768 © IWA Publishing 2014 Water Science & Technology | 69.

4 | 2014

Application of artificial neural network for modeling of

phenol mineralization by photo-Fenton process using a
multi-lamp reactor
André L. N. Mota, Osvaldo Chiavone-Filho, Syllos S. da Silva,
Edson L. Foletto, José E. F. Moraes and Cláudio A. O. Nascimento

ABSTRACT
André L. N. Mota
An artificial neural network (ANN) was implemented for modeling phenol mineralization in aqueous
Department of Environmental Science and
solution using the photo-Fenton process. The experiments were conducted in a photochemical Technology,
Federal University of Rural Semi-Arid,
multi-lamp reactor equipped with twelve fluorescent black light lamps (40 W each) irradiating UV Mossoró, 59625-900,
Brazil
light. A three-layer neural network was optimized in order to model the behavior of the process. The
Osvaldo Chiavone-Filho
concentrations of ferrous ions and hydrogen peroxide, and the reaction time were introduced as Syllos S. da Silva
Department of Chemical Engineering,
inputs of the network and the efficiency of phenol mineralization was expressed in terms of
Federal University of Rio Grande do Norte,
dissolved organic carbon (DOC) as an output. Both concentrations of Fe2þ and H2O2 were shown to 59066-800, Natal,
Brazil
be significant parameters on the phenol mineralization process. The ANN model provided the best
Edson L. Foletto (corresponding author)
result through the application of six neurons in the hidden layer, resulting in a high determination Department of Chemical Engineering,
Federal University of Santa Maria,
coefficient. The ANN model was shown to be efficient in the simulation of phenol mineralization 97105-900, Santa Maria,
Brazil
through the photo-Fenton process using a multi-lamp reactor.
E-mail: efoletto@gmail.com
Key words | artificial neural networks, mineralization, modeling, phenol, photo-Fenton
José E. F. Moraes
Department of Exact and Earth Sciences,
Federal University of São Paulo,
09972-270, São Paulo,
Brazil

Cláudio A. O. Nascimento
Department of Chemical Engineering,
University of São Paulo,
05508-900, São Paulo,
Brazil

INTRODUCTION

Industrial effluents from petrochemistry, paper mills, manu-
facturers of resin, pharmaceuticals, herbicides, pesticides
and explosives may contain phenol. High toxicity, poor bio-
degradability and ecological aspects are some of the major
problems caused by the phenolic compounds (El-Ashtoukhy
et al. ). Several techniques have been used to degrade or
remove phenol in an aqueous solution such as adsorption
(Castro et al. ), photocatalysis (Chang & Tseng ), per-
vaporation (Hao et al. ), extraction (Jabrou ), ion
exchange (Oprea & Sandulescu ), catalytic ozonation
(Amin et al. ), membrane-based solvent extraction
(Lazarova & Boyadzhieva ), photo-Fenton (He & Lei
), sono-Fenton and sono-photo-Fenton (Babuponnu-
sami & Muthukumar ), and combined biological and
enzymatic treatments (Bevilaqua et al. ). Among these
methods, the advanced oxidation processes (AOP) stands
out as an alternative to degrade pollutant compounds in
industrial wastewater. Photo-Fenton is an AOP that has
been widely used for the removal of several types of organic
pollutants in wastewater (Moraes et al. ; Lucas & Peres
; Silva et al. ).
The use of conventional or phenomenological mathemat-
ical models to describe a wastewater treatment by advanced
oxidation process can be unfeasible due to complexity of
the system. Recently, artificial neural networks (ANNs)
have been applied in modeling and predicting of wastewater
treatment using AOP (Khataee & Kasiri ). One of the
advantages of modeling based on ANN is that it
requires less time for model development compared with
traditional mathematical models (Elmolla et al. ).

