Chemical Engineering Journal 197 (2012) 181–192

Contents lists available at SciVerse ScienceDirect

Chemical Engineering Journal

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

Degradation of phenol in photo-Fenton process by phosphoric acid modified

kaolin supported ferric-oxalate catalyst: Optimization and kinetic modeling
O.B. Ayodele a,b, J.K. Lim a, B.H. Hameed a,⇑
a
School of Chemical Engineering, Engineering Campus, Universiti Sains Malaysia, 14300 Nibong Tebal, Penang, Malaysia
b
Process and Product Design Unit, National Engineering Design Development Institute, Nnewi, Nigeria

h i g h l i g h t s

" Phosphoric acid modification of raw kaolin clay.

" Incorporation of ferric-oxalate into acid modified kaolin clay.
" Degradation of phenol with modified kaolin supported ferric-oxalate catalyst.
" Optimization and kinetic study of phenol degradation with ferric-oxalate catalyst.
" Reusability studies on the acid modified kaolin supported ferric-oxalate catalyst.

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

Article history: Phenol was degraded with phosphoric acid modified kaolin clay supported ferric-oxalate catalyst
Received 12 January 2012 (AMKC). The degradation was achieved without initial pH adjustments to avoid the interference of buf-
Received in revised form 18 April 2012 fering on the degradation kinetics. The degradation process was optimized to minimize the superfluous
Accepted 18 April 2012
scavenging effect of excess dosage of hydrogen peroxide (HP) and AMKC on the kinetics study. The pres-
Available online 9 May 2012
ence of Fe was confirmed by X-ray diffraction, Fourier Transform Infrared Spectroscopy, XRF and EDX
results. Brunauer–Emmet–Teller result showed an increment in the surface area from 19 to 45 m2/g after
Keywords:
the acid modification which led to structural and morphological changes as revealed by the Scanning
Phenol degradation
Photo-Fenton
Electron Microscopy (SEM). The best optimization result of the degradation of phenol obtained from
Ferric-oxalate the desirability plot gave 18.2% excess HP, 2.23 g of AMKC as the best condition to achieve 99.15% deg-
Optimization radation of 100 ppm initial concentration of phenol at 30 °C in 5 min reaction time. Strong correlation
Kinetic modeling between the experimental and predicted responses was observed with R2 and R2adj values of 0.9921
and 0.9810, respectively. In the kinetic study, degradation rate 50 ppm is 1.38 times faster than
200 ppm while the selectivity of AMKC for direct oxidation of phenol is 3.4 times higher than through
intermediates. Only about 4% drop in catalyst activity was observed during the reusability studies after
five experiments. This makes AMKC reliable for treating phenol polluted water.
Ó 2012 Elsevier B.V. All rights reserved.

1. Introduction citrant nature of phenol, traditional wastewater treatment meth-

The quest for newer products and technological developments
has led to the generation of different environmental pollutants.
Phenol is one of such pollutant that seriously damages our ecosys-
tems and it is a foremost pollutant in USEPA list with limits of dis-
charge less than 0.5 ppm [1]. It is a lethal and hazardous
contaminant which is believed to be carcinogenic. Its industrial
applications include the production of polymerization inhibitors,
petrochemical, paint, textile, oil-refineries, food, photographic
chemicals, antioxidants and flavoring agents [2]. Due to the recal-
⇑ Corresponding author. Tel.: +60 45996422; fax: +60 45941013.
E-mail address: chbassim@eng.usm.my (B.H. Hameed).
ods like biological treatment, adsorption and stripping cannot
readily mineralize it. However, many researchers had made frantic
efforts at finding ways to eliminate this pollutant from the envi-
ronment using some other advanced techniques like catalytic
wet oxidation [3], Fenton process [4], photo-Fenton process [5–7]
and combined sono–photo-Fenton process [8]. In all these pro-
cesses, photo-Fenton appears to be the most promising method
considering the overall process efficiency based on pollutant re-
moval and cost of operation [8]. The process requires an oxidant
to degrade the organic pollutants. Hydrogen peroxide (HP) appears
to be an appropriate and potential oxidant because it is relatively
cheap, environmentally friendly and has high oxygen content
yielding water as the only by-product [9], and in the presence of

