chemical engineering research and design 1 0 0 ( 2 0 1 5 ) 302–310

Contents lists available at ScienceDirect

Chemical Engineering Research and Design

journal homepage: www.elsevier.com/locate/cherd

Fixed bed adsorption of Methylene Blue by

ultrasonic surface modified chitin supported on
sand

G.L. Dotto a,∗ , J.M. Nascimento dos Santos a , R. Rosa a , L.A.A. Pinto b ,
F.A. Pavan c , E.C. Lima d
a Environmental Processes Laboratory, Chemical Engineering Department, Federal University of Santa Maria, UFSM,
Roraima Avenue, 1000, 97105-900 Santa Maria, RS, Brazil
b Unit Operation Laboratory, School of Chemistry and Food, Federal University of Rio Grande—FURG, Km 08 Italy

Avenue, 96203-900 Rio Grande, RS, Brazil

c Institute of Chemistry, Federal University of Pampa, UNIPAMPA, Bagé, RS, Brazil
d Institute of Chemistry, Federal University of Rio Grande do Sul, UFRGS, Porto Alegre, RS, Brazil.

a r t i c l e i n f o a b s t r a c t

Article history: In this research, fixed bed adsorption of Methylene Blue (MB) by ultrasonic surface modi-
Received 6 April 2015 fied chitin supported on sand (USM-chitin/sand) was investigated, aiming future scale-up
Received in revised form 28 May purposes. USM-chitin was prepared, characterized and supported on sand for the fixed bed
2015 assays. Breakthrough curves were obtained at different flow rates and initial MB concen-
Accepted 1 June 2015 trations. These parameters were optimized by response surface methodology (RSM). Some
Available online 8 June 2015 dynamic models were fitted to the experimental data and the bed regeneration was stud-
ied. The optimal conditions for the fixed bed adsorption of MB on USM-chitin/sand were
Keywords: flow rate of 10 mL min−1 and initial MB concentration of 50.0 mg L−1 . Under these con-
Breakthrough curves ditions, the breakthrough time was 370 min, the maximum capacity of the column was
Dynamic models 51.8 mg g−1 and the removal percentage was 51.5%. The dynamic models were suitable to
Flow rate represent the experimental data. The regeneration was possible for five times, maintaining
Scale-up the same bed performance. These results indicated that the fixed bed adsorption of MB on
USM-chitin/sand is technically viable and suitable for a future scale-up.
© 2015 The Institution of Chemical Engineers. Published by Elsevier B.V. All rights reserved.

1. Introduction ozonation, adsorption, chemical oxidation and membrane

The dye containing effluents from different industries such
as, textile, pulp, paper, leather and paint are very difficult
to treat, since the dyes are stable and recalcitrant molecules
(Koprivanac and Kusic, 2008). If they are incorrectly treated,
these effluents can cause serious environmental impacts in
the receiving water bodies (Gupta and Suhas, 2009). Thus
several technologies, such as, ion exchange, photo-oxidation,
flocculation, precipitation, microbiological decomposition,
separation are currently applied for dye removal from aqueous
media (Gupta and Suhas, 2009; Srinivasan and Viraraghavan,
2010; Saratale et al., 2011; Verma et al., 2012). Among these,
adsorption is an efficient way, due its low capital investment,
abundant raw material source, simplicity in design and oper-
ation and non-toxicity (Moussavi and Khosravi, 2011; Dotto
et al., 2014; Tovar-Gómez et al., 2015).
The most common used adsorbent for dyes removal is
activated carbon, but it is expensive. Thus several low-cost

