Reac Kinet Mech Cat

DOI 10.1007/s11144-014-0824-x

Studies on the catalyst preparation methods and kinetic

behavior of supported cobalt catalysts for the complete
oxidation of cyclohexane
Mohammad Zabihi Farhad Khorasheh
Jalal Shayegan

Received: 12 October 2014 / Accepted: 16 December 2014

Akademiai Kiado, Budapest, Hungary 2015

Abstract Low cost dispersed supported cobalt oxide nanocatalysts on activated

carbon (AC) were prepared by two different methods: (1) combined impregnation
and depositionprecipitation (IMP-DP) and (2) heterogeneous depositionprecipitation (HDP). XRD, TEM, FESEM, BET and Boehm techniques were used for the
characterization of the support and the catalysts. Characterization analyses indicated
the negative effect of the wet impregnation method on the IMP-DP technique
for the preparation of catalysts for the total oxidation of cyclohexane in air. The
catalysts prepared by HDP and IMP-DP methods were found to have significant
differences in oxidation activity, morphology, particle size, and shape of active
sites. The HDP preparation method resulted in dispersed catalysts with particle sizes
less than 15 nm, which were smaller than those prepared by the IMP-DP method.
The morphology of cobalt oxide on activated carbon indicated lamellar and
sphere shapes for catalysts prepared by the IMP-DP and HDP method, respectively. Higher removal efficiencies for cyclohexane were obtained for catalysts
synthesized by HDP compared with those prepared by the IMP-DP method. The
EleyRideal rate expression was found to be appropriate to describe the kinetics of
cyclohexane oxidation over the range of experimental conditions employed in this
study.
Keywords Cyclohexane  Catalytic oxidation  Impregnation 
Depositionprecipitation  Cobalt  Activated carbon

Electronic supplementary material The online version of this article (doi:10.1007/s11144-014-0824x) contains supplementary material, which is available to authorized users.
M. Zabihi  F. Khorasheh (&)  J. Shayegan
Department of Chemical and Petroleum Engineering, Sharif University of Technology,
Azadi Avenue, P.O. Box 11155-9465, Tehran, Iran
e-mail: khorashe@sharif.ir

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List of symbols
Ci
Inlet feed concentration (ppm)
Ce
Exit gas concentration (ppm)
D
Mean crystallite diameter (nm)
K
Dimensionless shape factor = 0.9
k
X-ray wavelength
B
Line broadening at half maximum intensity
H
Bragg angle
XT
Steady state conversion of the cyclohexane
W
Weight of catalyst loaded in reactor (g)
V
Inlet molar flow rate of cyclohexane (mol/s)
r
Rate of cyclohexane oxidation (mol/g s)
Objective F Objective function of GA methodology for estimating
kinetic constants was the absolute error
E
Activation energy (kJ/mol)
DH
Adsorption enthalpy (kJ/mol)
R
Gas constant (J/mol/K)
R2
Correlation coefficient
N
Reaction order
kr
Kinetic constant (mol g-1 s-1)
Kads,c
Adsorption constant of cylohexane

Introduction
From an environmental point of view, volatile organic compounds (VOCs) must be
removed from contaminated air due to their harmful effects on plants, animals, and
humans. VOC removal or degradation can be achieved by various available
technologies including adsorption [1], thermal oxidation [2], catalytic oxidation [3],
photocatalytic oxidation [4, 5], bio-filtration [6] and membranes [7]. The important
advantage of catalytic oxidation processes is their lower operating temperature and
higher efficiency for the removal of VOCs from air.
The catalytic oxidation of VOCs in air to carbon dioxide and water has been
reported as an efficient technique for the removal of VOCs [2]. Cyclohexane as a
volatile organic compound can cause a variety of adverse health problems for
humans [8]. To our knowledge, there are only a few investigations in the open

Table 1 Previous studies on

the complete oxidation of
cyclohexane in air

123

Number

Catalyst and Method

Ref.

CeO2/Al2O3, catalytic oxidation

[9]

Mn/Al2O3 and Ce/Al2O3, catalytic oxidation

[10]

Pt/TiO2, photocatalytic oxidation

[11]

TiO2, photocatalytic oxidation

[12]