1385-8947/$ - see front matter Ó 2012 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.cej.2012.04.053
182 O.B. Ayodele et al. / Chemical Engineering Journal 197 (2012) 181–192
ferrous ion it has the ability to generate hydroxyl radical with a
very high oxidation potential of 2.8 eV which is capable of degrad-
ing most organic pollutants [6,7].
Both HP dosage and catalyst loadings affect the degradation effi-
ciency of photo-Fenton process [6–14], besides the serious environ-
mental impact of leached Fe and the increase in the capital and
operational costs effects of overdosing a Fenton process with either
or both Fe ion and HP, there is also scavenging effects which drasti-
cally affect the degradation kinetics. In order to avoid these serious
problems, optimization of the process becomes inevitable. Due to
the complex systems of photo-Fenton catalytic degradation process,
application of one-factor-at-a-time-optimization approach could
mislead the optimization process because of the lack of cross-factor
effects [15,16]. Thus, the application of the design of experiments
(DOEs) seems to be an alternative option. A good example of such
methods that consider the simultaneous varying of influencing pro-
cess parameters and still take into account the interactions between
them is referred to as response surface methodology (RSM) [7,17].
D-optimal design is a good example of RSM and it is quite attractive
and robust for researchers. Its application provides maximal accu-
racy in estimating regression coefficients and it was developed to
select design points in a way that minimizes the variance associated
with the estimates of specified model coefficients [17–20].
Recently, it had been reported that oxalate based Fenton catalyst
can degrade pollutants without pH adjustment or at near neutral
pH due to the presence of suitable ligands [21,22]. In fact, Bautitz
and Nogueira [23] reported that Fe-oxalate catalysts have higher
catalytic ability at generating the required hydroxyl radical than
the iron from the convectional nitrate and sulfate salts apparently
due to the presence of some suitable organic ligands. All these stud-
ies were conducted in the homogeneous photo-Fenton process. The
major drawback of homogeneous Fenton’s process is its inability to
easily recover the catalysts due to the formation ferric sludge which
makes the process requires additional processing steps like coagu-
lation and sedimentation [10]. Thus, replacement of the homoge-
neous catalysts with heterogeneous catalysts where the active
metal can be incorporated into a support became an alternative.
Although heterogeneous catalyst could be relatively slower than
homogeneous catalyst due to diffusion resistances of the reactants
into the pore and products out of the pore, this problem can be min-
imized or completely solved with acid modification of the support
which opens up the pore, increases the surface area [20] and re-
duces or eliminates the diffusion resistances in the catalysts.
In this study, heterogeneous ferric-oxalate catalyst was pre-
pared by incorporating ferric-oxalate into phosphoric acid modi-
fied kaolin clay and its activity was tested on the degradation of
phenol. The pH of the degradation process was not adjusted be-
cause of the possible interference of the presence of buffer solution
on the kinetics of the investigated processes [24] and in order to
really investigate the catalytic ability of the oxalate based catalyst.
The degradation process was optimized for the purpose of develop-
ing a phenomenological mathematical model that will not only
accurately and consistently describe the degradation kinetics but
be able to predict the process performance.
2. Materials and methods
2.1. Materials
Kaolin powder was supplied by R&M marketing, Essex, UK Com-
pany with CAS number 1332-58-7. Analytical grade phenol and
hydrogen peroxide (HP) solution (30%) were obtained from Fluka.
The iron hydroxide, oxalic acid, and phosphoric acid were pur-
chased from Merck (Germany). Double distilled water was used
throughout the experiment.
2.2. Catalyst preparation
The catalyst was prepared by treating 50.0 g of raw kaolin (RK)
clay with 200 ml of 5 M phosphoric acid in a round bottomed flask
equipped with a reflux condenser refluxing at 110 °C for 2 h fol-
lowing a modification to the procedure described by Panda et al.
[20]. The reaction mixture was immediately quenched by adding
iced water followed by filtration and repeated washing with dou-
ble distilled water to remove any unspent acid until pH becomes
neutral. The phosphoric acid modified kaolin (AMK) clay support
obtained was dried in an oven at 110 °C for 12 h and grinded to
powder with a mortar and pastel. The phosphoric acid modified
kaolin catalyst (AMKC) was prepared by reacting 1.44 g of oxalic
acid and 1.14 g of iron hydroxide in stoichiometric ratio (Eq. (1))
to produce 2 g of ferric-oxalate. After 1 h, the reacting species were
continuously added to the already prepared AMK suspension and
stirred for 6 h at 50 °C. The product was dried in the oven at
110 °C for 12 h, grinded to powder and calcined at 450 °C for 4 h
in a muffle furnace according to the thermo gravimetric analysis
(TGA) result.
2FeðOHÞ3 þ 3C2 H2 O4 ! C6 O12 Fe2 þ 6H2 O ð1Þ
2.3. Catalyst characterization techniques
The XRF analyses of the samples were done using a Philips Mod-
el-PW2400 and X-ray tube of rhodium anode and scintillation
detector operating on a 40 mA current and 40 mV voltage, while
their X-ray diffraction (XRD) patterns were measured with SIE-
MENS XRD D5000 equipped with Cu Ka radiation and recorded
in the range of 5–90° with a scanning rate of 2°/min. The Energy
Dispersive X-ray (EDX) analysis was performed to determine the
elemental composition of the RK and AMKC samples using certain
equipment mounted on the Scanning Electron Microscopy (SEM)
instrument. The samples were analyzed three times and the aver-
age values were recorded. The results of analysis were presented in
weight percent. The Fourier Transformed Infrared Spectroscopy
(FTIR) analyses were performed on the samples, using a Perkin-El-
mer Spectrum GX Infrared Spectrometer with resolution of 4 cm1,
in the range of 4000–400 cm1. The sample and analytical grade
KBr were dried at 100 °C over-night prior to the FTIR analysis
and were prepared with the disc technique using a finely ground
mixture of 0.25 mg of sample and 100 mg of KBr pressed at 4 Mbar.
The Nitrogen adsorption–desorption measurements (BET meth-
od) were performed at liquid nitrogen temperature (196 °C) with
an autosorb BET apparatus, Micromeritics ASAP 2020, surface area
and porosity analyzer. The analysis procedure is automated and
operates with the static volumetric technique. Before each mea-
surement, the samples were first degassed at 200 °C for 2 h. Scan-
ning Electron Microscopy (SEM) was used to study the surface
morphology of the RK and AMKC samples. The analysis was carried
out using a scanning electron microscope (Model EMJEOL-
JSM6301-F) with an Oxford INCA/ENERGY-350 microanalysis sys-
tem. Thermal Gravimetric Analysis (TGA) analyses were carried
out with a SHIMADZU DTG-60/60H instrument. The sample was
heated in a silica crucible at a constant heating rate of 10 °C/min
operating in a stream of N2 atmosphere with a flow rate of
40 mL/min from 25 to 700 °C and weight loss per time and temper-
ature increment were recorded.
2.4. Photo-Fenton reactor and photodegradation procedure
A 1.0 L stirred glass reactor filled with 500 mL of phenol was
used as photo-Fenton reactor. It was fitted with 254 nm UV lamp
supported by retort stand. The stirred glass reactor was immersed
in a 2 L beaker partly filled with water located on a hot plate with
 O.B. Ayodele et al. / Chemical Engineering Journal 197 (2012) 181–192
variable magnetic stirring and a temperature control facility. The
temperature of the phenol solution was adjusted by the tempera-
ture control knob until ±2 °C of the desired value. The temperature
and pH was monitored by EcoScan SC11-4115 (Exatech Enterprise)
pH meter. The initial pH of the aqueous solution of phenol was not
adjusted except for the preliminary study on the effect of pH
adjustment. After stabilizing the temperature, the AMKC was
added to the solution and the reaction was initiated by adding
HP under predetermined optimal magnetic stirring speed of
340 rpm. All the experiments were performed at 30 °C ± 2 except
when the effect of temperature was studied.
2.5. Analytical methods
UV–Vis spectrophotometer was used as the analytical tech-
nique for monitoring concentration reduction of phenol during
the experiment because of its simplicity of use and ability to mea-
sure concentration within a short time. The maximum absorbance
wavelength (kmax) of phenol measured from 500 to 200 nm using a
spectrophotometric quartz cell in a UV–Vis spectrophotometer
(Shimadzu, model UV 1700 PharmaSpec, Japan) was found at
272.5 nm. The withdrawn filtered samples were quickly analyzed
to minimize experimental errors since the reaction could still con-
tinue after withdrawal. However, following the observation and
suggestion made by Khokhawala et al. [25], caution has been taken
accordingly to check if there is any influence or interference of the
HP or any intermediate products generated in the course of reac-
tion on the extent of absorbance of phenol at the obtained maxi-
mum wavelength. The maximum absorbance spectrum of HP
was found at 198 nm which indicated that there was no interfer-
ence in the concentration of phenol due to HP, or any intermedi-
ates as the absorbance spectrum of the samples measured
remained similar to the pure phenol solution. Similar works on
the use of spectrophotometer for monitoring reduction in phenol
concentrations with time also observed similar protocol [26–28].
The extent of mineralization was determined by Hach COD ana-
lyzer (model 2800, United States). The Hach COD analyzer kit com-
prises of 0–1500 ppm COD digestion solution, a Hach DRB 200
digestion chamber and a Hach DR 890 COD colorimeter where
the chemical oxygen demand (COD) of the withdrawn samples
were measured. The samples were first modified with 1.0 M NaOH
to scavenge any residual HP so as to stop the reaction before add-
ing the samples to the COD digestion solution. The application of
NaOH has been reported not to interfere with the COD value [8].
The degradation efficiency and COD removal efficiency of phenol
were evaluated as follows:
 