∗
Corresponding author. Tel.: +55 55 3220 8448.
E-mail addresses: guilherme dotto@yahoo.com.br (G.L. Dotto), juhmnsantos@hotmail.com (J.M.N.d. Santos), rejirr@hotmail.com
(R. Rosa), dqmpinto@furg.br (L.A.A. Pinto), flavio.pavan@unipampa.edu.br (F.A. Pavan), profederlima@gmail.com (E.C. Lima).
http://dx.doi.org/10.1016/j.cherd.2015.06.003
0263-8762/© 2015 The Institution of Chemical Engineers. Published by Elsevier B.V. All rights reserved.
 chemical engineering research and design 1 0 0 ( 2 0 1 5 ) 302–310 303

size) can introduce limitations to the system, such as hydrody-

Nomenclature namic pressure drop, obstruction of the column and formation
of preferential ways (Dotto et al., 2015b). An alternative to solve
C0 initial MB concentration (mg L−1 ) these problems is the use of support materials, such as, glass
Ct MB concentration at the outlet of the column beads (Vieira et al., 2014), sand (Wan et al., 2010) or bentonite
(mg L−1 ) (Futalan et al., 2011). Based on the best of our knowledge, there
h bed depth of fixed-bed (cm) are no studies regarding the use of ultrasonic surface modified
K adsorption constant rate (mL mg−1 min−1 ) chitin for fixed bed adsorption.
kTh constant rate of Thomas model This work aimed to study the fixed bed adsorption of
(mL mg−1 min−1 ) Methylene Blue (MB) by ultrasonic surface modified chitin
kYN constant rate of Yoon–Nelson model (min−1 ) supported on sand (USM-chitin/sand), aiming future scale-
m amount of adsorbent in column (g) up purposes. The adsorbent was prepared and characterized.
N0 adsorption capacity (mg L−1 ) Response surface methodology (RSM) was used to optimize
qeq maximum capacity of the column (mg g−1 ) the fixed bed adsorption as a function of flow rate and initial
Q flow rate (mL min−1 ) MB concentration. The considered responses were break-
R MB removal percentage (%) through time, maximum capacity of the column and removal
R2 coefficient of determination (dimensionless) percentage. In the optimal conditions, bed depth service time
t time (min) (BDST), Thomas and Yoon–Nelson models were fitted to the
tb breakthrough time (min) experimental data. The bed regeneration was also investi-
te exhaustion time (min) gated.
ttotal total operation time (min)
u linear flow rate (cm min−1 ) 2. Materials and methods
Veff volume of the effluent (mL)
Y response variable of Eq. (8) (min or mg g−1 or %) 2.1. Materials and reagents
Z bed length (cm)
Zm length of mass transfer zone (cm) Sand (density of 2150 kg m−3 , sphericity of 0.75 and particle
size ranging from 1.71 to 2.36 mm) was obtained from a local
Greek symbols
industry (Santa Maria—RS—Brazil). The sand samples were
˛ regression coefficient of Eq. (8)
washed with distilled water and oven dried at 60 ◦ C before the
ˇ regression coefficient of Eq. (8)
experiments.
 regression coefficient of Eq. (8)
Methylene Blue dye (MB) (purity of 99.0%, color index 52015,
ı regression coefficient of Eq. (8)
molecular weight of 319.8 g mol−1 , max = 664 nm, pKa = 5.6)
ε regression coefficient of Eq. (8)
was purchased from Plury chemical Ltda., Brazil. For the fixed
 regression coefficient of Eq. (8)
bed assays, MB solutions with pH of 10.0 were prepared using
max maximum absorption wavelength of MB.
NaOH (Dotto et al., 2015b). The optimized three-dimensional
 time required for 50% adsorbate breakthrough
structural formula of MB was obtained from MarvinSketch
from Yoon–Nelson model (min)
software, version 14.9.22.0, and is presented in Fig. 1. The other
reagents utilized were of analytical grade and deionized water
was used to prepare all solutions.
adsorbents have been tested in order to substitute activated
carbon (Gupta and Suhas, 2009; Srinivasan and Viraraghavan,
2010). These materials include agricultural wastes, algae
biomass, bacterial biomass, chitosan/chitin and fungal
biomass (Dotto et al., 2015a). Particularly, chitin can be used
as adsorbent since is the second most abundant polysac-
charide worldwide and, it can be obtained from wastes, is
biodegradable, renewable and presents a compact structure
containing hydroxyl and N-acetyl groups (Dotto et al., 2012,
2013, 2015a, 2015b). In our recent work (Dotto et al., 2015b),
it was proved that ultrasonic surface modified chitin is
more efficient than chitin for the removal of Methylene Blue
from aqueous solutions. However, the study was performed
only in batch system. In this way, the fixed bed adsorption
study is essential for future scale-up purposes and industrial
applications (Shafeeyan et al., 2014; Vieira et al., 2014).
In the field of dyes adsorption onto chitin/chitosan, it is rec-
