Journal of Hazardous Materials 248–249 (2013) 355–363

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Journal of Hazardous Materials

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Catalytic wet peroxidation of pyridine bearing wastewater by cerium supported

SBA-15
V. Subbaramaiah, Vimal Chandra Srivastava ∗ , Indra Deo Mall
Department of Chemical Engineering, Indian Institute of Technology Roorkee, Roorkee 247667 Uttarakhand, India

h i g h l i g h t s

 Cerium supported SBA-15 (Ce/SBA-15) synthesized by two-step synthesis.

 Characterization of Ce/SBA-15 by FTIR, XRD and BET surface area.
 Catalytic peroxidation of pyridine by Ce/SBA-15.
 Optimization of parameters like catalyst dose, H2 O2 dose, initial concentration and temperature.
 Catalyst reusability and leaching study performed.

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

Article history: Cerium supported SBA-15 (Ce/SBA-15) was synthesized by two-step synthesis method in acidic
Received 13 October 2012 medium. It was further characterized by various characterization techniques such as X-ray diffrac-
Received in revised form tion, field-emission scanning electron microscopy, Fourier transform infrared spectroscopy and N2
13 December 2012
adsorption–desorption pore size distribution analysis. The Ce/SBA-15 showed highly ordered meso-
Accepted 9 January 2013
Available online 16 January 2013 structure with pore diameter ≈ 70–100 Å´ and pore volume ≈ 0.025 cm3 /g. Ce/SBA-15 was further
evaluated as a catalyst for the oxidation of highly toxic and non-biodegradable material, pyridine, by
Keywords: catalytic wet-peroxidation method. The effects of various operating parameters such as catalyst dose
Pyridine (0.5–6 g/l), stoichiometric ratio of H2 O2 /pyridine (1–6), initial pyridine concentration (50–800 mg/l) and
Wet peroxidation temperature (313–358 K) have been evaluated and optimized. Ce/SBA-15 showed stable performance
Ce/SBA-15 during reuse for six cycles with negligible cerium leaching. Kinetic and thermodynamic parameters and
Oxidation operation cost have also been determined.
Catalyst characterization © 2013 Elsevier B.V. All rights reserved.

1. Introduction Typical concentration of pyridine and its associated compounds in

Discharge of newer chemicals, toxic and refractory materials
has necessitated research on advance treatment methods for the
control of these materials. Aromatic heterocyclic compounds are
generated from many industries. Most of these chemicals are
toxic to human health and certain life forms [1]. Pyridine is one
of the parent chemical from which series of chemicals are man-
ufactured, it is used as a solvent in paint and rubber preparation,
as an intermediate in making insecticides, pharmaceuticals and
herbicides for agricultural applications [2]. Pyridine creates severe
health hazards because of its toxic and teratogenic nature [3]. The
United States environmental protection agency (USEPA) has listed
pyridine as one of the priority organic pollutants [4]. It mixes very
easily with water and is soluble in alcohol, ether, and benzene.
∗ Corresponding author. Tel.: +91 1332 285889; fax: +91 1332 276535/273560.
E-mail address: vimalcsr@yahoo.co.in (V.C. Srivastava).
wastewater may vary in the range of 20–300 mg/l [5].
Numerous treatment methods are used for the treatment of
pyridine and associated compounds such as adsorption [5,6],
electrochemical method [7], biological methods [1,8], catalytic
supercritical oxidation/catalytic oxidation [2,9–11], Fenton oxida-
tion [12], photo catalytic oxidation [13,14], ozonation [15], and ion
exchange [16]. Table 1 shows various oxidation methods used in
the literature for the treatment of pyridine bearing wastewater.
Catalytic wet peroxidation (CWPO) is promising technology that
has emerged as a feasible substitute technology for the treatment of
medium to high organic loading wastewater using hydrogen per-
oxide as the oxidant [17]. Wet peroxide oxidation is a process in
which hydrogen peroxide is used as an oxidative agent. In CWPO
process, catalysts (homogeneous or heterogeneous) increase the
rate of production of hydroxyl radical from hydrogen peroxide.
These hydroxyl radicals have high potential to oxidize wide range of
organics present in wastewater under mild conditions i.e. at atmo-
spheric pressure and temperature below 353 K with low energy

0304-3894/$ – see front matter © 2013 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.jhazmat.2013.01.018
356 V. Subbaramaiah et al. / Journal of Hazardous Materials 248–249 (2013) 355–363

Table 1
Studies on treatment of pyridine using various oxidation methods.