Co  Ct
Degradation efficiency ¼ 100%
Co
 
CODo  CODt
COD removal efficiency ¼ 100%
CODo
where Co and CODo (ppm) are the initial concentration and COD of
phenol, while Ct and CODt (ppm) are the measured concentration
and COD at the time of withdrawal, respectively.
2.6. Degradation of phenol UV/HP/AMKC process
Prior to the commencement of the experimental design with re-
sponse surface methodology, preliminary experiments were car-
ried out in the following order to understudy the contributory
role of the process parameters. The first preliminary experiment
was carried out to determine the effect of HP on the degradation
of phenol. This was achieved by adding only AMKC to phenol solu-
tion and stirred without HP but in the presence of UV irradiation,
183
the aim is to establish if the decrease in concentration of phenol
as recorded by the UV–Vis spectrophotometer was due to adsorp-
tion, catalytic reaction or both. Secondly, the extent of reaction in
dark Fenton process was also evaluated by carrying out the reac-
tion of phenol with HP and AMKC, but in the absence of UV irradi-
ation, the aim is to study the contributory role of UV irradiation on
the photo-reduction process of Fe3+ to Fe2+. The role of the AMKC
was also verified in an experiment by reacting phenol with HP un-
der UV irradiation but in the absence of the catalyst, the aim is to
determine the extent of degradation reaction without catalyst. Fi-
nally, the effect of pH adjustment on the degradation of phenol
was studied at three different pH values of 3.02, unadjusted pH
(5.4) and 7.2 in the presence of AMKC, HP and UV irradiation.
2.7. Experimental design and statistical analysis
A four factor D-optimal design was used to determine the opti-
mum operating conditions for maximizing the phenol degradation
efficiency. The four factors selected as independent variables are
based on previous experience and as a prerequisite for process/
product design of phenol treatment facility in industrial applica-
tions. They are HP dosage, AMKC loading, degradation time and
the initial concentration of phenol and they are assigned with
the following notations X1, X2, X3 and X4, respectively. The agitation
speed and temperature were set at 340 rpm and 30 °C, respectively
and they were considered noise contributions. The objective func-
tion to be optimized is degradation efficiency of phenol, denoted as
Y. The number of experiments for the four independent variables
was calculated as follows according to DOE configuration using De-
sign-Expert 7.1.6 from Stat Ease Inc., minimum model points, 15;
lack of fits estimate points, 5; replicates points, 5 and the total
experiments summed up to 25.
Application of D-optimal design as an optimization technique
requires the selections of a model at the beginning, in this partic-
ular case study, quadratic model was chosen as shown in Eq. (4).
The adequacy of the final model was verified by graphical and
numerical analysis followed by evaluation for the response func-
tion and finally the experimental data were analyzed statistically
applying analysis of variance (ANOVA).
Y ¼ b0 þ b1 X 1 þ b2 X 2 þ b3 X 3 þ b4 X 4 þ b12 X 1 X 2 þ b13 X 1 X 3
þ b14 X 1 X 4 þ b23 X 2 X 3 þ b24 X 2 X 4 þ b34 X 3 X 4 þ b124 X 1 X 2 X 4
þ b1 X 21 þ b2 X 22 þ b3 X 33 ð4Þ
where bn is the coefficient associated with each nth factor, and com-
bination of factors (such as X1X2) represents interactions between
ð2Þ the individual factors in that term.
3. Results and discussion
ð3Þ
3.1. Catalyst characterization results
3.1.1. Energy dispersive X-ray (EDX)
The results shown in Fig. 1 revealed that there is an increment
in the Fe content of the AMKC sample, but its aluminum and oxy-
gen contents were reduced. The reduction in the former is due to
the phosphoric acid modification effect that caused leaching of alu-
minum content of the RK while that of the latter is as a result of the
calcination of the AMKC that removed the physisorbed water (see
FTIR result) which consequently reduced the oxygen content. But
since EDX is a point analysis and the values of elemental analysis
could vary from different points, and also in order to determine
the chemical composition, that is, the oxide of the elements that
were present, (XRF) analysis was performed.
184 O.B. Ayodele et al. / Chemical Engineering Journal 197 (2012) 181–192

Fig. 1. EDX spectrum and data of RK and AMKC.

3.1.2. X-ray fluorescence spectroscopy (XRF)
The result of XRF analysis is shown in Table 1. The major con-
stituents of the RK are alumina and silica while sodium, iron,
potassium and titanium oxides are present in minute quantities.
After the phosphoric acid modification, a considerable change in
the composition of the RK was observed. The fraction of SiO2 was
found to increase from 54.21% to 65.82% while Al2O3 fraction re-
duced from 43.51% to 32.24% and other constituents like TiO2,
Fe2O3 and K2O fraction in the acid modified sample also decreased.
This resulted in the increase of the Si/Al ratio from 1.10 to 1.76,
respectively in RK and AMK. This de-alumination of the AMK sam-
ple can be ascribed to the leaching of the Al3+ ions from the octa-
hedral layer due to hydrolysis under acidic conditions [20] as can
be seen in Eq. (5) in a reaction between phosphoric acid and kao-
linite. This observation is due to the presence of Al–O–Si bonds
at the octahedral layer that was attacked during acid modification
to a greater extent and finally resulted in rapid solubility. The per-
centage of iron content increased from 0.73 in the RK to 5.82 in
AMKC signifying successful incorporation of iron into the AMKC.
Al2 O3  2SiO2  2H2 O þ 3H3 PO4 ! Al2 ðPO4 Þ3 þ 2SiO2 þ 5H2 O
þ 3=2H2
3.1.3. X-ray diffraction (XRD)
The XRF result successfully confirms the incorporation of iron
into the AMKC sample, but there is need to determine the phase
in which the iron is present after the calcination process. It has
been reported that calcination process is capable of transforming
a metal from crystalline phase into amorphous which enhances
its anchoring onto the support by transforming the metal into
insoluble form [29,30]. XRD result (Fig. 2a and b) shows the effect
of acid modification and incorporation of iron on AMKC. In Fig. 2a
(RK), two well-defined characteristic peaks of kaolinite at 2h value
of 12° and 25° corresponding to the reflections from [0 0 1] and d
values of 7.154 Å can be seen. Other peaks corresponding to the
2h value 34–36°, 38–42°, 45–50°, and 54–63° were also visible
but may vary for kaolinites from different origin [31]. These peaks
were significantly reduced in Fig. 2b due to the structural disorder
that occurred as a result of the acid modification which distorted
the crystallinity of the RK and disintegrates its layered structure.
From Fig. 2b, some of the iron oxide phases observed are related
to phase a-Fe2O3 with 2h = 24.16°, 30.6°, 32.4°, 41.3°, 48.6° and
56.18° [12,32], while 35.5°, 43°, 57° and 62.5° corresponds to
Fe3O4 and 36° and 42° are ascribed to FeO [33]. The peaks of the
diffractogram correspond to the standard card of magnetite
(JCPDS: 19-0629) and hematite (JCPDS card no. 33-0664) [32,33].
3.1.4. Nitrogen adsorption/desorption isotherm (BET and BJH) studies
The textural property of the samples is shown Table 1. The RK,
AMK and AMKC have BET surface area of 19, 45 and 36 m2 g1,
respectively. The increment in the surface area of AMK was due
to the acid modification that opens up the RK pores, while the
slight reduction observed in the AMKC sample could be due to
the blocking of the pores by the loaded metal after the incorpora-
ð5Þ tion of ferric-oxalate precursor, Fabriozioli et al. [34] also observed
this phenomenal. Both the RK and AMKC samples showed Type IV
isotherms (Fig. 3). According to the IUPAC classification, Type IV
isotherms are generally observed for mesoporous solids
[20,34,35]. RK sample showed hysteresis loop at P/Po (0.82–1)
which increased to (0.24–1) in AMKC which suggests an increase
in the number of mesopores in AMKC sample due to the effect of
phosphoric acid modification.
3.1.5. Fourier Transformed Infrared Spectroscopy (FTIR)
Extensive reports on the FTIR bands for kaolin clay loaded with
metal had been well reported in the literature [20,34–39], however

Table 1
Compositional analysis and textural properties of RK, AMC and AMKC samples.

