Desalination 259 (2010) 249–257

Contents lists available at ScienceDirect

Desalination
j o u r n a l h o m e p a g e : w w w. e l s e v i e r. c o m / l o c a t e / d e s a l

Removal of methylene blue from aqueous waste using rice husk and rice husk ash
Pankaj Sharma a,⁎, Ramnit Kaur b, Chinnappan Baskar a, Wook-Jin Chung a
a
Energy and Environment Fusion Technology Center, Department of Environmental Engineering and Biotechnology, Myongji University, San 38-2, Nam-dong,
Cheoin-Gu, Yongin-Si 449-728, Republic of Korea
b
Department of Chemistry, Lovely School of Sciences, Lovely Professional University, Phagwara 144402, Punjab, India

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

Article history: Present study investigates the potential use of pretreated rice husk (RH) and rice husk ash (RHA) for the
Received 12 January 2010 removal of methylene blue (MB) from wastewater. A series of batch experiments were carried out to
Received in revised form 2 March 2010 determine the influence of different system variables. Neutral pH was optimum for the removal of MB.
Accepted 23 March 2010
Adsorption of MB on RH and RHA was favorably influenced by an increase in the temperature of the
Available online 13 May 2010
operation. The comparative studies of these two adsorbents, RA and RHA with the earlier reported
Keywords:
adsorbents obtained from agricultural and industrial waste products, inorganic materials and bioadsorbents,
Rice husk reveals that RH and RHA have maximum adsorption capacity. Adsorption data was fitted to the Langmuir,
Dye and Freundlich adsorption model. The former model achieved best fit with the experimental data and its
Adsorption calculated maximum monolayer adsorption capacity have a value of 1347.7 mg g− 1 for adsorption on RH
Methylene blue and 1455.6 mg g− 1 for adsorption on RHA at a temperature of 323 K. The change in heat of adsorption (ΔHo)
Isotherm and entropy (ΔSo) values for MB adsorption on RH as well as RHA were positive. The high negative values for
Pretreatment Gibbs free energy (ΔGo) indicate the feasible and spontaneous adsorption of MB on RH and RHA.
© 2010 Elsevier B.V. All rights reserved.

1. Introduction wastewater can be carried out by flotation, chemical coagulation,

Synthetic dyes have been used widely in various industries including
paper printers, dye houses and textile dyers. Considerable amounts of
synthetic dyes are lost annually to waste streams during textile
processing, which ultimately enters the environment. The presence of
small amounts of dyes in water is highly visible and undesirable [1]. The
effluents from textile, leather, food processing, dyeing, cosmetics, paper,
and dye manufacturing industries are the major sources of dye
pollution. Various kinds of dyes and their break down products are
toxic for the living organisms. Fifteen percent of the total world
production of dyes goes off during the dyeing process and have been
released in textile effluents [2]. The release of this colored wastewater is
hazardous for the aquatic life. At the receiving streams, the colored
wastes interfere with the transmission of sunlight into streams and
reduce the photosynthetic activity. From the environmental point of
view, the removal of synthetic dyes is of great concern. Since some of the
dyes and their degradation products may be carcinogenic and toxic,
such that, their treatment cannot be left upon the bio-degradation alone.
Recently, an increased interest has been focused on removing dyes from
the water due to its refractory bio-degradation and toxic nature which
affects the aquatic biota and food web [3]. The removal of color from
⁎ Corresponding author. Tel.: +82 31 336 8471; fax: +82 31 337 2902.
E-mail address: sharmapankaj47@yahoo.com (P. Sharma).
chemical oxidation and adsorption. Adsorption technique is quite
popular due to its simplicity as well as the availability of a wide range
of adsorbents. Moreover it's been proved to be an effective and attractive
process for removal of non-biodegradable pollutants (including dyes)
from wastewater [4]. A commonly used adsorbent activated carbon has
a good capacity for the removal of organic pollutants [5–11]. But some of
its disadvantages are the high price of treatment and difficult
regeneration, which increases the cost of wastewater treatment. Thus,
there is a demand for the other adsorbents, which are made up of
inexpensive material and does not require any additional pretreatment,
such that the adsorption process will become economically viable. A
successful adsorption process not only depends on dye adsorption
performance of the adsorbents, but also on the constant supply of the
materials for this process. So it is preferable to use low-cost adsorbents,
such as rice husk and rice husk ash. Rice husk is an agricultural waste,
accounting for about one-fifth of the annual gross rice production (545
million metric tonnes) of the world. Rice husk is used as a fuel by a
number of industries to produce steam, thus, conserving both energy
and resources. During the burning of rice husk, the residual ash, called
rice husk ash (RHA) is collected from the dust collection device attached
upstream to the stacks of rice husk-fired boilers and furnaces. The RHA
possesses good adsorptive properties and has been used previously for
the adsorptive removal of metal ions and dye from the water.
Methylene blue is a heterocyclic aromatic chemical compound
with molecular formula: C16H18ClN3S3H2O. Due to its toxic nature it is