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literature that have reported the complete oxidation of cyclohexane in air to water
and carbon dioxide over supported metal catalysts (Table 1). Catalyst activity and
selectivity are strongly dependent on parameters such as catalyst preparation
method, support texture, types of metals, and dispersion and size of active sites [13
16]. Transition metals, due to their low price and availability, have been identified
as one of the most suitable materials for catalyst synthesis [15, 1725]. Activated
carbon (AC) appears to be an appropriate support due to its high surface area and
pore volume [1417], flexible surface [20, 21] and hydrophobicity [2631].
Different preparation methods can be used to obtain dispersed nanocatalysts
including wet impregnation [1325], depositionprecipitation (heterogeneous and
homogenous) [31], citric acid sol gel [33, 34], and atomic layer deposition [35, 36].
Many reported studies in the open literature have focused on the use of
impregnation and depositionprecipitation for the preparation of supported transition metal catalysts [32]. The catalyst preparation method can affect properties such
as the metal dispersion, metal particle size, and the formation of various metal
phases that play an important role in the complete oxidation of VOCs in air [3740].
Supported transition metals over porous activated carbons are generally prepared by
impregnation. Impregnation temperature, the pH of the impregnation solution, and
the pore size of activated carbon are important parameters that affect the metal
loading efficiency over activated carbons. Adsorption of transition metals on
activated carbons occurs during the impregnation and it is well recognized that
diffusion resistance plays a vital role in the overall transport of the ions. Previous
studies [4144] have indicated that there is a significant difference in the amounts of
metals adsorbed at different temperatures in the range of 2570 C. The pH of the
metal ions solution is also an important factor in any adsorption process. Some
investigations [45] indicated that the adsorption of metal ions on activated carbon
increased with increasing pH of the solution. Pore size distribution is another
significant factor in the adsorption of metal ions. Metal loading efficiency by
impregnation on activated carbons increased with increasing mesopore area due to
ion size and interaction between ions [46]. Activated carbons with mesopore
morphology that are mainly prepared by the physical activation methods (CO2 or
water vapor as a chemical agent) are, therefore, an adequate support for catalyst
preparation. Depositionprecipitation with slow precipitation by hydrolysis of urea
(homogenous DP) and use of ammonia (heterogeneous DP) is used for preparation
of the nanocatalysts with high dispersion. The pH (1011) and temperature
(7080 C) of the solution are important parameters in the depositionprecipitation
method. Despite numerous investigations reported in the literature on the removal of
VOCs from contaminated air using supported transition metal catalysts prepared by
depositionprecipitation method [32], no previous investigation has dealt with
almond shell based activated carbon as an appropriate support for complete
oxidation of cyclohexane. The main scope of the present study was to investigate
the combined impregnation and depositionprecipitation method for catalyst
preparation and compare it with the heterogeneous depositionprecipitation technique for the synthesis of cobalt oxide catalysts supported on activated carbon
for the complete oxidation of cyclohexane in air. Activated carbon with mesopore
surface area was prepared by water vapor activation at 800 C from Iranian local

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almond shells. Catalyst and support properties were determined by an X-ray powder
diffractometer (XRD), transmission electron microscopy (TEM), field-emission
scanning electron microscope (FESEM), and BrunauerEmmettTeller (BET)
surface area measurements. The kinetic behavior of the supported catalysts on
activated carbon for the conversion of cyclohexane was explored using a fixed bed
tubular reactor. Kinetic parameters were estimated using catalytic activity tests at
different reaction temperatures and inlet feed cyclohexane concentrations.

Methods and materials

Catalyst preparation methods
Almond shells were obtained from an Iranian local source as an agricultural solid
waste. Powder activated carbon was produced by drying the original almond shells
at 120 C for 24 h. The dried shells were grinded then carbonized and activated
under water vapor at 800 C in a tubular furnace. The prepared activated carbon was
washed with distilled water several times to remove all undesirable materials and
was then dried in an oven at 110 C overnight. Supported cobalt oxide catalysts
with 8 wt% metal loading were prepared by the following two methods: (1)
heterogeneous depositionprecipitation (HDP) and (2) combined impregnation and
depositionprecipitation (IMP-DP). In the HDP method, powder almond activated
carbon (below mesh No. 40) was placed in a cobalt nitrate solution (Co(NO3)26H2O) (0.04 M) with heating at 7080 C and stirring for about 8 h. Cobalt ions
were precipitated by the addition of NaOH solution (6 wt%) until reaching a basic
solution of pH = 1011. In the second method, activated carbon was impregnated
with cobalt solution at room temperature for about 3 h. The impregnated solution
was then heated to reach a temperature in the range of 7080 C. Heterogeneous DP
was then carried out after the impregnation step for 4 h using NaOH. The catalysts
prepared by each method were then washed to reach pH = 7 and dried at 110 C for
6 h. The dried samples were calcined for 3 h under N2 at 500 C. Supported cobalt
oxide catalysts over almond activated carbon were named IMP-DPCo8/AC500 and
HDPCo8/AC500 for IMP-DP and HDP method, respectively. Details and the flow
charts (Figs. S5, S6) for the catalyst preparation techniques are presented in the
supplementary information file.
Catalyst activity tests
A tubular flow reactor was used to carry out the complete oxidation of cyclohexane
in air at atmospheric pressure. The desired inlet concentration of cyclohexane was
obtained by introducing an air stream at a constant flow rate to an isolated bubbling
saturator filled by liquid cyclohexane, which was kept in a refrigeration unit to hold
the saturator at a constant temperature. The concentration of cyclohexane in the air
flow was calculated by the vapor pressure of cyclohexane at the saturator
temperature. A thermocouple was located at the center of the packed reactor to
record the oxidation temperature. The feed flow rate was set by rotameters. 1 g of

