Bioresource Technology 163 (2014) 199205

Contents lists available at ScienceDirect

Bioresource Technology
journal homepage: www.elsevier.com/locate/biortech

A new absorbent by modifying walnut shell for the removal of anionic

dye: Kinetic and thermodynamic studies
Jia-Shun Cao a,b, Jun-Xiong Lin b, Fang Fang a,b,, Ming-Ting Zhang b, Zhi-Rong Hu c
a

Key Laboratory of Integrated Regulation and Resource Development on Shallow Lakes, Ministry of Education, Hohai University, Nanjing 210098, China
College of Environment, Hohai University, Nanjing 210098, China
c
EnviroSim Associates Ltd, McMaster Innovation Park, 175 Longwood Road South, Suite 114A, Hamilton, Ontario L8P 0A1, Canada
b

h i g h l i g h t s

g r a p h i c a l a b s t r a c t

 Walnut shell was modied as an

innovative biosorbent for dye

removal.
 The effects of pH and absorbent
dosage on adsorption capacity were
evaluated.
 Adsorption process ts Langmuir
isotherm and pseudo-second-order
kinetic model.
 The modied walnut shell was an
excellent biosorbent for K-2BP
removal.

a r t i c l e

i n f o

Article history:
Received 5 February 2014
Received in revised form 11 April 2014
Accepted 14 April 2014
Available online 24 April 2014
Keywords:
Adsorption
Modied walnut shell (MWNS)
Reactive brilliant red K-2BP (K-2BP)
Kinetics
Thermodynamics

a b s t r a c t
A novel, low cost and easy regeneration biosorbent, chem-modied walnut shell (MWNS), was studied to
investigate its potential for removal of an anionic dye, reactive brilliant red K-2BP. The MWNS was
synthesized with epichlorohydrin and diethylenetriamine as etherifying agent and crosslinking agent,
respectively, and its characteristics were performed with Fourier transform infrared spectroscopy,
scanning electron microscope, electron dispersive spectroscopy and thermogravimetric analysis. The
inuences of pH (0.511) and adsorbent dosage (0.16 g/L) on adsorption capacity of MWNS were evaluated. The maximum K-2BP adsorption capacities (Qm) calculated by best tting model (Langmuir) were
568.18 mg/g at 313 K, which was almost 10 times than that of raw material. The adsorption kinetic was
well conrmed with pseudo-second-order equation. Thermodynamic studies demonstrated adsorption
process by MWNS was spontaneous and endothermic. Furthermore, the regeneration capability of MWNS
implied MWNS was a cheap, excellent and promising biosorbent for K-2BP removal in azo dye wastewater treatment.
2014 Elsevier Ltd. All rights reserved.

1. Introduction
Annually, over seven million tons of dyes are produced in the
world and widely utilized in different industries, including paper,
Corresponding author at: Key Laboratory of Integrated Regulation and Resource
Development on Shallow Lakes, Ministry of Education, Hohai University, Nanjing
210098, China. Tel.: +86 25 83787935; fax: +86 25 83786701.
E-mail address: ffang65@hhu.edu.cn (F. Fang).
http://dx.doi.org/10.1016/j.biortech.2014.04.046
0960-8524/ 2014 Elsevier Ltd. All rights reserved.

plastics, leather, pharmaceutical, food, cosmetics, dyestuffs, and

textiles industries (Afkhami and Moosavi, 2010). In these dyes,
azo dyes are the largest class of dyes and up to 6070% of industrially synthetic dyes (Van der Zee et al., 2001). Considerable amount
of dye-contaminated wastewater discharge in these industries
resulted in a potential risk to human health and ecosystem, since
colored dye efuents would interfere with light penetration in
the receiving water bodies and the degraded by-products had toxic
effects on mammals and aquatic organisms (Guo et al., 2012;

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J.-S. Cao et al. / Bioresource Technology 163 (2014) 199205

