Adsorption of textile dye Reactive Red 120 by the chitosanFe(III)-crosslinked:

Batch and xed-bed studies

Carla Albertina Demarchi, Mayara Campos, Clo vis Antonio Rodrigues *
Nucleo de Investigacoes Qumico-Farmaceuticas (NIQFAR), Universidade do Vale do Itaja (UNIVALI), Itaja 88302-202, Santa Catarina, Brazil
Introduction
Many industries, such as the textiles, leather, cosmetics, paper,
printing and plastics industries, use synthetic dyes as part of their
production processes. Efuents from these industries therefore
contain various kinds of synthetic dye stuffs [1]. Dye contamina-
tion in aqueous wastewater from industries is a serious problem
because dyes are not biodegradable, and tend to suppress
photosynthetic activity in aquatic habitats by preventing the
penetration of sunlight [2]. Moreover, most of these dyes can cause
allergy, dermatitis, and skin irritation [3], and can also lead to
genetic mutations in humans [4].
Compared to traditional methods of decontamination of
efuents containing dyes, the adsorption method is the best
alternative, and has been widely used to remove pollutants from
efuents [5], due to its low cost, simplicity of design, availability
and ability to treat dyes in more concentrated form [6,7]. Most
commercial systems use activated carbon as adsorbent to remove
dyes in water, because of its great adsorption capacity. However,
its widespread use is restricted due to its cost. In order to decrease
the cost of treatment, some attempts have been made to nd low-
cost alternative adsorbents [1]. Chitosan is derived from a natural
polysaccharide, chitin, which is the second most abundant
polysaccharide in nature. It is relatively cheap and exhibits higher
dye adsorption capacities [8,9].
Absorbents containing iron have received a great deal of
attention, due to their chemical stability and high absorption
capacity [1013]. Chitosaniron complex has been used to remove
oxyanions, such as, Cr (VI) [14,15], As(III) [16] and As (V) [17] from
aqueous solutions, however the uses of chitosaniron complex for
adsorption dyes have not been reported.
A great number of publications related to adsorption of textile
dyes by magnetic chitosan and its derivatives have recently been
reported in the literature [10,1822]. However, the use of magnetic
particles is restricted to the separation process using the batch
method, and it is not appropriate for xed-bed process. Another
disadvantage of magnetic particles, as compared with the
chitosaniron complex, is related to the fact that their synthesis
involves many steps. On the other hand, the ironchitosan
complex is easily synthesized.
This paper presents a study of the use of chitosaniron(III)
crosslinked with glutaraldehyde (Ch-Fe), as an adsorbent for the
textile anionic dye Reactive Red 120 (RR120). This work involves
studies of equilibrium and kinetics of adsorption in different
conditions of pH and temperature, study of recovery and reuse of
the adsorbent, and also factorial design in batch studies, and xed-
bed studies to predict adsorption on an industrial scale.
Experimental
Materials
The chitosan (viscosimetric molecular weight of 2.5 10
5
g/
mol, and desacetylation degree of 85%) was obtained from
Purifarma (Sao Paulo). The dye Reactive Red 120 (Procion Red
HE-3B; MF: C
44
H
24
Cl
2
N
14
O
20
S
6
Na
6
; MW: 1469.98) was kindly
Journal of Environmental Chemical Engineering 1 (2013) 13501358
A R T I C L E I N F O
Article history:
Received 16 August 2013
Received in revised form 7 October 2013
Accepted 8 October 2013
Keywords:
Reactive Red 120
Chitosaniron(III)
Textile wastewater
Factorial design
A B S T R A C T
This paper presents a study of the use of chitosaniron(III) crosslinked with glutaraldehyde (Ch-Fe) as an
adsorbent for the textile anionic dye Reactive Red 120 (RR120) in batch and xed-bed systems. The
maximum adsorption capacity was calculated from the adsorption isotherms, and well tted by the
LangumirFreudlich isothermmodel. The process followed the kinetic model of pseudo-second-order. In
xed-bed studies, the Thomas, Adams-Bahort and Clark models were applied to the breakthrough
curves. The thermodynamic parameters showed that the adsorption process is spontaneous and
favorable. The adsorbent can be easily regenerated and reused. The adsorption of the RR120 was
optimized using a 3
3
factorial design, and the initial pH of the dye solution had a signicant effect.
2013 Elsevier Ltd. All rights reserved.
* Corresponding author at: Universidade do Vale do Itaja, Itaja CEP 88302-202,
SC, Brazil. Tel.: +55 47 3341 7664; fax: +55 47 3341 7600.
E-mail address: crodrigues@univali.br (C.A. Rodrigues).
Contents lists available at ScienceDirect
Journal of Environmental Chemical Engineering
j our nal homepage: www. el sevi er . com/ l ocat e/ j ece
2213-3437/$ see front matter 2013 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.jece.2013.10.005
donated by Trento Brasil Beneciamento Textil (Nova Trento,
Brazil). All the other reagents used were of analytic grade, and were
used without purication. The adsorbent Ch-Fe was prepared and
characterized as described by Klepka et al. [23]. The average
particle size was determined using SEM (scanning electron
microscopy) and was 4.7 1.7 mm [16]. The zero-point of charge
(pH
zpc
) was determined by potentiometric titration [24] and was
found to be 8.5. The quantity of iron in the sample was determined by
colorimetric methods using 1.10 phenanthroline and a double beam
UVvis spectrophotometer (Spectrovision mod. DB 188S, China), and
was found to be 80.5 mg/g.
Batch studies
Adsorption kinetics
The adsorption kinetics were performed in the system,
thermostated at 25 8C using 25 mg of adsorbent, 20 mL of
RR120 solution 400 mg/L, under continuous agitation. Ali-
quots were removed at certain time intervals (5, 15, 30, 45,
60, 90 and 120 min), the adsorbent was separated by
centrifugation, and the quantity of dye present in the
supernatant was spectrophotometrically determined based
on an analytical curve (adsorbance at 540 nm vs. dye
concentration), using a UVvis spectrophotometer Spectro-
vision mod. DB 188S, China.
Adsorption isotherms
The adsorption isotherms were obtained using a thermostatic
bath with continuous agitation, with 20 mL of dye solution at
concentrations between 100 and 500 mg/L containing 25 mg of
adsorbent, and agitation time of 60 min. The studies were
conducted in buffer solution with a concentration of 0.05 M:
monochloroacetic acid (pH 2.0), sodium acetate (pH 5.0) and
(tris)hydroxymethyl aminomethane (pH 9.0) to evaluate the pH
effect. To evaluate the effect of temperature, the isotherms were
performed in non-buffered dye solution (pH 3.6) at 25 8C, 40 8C
and 55 8C. After agitation, the solutions were centrifuged and the
dye concentration was determined in a spectrophotometer at
540 nm.
The adsorption capacity (q
e
) was calculated according to Eq. (1)
[22]:
q
e