0011-9164/$ – see front matter © 2010 Elsevier B.V. All rights reserved.
doi:10.1016/j.desal.2010.03.044
250 P. Sharma et al. / Desalination 259 (2010) 249–257

harmful if swallowed and may create some problems if inhaled or
made in contact with skin or eye.
in the oven and rest of the RH dried at room temperature. The biomass
was sieved and 20–40 mesh was used for the batch experiment. RHA
used as obtained from a nearby paper mill (Barnala paper mill, Punjab,
India) and then properly grinded into fine powder for the removal of
methylene blue from waste water by batch treatment process. The
following were the starting materials used for the adsorption studies
of MB dye: pretreated RH and RHA, moreover before each adsorption
study these adsorbents are activated by placing the adsorbent in
preheated oven at 343 K for 4 h.

2.2. Infrared and electron microscopic studies of RH and RHA

Fourier transformation infrared (FTIR) spectra of RH and RHA were

As methylene blue is used in various studies, so during its use
obtained using KBr pellets in conjunction with Shimadzu FTIR 8400S
considerable amount of methylene blue goes with wastewater to the
spectrometer. The pellet for infrared studies was prepared by mixing a
oceans and make hazardous for the aquatic lives. Therefore,
given sample with KBr crystals and pressed into a pellet. A spectrum
decolorization of dyes is important aspects of wastewater treatment
was recorded in the mid-IR range from 4000 to 400 cm− 1 with a
before discharge.
resolution of 1 cm− 1. The resulting spectra were the average of 20
Most of the adsorption studies have been focused on untreated
scans. The surface morphology, textures, porosity and particle size of
plant wastes because of low cost, easy availability, easy to handle
RA and RHA were examined by scanning electron microscopy (SEM).
[12,13]. A large number of studies on cellulosic agricultural waste
For scanning electron microscopic studies, the sample was dispersed
materials have been reported for the treatment of industrial waste
onto carbon tape and coated with gold using a sputter coater system
water [14]. The applicability of these low-cost adsorbents obtained
to prevent charge accumulation on the sample. The RH and RHA were
from plants waste, acts as an important replacement for costly
then observed on a JEOL JSM-5800 microscope operating in the SEM
conventional methods of removing organic dyes as well as toxic heavy
mode at 20 kV.
metal ions from different waste streams. In general, an adsorbent can
be assumed as “low cost” if it requires little processing, is abundant in
2.3. Batch adsorption experiments
nature, or is a by-product or waste material from another industry.
Thus, adsorption is a well known equilibrium separation process and
The adsorption experiments were carried out in a batch process.
an effective method for water decontamination applications. Several
Variables parameters such as, initial methylene blue concentration,
kinds of agricultural by-product such as rice husk [15], cereal chaff
adsorbent amount, contact time, temperature and pH of the medium
[16], Azadirachta indica leaf powder [17], A. indica leaf powder [18],
were studied. All experiments were performed by using conical flask
giant duckweed [19], and fly ash [20], have been reported for the
of 100 mL capacity containing 50–1250 mg of RH/RHA suspended in
removal of methylene blue from waste water. Apart from these
25 mL of dye solution. The initial pH adjustments were carried out
adsorbents there are so many other natural adsorbents which had
either by hydrochloric acid or sodium hydroxide solutions before
been used to make waste water free from methylene blue [21–26].
adding the RH/RHA. Digital pH meter was used for the pH
The importance of biomasses for the removal of colored/hazardous
measurements and was calibrated with two buffer solutions having
dye methylene blue from aqueous waste can be judged from the
a pH value of 4 and 7 prior to use. All the adsorption experiments have
recent reported data in the literature [27–32]. In general, pretreated
been carried out in duplicate and the results given are the average
and chemically modified plant wastes exhibit higher adsorption
values. The reaction mixture has mixed with the help of a horizontal
capacities than the unmodified forms [33–36]. The previous adsorp-
shaker with an intensity of agitation 4 rps for desired time and after
tion studies of rice husk and rice husk ash reveal that these are
that, samples were filtered out by using Whatman filter paper
prominent adsorbent for metal ions, oil products removal from
number-42 and care has been taken to repeatedly centrifuge the
aqueous waste and have potential to remove arsenic from industrial
solution at high speed to avoid any solid particles in the solution
waste streams [37–41].
phase. The left out concentration in the supernatant solution after
The main objective of this work is to study the adsorption potential
adsorption process was analyzed using an ELICO SL 159 UV–VIS
of low cost bioadsorbent, rice husk and rice husk ash for the removal
spectrophotometer by recording the absorbance changes at a
of hazardous dye methylene blue from the waste water. Apart from
wavelength of maximum absorbance (664 nm). The amount of dye
this, another objective of this work is to evaluate the effect of dye
adsorbed on the adsorbent surface was calculated from the concen-
concentration, adsorbent dose, contact time, temperature, and pH of
trations difference in solution before and after adsorption, observed
the medium, on the adsorption characteristic of pretreated RH and
from absorption values. The obtained results are expressed in terms of
RHA in order to make a comparison between them. This paper also
adsorption percentage.
discusses the Langmuir and Freundlich adsorption isotherm model
The distribution of dye between the adsorbents and the solvent
and various thermodynamic parameters such as Gibbs free energy
gives the measure of the selectivity of the particular adsorbent for
change (ΔGo), heat of adsorption (ΔHo) and entropy change (ΔSo) as
corresponding dye. The distribution coefficient (Kd) can be used to
applied to the adsorption of methylene blue onto the RH and RHA.
calculate the volume of adsorbent that is needed to achieve a desired
decontamination for a certain amount of liquid in a batch process. The
2. Materials and methods distribution coefficient is expressed as:
  