Material Component content (%) Si/Al ratio BET surface area (m2 g1) Pore volume (cm3 g1) Pore size (nm)
SiO2 Al2O3 Na2O Fe2O3 TiO2 K2O
RK 54.21 43.51 0.15 0.73 0.77 0.2 1.1 19 0.1 21.2
AMK 65.82 32.24 0.04 0.61 0.71 0.17 1.76 45 0.17 26.7
AMKC 64.27 29.8 0.02 5.82 0.69 0.13 1.69 36 0.15 24.8

there are three major features that are worthy of note in FTIR spec-
tra of RK and AMKC samples shown in Fig. 4. (1) The infrared bands
in the bending region mode of RK sample with peak maxima at
916, 795 and 745 cm1 which can be respectively assigned to the
Al–Al–OH, Al–Mg–OH and Si–O–Al vibration of the clay sheet, they
are quite intense and can be attributed to the bending vibration
mode of physisorbed water on the surface of free silica [36]. These
peaks reduced slightly in AMK due to structural disintegration
caused by acid modification. Further reduction of those peaks
was observed in AMKC due to combined effect of structural disin-
tegration caused by acid modification and calcinations. (2) The
peak at 1385 cm1 is quite intense as it appeared in both RK and
AMK and it can be attributed to the physisorbed water molecules
that are present in the first coordination sphere of the interlayer
ions as the peak disappeared in AMKC after calcinations at
450 °C. (3) There was a shift in the Si–O–Si bond from 1090 to
1082 cm1 following the incorporation of the ferric-oxalate, the
peak intensity at 972 cm1 which was assigned as Si–OH bond
was found to decrease progressively showing the formation of
the Si–O–Fe bond structure. These in conjunction with the shift
in the 1100 cm1 band and the peak at 916 cm1 which is associ-
ated with the bending of Fe–O–Fe bond gave further credence to
the formation of the Si–O–Fe bond structure and the presence of
hematite, respectively [1,3]. The peak at 2330 cm1 confirmed
100
Quantity adsorbed (cm3 g-1 STP)
80
RK- Adsorption
RK - Desorption
60
AMKC - Adsorption
AMKC - Desorption
40
20
0 3.2. Degradation of phenol UV/HP/AMKC process
0 0.2
Relative pressure (P/Po)
Fig. 3. The N2 adsorption desorption isotherms of RK and AMKC samples.
O.B. Ayodele et al. / Chemical Engineering Journal 197 (2012) 181–192 185
Fig. 2. XRD diffractogram of RK and AMKC.
the successful incorporation of the ferrioxalate complex. The FTIR
result supports the EDX, XRF and XRD studies.
3.1.6. Scanning Electron Microscopy (SEM)
The morphologies of RK and AMKC samples (Fig. 5a and b)
showed that AMKC had undergone some changes owing to the ef-
fect of the acid modification, subsequent incorporation of the cat-
alyst precursor and calcination. The effect of acid modification that
resulted in the de-alumination of the RK which consequently in-
creased the sample surface area according to BET result can be seen
to have changed the appearance of the RK from lumpy in Fig. 5a to
flaky and crispy in Fig. 5b.
3.1.7. Thermo Gravimetry Analysis (TGA)
From the profile of effect of thermal treatments on the samples,
three characteristics regions can be seen from Fig. 6: (1) The inter-
layer and physisorbed water molecules which are mobile and
freely bound to the clay sheets and as a result are easily removable
at temperature below 150 °C, (2) the strongly bonded water mole-
cules that are present in the first coordination sphere of the inter-
layer ions of the clay sheet which may require heat treatment in
the temperature range of 300–500 °C for their removal and (3)
the structural hydroxyl groups that will condense and dehydrate
at temperatures above 600 °C [20]. The result of effect of thermal
treatment showed that the amount of moisture content to be re-
moved increase in the order of AMKC > AMK > RK. This is due to
the hydration effects during acid modification of AMK and com-
bined acid modification and incorporation of catalyst precursor
in AMKC. This is in agreement with the FTIR studies (Fig. 4) that
showed increase in the physisorbed water at 1385 cm1 for the
AMK sample, the physisorbed water was removed in the AMKC
sample due to calcination at 450 °C. The increment in surface area
due to acid modification shown by the BET result (Table 1) could
also be thought to have provided large surface area for absorption
of water molecules in AMK sample.
0.4 0.6 0.8 1
From the preliminary studies, photo-degradation reaction in the
absence of HP showed a very poor phenol degradation efficiency of
186 O.B. Ayodele et al. / Chemical Engineering Journal 197 (2012) 181–192

Fig. 4. FTIR spectra of the RK, AMK and AMKC samples.

Fig. 5. SEM of (a) RK and (b) AMKC (magnification = 3000).

2.16% in 60 min because the highly reactive HO required for the
degradation cannot be generated according to Eq. (6). This implied
that the decrease in phenol concentration observed in subsequent
reactions were due to catalytic process and not adsorption of phe-
nol onto the AMKC. The reaction in the absence of UV light (dark
Fenton) proceeded though slowly relative to photo-Fenton process
after 4 min of reaction time because the rate of Fe3+ reduction to
Fe2+ employed in the absence of UV is not as efficient as the
photo-reduction process depicted by Eq. (7). De Leon et al. [40] re-
ported that Fe3+ regeneration can also take place through a series
of reactions involving hydroperoxyl radicals (HO2 ), Eq. (8), but
the overall rate of regeneration and process efficiency are lower
compared to Eq. (7) which has the ability to generate HO during
the photo-reduction process. The major challenge to this reduction
process is the scavenging effect of the HO2 produced on Fe2+ as
shown by Eq. (9). The percent degradation obtained was 48.6% in
60 min.
60 min because phenol was relatively stable due to the poor oxida-
tion potential of HP as compared to HO [11]. The mechanism of HO
generation employed under this condition is based on Eq. (10),
which is a relatively slower process compared to Eq. (6). Conversely,
appreciable decrease in the concentration of phenol was observed
when the combination of the UV irradiation, HP and catalyst were
used with about 95% phenol removal in less than 20 min at 30 °C
using stoichiometric amount of HP and 1.5 g AMKC. Finally, the re-
sult of study on the effect of pH showed insignificant difference at
the three studied pH. The degradation efficiencies obtained after
100
96
Weight loss (%)

Fe2þ þ HP ! Fe3þ þ OH þ HO ð6Þ

92 RK
Fe3þ ðOH Þ þ hv ! Fe2þ þ HO ð7Þ
AMK
3þ 2þ þ
Fe 
þ HP ! Fe þ HO2 þH ð8Þ 88 AMKC

Fe2þ þ HO2 ! Fe3þ þ HO2 ð9Þ

84
HP þ hv ! HO ð10Þ 25 125 225 325 425 525 625 725
Temperature (ºC)
The reaction of phenol with HP under the influence of UV irradia-
tion but without catalyst showed only 28.7% degradation after Fig. 6. TGA of (a) RK, (b) AMK and (c) AMKC.
 O.B. Ayodele et al. / Chemical Engineering Journal 197 (2012) 181–192 187

Table 2
Experimental design and response based on experimental runs proposed by D-optimal design.

Run number Factors Response (degradation) Residual

X1 (HP dosage) X2 (AMKC loading) X3 (time) X4 (phenol conc.) Experimental (%) Predicted (%)
1 15 3 6 200 52.95 54.58 1.63
2 20 2 6 200 79.78 79.00 0.77
3 15 2.5 4 150 74.51 70.44 4.05
4 20 2 2 100 48.99 45.83 3.15
5 15 3 2 100 38.92 40.18 1.28
6 15 2 2 200 25.84 26.08 0.24
7 25 2.5 6 100 94.18 93.34 0.83
8 25 2 2 200 49.90 49.28 0.61
9 25 3 2 100 42.60 42.42 0.17
10 20 3 6 100 90.60 91.58 0.98
11 25 2 4 100 77.07 78.07 1.00
12 15 2 6 100 88.63 89.12 0.52
13 25 2 6 150 84.50 83.83 0.66
14 25 3 6 200 59.42 59.82 0.42
15 20 3 2 200 32.37 31.39 0.97
16 22.5 2.5 4 150 77.92 80.41 3.21
17 20 2 4 150 75.64 75.90 3.26
18 20 3 4 150 71.83 68.36 3.43
19 20 2.5 2 150 45.03 48.94 3.91
20 20 2.5 6 150 91.35 89.11 2.23
21 25 3 2 100 42.64 42.42 0.17
22 25 2 2 200 49.91 49.28 0.61
23 25 3 6 200 59.43 59.82 0.42
24 15 2 6 100 88.63 89.12 0.52
25 15 2 2 200 25.84 26.08 0.24

