surface during non-oxidative runs at elevated temperature,
the catalysts were recovered from the nally treated wastewater
samples and 25 mg of the oven-dried residue was dissolved in
3 ml aqua-regia. The recovered solid residue (i.e., catalyst with
adsorbed organics) was found to have only around 50% of the total
TOC removed from the wastewater.
In order to estimate the oxidative potential of aqua-regia for the
adsorbed organics on the catalyst, a TOC balance was also done for
the synthetic wastewater samples treated with catalysts in the
absence of oxygen at ambient temperature. Only adsorption of
the organics can be expected during the process but the sum of
TOC from treated wastewater and recovered solid residue was less
than the original TOC of the synthetic untreated wastewater. This
result conrmed that a fraction of the adsorbed ferulic acid (in
the form of TOC) was oxidized by aqua-regia. On an average, 40
50 mg/l of TOC (2227% of the total adsorbed TOC) was removed
by the oxidative action of aqua-regia. The other possible by-prod-
uct, i.e., oxalic acid, showed lower retention on the catalyst surface
and the oxidation of the compound by aqua-regia was much lower
than ferulic acid.
The contribution of AC to the TOC, around 25 mg of the adsor-
bent (calcined at 300 C temperature) was dissolved in aqua regia.
The TOC of the sample was insignicant and thus it was assumed
that AC did not add to the nal TOC of the adsorbed species.
Based on the above results, 50 mg/l of additional TOC (the max-
imum value) was also assumed to be adsorbed on the catalyst
which was removed due to the oxidation by aqua-regia. Hence, it
can be suggested that adsorption has signicant contribution in
the removal of TOC or COD from the treated wastewater during
CWO process (2230% of the total TOC removed). The detailed
results are presented in Table 2. Furthermore, the CO2 production
during CWO process was estimated based on the TOC data. The cal-
culated CO2 for AC supported catalysts was found to be the highest
(1350 and 1367 mg/l).
3.3. Reaction kinetics
Zhang and Chuang [28] proposed a lumped kinetic model for
CWO reaction. The complete or partial oxidation of the organic
compounds can be expressed as follows:
A + nO2 2
k2
B + H2O (partial)
where A is the parent organic compound in wastewater, B the inter-
mediates/byproducts formed during the oxidation process. k1 and
k2 are the reaction rate constants for complete and partial reaction
steps. Since the industrial efuents or even a single compound may
form a number of intermediates which are difcult to determine, a
lumped parameter (TOC or COD) is substituted for A and B. In the
present study, the concentration of A or B is expressed in form of
TOC. To develop the model equations, the rst order kinetic behav-
ior was assumed with respect to A for both the reactions. Further-
more, the excess oxygen is also assumed to be available for the
oxidation process. In the present experimental study, the theoreti-
cal oxygen was almost 5 times higher than the stoichiometric con-
centration. The reaction rates can be represented mathematically as
follows:
dA
 k1 k2 A 3
dt
dB
k2 A 4
dt
Integrating the above equations and applying the initial condi-
tions (i.e. at time t = 0, [A] = [A]0, and [B] = 0), the following expres-
sion will be obtained:
A
ek1 k2 t 5
A0 
A A0 ek1 k2 t 6
k2 A0  
B 1  ek1 k2 t 7
k1 k2
By adding Eqs. (6) and (7) and replacing [A] + [B] = [TOC] at time
t, [A]0 = [TOC]0, the resulting expression will be:
 
TOC k2 k1
ek1 k2 t 8
TOC0 k1 k2 k1 k2
The kinetic rate constants (i.e. k1 and k2) were estimated by t-
ting the experimental data to the model Eq. (8) and shown in Fig. 5
with the patterns for the ferulic acid degradation and formation of
intermediates or byproducts. The rate constants suggest that the
ferulic acid mineralization rate was faster than the partial oxida-
tion rate for all catalytic runs. It can be seen that k1 was twice
the k2 value for the two best performed catalysts (i.e. Cu/Ce/AC
and Cu/Ce/Al2O3). For non-catalytic reaction, the reaction rates
were much lower compared to CWO and the rate constants for
both the pathways were almost equal (0.0100.012).
3.4. Catalytic reusability studies
3.4.1. Characterization of the regenerated catalysts
The catalysts were recovered from the treated wastewater and
subjected to the thermal regeneration. The XRD spectra of the
regenerated catalysts were more or less similar to that obtained
for the respective fresh catalysts and are provided in the support-
ing information (Fig. S2).
The particles of regenerated Cu/Ce/AC catalyst were much smal-
ler than the fresh catalyst and this size reduction may be due to the
attrition as well as shearing action of the impeller on the catalyst
particles. As a result, the surface area of the catalyst might have
increased by 2.5 times the fresh catalyst (Table 3). Generally,
 B.R. Yadav, A. Garg / Chemical Engineering Journal 252 (2014) 185193 191