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the supported catalyst was placed in the horizontal quartz tubular reactor that was
10 cm in length and 12 mm internal diameter. The supported cobalt oxide catalyst
was packed with glass beads into the middle section of the reactor in between glass
wool to prevent flow channeling. The reactor was heated to the reaction temperature
in the range of (150300 C) and maintained at that temperature using a PID
controller. The concentration of cyclohexane in the feed was adjusted in range of
5,00020,000 ppm. The schematic of the experimental set-up is shown in Fig. S1 of
the Supplementary Information. The reactor exit was analyzed using a gas
chromatographymass spectroscopy (GC-Mass, Agilent model) system that was
equipped with 5975C mass detector and HP-5MS stainless steel column with 30 m
(FID column), at regular time intervals from the start of each run. Typical GCMS
spectra for products for different times from the start of a run are presented in Fig.
S2 of the Supplementary Information. No intermediate oxidation products, carbon
monoxide, hydrogen, cyclohexene or cyclohexanol were detected by GCMS, and
the products included carbon dioxide, water, and unreacted cyclohexane. To
investigate the kinetic behavior of the complete oxidation of cyclohexane over HDP
catalyst, several experiments were performed to determine the appropriate
conditions (catalyst particles size and feed flow rate) to eliminate both internal
and external mass transfer resistances. All kinetic experiments were performed with
particle size below Mesh number 40 using a feed flow rate of 166 ml/min which
gave a gas hourly space velocity (GHSV) of 40,44954,449 h-1.
Characterizations
Several techniques were used for the characterization of the prepared catalysts. The
X-ray powder diffractometer (XRD) test was carried out for the determination of
the support and active site phases using an equipment model D-64295 from STOE
Company. XRD analysis was implemented at 30 kV, 20 mA, copper Ka radiation
and scanning rate of 3 C/min. The surface acidic and basic functional groups of the
AC support were quantified by the Boehm test. High resolution surface images of
the synthesized catalysts to determine the morphology, dispersion, and the size
range of active sites over the support were obtained by a field-emission scanning
electron microscope (FESEM) using an S-4160 Hitachi equipment. Nitrogen
adsorptiondesorption analyses was performed using an ASAP-1100 micromesetics
equipment with catalyst pretreatment at 300 C overnight before the nitrogen
adsorption measurements. The specific surface areas were calculated using BET,
t-plot and pore size of samples were estimated by Barrett-Joyner-Halenda (BJH)
methods. The pore volume was obtained from the amount of N2 adsorbed at a
relative pressure of 0.99. The sharp increase in the adsorbed volume at low pressure
was due to the enhanced potential of micropores, and the gradual increase at higher
pressures indicated the presence of mesopores in the sample. Transmission electron
microscopy (TEM) micrographs were used to determine the morphology and
crystallites size distribution of the samples using a CM30-Philips instrument
equipped with a Schottky field emission gun operated at 150 keV.

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Optimization strategies for estimation of kinetic parameters

Literature kinetic models of VOC oxidation are based on a simple power law model
[47], Marsvan Krevelen, EleyRideal and LangmuirHinshelwood mechanisms
[15]. The most widely used forms of the rate expression are presented in Table 2.
There are common methods for kinetic parameter estimation using constrained
non-linear optimization algorithms including the genetic algorithm (GA) [48],
simulated annealing (SA) [49] and pattern search (PS) [50]. Fig. S3 in the
Supplementary Information represents the GA procedure used in this study that can
avoid the trapping in the local optimum. Matlab software version 7.8 was used with
appropriate specified parameters included generation size (1,000), population size
(30), elitecount, crossover fraction (0.9), crossover, and mutation functions.
Isothermal plug flow with constant fluid velocity and negligible pressure drop
was considered as a simple reactor model. The steady state conversion of
cyclohexane (XC) at reactor exit was defined by:
XC

Ci  Ce
Ci

Here, Ci and Ce are the cyclohexane concentrations at the reactor inlet and exit,
respectively. The continuity equation for the plug flow reactor is presented by
Eq. (2):
Z X
dX
W

2
r
v
0
Here, W is the mass of the HDP catalyst loaded into the reactor, t is the inlet molar
rate of the cyclohexane and r is the reaction rate for total oxidation of cyclohexane.
The non-linear equation derived from the integration of Eq. 2 was solved by a
modified NewtonRaphson method. The objective function for the GA methodology for determination of the kinetic parameters was the relative absolute error
defined by:


X
Xexp  Xmodel
Objective F
abs
3
i
Xexp
The temperature dependence of the adsorption equilibrium constant and reaction
rate constant were defined by the following equations:
Table 2 General mechanisms
and equations for total oxidation
of VOCs

Mechanism

Equation

LangmuirHinshelwood

r 1Kr ads;CC ads;O

K

kK

ads;C

EleyRideal

Marsvan Krevelen

123

r

kr Kads;C CC CO
1Kads;C CC

r

kr Kads;O CC CO
1Kads;O CO
kK

C C

CC CO

ads;O CO

C O
r 9krrCCads;O
Kads;O CO

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DH
Kads;c Ka0 exp
RT
 
E
kr kr0 exp
RT

Here, Ka0 and kr0 are the pre-exponential factors, and E and DH are the activation
energy and adsorption enthalpy, respectively.

Results and discussion

Support and catalyst characterizations
The amounts of functional groups of almond shell and almond activated carbon were
obtained from the Boehm test [41], where basic, lactonic, carboxylic and phenolic
groups were 0.00, 0.43, 0.042 and 0.973, and 0.00, 0.63, 0.10 and 0.97 mequiv./g for
almond shell and almond activated carbon, respectively. The amounts of acidic groups
represent oxygen groups on the surface of almond shells (1.46 mequiv./g) and almond
activated carbon (1.70 mequiv./g) that can be an important property for complete
oxidation of cyclohexane over supported catalysts on almond shell-based activated
carbon. The almond shells contain 53.38 wt% carbon which allows the production of
activated carbon with high surface area (SBET = 860.7 m2/g and iodine number
[41] = 800 mg/g). The high surface area hydrophobic activated carbon containing
significant mesopore volume would make an ideal support for dispersed cobalt oxide

Fig. 1 XRD patterns for the supported cobalt catalyst prepared by HDP and IMP-DP methods (metal
content = 8 wt%, calcination temperature = 500 C)