doi: 10.2166/wst.2013.731
 769 A. L. N. Mota et al. | Artificial neural network for modeling of phenol mineralization
Application of an ANN model to describe the removal of
organics pollutants in wastewater has been reported in sev-
eral works in the literature (Göb et al. ; Nascimento
et al. ; Nascimento et al. ). However, few studies
on the application of an ANN model to predict the treatment
of wastewater containing phenol by photo-Fenton have been
reported (Nogueira et al.  , Borges et al. ).
In this context, the present investigation evaluated the
use of an ANN model to correlate and predict the results
of phenol mineralization in aqueous solution by photo-
Fenton process, using a multi-lamp reactor.
MATERIALS AND METHODS
Materials
All reagents used were of analytical grade and supplied by
VETEC: phenol (C6H5OH), ferrous sulfate heptahydrate
(FeSO4·7H2O), hydrogen peroxide (H2O2; 30%, v/v), sulfu-
ric acid (H2SO4), sodium hydroxide (NaOH), potassium
iodide (KI) and sodium sulfite (Na2SO3).
Figure 1 | Scheme of multi-lamp reactor.
Water Science & Technology | 69.4 | 2014
Apparatus and experimental procedure
The multi-lamp tubular reactor (Figure 1) used for the phenol
mineralization was composed of a set of twelve blacklight flu-
orescent lamps, as a UV light source (40 W/lamp), attached
vertically onto the inner surface of a metallic cylinder (diam-
eter ¼ 0.40 m and length ¼ 1.20 m) made of stainless steel. A
borosilicate tube (external diameter ¼ 0.036 m, inner diam-
eter ¼ 0.030 m and length ¼ 1 m) was positioned in its
center. The reactor was connected with a 10 L reservoir
tank. The solution was circulated through the borosilicate
tube by a centrifugal pump (450 L h1). A digital ther-
W
mometer was used for monitoring the temperature (25 C).
The fluorescent lamps were connected to a switch-box-set
that allows the turning on of each UV lamp independently.
A fan was coupled to the top of the reactor in order to
avoid over heating caused by the lamps. The total irradiated
area of the inner tube of the reactor is 0.0942 m2.
Synthetic solution was prepared by diluting the phenol in
distilled water in order obtain the desired initial concentration
of dissolved organic carbon content of 100 mgC L1.
Solution pH was adjusted at 3.0 using an H2SO4 solution.
W
The temperature of the solution was kept constant at 20 C.
 770 A. L. N. Mota et al. | Artificial neural network for modeling of phenol mineralization Water Science & Technology | 69.4 | 2014

Then, ferrous sulfate was added into the reaction medium. organic carbon (DOC) (Shimadzu 5000A analyzer). The
H2O2 dosages were carried out in the system at pre- time evolution of phenol mineralization was monitored by
determined reaction times (0, 30, 60 and 90 min). Samples the DOC-time profiles. The process performance was calcu-
were collected at pre-determined times and an inhibitor sol- lated by Equation (1), where DOCo and DOCt are the
ution was added (NaOH, Na2SO3 and KI – 0.1 M each) in concentrations of the initial dissolved organic carbon and at
order to interrupt the reaction. Samples were filtered time t, respectively.
(0.22 μm Millipore membrane) before analysis of dissolved
DOC removal (%) ¼ (DOCo  DOCt )=DOCo × 100 (1)

Artificial neural network

The ANN model, compiled with FORTRAN software, was

Figure 2 | (a) Comparison between calculated and experimental values for the training
set using six neurons in the hidden layer and (b) residual distribution for DOC
removal (experimental – calculated) versus experimental values.
applied for modeling and predicting of DOC removal. The
input variables were initial concentrations of Fe2þ (0.27 to
3 mM) and H2O2 (20 to 200 mM), and reaction time (0 to
200 min), while the output variable was DOC removal (0
to 100%). The ranges of input and output variables were
chosen from a previous study in the domain of interest
(Mota et al. ). The aim was to get the maximum
reduction of organic load and investigate the effects of
system concentrations in the photochemical degradation.
All the experiments started with 100 mgC L1 of phenol
concentration. The minimum value of H2O2 (20 mM) con-
centration corresponds to the stochiometric value. A ratio
of the ferrous ions and H2O2 used in the experiments
were on average 1:68, varying not more than 7%. A total
of 99 experimental measurements or samples at different
operational conditions were used to test and train the
ANN model. These measurements were distributed between
the learning data set (80 samples) and the test data set
(19 samples). The ANN model was composed of three
nodes in the input layer and one node in the output layer.
The number of hidden nodes ranged from 2 to 8 in the
optimization procedure.