System Supporting Catalyst Type of rector Temperature, Initial conc. (mg/l) Reaction Removal efficiency References
materials pressure, pH time (min)

Catalytic oxidation Zeolite, Cu Micro-reactor 250–700 ◦ C, 600 30 100% conversion Zhou et al. [10]
MCM-41, Normal
and
␥-Al2 O3
Catalytic wet air Carbon Cu–Co, CuSO4 Stainless steel 140–160 ◦ C, 10 90 64% at 160 ◦ C Chaudhary et al. [11]
oxidation reactor 9 bar, pH 4
Catalytic oxidation ␥-Al2 O3 Pt 350–520 ◦ C 0.1–0.85 vol.% Ismagilov et al. [9]
Fenton’s oxidation H2 O2 and Fe2+ 1 l glass beaker 1–4 pH COD 60,000 and 240 62.2% COD Padoley et al. [12]
23,000 mg/l
Fenton’s oxidation H2 O2 and Fe2+ 500 ml glass 2–4 pH 12,500 120 74.0% COD at pH 2 Bag et al. [13]
beaker
Photo assisted H2 O2 , Fe2+ and 2–4 pH 67.0% COD at pH 4 Bag et al. [13]
Fenton’s sunlight
Photo-catalysis TiO2 /hv/O2 4 pH Bag et al. [13]
Wet peroxidation Ce/SBA-15 250 ml oil bath 85 ◦ C, 2 g/l 100–1000 300 89% removal 75% TOC, Present study
reactor 77% COD

