Journal of Environmental Chemical Engineering 1 (2013) 13501358

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Journal of Environmental Chemical Engineering

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

Batch and xed-bed studies
Carla Albertina Demarchi, Mayara Campos, Clovis Antonio Rodrigues *
Nucleo de Investigacoes Qumico-Farmaceuticas (NIQFAR), Universidade do Vale do Itaja (UNIVALI), Itaja 88302-202, Santa Catarina, Brazil

A R T I C L E I N F O

A B S T R A C T

Article history:
Received 16 August 2013
Received in revised form 7 October 2013
Accepted 8 October 2013

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 isotherm model. 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 33 factorial design, and the initial pH of the dye solution had a signicant effect.
2013 Elsevier Ltd. All rights reserved.

Keywords:
Reactive Red 120
Chitosaniron(III)
Textile wastewater
Factorial design

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 contamination 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 lowcost 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 xedbed studies to predict adsorption on an industrial scale.
Experimental
Materials

* 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).
2213-3437/$ see front matter 2013 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.jece.2013.10.005

The chitosan (viscosimetric molecular weight of 2.5  105 g/

mol, and desacetylation degree of 85%) was obtained from
Purifarma (Sao Paulo). The dye Reactive Red 120 (Procion Red
HE-3B; MF: C44H24Cl2N14O20S6Na6; MW: 1469.98) was kindly

C.A. Demarchi et al. / Journal of Environmental Chemical Engineering 1 (2013) 13501358

1351

Table 1
Matrix of factorial design and results of experiments.
Experiment

pH (A)

Temperature (B)

Ci(C)

Amount adsorbed (mg/g)

1
2
3
4
5
6
7
8
9
10
11
12
13
14
15

0
0

+

+
0


+
0
0
0
+
0

+
0
+
+
0
0


0

0
0
+
0



0
0
0
+

+
0

0
0
0
+
+


227.5
169.6
315.8
109.3
312.8
81.6
246.4
286.4
235.9
96.0
169.6
169.6
255.3
112.7
208.1

pH: 2(), 5(0), 8(); Temperature: 55 8C(+), 40 8C(0), 25 8C(); concentration: 300 mg/L(), 400 mg/L(0), 500 mg/L(+).

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
(pHzpc) 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. Aliquots 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 Spectrovision 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 (qe) was calculated according to Eq. (1)
[22]:
qe

C 0  C e  v
m

(1)

Regeneration and reuse of the adsorbent

For the regeneration, 100 mg of the adsorbent saturated with a
RR120 solution was used. The dye was removed with 50 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 (Ci), pH
solution and agitation temperature. Table 1 shows the levels of the
independent factors and experimental designs. The software
Statistica1 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 bottom of 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 column were 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
between their inlet concentration (C0) and outlet concentrations (Ct).
The breakthrough curves, which showed the performance of the
xed-bed column, were plotted in terms of normalized concentration, Ct/C0, (which is dened as the ratio of efuent dye
concentration, Ct (mg/L), to inlet dye concentration, C0 (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

where C0 and Ce (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.

The kinetic behavior of the adsorption process was studied with

an initial concentration of 400 mg/L, pH 3.6 (non-buffered dye

C.A. Demarchi et al. / Journal of Environmental Chemical Engineering 1 (2013) 13501358

1352

Table 2
Kinetic parameters of the adsorption of the dye RR120 by the Ch-Fe.
Pseudo-rst order
k1 (min)

Pseudo-second order
2

qe (mg/g)
1

4.25  10

1/2

246.69

k2 (g/mg min

3

0.9766

3.85  10

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 adsorption 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 intraparticle models in non-linear forms were used (Fig. 2). The pseudorst-order model [25] is represented by Eq. (2):
qt qe 1  ek1 t

(2)

where k1 (1/min) is the constant of the rst order adsorption, qe

(mg/g) is the amount of dye adsorbed at equilibrium and qt (mg/g)
is the amount of dye adsorbed at time t (min).
The pseudo-second-order model [26], is represented by Eq. (3).
qt

k2 q2e t
1 k2 q2e t

(3)

where k2 (1/min) is the constant of the second order adsorption, qe

(mg/g) is the amount of dye adsorbed at equilibrium and qt (mg/g)
is the amount of dye adsorbed at time t (min).
Another kinetic model used was the intraparticle diffusion [27]
(Eq. (4))
qt ki t 0:5