Table 2
TOC balance for synthetic wastewater treated by CWO process and prediction of CO2 generation.

Catalyst TOCi (mg/l) TOCf (mg/l) TOCads (mg/l) TOCox,ar (mg/l) TOCconv (mg/l) CCO2 (mg/l)
Cu/Ce/AC 530 93 63 50 324 1367
Cu/Ce/Al2O3 530 113 76 50 291 1247
Cu/Mn/Ce 530 130 68 50 282 1214
Cu/Mn/Al2O3 530 133 63 50 284 1221
Cu/Mn/AC 530 119 42 50 319 1349

TOCi = initial TOC, TOCf = nal TOC, TOCads = TOC adsorbed on catalyst (as measured), TOCox,ar = actually adsorbed but oxidized by aqua-regia during the dissolution of the
recovered solid, TOCconv = TOC converted in CO2 = TOCi  (TOCf + TOCads + TOCox,ar), CCO2 = estimated CO2 concentration produced.

the macro and mesopore areas in the catalysts were increased after
the reaction (except for Cu/Mn/Al2O3 catalyst). The leaching of
metal species had the pronounced impact on surface area of the
catalysts recovered after rst use. Cu and Mn were susceptible to
the leaching under prevailing reaction conditions (acidic environ-
ment and elevated temperature) which might have caused in the
increase in surface area and pore volume of the catalysts. After rst
use, around 1928% of the original Cu loading was leached out
while Mn leaching was much higher (3342%). On the other
hand, the least leaching was observed for Ce (812% only). The
results from the leaching tests are presented in Table 4.
3.4.2. Reuse of the regenerated catalysts for CWO reaction and metal
leaching
The regenerated catalysts were reused for the catalytic
oxidation of ferulic acid under the same operating conditions
(i.e. temperature = 120 C and oxygen partial pressure = 0.5 MPa).
The reduction in COD and TOC after rst reuse was slightly lower
than that obtained with fresh catalyst (Fig. 6). Around 84% and
76% reductions in COD and TOC (nal COD = 240 mg/l and
TOC = 124 mg/l) were obtained after 3 h reaction with Cu/Ce/AC
catalyst which were 6% lesser than those achieved with the fresh
catalyst.
The reused catalysts were again recovered and thermally trea-
ted (oven drying followed by calcinations) before using for ferulic
acid treatment. No considerable reduction in the activity of various
catalysts could be found after second use which is evident from the
nal TOC and COD values. Thus the catalysts could be used three
times without signicant depletion in their efciencies.
The extent of metal leaching from the catalysts due to the
repeated use in CWO reaction is presented in Table 4. As expected,
the leaching occurred in each cycle though the leached amount of
metal was reduced in the subsequent cycles. It can be seen that up
to 50% and 80% of the total Cu and Mn loadings, respectively, were
found in the treated wastewater after three cycles. Despite the loss
of active species, the comparable TOC removals from the wastewa-
ter may be primarily due to the adsorption of organics on the
catalyst surface.

Fig. 5. Determination of rate constants by curve tting of experimental data into the kinetic model: (a) without catalyst, (b) Cu/Ce/AC, (c) Cu/Ce/Al2O3, (d) Cu/Mn/Ce, (e) Cu/
Mn/Al2O3 and (f) Cu/Mn/AC.
192 B.R. Yadav, A. Garg / Chemical Engineering Journal 252 (2014) 185193

Table 3
Surface area and pore characteristics of the regenerated catalysts.