ognized that the majority of the studies are conducted only in
static batch experiments (Crini and Badot, 2008; Wan Ngah
et al., 2011; Dotto and Pinto, 2011; Dotto et al., 2012). This sce-
nario shows the necessity of fixed bed column studies, which
are more relevant to real operating systems (Yin et al., 2009;
Auta and Hameed, 2014). However, the application of ultra-
sonic surface modified chitin for dye adsorption in fixed bed is Fig. 1 – Optimized three-dimensional structural formulae of
hindered, since the particle characteristics (density, shape and Methylene Blue (MB).
304 chemical engineering research and design 1 0 0 ( 2 0 1 5 ) 302–310
2.2. Preparation and characterization of ultrasonic
surface modified chitin
The ultrasonic surface modified chitin (USM-chitin) was pre-
pared according to our previous works (Dotto and Pinto, 2011;
Dotto et al., 2015b). First, chitin was obtained from shrimp
wastes (Penaeus brasiliensis) by demineralization, deproteiniza-
tion, deodorization and drying steps (Dotto and Pinto, 2011).
The samples were ground (Wiley Mill Standard, model 03, USA)
and sieved until the discrete particle size ranging from 105
to 125 ␮m. Afterwards, the chitin samples were mixed with
deionized water and, the water/chitin mixture was treated by
an ultrasonic processor (UP400S, Hielscher, Germany) of 400 W
equiped with a titanium sonotrode during 1 h at 24 kHz (the
treatment was performed a cycle of 1.00 and amplitude of
60%) (Dotto et al., 2015b). Finally, chitin slurry was separated
by filtration, oven dried (40 ◦ C, 24 h) and stored for further use.
The textural characteristics of chitin and USM-chitin were
visualized by scanning electron microscopy (SEM) with mag-
nification of 100× and accelerating voltage of 15 kV (Jeol,
JSM-6610LV, Japan) (Goldstein et al., 1992). The specific sur-
face area was determined by a volumetric adsorption analyzer
(Quantachrome Instruments, New Win 2, USA) using the
Brunauer, Emmet, Teller (BET) method (Brunauer et al., 1938).
The functional groups and the deacetylation degree of the
adsorbent were identified by Fourier transform infrared spec-
troscopy (FT-IR) (Prestige, 21210045, Japan) (Sabnis and Block,
1997; Silverstein et al., 2007). The crystallinity index was deter-
mined by X-ray powder diffractometry (XRD) (Rigaku, Miniflex
300, Japan) (Al-Sagheer et al., 2009).
2.3. Fixed bed experiments
The fixed bed experiments were performed in a laboratory
system, as presented in Fig. 2. The breakthrough curves were
constructed at different flow rates (10, 15 and 20 mL min−1 )
and initial MB concentrations (50, 100 and 150 mg L−1 ).
The acrylic cylindrical column (internal diameter of 2.5 cm
and height of 25.0 cm) was filled with 5.00 g of USM-chitin
and 180.0 g of sand (USM-chitin and sand were manually
mixed to guarantee the homogeneity) (these conditions were
selected by several preliminary tests. In these tests the USM-
chitin/sand ratio was studied and, it was concluded that 5.00 g
of USM-chitin and 180.0 g of sand was a more adequate ratio).
The MB solutions were then pumped upward through the col-
umn by a peristaltic pump (Master Flex, 07553-75, Canada). At
the column top, samples were collected at regular time inter-
vals until the bed saturation and, the MB concentration was
determined by spectrophotometry at 664 nm (Quimis, Q108
Fig. 2 – Experimental setup for the fixed bed adsorption
tests.
DRM, Brazil). The bed saturation was considered when the
outlet MB concentration was the same that the initial MB
concentration. The assays were carried out in replicate (n = 3),
and blanks were performed using sand without USM-chitin
(any significant adsorption occurred when sand without USM-
chitin was used).
2.4. Column data analysis
The column data analysis was performed in order to obtain
the breakthrough time (tb ), exhaustion time (te ), length of
mass transfer zone (Zm ), effluent volume (Veff ), maximum
capacity of the column (qeq ) and removal percentage (R),
for each experimental breakthrough curve (Geankoplis, 1998;
Shafeeyan et al., 2014; Vieira et al., 2014). The breakthrough
time (tb , min) was considered when the outlet MB concen-
tration attained 5% of the initial MB concentration and, the
exhaustion time (te , min) was considered when the outlet MB
concentration attained 95% of the initial MB concentration
(Suzuki, 1990). The Zm (cm) reflects the shortest possible adsor-
bent bed length needed to obtain the breakthrough time tb
at t = 0. The metric length of this zone was calculated by the
following equation (Suzuki, 1990):
 tb