C
0
C
e
v
m
(1)
where C
0
and C
e
(mg/L) are the initial and equilibrium dye
concentrations in the liquid phase, respectively, v (L) is the volume
of solution and m (g) is the amount of adsorbent.
Regeneration and reuse of the adsorbent
For the regeneration, 100 mg of the adsorbent saturated with a
RR120solutionwas used. Thedye was removedwith50 mL of NaOH
0.1 M. The dye concentration was determined as described
previously. The adsorbent was then washed with HCl 0.01 M and
distilled water to neutralize the excess NaOH and recondition the
adsorbent. This procedure was repeated three times for each
adsorption/regeneration cycle.
Factorial analysis
The studies using systems of factorial design of experiments
were performed using the variables initial concentration (C
i
), pH
solution and agitation temperature. Table 1 shows the levels of the
independent factors and experimental designs. The software
Statistica
1
version 6.0 was used to t the experimental results
from the factorial design, and the main effects and interactions
between the factors were determined.
Fixed-bed studies
The xed-bed column was made of polyethylene tube with an
inner diameter of 0.75 cm and height of 5.5 cm. A sintered glass
was attached to the bottomof the column. A known quantity of the
material was packed in the column to give the desired bed heights
of the adsorbent: 17 mm, 36 mm and 64 mm. RR120 solution with
concentration of 100 mg/L at non-buffered pH (3.6) was pumped
through the column at a ow rate of 2.0 mL/min controlled by a
peristaltic pump (Spectrovision, mod PP2).
The RR120 solutions at the outlet of the columnwere collected at
regular time intervals. Aliquots were removed at certain time
intervals, and the quantity of dye present in the efuent was
spectrophotometrically determined at a wavelength of 540 nm. The
amount of RR120 adsorbed was calculated based on the difference
betweentheir inlet concentration(C
0
) andoutlet concentrations (C
t
).
The breakthroughcurves, which showed the performance of the
xed-bed column, were plotted in terms of normalized concen-
tration, C
t
/C
0
, (which is dened as the ratio of efuent dye
concentration, C
t
(mg/L), to inlet dye concentration, C
0
(mg/L)) as a
function of time. The experimental curves were mathematically
modeled using non-linear regression, and the parameters were
estimated using the software OriginPro 8.5.
Results and discussion
Adsorption kinetic
The kinetic behavior of the adsorption process was studied with
an initial concentration of 400 mg/L, pH 3.6 (non-buffered dye
Table 1
Matrix of factorial design and results of experiments.
Experiment pH (A) Temperature (B) C
i
(C) Amount adsorbed (mg/g)
1 0 + 227.5
2 0 0 0 169.6
3 + 0 315.8
4 + + 0 109.3
5 0 + 312.8
6 + 0 81.6
7 0 + 246.4
8 0 286.4
9 0 235.9
10 + 0 96.0
11 0 0 0 169.6
12 0 0 0 169.6
13 0 + + 255.3
14 + 0 + 112.7
15 0 208.1
pH: 2(), 5(0), 8(); Temperature: 558C(+), 408C(0), 258C(); concentration: 300mg/L(), 400mg/L(0), 500mg/L(+).
C.A. Demarchi et al. / Journal of Environmental Chemical Engineering 1 (2013) 13501358 1351
solution), temperature 25 8C and with 25 mg of Ch-Fe. It can be
observed from Fig. 1 that RR120 uptake on Ch-Fe was a very fast
process. The amount of adsorption increased rapidly in the rst
5 min, contributing to 80% of the total adsorption. This same
behavior was observed for the adsorption of the acid dyes by a
magnetic chitosanFe(III) hydrogel in alkaline condition [18].
For examination of the controlling mechanisms of the adsorp-
tion process, such as chemical reaction, diffusion control and mass
transfer, several kinetic models were used to test the experimental
data. The pseudo-rst-order, pseudo-second-order and intrapar-
ticle models in non-linear forms were used (Fig. 2). The pseudo-
rst-order model [25] is represented by Eq. (2):
q
t
q
e
1 e
k
1
t
(2)
where k
1
(1/min) is the constant of the rst order adsorption, q
e
(mg/g) is the amount of dye adsorbed at equilibrium and q
t
(mg/g)
is the amount of dye adsorbed at time t (min).
The pseudo-second-order model [26], is represented by Eq. (3).
q
t

k
2
q
2
e
t
1 k
2
q
2
e
t
(3)
where k
2
(1/min) is the constant of the second order adsorption, q
e
(mg/g) is the amount of dye adsorbed at equilibrium and q
t
(mg/g)
is the amount of dye adsorbed at time t (min).
Another kinetic model used was the intraparticle diffusion [27]
(Eq. (4))
q
t
k
i
t
0:5
(4)
where k
i
(mg/g min
1/2
) is the intraparticle diffusion constant and q
t
(mg/g) is the amount of dye adsorbed at time t (min).
Based on its calculated q
e
value of 254.2 mg/g, which is close to
the experimental values, q
ex
(269.9 mg/g), the pseudo-second-
order equation kinetic was the best kinetic model to explain the
adsorption process, indicating a chemisorption process. The
pseudo-second-order kinetic model was also the best kinetic
model observed for the other adsorbents in the adsorption of acid
dyes [18,2831] (Table 2).
Adsorption isotherms
Isotherm adsorption models are useful for predicting the
adsorption parameters and optimizing the design of an adsorption
system. The adsorption equilibrium isotherm data were studied
using the Langmuir (Eq. (5)) [32], Freundlich (Eq. (6)) [33] and
LangmuirFreundlich (Eq. (7)) [34] models (Fig. 2). The non-linear
form of the isotherm models are given as:
q
e