Catalyst A (m2/g) Amicro (m2/g) Amacro& meso (m2/g) Vmicro (cm3/g) Vmacro&meso (cm3/g) dpore ()
Cu/Ce/AC 44.71 48.49 0.150 124.05
Cu/Ce/Al2O3 48.90 52.91 0.145 109.99
Cu/Mn/Ce 27.74 27.25 0.144 212.61
Cu/Mn/Al2O3 73.29 68.26 5.028 0.0021 0.195 110.23
Cu/Mn/AC 156.83 48.87 63.33 0.0377 0.109 69.35

Table 4
Metal leaching from catalysts after repeated use in CWO process.

Catalyst Mass concentration in fresh catalyst (mg/g of catalyst) % Metal leaching (of the original concentration)
After rst use After second use After third use
Cu/Ce/AC Cu = 299.3, Ce = 207 Cu = 26.6, Ce = 10.1 Cu = 39.4, Ce = 16.1 Cu = 47.8, Ce = 20.5
Cu/Ce/Al2O3 Cu = 259.5, Ce = 190.1 Cu = 27.9, Ce = 7.9 Cu = 38.2, Ce = 14.4 Cu = 48.1, Ce = 19.1
Cu/Mn/Ce Cu = 201.1, Mn = 168.58, Ce = 234.9 Cu = 21.2, Mn = 41.6, Ce = 12.1 Cu = 34.0, Mn = 60.7, Ce = 17.7 Cu = 44.1, Mn = 79.3, Ce = 22
Cu/Mn/Al2O3 Cu = 174.3, Mn = 176.8 Cu = 20.5, Mn = 33.0 Cu = 35.3, Mn = 47.2 Cu = 49.8, Mn = 61.2
Cu/Mn/AC Cu = 235.6, Mn = 191.7 Cu = 19.4, Mn = 37.2 Cu = 30.7, Mn = 49.8 Cu = 41.5, Mn = 61

activity was observed even after second use. Adsorption may be

considered the dominant pollutant removal mechanism during
the CWO with regenerated catalysts. To improve the oxidative
degradation of ferulic acid, the reaction at higher temperature
(150200 C temperature) should be performed. The future study
should also determine the effect on the wastewater biodegradabil-
ity after catalytic treatment. To evaluate the potential of activated
carbon based catalysts, the CWO runs on pulping efuent
(obtained from a pulp and paper mill) should be planned.

Acknowledgments

The rst author acknowledges the nancial support of Ministry

Fig. 6. Reduction in COD and TOC after 3 h CWO reaction with the regenerated
catalysts at mild operation conditions.
of Human Resources and Development (MHRD), New Delhi, India
for pursuing doctorate degree. We also recognize the support of
the Sophisticated Analytical Instrumentation Facility (SAIF), IIT
Bombay, the Metallurgical Engineering & Materials Science Depart-
ment, and the Department of Chemical Engineering, IIT Bombay,
for helping us in the catalyst characterization.

4. Conclusions
In the present study, ve non-noble metal based heterogeneous
supported catalysts were used for the oxidative degradation of
ferulic acid (a lignin model compound) by CWO process at mild
operating conditions (temperature = 120 C and oxygen partial
pressure = 0.5 MPa). The addition of catalysts improved the degra-
dation of ferulic acid mainly by a combination of oxidation and
adsorption processes. Cu/Ce/AC catalyst was found to be the best
and showed high COD and TOC reductions (88% and 82%, respec-
tively) from the wastewater despite much lower surface area com-
pared to the alumina supported catalysts. Adsorption on the
catalyst surface accounted for around 2230% of the total TOC
reduction. The reaction rate constants obtained from the kinetic
modeling suggested that the complete conversion of ferulic acid
into gaseous end products (like CO2 and H2O) was more favorable
than the partial oxidation for the catalytic runs.
The regenerated catalysts showed signicant change in the sur-
face properties and their metal composition. BET surface area of all
the catalysts was increased substantially during CWO reaction.
This may be attributed to the signicant leaching of the metals
(like Cu and Mn) which may have opened the pores of the catalysts.
The catalysts were found susceptible to the thermal reaction
conditions. However, no considerable change in the catalytic
Appendix A. Supplementary material
Supplementary data associated with this article can be found, in
the online version, at http://dx.doi.org/10.1016/j.cej.2014.04.110.
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