Chemical Engineering Communications

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Continuous Adsorption of a Cationic Dye

on Surface Modified Rice Husk: Statistical
Optimization and Dynamic Models

Dison S. P. Franco, Eduardo H. Tanabe & Guilherme L. Dotto

To cite this article: Dison S. P. Franco, Eduardo H. Tanabe & Guilherme L. Dotto (2017)
Continuous Adsorption of a Cationic Dye on Surface Modified Rice Husk: Statistical Optimization
and Dynamic Models, Chemical Engineering Communications, 204:6, 625-634, DOI:
10.1080/00986445.2017.1300150

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Chemical Engineering Communications, 204:625–634, 2017
Copyright © Taylor & Francis Group, LLC
ISSN: 0098-6445 print/1563-5201 online
DOI: 10.1080/00986445.2017.1300150

Continuous Adsorption of a Cationic Dye on Surface Modified

Rice Husk: Statistical Optimization and Dynamic Models
DISON S. P. FRANCO, EDUARDO H. TANABE, and GUILHERME L. DOTTO
Chemical Engineering Department, Federal University of Santa Maria–UFSM, Santa Maria, Brazil

The continuous adsorption of a cationic dye (Methylene Blue, MB) on surface-modified rice husk was investigated. First, rice husk was
submitted to ultrasound-assisted, supercritical CO2 and NaOH treatments. The adsorbents were characterized. Then, the continuous
adsorption was optimized by response surface methodology (RSM), using raw rice husk as the adsorbent. Finally, under the optimal
conditions, breakthrough curves were obtained using all adsorbents and the models were used to interpret these curves. The optimal
bed performance was reached at a flow rate of 5 mL min 1 and an initial MB concentration of 10 mg L 1. Under these conditions,
the breakthrough time was 109 min, the length of the mass transfer zone was 20.1 cm, and the maximum capacity of the column was
1.55 mg g 1. All surface modifications were able to improve the rice husk characteristics in relation to the MB adsorption. Consequently,
the bed performance was significantly improved when the surface-modified adsorbents were used. The breakthrough times were 109, 240,
155, and 385 min, respectively, when raw rice husk, UA–rice husk, SCO2–rice husk, and NaOH–rice husk were used. The length of the
mass transfer zone was 20.1, 7.9, 15.9, and 9.3 cm for raw rice husk, UA–rice husk, SCO2–rice husk, and NaOH–rice husk, respectively.
The dynamic models were able to fit the adsorption data and provided physically consistent parameters.
Keywords: Adsorption; Dynamic models; Optimization; Supercritical; Ultrasound

Introduction
It is estimated that the textile industry generates about 25.000 L
of dye containing effluents per ton of manufactured product
(Kant, 2013; Dod et al., 2015). These colored effluents cause
different effects to the environment, including reduction of
sunlight penetration and photosynthetic activity. Furthermore,
it can be toxic, mutagenic, and carcinogenic (Gupta and Suhas,
2009). Methylene Blue (MB) is a common cationic dye present
in textile effluents, which, at low concentrations (<2 mg L 1),
has many uses, but is toxic at higher concentrations (Ginimuge
and Jyothi, 2010).
Currently, several methods are used to treat colored effluents,
such as chemical precipitation, coagulation, flocculation,
advanced oxidation, adsorption, and others. Among these,
adsorption stands out due its low cost, low energy requirements,
high efficiency, and ease of operation (Dotto et al., 2015a;
Dobre et al., 2016). Continuous adsorption is suitable for the
treatment of large volumes of colored effluents and is a funda-
mental step to scale up the adsorption operation. In continuous
fixed-bed adsorption, activated carbon is normally used as an
adsorbent, but its preparation and regeneration are costly. This
Address correspondence to Guilherme L. Dotto, Chemical
Engineering Department, Federal University of Santa Maria–
UFSM, 1000 Roraima Avenue, 97105–900, Santa Maria, RS,
Brazil. E-mail: guilherme_dotto@yahoo.com.br
Color versions of one or more of the figures in the article can
be found online at www.tandfonline.com/gcec.
aspect makes the search for low-cost adsorbents a field of major
interest (Gupta and Suhas, 2009; Weng et al., 2009; Guo et al.,
2011).
Rice husk, for example, is a low-cost and high-available
waste. Only in the last year, it was estimated a production of
740.2 million tons of paddy rice. As a consequence, 148 million
tons of rice husk were generated (Soltani et al., 2014; FAO,
2015). Despite its adsorbent potential, due the presence of
organic compounds like hemicellulose, cellulose, and lignin,
rice husk has a low surface area. This feature is not desirable
for the adsorption process (Soltani et al., 2014; Thakur, 2014).
An alternative to overcome this drawback is the application of
surface treatments, such as ultrasound assisted, supercritical
CO2, NaOH solutions, and others. The literature shows that
these treatments were able to improve the characteristics of
some adsorbents (Chakraborty et al., 2011; Lin et al., 2012,
2013; Chen et al., 2013; Dotto et al., 2015a,b). Based on this
literature, it is expected that these treatments provoke surface
modifications on the rice husk, which are desirable for MB
adsorption. It should be highlighted that the modifications of
rice husk using these treatments are scarce in the literature.
The majority of these modified materials are applied only in
batch adsorption. However, the influence of these surface
modifications on bed performance was not yet investigated.
Here, the continuous adsorption of a cationic dye (MB) onto
raw rice husk and surface-modified rice husks was addressed.
Rice husk surface was modified using ultrasound-assisted,
supercritical CO2 and NaOH treatments. All samples were
analyzed by scanning electron microscopy (SEM) and Fourier
626 D. S. P. Franco et al.