Zm = Z 1 − (1)
te
where Z is the bed length (25 cm).
The volume of the effluent, Veff (mL), is given by the follow-
ing equation (Martín-Lara et al., 2012):
Veff = Qttotal (2)
where Q is the flow rate (mL min−1 ) and ttotal is the total oper-
ation time (min).
The maximum capacity of the column (qeq , mg g−1 ) is given
by the following equation (Sugashini and Begum, 2013):
 ttotal
(QC0 /1000) 0
(1 − (Ct /C0 )) dt
qeq = (3)
m
where C0 is the initial MB concentration (mg L−1 ) and m is the
amount of USM-chitin in the bed (5.00 g). The integral in Eq.
(3) is the area above the breakthrough curve from Ct /C0 = 0 to
Ct /C0 = 1. This area was estimated by Microcal origin 6.0 soft-
ware, using analysis/calculus/integrate tool.
The MB removal percentage (R) was calculated by the fol-
lowing equation (Sugashini and Begum, 2013):
 ttotal
0
(1 − (Ct /C0 )) dt
R= 100 (4)
ttotal
2.5. Statistical optimization
The fixed bed adsorption of MB by USM-chitin supported
on sand was optimized using response surface methodol-
ogy (RSM) (Myers and Montgomery, 2002). The effects of flow
rate (10, 15 and 20 mL min−1 ) and initial MB concentration
(50, 100 and 150 mg L−1 ) were investigated and, the consid-
ered responses were breakthrough time (tb ) (min), maximum
capacity of the column (qeq ) (mg g−1 ) and removal percentage
(R) (%). These levels and factors were based on preliminary
tests and literature. The responses (tb , qeq and R) were repre-
sented as a function of independent variables according to a
 chemical engineering research and design 1 0 0 ( 2 0 1 5 ) 302–310 305

quadratic polynomial model. The statistical significance of the

nonlinear regression was determined by Student’s test. The
second order model was evaluated by Fischer’s test and the
proportion of variance explained by the model obtained was
given by the coefficient of determination, R2 . Experimental
runs were performed at random and the results were analyzed
by Statistic version 9.1 (StatSoft Inc., USA) software.

2.6. Application of dynamic models

Three common dynamic models, called of bed depth ser-

vice time (BDST) (Eq. (5)) (Hutchins, 1973), Thomas (Eq. (6))
(Thomas, 1944) and Yoon–Nelson (Eq. (7)) (Yoon and Nelson,
1984) were fitted to the experimental data in the optimal con-
ditions.