20 min were 93.8%, 95% and 92.5%, respectively at pH 3.02, 5.4
(unadjusted) and 7.2. This ability was due to the presence of ferri-
oxalate ligands in the AMKC that make the catalyst relatively insen-
sitive to pH variation [21–23].
3.3. D-optimal experimental design
3.3.1. Development of regression model equations and analysis
The data generated from performing experimental runs at the
process variables (HP dosage, 15–25% excess; AMKC loading, 2–
3 g; time, 2–6 min and phenol concentration, 100–200 ppm) varied
conditions are presented in Table 2 that present the experimental
and predicted response values. The coefficients of independent
variables (X1, X2, X3 and X4), polynomials and their interaction ef-
fects on the response function, Y (phenol degradation efficiency)
were determined and the corresponding statistical polynomial
model was obtained by multiple regressions as shown in Eq. (11).
Values of ‘‘Prob > F’’ less than 0.0500 indicated that model terms
are also significant. In this case X 1 ; X 2 ; X 3 ; X 4 ; X 21 ; X 22 ; X 23 ; X 1 X 2 ; X 1 X 3 ;
X 1 X 4 ; X 2 X 4 ; X 3 X 4 are significant model terms. The obtained R2 is
0.9921 and the adjusted regression coefficient, R2adj , that corrects
regression coefficient, R2, for the sample size and the number of
terms in the models is 0.9810. Generally, if a model contains many
terms and has small sample size this could result in a much lower
R2adj when compared to R2 [41,42], in this case the model has high
R2 and R2adj which confirms that the chosen quadratic model in
D-optimal design for response surface method adequately describe
the experimental data in the range of the operating parameters.
Two important information to check if there is any deficiency or
descripancy in the model fitting to the experimental data on the
performance of the model can be seen in the plot of internally
studentized residuals vs. normal probability (Fig. 7a) and the plot
of run number vs. outlier T points (Fig. 7b). The normal probability
plot shows orchestrated points and points cluster in close

%Phenol degradation ¼ 354:20 þ 10:78  X 1 þ 187:30

 X 2 þ 44:47  X 3  0:04  X 4 Table 3
ANOVA test for the response model Y (% phenol degradation).
 0:22  X 21  31:06  X 22  2:71
Source Sum of squares DF Mean square F-value Prob > F
 X 23 þ 2:78E  4  X 24  0:78  X 1
Model 11302.14 14 807.29 89.37 < 0.0001
 X 2  0:25  X 1  X 3 þ 0:013  X 1 X1 216.55 1 216.55 23.97 0.0006
X2 215.22 1 215.22 23.82 0.0006
 X 4  1:06  X 2  X 3  0:13  X 2 X3 6086.33 1 6086.33 673.84 < 0.0001
 X 4  0:03  X 3  X 4 ð11Þ X4 765.70 1 765.70 84.77 < 0.0001
X 21 135.88 1 135.84 15.03 0.0031
In order to establish a correlation between the model prediction X 22 134.59 1 134.57 14.89 0.0032
and the experimental response, analysis of variance (ANOVA) was X 23 260.31 1 260.31 28.82 0.0003
used to test the goodness of fit for the polynomial coefficients of X 24 0.80 1 0.80 0.09 0.7716
the response Y and the results are presented in Table 3. The mean X1X2 47.11 1 47.11 5.21 0.0455
squares were obtained by dividing the sum of squares for each var- X1X3 77.90 1 77.90 8.62 0.0149
X1X4 126.07 1 126.07 13.95 0.0039
iation by their respective degrees of freedom while the F-value was X2X3 13.37 1 13.37 1.48 0.2515
calculated by dividing the obtained mean squares with the residual X2X4 129.82 1 129.82 14.37 0.0035
mean square (9.03). The Model F-value is 89.37 for the response func- X3X4 134.86 1 134.84 14.92 0.0031
tion, which implied that the model is significant, and there is only a Residual 90.32 10 9.03
Lack of fit 90.32 5 18.06
0.01% chance that Model F-values this large could occur due to mod-
Pure error 0 5 0
el error, although it may be associated to experimental error [41].
188 O.B. Ayodele et al. / Chemical Engineering Journal 197 (2012) 181–192
Fig. 7. Diagnostics of Y model: (a) Normal probability of residuals and (b) internally outliers T points.
neighborhood of the diagonal line in Fig. 7a, an indication of the
homogeneousity of the error variances and independent style of
the residuals which confirms that errors are normally distributed
and independent of each other [7,28,41,43].
From the plot of run numbers vs. outliers T points that can used
to evaluate the assumption of constant variance (Fig. 7b), it was ob-
served that the points are randomly scattered and structureless
which confirm that all the information are well extracted and the
residuals are unrelated to any other variables [7,28]. All the points
lie within the range 3.5 and +3.5 which is considered as the bottom
and top outlier detection limits. Since all the points were captured
within the range, it can be concluded that the response transforma-
tion is appropriate and successful in capturing the correlation be-
tween the four studied parameters influencing the degradation of
phenol without any apparent problem with the normality [7,41,43].
3.4. Response surface plot of phenol/UV/HP/AMKC degradation process
3.4.1. Effect of hydrogen peroxide dosage and catalyst loading
Based on the established material balance of Eq. (12), stoichi-
ometric amount of HP was calculated, and for the purpose of
enhancing the generation of HO, 15–25% excess HP were experi-
mented as discussed earlier. The result (Fig. 8a) shows that initial
increment in the HP dosage significantly enhances phenol degrada-
tion due to the availability of sufficient HO required for the reac-
tion. Further increment showed decrease in the degradation
efficiency. This observation can be due to the scavenging effect of
HP on HO as shown in Eq. (13) to form the hydroperoxy radical
(HO2 ) with lower reactivity and oxidation potential of 1.7 eV com-
pared to 2.8 eV of hydroxyl radical. Excess HP could also generate
excess HO radicals that are capable of dimerizing to form HP
according to Eq. (14) and these cumulative effects inhibit the deg-
radation rate of phenol [3–14,21].
C6 H6 O þ 14HP ! 6CO2 þ 17H2 O
HP þ HO ! HO2 þ H2 O
HO þ HO ! HP
Similarly, initial increase in the catalyst loading drastically in-
creases the degradation rate up to the saturation point beyond
which further loading retards the degradation rate, an observation
that is similar to the effect of HP dosage. This retardation can be
attributed to the scavenging effect of excess iron on the reactive
hydroxyl radical as depicted in Eq. (15). It can be seen that the plot
is predominantly quadratic as revealed by the contour lines on the
HP dosage - catalyst loading plane. This implied that both HP dos-
age and catalyst loading significantly influenced the phenol degra-
dation efficiency as earlier reported [5–14,21,24].
Fe2þ þ HO ! Fe3þ þ OH ð15Þ
3.4.2. Effect of phenol initial concentration
Fig. 8b shows the response plot for the effect of variation in the
initial concentration of phenol, it is obvious that as the treatment
time increases the degradation efficiency improves within the
range of experimental studies. At lower initial concentration of
100 ppm, the degradation efficiency is higher than at higher con-
centration of 200 ppm as revealed by the RSM plot. This is because
as the initial concentration was increased other factors affecting
the rate of degradation were not simultaneously increased, thereby
making the available HO insufficient for the degradation of phenol.
It can also be seen that after 5 min of reaction with 100 ppm initial
concentration, the response plot shows a parallel plot with the
time axis until 6 min of treatment time, this implies that any treat-
ment within that range does not reflect in any removal of phenol
concentration. The plot shows linear relationship between initial
concentration axis and a non linear relationship with the time axis
which confirms the validity of the predictive model chosen. It can
be concluded that degradation is favored at lower initial concen-
tration and this observation is not at variance with what had been
reported earlier [4–10,13–14].
ð12Þ
3.4.3. Optimization and desirability plot
ð13Þ The optimum condition for the degradation of phenol was ob-
tained from the desirability plot (Fig. 9). The optimized degrada-
ð14Þ
tion conditions based on the interaction between the
 O.B. Ayodele et al. / Chemical Engineering Journal 197 (2012) 181–192 189

Fig. 9. Desirability plot for the degradation of phenol with AMKC at 30 °C.