transform infrared microscopy (FTIR). Response surface

methodology (RSM) was used to optimize the continuous
adsorption as a function of flow rate and initial MB concen-
tration, using raw rice husk as the adsorbent. The breakthrough
time, maximum capacity of the column, and mass transfer zone
were used as responses. In the optimal conditions, fixed-bed
experiments were carried out using raw and surface-modified
adsorbents. Finally, Bed Depth Service Time (BDST), Thomas
and Yoon–Nelson models were fitted to the experimental data.

Material and Methods

Material Obtainment and Surface Treatments
Raw rice husk was received from a local milling industry,
located in southern Brazil. First, rice husk was washed several
times to remove any dust or contaminants. Later, it was dried
at 313 K for 24 h. Raw rice husk surface was modified using
ultrasound-assisted, supercritical CO2 and NaOH treatments.
For the ultrasound-assisted treatment, raw rice husk was mixed
with 700 mL of distilled water and treated using a 400 W
titanium processor (Ultrasonic processor, UP400S, Hielscher,
Germany) with a cycle of 1 and amplitude of 90%. The super-
critical CO2 (White Martins, 99.5%) treatment was performed
using a high-pressure syringe pump (500D, Teledyne Isco,
USA) at 200 bar, in a sealed jacketed stainless steel 304 reactor.
For the NaOH treatment, raw rice husk was mixed with 700 mL
sodium hydroxide solution (2.5 mol L 1) under constant stir-
ring. Each treatment was performed during 2 h using 20 g of rice
husk. The samples were named: raw rice husk, UA–rice husk,
SCO2–rice husk, and NaOH–rice husk. The samples were stored
for further characterization and use. These procedures and con-
ditions were based on preliminary tests.
Characterization Techniques
The adsorbents were analyzed by SEM and FTIR. SEM was
performed (Jeol, JSM 6060, Japan) to visualize the adsorbents
surface (Goldstein et al., 1992). FTIR (Shimadzu, Prestige 21,
Japan) was performed in the range of 500–3500 cm 1 to identify
possible changes in the functional groups (Silverstein et al.,
2007).
Fig. 1. Experimental apparatus for the fixed-bed adsorption.
wavelength of 664 nm, using a UV–Vis spectrophotometer
(Shimadzu, UV mini 1240, Japan). All assays were made in rep-
licate (n ¼ 3) and blanks were performed. For all experimental
points presented in this work, the maximum standard deviation
was 6.4%.
Fixed-Bed Data Analysis
The fixed-bed adsorption data are generally used to obtain oper-
ational parameters. The breakthrough curve is used to obtain the
breakthrough time (tb) and exhaustion time (te). These times are
determined when the outlet MB concentration reaches 5% and
95% of the initial MB concentration, respectively (Suzuki,
1990). Based on the breakthrough and exhaustion times, it is
possible to estimate the length of the mass transfer zone (Zm):
� �
tb
Zm ¼ Z 1 ð1Þ
te
where Z is the bed length (cm). This length represents the
shortest possible adsorbent bed length necessary to obtain the
breakthrough time at t ¼ 0 (Suzuki, 1990).
Considering the total adsorption time, it is possible to deter-
mine the volume of the treated effluent (Dotto et al., 2015a):
Veff ¼ Qttotal ð2Þ