consumption [18]. Hydroxyl radicals which get produced during
the CWPO process react with wide range of organic compounds
at almost diffusion controlled rate converting them to either non-
toxic compounds or to end products such as CO2 and H2 O [19].
SBA-15 has received rapid attention in material science and
catalysis since its inception, due to its straightforward synthesis
route, narrow and controllable pore size, high surface area, high
thermal stability, etc. [20]. Cerium (Ce) containing materials are
powerful one-electron oxidants that are used as catalysts for oxi-
dation of organic compounds [21]. Incorporation of cerium atoms
into the walls of mesoporous silica material allows creation of Lewis
and Bronsted acid sites [21]. Cerium incorporated SBA-15 can be
used under high temperature and high pressure or in hydrothermal
system owing to its high hydrothermal stability [22]. Thus, Ce
loaded SBA-15 when coupled with advance oxidation process such
as CWPO can oxidize recalcitrant compounds from wastewater.
Few authors have previously synthesized cerium impregnated SBA-
15 and used it for different applications such as steam reforming,
hydroxylation, and partial and complete oxidation [21]. However,
Ce/SBA-15 has never been used for CWPO of any recalcitrant com-
pound. Moreover, most of previous researchers did not report on
reusability of the catalyst which is very essential considering the
high cost of SBA-15.
In the present study, Ce was impregnated in SBA-15 and this
material (Ce/SBA-15) was characterized by various techniques.
Main aim of this study was also to optimize the operating parame-
ters such as catalyst dose, stoichiometric ratio of H2 O2 /pyridine,
initial concentration of pyridine, and temperature for the cat-
alytic wet peroxidation of pyridine present in aqueous solution by
Ce/SBA-15. Kinetic and thermodynamic parameters and operation
cost have also been determined.
2. Methods and materials
2.1. Materials
All the chemicals used in the study were of analytical reagent
(AR) grade. Tetraethylorthosilicate (TEOS) (Aldrich, Germany),
pluronic P123 (PEO20-PPO70-PEO20, Aldrich, Germany), cerium
nitrate (S.D. Fine Chemicals, India), pyridine (S.D. Fine Chemicals,
India), HCl (Ranken, India), 30 wt% hydrogen peroxide (Ranken,
India), etc. were purchased from various companies.
2.2. Synthesis of catalyst and its characterization
SBA-15 was synthesized by two-step synthesis method as
reported in the literature [20]. First, 4 g pluronic P123 was dispersed
in 150 ml HCl (2 M) with continuous stirring. The solution was
heated to 40 ◦ C over a water bath and 9 ml of TEOS was added
drop-wise with constant stirring. The mixture was sealed in a
polypropylene bottle, stirred at 40 ◦ C for 24 h, and then hydrother-
mally heated at 90 ◦ C under static conditions for another 24 h. The
solid product was washed with deionized water, and dried at 100 ◦ C
overnight. The P123 templates were removed by calcinations of
the material at 500 ◦ C in air for 6 h. The calcined samples were
designated as SBA-15.
Required amount of cerium nitrate precursor was dissolved
in millipore water after that, 1 g of SBA-15 was further added in
this solution and it was then stirred up to 2 h. Mixture was then
hydrothermally heated at 90 ◦ C under static condition for 24 h. It
was then calcined at 500 ◦ C for 6 h. The calcined sample was desig-
nated as Ce/SBA-15.
The textural properties of the samples were analyzed by
N2 adsorption–desorption isotherms obtained at 77 K using
Micromeritics ASAP 2020 apparatus. Before the analysis, the sample
was degassed at 300 ◦ C for about 6 h. The surface area was obtained
using Brunauer–Emmett–Teller (BET) model for adsorption data
in a relative pressure range of 0.05–0.30. The total pore volumes
were calculated from the amount of N2 vapor adsorbed at a rela-
tive pressure of 0.99. The pore diameter distribution was calculated
from the inflection point of the cumulative pore volume versus
diameter curve obtained using Barrett–Joyner–Halenda (BJH)
method.
To understand the morphology, a field emission scanning elec-
tron microscope (FE-SEM)/energy-dispersed X-ray spectra (EDX)
QUANTA, Model 200 FEG, USA was used. The samples were first
grounded to make the samples homogeneous and then spread on
sample holders in such a manner to produce flat surfaces. After
this, the samples were gold coated using sputter coater (Edwards
S150) to provide conductivity to the samples, and then the images
of FE-SEM were taken at an acceleration voltage of 20 kV under low
vacuum and then EDX were taken to find metal content of sample.
The error in the content of elements determined using this method
is between 5 and 10%.
Powder X-ray diffraction (XRD) patterns were collected on a
scanter diffractometer using Cu-K␣ radiation ( = 0.154 nm). The
scanning range was 10–90◦ with a step size of 0.01◦ . Compound
identification in the samples was accomplished by comparison of
the peaks with joint committee on powder diffraction standards
(JCPDS) data files.
Fourier transform infrared (FTIR) spectra were obtained over a
range of 4000–400 cm−1 with a Nicolet Avatar 370 CSI spectrometer
(Thermo-Electron Corporation, USA). The sample to be character-
ized was grounded using KBr pellet technique.
 V. Subbaramaiah et al. / Journal of Hazardous Materials 248–249 (2013) 355–363
2.3. Experimental
The experimental studies were carried out in a 250 ml three-
necked round bottom glass reactor and equipped with a total reflux
system. The total reflux prevented any loss of pyridine vapor. Mag-
netic stirrer was used to agitate the mixture and keep the solution
homogeneous during the experimentation. The temperature of the
reaction mixture was raised using the hot-plate to the desired
value, and it was kept constant during the experimental run. In
each run, the reactor was charged with 50 ml pyridine solution
of required concentration. The oil bath was then heated up and
stabilized to the desired reaction temperature called time zero
(time t = 0 for the reaction was taken when the final temperature
was reached). When thermal equilibrium was reached, required
amount of catalyst (Ce/SBA-15) and oxidation agent (hydrogen
peroxide) were added to the reaction mixture. If complete min-
eralization of pyridine by hydrogen peroxide occurs in the reaction
(2C5 H5 N + 29H2 O2 → 10CO2 + 34H2 O + 2NO2 ), it is possible to esti-
mate the stoichiometric amount of hydrogen peroxide for pyridine