K
L
q
m
C
e
1 K
L
C
e
(5)
q
e
K
F
C
1=n
e
(6)
q
e

K
LF
q
m
C
n
e
1 K
LF
C
n
e
(7)
where C
e
(mg/L) is the equilibrium concentration of RR120
adsorbed and q
e
(mg/g) is the experimental adsorption capacity
of RR120, Langmuir constants q
m
(mg/g) and K
L
(L/mg) are the
monolayer adsorption capacity and afnity of adsorbent toward
the adsorbate, respectively. Freundlich constants K
F
(L/mg) and n
give information on the extent of adsorption and the degree of
nonlinearity between the adsorption and the solution concentra-
tion, respectively. Absorption intensity is evaluated by the inverse
of n (1/n).
The Langmuir and LangmuirFreundlich models indicate that
the maximum adsorption capacity of RR120 (Table 3) increases as
the temperature increases, and decreases as the pH decreases. The
adsorption mechanism of adsorption, in this case, is electrostatic
interactions between the adsorption sites of the positively charged
Ch-Fe (Fe
3+
) and the SO
3

groups present in the dye RR120. In Ch-

Fe crosslinked with glutaraldehyde, the free NH
2
groups are not
present due to a reaction with glutaraldehyde. As a result, non-
specic interactions between the (NH
3
+
) and sulfonate groups of

0 20 40 60 80 100 120
0
50
100
150
200
250
300
pseudo-first order
pseudo-second order
Intraparticle
q
t
(
m
g
/
g
)
Time (min)
Fig. 1. Adsorption kinetics of RR120 by Ch-Fe. RR120 concentration 400 mg/L
(20 mL), 25 mg of Ch-Fe, pH 3.6, temperature 25 8C.

Fig. 2. Adsorption isotherms of the RR120 by Ch-Fe, temperature 25 8C, pH 5.0.

Table 2
Kinetic parameters of the adsorption of the dye RR120 by the Ch-Fe.
Pseudo-rst order Pseudo-second order Intraparticle
k
1
(min) q
e
(mg/g) r
2
k
2
(g/mg min
1/2
) q
e
(mg/g) r
2
C (mg/g) q
e
(mg/g) r
2
4.2510
1
246.69 0.9766 3.8510
3
254.20 0.9859 105.95 18.273 0.5938
C.A. Demarchi et al. / Journal of Environmental Chemical Engineering 1 (2013) 13501358 1352
the dye reported in the literature [29] are not possible. The
increased adsorption capacity in acid pH can be explained by the
competition between OH

(present in a buffered medium) and dye

on the Fe
3+
binding sites of the adsorbent. Similar results were
recently reported for the adsorption of anionic dyes [35]. This
behavior usually occurs in adsorbent containing Fe
3+
by the
formation of Fe(OH)
3
on the adsorbent surface.
Comparing the different adsorption models, the results show
that the model that was best correlated with the adsorption
process of RR120 by Ch-Fe was the LangmuirFreundlich model,
because it showed higher correlation coefcients, when compared
with the other two models. The LangmuirFreundlich model is a
combination of the Freundlich and Langmuir models. This model
assumes that at low concentrations of adsorbate, this model
approaches the Freundlich model (which describes heterogeneous
systems) and in high concentrations of adsorbate, provides
monolayer adsorption capacity that is characteristic of the
Langmuir isotherm.
Table 4 shows a comparison of the maximum adsorption
capacity of the dye RR120 of various adsorbents. The q
e
(mg/g) is
according to the Langmuir model. The adsorbent Ch-Fe has a
higher capacity than other adsorbents reported in the literature.
Thermodynamic parameters
The thermodynamic parameters, like change in Gibbs free
energy (DG8, kJ/mol), enthalpy (DH8, kJ/mol), and entropy (DS8, J/
mol K) were determined using Eqs. (8)(10) [44]:
K
D