(4)
1/2

where ki (mg/g min ) is the intraparticle diffusion constant and qt

(mg/g) is the amount of dye adsorbed at time t (min).
Based on its calculated qe value of 254.2 mg/g, which is close to
the experimental values, qex (269.9 mg/g), the pseudo-secondorder 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
[(Fig._1)TD$IG]

Intraparticle
2

qe (mg/g)

C (mg/g)

qe (mg/g)

r2

254.20

0.9859

105.95

18.273

0.5938

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:
qe

K L qm C e
1 K LCe
1=n

qe K F Ce
qe

K LF qm Cen
1 K LF Cen

(5)
(6)
(7)

where Ce (mg/L) is the equilibrium concentration of RR120

adsorbed and qe (mg/g) is the experimental adsorption capacity
of RR120, Langmuir constants qm (mg/g) and KL (L/mg) are the
monolayer adsorption capacity and afnity of adsorbent toward
the adsorbate, respectively. Freundlich constants KF (L/mg) and n
give information on the extent of adsorption and the degree of
nonlinearity between the adsorption and the solution concentration, 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 (Fe3+) and the SO3 groups present in the dye RR120. In ChFe crosslinked with glutaraldehyde, the free NH2 groups are not
present due to a reaction with glutaraldehyde. As a result, nonspecic
interactions between the (NH3+) and sulfonate groups of
[(Fig._2)TD$IG]

300

250

qt(mg/g)

200

150

100
pseudo-first order
pseudo-second order
Intraparticle

50

0
0

20

40

60

80

100

120

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.

C.A. Demarchi et al. / Journal of Environmental Chemical Engineering 1 (2013) 13501358

1353

Table 3
Study of temperature and pH variation on the adsorption isotherms of the dye RR120.
Langmuir

T (8C)
25
40
55

LangmuirFreundlich
2

KL (L/g)

qm (mg/g)

KF (L/g)

0.3920
0.3747
0.5224

290.70
331.35
361.96

0.8117
0.7547
0.8543

111.10
131.67
230.68

0.219
0.207
0.095

0.8417
0.6800
0.7465

0.3102
0.0033
0.0135

0.4657
0.4387
0.0503

336.77
230.08
135.69

0.7972
0.9399
0.8484

192.38
100.16
36.635

0.120
0.177
0.229

0.9579
0.9605
0.9382

0.7198
0.4403
1.393

KLF (L/g)

qm (mg/g)

r2

pHb
2.0
5.0
9.0
a

Freundlich
2

433.84
309.94
350.42

380.57
283.57
14.756

0.427
7.241
3.250

0.8473
0.8487
0.9882

0.486
0.493
0.0381

0.8946
0.9908
0.9353

pH 3.6 non-buffered dye solution.

Temperature 25 8C.

mol K) were determined using Eqs. (8)(10) [44]:

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 Fe3+ binding sites of the adsorbent. Similar results were
recently reported for the adsorption of anionic dyes [35]. This
behavior usually occurs in adsorbent containing Fe3+ 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 qe (mg/g) is
according to the Langmuir model. The adsorbent Ch-Fe has a
higher capacity than other adsorbents reported in the literature.

where KD is the equilibrium constant, Cs is the amount of dye

adsorbed (mg/g), Ce 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 KD 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 system is not gaining energy from any external source
[28].

Thermodynamic parameters

Regeneration and reuse of the adsorbent

The thermodynamic parameters, like change in Gibbs free

energy (DG8, kJ/mol), enthalpy (DH8, kJ/mol), and entropy (DS8, J/

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 NaOH 0.5 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.

Table 4
Comparison of different sorbents in the adsorption of textile dye RR120. Maximum
adsorption capacity calculated with the Langmuir model.
Adsorbent

qe (mg/g)

Reference

Ch-Fe
Chitosan/modied montmorillonite
Commercial activated carbon
Jatropha curcas shells
Chara contraria
Activated carbonaceous Brazilian pine-fruit-shell
nanoparticles of Fe3O4
Cetylpyridiniun-Bentonite
Pistachio husk

361.9
5.6
293.1
42.5
112.8
275.0
166.67
81.97
324.88

In this study
[36]
[37]
[38]
[39]
[40]
[41]
[42]
[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 (25 8C)

6.46 (40 8C)
10.26 55 8C

KD

Cs
Ce

(8)

DG RT ln K D
ln K D

DS
R

(9)

DH 

(10)

RT

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 6
Desorption of RR120 and reuse of Ch-Fe. Dye concentration 500 mg/L; volume of
solution 80 mL, 100 mg of adsorbent; temperature 55 8C, pH 3.6, contact time
60 min.
Cycle

RR120 adsorbed (mg/g)

Desorption (%)

1
2
3
4

361.2
321.8
304.1
249.3

57.7
81.4
83.4
84.8

C.A. Demarchi et al. / Journal of Environmental Chemical Engineering 1 (2013) 13501358

1354

Table 7
Effect estimated coefcients for the adsorption of the dye RR120.