Fig. 8a. Response surface plot for catalyst loading and HP dosage; [phe-
nol]o = 100 ppm, temperature = 30 °C.

Scheme 1. Reaction path way for the degradation of phenol.

and in view of the complexity that could be associated with the

identification and quantification of the numerous intermediates,
a Lumped Kinetic Model (LKM) was adopted [6,44] to study the
kinetics of the mineralization of phenol in this study based on
the reaction pathways shown in Scheme 1.
A, I and C represents phenol, organic intermediates such as ace-
tic acid, maleic acid etc., and the final substrates – CO2 and H2O,
respectively. ki (i = 1–3) is the apparent rate constant (min1).
The pathway from A to C with apparent rate constant k1 represents
the direct oxidation of phenol into the final substrates while the
reaction pathway A to I to C (apparent rate constants k2 and k3)
represents the oxidation of phenol through the formation of some
intermediates compounds. Pseudofirst-order kinetics was assumed
because the concentration of the catalyst is considered (effect
Fig. 8b. Response surface plot for effect of initial concentration of phenol, 20% AMKC loading) in this heterogeneous photo-Fenton process; con-
excess HP dosage catalyst loading = 2.0 g, temperature = 30 °C. sequently, the unit of the rate constant will be expressed in min1
[44].
The following set of differential equations was obtained accord-
independent factors were presented as contour lines and the desir-
ing to the reaction pathway in Scheme 1 [44].
ability increases towards the centre of the plot. The best desirabil-
ity point on the contour gave the optimum condition to achieve dC A
99.15% degradation 100 ppm phenol to be 18.2% excess HP, ¼ ðk1 þ k2 ÞC A ð16Þ
dt
2.23 g of AMKC in 5 min reaction time. The optimized condition
was used for the kinetics study. dC I
¼ ðk2 C A  k3 ÞC I ð17Þ
dt
From Eq. (16),
3.5. Kinetic study of phenol mineralization
C A ¼ C Ao  eðk1 þk2 Þt ð18Þ
Phenol degradation in Fenton and all modified-Fenton process
had been reported to proceed via two pathways: complex oxida- Substituting the Eq. (18) into Eq. (17) and integrate;
tion via intermediates and hydroxyl radical oxidation [6,8,44],
dC I
the predominance of either path ways depends more on the selec- ¼ ðk2 C Ao  eðk1 þk2 Þt  k3 ÞC I ð19Þ
dt
tivity of the catalyst [44]. A good Fenton catalyst is expected to
have a higher selectivity for the latter so as to minimize the k2 C A  eðk3 Þt k2 C A  eðk1 þk2 Þt
amount of intermediate compounds that may prolong the reaction C I ¼ C Io  eðk3 Þt þ þ ð20Þ
ðk1 þ k2  k3 Þ ðk1 þ k2  k3 Þ
time and threatening the life span of the catalyst through deactiva-
tion, leaching and even poisoning. Based on the above pathways Boundary conditions: t = 0
190 O.B. Ayodele et al. / Chemical Engineering Journal 197 (2012) 181–192

1.000
Model

0.800 50 ppm phenol

100 ppm phenol
[COD]/[COD]o

200 ppm phenol

0.600

0.400

0.200

0.000
0.0 5.0 10.0 15.0 20.0
Time (min) Fig. 11. Effect of initial concentration on the selectivity and total apparent removal
of phenol; HP dosage = 18.2% excess HP, AMKC loading = 2.23 g.
Fig. 10. Phenol COD removal at the optimized condition; HP dosage = 18.2% excess
HP, AMKC loading = 2.23 g.

the reaction rate. The steepness is more reduced in the selectivity

C A ¼ ½C Ao þ C Io  ¼ ½CODo
C I ¼ C Io ¼ 0
Similarly, the total chemical oxygen demand (COD) of the reaction
medium at any time during the reaction can be evaluated based
on the concentration of phenol and intermediates [6,44] by combin-
ing Eqs. (18) and (20); i.e. [CA + CI]t = [COD]t
Therefore,
 
½CODt k2 eðk3 Þt ðk1  k3 Þ  eðk1 þk2 Þt
¼ þ
½CODo ðk1 þ k2  k3 Þ ðk1 þ k2  k3 Þ
Eq. (21) describes the relative reduction of phenol COD with
reaction time. The feasibility and reliability of the developed ki-
netic model was explored for phenol degradation at different initial
concentrations. As it can been seen from Fig. 10 the experimental
data fitted well into the developed model which validated the coef-
ficients obtained from the non-linear regression of the experimen-
tal data. The selectivity, a, (k1/k2) of the AMKC which is defined as
the rate of direct oxidation of phenol to the rate of oxidation
through intermediates and the total apparent reaction rate con-
stant for phenol elimination defined as K = k1 + k2 were presented
in Table 4.
The results in Table 4 show that both the selectivity and the to-
tal apparent reaction rate were higher at lower initial concentra-
tion than at higher concentration. This observation is in
agreement with the observation in RSM studies (Fig. 8b) which
shows higher degradation efficiency at lower concentration of
100 ppm than at 200 ppm phenol. The reason in not unconnected
with earlier explanation that as the concentration of pollutants
were increased the values of other parameters affecting the degra-
dation rate were not increased. Therefore, the phenol molecules
will have to compete for the scarcely available HO, and in this
way the degradation efficiency reduces. Also from Fig. 11, it is very
obvious that the gradient in the two curves are more steep be-
tween 50 and 100 ppm than 100 and 200 ppm initial concentration
of phenol, this confirms that there is intense competition for reac-
tion at higher initial concentration which consequently slow down
curve signifying that the effect of initial concentration affects
selectivity more than total apparent degradation. Therefore, it
can be concluded that more intermediate compounds are produced
at higher initial concentration of phenol which probably accounts
for lower degradation efficiency within the same reaction time.
This is because more time will be required to degrade not only
the phenol but also the intermediate compounds formed. Hence
the selectivity AMKC is a better for direct oxidation at lower con-
centration than at higher concentration, similar observation was
also reported by Feng and Le-cheng [6].
ð21Þ
3.6. Effect of temperature on the degradation of phenol
The effect of temperature on the photo-Fenton degradation of
phenol with AMKC was studied and the result is shown in
Fig. 12. The result revealed that temperature variation is significant
in the degradation reaction of phenol. For example, after 4 min of
reaction, degradation efficiency increases from about 87.21% in
30 °C to 97.46 in 40 °C. This enhanced degradation rate can be as-
cribed to the Arrhenius theory of rate constants dependence on
temperature. The increase in temperature increased the rate of
hydroxylation at the catalyst active sites producing more HO with
energy in excess of the activation energy and this led to higher col-
lision frequency between the HO and the phenol molecules which
eventually resulted in faster degradation. The increase in amount
of phenol degraded from 87.21% to 97.46% showed that increase
in the temperature also affected the thermodynamics of the reac-
tion by enhancing the feasibility of the degradation process.
Temperature is a strong factor in thermodynamic science as it
shifts reaction equilibrium in such a way to favor the accumula-
tion/consumption of substances that are formed/consumed by
reaction which requires heat energy from the surrounding [45].
When the reaction temperature was increased to 50 °C, the degra-
dation efficiency reduced probably due to thermal decomposition
HP according to Eq. (22) and the HO is subjected to scavenging
effect [46–48]. Yip et al. reported that HP is thermally unstable
at elevated temperature [47], although the rate of decomposition
of HP is dependent not only on the temperature, but also concen-

Table 4
Rate constants, selectivity and degradation rate of phenol degradation with AMKC.