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catalyst compared with other hydrophilic support materials for complete oxidation of
cyclohexane.
The XRD patterns for the cobalt oxide catalysts prepared by two different
catalyst preparation methods (HDP and IMP-DP) are presented in Fig. 1. Two
phases are identified from the XRD patterns including the amorphous phase
representing a carbonaceous support and the second phase corresponding to CoO
(00-001-1227, ICCD) crystallites. Two different types of cobalt oxide peaks are
detected in the XRD profiles as two different methods (IMP and DP) were used
sequentially for preparation of IMP-DPCo8/AC500 catalyst on the AC support. The
large crystallites with high intensity (CoO at 2h = 4849) and the small crystallites
with low intensity (CoO at 2h = 6566) were formed during the impregnation and
depositionprecipitation steps, respectively. All of Co(OH)2 were reformed to CoO
and there were no Co3O4 (00-001-1152, ICCD) and Co2O3 (00-002-0770, ICCD)
crystallites detected over almond activated carbon during both preparation methods.
The XRD profiles for supported cobalt oxide catalysts prepared by the HDP
method (HDPCo8/AC500) show almost uniform peaks with similar intensity due to
CoO crystallites. There are no appreciable cobalt oxide peaks with high intensity
indicating high dispersion of cobalt oxide crystallites supported on almond activated
carbon. Cobalt oxide peaks in the XRD profiles were influenced by the catalyst
preparation method as they had wider line broadening in HDP catalysts compared
with IMP-DP catalysts indicating that the HDP method can provide smaller well-

Fig. 2 TEM and FESEM images for a IMP-DPCo8/AC500 and b HDPCo8/AC500 (metal
content = 8 wt%, calcination temperature = 500 C)

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dispersed active sites compared with the IMP-DP method. Similar results were
reported in previous works by Gurbani et al. [51] that metal oxide particle size is
influenced by the catalyst preparation method. The crystallite sizes were calculated
by the Scherrer equation (shown in Eq. 6) assuming spherical shapes:
D

Kk
b cos h

Here, D is the mean crystallite diameter (nm), K is the dimensionless shape factor
(for sphere: K = 0.9), k is the X-ray wavelength (X-ray tube: Cu, k = 0.154 nm), b
is the line broadening at half the maximum intensity and h is the Bragg angle. The
results indicate that the size of crystallites formed on almond activated carbon were
less than 30 and 15 nm for IMP-DP and HDP methods, respectively. The results
demonstrated the effect of the catalyst preparation method on the size of the cobalt
oxide crystallites with the HDP method providing smaller cobalt oxide crystallites
over activated carbon compared with the IMP-DP method. It is clear that the
impregnation method has a negative effect on resulting catalyst as it leads to the
formation of large crystallites on the support.
TEM and FESEM images are presented in Fig. 2 illustrating the active sites
morphology and size distributions of HDPCo8/AC500 and IMP-DPCo8/AC500
catalysts. Cobalt oxide crystallites with approximately 2030 nm were formed with
lamellar shape by the IMP-DP method while cobalt oxide active sites with a
sphere shape, high dispersion and smaller in size (less than 15 nm) were formed
by the HDP method as shown in TEM and FESEM micrographs. XRD results are
further confirmed by the TEM and FESEM images that the HDP method can

Fig. 3 Nitrogen adsorption and desorption results for cobalt catalysts. (Adsorption temperature = 77 K
and sample weight = 0.03 g)

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generate a more dispersed nanocatalyst with smaller active sites compared with the
IMP-DP method. Statistical analyses and particle size distributions were performed
by Clemex vision software to determine the particle size range of HDPCo8/AC500.
Image analysis results show that cobalt oxide crystallites with sizes below 15 nm
were found over activated carbon. The average particle sizes were estimated 10 nm
as seen in Fig. 2.
Fig. 3 shows the results of nitrogen adsorption and desorption of HDPCo8/
AC500 and IMP-DPCo8/AC500 catalysts. The adsorbed volume of nitrogen is due
to the adsorption of nitrogen over almond activated carbon, as N2 cannot adsorb on
the cobalt oxide particles. Therefore, HDP catalyst with well-dispersed nanoparticles of cobalt can adsorb a lower nitrogen volume compared with IMP-DP
catalyst. BET surface area results show that HDP catalyst has lower surface area
than IMP-DP catalyst which is confirmed by BJH and t-plot tests (Table 3). There is
an inverse relation between specific surface area and the dispersion of cobalt oxide
particles on the almond activated carbon. The obtained results are in agreement with
the XRD, FESEM and TEM observations. The HDP method can provide welldispersed nanocatalyst over the mesopore surface of activated carbon. Cobalt oxide
particles agglomerated on the activated carbon and formed larger crystallites in the
impregnation method. It is therefore expected to have two different sizes of
crystallites in the IMP-DP method as was illustrated in the XRD profiles and
micrographs. These characterization results distinguish the effect of catalyst
preparation methods on the catalyst structure and the antonym effect of impregnation on the depositionprecipitation technique.
Effect of temperature and feed concentration on cyclohexane conversion
Catalyst activity tests were performed at different temperatures in the range of
150300 C and cyclohexane feed concentrations in the range of
5,00020,000 ppm. In each experiment, the feed flow rate and the mass of catalyst
loaded in the reactor were kept at 166 ml/min and 1 g, respectively. As shown in
Figs. 4 and 5, cyclohexane conversion increased with increasing the reaction
temperature. No significant oxidation of cyclohexane was observed at 150 C while
at the oxidation temperature of 300 C, the conversion of cyclohexane was about
90 %. Cyclohexane conversion also slightly decreased with increasing feed
concentration. Other investigators have also observed similar results for oxidation
of VOCs. For example, Gaur et al. [15] investigated the oxidation of VOCs by

