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Mathematical modelling of photocatalytic degradation of methylene blue under

visible light irradiation


D. Sannino*, V. Vaiano, O. Sacco, P. Ciambelli
Department of Industrial Engineering, University of Salerno, Via Ponte Don Melillo, 84084 Fisciano (Salerno), Italy
Introduction
Large amounts of coloured wastewater are generated in
industries which use dyes to impart a desired colour to their
products (food, paper, rubber, textile, plastics), and are discharged
into natural hydric bodies with undesirable consequences to the
environment and to human health [15]. The presence of dyes in
natural streams can cause serious harm to the aquatic life by
increasing toxicity and chemical oxygen demand, and by hindering
photosynthetic phenomena through reduction of light penetration
[2]. Also, some dyes, such as methylene blue (MB) (3,7-
bis(dimethylamino)-phenothiazin-5-iumchloride) is commonly
used for dye paper, temporary hair colorant, dyeing cottons, and
wools. Such extensive use often causes problems and thus
adequate treatments need to be employed for its removal prior
to discharge into receiving water streams. MB has a complicated
chemical structure; it is difcult to be removed from wastewaters
by commonly used techniques (biological treatment and chemical
precipitation). To protect the aquatic environment, many methods
such as adsorption, electrocoagulation, ultrasonic decomposition,
advanced chemical oxidation, nanoltration, and chemical coagu-
lation followed by sedimentation were used to remove dyes from
wastewater.
Specially advanced oxidation processes (AOPs) involving
hydroxyl radical, a very powerful chemical oxidant that can
destroy a wide range of tough organic contaminants, are
introduced to treat textile dyes efuents. Among AOPs, Photo-
Fenton oxidation [68] and heterogeneous photocatalysis are
studied both for environmental applications and to produce
organic compounds with high added values [913].
In the last years, photocatalytic oxidation with TiO
2
in presence
of visible light has been gaining industrial and academic attention.
Most studies on organic compound decomposition with TiO
2
/
UV investigated some factors that might inuence the degradation
rate of the organic compounds and proposed some kinetic models
to explain their results. In addition they used traditional UV lamps
to irradiate the photocatalysts [1416]. Nowadays, LEDs are
replacing traditional UV lamps in many applications, owing to the
much higher efciency in light-electricity conversion, since the
light emission by LEDs is induced by the recombination of
electrons and holes excess [1722]. Further advantages of LEDs
derive from the small dimensions, robustness, and the long lasting
(hundred thousands of hours compared to thousands of hours in
the case of classical lamps) [18,2328]. On the other hand, only few
papers regarding the mathematical modelling of the photocata-
lytic degradation of MB under visible light were developed. This
last issue is important to properly design a photocatalytic reactor,
effective in the treatment of organic dyes in very different
operating conditions. For this reason, this work has been focused
on the developing of a lumped mathematical model for
Journal of Environmental Chemical Engineering 1 (2013) 5660
A R T I C L E I N F O
Article history:
Received 7 February 2013
Accepted 17 March 2013
Keywords:
Methylene blue
Visible light
Batch photoreactor
Mathematical modelling
A B S T R A C T
The aim of this work was the developing and the verication of a mathematical model for the
photocatalytic degradation of methylene blue (MB) with N-doped TiO
2
under visible light in a batch
photoreactor. To dene the reaction system and its advancement, an innovative approach, conducted
both performing the mass balance on carbon in liquid and gaseous phase, and determining the reaction
products in gaseous evolved phase, was proposed. Total oxidation of MB was achieved, yielding CO
2
, SO
2
,
N
2
and Cl
2
as gaseous products. The mathematical modeling of the systemhas been developed by using
the LangmuirHinshelwood type kinetics for MB consumption. To consider the effect of photocatalyst
screening, a LambertBeer type relation for the effective light energy received by the N-doped TiO
2
particles was used. Moreover the dependence of reaction rate on photonic ux was modeled considering
that photons can be treated as immaterial reactants. Model parameters estimation was realized by
individuating the best agreement between the calculated values and experimental data as a function of
irradiation time. On the basis of these results, the accuracy of the model was tested in different
experimental conditions, evidencing the ability of the mathematical model to be predictive.