C
s
C
e
(8)
DG

RT lnK
D
(9)
lnK
D

DS

R

DH

RT
(10)
where K
D
is the equilibrium constant, C
s
is the amount of dye
adsorbed (mg/g), C
e
is the equilibrium concentration (mg/L), R is
the universal gas constant (8.314 kJ/mol), and T is absolute
temperature (K). By plotting a graph of ln K
D
versus 1/T, DH8
and DS8 values can be determined from the slopes and intercept,
respectively.
The results are shown in Table 5. The positive DS8 value
indicates the increased degree of freedom of the system,
suggesting randomness at the solid/liquid interface. The negative
value of DH8 shows the adsorption to be exothermic. The negative
values of DG8 demonstrate that the dye adsorption is spontaneous
and that the systemis not gaining energy fromany external source
[28].
Regeneration and reuse of the adsorbent
The regeneration of the adsorbent is important for lowering the
cost of the adsorption process and for possibly recovering the
pollutant extracted from wastewater [18]. Table 6 shows the
results of RR120 desorption and adsorbent reuse. With the
exception of the rst cycle, there was no signicant difference
in the ability to remove the dye in cycles of adsorption/desorption.
These results show that the adsorbent is stable when subjected to
the process of removing and reconditioning by adding NaOH0.5 M
and HCl 0.01 M. The capacity of adsorption reduces slightly in each
cycle, and in the last cycle, the reduction was 30%. Therefore, Ch-Fe
can be easily regenerated and reused.
Factorial analysis
The goal of the factorial design was to nd the parameters of the
process that have a signicant inuence on the process, and to nd
Table 3
Study of temperature and pH variation on the adsorption isotherms of the dye RR120.
Langmuir Freundlich LangmuirFreundlich
K
L
(L/g) q
m
(mg/g) r
2
K
F
(L/g) n r
2
K
LF
(L/g) q
m
(mg/g) n r
2
T (8C)
a
25 0.3920 290.70 0.8117 111.10 0.219 0.8417 0.3102 433.84 0.427 0.8473
40 0.3747 331.35 0.7547 131.67 0.207 0.6800 0.0033 309.94 7.241 0.8487
55 0.5224 361.96 0.8543 230.68 0.095 0.7465 0.0135 350.42 3.250 0.9882
pH
b
2.0 0.4657 336.77 0.7972 192.38 0.120 0.9579 0.7198 380.57 0.486 0.8946
5.0 0.4387 230.08 0.9399 100.16 0.177 0.9605 0.4403 283.57 0.493 0.9908
9.0 0.0503 135.69 0.8484 36.635 0.229 0.9382 1.393 14.756 0.0381 0.9353
a
pH 3.6 non-buffered dye solution.
b
Temperature 258C.
Table 4
Comparison of different sorbents in the adsorption of textile dye RR120. Maximum
adsorption capacity calculated with the Langmuir model.
Adsorbent q
e
(mg/g) Reference
Ch-Fe 361.9 In this study
Chitosan/modied montmorillonite 5.6 [36]
Commercial activated carbon 293.1 [37]
Jatropha curcas shells 42.5 [38]
Chara contraria 112.8 [39]
Activated carbonaceous Brazilian pine-fruit-shell 275.0 [40]
nanoparticles of Fe
3
O
4
166.67 [41]
Cetylpyridiniun-Bentonite 81.97 [42]
Pistachio husk 324.88 [43]
Table 5
Thermodynamic parameters for the adsorption of RR120 on the Ch-Fe.
DS8 (J/mol K) DH8 (kJ/mol) DG8 (kJ/mol)
248.32 71.2 2.80 (258C)
6.46 (408C)
10.26 558C
Table 6
Desorption of RR120 and reuse of Ch-Fe. Dye concentration 500mg/L; volume of
solution 80mL, 100mg of adsorbent; temperature 558C, pH 3.6, contact time
60min.
Cycle RR120 adsorbed (mg/g) Desorption (%)
1 361.2 57.7
2 321.8 81.4
3 304.1 83.4
4 249.3 84.8
C.A. Demarchi et al. / Journal of Environmental Chemical Engineering 1 (2013) 13501358 1353
the setting values of the principal parameters for setting the results
of the process on the desired values [45].
The matrix codes used for the factorial design, and the results,
are shown in Table 1. The effects, standard error, t value, p value,
errors of coefcients and regression coefcient are shown in
Table 7.
The quadratic model was used for the initial calculation of the
regression
Q
e
b
0
b
1
x
A
b
2
x
2
A
b
3
x
B
b
4
x
2
B
b
5
x
C
b
6
x
2
C
b
7
x
A
x
B
b
8
x
A
x
C
b
9
x
B
x
C
(11)
where b
0
is the global mean, b
i
represents the regression
coefcient relating to the main factor effects and interactions,
and A, B and C represent the pH, temperature and initial
concentration, respectively.
Replacing the b
i
coefcients with their respective values
(Table 6), it was possible to derive an equation model linking
the parameters to the adsorption of the dye RR120.
Q
e
207:2 187:4pH 8:15pH
2
17:9T 40:3T
2
43:2Ci 24:4Ci
2
8:25pHT
22:3pHCi 5:25CiT
(12)
The values of the effects of principal factors are shown in the
Pareto graph in Fig. 3 (horizontal columns). To indicate the
minimum statistically signicant effect, for p = 0.05, a vertical line
was drawn. The linear factors pH (A), quadratic factor temperature
(B
2
), initial concentration (C) and quadratic factor initial concen-
tration (C
2
) are the most signicant. The graph shows that the
effect of pH is the most important effect, followed by the
temperature.
Fig. 4 shows the graphs, constructed using the surface response
method that correlates with the initial concentration factors
temperature pH (Fig. 4A), (C
i
) pH (Fig. 4B) and C
i
tempera-
temperature (Fig. 4C). The experiments that resulted in Fig. 4A
were conducted with an initial concentration of 400 mg/L, and the
pH in this condition is an essential factor in determining the
amount of dye adsorbed. In the case of Fig. 4B, the experiments
were conducted at a constant temperature of 40 8C, and pH was
also a major factor responsible for the adsorption of the dye. The
experiments that resulted in Fig. 4C were conducted at pH 5.0 and
in this case, C
i
and temperature had no signicant effect on
adsorption of the dye.
Fixed-bed studies
The objective of using a xed-bed system is to reduce the
concentration of a substance that is considered, by the government
agencies, to be polluting up to a predetermined value. At the
beginning of the adsorption operation, when the sorbent material
is still unused, the nal concentrationis actually lower than what is
permitted by the regulatory agencies, but as adsorption proceeds
and the sorbent material gradually becomes saturated, the efuent
concentration increases and reaches the so-called breakthrough
point, or breakdown of the efciency of the column [46].
The desired breakthrough volume (V
b
) was determined at 5% of
the inlet solution concentration. The ow through the tested
column was continued until the RR120 concentration of the
column efuent approached 95% of the inuent solution concen-
tration, indicating the exhaustion volume (V
e
).
The capacity at exhaustion was determined by calculating the
total area below the breakthrough curve (plot of C
t
/C
0
against t
(min)). The column capacity was estimated by Eq. (13) [47].
q
total