C0
 KN h 
0
= 1 + exp − KC0 t (5)
Ct u
 
C0 kTh qeq m
= 1 + exp − kTh C0 t (6)
Ct Q

C0
= 1 + exp (kYN  − kYN t) (7)
Ct

where K is the adsorption constant rate (mL mg−1 min−1 ), N0

is the adsorption capacity (mg L−1 ), h is the bed depth of
fixed-bed (cm), u is the linear flow rate (cm min−1 ), kTh is
the constant rate of Thomas model (mL mg−1 min−1 ), qeq is
the equilibrium adsorption capacity from the Thomas model
(mg g−1 ), m is the amount of adsorbent in column (g), kYN is the
constant rate of Yoon–Nelson model (min−1 ) and  is the time
required for 50% adsorbate breakthrough from Yoon–Nelson
model (min).
The dynamic parameters were determined by nonlinear
regression using the software Statistic 9.1 (StatSoft Inc., USA).
The objective function was Quasi–Newton. The fit quality was Fig. 3 – SEM images of (a) chitin and (b) USM-chitin.
measured according to the coefficient of determination (R2 )
and sum of square errors (SSE) (El-Khaiary and Malash, 2011).
some cavities. The specific surface areas of chitin and USM-
chitin were, respectively, 2.5 and 50.8 m2 g−1 . The FT-IR bands
2.7. Elution tests and its respective assignments for USM-chitin are presented in
Table 1 (the same bands were found for chitin). For both, chitin
The elution tests were performed ten times in order to ver- and USM-chitin the deacetylation degree was 45 ± 1%. The
ify the bed regeneration and reuse for several consecutive crystallinity index was 85% for chitin and 63% for USM-chitin.
cycles. After the adsorption, USM-chitin/sand loaded with MB These results are in accordance with our previous works (Dotto
(obtained in the optimal adsorption conditions according Sec- et al., 2015b) and confirm that USM-chitin has more adequate
tion 3.3) was removed from the bed, oven dried at 60 ◦ C for 24 h characteristics for adsorption purposes than raw chitin.
and, placed in the bed again. The elution tests were performed
in a laboratory system (Fig. 2) using HCl solution 0.3 mol L−1
3.2. Interpretation of the breakthrough curves
(Dotto et al., 2015b) at flow rate of 20 mL min−1 . The MB con-
centration at the column top was determined according to
The breakthrough curves were constructed at different flow
Section 2.3.
rates (10, 15 and 20 mL min−1 ) and initial MB concentrations
(50, 100 and 150 mg L−1 ) and, are presented in Fig. 4. The results
3. Results and discussion

3.1. Characteristics of ultrasonic surface modified Table 1 – FT-IR bands and assignments of USM-chitin.
chitin Bands (cm−1 ) Assignments

3350 O H and N H stretchings

USM-chitin was characterized by SEM, specific surface area 3000 CH2 stretching
(BET), FT-IR, deacetylation degree and crystallinity index 2800 CH3 stretching
(XRD). The SEM images of chitin and USM-chitin are shown in 1652 C O secondary amide stretch
Fig. 3. A rigid ad smooth surface, without visible pores or cavi- 1551 N H bend and C N stretch of amide I
ties can be observed for chitin (Fig. 3(a)). However, USM-chitin 1018 C O asymmetric stretch in phase ring
745 NH out of plane bending
(Fig. 3(b)) presented a rough surface with protuberances and
306 chemical engineering research and design 1 0 0 ( 2 0 1 5 ) 302–310

Table 2 – Experimental conditions and results for the adsorption of MB on USM-chitin supported sand.
Exp. Flow rate, Q (mL min−1 ) C0 (mg L−1 ) tb (min)* te (min)* Zm (cm)* Veff (mL)* qeq (mg g−1 )* R (%)*

1 10 (−1) 50 (−1) 370 922 15.0 9920 51.8 51.5

2 10 (−1) 100 (0) 123 215 10.7 2800 29.8 54.0
3 10 (−1) 150 (+1) 93 200 13.4 2600 37.6 47.9
4 15 (0) 50 (−1) 171 400 14.3 6600 38.1 58.7
5 15 (0) 100 (0) 81 195 14.6 3150 35.6 57.6
6 15 (0) 150 (+1) 60 155 15.3 3300 38.1 39.5
7 20 (+1) 50 (−1) 122 250 12.9 7500 38.7 51.3
8 20 (+1) 100 (0) 50 135 15.7 3100 31.0 50.3
9 20 (+1) 150 (+1) 45 105 14.3 2600 33.8 44.6

∗
Mean values for two experiments (the maximum error for all values was 6.4%).