Table 3 BET, BJH and t-plot results for cobalt oxide catalysts
Sample

BET
Surface area
(m2/g)

Total pore
volume (cm3/g)

BJH

t-plot

Volume
pore (cm3/g)

Surface area
(m2/g)

IMP-DPCo8/AC500

696

0.4697

0.1924

755

HDPCo8/AC500

650

0.535

0.1013

745

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Fig. 4 Effect of feed concentration and reaction temperature on cyclohexane conversion on IMPDPCo8/AC500 (feed flow rate = 166 ml/min, catalyst dosage = 1 g, cyclohexane concentration in
feed = 5,00020,000 ppm and oxidation temperature = 150300 C)

Fig. 5 Effect of feed concentration and reaction temperature on cyclohexane conversion on HDPCo8/
AC500 (feed flow rate = 166 ml/min, catalyst dosage = 1 g, cyclohexane concentration in
feed = 5,00020,000 ppm and oxidation temperature = 150300 C)

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supported transition metal catalysts on activated carbon and reported that the VOC
conversion increased linearly with decreasing initial concentration of VOCs. In
addition, our results indicate that higher conversions of cyclohexane were achieved
by the HDP catalyst compared with those by the IMP-DP method confirming the
antonym effect of impregnation method. HDP method can provide efficient welldispersed nanocatalysts for complete oxidation of cyclohexane in air.
A comparison of the catalyst activity for deep oxidation of cyclohexane was made
between the most efficient catalyst prepared in this work and the few reported
investigations in the open literature. Quantitative comparison, however, is difficult
because of different operating conditions employed in each investigation. Hettige et al.
[10] evaluated the complete conversion of cyclohexane over supported metal oxides
such as Mn, Cu, Mo, Ni, V, Zn and Ce on a-alumina at various reaction temperatures in
range of 300550 C. Maximum conversion of cyclohexane was achieved over
supported Mn and Cu oxide samples. Ce and Mn oxide/a-alumina also showed 100 %
selectivity towards carbon dioxide and water vapor at oxidation temperatures above
500 C. In a separate study [52] La0.8Sr0.2MnO3?x perovskite was used for the
conversion of cyclohexane in air when with 217 and 277 C reaction temperatures
required for 50 and 99 % conversion of cyclohexane, respectively. However, benzene
was detected as a product at a reaction temperature of 152 C and its production
increased with increasing reaction temperature. In our study, the complete oxidation of
cyclohexane with no by-products such as benzene was achieved at reaction temperatures
up to 300 C.
In the recent years, photo-catalytic oxidation (PCO) of cyclohexane has been
reported by several investigators. Murcia et al. [11] used TiO2 for oxidation of
cyclohexane in humidified air at low temperatures (60100 C) for feeds containing
200 and 320 ppm of cyclohexane and water vapor, respectively. The serious
drawback of PCO is the humidity requirement to avoid the deactivation of
photocatalyst by carbon deposits as catalyst regeneration was accomplished in
presence of water vapor. Einaga et al. [12] studied the complete degradation of
cyclohexane over TiO2 as a photocatalyst and reported an optimum concentration of
493 ppm of cyclohexane in inlet air. The other drawback of photocatalytic systems
is that they are appropriate for only low concentration of cyclohexane in the feed.
Kinetic behavior of cyclohexane oxidation
Oxidation of cyclohexane was accomplished without any by-products over
HDPCo8/AC500. A simple power law was considered initially for determination
of activation energy and reaction constant of cyclohexane oxidation. Due to large
excess of oxygen, the power law equation can be expressed as follows:
r kr Ccn

-1
Here, r is the reaction rate (molg-1
catalysts ), kr is the kinetic constant, Cc is the
3
cyclohexane concentration (mol/m ) and n is the reaction order. The estimated
activation energy (kJ/mol) and reaction order were 44.63 and 0.100.64, respectively, which illustrate the acceptable correlation coefficient (R2 = 0.95) and that

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adequately predict cyclohexane conversions. The reaction order n increased with

increasing reaction temperature and the activation energy was estimated to be
44.6 kJ/mol for total oxidation of cyclohexane.
The power law expression may only be proper to establish a preliminary
dependency of the reaction rate on cyclohexane and oxygen concentrations. Besides
the power law, several mechanisms such as EleyRideal, LangmuirHinshelwood,
Marsvan Krevelen and lattice oxygen model [47], were considered for the
oxidation of cyclohexane in this study. A precise investigation on molecular
mechanism is required to describe the kinetic behavior of the catalyst for total
oxidation of cyclohexane. Aliphatic hydrocarbons can be easily adsorbed on the
hydrophobic surface of almond shell based activated carbon. There are different
possibilities for oxygen to participate in the reaction. In the EleyRideal
mechanism, adsorbed cyclohexane reacts with gaseous oxygen to form the products
according to mechanism 1:
Mechanism 1:
Kads;c

(1)

A + h () Ah

(2)

Ah + O2 ! CO2 + H2 O h

kr

Here, Kads,c, A and h represent the equilibrium adsorption constant of cyclohexane,

cyclohexane, and active sites on the activated carbon surface, respectively. A
similar mechanism was suggested by Gaur et al. [15] for hydrocarbon oxidation
according to mechanism 2:
Mechanism 2:
Kads;c

(1)

A + h () Ah

(2)

Ah + O2 () AOh

(3)