Z
ve
v
b
C
E
C
B
dQ
x
(13)
where q
total
is the column capacity adsorption (mg), C
B
and C
E
are
breakthrough and exhaustion RR120 concentration (mg/L) respec-
tively, Q is the ow rate in (mL/min) and x is the Ch-Fe mass (g).
The value of adsorption capacity, determined experimentally,
q
e(exp)
(mg/g) is calculated as follows [48]:
q
eexp

q
total
x
(14)
where x (g) is the total dry weight of the adsorbent in the column.
The breakthrough curves of the (C
t
/C
0
) versus time for various
bed depth of 17, 34 and 66 mm (150, 100 and 150 mg), at a
constant owrate of 2 mL/min and RR120 and initial concentration
of 100 mg/L, are shown in Fig. 5. FromFig. 5, the breakthrough time
and exhaustion time increased with the increase in bed depth. As
the bed depth (Ch-Fe mass) and number of active sites of
adsorption (Fe
3+
) increased, RR120 had more time to contact with
Table 7
Effect estimated coefcients for the adsorption of the dye RR120.
Effect Standard error Effect T value P value Coefcient Standard error of coefcient
Interactions media 207.18 2.823407 73.380 0.000000 207.18 2.823407
pH 187.47 6.915906 27.108 0.000001 93.738 3.457953
pH
2
8.150 5.089969 1.6012 0.170234 4.0750 2.544984
T 17.900 6.915906 2.5882 0.048941 8.9500 3.457953
T
2
40.325 5.089969 7.9224 0.000516 20.1625 2.544984
C
i
43.225 6.915906 6.2501 0.001537 21.6125 3.457953
C
i
2
24.200 5.089969 4.7544 0.005084 12.1000 2.544984
pHT 8.250 9.780567 0.8435 0.437425 4.1250 4.890284
pHC
i
22.300 9.780567 2.2800 0.071535 11.1500 4.890284
TC
i
5.250 9.780567 0.5368 0.614435 2.6250 4.890284
R
2
=0.99431; R
2
adjusted 0.98406.

Fig. 3. Pareto graph of the effects.

C.A. Demarchi et al. / Journal of Environmental Chemical Engineering 1 (2013) 13501358 1354
Ch-Fe, resulting in higher removal efciency of RR120 in the
column. The higher bed depth therefore resulted in a decrease in
the efuent concentration at the same service time. The
parameters shown in Table 8 V
b
and V
e
depend on the higher
of the bed and increased with bed depth. High adsorption capacity
in breakthrough (q
b
) and adsorption capacity in exhaustion (q
e
)
were observed at the highest bed depth, due to an increase in the
surface area of adsorbent, providing more binding sites for the
adsorption.
The success of the column design for the adsorption process
requires predicting the effect prole concentration-time curves of
the efuents. Over the years, various mathematical models have
been developed to analyze the column studies in the laboratory, in
order to plan columns on an industrial scale. This study applies the
mathematical models of Thomas, Adams-Bohart and Clark in non-
linear forms.
The Adams-Bohart model is used to describe the initial part of
the breakthrough curve. This model assumes that the adsorption
rate is proportional to both the residual capacity of the adsorbent
and the concentration of the adsorbing species, and is expressed as
[49]
C
t
C
0
exp k
AB
C
0
t k
AB
N
0
Z
F

(15)
where C
0
is the inlet concentration (mg/L), C
t
is the exit outlet
concentration (mg/L), k
AB
is the mass transfer coefcient (L/

Fig. 4. Surface response amount adsorbed (mg/g). (A) Effect of temperature and pH. (B) Effect of the initial concentration (C
i
) and pH. (C) Effect of C
i
and temperature. In all
experiments, the agitation time (1 h) and the amount of adsorbent (25 mg) and volume of solution (20 mL) were kept constant.
Table 8
Column data and parameters obtained at different bed heights on the adsorption of
the dye RR120. Initial concentration 100mg/L, ow rate 2mL/min.
Bed height (mm) 17 36 64
V
b
(mL) 60 80 350
V
e
(mL) 340 600 850
q
b
(mg/g) 60 80 350
q
e
(mg/g) 250 510 680
C.A. Demarchi et al. / Journal of Environmental Chemical Engineering 1 (2013) 13501358 1355
mg min), N
0
is the saturation concentration (mg/L), Z is the bed
height (cm) and F is the linear velocity (1/cm).
Plotting C
t
/C
0
against t also gave the breakthrough curves
predicted by the Bohart-Adams model (Fig. 5C), and the
experimental points. For all breakthrough curves using non-
linear regression analysis, respective values of K
AB
and N
0
were calculated and are presented in Table 9, along with
the correlation coefcients (r
2
). Table 9 also shows that the
values of K
AB
and N
0
increased with increasing bed depth.
This shows that the overall system kinetics was dominated
by external mass transfer in the initial part of adsorption in
the column [48].
Another model that was employed is the Thomas model, which
is one of the most widely used models in column performance
theory. The Thomas model is based on the assumption that the
process follows Langmuir kinetics with no axial dispersion.

-50 0 50 100 150 200 250 300 350 400 450

-0,1
0,0
0,1
0,2
0,3
0,4
0,5
0,6
0,7
0,8
0,9
1,0
1,1
(A)
50 mg
100 mg
150 mg
C
t
/
C
0

(
m
g
/
L
)
Time (min)
-50 0 50 100 150 200 250 300 350 400 450
-0,1
0,0
0,1
0,2
0,3
0,4
0,5
0,6
0,7
0,8
0,9
1,0
1,1
(B)
50 mg
100 mg
150 mg
C
t
/
C
0

(
m
g
/
L
)
Time (min)
-50 0 50 100 150 200 250 300 350 400 450
-0,1
0,0
0,1
0,2
0,3
0,4
0,5
0,6
0,7
0,8
0,9
1,0
1,1
1,2
(C)
50 mg
100 mg
150 mg
C
t
/
C
0