Interactions media
pH
pH2
T
T2
Ci
Ci 2
pH  T
pH  Ci
T  Ci

Effect

Standard error Effect

T value

P value

Coefcient

Standard error of coefcient

207.18
187.47
8.150
17.900
40.325
43.225
24.200
8.250
22.300
5.250

2.823407
6.915906
5.089969
6.915906
5.089969
6.915906
5.089969
9.780567
9.780567
9.780567

73.380
27.108
1.6012
2.5882
7.9224
6.2501
4.7544
0.8435
2.2800
0.5368

0.000000
0.000001
0.170234
0.048941
0.000516
0.001537
0.005084
0.437425
0.071535
0.614435

207.18
93.738
4.0750
8.9500
20.1625
21.6125
12.1000
4.1250
11.1500
2.6250

2.823407
3.457953
2.544984
3.457953
2.544984
3.457953
2.544984
4.890284
4.890284
4.890284

R2 = 0.99431; R2 adjusted 0.98406.

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 b0 b1 xA b2 x2A b3 xB b4 x2B b5 xC b6 x2C
b7 xA xB b8 xA xC b9 xB xC

(11)

where b0 is the global mean, bi 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 bi 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  187:4 pH 8:15 pH2 17:9T  40:3T 2

43:2Ci  24:4Ci2  8:25 pHT

(12)

22:3 pHCi  5:25CiT

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
(B2), initial concentration (C) and quadratic factor initial concentration (C2) are the most signicant. The graph shows that the
effect of pH is the most important effect, followed by the
temperature.

[(Fig._3)TD$IG]

Fig. 4 shows the graphs, constructed using the surface response

method that correlates with the initial concentration factors
temperature  pH (Fig. 4A), (Ci)  pH (Fig. 4B) and Ci  temperatemperature (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, Ci 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 concentration is 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 (Vb) 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 concentration, indicating the exhaustion volume (Ve).
The capacity at exhaustion was determined by calculating the
total area below the breakthrough curve (plot of Ct/C0 against t
(min)). The column capacity was estimated by Eq. (13) [47].
Z ve
C E C B dQ
(13)
qtotal
x
vb
where qtotal is the column capacity adsorption (mg), CB and CE are
breakthrough and exhaustion RR120 concentration (mg/L) respectively, Q is the ow rate in (mL/min) and x is the Ch-Fe mass (g).
The value of adsorption capacity, determined experimentally,
qe(exp) (mg/g) is calculated as follows [48]:
qeexp

Fig. 3. Pareto graph of the effects.

qtotal
x

(14)

where x (g) is the total dry weight of the adsorbent in the column.
The breakthrough curves of the (Ct/C0) versus time for various
bed depth of 17, 34 and 66 mm (150, 100 and 150 mg), at a
constant ow rate of 2 mL/min and RR120 and initial concentration
of 100 mg/L, are shown in Fig. 5. From Fig. 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 (Fe3+) increased, RR120 had more time to contact with

[(Fig._4)TD$IG]

C.A. Demarchi et al. / Journal of Environmental Chemical Engineering 1 (2013) 13501358

1355

Fig. 4. Surface response amount adsorbed (mg/g). (A) Effect of temperature and pH. (B) Effect of the initial concentration (Ci) and pH. (C) Effect of Ci 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.

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 Vb and Ve depend on the higher
of the bed and increased with bed depth. High adsorption capacity
in breakthrough (qb) and adsorption capacity in exhaustion (qe)
were observed at the highest bed depth, due to an increase in the
surface area of adsorbent, providing more binding sites for the
adsorption.
Table 8
Column data and parameters obtained at different bed heights on the adsorption of
the dye RR120. Initial concentration 100 mg/L, ow rate 2 mL/min.
Bed height (mm)

17

36

64

Vb (mL)
Ve (mL)
qb (mg/g)
qe (mg/g)

60
340
60
250

80
600
80
510

350
850
350
680

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 nonlinear 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]