2.1. Pretreatment of rice husk (RH) and rice husk ash (RHA) Co −Ce V
Kd = : ð1Þ
Ce W
Rice husk is a farming waste, obtained from the rice mills after the
separation of rice from paddy. In the present study rice husk with where, Co represents the initial concentration of the dye solution
fresh biomass was collected from nearby rice mill of Dasuya, Punjab, (mg L− 1) and Ce concentration of solution (mg L− 1) at equilibrium.
India. This obtained rice husk was washed four to five times with The effect of initial dye concentration and adsorbent dose on the
distilled water, then half the amount of RH was dried for 48 h at 373 K adsorption of MB dye was investigated by employing different dosage
 P. Sharma et al. / Desalination 259 (2010) 249–257
of RH and RHA varying from 250–1250 mg to different concentrations
(50–2000 mg L− 1) of dye solutions. This adsorption experiment is
performed at fixed values of pH equals 7, temperature equals 303 ±
1 K, equilibration time 30 min. Batch adsorption studies were also
conducted at different contact times (20–180 min) at initial concen-
tration of MB 500 mg L− 1 and adsorbent concentration 40 mg mL− 1
in 25 mL solution. Adsorbent and solution were separated at pre-
decided time intervals, filtered, centrifuged and analyzed for residual
MB concentrations in the solution phase spectrophotometrically. The
influence of pH on the adsorption potential of RH as well as RHA was
studied at different pH values, as it is an important parameter for
interaction that take place between adsorbent and adsorbate on the
adsorbent surface. The role of pH on the adsorption capacity of RH and
RHA was studied in the pH range 1.0–9.0 at MB concentration
1000 mg L− 1, temperature 303 ± 1 K, equilibration time 30 min and
adsorbent dose 500 mg (i.e. 20 mg mL− 1). As we know that
temperature of the system have remarkable effect on the adsorption
process, therefore in order to optimize the system temperature for
maximum removal efficiency, experiments were conducted at three
different temperatures viz. 303, 313, and 323 ± 1 K by varying dye
concentration and keeping other parameters constant such as pH 7,
equilibration time 30 min and adsorbent dose 20 mg mL− 1.
The Gibbs free energy change of the adsorption process is related
to the equilibrium constant by the classic Van't Hoff equation:
o
ΔG = −RT ln Kd :
According to thermodynamics, the Gibbs free energy change is also
related to the entropy change and heat of adsorption at constant
temperature by the following equation:
  