(
m
g
/
L
)
Time (min)
Fig. 5. Comparison of tted curves and experimental data, Thomas (A), Clark (B), Adams-Bahort (C). Initial concentration 100 mg/L, ow rate 2 mL/min.
Table 9
Thomas, Adams-Bahort and Clark models constants at different bed heights. Initial concentration 100mg/L, ow rate 2mL/min.
Thomas
Bed height (mm) K
Th
(mL/mgmin) q
e
(mg/g) r
2
x
2
SSE
17 0.4384 136.48 0.9463 0.00631 0.17663
36 0.1338 363.65 0.9019 0.00633 0.29138
64 0.1524 671.79 0.9802 0.00136 0.08857
Adams-Bahort
Bed height (mm) k
AB
(L/mg/min) N
0
(mg/L) r
2
x
2
SSE
17 0.0920 73.11 0.7413 0.85121 0.07187
36 0.0592 150.15 0.8009 0.59148 0.04666
64 0.0837 200.39 0.9438 0.25171 0.08698
Clark
Bed height (mm) A K
C
(1/min) n r
2
x
2
SSE
17 43.84 0.0639 2.1 0.9782 0.00104 0.04666
36 34.47 0.0294 2.4 0.9843 0.00266 0.07187
64 185.81 0.0160 2.1 0.9806 0.00136 0.08698
C.A. Demarchi et al. / Journal of Environmental Chemical Engineering 1 (2013) 13501358 1356
The Thomas model has the following form [50]:
C
t
C
0

1
1 expK
Th
q
e
x=Q C
0
t
(16)
where Q is the owrate in (mL/min), x the adsorbent mass (g), q
e
is
the maximum adsorption capacity (mg/g) and K
Th
is the velocity
constant (mL/mg min).
Plotting C
t
/C
0
against t also gave the breakthrough curves
predicted by the Thomas model (Fig. 5A), and the experimental
points. It can be clearly seen in Table 9 that as the bed depth
increased, the value of K
Th
decreased and the value of q
e
increased.
The high values of correlation r
2
(>0.90) calculated for the tested
parameters suggest that the Thomas model can satisfactorily
describe the adsorption of RR120 in the xed bed column Ch-Fe.
The Thomas model is suitable for adsorption processes where the
external and internal diffusions are not the limiting step [48].
Adsorption capacity depended mainly on the amount of adsorbent
available for adsorption. The breakthrough time and exhaustion
time increased with the increase in bed height, since more time
was required to exhaust more adsorbent.
Another model developed by Clark was based on the use of a
mass-transfer concept, but in the form of the Freundlich
adsorption equation [51]:
C
t
C
0

1
1 Ae
Kct

1=n1
(17)
where n is the Freundlich adsorption constant, A is the Clark model
constant, and K
C
is the adsorption rate (mg/L min). Based on a plot
of C
t
/C
0
against t at a given bed height, and ow rate using
nonlinear regressive analysis, the values of A and K
C
can be
obtained [51]. In bath studies, the adsorption does not follow the
Freundlich model (poor correlation coefcients), and the Freun-
dlich constant n was estimated by nonlinear regression along with
the parameters A and K
C
in the Clark model.
Plotting C
t
/C
0
against t also gave the breakthrough curves
predicted by the Clark model and the experimental points, as
shown in Fig. 5B. As shown in Table 9, the values of the rate of mass
transfer K
c
decreased as the bed depth increased. This is due to the
increase in the amount of adsorbent available for interactions,
resulting in a reduction in the mass transfer rate [52]. From the
experimental results and data regression, the model proposed by
the Clark model provided good correlation on the effects of bed
depth.
Comparison of the Bohart-Adams, Clark and the Thomas models
The coefcient of determination (r
2
), non-linear chi-square test
x
2
(Eq. (18)), and sum square errors (SSE) (Eq. (19)), were used to
determine the best-t model:
x
2

X
n
1l
q
e;calc
q
e;exp

q
e;meas
2
(18)
SSE
X
n
il
q
e;calc
q
e;exp

2
i
(19)
where q
e,cal
is the amount of dye adsorbed in equilibrium (mg g
1
)
calculated by the mathematical model and q
e,exp
is the amount of
dye adsorbed in equilibrium (mg g
1
).
Among the Bohart-Adams, Clark and the Thomas models, the
values of r
2
fromthe Clark model and the Thomas model are higher
than those of the Bohart-Adams model. The SSE and x
2
for the Clark
model was the lowest for all the experimental conditions shown in
Table 9. In all the conditions examined, the predicted breakthrough
curves from the Clark model showed reasonably better agreement
with the experimental curves than the Thomas and Bohart-Adams
models, as shown in Fig. 5. Thus, it was concluded that the Clark
model was better able to predict the RR120 adsorption on CH-Fe
column than the Thomas and Bohart-Adams models.
Conclusions
Ch-Fe has high capacity for adsorption of the dye RR120, both
batch (380 mg/g) and xed-bed (680 mg/g). The adsorption was
improved by decreasing the pH and increasing temperature. The
adsorption kinetics follows the pseudo-second-order. In bath
studies follows the LangmuirFreundlich model and in xed-bed
studies, can be explained by the Clark model. The adsorbent proved
to be stable enough to enable its regeneration and reuse. The
results of the factorial design showed that pHis the principal factor
in the process of adsorption of the RR120 by the Ch-Fe.
Acknowledgements
The authors would like to thank CAPES (Brazilian Agency for
Improvement of Graduate Personnel) and CNPq (National Council
of Science and Technological Development) for the nancial
support.
References
[1] P. Sharma, H. Kaur, M. Sharma, V. Sahore, A review on applicability of naturally
available adsorbents for removal of hazardous dyes fromaqueous waste, Environ.
Monit. Assess. 183 (2011) 151195.
[2] B. Balci, O. Keskinkan, M. Avci, Use of BDST and an ANNmodel for prediction of dye
adsorption efciency of Eucalyptus camaldulensis barks in xed-bed system,
Expert Syst. Appl. 38 (2011) 949956.
[3] D.S. Brookstein, Factors associated with textile pattern dermatitis caused by
contact allergy to dyes, nishes, foams, and preservatives, Dermatol. Clin. 27
(2009) 309322.
[4] P.A. Carneiro, G.A. Umbuzeiro, D.P. Oliveira, M.V.B. Zanoni, Assessment of water
contamination caused by a mutagenic textile efuent/dyehouse efuent bearing
disperse dyes, J. Hazard. Mater. 174 (2010) 694699.
[5] L. Wang, J. Li, Adsorption of C.I. Reactive Red 228 dye from aqueous solution by
modied cellulose from ax shive: kinetics, equilibrium, and thermodynamics,
Ind. Crop. Prod. 42 (2013) 153158.
[6] K.M. Doke, E.M. Khan, Adsorption thermodynamics to clean up wastewater;
critical review, Rev. Environ. Sci. Biotechnol. 12 (2013) 2544.
[7] M. Sharma, R.K. Vyas, K. Singh, A review on reactive adsorption for potential
environmental applications, Adsorption 19 (2013) 161188.
[8] G.L. Dotto, M.L.G. Vieira, L.A.A. Pinto, Kinetics and mechanism of tartrazine
adsorption onto chitin and chitosan, Ind. Eng. Chem. Res. 51 (2012) 68626868.
[9] A. Pal, S. Pan, S. Saha, Synergistically improved adsorption of anionic surfac-
tant and crystal violet on chitosan hydrogel beads, Chem. Eng. J. 217 (2013)
426434.
[10] L. Zhou, J. Jin, Z. Liu, X. Liang, C. Shang, Adsorption of acid dyes from aqueous
solutions by the ethylenediamine-modied magnetic chitosan nanoparticles, J.
Hazard. Mater. 185 (2011) 10451052.
[11] I.M. Ahmed, M.S. Gasser, Adsorption study of anionic reactive dye from aqueous
solution to MgFeCO
3
layered double hydroxide (LDH), Appl. Surf. Sci. 259
(2012) 650656.
[12] E. Rosales, O. Iglesias, M. Pazos, M.A. Sanroma n, Decolourisation of dyes under
electro-Fenton process using Fe alginate gel beads, J. Hazard. Mater. 213 (2012)
369377.
[13] J. Trujillo-Reyes, M. Solache-Ros, A.R. Vilchis-Nestor, V. Sa nchez-Mendieta, A.
Coln-Cruz, FeNi nanostructures and c/FeNi composites as adsorbents for the
removal of a textile dye from aqueous solution, Water Air Soil Pollut. 223 (2011)
13311341.
[14] A.C. Zimmermann, A. Mecabo, T. Fagundes, C.A. Rodrigues, Adsorption of Cr(VI)
using Fe-crosslinked chitosan complex (ChFe), J. Hazard. Mater. 179 (2010) 192
196.
[15] C. Shen, H. Chen, S. Wu, Y. Wen, L. Li, Z. Jiang, M. Li, W. Liu, Highly efcient
detoxication of Cr(VI) by chitosanFe(III) complex: process and mechanism
studies, J. Hazard. Mater. 244 (2013) 689697.
[16] H.H. Santos, C.A. Demarchi, C.A. Rodrigues, J.M. Greneche, N. Nedelko, A. S