Zhang et al., 2012). Due to the resistance of most azo dyes to

normal treatment process, disposal of azo dye wastewater poses
a major environmental problem (Wang et al., 2011). Therefore, efcient and effective treatment approaches are necessary to overcome these problems.
At present, many treatment technologies, such as adsorption,
occulation, super lter lm, oxidation and electrolysis, have been
employed for dye removal from wastewaters (Guo et al., 2012).
Among these methods, adsorption process provides an attractive
alternative for the treatment of dye wastewater, especially the
inexpensive adsorbent (Sureshkumar and Namasivayam, 2008).
Activated carbon, the prevalent adsorbent, is effective for dye
removal. However, because of its high price and hard regeneration
the wide applications of activated carbon were limited (Xia et al.,
2011; Zhang et al., 2012). Thus, more economic, efcient and practical adsorbents are necessary for the dye removal.
Recently, the use of agricultural and forestry wastes as biosorbent for dye removal have attracted great attentions due to their
abundance and low prices (Ardejani et al., 2008; Mall et al.,
2006; Zhang et al., 2012). Walnut shell (WNS), an abundant agricultural residue with good stability, large specic surface area, high
mechanical strength, good chemical stability and easy regeneration, has been successfully used in the removal of heavy metals
in wastewater such as cesium, copper, chromium (VI), zinc and
mercury by adsorption (Ding et al., 2013; Kim et al., 2001;
Pehlivan and Altun, 2008). Especially, after the modication of
WNS with amino groups, the adsorption efciency of the modied
WNS for metal ions removal improved signicantly due to the
binding reaction, complexation or electrostatic action between
the modied material and metal ions (Chen et al., 2010; Zhang
et al., 2011). However, studies on walnut shell modication for
contaminant removal are still insufcient, especially for anionic
dye removal.
Therefore, in this study modied walnut shell (MWNS) was
synthesized, characterized and used for the removal of a model
azo-Reactive Brilliant Red K-2BP (abbreviated as K-2BP hereinafter). The inuences of pH and absorbent dose on dye absorption
were investigated. The mechanism of K-2BP absorption by MWNS
was deduced with isotherms, kinetics and thermodynamics
results. Furthermore, desorption and reusability of the modied
adsorbents was evaluated after adsorption of dyes. The aim of this
study is to provide a cheap, excellent and promising biosorbent of
MWNS for K-2BP removal in azo dye wastewater treatment.
2. Methods
2.1. Reagents
Diethylenetriamine (DETA) and epichlorohydrin were
purchased from KeLong Chemical Co. Ltd. (China), and Reactive
brilliant red K-2BP (C25H14Cl2N7Na3O10S3, molecular weight of
808.48 g/mol) was purchased from Jinan Xinxing Dye Chemical
Co. Ltd. (China). All chemical reagents were of analytical grade
and all solutions used in the experiments were prepared with distilled water (resistivity 18.24 X cm).

size in the range of 6575 lm. The sieved WNS was stored in a
desiccator for further use or modication.
The modication process of WNS was performed as follows:
rstly, 15 mL of NaOH (1.25 M) was blended with 10 mL epichlorohydrin on a shaker at room temperature. Then, 1 g of prepared
WNS was immersed into the solution at 40 C for 30 min equipped
with thermostat. After the mixtures washed several times to the
eluent pH neutral, the obtained materials (called M1-WNS) was
dried at 65 C until reaching constant weight.
Afterwards, the admixture solution with 15 mL of NaOH
(0.125 M) and 2.5 mL of DETA was added into M1-WNS powder
captured previously. The mixtures were mechanically stirred at
65 C for 60 min, and subsequently were washed with deionized
water until the pH of eluent reached almost neutral. Finally, the
washed powder was dried in vacuum at 65 C for 3 h, grinding
sieved to get cationic amino-modied sorbent products of modied walnut shell (MWNS). The modication process involved a series of associated reactions is illustrated in Fig. 1.
2.3. Absorption experiment
The absorptions of K-2BP from aqueous solutions were carried
out in a series of 100 mL Erlenmeyer asks with MWNS mentioned
above. The effect of initial solution pH on the removal of K-2BP was
performed in the range of 0.511, containing 50 mL of dye solution
with its concentration of 200 mg/L. The pH was adjusted using
0.1 M HCl or 0.1 M NaOH. Adsorbent doses varied from 0.1 to
6 g/L were conducted to investigate the inuences of adsorbent
content on K-2BP removal. Besides, the adsorption equilibrium
studies were analyzed at initial K-2BP concentration ranged from
20 to 1000 mg/L (pH 2.5), and different temperatures of 283, 298
and 313 K were considered for thermodynamic studies. The experimental conditions of kinetic studies were identical to those of pH
tests. During the batch adsorption studies, the asks containing
adsorbent and adsorbate were agitated with 180 rpm in a thermostatic shaker (Constat-temperature shaker SHZ-82) and the aqueous samples were taken at preset time intervals. Afterwards, the
asks were withdrawn and the residual dye concentrations were
measured spectrophotometrically. All tests were performed with
three replicates and the mean values were used for subsequent
analysis.
2.4. Desorption and regeneration studies
To regenerate the used MWMS for further dye removal, desorption and regeneration experiments were conducted in batch mode.
Firstly, the 200 mg/g K-2BP loaded MWNS (K-2BP-MWNS) was
obtained by immerging 0.5 g adsorbent into 1 L K-2BP solution.
Subsequently, the K-2BP-MWNS was placed into NaOH solution
with different concentrations ranged from 0.1 to 0.5 M, and then
was shaken on gas bath constant temperature oscillator at room
temperature for 5 h. The spent MWNS were followed neutralized
with HCl of 0.5 mol/L for another 5 h. Furthermore, the reusability
of the regenerated MWMS was tested by executing further 8
consecutive adsorptiondesorption experiments at the same
adsorption conditions.