ΔG = ΔH −TΔS :
On combining Eqs. (2) and (3), we get




 and C–O–H (899 cm− 1) [14]. These were replaced by the primary
ln Kd = −ΔG = RT = ΔS = R −ΔH = RT
where ΔGo is the free energy change (kJ mol− 1), ΔHo the change in
enthalpy (kJ mol− 1), ΔSo the entropy change (J mol− 1 K− 1), T the
absolute temperature (K) and R the universal gas constant
(8.314 J mol− 1 K− 1). Thus ΔSo can be recorded from the intercept
and ΔHo can be determined by the slope of the linear Van't Hoff plot,
i.e., as lnKd versus 1/T.
The adsorption isotherms were studied for the initial MB
concentration ranging from 100–1000 mg L− 1. Using a method of
linear regression, the adsorption data were fitted to Langmuir [42]
and Freundlich [43] adsorption model to describe the adsorption
processes between solid–liquid interface.
Langmuir isotherm;
Ce = qe = 1 = ðKa qm Þ + Ce = qm
where, qe is the amount of MB adsorbed per unit weight of adsorbent
(mg g− 1), Ce (mg L− 1) is the equilibrium concentration of the MB in
the solution. Ka and qm are the Langmuir coefficients representing the
equilibrium constant for the adsorbate–adsorbent equilibrium and
the monolayer capacity respectively.
Freundlich isotherm;
1 enhances the adsorption uptake of dye.
log qe = log KF + log Ce
n
where, KF and 1/n are the Freundlich constants. The value of KF (mg g− 1)
can be taken as a relative indicator of adsorption capacity, while 1/n
shows the energy or intensity of adsorption.
Furthermore the feasibility of the adsorption process is evaluated
by the method suggested by Weber and Chakraborti [44]. One of the
251
essential characteristics of Langmuir equation could be expressed by a
dimensionless constant called equilibrium parameter or separation
factor, RL which can be calculated by the following equation [45]:
RL = 1 = ð1 + Ka Co Þ: ð7Þ
Generally, a suitable non-conventional low-cost adsorbent for dye
adsorption should meet the following requirements: (i) efficient for
removal of dye; (ii) high adsorption capacity and rate of adsorption;
(iii) high selectivity; and (iv) tolerant of a wide range of wastewater
parameters. By keeping all these points in mind we tried to make a
comparative study between the naturally available low-cost adsor-
bents such as agricultural by products, industrial waste materials,
plants and fruit waste, naturally available inorganic materials and
biosorbents on the basis of their adsorption capacity for MB removal.
Several research groups have investigated the application of com-
mercial and non-commercial naturally available adsorbents for the
treatment of industrial effluent contaminated with organic dyes by
adsorption process but no one have compared their adsorption
capacities.
3. Results and discussion
3.1. Characterization of RH and RHA
ð2Þ
FTIR spectra showed that rice husk and rice husk ash contained
functional groups of the standard polymers α-cellulose, and coirpith-
lignin (Fig. 1). The spectrum of RH-cellulose extracted from rice husk
is very similar to that of α-cellulose. The FTIR spectrum of RH/RHA
shows functional groups from Si–O–Si (1096 cm− 1), Si–H (801 cm− 1,
ð3Þ 469 cm− 1) and Si–OH (3000–3700 cm− 1 broad band). Heating RHA
at 300 °C resulted in a loss of C–H stretching bands (2910 cm− 1), C–C
and C–H (1021 cm− 1), C–O and C–O–C (1060 cm− 1 and 1115 cm− 1),
ð4Þ functional groups of NC O (1715 cm− 1), N C O and/or aromatic ring
(1611 cm− 1) [15], and dominated the silica functional groups of Si–
O–Si (1096 cm− 1), Si–H (801, 469 cm− 1) and OH and Si–OH (3000–
3700 cm− 1) [16]. FTIR spectra of rice husk and rice husk ash are
shown in Fig. 1. The spectra are virtually identical. The electron
microscopic studies (Fig. 2) of both the adsorbent reveals that RH
have fibrous character with particle size of 40–100 μm, but on the
other hand the RHA have particles of comparatively smaller size,
moreover these particles are of spherical shape.
3.2. Effect of dye concentration and adsorbent dosage
Before designing an adsorption treatment process it is very much
necessary to optimize dye concentration and the amount of adsorbent