lawska-
Waniewska, Adsorption of As(III) on chitosanFe-crosslinked complex (Ch-Fe),
Chemosphere 82 (2011) 278283.
[17] T. Fagundes, A.W.L. Bachmann, H.S.O. Tomaz, C.A. Rodrigues, Adsorcao de
Arsenio(V) pela quitosana ferro-III reticulada, Quim. Nova 31 (2008) 13051309.
[18] C. Shen, Y. Shen, Y. Wen, H. Wang, W. Liu, Fast and highly efcient removal of dyes
under alkaline conditions using magnetic chitosanFe(III) hydrogel, Water Res.
45 (2011) 52005210.
C.A. Demarchi et al. / Journal of Environmental Chemical Engineering 1 (2013) 13501358 1357
[19] A. Debrassi, T. Baccarin, C.A. Demarchi, N. Nedelko, A. Slawska-Waniewska, K.
Sobczak, P. Duzewski, M. Bilska, C.A. Rodrigues, Adsorption of Remazol Red 198
onto magnetic N-lauryl chitosan particles: equilibrium, kinetics, reuse and facto-
rial design, Environ. Sci. Pollut. Res. 19 (2012) 15941604.
[20] H-Y. Zhu, Y-Q. Fu, R. Jiang, J. Yao, L. Xiao, G.-M. Zeng, Novel magnetic chitosan/
poly(vinyl alcohol) hydrogel beads: preparation, characterization and application
for adsorption of dye from aqueous solution, Bioresour. Technol. 105 (2012)
2430.
[21] N.A. Travlou, G.Z. Kyzas, N.K. Lazaridis, E.A. Deliyanni, Functionalization of
graphite oxide with magnetic chitosan for the preparation of a nanocomposite
dye adsorbent, Langmuir 29 (2013) 16571668.
[22] H. Yan, H. Li, H. Yang, A. Li, R. Cheng, Removal of various cationic dyes from
aqueous solutions using a kind of fully biodegradable magnetic composite
microsphere, Chem. Eng. J. 223 (2013) 402411.
[23] M.T. Klepka, N. Nedelko, J.M. Greneche, K. Lawniczak-Jablonska, I.N. Demchenko,
A. Slawska-Waniewska, C.A. Rodrigues, A. Debrassi, C. Bordini, Local atomic
structure and magnetic ordering of iron in Fechitosan complexes, Biomacro-
molecules 9 (2008) 15861594.
[24] V. Ponnusami, V. Gunasekar, S.N. Srivastava, Kinetics of methylene blue removal
from aqueous solution using gulmohar (Delonix regia) plant leaf powder: multi-
variate regression analysis, J. Hazard. Mater. 169 (2009) 119127.
[25] Y. Liu, Y.J. Liu, Biosorption isotherms, kinetics and thermodynamics, Sep. Pur.
Technol. 61 (2008) 229242.
[26] Y.S. Ho, G. Mckay, Pseudo-second order model for sorption processes, Process
Biochem. 34 (1999) 451465.
[27] W.J. Weber, J.C. Morris, Kinetics of adsorption on carbon from solution, J. Sanit.
Eng. Div. 89 (1963) 3160.
[28] N.M. Mahmoodi, B. Hayati, M. Arami, C. Lan, Adsorption of textile dyes on Pine
cone from colored wastewater: kinetic, equilibrium and thermodynamic studies,
Desalination 268 (2011) 117125.
[29] G.L. Dotto, L.A.A. Pinto, Adsorption of food dyes acid blue 9 and food yellow3 onto
chitosan: stirring rate effect in kinetics and mechanism, J. Hazard. Mater. 187
(2011) 164170.
[30] G.J. Copello, A.M. Mebert, M. Raineri, M.P. Pesenti, L.E. Diaz, Removal of dyes from
water using chitosan hydrogel/SiO
2
and chitin hydrogel/SiO
2
hybrid materials
obtained by the solgel method, J. Hazard. Mater. 186 (2011) 932939.
[31] C.Y. Chen, J.C. Chang, A.H. Chen, Competitive biosorption of azo dyes from
aqueous solution on the template crosslinked-chitosan nanoparticles, J. Hazard.
Mater. 185 (2011) 430441.
[32] I. Langmuir, The adsorption of gases on plane surfaces of glass, mica and platinum,
J. Am. Chem. Soc. 40 (1918) 13611403.
[33] H.M.F. Freundlich, Over theadsorptioninsolution, J. Phys. Chem. 57(1906) 385471.
[34] R. Sips, On the structure of a catalyst surface II, J. Chem. Phys. 18 (1950)
10241027.
[35] L.G. Silva, R. Ruggiero, P.M. Gontijo, R.B. Pinto, B. Royer, E.C. Lima, T.H.M. Fernades,
T. Calvete, Adsorption of Brilliant Red 2BE dye from water solutions by a