Table 1 | Weights of the neural network model fit to the experimental data, using six neurons in the hidden layer

Input variable layer 1 2 3 4 5 6

Time  4.25 0.42  0.37  0.78 3.59  55.84

2þ
Concentration of Fe  0.60 1.73  15.82  3.76  0.37 0.36
Concentration of H2O2  0.36 0.32  1.58 34.14  30.65 1.25
Bias 0.44 0.93 0.78 0.36 0.08 0.70

Output variable layer 1 2 3 4 5 6 Bias

DOC (%)  7.92  9.21  7.07 10.16 5.2  61.97 0.18

 771 A. L. N. Mota et al. | Artificial neural network for modeling of phenol mineralization Water Science & Technology | 69.4 | 2014

Figure 3 | Comparison between calculated (symbol: o) and experimental (symbol: Δ) values of the output variable (DOC removal efficiency) as function of reaction time. Experimental
conditions: (a) [H2O2] ¼ 173.64 mM, [Fe2þ] ¼ 2.6 mM; (b) [H2O2] ¼ 110 mM, [Fe2þ] ¼ 1.634 mM; (c) [H2O2] ¼ 110 mM, [Fe2þ] ¼ 0.268 mM; (d) [H2O2] ¼ 110 mM, [Fe2þ] ¼ 3 mM;
(e) [H2O2] ¼ 46.36 mM, [Fe2þ] ¼ 0.668 mM.
 772 A. L. N. Mota et al. | Artificial neural network for modeling of phenol mineralization
RESULTS AND DISCUSSION
In order to optimize the number of neurons, determination
coefficients of the training set were determined for each con-
figuration of ANN model tested. Determination coefficient
(R 2) values and the root-mean-square deviation (RMSD)
for the different hidden neuron numbers tested in the
ANN model were 0.950 and 7.70 (2 neurons), 0.970 and
6.00 (3 neurons), 0.980 and 4.85 (4 neurons), 0.983
and 3.54 (5 neurons), 0.989 and 3.82 (6 neurons), 0.989
and 7.35 (7 neurons) and 0.990 and 3.54 (8 neurons),
respectively. From these results, it can be seen that the
increasing of neurons above six did not significantly
change the R 2 values and with five, six and eight neurons,
the best results were obtained in terms of RMSD. Thus, six
neurons were selected as the optimum number of neurons.
Figure 2(a) shows a comparison between calculated
values and experimental DOC removal values using the
ANN model with six neurons in the hidden layer. The deter-
mination coefficient (R 2) value is 0.989, which is very close
to one, indicating that the ANN model is able to describe
precisely the experimental results of phenol mineralization
in aqueous solution. Figure 2(b) shows the residual distri-
bution (difference between calculated and experimental
values) for the experiments in terms of DOC removal, and
Figure 4 | Simulation of response surface for DOC removal (at 60 min of reaction) as a function of H2O2 and Fe2þ concentrations.
Water Science & Technology | 69.4 | 2014
also shows that the residual values are reasonably well dis-
tributed around the x-axis (zero). It indicates the
satisfactoriness of the ANN model in representing the
phenol mineralization within the experimental adopted
range.
Table 1 lists the weights obtained by the ANN model
used in this work, with six neurons in the hidden layer
and 500,000 iterations. This number was found to be suffi-
cient to ensure stabilization of the residual distribution.
Figure 3 shows a comparison between experimental and
calculated values of DOC removal as a function of reaction
time for all experimental conditions used in this work. As
can be seen from Figure 3, the predicted values are in agree-
ment with the experimental results. This indicates that the
ANN model is able to describe adequately the phenol miner-
alization process in the multi-lamp photochemical reactor,
within the experimental ranges adopted in this work.
Figure 4 illustrates the response surface generated from
the simulated data of the ANN model. The DOC removal
(for 60 min of reaction time) as a function of the H2O2
and Fe2þ concentrations is shown in this figure. At low con-
centrations of H2O2, increasing the concentration of Fe2þ
favors the increase of the DOC removal, until it reaches a
stage of maximum removal, and thereafter slowly
decreases. Conversely for low concentrations of Fe2þ,
 773 A. L. N. Mota et al. | Artificial neural network for modeling of phenol mineralization