oxidation. As per the reaction, 14.5 mole of H2 O2 is required to
completely oxidize 1 mole of pyridine.
Initially complementary experiments were conducted for the
oxidation of pyridine bearing wastewater with H2 O2 and without
catalyst. In this experiment, oxidation of pyridine was <10%. Addi-
tional experiments were carried out with catalyst but without H2 O2
to discriminate the effect of adsorption. In these experiments, max-
imum pyridine disappearance of 8% was observed after 6 h which
was considered as marginal. Step wise addition of hydrogen perox-
ide (30%) was also tested. It was found that if the total amount of
added H2 O2 was kept constant, single-step, two-step or three step
H2 O2 additions did not significantly altered the overall oxidation of
pyridine bearing wastewater. Therefore, most of the experiments
were carried out with one-step addition of H2 O2 at the desired
stoichiometric H2 O2 /pyridine molar ratio.
2.4. Analysis of pyridine concentration and TOC
Pyridine concentration was determined using gas chromato-
graph equipped with flame ionization detector (GC-FID). COD was
measured using a digestion unit (DRB 200, HACH, USA) and a dou-
ble beam UV visible spectrophotometer (HACH, DR 5000, USA) as
per American Public Health Association (APHA) method [23]. Ini-
tially 3 ml of sample was mixed with 1.5 ml of digestion reagent (as
per COD standard procedure-5220 D standard solution) along with
3.5 ml of sulfuric acid reagent into COD vial. This COD vial was kept
in solid block digestion unit in which sample was heated at 150 ◦ C
within ±1% accuracy with utmost uniformity of temperature for
2 h. Thereafter, sample vial was cooled to room temperature and
the absorbance of the solution was measured by using UV visible
spectrometer at 600 nm. The results were compared with calibrated
data obtained using potassium hydrogen phthalate as calibration
standard. The hydrogen peroxide interference in the standard COD
test was eliminated as per the standard protocol [24]. The total
organic carbon (TOC) at the optimized conditions was determined
using TOC analyzer (Shimadzu TOC-V). The percentage removal of
pyridine or COD or TOC was calculated using the following equa-
tion:
C − C 
o t
Percentage removal (X) = × 100
Co
where Co is the initial pyridine or COD or TOC concentration (mg/l),
Ct is the pyridine or COD or TOC concentration (mg/l) after time (t).
All the experiments were done in triplicate and results were found
to show ±5% deviation from the average value. Reported results are
average of three runs. The cerium contents of Ce/SBA-15 catalysts
were analyzed by ion chromatography (IC) (Mehtrom) equipped
357
Table 2
Textural characteristics of the cerium-containing mesoporous silica materials.
Sample Ce/Si SBET (m2 /g) Vp (cm3 /g) Dp (nm)
SBA-15 – 419.3 0.77 6.71
Ce-SBA-15 0.10 160.6 0.28 6.49
SBET , BET surface area; Vp , total pore volumes were obtained at P/Po = 0.99; Dp , aver-
age pore diameter calculated by BJH method.
with professional UV/vis detector. The samples were digested in
nitric acid, and filtrated through membrane filter (0.25 ␮m).
3. Results and discussion
3.1. Characterization
In order to investigate the mesoporous structure of Ce/SBA-
15, the textural properties were calculated from nitrogen
adsorption–desorption isotherms. Fig. 1 displays the nitrogen
adsorption–desorption isotherms (A) and BJH pore size distribu-
tion (B) of SBA-15 and Ce/SBA-15. It seems that the impregnation
of the Ce lead to an overall reduction of the surface area and pore
volume whereas mean pore size was only slightly modified.
The N2 adsorption–desorption isotherm of pure SBA-15 exhib-
ited a type IV isotherm curve with H1-type hysteresis loop, which
represents a typical mesoporous structure according to the IUPAC
classification [25]. However, Ce/SBA-15 showed H2 type hysteresis
loop corresponding to ink-bottle pores and reduction of the pore
volume. The hysteresis loop of the Ce/SBA-15 was due to perco-
lation effect caused by small Ce nanocrystals settling within the
mesopores and effectively forming ink-bottle type pores [26]. The
BJH average pore diameter of SBA-15 was found to be 6.70 nm
whereas it was 6.49 nm for Ce/SBA-15. The textural properties of
SBA-15 and Ce/SBA-15 are also summarized in Table 2. The surface
area (SBET ), pore volume (Vp ) and pore diameter (Dp ) decreased
gradually in Ce loaded SBA-15 samples while the trend for wall
thickness (W) was in reverse. These results indicate that the incor-
poration of Ce species into the silica framework did not block
the mesopores [27]. Melero et al. [28], Hu et al. [29] and Zhong
et al. [30] reported BET surface of blank SBA-15 to 700, 784 and
486 m2 /g. However, after loading with Fe, Co and Cu, BET surface
reduced to 468, 587 and 447 m2 /g, respectively. Han et al. [31]
found that the pore volume and specific surface areas decreased
from 1.27 cm3 /g and 937 m2 /g for bare SBA-15 to 0.49 cm3 /g and
299 m2 /g for the Mn3 O4 /SBA-15, respectively. Mesoporous diame-
ter for SBA-15 decreased from 7.7 nm to 6.3 nm for Mn3 O4 /SBA-15.
The decrease of the mesopore dimension was suggested due to the
uniform coating of Mn3 O4 on the inner walls of SBA-15. Hu et al.
[29] also reported decrease in pore size of SBA-15 from 7.0 nm to
6.2 nm after loading with Co.
The morphology of Ce on SBA-15 structure was analyzed using
SEM images combined with the EDX analysis. EDX mapping analy-
sis was used to reveal the distribution of Ce on the surface of SBA-15.
Typical element images are shown in Fig. 2. According to the EDX
images (Fig. 2(b)–(d)), mainly Ce, Si, C and O are present in the sam-
ples. From the EDX mapping data, it is conformed that Ce was well
dispersed on SBA-15. However, it seems that at some place Ce is
present in greater amount than at other places. This may be due to
(1) the difference in atomic radius of silica and cerium.
The wide-angle powder X-ray diffraction spectra of the pure
SBA-15 and Ce/SBA-15 samples were obtained (figure not shown).
XRD of SBA-15 did not show any diffraction peaks, only a wide
hump was observed in the 2 range of 20–30◦ which corresponded
to amorphous silica. In the case of Ce/SBA-15, four well-resolved
diffraction lines were observed at 28.6, 33.1, 47.5 and 56.3 with
miller indices (1 1 1), (2 0 0), (2 2 0) and (3 1 1). Bragg angle as
358 V. Subbaramaiah et al. / Journal of Hazardous Materials 248–249 (2013) 355–363