2013 Elsevier Ltd All rights reserved.
* Corresponding author. Tel.: +39 3207979024; fax: +39 089964057.
E-mail address: dsannino@unisa.it (D. Sannino).
Contents lists available at SciVerse ScienceDirect
Journal of Environmental Chemical Engineering
j ou r n al h o mepag e: w ww. el sevi er . co m / l ocat e/ j ec e
2213-3437/$ see front matter 2013 Elsevier Ltd All rights reserved.
http://dx.doi.org/10.1016/j.jece.2013.03.003
photocatalytic degradation of MB using an N-doped TiO
2
catalyst
active with visible light [2938]. The effects of many operating
factors such as initial MB concentration, N-doped TiO
2
dosage, and
visible light intensity were investigated and used to verify the
ability of the model to predict the experimental results.
Materials and methods
Synthesis and characterization of N-doped photocatalyst
N-doped TiO
2
photocatalyst (TD) was prepared by solgel
method, following indications of the modied synthetic route
described by Sato [29]. A volume of 100 mL ammonia aqueous
solution at 30 wt%, supplied by Carlo Erba, was quickly added to
25 mL of 97 wt% titanium tetraisopropoxide (TTIP by Sigma
Aldrich) at 0 8C during a vigorous stirring of the solution in which a
white precipitate was progressively formed. The precipitate was
then carefully washed with bidistilled water and centrifuged to be
separated. After the separation of settled solids, nally, the
obtained powders were dried and calcined at 450 8C for 30 min
to get N-doped TiO
2
. The nominal N/Ti molar ratio is equal to 18.6
and corresponds to an optimized catalyst formulation found in a
previous work [38].
The catalyst was characterized by X-ray diffraction (XRD).
Measurements were realized using an X-ray micro diffractometer
Rigaku D-max-RAPID, using Cu Ka radiation.
Table 1 reports the XRD analysis for a commercial undoped
titania in anatase form (PC50 from Millennium Inorganic
Chemicals) and for TD. The data indicate that the one crystalline
phase of TD, anatase, is mainly detected [39,40]. The band-gap
energy of TD was moved in the visible range from 3.3 eV (typical
value for undoped TiO
2
) to 2.5 eV [38].
Photocatalytic tests
In a typical activity test a dened amount of photocatalyst was
suspended in 100 mL of MB solution. The suspension was left in
dark condition for 2 h to reach the adsorption equilibrium,
checking the achieving of stable value of MB concentration, and
then photocatalytic reaction was initiated under visible light up to
3 h. The experiments were performed with a pyrex cylindrical
photoreactor (ID = 2.5 cm) equipped with a gas distributor device
to feed air (Q
air
= 150 cm
3
/min (STP)) or a mixture of He and O
2
(Q
mix
= 150 cm
3
/min (STP)), acting also as carrier for the gaseous
analysis, a magnetic stirrer to maintain the photocatalyst
suspended in the aqueous solution, and nally with a thermocou-
ple to monitor the temperature. The photoreactor was irradiated
by a strip composed by 30 white light LEDs (nominal power: 6 W)
whose emission spectrum is shown in Fig. 1. The LEDs strip was
positioned around the reactor so that the light source uniformly
illuminated the reaction volume. Slurry samples were collected at
xed time intervals, and centrifuged for 20 min at 4000 rpm for
removing photocatalyst particles. The centrifuged samples were
analysed to determine the change of MB concentration, measured
with a Perkin Elmer UV-Vis spectrophotometer at l = 663 nm. A
standard calibration curve was obtained for different MB
concentration, and allowed to convert absorbance to concentration
(mg/L) units. Gas phase analysis was performed by means of a
continuous CO, CO
2
, SO
2
Not-dispersive infrared analyzer (ABB
Advance Optima) and an on-line quadrupole mass detector (Trace
MS, ThermoElectron), following the trends of mass fragments in
the range 51000 m/z.
Results and discussion
Experimental results
A typical trend found during photocatalytic oxidation of MB
tests is reported in Fig. 2. The initial concentration of MB was
7.5 ppm.
Before the light switching on, an air stream was uxed through
the reactor in the dark at ambient temperature. In dark conditions
a decrease of MB concentration was observed during the rst hour
of the test reaching the value of 2.7 ppm and it was unchanged in
the second hour, indicating that the adsorption equilibrium of dye
on catalyst surface was reached [5]. The analysis of the gaseous
Table 1
XRD analysis for a commercial undoped titania in anatase form (PC50 from
Millennium Inorganic Chemicals) and for N-doped TiO
2
(TD).
2u degree Relative
intensity
2u degree Relative
intensity
PC50 25.3 1 TD 25.3 1
38.0 0.18 37.9 0.18
48.2 0.27 48.3 0.23
54.0 0.14 54.0 0.14
55.2 0.15 55.2 0.15
62.1 0.11 63.1 0.11
68.8 0.04 68.8 0.05
70.3 0.04 70.5 0.05
75.2 0.07 75.2 0.08
0
0.2
0.4
0.6
0.8
1
380 480 580 680 780
Wavelenght [nm]
O
p
t
i
c
a
l