Ct
Z
exp kAB C 0 t  kAB N 0
F
C0

(15)

where C0 is the inlet concentration (mg/L), Ct is the exit outlet

concentration (mg/L), kAB is the mass transfer coefcient (L/

[(Fig._5)TD$IG]

1356

C.A. Demarchi et al. / Journal of Environmental Chemical Engineering 1 (2013) 13501358

1,1
1,1

1,0

1,0

(A)

(B)

0,9

0,9

0,8
0,8

0,7

Ct/C0 (mg/L)

Ct/C0 (mg/L)

0,7
0,6
0,5
0,4
0,3

0,6
0,5
0,4
0,3

50 mg
100 mg
150 mg

0,2

50 mg
100 mg
150 mg

0,2
0,1

0,1

0,0

0,0

-0,1

-0,1
-50

50

100

150

200

250

300

350

400

-50

450

50

100

150

200

250

300

350

400

450

Time (min)

Time (min)

1,2
1,1

(C)

1,0
0,9

Ct/C0 (mg/L)

0,8
0,7
0,6
0,5
0,4
0,3

50 mg
100 mg
150 mg

0,2
0,1
0,0
-0,1
-50

50

100

150

200

250

300

350

400

450

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.

mg min), N0 is the saturation concentration (mg/L), Z is the bed

height (cm) and F is the linear velocity (1/cm).
Plotting Ct/C0 against t also gave the breakthrough curves
predicted by the Bohart-Adams model (Fig. 5C), and the
experimental points. For all breakthrough curves using nonlinear regression analysis, respective values of KAB and N0
were calculated and are presented in Table 9, along with
the correlation coefcients (r2). Table 9 also shows that the

values of KAB and N0 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.

Table 9
Thomas, Adams-Bahort and Clark models constants at different bed heights. Initial concentration 100 mg/L, ow rate 2 mL/min.
Thomas
Bed height (mm)

KTh (mL/mg min)

qe (mg/g)

r2

x2

SSE

17
36
64

0.4384
0.1338
0.1524

136.48
363.65
671.79

0.9463
0.9019
0.9802

0.00631
0.00633
0.00136

0.17663
0.29138
0.08857

Adams-Bahort
Bed height (mm)

kAB (L/mg/min)

N0 (mg/L)

r2

x2

SSE

17
36
64

0.0920
0.0592
0.0837

73.11
150.15
200.39

0.7413
0.8009
0.9438

0.85121
0.59148
0.25171

0.07187
0.04666
0.08698

Clark
Bed height (mm)

KC (1/min)

r2

x2

SSE

17
36
64

43.84
34.47
185.81

0.0639
0.0294
0.0160

2.1
2.4
2.1

0.9782
0.9843
0.9806

0.00104
0.00266
0.00136

0.04666
0.07187
0.08698

C.A. Demarchi et al. / Journal of Environmental Chemical Engineering 1 (2013) 13501358

The Thomas model has the following form [50]:

Ct
1

C 0 1 expK Th qe x=Q  C 0 t

(16)

where Q is the ow rate in (mL/min), x the adsorbent mass (g), qe is

the maximum adsorption capacity (mg/g) and KTh is the velocity
constant (mL/mg min).
Plotting Ct/C0 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 KTh decreased and the value of qe increased.
The high values of correlation r2 (>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]:
Ct

C0

1
1 AeKct

1=n1

(17)

where n is the Freundlich adsorption constant, A is the Clark model

constant, and KC is the adsorption rate (mg/L min). Based on a plot
of Ct/C0 against t at a given bed height, and ow rate using
nonlinear regressive analysis, the values of A and KC can be
obtained [51]. In bath studies, the adsorption does not follow the
Freundlich model (poor correlation coefcients), and the Freundlich constant n was estimated by nonlinear regression along with
the parameters A and KC in the Clark model.
Plotting Ct/C0 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 Kc 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 (r2), non-linear chi-square test
x (Eq. (18)), and sum square errors (SSE) (Eq. (19)), were used to
determine the best-t model:
2

x2

n
X
qe;calc  qe;exp 2
qe;meas
1l

SSE

n
X
qe;calc  qe;exp 2i

(18)

(19)

il

where qe,cal is the amount of dye adsorbed in equilibrium (mg g1)

calculated by the mathematical model and qe,exp is the amount of
dye adsorbed in equilibrium (mg g1).
Among the Bohart-Adams, Clark and the Thomas models, the
values of r2 from the Clark model and the Thomas model are higher
than those of the Bohart-Adams model. The SSE and x2 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

1357

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 pH is 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.
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