regarding breakthrough time (tb ), exhaustion time (te ), length
of mass transfer zone (Zm ), effluent volume (Veff ), maximum
capacity of the column (qeq ) and removal percentage (R) are
shown in Table 2.
It was found in Fig. 4 and Table 2 that the column per-
formance was, in general, improved at lowest initial MB
concentration and flow rate. Three specific facts can be seen
in Fig. 4 and Table 2: (1) the C0 and Q decrease provided longer
breakthrough and exhaustion times; (2) the higher values for
qeq and Veff were found using 50 mg L−1 and 10 mL min−1 ;
(3) In spite of the good bed performance at 50 mg L−1 and
10 mL min−1 , the higher R value was not found in this condi-
tion. The first fact is because at lower concentration gradients
a slower mass transfer occurred, increasing the residence
time in the bed and, allowing the interaction between USM-
chitin and MB. Furthermore, at lowest flow rates, the residence
time of the solute in the bed is sufficient to guarantee the
MB diffussion in the USM-chitin structure. When the flow
rate is increased, the residence time became insufficient to
attain a suitable adsorption capacity. The second fact occurred
because, at lower initial MB concentration and flow rate,
extended breakthrough curves were obtained (Fig. 4), indicat-
ing that a higher effluent volume could be treated (Table 2). As
consequence, the area above the curve was higher, improv-
ing the bed performance. The third fact occurred because the
high length of mass transfer zone found for the experiment
1 (Table 2), which provided a high MB concentration at the
bed outlet for a long time (Fig. 4). Similar trends regarding the
effects of flow rate and initial concentration were found by Tan
et al. (2008) in the MB adsorption onto palm shell activated
carbon and, Ahmad and Hameed (2010) in the adsorption of
reactive dye onto activated carbon from bamboo.
3.3. Determination of the optimal adsorption
conditions
Aiming to obtain the optimal fixed bed adsorption conditions,
the responses, breakthrough time (tb ), maximum capacity
of the column (qeq ) and removal percentage (R) (%) were
optimized as a function of flow rate (Q) and initial MB con-
centration, using the response surface methodology. The
experimental conditions (real and coded) and results are
shown in Table 2.
To verify the significance of Q and C0 on the responses,
Pareto charts were constructed (Fig. 5). As presented in
Fig. 5(a)–(c), all linear, quadratic and interaction effects were
significant on the responses tb , qeq and R (p < 0.05). The sta-
tistical polynomial quadratic model, which represents the
dependence of tb , qeq and R in relation to Q (coded value) and
C0 (coded value) is given by the following equation:
Y =  + ˛Q + ˇQ 2 + C0 + ıC20 + εQC0 (8)
being, Y the considered response (tb , qeq or R), , ˛,
ˇ, , ı and ε, the regression coefficients, which are presented,
for each response, in Table 3.
For an adequate representation of the experimental data,
the statistical model (Eq. (8)) should be predictive and sig-
nificant (Myers and Montgomery, 2002). The prediction and
significance of the statistical model were evaluated by analysis
of variance and Fischer’s F test. The coefficients of determina-
tion were higher than 0.81 and were considered suitable (see
Table 3). Then the models were significant. It was found in
Table 3 that the calculated F values (FCALC ) were higher than
the standard F value showing that the models were predictive.
In addition, the reliability of the models was evaluated com-
paring the experimental versus predicted values (Fig. 6). The
model reliability can be confirmed on the basis in Fig. 6. Once is
statistically suitable, the model (Eq. (8)) was used to generate
response surfaces, which represents tb , qeq and R as a func-
tion of flow rate and initial MB concentration. These response
surfaces are shown in Fig. 7.
Based on the response surfaces and Eq. (8), the optimal
conditions for the fixed bed adsorption of MB on USM-chitin
supported on sand were determined. These conditions were:
flow rate of 10 mL min−1 and initial MB concentration of
50.0 mg L−1 . Under these conditions, the breakthrough time
was 370 min, the maximum capacity of the column was

Table 3 – Regression coefficients and statistical parameters of the quadratic models which represent the breakthrough
time (tb ), maximum capacity of the column (qeq ) and removal percentage (R).
Response Regression coefficients Statistical parameters

 ˛ ˇ  ı ε R2 Fcalc Ftab *

tb (min) 124.22 −122.00 −30.83 −155.83 −59.08 102.50 0.9502 45.76 3.11
qeq (mg g−1 ) 32.49 −2.57 −0.29 −3.11 7.33 2.27 0.8121 6.19
R (%) 55.35 −1.26 −2.14 −4.85 −5.10 −0.88 0.8327 6.68