AOh ! CO2 + H2 O + h

Kads;O

kr

AOh and Kads;O denote adsorbed cyclohexane and oxygen species, and adsorption
constant of oxygen on adsorbed cyclohexane sites, respectively. In step 3, the
transition complex is desorbed from surface to generate the products. With the
assumption of excess oxygen concentration, the rate expression for both mechanisms 1 and 2 is given by Eq. 8:
r

kr Kads;c Cc
1 Kads;c Cc

The EleyRideal mechanism 1 and mechanism 2, however, would result in the

same rate expression as the more common lattice oxygen [47] and Marsvan
Krevelen [15] models if lattice oxygen provided by cobalt oxide participates in the
oxidation of cyclohexane and oxygen concentration is assumed constant during the
reaction. From the mechanistic point of view, mechanism 3 can be summarized
from the lattice oxygen model as follow:

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Fig. 6 Predicted (Kinetic rate equation) and experimental reaction rate for cyclohexane oxidation over
HDPCo8/AC500 at operating conditions containing; various oxidation temperatures (150300 C), inlet
concentrations (0.20.8 mol/m3), feed flow rate = 166 ml/min and catalyst dosage = 1 g

Mechanism 3:
Kads;c

(1)

A h () Ah

(2)

1
2 O2

(3)

Ah + Oh ! CO2 + H2 O + h

KO

() Oh
kr

Here, KO, Oh and Oh denote equilibrium adsorption constant for oxygen, oxidized
site and lattice oxygen, respectively. According to step 2 as the rate determining
step in mechanism 3, the resulting rate expression would be given by Eq. 9:
r

kr Kads;c KO Cc CO0:5
1 Kads;c Cc

This would result in a similar expression as given by Eq. 8 under excess oxygen
concentrations. It is difficult to claim one mechanism over the others based on the
limited data that was obtained in our investigation. We proceeded to obtain the
kinetic parameters for the EleyRideal rate expression that was more consistent with
the experimental data compared with other rate expressions reported in Table 2.
The kinetic parameters of Eq. 8 derived by the GA method including activation
energy (kJ/mol), adsorption enthalpy (DH (kJ/mol)), and pre-exponential factors

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Fig. 7 Experimental versus predicted (kinetic rate equation) conversions for total oxidation of
cyclohexane over HDPCo8/AC500 at operating conditions containing; various oxidation temperatures
(150300 C), inlet concentrations (0.20.8 mol/m3), feed flow rate = 166 ml/min and catalyst
dosage = 1 g

(k0r(mol/g s) and K0ads) of reaction and adsorption were obtained 39.12, 9.16, 129 9
10-4 and 94.8 9 10-2. The average correlation coefficient (R2 = 0.96) shows that
proposed equation rate can adequately describe the catalytic oxidation of
cyclohexane over HDPCo8/AC500. Calculated reaction rates presented in Fig. 6
indicate that at low oxidation temperatures (150 C), the KadsCc term in the
denominator of the derived equation rate in this work is significant and that the
reaction is approximately zeroth order and the reaction rate is independent of
cyclohexane concentration. With increasing reaction temperature, however, the
adsorption constant for cyclohexane decreases sharply and the reaction rate
approaches first order with respect to cyclohexane concentration leading to an
increase in reaction rate with increasing cyclohexane concentration (Fig. 6). A
parity plot between experimental and predicted cyclohexane conversions using
Eq. 8 is presented in Fig. 7 indicating a very good agreement.

Conclusions
Complete oxidation of cyclohexane in air was investigated using supported cobalt
oxide catalyst on activated carbon. Two different catalyst preparation methods were
employed to investigate the effect of impregnation technique during catalyst
preparation by depositionprecipitation. Dispersed cobalt oxide catalysts on
activated carbon were characterized and subsequently tested in a tubular reactor
to determine their activity towards oxidation of cyclohexane. Almond shells as a
low cost agricultural solid waste were used to prepare the activated carbon support

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Reac Kinet Mech Cat

with high surface area and appropriate functional groups. The most important
conclusions are given below:
(1)

(2)

(3)

(4)

(5)
(6)

(7)

Significant amounts of oxygen groups and the carbon content of Iranian

almond shells make it a suitable low cost material for preparing the activated
carbon support for supported cobalt oxide catalysts for total oxidation of
cyclohexane.
GCMS results showed that no by-products were produced indicating the
complete oxidation of cyclohexane by the prepared supported cobalt oxide
catalysts.
XRD, TEM and FESEM results indicated that two different cobalt oxide
crystallites were formed on the activated carbon by using the IMP-DP
technique; large crystallites from the impregnation step and small crystallites
from the depositionprecipitation step. The XRD results indicated that HDP
catalysts had two phases (amorphous and cobalt oxide crystallites) with
uniform shape and size. The HDP method resulted in dispersed nanoparticles
on the activated carbon with sphere shapes.
The BET surface area for the HDP catalyst was lower that for the IMP-DP
catalyst as the cobalt nanoparticles for the former catalyst were well dispersed
over the AC surface.
In catalyst activity tests, cyclohexane conversion decreased with increasing
feed concentration and increased with increasing oxidation temperature.
The EleyRideal rate expression was found to be appropriate to describe the
kinetics of cyclohexane oxidation over the range of experimental conditions
employed in this study.
Impregnation technique had an antonym effect on the depositionprecipitation method in the preparation of supported cobalt oxide catalysts.

Acknowledgments The authors gratefully acknowledge the financial assistance of Iran National
Science Foundation (INSF).

