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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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