p
o
w
e
r

[
a
.
u
.
]
Fig. 1. Emission spectrum of the white LEDs.
0
0.5
1
1.5
2
2.5
3
0 50 100 150 200
0
10
20
30
40
50
60
C
O
2

S
O
2

[
p
p
m
]
TOC removal
97%
Light on Light off
SO2
CO2
Run time [min]
M
B

c
o
n
c
e
n
t
r
a
t
i
o
n

[
p
p
m
]
Fig. 2. Decolourization of MB under visible light generated by white LEDs and gas
analysis of CO
2
and SO
2
by continuous analyzer. Aqueous phase; catalyst weight:
0.3 g; initial MB concentration: 7.5 ppm. Gaseous phase air ow rate:
150 Ncc min
1
.
D. Sannino et al. / Journal of Environmental Chemical Engineering 1 (2013) 5660 57
phase evidenced that no formation of CO
2
was observed. This
demonstrates that the disappearance of MB from the solution is
due to the ability of the catalyst to adsorb the dye on its surface.
As shown in Fig. 2 when LEDs were switched on, the MB
concentration decreased. After 130 min of irradiation the overall
conversion of MB was 91% and TOC removal was 97% (Fig. 2).
The analysis of gaseous stream coming from the photoreactor
during the irradiation revealed the presence of CO
2
and SO
2
. The
CO
2
observed in the gas phase was due to the oxidation of MB
which started at high reaction rate after few minutes of irradiation.
Through a comparison between the amount of carbon consumed
during the reaction (as assessed by the analysis of MB concentra-
tion in liquid phase) and the amount of carbon released as CO
2
in
the gaseous phase, the total carbon mass balance was closed to
about 100%. This allowed afrming that the MB is selectively
converted to CO
2
according to reaction (R).
C
16
H
18
ClN
3
S
43
2
O
2
! 16CO
2
9H
2
O SO
2

3
2
N
2

1
2
Cl
2
(R)
The pH of the solution during the photocatalytic test was in the
range 67 during the overall test. The occurrence of the reaction (R)
was conrmed by the analysis of gases through mass spectrometer.
When the LEDs modules were switched on, the detected products
in the outlet gaseous stream (Fig. 3) were the presence of nitrogen,
chlorine, carbon dioxide and sulphur dioxide, as identied from the
characteristic fragments m/z 28, 35, 44 and 64, respectively. No
presence of carbon monoxide was disclosed.
Adsorption of methylene blue in dark conditions
Considering that the adsorption equilibrium was reached after
2 h [5] of run time, the behaviour of the amount of MB adsorbed on
catalyst (C
*
) as a function of the concentration of MB in solution
(C
0
) is similar to a Langmuir adsorption isotherm (Fig. 4 insert).
Thus for the adsorption of MB on the active surface [41], it is
possible to write:
C


b C
0
1 b C
0
(1)
where C* is the amount of MB adsorbed on catalyst (g
MB
/g
TD
). C
m
is
the maximum absorbable value of C*. C
0
is the concentration of MB
in solution after dark adsorption (mg L
1
). b is the adsorption
constant of MB (L mg
1
).
The Langmuir isotherm can be rearranged to give:
C
0
C