Continuous Adsorption Assays where Q is the flow rate (mL min 1) and ttotal is the total oper-
ation time (min).
The cationic dye, MB (color index 52015, molar weight of The maximum capacity of the column (qeq) can be estimated
319.8 g mol 1, λmax ¼ 664 nm, pKa ¼ 5.6) was purchased from as follows:
Plury chemical Ltda., Brazil. This dye was selected since it is � �
ttotal � � ��
QC0 Z
a common contaminant present in textile effluents. 1000 Ct
The assays were conducted in a laboratory-scale acrylic qeq ¼ 1 dt ð3Þ
m 0 C0
column (height 25 cm and diameter 2.5 cm) as shown in
Figure 1. The column was filled with 11.00 g of raw rice husk where C0 is the initial MB concentration (mg L 1), Ct is the MB
(the adsorbent height inside the bed was 25 cm). The MB sol- concentration along the time (mg L 1), and m is the adsorbent
ution (pH 11, which was adjusted with NaOH) was pumped amount (g).
from the dye reservoir to the column by a peristaltic pump The MB removal percentage (R) can be estimated as follows:
(AWG 5900 ABS, Provitec, Brazil). At the column top, samples Z � � ��
100 ttotal Ct
were collected each 2 min until the bed saturation. The experi- R¼ 1 dt ð4Þ
ttotal 0 C0
ments were performed under different flow rates (5, 10, and
15 mL min 1) and initial MB concentrations (10, 30, and The numerical values of the area above the breakthrough curve
50 mg L 1). The MB concentration was determined at a were estimated by Origin (Origin Lab Corp., USA) software.
Continuous Adsorption of MB Using Modified Rice Husk 627

Statistical Optimization
The MB adsorption onto raw rice husk was optimized by
RSM (Myers and Montgomery, 2002). Flow rate (Q) (5, 10,
and 15 mL min 1) and initial MB concentration (C0) (10, 30,
and 50 mol L 1) were selected as independent variables. The
breakthrough time (tb), maximum capacity of the column
(qeq), and length of the transfer zone (Zm) were used as
responses. A quadratic polynomial model was employed to rep-
resent the dependent variables as a function of the studied
effects. The statistical significance and prediction of the models
were determined by Student's and Fischer tests, respectively.
The model variance was explained by the coefficient of determi-
nation (R2). Experiments were carried out at random. The results
were analyzed by Statistic 9.1 software (Statsoft, USA).