increasing concentration of H2O2 increases DOC removal.
In Figure 4, may be observed a darker area of the best
experimental conditions that achieve maximum DOC
removal. The response surfaces indicate that the
photochemical system is more sensitive to Fe2þ concen-
tration than to H2O2 concentration, which is of
advantage in terms of economical feasibility of the process
(Göb et al. ).
Figure 5 shows simulated values by the ANN model and
experimental values of DOC removal as a function of Fe2þ
(keeping constant [H2O2] at 110 mM) (Figure 5(a)) and
H2O2 (keeping constant [Fe2þ] at 1.634 mM) (Figure 5(b))
concentrations, at 60 min of reaction. Both Figures 5(a)
and 5(b) show that simulated values are in good agreement
with the experimental results. Figure 5(a) shows that DOC
removal grows with increasing concentration of Fe2þ until
Figure 5 | Comparison between ANN output and experimental results as a function of (a)
[Fe2þ] (keeping constant [H2O2] ¼ 110 mM) and (b) [H2O2] (keeping constant
[Fe2þ] ¼ 1.634 mM), at 60 min of reaction for both conditions.
Water Science & Technology | 69.4 | 2014
reaching a maximum value (79%, at [Fe2þ] ¼ 0.814 mM), at
which point, above this value, the DOC removal begins to
decrease. This may be due to the direct reaction of HO• rad-
ical with ferrous ions at high concentrations of Fe2þ
(Elmolla et al. ) as in Equation (2).
Fe2þ þ HO ! Fe3þ þ HO (2)
In Figure 5(b), it can also be seen that the DOC removal
increased abruptly with the increase of hydrogen peroxide
concentration up to 50 mM. Further increases in hydrogen
peroxide concentration above 50 mM did not improve the
phenol removal. This may be due to scavenging of HO• rad-
ical by H2O2 at high concentrations of H2O2 (Elmolla et al.
) as in Equation (3).
HO þ H2 O2 ! H2 O þ HO2 (3)
Approximately 50 mM of H2O2 obtained 73% of DOC
removal against 75% for 185 mM of H2O2 with the same
amount of iron. This is of interest in terms of application
that a considerably reduced quantity of oxidant is required
to remove practically the same organic load.
CONCLUSIONS
The series of experimental data of phenol degradation by
photo-Fenton using a multi-lamp reactor was successfully
described by a three-layered artificial neural network, with
six neurons in the hidden layer. All studied variables, i.e.,
iron ions and hydrogen peroxide concentrations and reac-
tion time were demonstrated to be of significant impact on
phenol mineralization. The resulting ANN model can be
applied for design and simulation purposes to the photo-
Fenton process of phenol mineralization.
ACKNOWLEDGEMENTS
Brazilian financial support provided by ANP (Agência
Nacional de Petróleo, Gás Natural e Biocombustíveis), Pet-
robras, CAPES (Coordenação de Aperfeiçoamento de
Pessoal de Nível Superior), CNPq (Conselho Nacional de
Desenvolvimento Científico e Tecnológico) and INCT of
Enviromental Studies (Institutos Nacionais de Ciência e
 774 A. L. N. Mota et al. | Artificial neural network for modeling of phenol mineralization
Tecnologia de Estudos do Meio Ambiente) is gratefully
acknowledged.
REFERENCES
Amin, N. A. S., Akhtar, J. & Rai, H. K.  Catalytic ozonation of
aqueous phenol over metal-loaded HZSM-5. Water Science
and Technology 63 (8), 1651–1656.
Babuponnusami, A. & Muthukumar, K.  Degradation of
phenol in aqueous solution by Fenton, sono-Fenton and
sono-photo-Fenton methods. Clean – Soil Air Water 39 (2),
142–147.
Bevilaqua, J. V., Cammarota, M. C., Freire, D. M. & Santanna Jr,
G. G. L.  Combined biological and enzymatic treatments,
phenol removal through combined biological and enzymatic
treatments. Brazilian Journal of Chemical Engineering 19 (2),
151–158.
Borges, F. J., Balmann, H. R. & Guardani, R.  Modeling
electrodialysis and photochemical process for their
integration in saline wastewater treatment. Computer Aided
Chemical Engineering 27, 741–746.
Castro, C. S., Abreu, A. L., Silva, C. L. T. & Guerreiro, M. C. 
Phenol adsorption by activated carbon produced from spent