to be used for that dye's removal. It has been found that (Fig. 3) with
ð5Þ the increase in concentration of the adsorbate, the adsorption
percentage decreases, while the amount of dye removed at equilib-
rium increased, with the increase in dye concentration in both the
cases. This is so because the initial dye concentration provides the
driving force to overcome the resistance to the mass transfer of dye
between the aqueous and solid phase. The increase in initial
concentration also enhances the interaction between adsorbent and
dye. Therefore, an increase in initial concentration of dye solution
ð6Þ Fig. 3 also reveals that that the dye removal increases with increase
in adsorbent dosage. An increase in the adsorption with adsorbent
dosage can be attributed to greater surface area and the availability of
more adsorption sites. It can be seen that 750 mg of RH in 25 ml of
500 mg L− 1, and 500 mg of RHA in 25 mL of 1000 mg L− 1 initial MB
concentration after agitation time of 30 min respectively, the amount
of dye being adsorbed was nearly 100%. With this data, it was decided
252 P. Sharma et al. / Desalination 259 (2010) 249–257
Fig. 1. Infra red spectra of RH and RHA.
that 750 mg of adsorbent in case of RH and 500 mg in case of RHA is
sufficient for these adsorption studies.
3.3. Effect of equilibration time study
For the evaluation of adsorption process as a function of contact
time between adsorbate and adsorbent, 20 to 180 min contact interval
Fig. 2. Scanning electron microscopic images of RH and RHA.
is applied for both the adsorbents. Effect of equilibration time on
adsorption of MB dye onto RH and RHA is presented in Fig. 4. The
study of the graph reveals that as the contact time increases, rate of
adsorption first increases and then remains almost constant. Fig. 4
illustrated that rate of adsorption of MB was very fast during the initial
stage of the adsorption processes. After fast initial rate of adsorption,
the MB uptake capacity for both the adsorbents RH and RHA increased
with the time and reached equilibrium value at about 30 min, since
maximum adsorption is attained during this period. The concentra-
tion gradient will be responsible for these changes in the rate of
adsorption. In the beginning because of high concentration gradient
the driving force helped in this rapid adsorption. However as the
concentration gradient decreased with time the rate was reduced till
it achieved equilibrium. This may be the reason that after a particular
time interval adsorption percentage remains almost constant.
3.4. Influence of acidity/basicity of the adsorption medium
The pH value of the solution is an important factor that must be
considered during adsorption studies. The pH has two kinds of
influence on dye: an effect on the solubility and speciation of dye in
the solution. The effect of pH on the adsorption of MB onto RH and
RHA is shown in Fig. 5. It has been found that dye's adsorption
increases with increase in pH and maximum adsorption is found
around a pH value of 7. This may be due to the fact that at higher pH
values, the surface of adsorbent becomes negative which enhances
the adsorption of positively charged MB cationic dye through
electrostatic force of attraction. At pH 9 there is slight decrease in
adsorption due to repulsion between the adsorbent surface and
presence of partial negative charge on MB due to chloride ions.
3.5. Thermodynamic parameters
While keeping the importance of temperature in the studies of
adsorption of dyes, the present work was initiated with an aim of
using thermodynamic approach to dyes adsorption. It was decided to
conduct an experiment under controlled conditions to study how
different system temperatures affect the adsorption of dyes onto RH
and RHA. The effect of temperature on the adsorption of MB on both
RH and RHA was investigated at 303, 313 and 323 ± 1 K. Temperature
has two major effects on the adsorption process. Increasing the
temperature is known to increase the rate of diffusion of the adsorbate
molecule across the external boundary layer and in the internal pores
 P. Sharma et al. / Desalination 259 (2010) 249–257 253