Fig. 1. Nitrogen adsorption (A)–desorption (D) isotherms and pore size distribution of SBA-15 and Ce-SBA-15.

calculated using Bragg’s equation corresponding to these miller
indices were 3.12◦ , 2.71◦ , 1.91◦ and 1.63◦ , respectively [32]. It con-
firmed that the cerium species are present on the surface of pore
walls in the mesoporous materials. All diffraction peaks in Ce/SBA-
15 were readily indexed to cubic Ce structure consistent with
standard PDF data base (JCPDS file no. 43-1002). The full width
at half maxima (FWHM) of major peaks decreased and confirmed
growth of the grain size.
The FTIR absorption spectra of pure silica SBA-15 and Ce-
SBA-15 samples are shown in Fig. 3. In SBA-15, a weaker band
observed at 801 cm−1 was due to Si O Si symmetric stretching,
and a strong band identified at 465 cm−1 was due to vibration of
Si O Si. For Ce/SBA-15, the strong band observed at 966 cm−1
can be attributed to the Si O Ce vibration, however, in pure
SBA-15 the band at 966 cm−1 was absent [33]. This validates the
Ce incorporation into SBA-15 framework effectively. In the finger
print region (400–1300 cm−1 ), the vibration absorption band at
1090 cm−1 and 802 cm−1 may be assigned to mass (Si O Si)
and tetrahedron Si O, respectively. The wave numbers generally
shift and decrease in Ce/SBA-15, for instance the peak shifts
to 1086 cm−1 and 787 cm−1 . This shift of the absorption peaks
toward the lower wave number is due to Ce incorporation into the
framework of silica tetrahedron [22].
3.2. Effect of the catalyst dose
Catalyst dose is the main factor in wet peroxidation reac-
tion that catalytically decomposes the H2 O2 to generate ·OH free

Fig. 2. EDAX element maps of Ce-SBA-15.