Dynamic Models
In the optimal operational conditions, which were obtained
using raw rice husk, new breakthrough curves were constructed
for MB adsorption on UA–rice husk, SCO2–rice husk, and
NaOH–rice husk. The BDST (Hutchins, 1973), Thomas
(Thomas, 1944), and Yoon–Nelson (Yoon and Nelson, 1984)
models were fitted with the experimental data (Eqs. 6, 7, and 8).
� �
C0 KN0 h
¼ 1 þ exp KC 0t ð6Þ
Ct u
� �
C0 kth qeq m
¼ 1 þ exp kth C0 t ð7Þ
Ct Q
C0
¼ 1 þ expðkYN s kYN tÞ ð8Þ
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 height (cm), u is
the linear flow rate (cm min 1), kth is the constant of Thomas
(mL mg 1 min 1), qeq is the adsorption capacity (mg g 1),
kYN is the constant rate of Yoon–Nelson (min 1), and s is the
time required for 50% of the adsorbate breakthrough (min).
The parameters were estimated by nonlinear regression using
the software Statistic 9.1 (StatSoft Inc., USA). The fit quality
was measured according to the coefficient of determination
(R2) and sum of square errors (SSE) (Dotto et al., 2015a).
Results and Discussion
Adsorbents Characterization
Raw rice husk, UA–rice husk, SCO2–rice husk, and NaOH–rice
husk were characterized by SEM and FTIR. In addition, the
particle size, specific mass, and sphericity were determined
(Tanabe et al., 2016). The particle size, specific mass, and spher-
icity presented no significant differences between the samples
(p > 0.05). For all samples, the particle size was 5.7 � 0.3 mm,
the specific mass was 135 � 5 kg m 3, and the sphericity was
0.35 � 0.02. This indicates that the employed treatments caused
no macroscopic changes on the rice husk.
The SEM images of raw rice husk, NaOH–rice husk, UA–rice
husk, and SCO2–rice husk are shown in Figure 2. For raw rice
husk (a), the surface (lemma) and the silica deposits confirmed
Fig. 2. SEM images of (a) raw rice husk, (b) NaOH–rice husk, (c)
UA–rice husk, and (d) SCO2–rice husk (500�, 30 kV).
by EDS (see red circles and Figure S1) are visualized. In the
NaOH–rice husk (b) the lemma was torn, exposing the tube cells.
In the UA–rice husk (c), the silica deposits on the surface disap-
peared. The SCO2–rice husk (d) presented minor exposures of the
tube cells. The SEM images indicated that microscopic modifica-
tions occurred on the rice husk surface after the treatments. It is
expected that these modifications are favorable for MB adsorp-
tion, due to the exposure of more active sites. Similar surface
modifications were found by Chakraborty et al. (2011) in the
adsorption of Crystal Violet from aqueous solution onto NaOH-
modified rice husk and by Dotto et al. (2015a) in the adsorption
of MB on ultrasonic surface-modified chitin.
FTIR showed that no new bands were formed/removed in
comparison with the raw rice husk. The main identified groups
are presented in Table I. These groups are constituents of
cellulose, hemicellulose, and lignin and are commonly present
in lignocellulosic materials (Thakur, 2014) such as rice husk.
FTIR suggests that the applied treatments affected only the
physical features of the rice husk, since the formation or break
of new links were not detected.
Table I. FTIR bands and assignments for raw rice husk
Bands (cm 1) Assignments
450 Si–O–Si bend
1065 Si–O–SI asymmetric stretch
1429 C–C, C–O ring
1650 C=O
2910 C–H alkane stretch
3450 –OH stretching vibrations
628 D. S. P. Franco et al.

Fig. 3. Breakthrough curves for the adsorption of MB onto raw rice husk: (a) Q ¼ 5 mL min 1, (b) Q ¼ 10 mL min 1, and (c) Q ¼ 15 mL
min 1 (▪ 50 mg L 1, ○ 30 mg L 1, and Δ 50 mg L 1).

For all samples, N2 isotherms were obtained in an adsorption
analyzer (Micromeritcs, ASAP 2020, USA) at 196°C. The
multipoint Brunauer–Emmett–Teller (BET) method was used
to estimate the specific surface area (Brunauer et al., 1938).
The values of specific surface areas were 3.2 � 0.2, 22.5 �
1.3, 13.0 � 0.6, and 47.2 � 1.7 m2 g 1, respectively, for raw rice
husk, UA–rice husk, SCO2–rice husk, and NaOH–rice husk.
These findings confirm that all the treatments were efficient to
increase the available area for MB adsorption.
Column Data Interpretation
The experimental data (breakthrough curves) obtained at
different flow rates and initial MB concentrations are pre-
sented in Figure 3. All operational conditions and process
variables, such as breakthrough time, exhaustion time, length
of mass transfer zone, volume of effluent, maximum capacity
of the column, and removal percentage, are presented in
Table II.