2.2. Synthesis of modied WNS

2.5. Analytic methods

The walnut shell used in this study was obtained from Nanjing,
China. Prior to modication, WNS was boiled for 60 min to get rid
of the pulp and residual seed capsule. Then, it was rinsed thoroughly with deionized water (changed daily) to wipe off y ash,
residual adhesive esh and other inorganic impurities. The clean
WNS was dried for over 24 h at 105 C until constant weight, followed by crushed and sieved to obtain the powders with particle

The dye concentrations were measured using a UVVIS spectrophotometer (ALPHA-1506, China) at the maximum wavelength of
539 nm. The surface features of WNS, MWNS and K-2BP adsorbed
MWNS (abbreviated as K-2BP-MWNS) were performed by scanning electron microscope (SEM), (HITACHIS-4800 N, Japan). The
working distance and acceleration voltage of SEM were set as
25 mm and 3.0 kV, respectively. The specic surface area, total

J.-S. Cao et al. / Bioresource Technology 163 (2014) 199205

201

Fig. 1. (A) The modication process of MWNS; and (B) the associated reactions of the modication process.

pore volume and average pore diameter of WNS and MWNS were
calculated by automatic specic surface area/pore size distribution
measurement (BelSorp Max, Japan). The element compositions of
WNS, MWNS and K-2BP-MWNS were determined using energy
dispersive X-ray spectroscopy (EDS) (EX-250, Japan). The surface
functional groups and structure of WNS and MWNS were conducted with Fourier transform infrared spectroscopy (FTIR) (Nexus
870, USA). The thermal stabilities of WNS and MWNS were investigated using thermogravimetric analysis (TGA) (Pyris 1 DSC, USA).
The zeta potential of the modied material at various acidities was
measured by solid addition method (Kiefer et al., 1997).
2.6. Calculations
The removal efciency (%) and adsorption capacity of
WNS and MWNS were determined according to the following
equations:

Efficiency %

qt

C0  Ct
 100%
C0

C 0  C t  V
M

where C0 and Ct (mg/L) are the dye concentrations at initial condition and time t, respectively; V (L) is the volume of solution; M (g) is
the mass of adsorbent; and qt (mg/g) is the amount of dye adsorbed
onto MWNS at time t.
3. Results and discussion
3.1. Characterization of modied WNS
3.1.1. FTIR analysis
The FTIR spectrum of WNS without any modication is illustrated in Fig. S1. The pronounced peak located at 3358
3396 cm1 is assigned to the OH stretching vibration of hydroxyl
groups or adsorbed water (Yang and Qiu, 2010; Yu et al., 2013). The
bands at around 2935 and 2883 cm1 are attributed to CH
stretching vibrations in methyl and methylene groups, while the
CH in-plane bending vibrations in methyl and methylene groups
cause the band at around 1462 and 1376 cm1 (Sun and Webley,
2010; Yang and Qiu, 2010). The C@C stretching vibrations result