Fig. 3. Effect of adsorbate concentration and adsorbent dose on the adsorption percentage of MB onto RH and RHA.

of the adsorbent particle, owing to decrease in the velocity of the
solution. In addition changing the temperature will change the
equilibrium capacity of the adsorbent for particle adsorbate.
Experimental results concerning the effect of temperature on the
system of dyes adsorption at different initial dye concentration are
demonstrated in Fig. 6. In both the cases of MB adsorption on RH and
RHA, the adsorption percentage increases when the temperature of
solution increased from 303 to 323 ± 1 K, indicating the process to be
endothermic in nature. Better adsorption at higher temperature may
be either due to acceleration of some originally slow sorption steps or
due to creation of new active sites on the sorbent surface. Thus an
increase in temperature will reduce the electrostatic repulsion
between the surface and the adsorbing species, allowing adsorption
to occur more readily. This could also be due to enhanced mobility of
dye molecules from solution to the adsorbent surface. Furthermore,
increasing temperature may produce a swelling effect within the
internal structure of RH and RHA enabling large dye to penetrate
further. The close examination of the Fig. 6 reveals that even though at
high initial dye concentration, we can achieve 100 percent dye
removal by raising the temperature by 10–15 K, which is compara-
tively low at lower temperature.
In environmental engineering practice, both energy and entropy
factors must be considered in order to determine which process will
occur spontaneously. The ΔGo is the fundamental criterion of
spontaneity. The calculated apparent thermodynamic parameters
for adsorption of MB onto RH as well as RHA are summarized in
Table 1 and the Van't Hoff plot is represented in Fig. 7. The negative
values of ΔGo are due to the fact that the adsorption process is
spontaneous with high affinity of MB to RH and RHA. Moreover, the
negative value of ΔGo becomes more and more negative which
indicates that the adsorption process becomes more spontaneous
with rise in temperature, which favors the adsorption process.
Positive value of ΔHo confirms the endothermic nature of the sorption
process. Hence, by increasing temperature, the degree of adsorption

Fig. 4. Effect of time contact between the solid and liquid phase on the adsorption percentage of MB onto RH and RHA.
254 P. Sharma et al. / Desalination 259 (2010) 249–257

Fig. 5. Effect of pH of the aqueous phase on the adsorption percentage of MB onto RH and RHA.

will increase. The numerical value of ΔHo also, predicts the
physicosorption behavior of these adsorption processes. The positive
value of ΔSo reflected the affinity of the adsorbent for particular dye
and confirms the increased randomness at the solid–solution
interface during adsorption.
3.6. Equilibrium parameters
Equilibrium data, commonly known as adsorption isotherms, are
basic requirements for the design of adsorption systems. The most
widely used isotherms equation for modeling of the adsorption data
are the Langmuir and Freundlich equations. Adsorption isotherms
constants depend on certain parameters, whose values express the
surface properties and the affinity of the adsorbent. They can also we
used to compare the adsorptive capacity of different adsorbents for
different dyes. Experimental results obtained for MB adsorption onto
respective adsorbent (RH/RHA) at three different temperatures (303,
313, and 323 ± 1 K) were fitted to Langmuir isotherm model, the plot
between Ce/qe and Ce yield straight lines (Fig. 8) with very high
correlation coefficient values (R2) and low standard deviation (SD)
value. Adsorption equilibrium parameters and statistical error
variable (R2 and SD) for MB adsorption onto RH and RHA were
displayed in the same order in Table 2. However, the Langmuir
adsorption isotherms are presented in Fig. 8. The maximum value of
adsorption capacity obtained from Langmuir adsorption isotherm was
1455.6 mg g− 1 i.e. for MB adsorption on RHA. The adsorption capacity
data also reveals that an adsorption capacity increases with rise in
temperature in both the cases. A high Ka value indicates the high
affinity of adsorbent for MB adsorption. Moreover in case of RHA,
when the adsorption experiments were carried out at 313 and 323 K,
the Ka values comes out infinity, as in these two cases 100% adsorption
occur (means Ce was zero). Therefore higher the temperature, higher
the Ka and maximum adsorption capacity (qm), a higher temperature
is also favorable for adsorption. This increase in adsorption intensity
and adsorption capacity may be due to the change in pore size/volume
and enhanced rate of intra-particle diffusion of solute, as diffusion is
an endothermic process.
Evolution of Freundlich adsorption isotherms is also an important
step in characterizing the adsorption process as it provides an
approximate estimation of sorption capacity of the adsorbent. The