1
b C
m

1
C
m
C
0
(2)
Accordingly, a plot of C
0
/C* as a function of C
0
produces a
straight line with: slope = 1/C
m
and intercept = 1/bC
m
(Fig. 4).
The value of b was calculated from Eq. (2) utilizing the data
reported in Fig. 4 and it was equal to 0.82 (L mg
1
).
Mathematical modelling
The mathematical model has been realized considering that in
the batch reactor under white LEDs irradiation, occur mainly the
catalytic oxidation of MB (R).
MB mass balance can be written as:
V
dCt
dt
rC; I W
TD
(3)
where V is the solution volume (L). C
1
(t) is the MB concentration
(mg L
1
). r is the reaction rate (g L
1
min
1
). W
TD
is the catalyst
amount (g). I is the light intensity reaching the photocatalyst
surface (mW cm
2
).
The initial conditions are:
t 0 C C
in
The kinetic expressions employed in the model is the following
r K
1
f
C
g
I
(4)
f
c

b C
1 b C
(5)
g
I

a I
1 a I
(6)
where K
1
is the kinetic constant (mg g
1
min
1
); a is the light
absorption coefcient (cm
2
mW
1
); I is the light intensity reaching
the photocatalyst surface (mW cm
2
).
Eq. (5) is similar to the LangmuirHinshelwood rate law used in
other studies [42].
In the hypothesis of keeping the reactant concentration
constant, the dependence of reaction rate on photonic ux
(Eq. (6)) is the same reported in literature [12,43], which presented
a simple approach for the design of photocatalytic reactors,
considering that photons can be treated as immaterial reactants.
This expression allows taking into account that only a fraction of
light intensity reaching the photocatalyst particle, is absorbed by
itself. This effect was evaluated utilizing the parameter a

5 15 25 35 45 55 65
Light on Light off
m/z=44 m/z=28
m/z=35
m/z=64
M
S

s
i
g
n
a
l

[
a
.
u
.
]
Time [min]
Fig. 3. Outlet gaseous products traces (a.u.) of chlorine (m/z = 35), nitrogen (m/
z = 28), carbon dioxide (m/z = 44) and sulphur dioxide (m/z = 64), as a function of
run time. Initial aqueous MB concentration 10 ppm; incident light intensity
32 mW cm
2
. He and O
2
ow rate: 150 Ncc min
1
.
y = 98.61x + 122.43
R
2
= 0.9999
0
2000
4000
6000
8000
10000
0 10 20 30 40 50 60 70 80 90 100
C
0
[mgL
-1
]
C
0
/
C
*

[
-
]
0
0.004
0.008
0.012
0 20 40 60 80 100
C
0
[mg L
-1
]
C
*
1/Cm
1/bCm
Fig. 4. Evaluation of MB adsorption constant by equilibrium adsorption curve of MB
on N-doped TiO
2
(insert).
D. Sannino et al. / Journal of Environmental Chemical Engineering 1 (2013) 5660 58
Moreover, it is important to consider that the availability of
active sites increases with the catalyst concentration in the
suspension, but the light penetration decreases with the catalyst
concentration in the suspension due to screening effect [44]. This
suggests that only a part of the light intensity entering in the
reactor, will be reach the photocatalyst particles. To consider this
screening effect, a rst order correlation, similar to LambertBeer
law, for the effective light energy received by the TiO
2
particles was
used:
I I
0
e
k
I
TiO
2

(7)
where k
I
is the specic extinction coefcient per unit catalyst mass
(L mg
1
); I is the light intensity reaching the photocatalyst surface
(mW cm
2
); I
0
is the light intensity incident on the reactor surface
(mW cm
2
); [TiO
2
] is the catalysts dosage (mg L
1
).
Utilizing Eqs. (4) and (7), MB mass balance can be written as:
V
dCt
dt
K
1