 V. Subbaramaiah et al. / Journal of Hazardous Materials 248–249 (2013) 355–363
Fig. 3. FT-IR spectra of Si-SBA-15 and Ce-SBA-15.
radicals. In the present study, catalyst dose was varied in the
range of 0.25–6 g/l, other parameters were kept constant (temper-
ature = 328 K, stoichiometric ratio of H2 O2 /pyridine = 1.5, pyridine
concentration = 100 mg/l). With an increase in catalyst dose, there
was decrease in the residual concentration of pyridine in the solu-
tion indicating increase in the degradation of pyridine (Fig. 4a). It
may be seen in Fig. 4(a) that for Ce/SBA-15 dose > 2 g/l, removal
efficiency decreased marginally. This may be due to the self-
scavenging effect of ·OH radical at higher catalyst dose (Eq. (2))
which may lead to decrease in pyridine removal.
Ce3+ + • OH → Ce4+ + OH−
Kang and Hwang [34] reported similar trend during Fenton
oxidation at higher concentration of iron species. Also at high
Ce/SBA-15 dose (>2 g/l), numbers of active sites are much more than
the number of pyridine molecules, thus the additional amount of
catalyst does not gets involved in the catalytic activity and the rate
does not increase with an increase for catalyst beyond a certain
limit [35]. Also, at higher catalyst dose, agglomeration of the cata-
lysts particles, block the active sites and do not help in increasing
the pyridine oxidation at higher catalyst dose.
3.3. Effect of H2 O2 /pyridine molar ratio
Many authors have varied H2 O2 concentrations between 0.7 and
1.5 times the stoichiometric requirement [36,37]. Few investiga-
tors have also checked the effect at high concentrations between
3.5 and 4 times the stoichiometric requirement [38,39]. In the
present study, the effect of H2 O2 /pyridine molar ratio was stud-
ied by varying the stoichiometric H2 O2 /pyridine molar ratio in
the range of 1–6 whereas catalyst dose was maintained at the
observed optimum (2 g/l of Ce/SBA-15), pyridine concentration
was 100 mg/l and the temperature was kept constant at 328 K.
Pyridine removal increased with an increase in H2 O2 /pyridine
molar ratio till the ratio was ≤4. However, an excess amount
of H2 O2 addition (stoichiometric ratio of H2 O2 /pyridine > 4) led
to decrease in pyridine removal (Fig. 4(b)). This may be because
of the formation of hydroperoxyl radicals (HOO•) from hydroxyl
radicals that are already formed. The hydroperoxyl radicals do
not contribute to the oxidative degradation of the organic sub-
strate and are much less reactive. The degradation of the organic
359
substrate occurs only by reaction with HO• [40]. Furthermore,
the removal of organic compounds increases with an increase in
H2 O2 dose until a critical H2 O2 /pyridine molar ratio is achieved.
However, when H2 O2 /pyridine molar ratio was higher than the
critical H2 O2 /pyridine molar ratio, the degradation rate of organic
compounds decreases due to the so-called scavenging effect as
discussed earlier [41]. Tang and Huang [42] reported same phe-
nomenon in Fenton oxidation for 2–4 dichlorophenol degradation.
It is always better to use optimum amount H2 O2 so as to avoid
build up of undesirable intermediates in the system [12]. This study
shows that the molar ratio of H2 O2 to pyridine required for maxi-
(2) mum removal pyridine is around 4 times the stoichiometric ratio
required for complete oxidation of pyridine.
3.4. Effect of the initial pyridine concentration
The effect of initial concentration of pyridine on CWPO was
studied with varying initial concentrations (50–800 mg/l) at con-
stant catalyst dose of 2 g/l, temperature 328 K and stoichiometric
H2 O2 /pyridine ratio of 4. Results as depicted in Fig. 4(c) show that
the removal increases with an increase in pyridine concentration.
The synthesized Ce/SBA-15 has mesoporous structure with high
surface area and high potential to adsorbed high concentration
of pyridine molecules at catalyst dose of 2 g/l. At lower pyridine
concentration, availability of pyridine molecule to adsorb on to
Ce/SBA-15 was not sufficient [35]. The effect of pyridine concen-
tration on reaction rate agrees with the basic chemical principles,
namely the increase of reactants concentration increases the colli-
sion frequency of molecules, and thus accelerates the reaction rate.
This shows that the parameters catalyst dose of 2 g/l and stoichio-
metric ratio of H2 O2 /pyridine of 4 that were optimized earlier are
more efficient at higher pyridine concentration also.
3.5. Effect of operating temperature
Reaction temperature is an important operating parameter in
CWPO. In this study, experiments were conducted by varying tem-
perature in the range of 313–358 K, and the results are shown in
Fig. 4(d). It may be seen that the pyridine removal increased with an
increase in the temperature from 313 to 358 K. At 313 K, for exam-
ple, the pyridine removal was found to be 44% which increased
360 V. Subbaramaiah et al. / Journal of Hazardous Materials 248–249 (2013) 355–363

Fig. 4. Effect of various parameters on wet-peroxidation of pyridine. (a) Influence of the catalyst dose, T = 328 K, stoichiometric ratio of H2 O2 /pyridine = 1.5, Co = 100 mg/l,
time = 5 h; (b) influence of H2 O2 /pyridine molar ratio. T = 328 K, Ce/SBA-15 dose 2 g/l, Co = 100 mg/l, time = 5 h; (c) influence of initial concentration of pyridine. T = 328 K, Ce/SBA-
15 dose 2 g/l, stoichiometric ratio of H2 O2 /pyridine = 4, time = 5 h; and (d) influence of operating temperature. Ce/SBA-15 dose 2 g/l, stoichiometric ratio of H2 O2 /pyridine = 4,
Co = 100 mg/l, time = 5 h.