∗
Significance level of 95% (p < 0.05); the degree of freedom for regression and residues were, respectively, 5 and 12 for all responses.
 chemical engineering research and design 1 0 0 ( 2 0 1 5 ) 302–310 307

1.0

0.8

0.6
C t/ C 0

0.4 -1
(a) 10 mL min
-1
0.2 50 mg L
-1
100 mg L
-1
0.0 150 mg L

0 200 400 600 800 1000

Time (min)

1.0

0.8

0.6
C t/ C 0

0.4 -1
(b) 15 mL min
-1
0.2 50 mg L
-1
100 mg L
-1
0.0 150 mg L

0 100 200 300 400

Time (min)

1.0

0.8

0.6
C t/ C 0

0.4 -1
(c) 20 mL min
-1
0.2 50 mg L
-1
Fig. 5 – Pareto charts for the responses: (a) breakthrough
100 mg L time, (b) maximum capacity of the column and (c) removal
-1
0.0 150 mg L percentage.

0 50 100 150 200 250 300 350

Time (min)
Fig. 4 – Breakthrough curves for the adsorption of MB by
USM-chitin supported on sand: (a) Q = 10 mL min−1 , (b)
Q = 15 mL min−1 and (c) Q = 20 mL min−1 (䊉C0 = 50 mg L−1 ; 
C0 = 100 mg L−1 ;  C0 = 150 mg L−1 ).
51.8 mg g−1 and the removal percentage was 51.5%. Also, the
mass transfer zone was 15.0 cm and the effluent volume
was 9920 mL. The effluent volume treated until the break-
through time was 3700 mL. Auta and Hameed (2014) studied
adsorption of Methylene Blue by chitosan–clay composite
in a fixed-bed column (internal diameter of 1.2 cm, height
of 2.5 cm, C0 = 50 mg L−1 and Q = 5 mL min−1 ). They found tb
lower than 50 min and qeq of 40.8 mg g−1 . Han et al. (2009)
studied adsorption of Methylene Blue by phoenix tree leaf
powder in a fixed-bed column (internal diameter of 1.2 cm,
height of 15.0 cm, C0 = 50 mg L−1 and Q = 8 mL min−1 ). They
found tb about 150 min, qeq of 145 mg g−1 and R of 50.6%. Gong
et al. (2015) studied adsorption of methylene blue by graphite
oxide coated sand in a fixed-bed column (internal diameter of
2.0 cm, height of 15.0 cm, C0 = 50 mg L−1 and Q = 2 mL min−1 ).
They found tb lower than 200 min and qeq of 0.40 mg g−1 .
Comparing our results with the literature, it can be affirmed
that the fixed bed adsorption of MB on USM-chitin/sand is
308 chemical engineering research and design 1 0 0 ( 2 0 1 5 ) 302–310

400
(a)
350

300 350

250 300
Predicted Values

250
200
tb (min) 200
150
150
100
100
50 50
(a) Breakthrough time
0

20
0 50 100 150 200 250 300 350 400 450 Fl
Observed Values
ow 50
Ra
50 te -1 )
(m

15
L 100 mg L
48 m (
in -1 C0
46 ) 0
15

10
44

42
(b)
Predicted Values

40

38 50
36

34 45
32
40
30
qeq (mg g-1)
28 (b) Maximum capacity of the column 35
26
25 30 35 40 45 50 55
30
Observed Values
58
20
Fl

50
56 ow
Ra
54 te -1 )
0
(m gL
15

L 10
52 m (m
in -1 C 0
Predicted Values

10 0
50 ) 15
48

46
(c)
44

42 60
40 (c) Removal percentage

38
55
36 38 40 42 44 46 48 50 52 54 56 58 60 62
Observed Values
R (%) 50
Fig. 6 – Observed versus predicted values for (a)
45
breakthrough time, (b) maximum capacity of the column
and (c) removal percentage.
40
20
Fl
ow 50
technically viable and suitable for future scale-up purposes, Ra
te -1 )
since a promising column performance was obtained. (m 15 0
10 mg L
L (
mi
n -1 10 C0
) 0
3.4. Dynamic models 15