chemically modied sugarcane bagasse lignin, Chem. Eng. J. 168 (2011) 620628.
[36] S. Kittinaovarat, P. Kansomwan, N. Jiratumnukul, Chitosan/modied montmoril-
lonite beads and adsorption Reactive Red 120, Appl. Clay Sci. 48 (2010) 8791.
[37] N.F. Cardoso, E.C. Lima, B. Royer, M.V. Bach, G.L. Dotto, L.A.A. Pinto, T. Calvete,
Comparision of Spirulina platensis microalgae and commercial activated carbon as
adsorbents for the removal of Reactive Res 120 dye from aqueous efuents, J.
Hazard. Mater. 241 (2010) 146153.
[38] L.D.T. Prola, E. Acayanka, E.C. Lima, C.S. Umpierres, J.C.P. Vaghetti, W.O. Santos, S.
Laminsi, P.T. Djifon, Comparison of Jatropha curcas shells in natural form and
treated by non-thermal plasma as biosorbents for removal of Reactive Red 120
textile dye from aqueous solution, Ind. Crop. Prod. 46 (2013) 328340.
[39] A. Celeklia, G. Ilgu na, H. Bozkurtb, Sorption equilibrium, kinetic, thermodynamic,
and desorption studies of Reactive Red 120 on Chara contraria, Chem. Eng. J. 191
(2012) 228235.
[40] T. Calvete, E.C. Lima, N.F. Cardoso, S.L.P. Dias, F.A. Pavan, Application of carbon
adsorbents prepared fromBrazilian pine-fruit-shell for the removal o Procion Red
MX 3B from aqueous solutionkinetic, equilibrium, and thermodynamic studies,
Chem. Eng. J. 155 (2009) 627636.
[41] G. Absalan, M. Asadia, S. Kamrana, L. Sheikhiana, D.M. Goltz, Removal of reactive
red-120 and 4-(2-pyridylazo) resorcinol from aqueous samples by Fe
3
O
4
mag-
netic nanoparticles using ionic liquid as modier, J. Hazard. Mater. 192 (2011)
476484.
[42] A. Tabak, N. Baltas, B. Afsin, M. Emirik, B. Caglar, E. Eren, Adsorption of Reactive
Red 120 from aqueous solutions by cetylpyridinium-bentonite, J. Chem. Technol.
Biotechnol. 85 (2010) 11991207.
[43] A. Celekli, M. Yavuzatmaca, H. Bozkurt, Modeling the removal of Reactive Red 120
on Pistachio husk, Clean 38 (2010) 173180.
[44] S. Chatterjee, S. Chatterjee, B.P. Chatterjee, A.R. Das, A.K. Guha, Adsorption of a
model anionic dye, eosin Y, from aqueous solution by chitosan hydrobeads,
Colloid. Interface Sci. 288 (2005) 3035.
[45] M. Ciopec, C.M. Davidescu, A. Negrea, I. Grozav, L. Lupa, P. Negrea, A. Popa,
Adsorption studies of Cr(III) ions from aqueous solutions by DEHPA impregnated
onto Amberlite XAD7factorial design analysis, Chem. Eng. Res. Des. 90 (2012)
16601670.
[46] E.A. Deliyanni, E.N. Peleka, K.A. Matis, Modeling the sorption of metal ions from
aqueous solution by iron-based adsorbents, J. Hazard. Mater. 172 (2009)
550558.
[47] Y.S. Al-Degs, M.A.M. Khraisheh, S.J. Allen, M.N. Ahmad, Adsorption characteristics
of reactive dyes in columns of activated carbon, J. Hazard. Mater. 165 (2009) 944
949.
[48] Z. Aksu, F. Gonen, Biosorption of phenol by immobilized activated sludge in a
continuous packed bed: prediction of breakthrough curves, Process Biochem. 39
(2004) 599613.
[49] G. Bohart, E.Q. Adams, Some aspects of the behaviour of charcoal with respect to
chlorine, J. Am. Chem. Soc. 42 (1920) 523544.
[50] H.C. Thomas, Heterogeneous ion exchange in a owing system, J. Am. Chem. Soc.
66 (1944) 16641666.
[51] R.M. Clark, Evaluating the cost and performance of eld-scale granular activated
carbon systems, Environ. Sci. Technol. 21 (1987) 573580.
[52] E.I. Unuabonah, M.I. El-Khaiary, B.I. Olu-Owolabi, K.O. Adebowale, Predicting the
dynamics and performance of a polymerclay based composite in a xed bed
systemfor the removal of lead (II) ion, Chem. Eng. Res. Des. 90 (2012) 11051115.
C.A. Demarchi et al. / Journal of Environmental Chemical Engineering 1 (2013) 13501358 1358