Fig. 6. Effect of system temperature on the adsorption percentage of MB onto RH and RHA studied at different initial dye concentrations.
 P. Sharma et al. / Desalination 259 (2010) 249–257 255

Table 1 Furthermore, RL values tabulated in Table 2 for the MB adsorption

Thermodynamic parameters for MB adsorption onto RH and RHA at initial dye onto the respective adsorbent, reveals that in all the cases the values
concentration of 2000 ppm.
of RL were positive and less than unity, indicating thereby a highly
Adsorbent ΔGo (kJ mol− 1) ΔHo ΔSo favorable adsorption in all the three cases at all the three temperature
(kJ mol− 1) (J mol− 1 K− 1) conditions. The very low, separation factor values RL (0.0–0.0009) in
303 K 313 K 323 K
case of MB adsorption onto RHA was, indicates that the dye preferred
RH − 09.95 − 11.05 − 12.14 23.28 109.66
RHA − 11.15 − 12.16 − 13.16 19.31 100.52 to remain bound on the adsorbent surface and shows the irreversible
nature of the adsorption process.

3.7. Comparison of adsorption efficiency

Freundlich constants KF and n were calculated from the equilibrium
data for adsorption of MB on RH and RHA respectively at three
different temperatures 303, 313, and 323 K and are tabulated in
Table 2 along with the correlation coefficient (R2) and standard
deviation (SD) values. From these data we can conclude that the
Freundlich adsorption isotherm model unable to gave the best fitting
of the experimental results as these plots have very low R2 value and
large deviation in between the data points. This indicates that there
was only monolayer adsorption take place and no surface heteroge-
neity and the exponential distribution of active sites and their
energies.
A number of industrial waste products, agricultural by products,
natural materials and biosorbents have been tested and proposed for
methylene blue removal and each adsorbent has its own specific
physical and chemical characteristics such as porosity, stability,
surface area, surface morphology and physical strength, as well as
inherent advantages and disadvantages in wastewater treatment. In
addition, adsorption capacities of adsorbents also vary, depending on
the experimental conditions. Therefore, comparison of adsorption
performance is difficult to make. However, it is clear from the present
study and the literature survey that non-conventional adsorbents RH

Fig. 7. Variation of lnKd with temperature (1/T) for the adsorption of MB onto RH and RHA at initial dye concentration of 2000 ppm (Van't Hoff plot).

Fig. 8. Langmuir adsorption isotherm for the MB adsorption onto RH and RHA at three different temperatures.
256 P. Sharma et al. / Desalination 259 (2010) 249–257

Table 2
Adsorption isotherm constants for MB adsorption onto RH and RHA at three different temperatures.

Langmuir constants

Temperature RH RHA
2
Ka qm R SD RL Ka qm R2 SD RL
(L mg−1) (mg g−1) (L mg− 1) (mg g−1)

303 K 0.266 1015.7 0.999 0.005 0.00188 0.525 1253.1 1.0 0.002 0.00095
313 K 0.521 1191.5 0.999 0.003 0.00096 ∞* 1377.4 1.0 0.000 0.0
323 K 0.618 1347.7 0.999 0.002 0.00081 ∞* 1455.6 1.0 0.000 0.0

Freundlich constants

Temperature RH RHA

KF n R2 SD KF n R2 SD

303 K 7.08E−13 0.205 0.705 0.774 1.74E−15 0.188 0.552 0.766

313 K 3.89E−20 0.140 0.933 0.774 4.79E−15 0.194 0.591 –
323 K 2.63E−18 0.155 0.918 0.774 5.25E−16 0.175 0.817 –

*Ka = slope/intercept, and in these two cases intercept value is zero.