Table II. Experimental conditions and results for the fixed-bed adsorption of MB onto raw rice husk

Run Q (mL min 1) Co (mg L 1) tb (min)* te (min)* Zm (cm)* Veff (mL)* qeq (mg g 1)* R (%)*
1 5 ( 1) 10 ( 1) 109 552 20.1 3275 1.55 54.01
2 5 ( 1) 30 (0) 50 330 20.8 1900 2.34 48.22
3 5 ( 1) 50 (þ1) 19 275 23.3 1650 3.52 48.72
4 10 (0) 10 ( 1) 36 410 22.8 4975 1.27 29.25
5 10 (0) 30 (0) 26 260 22.5 3025 2.44 30.91
6 10 (0) 50 (þ1) 4 150 24.4 2325 2.69 26.58
7 15 (þ1) 10 ( 1) 25 370 23.3 6790 1.73 29.39
8 15 (þ1) 30 (0) 13 215 23.5 3940 2.58 25.09
9 15 (þ1) 50 (þ1) 2 190 24.8 3190 2.76 19.95
*Mean value in replicate (n ¼ 3). The maximum deviation was 3.2%.
Continuous Adsorption of MB Using Modified Rice Husk
From Figure 3 and Table II, it is possible to determine some
important trends: (1) when the flow rate (Q) and/or the initial
MB concentration (C0) were increased, the breakthrough and
exhaustion times decreased; (2) the lower Zm value and the
higher removal percentage (R) were found at a flow rate of
5 mL min 1 and an initial MB concentration of 10 mg L 1; (3)
the high value for the maximum capacity of the column (qeq)
was found for the low volume of the treated effluent (Veff).
All cited facts are directly related with the mass transfer stability
during the experiment. At lower flow rates, the residence time is
higher. This provides a more stable and continuous mass transfer
of MB onto the raw rice husk. The other important aspect is the
role of MB initial concentration. Under high MB concentrations,
the mass transfer gradient is high. This leads to a high value of
maximum adsorption capacity. Similar trends were reported by
Han et al. (2007) in the adsorption of MB onto raw rice husk.
Determination of the Optimal Adsorption Condition
RSM was applied to determine the optimal adsorption condition
for the selected responses (tb, Zm, qeq) as a function of the flow
rate and initial MB concentration. Moreover, RSM was used to
obtain predictive equations, which can represent the responses
as a function of the independent variables. The experimental
conditions (coded and real values) and the respective responses
are presented in Table II. For each response, a statistical
polynomial model, Equation (9), was applied to represent the
Fig. 4. Pareto charts for the responses: (a) breakthrough time, (b) maximum adsorption capacity, and (c) length of the mass transfer zone.
629
response as a function of the independent variables (Myers
and Montgomery, 2002):
Y ¼ l þ aC0 þ bC02 þ cQ þ dQ2 þ eC0 Q ð9Þ
where Y is the response (tb, Zm, qeq); a, b, c, d, and e are the
regression coefficients.
The significance of the linear, quadratic, and interaction
effects on each response was evaluated through Pareto charts
as shown in Figure 4. The results revealed that the majority of
linear, quadratic, and interaction effects were significant for
the tb, Zm, and qeq responses (p < 0.05). The nonsignificant
effects were removed from the analysis. The statistical
polynomial equation should be significant, predictive, and
reliable for a satisfactory representation of the experimental data
(Myers and Montgomery, 2002). The high values of the
coefficient of determination (R2 > 0.96) showed that the
polynomial quadratic models were significant (Table III).
Fischer’s F test was used, and all the F values for each model
were higher than the standard F, showing that the models were
predictive (Table III). Lastly, the reliability of the model was
evaluated by the comparison of the predicted and experimental
values, as presented in Figure 5. It can be seen in Figure 5, that
the models can predict satisfactorily the experimental data.
Based on the above-mentioned statistical evaluation, it can be
affirmed that the polynomial quadratic models were significant,
predictive, and reliable. In this way, tb, Zm, and qeq can be repre-
sented by these models.
630 D. S. P. Franco et al.

Table III. Regression coefficients and statistical parameters of the quadratic models for the responses, breakthrough time, maximum
adsorption capacity of the column, and length of the mass transfer zone

Regression coefficients Statistical parameters

2
Response µ a b c d e R Fcalc Fstandard
tb (min) 32.05 23.90 7.53 25.15 1.66 17.85 0.9725 55.85
qeq (mg g 1) 2.26 0.06 0.29 0.73 0.19 0.22 0.9621 53.36 3.11
Zm (cm) 22.68 1.25 0.62 1.07 0.83 0.45 0.9879 89.93