to 86% at 358 K. An increase in temperature accelerates the H2 O2
conversion into hydroxyl radicals, and thus the amount of H2 O2
available to scavenge these radicals is accordingly smaller [43].
Many authors reported same trend in catalytic oxidation of various
organic compounds [44].
At optimum condition (temperature = 358 K, Ce/SBA-15
dose = 2 g/l, stoichiometric ratio of H2 O2 /pyridine = 4, reaction
time 5 h), 75% TOC and 77% COD was achieved for 100 mg/l
pyridine solution. Comparative results for removal of pyridine
by various oxidation processes are given in Table 1. Padoley
et al. [12] reported 62.2% COD removal in 4 h time using Fenton
oxidation whereas Bag et al. [13] reported 74% COD removal in
2 h by the same process. In the present study, 89% pyridine, 75%
TOC and 77% COD removal was observed in 5 h using catalytic
wet peroxidation (CWPO) process. It may be pointed that Fenton
oxidation requires pH to be adjusted in the range of 2–4 whereas
CWPO was performed without any pH adjustment. Since the initial
concentrations are different in both processes, a direct comparison
of efficiency is not possible, though as per Table 1 it seems that
Fenton oxidation requires less time for treatment as compared to
CWPO. However, Fenton process has its own limitations too. First,
it should be carried out strictly around pH 3. Second, large amount
of Fe leaches at low pH and huge amount of sludge requires further
treatment [45].
3.6. Catalyst stability
The catalytic stability of Ce-SBA-15 catalyst was monitored
over six runs of the reaction, and the results are presented in
Fig. 5. The Ce/SBA-15 wrapped with the poly tetra fluoro ethyl-
ene (PTFE) membranes can effectively prevent loss of amorphous
catalyst. In the recycling study, 200 mg of Ce/SBA-15 catalyst was
 V. Subbaramaiah et al. / Journal of Hazardous Materials 248–249 (2013) 355–363 361

less than 0.4 mg/l which is within the permissible heavy metal
concentration for discharge of wastewater in India [46].

3.7. Kinetic study

Kinetic study for the treatment of pyridine bearing wastewater

using CWPO process was performed by determining the pyridine
concentration as a function of time. Simplified kinetic rate expres-
sion for pseudo-first-order kinetic model can be expressed as:

Ct = Co e−kf t (3)

where kf is the pseudo-first-order reaction rate constant. Sev-

Fig. 5. Reusability and leaching study of Ce/SBA-15 (Ce/SBA-15 dose = 2 g/l, stoichio-
metric ratio of H2 O2 /pyridine = 4, Co = 100 mg/l, time = 5 h).
wrapped in PTFE membrane. For this study, stoichiometric ratio
of H2 O2 /pyridine was 4 and pyridine concentration was 100 mg/l.
After reaching 328 K, H2 O2 and wrapped catalyst were added to the
reaction solution. It was observed that pyridine removal decreased
only marginally with each cycle and more than 70% removal
efficiency was still observed after six runs. Wrapped Ce/SBA-15 cat-
alyst retained high catalytic activity, demonstrating the satisfactory
reusability of the catalyst.
Ce leaching was also measured in each cycle using ion chromato-
graph equipped with UV/visual detector. Ce leaching was always
eral studies indicated that in presence of an excess of H2 O2 ,
the oxidation of organic wastewater compounds follows pseudo-
second-order kinetics [19,47] which is given as:
Co
Ct = (4)
(1 + ks tCo )
where ks is pseudo-second-order rate constant (l/mg min). Kinetic
data was fitted to both pseudo-first- and pseudo-second-order
models. Values of kf and ks at various temperatures are shown
in Table 3. Coefficient of determination (R2 ) values between the
experimental and the calculated values were found to be higher
for pseudo-second-order kinetic model, therefore, kinetic data was
found to be better represented by pseudo-second-order kinetic
model. The activation energy (E) and the frequency factor ko were
determined by Arrhenius equation given as:
kf or ks = ko exp−E/RT (5)
Values of E and ko were obtained from the slope and intercept of
Arrhenius plot (ln k versus 1/T plot). The values E and ko for pseudo-
second-order kinetic model were found to be 46.9 (kJ/mol K) and
2675 (l/mg min), respectively. Zhou et al. [48] and Inchaurrondo
et al. [49] fitted zero-order and first-order kinetic model for CWPO

Table 3
Kinetic and thermodynamic parameters for the pyridine removal.

Pseudo-first-order kinetic model Pseudo-second-order kinetic model

T (K) kf (1/min) R2 E (kJ/mol K) ko (1/min) kS (l/mg min) R2 E (kJ/mol K) ko (1/mg min)

313 0.0027 0.93 32.5 860 0.000039 0.95 46.9 2675

328 0.0052 0.87 0.000095 0.93
343 0.0082 0.95 0.000171 0.98
358 0.0221 0.93 0.000406 0.97

Table 4
Operating cost of pyridine treatment by CWPO process.