b Ct
1 b Ct

a I
0
e
k
I
TiO
2

1 a I
0
e
k
I
TiO
2

W
TD
(8)
Eq. (8), together with the initial condition, was solved by the
Eulero iterative method. Primary goal of the simulation by
mathematical model is to identify the constants K
1
, a, and K
I
by
tting experimental data reported in Fig. 5 as a function of
irradiation time. The tting procedure was realized by using the
least squares approach obtaining the value of K
1
: 0.46
(mg g
1
min
1
), a: 0.000925 (cm
2
mW
1
) and K
I
: 0.012 (L mg
1
).
After obtaining the model parameters, another series of
experiments in which the initial MB concentration was varied
from 6.5 to 95 ppm were carried out in order to analyse the ability
the model to predict the experimental data. The obtained results
are shown in Fig. 6. In this series of experiments, the incident light
intensity (I
0
) and N-TiO
2
dosage are kept constant equal to 0.3 g
and 32 mW cm
2
, respectively. At xed reaction times, the
increase of MB initial concentration determined a decrease of
the photocatalytic activity. This could be due to the increase of
colour intensity of the solution that reduces the light penetration
into the aqueous medium, meaning that the path length of photons
inside the solution decreases [38]. The calculated values in all case
are in good agreement with the experimental data. It is important
to note that for the higher concentration (90 ppm), the model is
also able to predict correctly the experimental data obtained after
24 and 25 h of irradiation time, as reported in Fig. 6.
Fig. 7 shows the effect of the amount of N-TiO
2
catalyst, on the
conversion of MB in the presence of white LEDs. At xed irradiation
time, the MB concentration decreased by increasing the N-TiO
2
amount as shown by the experimental results. For a content of
catalyst equal to 0.3 g, the complete decolourization was obtained
after about 250 min. For a catalyst amount of 1 and 1.5 g, the total
conversion of MB was achieved quickly and in particular after 80
and 50 min, respectively. Also by changing the catalyst dosage in
the solution, the transient predicted results obtained by the
mathematical model agree with the experimental results using the
same set of parameters determined by the tting procedure with
the data reported in Fig. 4.
0
1
2
3
4
5
6
7
8
0 50 100 150 200 250 300
Irradiation time [min]
model
experimental
M
B

c
o
n
c
e
n
t
r
a
t
i
o
n

[
p
p
m
]
Fig. 5. Comparison between model calculation and experimental data to nd the
model constant. Catalyst weight: 0.3 g and incident light intensity: 32 mW cm
2
.
0
0.2
0.4
0.6
0.8
1
1.2
0 50 100 150 200 250 300
Irradiation time [min]
C
/
C
i
n
experimental experimental
experimental experimental
experimental experimental
model
0.05 g
0.1 g
0.2 g
0.3 g
1 g
1.5 g
Fig. 7. Experimental and predicted data as a function of catalyst weight; initial MB
concentration: 10 ppm; incident light intensity: 32 mW cm
2
.
0
0.2
0.4
0.6
0.8
1
1.2
0 200 400 600 800 1000 1200 1400
C
/
C
i
n
experimental
experimental
experimental
model model
90 ppm
10 ppm
6.5 ppm
Irradiation time [min]
Fig. 6. Experimental and predicted data as a function of MB initial concentration;
catalyst weight: 0.3 g; incident light intensity: 32 mW cm
2
.
0
1
2
3
4
5
6
7
8
0 50 100 150 200 250
experimental
experimental
experimental
model
16 mW cm
-2
28 mW cm
-2
32 mW cm
-2
Irradiation time [min]
M
B

c
o
n
c
e
n
t
r
a
t
i
o
n

[
m
g
/
L
]
Fig. 8. Experimental and predicted data as a function of catalyst weight; initial MB
concentration: 6.5 ppm; catalyst weight: 0.3 g.
D. Sannino et al. / Journal of Environmental Chemical Engineering 1 (2013) 5660 59
The next series of experiments were carried out increasing the
incident light intensity from 8 to 32 mW cm
2
(Fig. 8). As expected,
the decolourization reaction rate increased with the LEDs light
intensity. Finally, also in this case, the experimental results of MB
decolourization were satisfactorily predicted by the model
developed in this study.
Conclusions
The photocatalytic degradation of methylene blue (MB) with N-
doped TiO
2
under visible light in a batch photoreactor was
investigated, performing the mass balance on carbon both in liquid
and in gaseous phase in different operative conditions. This
innovative approach lead to conclude that total oxidation of MB
occurs in the investigated reaction conditions, while the analysis of
the reaction products in gaseous evolved phase has evinced the
formation of CO
2
, SO
2
, N
2
and Cl
2
as gaseous products. A
mathematical model for the photocatalytic degradation of
methylene blue (MB) with N-doped TiO
2
under visible light in
the batch photoreactor was developed. The mathematical model-
ing was based on LangmuirHinshelwood type kinetics for MB
consumption. To consider the effect of photocatalyst screening, a
LambertBeer type relation for the effective light energy received
by the N-doped TiO
2
particles was used. Moreover the dependence
of reaction rate on photonic ux was modelled considering that
photons can be treated as immaterial reactants and it was similar
to Langmuir behaviour. Model parameters estimation was realized
by individuating the best agreement between the calculated values
and experimental data as a function of irradiation time. On the
basis of these results, the accuracy of the model was tested in
different experimental conditions, resulting able to be predictive in
different operating conditions.
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