Since the models were significant, predictive, and reliable,
response surfaces were constructed to represent tb, Zm, and
qeq as a function of Q and C0. These surfaces are presented
in Figure 6. Based on Figure 6 and Equation (9), an optimal
condition was obtained for the fixed-bed adsorption of MB.
This condition occurs when tb and qeq are maximized and
Zm is minimized. It was verified that under the studied
range, any point can simultaneously satisfy these conditions.
Since the bed operation is generally performed until tb, and
Zm is dependent on tb, these two responses were considered
the most relevant. In this sense, the optimal bed performance
was: flow rate of 5 mL min 1 and initial MB concentration
of 10 mg L 1. Under these conditions the breakthrough
time was 109 min, the length of the mass transfer zone was
20.1 cm, and the maximum capacity of the column was
1.55 mg g 1.

Fig. 5. Predicted versus observed values for (a) breakthrough time, (b) maximum adsorption capacity, and (c) length of the mass transfer
zone.
Continuous Adsorption of MB Using Modified Rice Husk
Fig. 6. Response surfaces for (a) breakthrough time, (b) maximum adsorption capacity, and (c) length of the mass transfer zone as
functions of the independent variables.
Effect of Rice Husk Surface Modification on Bed
Performance
In the optimal condition (obtained using raw rice husk), new
experiments were performed with raw rice husk, UA–rice husk,
SCO2–rice husk, and NaOH–rice husk as adsorbents, to investi-
gate the effect of surface modifications on bed performance.
These results are presented in Table IV and Figure 7.
It was verified in Figure 7 that all modifications on the rice
husk surface caused improvements on the breakthrough curves.
The more pronounced improvement was found when NaOH–
rice husk was used. In this case, the breakthrough time increased
631
from 109 to 385 min, the length of the mass transfer zone
decreased from 20.1 to 9.3 cm, the maximum capacity of the
column increased from 1.55 to 2.15 mg g 1, and the removal
percentage increased by 15% (compared with raw rice husk)
(Table IV). The possible explanations are: (1) the surface mod-
ifications provided new available sites for MB adsorption; (2)
the surface modifications caused ruptures on the rice husk,
and opened new possible paths for the influent flow, thus reach-
ing new places for adsorption; (3) the rice husk porosity was
changed, and thus the influent flow pattern and the mass transfer
rate were modified.
632 D. S. P. Franco et al.

Table IV. Experimental fixed-bed parameters for MB adsorption on raw rice husk, UA–rice husk, SCO2–rice husk, and NaOH–rice husk

Adsorbent tb (min)* te (min)* Zm (cm)* Veff (mL)* qeq (mg g 1)* R (%)*
Raw rice husk 109 552 20.1 3275 1.55 54.01
UA–rice husk 240 350 7.9 2125 1.30 67.20
SCO2–rice husk 155 425 15.9 2575 1.20 51.10
NaOH–rice husk 385 615 9.3 3350 2.15 70.01
*Mean value in replicate (n ¼ 3). The maximum deviation was 6.4%.

Table IV shows that NaOH–rice husk presented the best per-

Fig. 7. Effect of the rice husk surface modifications on the
breakthrough curves (▪ raw rice husk, ☆ NaOH–rice husk,
DUA–rice husk, ○ SCO2–rice husk, ___ Model predicted values)
(Q ¼ 5 mL min 1 and C0 ¼ 10 mg L 1).
formance to be applied in fixed-bed adsorption of MB. In this
work, using a column with a height of 25 cm and a diameter
of 2.5 cm, a flow rate of 5 mL min 1, and C0 of 10 mg L 1,
the results were tb of 385 min, Zm of 9.3 cm, and qeq of 2.15
mg g 1 (Table IV). Gong et al. (2015) studied the continuous
adsorption of MB by engineered graphite oxide-coated sand in
a fixed-bed column. They used a column with a diameter of
2 cm and verified the effects of initial concentration
(50–200 mg L 1), flow rate (1–3 mL min 1), and bed height
(10–20 cm). Under these conditions, the qeq values ranged from
0.22 to 0.96 mg g 1 and the maximum value for breakthrough
time was around 200 min. Han et al. (2007) evaluated the
biosorption of MB from aqueous solution by rice husk in a
fixed-bed column. They also studied the effects of initial con-
centration (35–100 mg L 1), flow rate (3.4–8.2 mL min 1),
and bed height (8.4–39 cm). They found the qeq values to be
from 3.23 to 6.63 mg g 1. However, the breakthrough time
was lower than 50 min for all conditions. These results shows
that the NaOH–rice husk used in this work can be an option
for fixed-bed adsorption of MB dye.