Fig. 7 – Response surfaces for (a) breakthrough time, (b)

In order to find a simple model to represent the fixed bed
maximum capacity of the column and (c) removal
adsorption of MB on USM-chitin/sand (in the optimal con-
percentage as a function of the independent variables.
ditions), the dynamic models called bed depth service time
(BDST) (Eq. (5)), Thomas (Eq. (6)) and Yoon–Nelson (Eq. (7)) were
fitted with the experimental data. The results are shown in The experimental qeq value (qeq(exp) ) was underestimated in
Fig. 8 and Table 4. only11.4% by the Thomas model (qeq ) (Table 4). The value
Based on the high values of R2 (R2 > 0.97) and low values of of  from the Yoon–Nelson model is in agreement with the
sum of square errors (SSE < 0.14) (Table 4) it can be affirmed experimental value ( (exp) ), with percentage deviation of 1.3%.
that all dynamic models were suitable to represent the exper- These facts can be visualized in Fig. 8. BDST, Thomas and
imental breakthrough curve (in the optimal condition). The Yoon–Nelson models were suitable for other fixed bed adsorp-
good fit can be visualized in Fig. 8. Since the models are math- tion systems (Yin et al., 2009; Sugashini and Begum, 2013;
ematically equal (Yin et al., 2009), R2 and SSE were also equal. Vieira et al., 2014).
 chemical engineering research and design 1 0 0 ( 2 0 1 5 ) 302–310 309

dye was removed from the bed until 150 min. The bed perfor-
mance in terms of tb , te , Zm , Veff , qeq and R was maintained for
five adsorption–elution cycles. After, the bed performance was
strongly impaired. These results confirm the technical viabil-
ity of the fixed bed adsorption of MB onto USM-chitin/sand.

4. Conclusion

The technical viability of the fixed bed adsorption of Methy-

lene Blue (MB) by ultrasonic surface modified chitin supported
on sand (USM-chitin/sand) was evaluated, aiming future
scale-up purposes. The optimal bed performance was attained
with flow rate of 10 mL min−1 and initial MB concentration
of 50 mg L−1 . The breakthrough time was 370 min, the maxi-
mum capacity of the column was 51.8 mg g−1 and the removal
percentage was 51.5%. The effluent volume was 9920 mL
and effluent volume treated until the breakthrough time
Fig. 8 – Experimental and predicted breakthrough curve (in
was 3700 mL. In the optimal conditions, BDST, Thomas and
the optimal condition).
Yoon–Nelson models were suitable to predict the bed parame-
ters, such as,  and qeq . The bed performance was maintained
Table 4 – Dynamic parameters for the MB adsorption
after five adsorption–elution cycles. In general lines, it was
according BDST, Thomas and Yoon–Nelson models.
demonstrated the technical viability of the fixed bed adsorp-
BDST model tion of MB on USM-chitin/sand, which is important for future
K (mL mg−1 min−1 ) 0.54
scale-up and industrial applications.
N0 (mg L−1 ) 1870
R2 0.9781
SSE 0.1361 Acknowledgements
Thomas model
The authors would like to thank CAPES (Coordination for
kTh (mL mg−1 min−1 ) 0.54
qeq (mg g−1 ) 45.9 the Improvement of Higher Education Personnel) and CNPq
qeq (exp) (mg g−1 ) 51.8 (National Council for Scientific and Technological Develop-
R2 0.9781 ment) for the financial support. We also thank to Chemaxon
SSE 0.1361 for furnishing an Academic Research license for the software
Yoon–Nelson model MarvinSketch Version 14.9.22.0, (http://www.chemaxon.com),
kYN (min−1 ) 0.027 2014, that was used for obtaining the physical properties
 (min) 458 of the dye. Furthermore, the authors would like to thank
 (exp) (min) 452 CEME-SUL/FURG (Electron Microscopy Center of South / Fed-
R2 0.9781
eral University of Rio Grande/RS/Brazil) due to the scanning
SSE 0.1361
electron microscopy images.

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