References
1. Bozbiyik B, Duerinck T, Lannoeye J, Vos DE, Baron GV, Denayer JFM (2014) Adsorption and
separation of n-hexane and cyclohexane on the UiO-66 metalorganic framework. Microporous
Mesoporous Mater 183:143149
2. Khan FI, Ghoshal AK (2000) Review: removal of volatile organic compounds from polluted air.
J Loss Prev Ind 13:527545
3. Ilieva L, Petrova P, Tabakova T, Zanella R, Kaszkur Z (2012) Gold catalysts on ceria doped with
MeOx (Me = Fe, Mn, Co and Sn) for complete benzene oxidation: effect of composition and
structure of the mixed supports. Reac Kinet Mech Cat 105:2337
4. Hussain M, Ceccarelli R, Marchisio DL, Fino D, Russo N, Geobaldo F (2010) Synthesis, characterization, and photo-catalytic application of novel TiO2 nano particles. Chem Eng J 157:4551
5. Hussain M, Russo N, Saracco G (2011) Photo-catalytic Abatement of VOCs by Novel Optimized
TiO2 Nanoparticles. Chem Eng J 166:138149
6. Padhi SK, Gokhale S (2014) Biological oxidation of gaseous VOCsrotating biological contactor a
promising and eco-friendly technique. J Environ Chem Eng 2:20852102

123

Reac Kinet Mech Cat

7. Liu L, Huang D, Yang F (2009) Toluene recovery from simulated gas effluent using POMS membrane separation technique. Sep Purifi Technol 66:411
8. www.epa.gov/iris, EPA 635/R-03/008
9. Rusu AO, Dumitriu E (2003) Destruction of volatile organic compounds by catalytic oxidation.
Environ Eng Manag J 2:273302
10. Hettige C, Mahanama KRR, Dissanayake DP (2001) Cyclohexane oxidation and carbon deposition
over metal oxide catalysts. Chemosphere 43:10791083
11. Murcia JJ, Hidalgo MC, Navo JA, Vaiano V, Sannino D, Ciambelli P (2013) Cyclohexane photocatalytic oxidation on Pt/TiO2 catalysts. Catal Today 209:164169
12. Einag H, Futamur S, Ibusuki T (2002) Heterogeneous photo-catalytic oxidation of benzene, toluene,
cyclohexene and cyclohexane in humidified air: comparison of decomposition behavior on photo
irradiated TiO2 catalyst. Appl Catal B 38:215225
13. Santos Xavier LPd, Rico-Perez V, Hernandez-Gimenez AM, Lozano-Castello D, Bueno-Lopez A
(2015) Simultaneous catalytic oxidation of carbon monoxide, hydrocarbons and soot with CeZrNd
mixed oxides in simulated diesel exhaust Appl. Catal B 162:412419
14. Merino MAA, Ribeiro MF, Silva JM, Marin FC, Hodar FJM (2004) Activated carbon and tungsten
oxide supported on activated carbon catalysts for toluene catalytic combustion. Environ Sci Technol
38:46644670
15. Gaur V, Sharma A, Verma N (2005) Catalytic oxidation of toluene and m-xylene by activated carbon
fiber impregnated with transition metals. Carbon 43:30413053
16. Shim WG, Kim SC (2010) Heterogeneous adsorption and catalytic oxidation of benzene, toluene and
xylene over spent and chemically regenerated platinum catalyst supported on activated carbon. Appl
Surf Sci 256:55665571
17. Lu CY, Wey MY (2007) Simultaneous removal of VOC and NO by activated carbon impregnated
with transition metal catalysts in combustion flue gas. Fuel Process Technol 88:557567
18. Wyrwalski F, Lamonier JF, Siffert S, Gengembre L, Abouka S (2007) Modified Co3O4/ZrO2 catalysts for VOC emissions abatement. Catal Today 119:332337
19. Bonelli R, Albonetti S, Morandic V, Ortolanic L, Riccobened PM, Scire S, Zacchini S (2010) Design
of nano-sized FeOx and Au/FeOx catalysts supported on CeO2 for total oxidation of VOC. Appl
Catal A 395:1018
20. Lu CY, Wey MY, Chen LI (2007) Application of polyol process to prepare AC-supported nano
catalyst for VOC oxidation. Appl Catal A 325:163174
21. Alvim-Ferraz MCM, Gaspar CMTB (2004) Active carbons impregnated before activation of olive
stones: catalytic activity to remove benzene from gaseous emissions. J Phys Chem Solids 65:655659
22. Nogueira FGE, Lopes JH, Silva AC, Lago RM, Fabris JD, Oliveira LCA (2011) Catalysts based on
clay and iron oxide for oxidation of toluene. Appl Clay Sci 51:385389
23. Li TY, Chiang SJ, Liaw BJ, Chen YZ (2011) Catalytic oxidation of benzene over CuO/Ce1 xMnxO2 catalysts. Appl Catal B 103:143148
24. Wyrwalski F, Lamonier JF, Siffert S, Aboukas A (2007) Additional effects of cobalt precursor and
zirconia support modifications for the design of efficient VOC oxidation catalysts. Appl Catal B
70:393399
25. Li WB, Wang JX, Gong H (2009) Catalytic combustion of VOCs on non-noble metal catalysts. Catal
Today 148:8187
26. Wu JCS, Lin ZA, Tsai FM, Pan JW (2000) Low temperature complete oxidation of BTX on Pt/
activated carbon catalysts. Catal Today 63:419426
27. Shaoyong H, Changbin Z, Hong H (2009) In situ adsorption-catalysis system for the removal of
o-xylene over an activated carbon supported Pd catalyst. Environ Sci 21:985990
28. Kang M, Bae YS, Lee CH (2005) Effect of heat treatment of activated carbon supports on the loading
and activity of Pt catalyst. Carbon 43:15121516
29. Torres SM, Hodar FJM, Cadenas AFP, Marn FC (2010) Design of low-temperature Pt-carbon
combustion catalysts for VOCs treatments. J Hazard Mater 183:814822
30. Bedia J, Rosas JM, Rodrguez-Mirasol J, Cordero T (2010) Pd supported on mesoporous activated
carbons with high oxidation resistance as catalysts for toluene oxidation. Appl Catal B 94:818
31. Lahouss C, Cors N, Ruaux V, Grange P, Cellier C (2006) Preparation of Pd on carbon black by
deposition- precipitation: study of the effect of the support functionalisation. Sci Bases Prep Heterog
Catal 162:601608