coffee grounds. Water Science and Technology 64 (10),
2059–2065.
Chang, C.-F. & Tseng, I.-P.  Degradation of phenol by using
magnetic photocatalysts of titania. Water Science and
Technology 67 (7), 1434–1441.
El-Ashtoukhy, E.-S. Z., El-Taweel, Y. A., Abdelwahab, O. &
Nassef, E. M.  Treatment of petrochemical wastewater
containing phenolic compounds by electrocoagulation using
a fixed bed electrochemical reactor. International Journal of
Electrochemical Science 8, 1534–1550.
Elmolla, E. S., Chaudhuri, M. & Eltoukhy, M. M.  The use
of artificial neural network (ANN) for modeling of COD
removal from antibiotic aqueous solution by the Fenton
process. Journal of Hazardous Materials 179 (1–3),
127–134.
Göb, S., Oliveros, E., Bossmann, S. H., Braun, A. M., Guardani, R.
& Nascimento, C. A. O.  Modeling the kinetics of a
photochemical water treatment process by means of artificial
neural networks. Chemical Engineering and Processing 38,
373–382.
Hao, X., Pritzker, M. & Feng, X.  Use of pervaporation for the
separation of phenol from dilute aqueous solutions. Journal
of Membrane Science 335 (1–2), 96–102.
He, F. & Lei, L. C.  Degradation kinetics and mechanisms of
phenol in photo-Fenton process. Journal of Zhejiang University
Science 5 (2), 198–205.
First received 2 July 2013; accepted in revised form 25 October 2013. Available online 4 December 2013
Water Science & Technology | 69.4 | 2014
Jabrou, S. N.  Extraction of phenol from industrial water using
different solvents. Research Journal of Chemical Sciences
2 (4), 1–12.
Khataee, A. R. & Kasiri, M. B.  Artificial neural networks
modeling of contaminated water treatment processes by
homogeneous and heterogeneous nanocatalysis. Journal of
Molecular Catalysis A: Chemical 331 (1–2), 86–100.
Lazarova, Z. & Boyadzhieva, S.  Treatment of phenol-
containing aqueous solutions by membrane-based solvent
extraction in coupled ultrafiltration modules. Chemical
Engineering Journal 100 (1–3), 129–138.
Lucas, M. S. & Peres, J. A.  Decolorization of the azo dye
Reactive Black 5 by Fenton and photo-Fenton oxidation.
Dyes and Pigments 71 (3), 236–244.
Moraes, J. E. F., Quina, F. H., Nascimento, C. A. O., Silva, D. N. &
Chiavone-Filho, O.  Treatment of saline wastewater
contaminated with hydrocarbons by the photo-Fenton
process. Environmental Science and Technology 38 (4),
1183–1187.
Mota, A. L. N., Chiavone-Filho, O., Nascimento, C. A. O., Moraes,
J. E. F. & Muranaka, C. T.  Estudo do tratamento de
efluentes de indústrias petroquímicas, contendo compostos
fenólicos, pelo processo foto-fenton. Petro & Química 278,
50–55.
Nascimento, C. A. O., Göb, S., Braun, A. M., Oliveros, E.,
Bossmann, S. H. & Guardani, R.  Modeling the kinetics
of a photochemical water treatment process by means of
artificial neural networks. Chemical Engineering and
Processing: Process Intensification 38 (4–6), 373–382.
Nascimento, C. A. O., Braun, A. M., Oliveros, E., Guardani, R.,
Göb, S. & Bossmann, S. H.  Optimal experimental design
and artificial neural networks applied to the photochemically
enhanced Fenton reaction. Water Science and Technology 44
(5), 339–345.
Nogueira, K. R. B., Teixeira, A. C. S. C., Nascimento, C. A. O. &
Guardani, R.  Use of solar energy in the treatment of
water contaminated with phenol by photochemical
processes. Brazilian Journal of Chemical Engineering 25 (4),
671–682.
Nogueira, K. R. B., Nascimento, C. A. O., Guardani, R. & Teixeira,
A. C. S. C.  Feasibility study of a solar reactor for phenol
treatment by the photo-Fenton process in aqueous solution.
Chemical Engineering & Technology 35 (12), 2125–2132.
Oprea, F. & Sandulescu, M.  Phenol removal from wastewater
and sour water using ion exchange adsorption. Environmental
Engineering and Management Journal 5 (5), 1051–1058.
Silva, S. S., Chiavone-Filho, O., Neto, E. L. B. & Nascimento,
C. A. O.  Integration of processes induced air flotation
and photo-Fenton for treatment of residual waters
contaminated with xylene. Journal of Hazardous Materials
199–200, 151–157.