in the band at around 1597 cm1, while the C@C skeletal vibrations
lead to another two bands at around 1506 and 1425 cm1 (Yang
and Qiu, 2010). The peak at 1245 cm1 and an intense band at
around 1051 cm1 can be attributed to CO stretching vibrations
in alcohols, phenols, or ether or ether groups (Garnier et al.,
1982; Yang and Qiu, 2010).
Fig. S1 also gives the FTIR spectra of the modied WNS and
K-2BP-MWNS. A strong broad band of the MWNS appeared in the
range of 33583396 cm1 mainly attributed to the NH stretching
vibrations, indicating that many amine groups were grafted on the
surface of MWNS after the modication (Deng et al., 2003). The
new band generated at 1649 cm1 can be ascribed to NH bend
vibrations (Wang et al., 2010). It eventually vanished after dye
adsorption, probably assigned to the K-2BP molecules occupied
the active sites of the adsorbent. The peak at 1739 cm1 assigned
to C@O stretching vibrations and that at 1158 cm1 attributed to
the CO stretching vibration indicated the presence of carboxyl
groups on the WNS (Fig. S1) (Liu et al., 2006; Yang and Qiu,
2010). Compared with WNS, the two function groups disappeared
in MWNS, suggesting the acylated condensation reaction between
the amino-group of DETA and carboxyl groups of WNS took place
in the modication process (Gong et al., 2005). Additionally, the
new peak of K-2BP-MWNS at 1539 cm1 emerged because aromatic heterocyclic existed in K-2BP and it proved the adsorption
of K-2BP on MWNS.

3.1.2. SEM image analysis and aperture size

The morphological microstructures and surface characteristics
of WNS, MWNS and K-2BP-MWNS at three different magnications were observed with SEM (Fig. S2). The surface morphology
of WNS has a texture with high microporosity and gyroscopic
rotary shapes, while the surfaces of MWNS became smooth like a
glossy biscuit due to lled with organic modiers during the chemical modication process. As listed in Table S1, the specic surface
area, total pore volume and average pore diameter of WNS and
MWNS varied considerably even though the particle size distribution of both was almost the same (Fig. S3). The surface morphology
of MWNS is obviously different after the loading of K-2BP and has a
rugged and coral-like structure (Fig. S2). These photomicrographs
conrm that adsorption occurred after the contact of MWNS with
K-2BP solution.

J.-S. Cao et al. / Bioresource Technology 163 (2014) 199205

400
Adsorption capacity-MWNS
Adsorption capacity- WNS

300

MWNS

250
200
150

80%

2
1
0

60%

-1
-2

pH

(A)

100

10

12

40%

20%

WNS

50

100%

Removal efficiency (%)

Removal efficiency-MWNS
350
Zeta potential(mv)

3.1.3. EDS spectra analysis and element composition

The EDS spectra of WNS depicted in Fig. S4(A) and the corresponding element compositions listed in Table S2 indicate that
the raw material mainly consists of C and O, and trace amounts
of Ca. The large proportions of carbon and oxygen attributed to
the polysaccharides such as cellulose, hemi cellulose and lignin
in WNS (Feng et al., 2013). After modication, the contents of C
and Ca had a slightly increase. Oppositely, the oxygen peak was
slightly decreased, resulting from the introduction of amino in
the modication process by DETA (Fig. S4B) and Table S2). Furthermore, the presence of S and Cl peaks in spectra was due to the
chemisorption process of K-2BP onto the surface of MWNS
(Fig. S4C). The mechanism of interaction between K-2BP molecules
and MWNS is illustrated in Fig. S5.