Initial concentration (ppm) Initial COD (ppm) k1 (min1) k2 (min1) k3 (min1) Selectivity [k1/k2] Degradation rate [k1 + k2] (min1)
50 100 0.512 0.040 0.430 12.80 0.552
100 221 0.390 0.060 0.30 6.50 0.450
200 496 0.316 0.084 0.190 3.76 0.400
 O.B. Ayodele et al. / Chemical Engineering Journal 197 (2012) 181–192
100
80
Degradation efficiency (%)
60
30 ºC
40 ºC
40
50 ºC
20
0 gands in the AMKC and the effect of phosphoric acid
0 2 4 6
Time (min)
Fig. 12. Degradation efficiency of phenol as a function of temperature at the
optimized condition; HP dosage = 18.2% excess HP, AMKC loading = 2.23 g.
tration of the peroxide, as well as the pH and the presence of impu-
rities and stabilizers which were not investigated in this work.
H2 O2 ! H2 O þ O2
3.7. Catalyst reusability study
The catalyst reusability study showed higher catalytic stability
with only about 4% drop in activity after five consecutive experi-
mental runs. The high catalytic reusability could be ascribed to
the ability of the AMKC to degrade at near neutral pH due to the
presence of the oxalate ligands. It is a known fact that Fe leaching
increases at lower pH values, Herney-Ramirez et al. [44] reported
that such leaching is severe at pH 3 and below. In addition, oxalate
ligand is known to be a strong chelator, providing strong bond be-
tween the Fe metal and the AMK support. FTIR plot shows the pres-
ence of the oxalate ligands at 2330 cm1 band. Also the effect of
acid modification on the catalyst support provided adequate and
proper anchoring for the Fe metal due to the monolayer of phos-
phate functional group introduced on the AMK surface after the
modification by H3PO4 [47]. Proper calcination also plays an
invaluable role at transforming the Fe metal into amorphous
(XRD plot) phase which make it insoluble and reduces the ten-
dency of metal leaching [28,29]. The relatively short reaction time
can also contribute to the stability of the catalyst since the catalyst
does not have to remain in the reaction medium for a very long
time. Finally another factor that has been thought to enhance the
stability and prolong activity of the catalyst is its selectivity (Ta-
ble 4 and Fig 11) to degrade larger part of phenol concentration
through direct oxidation into final substrates thereby minimizing
the amount of intermediate compounds that may deactivate or
poison the catalyst. Trovo et al. also reported that lesser quantities
of intermediate compounds were found in the degradation of
amoxicillin when using ferric-oxalate as compared to FeSO4 and
the intermediates degraded faster when using ferric-oxalate [49].
4. Conclusion
The AMKC developed through acid modification of kaolin clay
and incorporation of ferric-oxalate has demonstrated excellent re-
sult at degrading phenol pollutant. Prior to optimization studies,
preliminary experiments showed that HP dosage, AMKC loading,
treatment time and initial concentration of phenol play important
roles in the degradation of phenol. The factors interaction and
191
ANOVA studies result revealed strong correlation between the
experimental and predicted responses with R2 and R2adj values of
0.9921 and 0.9810, respectively. The optimization result based on
the best desirability plot gave 18.2% excess HP, 2.23 g of AMKC
and 5 min reaction time to achieve 99.15% degradation of
100 ppm initial concentration of phenol without pH adjustment.
The COD removal and kinetic study showed that higher COD re-
moval rate was achieved easily at 50 ppm compared to 200 ppm
initial concentration. The rate of degradation in 50 ppm is 1.38
times higher than that of 200 ppm while the selectivity is 3.4 times
higher. The selectivity is observed to be more sensitive to variation
in initial phenol concentration. Higher catalyst reusability of about
4% drop in activity was observed after five consecutive experi-
ments, this stability was based on the presence of the oxalate li-
8 modification. Hence, the catalyst is promising in the depuration
of phenol pollutant.
Acknowledgements
The first author acknowledges the scholarship grant provided
by the Niger Delta Development Commission (NDDC), Port Har-
court and the study leave approved by National Engineering Design
Development Institute, Nnewi, both in Nigeria.
ð22Þ
References
[1] F. Adam, J. Andas, I.Ab. Rahman, A study on the oxidation of phenol by
heterogeneous iron silica catalyst, Chem. Eng. J. 165 (2010) 658–667.
[2] S. Kannan, A. Dubey, H. Knozinger, Synthesis and characterization of CuMgAl
ternary hydrotalcites as catalysts for the hydroxylation of phenol, J. Catal. 231
(2005) 381–392.
[3] A. Xu, M. Yang, H. Yao, H. Du, C. Sun, Rectorite as catalyst for wet air oxidation
of phenol, Appl. Clay Sci. 43 (2009) 435–438.
[4] R.F.F. Pontes, J.E.F. Moraes, A. Machulek Jr., J.M. Pinto, A mechanistic kinetic
model for phenol degradation by the Fenton process, J. Hazard. Mater. 176
(2010) 402–413.
[5] M. Hongzhu, X. Zhang, M. Qingliang, B. Wang, Electro chemical catalytic
treatment of phenol wastewater, J. Hazard. Mater. 165 (2009) 475–481.
[6] H. Feng, L. Le-cheng, Degradation kinetics and mechanisms of phenol in photo-
Fenton process, J. Zhejiang Univ. Sci. 5 (2004) 198–205.
[7] B.H. Diya’uddeen, A.R. Abdul Aziz, W.M. Ashri Wan Daud, Oxidative
mineralisation of petroleum refinery effluent using Fenton-like process,
Chem. Eng. Res. Des. http://dx.doi.org/10.1016/j.cherd.2011.06.010.
[8] A. Babuponnusami, K. Muthukumar, Degradation of phenol in aqueous
solution by Fenton, sono-Fenton and sono–photo-Fenton methods, J. Clean-
Soil, Air, Water 39 (2011) 142–147.
[9] C. Samanta, Direct synthesis of hydrogen peroxide from hydrogen and oxygen:
an overview of recent developments in the process, Appl. Catal. A 350 (2008)
133–149.
[10] M. Vinita, R.P.J. Dorathi, K. Palanivelu, Degradation of 2,4,6-trichlorophenol by
photo Fenton’s like method using nano heterogeneous catalytic ferric ion, Sol.
Energy 84 (2010) 1613–1618.
[11] O.B. Ayodele, J.K. Lim, B.H. Hameed, Pillared montmorillonite supported ferric
oxalate as heterogeneous photo-Fenton catalyst for degradation of amoxicillin,
Appl. Catal. A 413–414 (2012) 301–309.
[12] H. Hassan, B.H. Hameed, Oxidative decolourization of acid red 1 solution by Fe-
zeolite type catalyst, Desalination 276 (2011) 45–52.
[13] A.N. Soon, B.H. Hameed, Heterogeneous catalytic treatment of synthetic dyes
in aqueous media using Fenton and photo-assisted Fenton process,
Desalination 269 (2011) 1–16.
[14] N.K. Daud, B.H. Hameed, Decolorization of acid red 1 dye solution by Fenton-