123

Reac Kinet Mech Cat

32. Huang Z, Cui F, Xue J, Zuo J, Chen J, Chungu X (2012) Cu/SiO2 catalysts prepared by hom- and
heterogeneous depositionprecipitation methods: texture, structure, and catalytic performance in the
hydrogenolysis of glycerol to 1,2-propanediol. Catal Today 183:4551
33. Luminita P, Barbara M, Marija K, Mariana C, Monica C, Maria Z (2007) Characterization of LaCoO3
powders obtained by water-based solgel method with citric acid. J Eur Ceram Soc 27:44074411
34. Rousseau S, Loridant S, Delichere P, Boreave A, Deloume JP, Vernoux P (2009) La(1-x)SrxCo(1-y)FeyO3 perovskites prepared by solgel method: characterization and relationships with catalytic properties for total oxidation of toluene. Appl Catal B 88:438447
35. Keranen J, Guimon C, Iiskola E, Niinisto L, Auroux A (2003) Atomic layer deposition and surface
characterization of highly dispersed titania/silica-supported vanadia catalysts. Catal Today
78:149157
36. Gould TD, Lubers AM, Neltner BT, Carrier JV, Weimer AW, Falconer JL, Medlin JW (2013)
Synthesis of supported Ni catalysts by atomic layer deposition. J Catal 303:915
37. Gayan P, Dueso C, Abad A, Adanez J, De Diego LF, Garca-Labiano F (2009) NiO/Al2O3 oxygen
carriers for chemical-looping combustion prepared by impregnation and depositionprecipitation
methods. Fuel 88:10161023
38. Menezes WG, Altmann L, Zielasek V, Thiel K, Baumer M (2013) Bimetallic CoPd catalysts: study
of preparation methods and their influence on the selective hydrogenation of acetylene. J Catal
300:125135
39. Lamallem M, Ayadi H, Gennequin C, Cousin R, Siffert S, Assi F, Aboukas A (2008) Effect of the
preparation method on Au/Ce-Ti-O catalysts activity for VOCs oxidation. Catal Today 137:367372
40. Sellick DR, Aranda A, Garca T, Lopez JM, Solsona B, Mastral AM, Morgan DJ, Carley AF, Taylor
SH (2013) Influence of the preparation method on the activity of ceria zirconia mixed oxides for
naphthalene total oxidation. Appl Catal B 132133:98106
41. Zabihi M, Ahmadpour A, HaghighiAsl A (2009) Removal of mercury from water by carbonaceous
sorbents derived from walnut shell. J Hazad Mater 167:230236
42. Zabihi M, HaghighiAsl A, Ahmadpour A (2010) Studies on adsorption of mercury from aqueous
solution on activated carbons prepared from walnut shell. J Hazard Mater 174:251256
43. Ahmadpour A, Zabihi M, Tahmasbi M, RohaniBastami T (2010) Effect of adsorbents and chemical
treatments on the removal of strontium from aqueous solutions. J Hazard Mater 182:552556
44. Ahmadpour A, RohaniBastami T, Tahmasbi M, Zabihi M (2012) Rapid removal of heavy metal ions
from aqueous solutions by low cost adsorbents. Int J Global Environ Issues 12:148151
45. Hasar H (2003) Adsorption of nickel (II) from aqueous solution onto activated carbon prepared from
almond husk. J Hazard Mater B97:4957
46. Lu CY, Wey MY, Chuang KH (2009) Catalytic treating of gas pollutants over cobalt catalyst
supported on porous carbons derived from rice husk and carbon nano tube. Appl Catal B 90:652661
47. Chaoquan H (2011) Catalytic combustion kinetics of acetone and toluene over Cu0.13Ce0.87Oy catalyst. Chem Eng J 168:11851192
48. Dhumal SS, Saha RK (2006) Application of genetic algorithm for evaluation of kinetic parameters of
coal pyrolysis. J Energy Environ 5:112124
49. Eftaxias A, Font J, Fortuny A, Fabregat A, Stuber F (2002) Non-linear kinetic parameter estimation
using simulated annealing. Comput Chem Eng 26:17251733
50. Junmeng C, Weixuan W, Ronghou L (2013) Sensitivity analysis of three-parallel-DAEM-reaction
model for describing rice straw pyrolysis. Bioresour Technol 132:423426
51. Gurbania A, Ayastuya JL, Gonzalez-Marcosa MP, Herrerob JE, Guilb JM, Gutierrez-Ortiz MA
(2009) Comparative study of CuOCeO2 catalysts prepared by wet impregnation and deposition
precipitation. Int J Hydrog Energy 34:547553
52. Blasin-Aube V, Belkouch J, Monceaux L (2003) General study of catalytic oxidation of various
VOCs over La0.8Sr0.2MnO3?x perovskite catalystinfluence of mixture. Appl Catal B 43:175186

123