Adsorption capacity (mg/g)

202

0
0

0%
12

10

pH
500

100%
Adsorption capacity-MWNS
Removal efficiency-MWNS

400

80%

Cl
NaSO3

OH

300
N

200

HN

C
NH

NaSO3

60%
Cl

NaSO3

40%

K-2BP

100

(B)

Removal efficiency (%)

Adsorption capacity (mg/g)

3.1.4. TGA analysis and chemical stability

Thermal analysis technique was used to analysis the relationship between substance mass and temperature. The thermal
stability of WNS and MWNS under air atmosphere from 25 C to
770 C with an increase rate of 20 C/min was evaluated (Fig. S6).
Initially, there was a slight decline in mass of both WNS and
MWNS up to 100 C by 10.15% and 13.22%, respectively, due to
the release of moisture from two adsorbents. The amplitude of
substance mass reduce of MWNS was greater than that of WNS,
probably because of high humidity of MWNS caused by chemical
modication. As shown in Fig. S6, the thermal degradation of
the WNS and MWNS both started after 280 C. The feature of
prepared adsorbent well proved appropriate for the real eld
application of MWNS in air atmosphere. In addition, the chemical
stability of the modied adsorbent was checked by soaking MWNS
in strong acidic (pH = 3) or alkaline medium (pH = 12) for 3 h
(Atia et al., 2009). No obvious dissolution of modied materials
was observed, demonstrating the favorable chemical stability
of MWNS.

20%

0
0

Dosage (g/L)
Fig. 2. (A) The effects of pH on K-2BP by WNS and MWNS (conditions: temperature,
25 1 C; adsorbent dosage, 0.5 g/L; stirring rate, 160 rpm; react time, 180 min;
initial dye concentration, 200 mg/L) and the zeta-potential curves for MWNS as a
function of pH; and (B) the effect of adsorbent dosage on the removal efciency
of dye.

3.2. Inuence of pH and dosage on K-2BP removal

The inuence of pH (0.511) on K-2BP adsorption is illustrated
in Fig. 2(A). The removal efciency of K-2BP was increased with the
decrease in pH. When solution pH was lower than 3, the adsorption
capacity of MWNS on K-2BP reached about 300 mg/g (pH = 2). The
value was almost 20 and 4 times higher than that of WNS and
commercial activated carbon, respectively, at the same reaction
conditions. This could be attributed to zeta potential changes in
surface electric charge of the MWNS (Fig. 2(A)) (Chen et al.,
2010; Kiefer et al., 1997). Various functional groups such as amine,
hydroxyl and carbonyl groups distributed on the surface of MWNS
(Fig. S5) were affected by solution pH (Dawood and Sen, 2012; Mall
et al., 2006). Lower pH led to a higher concentration of hydrogen
ion with positive charge in the solution, resulting in more amine
groups of MWNS protonated and distributed on the surface. Due
to the interaction of sulfonic acid groups of the dyes and protonated amino group (NH+3) of MWNS, the anionic dye could be
removed by electrostatic action (Eq. (3)) (Wang et al., 2010):

increased signicantly (from 25.9% to 99.6%) when the adsorbent

dosage was gradually raised from 0.1 to 1 g/L. However, the
adsorption capacity for per unit mass of adsorbent decreased sharply from 480.5 mg/g to 184.8 mg/g. When the dosage was further
increased (from 1 to 6 g/L), the adsorption capacity changed
slightly. As the adsorbent dosage increased, a substantial increase
in available adsorption sites resulted in a high percentage of
adsorption. Furthermore, the competition of dye molecules for
available adsorption sites, further agglomeration of the adsorbent
particles, and an increase in diffusion path length may be the reasons for the decrease in K-2BP uptake at higher adsorbent dosage
(Baral et al., 2008; Chen et al., 2010). Therefore, taking the removal
efciency of K-2BP and economy into account simultaneously, a
dosage of 1 g/L was chosen for later studies.

MWNS  NH2 NaSO3  A HCl ! MWMS  NH3  O3 S A NaCl

Adsorption isotherms are signicant prerequisites to establish

the most appropriate relationship between adsorbate and
adsorbent, and are critical in optimizing the design of an adsorption
system for dye removal (Parab and Sudersanan, 2010; Xia et al.,
2011). Lots of isotherm equations can be utilized to establish the
correlation, such as Langmuir, Freundlich and DubininRadushkevich (DR) models (Ding et al., 2013; Parab and Sudersanan,
2010). The corresponding isotherm equations are represented as:

By contrast, as pH increased, deprotonation started and the

reduction of electrostatic attraction resulted in the decrease in
adsorption capacity of the MWNS. The corresponding reaction
formula was shown in Fig. S7. As illustrated in Fig. S5, the strong
hydrogen bonding between K-2BP and MWNS could enhance the
sorption as the strong combination of hydrophilic functional
groups between dyes and MWNS (Wang et al., 2010).
The inuence of adsorbent dosage on K-2BP removal efciency
is depicted in Fig. 2(B). The adsorption removal efciency of K-2BP

3.3. Adsorption isotherms

Langmuir isotherm :

Ce
1
Ce

qe K L Q m Q m

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J.-S. Cao et al. / Bioresource Technology 163 (2014) 199205

where Ce (mg/L) is the ultimate concentration of K-2BP at equilibrium and qe (mg/g) is the corresponding adsorption capacity. Qm
(mg/g) is the theoretical maximum monolayer K-2BP adsorption
capacity of adsorbent, and KL (L/mg) is the Langmuir isotherm coefcients related to the free energy of adsorption:

Freundlich isotherm : ln qe ln K F

ln C e
n

where KF ((mg/g)(L/mg)1/n) and 1/n are the adsorption constants of

Freundlich model generally related to the strength of interaction
between adsorbate and sorbent:

DR equation : ln qe ln Q m  K D


2
1
RT ln 1
Ce

where KD (mol2/kJ2) is the DR model constant related to the free

energy of adsorption. R is the gas constant of 8.314 J/mol K and T
(K) is the absolute temperature of environmental conditions.
The adsorption isotherm constants of K-2BP adsorption process
on MWNS are listed in Table 1. The low value of the linear correlation coefcient R2 indicated the unsuitability of DR isotherm
model. The values of R2 for Freundlich model (0.885, 0.937 and
0.955 at 283 K, 298 K and 313 K, respectively) were high, indicating
that this model can be used to characterize the equilibrium adsorption. However, Freundlich model was not the best model in this
study. Langmuir models were tting well to the isotherm data at
various temperatures with highest R2 values, compared to DR
and Freundlich models. The results of Langmuir model demonstrated that homogeneous monolayer K-2BP was covered onto
MWNS particles (Yang et al., 2014; Yuvaraja et al., 2014). Furthermore, the results indicated that the adsorption of K-2BP was a
dynamic chemisorption process by the adsorption afnity in terms
of surface functional groups and bonding energy (Dawood and Sen,
2012; Feng et al., 2013). The maximum adsorption capacities (Qm)
of MWNS for K-2BP were 448.43 mg/g, 495.05 mg/g and
568.18 mg/g at 283 K, 298 K and 313 K, respectively, and were
almost the same as those of experiment dates.
A dimensionless constant called separation factor (RL) was
applied to evaluate the suitability of an adsorption process, and
it was dened as the following equation (zacar and Sengil,
2002; Xia et al., 2011):

RL

1
1 K LC0

where C0 (mg/L) is the initial dye concentration in solution and KL

(L/mg) is the Langmuir isotherm coefcients related to the free
energy of adsorption. As listed in Table 1, the values of RL at three
different temperatures were all in the range of 01, implying the
sorption process belonging to a favorable uptake of K-2BP by
MWNS (Atia et al., 2009; Bhaumik et al., 2013).

3.4. Adsorption kinetics

The adsorption dynamics were investigated to detect how
rapidly the adsorption progress was and whether the process
was controlled by chemical or physical adsorption (Chen et al.,
2010). Several kinetic models including pseudo-rst-order,
pseudo-second-order, Elovich equation and intraparticle diffusion
models were selected to determine the relationship between the
amount of adsorbate and reaction time. The four equations were
expressed as follows (Wang et al., 2011):

Pseudo-first-order kinetic model : lnqe  qt ln qe  k1 t

where qe (mg/g) and qt (mg/g) refer to the adsorption amount of K2BP for MWNS at equilibrium and at time t (min), respectively. k1
(1/min) is the equilibrium rate constant of pseudo-rst-order
adsorption:

Pseudo-second-order equation :

t
1
t

qt k2 q2e qe

where k2 (g/(mg min)) is the equilibrium rate constant of pseudosecond-order adsorption. Moreover, h (mg/g min) was used to calculated the initial adsorption rate constant determined by k2 and qe:

h k2 q2e

10

Elovich kinetic model : qt

1
1
lnab ln t
b
b

11

where a (mg/(g min)) is the initial adsorption rate of the Elovich

equation, and b (g/mg) is the desorption constant related to the
extent of surface coverage and activation energy constant for
chemisorption (Chang and Juang, 2005):