like process using Fe–montmorillonite K10 catalyst, Chem. Eng. J. 165 (2010)
111–116.
[15] S. Malato, P. Fernandez-Ibanez, M.I. Maldonado, J. Blanco, W. Gernjak,
Decontamination and disinfection of water by solar photocatalysis: recent
overview and trends, Catal. Today 147 (2009) 1–59.
[16] D.C. Montogomery, Design and Analysis of Experiments, John Wiley and Sons,
NY, USA, 2005.
[17] R.H. Myer, D.C. Montogomery, Response Surface Methodology: Process and
Product Optimization Using Designed Experiment, second ed., John Wiley and
Sons, NY, USA, 2002.
[18] I. Grcic, D. Vujevic, N. Koprivanac, The use of D-optimal design to model the
effects of process parameters on mineralization and discoloration kinetics of
Fenton-type oxidation, Chem. Eng. J. 157 (2010) 408–419.
[19] W.L. Poston, E.J. Wegman, J.L. Solka, D-optimal design methods for robust
estimation of multivariate location and scatter, J. Stat. Plan. Infer. 73 (1998)
205–213.
192 O.B. Ayodele et al. / Chemical Engineering Journal 197 (2012) 181–192
[20] A.K. Panda, B.G. Mishraa, D.K. Mishrac, R.K. Singha, Effect of sulphuric acid
treatment on the physico-chemical characteristics of kaolin clay, J. Colloids
Surf. A 363 (2010) 98–104.
[21] A. Safazadeh-Amiri, J.R. Bolton, S.R. Cater, Ferrioxalate-mediated
photodegradation of organic pollutants in contaminated water, Water Res.
31 (1997) 787–798.
[22] H. Katsumata, T. Okada, S. Kaneco, T. Suzuki, K. Ohta, Degradation of fenitrothion
by ultrasound/ferrioxalate/UV system, Ultrason. Sonochem. 17 (2010) 200–206.
[23] I.R. Bautitz, R.F. Pupo Nogueira, Photodegradation of lincomycin and diazepam
in sewage treatment plant effluent by photo-Fenton process, Catal. Today 151
(2010) 94–99.
[24] J. Kochany, G.G. Choudhry, G.R.B. Webster, Degradation of nitrobenzene and
nitrophenols by means of advanced oxidation processes in a homogeneous
phase: photolysis in the presence of hydrogen peroxide versus the Fenton
reaction, Arch. Environ. Contam. Toxicol. 19 (1990) 325–331.
[25] I.M. Khokhawala, P.R. Gogate, Degradation of phenol using a combination of
ultrasonic and UV irradiations at pilot scale operation, Ultrason. Sonochem. 17
(2010) 833–838.
[26] E.V. Rokhina, E. Repo, J. Virkutyte, Comparative kinetic analysis of silent and
ultrasound assisted catalytic wet peroxide oxidation of phenol, Ultrason.
Sonochem. 17 (2010) 541–546.
[27] S. Sonawane, P. Chaudhari, S. Ghodke, S. Ambade, S. Gulig, A. Mirikar, A. Bane,
Combined effect of ultrasound and nanoclay on adsorption of phenol, Ultrason.
Sonochem. 15 (2008) 1033–1037.
[28] T. Luenloi, B. Chalermsinsuwan, T. Sreethawong, N. Hinchiranan,
Photodegradation of phenol catalyzed by TiO2 coated on acrylic sheets:
kinetics and factorial design analysis, Desalination 274 (2011) 192–199.
[29] I. Chorkendorff, J.W. Niemantsverdriet, Concepts of Modern Catalysis and
Kinetics, WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim, ISBN:3-527-
30574-2, 2003, pp. 186–300.
[30] Jens Hagen, Industrial Catalysis: A Practical Approach, 2006 WILEY-VCH Verlag
GmbH & Co. KGaA, Weinheim, Germany, ISBN-13:978-3-527-31144-6, 2006,
pp. 200–244.
[31] A. Chaisena, K. Rangsriwatananon, Effect of thermal and acid treatment on
some physico-chemical properties of lamping diatomite, J. Sci. Technol. 11
(2004) 289–299.
[32] F.G.E. Nogueira, J.H. Lopes, A.C. Silva, R.M. Lago, J.D. Fabris, L.C.A. Oliveira,
Catalysts based on clay and iron oxide for oxidation of toluene, Appl. Clay Sci.
51 (2011) 385–389.
[33] W. Kugler, X-ray diffraction analysis in the forensic science: the last resort in
many criminal cases, JCPDS – International Centre for Diffraction Data, Adv. X-
Ray Anal. 46 (2003) 1–16.
[34] P. Fabriozioli, T. Burgi, M. Burgener, S.V. Doorslaer, A. Baiker, Synthesis,
structural and chemical properties of iron oxide silica aerogels, J. Mater. Chem.
12 (2002) 619–630.
[35] G. Choi, S.M. Yang, Effect of two-step sol–gel reaction on the mesoporous silica
structure, J. Colloid Interface Sci. 261 (2003) 127–132.
[36] J. Madejova, FTIR techniques in clay mineral studies, Vib. Spectrosc. 31 (2003)
1–10.
[37] B.N. Dudkin, I.V. Loukhina, E.G. Avvakumov, V.P. Isupov, Application of
mechanochemical treatment of disintegration of kaolinite with sulphuric
acid, Chem. Sust. Dev. 12 (2004) 327–330.
[38] H. Suquet, Effects of dry grinding and leaching on the crystal structure of
chrysotile, Clays Clay Miner. 37 (1989) 439–445.
[39] J.S. Choi, S.S. Yoon, S.H. Jang, W.S. Ahn, Phenol hydroxylation using Fe-MCM-41
catalysts, Catal. Today 111 (2006) 280–287.
[40] M.A. De León, J. Castiglionia, J. Bussi, M. Sergio, Catalytic activity of an iron-
pillared montmorillonitic clay mineral in heterogeneous photo-Fenton
process, Catal. Today 133–135 (2008) 600–605.
[41] K. Yetilmezsoy, S. Demirel, R.J. Vanderbei, Response surface modeling of Pb(II)
removal from aqueous solution by Pistacia vera L: Box–Behnken experimental
design, J. Hazard. Mater. 171 (2009) 551–562.
[42] M. Dopar, H. Kusic, N. Koprivanac, Treatment of simulated industrial
wastewater by photo-Fenton process. Part I: the optimization of process
parameters using design of experiments (DOE), Chem. Eng. J. http://dx.doi.org/
10.1016/j.cej.2010.09.070.
[43] Stat-Ease, Multifactor RSM Tutorial (Part 2 – Optimization), Design-Expert
Software Version 7.1.6 User’s Guide, 2008.
[44] J. Herney-Ramirez, M.A. Vicente, L.M. Madeira, Heterogeneous photo-Fenton
oxidation with pillared clay-based catalysts for wastewater treatment: a
review, Appl. Catal. B 98 (2010) 10–26.
[45] E.D. Sloanet, Handbook of Chemical Engineering Calculations, third ed.,
Prentice-Hall, 2002. pp. 126–173.
[46] S. Ray, J.A. Lalman, N. Biswas, Using the Box–Benkhen technique to statistically
model phenol photocatalytic degradation by titanium dioxide nanoparticles,
Chem. Eng. J. 150 (2009) 15–24.
[47] A.C.K. Yip, F.L.Y. Lam, X. Hu, Chemical-vapor-deposited of copper on acid-
activated bentonite clay as an applicable heterogeneous catalyst for the photo-
fenton-like oxidation of textile organic pollutants, Ind. Eng. Chem. Res. 44
(2005) 7983–7990.
[48] B. Muthukumari, K. Selvam, I. Muthuvel, M. Swaminathan, Photoassisted
hetero-Fenton mineralisation of azo dyes by Fe(II)–Al2O3 catalyst, Chem. Eng. J.
153 (2009) 9–15.
[49] A.G. Trovo, R.F.P. Nogueira, A. Aguera, A.R. Fernandez-Alba, S. Malato,
Degradation of the antibiotic amoxicillin by photo-Fenton process –
chemical and toxicological assessment, Water Res. 45 (2011) 1394–1402.