Considering all the fixed bed parameters, like tb, te, Zm, Veff,
qeq, and R, it can be stated that all the surface modifications
were favorable for the continuous adsorption of MB. Due to
these modifications, the bed performance was largely improved
as presented in Figure 7 and Table IV.
Application of Dynamic Models
The experimental curves in Figure 7 were fitted with the BDST,
Thomas and Yoon–Nelson dynamic models, in order to better
understand the fixed-bed adsorption of MB. The results are
presented in Table V.

Table V. Parameters of the dynamic models in the fixed-bed adsorption of MB on raw rice husk, UA–rice husk, SCO2–rice husk, and
NaOH–rice husk
Adsorbents
Models Raw rice husk UA–rice husk SCO2–rice husk NaOH–rice husk
Thomas
kth � 103 (L mg 1 min 1) 1.42 5.18 2.60 2.91
qeq (mg g 1) 1.30 1.30 1.17 2.13
qeq (exp)(mg g 1) 1.55 1.30 1.20 2.15
Yoon–Nelson
KYN (min 1) 0.0141 0.0518 0.0260 0.0291
s (min) 285 284 257 468
sexp (min) 275 282 252 465
BDST
K � 103 (L mg 1
min 1) 1.42 5.18 2.60 2.91
No (mg L 1) 115.8 115.3 104.1 189.4
Statistical parameters
R2 0.9853 0.9988 0.9930 0.9975
SSE 0.2748 0.0180 0.1246 0.0514
Continuous Adsorption of MB Using Modified Rice Husk
Based on the high values of the coefficient of determination
(R2 > 0.98) and the low values of the sum of squared errors
(SSE < 0.28), it can be stated that all the dynamic models were
able to represent the breakthrough curves. The R2 and SSE
values were the same for all the models, since these models
are mathematically similar (Yin et al., 2009). The fitted curves
were close to the experimental curves and the parameters were
physically consistent. The theoretical and experimental qeq
values were similar for all adsorbents. In the same way, the
experimental and theoretical s values were in accordance.
Column Regeneration
The column regeneration is a key factor regarding industrial
applications and costs of the adsorption process (Dotto et al.,
2015a). In this work, the regeneration was performed at a flow
rate of 5 mL min 1 using the adsorbent NaOH–rice husk. HCl
and HNO3 (0.5 mol L 1) were tested as eluents during four
cycles. The best results were found using HNO3. In this case,
the bed performance regarding tb, Zm, and qeq was maintained
for two cycles. Next, the bed performance was strongly
impaired. Since rice husk is a low-cost and available waste,
and also the NaOH treatment is of low cost, the application of
the adsorbent for two times is considered suitable.
Conclusion
The continuous adsorption of a cationic dye, MB, on surface-
modified rice husk was studied. It was found that all the
employed modifications caused changes on the rice husk
surface. The application of RSM indicated that the optimal
bed performance, using raw rice husk, was found a at flow rate
of 5 mL min 1 and an initial MB concentration of 10 mg L 1.
Under these conditions, the breakthrough time was 109 min,
the length of the mass transfer zone was 20.1 cm, and the
maximum capacity of the column was 1.55 mg g 1. When the
surface-modified adsorbents were applied, the bed performance
was significantly improved. The breakthrough times were 109,
240, 155, and 385 min, for raw rice husk, UA–rice husk,
SCO2–rice husk, and NaOH–rice husk, respectively. The length
of the mass transfer zone was 20.1, 7.9, 15.9, and 9.3 cm for raw
rice husk, UA–rice husk, SCO2–rice husk, and NaOH–rice husk,
respectively. The dynamic models were able to represent the
adsorption data and provided physically consistent parameters.
This work demonstrated that the surface modifications on the
rice husk were favorable to improve the bed performance in
the MB adsorption.
Supplemental Material
Supplemental data for this article can be accessed on the
publisher’s website at http://dx.doi.org/10.1080/00986445.2017.
1300150
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