Intraparticle diffusion equation : qt K p t 1=2 C

12

where C is a constant related to the thickness of the boundary layer,

Kp is the diffusion rate constant (Xia et al., 2011).
Table 2 summarizes the parameters of the four kinetic models
for adsorption of K-2BP on MWNS. The correlation coefcients of
intraparticle diffusion equation was below 0.9 (R2 = 0.891), indicating that the adsorption process was not consist of intraparticle diffusion (Dawood and Sen, 2012; Wang et al., 2010). The adsorption
of K-2BP on MWNS probably not obey the pseudo-rst-order
kinetic model because the obtained qe did not satisfy the experiment value despite of its high value of R2 (R2 = 0.934). The highest
R2 (R2 = 0.999) and well agree of calculated qe (qe,exp = 266 mg/g)
showed that the adsorption process could be best described by
the pseudo-second-order equation. This result indicated that
chemisorption was the rate-limiting step in adsorption process.
Previous studies reported the chemisorption involved valency
forces through sharing or exchange of electrons between adsorbate

Table 1
Adsorption isotherm constants for K-2BP adsorption onto the MWNS.
Isotherm models

Parameters

283 K

298 K

313 K

Langmuir

Qm (mg/g)
KL (L/mg)
RL
R2

448.43
0.045
0.0150.526
0.999

495.05
0.057
0.0120.467
0.999

568.18
0.060
0.0110.455
0.999

Freundlich

KF ((mg/g)(L/mg)1/n)
1/n
R2

106.58
0.2214
0.885

153.48
0.1777
0.937

168.38
0.1850
0.955

D-R

Qm (mg/g)
KD (mol2/kJ2)
R2

335.79
1E-07
0.847

353.58
1E-08
0.741

392.80
1E-08
0.764

445.50

490.80

560.58

Qexp (mg/g)

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J.-S. Cao et al. / Bioresource Technology 163 (2014) 199205

Table 2
Kinetic parameters for the adsorption of K-2BP on MWNS with different models.
qe (mg/g)

266

Pseudo-rst-order kinetic model

qe,cal (mg/g)
172.64

Pseudo-second-order kinetic model

qe,cal (mg/g)
277.78

Elovich model

h (mg/g min)
31.64

218.93

To better understand the inuences of temperature on the

adsorption of K-2BP on MWNS, three thermodynamic parameters
of the adsorption process were investigated, including the changes
in enthalpy (DH0), entropy (DS0) and free energy (DG0). The
changes in enthalpy and entropy were determined with the equations below (Gong et al., 2008; Lin et al., 2011):

DG0 DH0  T DS0

13

DS0 DH 0

R
RT

14

where KC (L/mol) is thermodynamic adsorption equilibrium constant and calculated by Eq. (15) below. Here, S0 (J/mol K) is standard
entropy, H0 is standard enthalpy, T is the absolute temperature and
R is the gas constant valued 8.314 J/(mol K). The values of H0 and S0
were determined from the slope and intercept of the tted curve,
respectively. The Gibbs free energy of adsorption (G0) subsequently
determined from the identied parameters H0 and S0 by Eq. (13)
(Gong et al., 2008):

qe
Ce

R2
0.983

3.6. Desorption experiments

The excellent regeneration capability is crucial for an absorbent
after adsorption of contaminants, promoting the reuse of adsorbent in contaminants removal. Thus, the regeneration capability
of MWNS was evaluated by performing desorption experiments.
In the desorption experiment, a range of concentrations of sodium
hydroxide solution (0.10.5 M) were added. As depicted in Fig. 3,
the regeneration capability of the novel adsorbent increased with
the increase in NaOH concentrations from 0.1 M to 0.4 M. However, when NaOH concentration was increased to 0.5 M, its regeneration capability was decreased to 96.7%. The K-2BP adsorption
capacity of MWNS for another 3 consecutive adsorption/desorption (0.4 M NaOH) is also presented in Fig. 3. It demonstrated that
the K-2BP adsorption capacity of the modied adsorbent decreased
slightly (the removal efciency maintained above 90%) even over
eight successive regeneration process.
For desorbing and regenerating the depleted adsorbent, the
ionic interaction was the primary removal mechanism. The elution
of K-2BP from MWNS was resulted from deprotonation of the
amine groups under basic conditions (Atia et al., 2009). The relevant chemical reaction, an electrostatic reaction equation, can be
expressed by Eq. (16), in which A is the hydrolyzed form of dye
(K-2BP) in solution:

100

Removal efficiency(%)

where qe is the equilibrium dye concentration on the adsorbent

(mg/L) and Ce is the equilibrium dye concentration in solution
(mg/L).
The obtained values of thermodynamic parameters for K-2BP
adsorption onto MWNS are listed in Table 3. The positive values
of H0 indicated that the adsorption process was endothermic and
physical in nature. An increase in temperature would lead to an
increase in adsorbate on MWNS (Chen et al., 2010). The positive
S0 corresponded to an increase in the degrees of freedom of the

98
100%

96

40%

94

92
0

20%

K-2BP
0

80%
60%

Table 3
Thermodynamic parameters of adsorption of K-2BP on MWNS.

283
298
313

b
0.025

solidliquid interface during adsorption process of K-2BP onto

MWNS. On the other hand, the negative values of G0 conrmed
that the appetent adsorption of the dye K-2BP on MWNS was spontaneous and thermodynamically favorable.

15

R2
0.999

H
(kJ/mol)

S
(J/(mol K))

TS
(kJ/mol)

G
(kJ/mol)

12.54

57.67

16.32
17.18
18.05

3.78
4.64
5.51

0.977

Removal efficiency

3.5. Thermodynamics studies

Temperature (K)

k2 (g/mg min)
0.00041

R2
0.891

and adsorbent (Dawood and Sen, 2012; Wang et al., 2010). The
high h value (Table 2) conrmed that the adsorption of K-2BP
may be carried out via surface exchange reactions until the surface
functional sites were occupied (Wang et al., 2010). On the other
hand, the high value of the correlation coefcients of Elovich equation (R2 = 0.983) revealed that the adsorption behavior of K-2BP on
MWNS was not only chemisorptions, but also an ion exchange
reaction (Zhang et al., 2012).

KC

R2
0.934

Kp (mg/gmin)
11.713

Intraparticle diffusion equation

ln K C

k1 (1/min)
0.062

0.1mol/L
0.2mol/L
0.3mol/L
0.4mol/L
0.5mol/L

0%

Adsorption/desorption cycle

Times
Fig. 3. Desorption of K-2BP from MWNS using 0.10.5 M NaOH solution and the
regeneration of MWNS using 0.4 M NaOH solution for 8 adsorption/desorption
cycles.

J.-S. Cao et al. / Bioresource Technology 163 (2014) 199205

MWNS  NH3 A NaOH ! MWNS  NH2 NaA H2 O

16

This characteristic may be attributed to the bonds between dye

molecules and modied sorbent substantially disconnected after
alkali treatment. The results showed that MWNS is an excellent
candidate for effective and efcient removal of K-2BP from dye
wastewater.
4. Conclusion
In this study, the modied WNS was effective in removal of
reactive brilliant red K-2BP. The adsorption isotherms indicated
that the surfaces of MWNS were distributed by a homogeneous
monolayer of K-2BP with a dynamic chemisorption process. The
adsorption kinetics studies suggested that the adsorption of K2BP on MWNS was chemisorption involving valency forces
through sharing or exchange of electrons between adsorbate and
adsorbent. Furthermore, the adsorption process was spontaneous,
endothermic and thermodynamically favorable. This work clearly
demonstrates that the MWNS is a feasible, effective, efcient, economic and promising candidate for azo-based dyeing wastewater
treatment.
Acknowledgements
This work was supported by the Natural Science Foundation of
China (51008112), and the Key Special Program for the Pollution
Control (2012ZX07101-003 and 2011ZX07301-002).
Appendix A. Supplementary data
Supplementary data associated with this article can be found, in
the online version, at http://dx.doi.org/10.1016/j.biortech.2014.04.
046.
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