Cost of chemical reagents for catalyst synthesis

Reagent Price per unit Reagent cost for each g of Ce-SBA-15

Tetra ethyl ortho silicate (TEOS) 1459 /500 ml 10.2 /3.5 ml

Pluronic P123 6596 /1 l 11.5 /1.733 ml
HCl 648 /5 l 3 /24 ml
Cerium nitrate hexahydrate 1710 /1 kg 0.530 /0.31 g
Cost of Ce-SBA-15 per g 25.3 /g or 0.45 $/g
Cost of Ce-SBA-15 prepared from commercial grade SBA-15a 3.28 /g or 0.06 $/g

Running cost of CWPO process

Reagent Price per unit Cost for each run Cost for 1 litre

H2 O2 1222 /5 l 0.06 /0.245 ml 0.6

Power consumption 3.5 /kWh 0.21 /5 h 2.1
Ce-SBA-15a 3.28 /g or 0.06 $/g 6.56 /2 g or 0.12 $/2 g 10.93 b
or 0.2 $
Total operational cost per litre solution 13.63
Total operational cost per m3 of solutionb 13,630 or 248 $

Note: 1 $ = 55 Rupee i.e. (Indian National Currency) as on December 01, 2012.

a
Calculated using cost of commercial grade SBA-15 = 5000$/100 kg (Hailong Tech Development Co. Ltd., Shenyang, China) (website).
b
Calculation based on the fact that 2 g of catalyst can be used for 6 runs (each treating 100 ml of solution) using recycling of catalyst.
362 V. Subbaramaiah et al. / Journal of Hazardous Materials 248–249 (2013) 355–363
of phenol oxidation by CuNiAlCO3 and CuO/Al2 O3 , respectively.
Respective E values were found to be 61.5 kJ/mol and 56.8 kJ/mol,
respectively. Thus, activation energy required for pyridine oxida-
tion by Ce/SBA-15 is lower as compared to phenol oxidation by
CuNiAlCO3 and CuO/Al2 O3.
3.8. Operation cost
Estimation of treatment cost is an important aspect for imple-
mentation of any research work on plant scale. Generally overall
cost of the any treatment is sum of capital cost, operating cost and
investment cost. A rough economic analysis of the operating costs
for the treatment of pyridine bearing wastewater by CWPO process
was estimated. The operation cost (in $/m3 wastewater) calculated
included cost of chemical reagents for SBA-15 synthesis, cost of
reagents for CWPO process and the cost of energy (Table 4). It is
essential to note that this analysis is just an approximate tool and
these values are purely determined experimentally, but in large
scale operation cost will decrease. It may be seen in Table 4 that
the cost of synthesis of catalyst decreased drastically when cost
of Ce/SBA-15 was calculated based upon the cost of commercial
grade SBA-15. Overall operational cost of pyridine by CWPO pro-
cess was found to be 248 $/m3 wastewater. Canizares et al. [50]
estimated operating cost for the treatment of butyric acid by ozona-
tion and Fenton oxidation to be 270 $/m3 and 46 $/m3 , respectively.
Similarly, for the treatment 2-propanol, operational cost by ozona-
tion and Fenton oxidation were found to be 145 $/m3 and 94 $/m3 ,
respectively. It must be emphasized that CWPO requires signifi-
cantly lower initial investment than the Fenton oxidation. Thus,
Fenton oxidation process requires dosing pump and reactor for
mixing so as to maintain pH in the range of 2–4. Also, sludge gener-
ated in Fenton oxidation requires thickening, drying and disposal,
consequently, requiring additional investment and operating cost
[51]. Fixed cost in CWPO is also low as compared to Fenton pro-
cess. The only costly thing in CWPO is the non-iron metal precursor
which is costlier than the iron precursor used in Fenton process.
4. Conclusion
This study shows the Ce/SBA-15 could be used as an efficient
catalyst for the catalytic wet peroxidation (CWPO) of pyridine bear-
ing wastewater. FTIR study showed shift of the absorption peaks
toward the lower wave number indicating Ce incorporation into
the framework of silica tetrahedral. From the EDX mapping data, it
is confirmed that Ce was well dispersed on SBA-15. Optimum oper-
ating parameters for CWPO of pyridine from aqueous solution by
cerium supported SBA-15 were found to be 358 K with Ce/SBA-15
dose of 2 g/l, stoichiometric ratio of H2 O2 /pyridine of 4 with opti-
mum reaction time of 5 h. At optimum conditions, 75% TOC and
77% COD was achieved for 100 mg/l pyridine solution. Wrapped
Ce/SBA-15 catalyst retained high catalytic activity, demonstrating
the satisfactory reusability of the catalyst. The reaction kinetic data
was best-represented by followed pseudo-second-order kinetic
model.
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