and RHA have maximum potential for the removal of methylene blue
from aqueous waste. Out of these two RHA was better adsorbent. The
RH and RHA can be used for the treatment of industrial effluent. Both
these adsorbent were readily available, inexpensive and are effective.
They also possess several other advantages that make them excellent
materials for environmental purposes, such as high capacity (Table 2
and Fig. 9) and rate of adsorption (Fig. 3), high selectivity for different
concentrations (Fig. 3), and also rapid kinetics. Fig. 9 presents a view
of some of the highest adsorption capacities reported [46–73] and
studied. From the recent literature reviewed, adsorbents that stand
out for high adsorption capacities are commercially activated carbon
(980.3 mg g− 1), bark (914.0), and activated carbon prepared from
plum kernels by NaOH activation (828 mg g− 1). These adsorbents are
efficient and can be used effectively for the removal of MB from
aqueous solutions, but these adsorbent have even less adsorption
capacity than that of RH and RHA. So after this study the first choice
will be the RHA and RH. This demonstrated that RHA can be used for
the decontamination of effluents. It offers both a procedure of choice
for extraction processes and a lot of promising benefits for commercial
purposes.
4. Conclusions
The adsorption treatment process will provide an attractive
technology, if the low-cost adsorbents are ready for use. Some time
adsorbents are physically and chemically treated to improve its
adsorption efficiency. These pretreatment processes were so chosen
that these should be cost effective. Generally these pretreatment
methods are not cost effective when we apply at large scale, but the
treatment process we adopted will be cost effective as the rice husk
ash used for adsorption studies was also obtained from the paper mill.

Fig. 9. Compared maximum adsorption capacities for methylene blue on several low-cost adsorbents, and RH and RHA.
 P. Sharma et al. / Desalination 259 (2010) 249–257
So RHA is also an industrial waste product. In our study we also found
out that pretreatment of the adsorbent, improve its adsorption
efficiency. Rice husk has low removal efficiencies and adsorption
capacities for MB removal, but on the other hand physical and
chemical treatment of RH and RHA significantly improve its
adsorption potential. The present investigation shows that RH and
RHA can be employed effectively for the treatment of dyeing effluents
containing methylene blue dye. The waste RH and RHA is abundantly
available in northern India and hence its application to the treatment
of dyeing wastewater is expected to be economically feasible. They
may also be useful in the treatment of other harmful and undesirable
species present in the effluent. Higher adsorption capacities for
selective removal of methylene blue with RH and RHA could be
carried out in an adsorption treatment process by adjusting the pH
around 7, equilibration time of 30 min, and system temperature of
323 K. The thermodynamic study indicated that the adsorption of
dyes was spontaneous and endothermic.
Symbols
ΔGo the Gibbs free energy change (kJ mol− 1)
ΔHo the heat of adsorption (kJ mol− 1)
ΔSo the entropy change (J mol− 1 K− 1)
Co the initial concentration of the dye solution (mg L− 1)
Ce the concentration of dye solution (mg L− 1) at equilibrium
qe the amount of dye adsorbed per unit weight of adsorbent
(mg g− 1)
Kd the distribution coefficient (mL g− 1)
V the solution volume (mL)
W the amount of adsorbent (g)
T the absolute temperature (K)
R the universal gas constant (8.314 J mol− 1 K− 1)
Ka the Langmuir constant representing the equilibrium con-
stant (L mg− 1)
qm the Langmuir constant representing the maximum mono-
layer capacity (mg g− 1)
KF the Freundlich constant as a relative indicator of adsorption
capacity (mg g− 1)
1/n the Freundlich constant as intensity of adsorption
RL the separation factor
Acknowledgements
A part of this work was supported by Priority Research Centers
Program through the National Research Foundation of Korea (NRF)
funded by the Ministry of Education, Science and Technology (2009-
0093816).
References
[1] G. Crini, Biores. Technol. 97 (2006) 1061–1085.
[2] H. Zollinger, Synthesis, Properties Applications Organic Dyes Pigments, Color
Chem., VCH Publishers, New York, 1987, pp. 92–102.
[3] A.R. Gregory, S. Elliot, P. Kluge, J. Appl. Toxicol. 1 (1991) 308–313.
[4] Z. Aksu, Process Biochem. 40 (2005) 997–1026.
[5] G.M. Walker, L.R. Weatherley, Water Res. 1 (1997) 32093–32101.
[6] G.M. Walker, L.R. Weatherley, Environ. Poll. 99 (1998) 133–136.
[7] K.V. Kumar, J. Hazard. Mater. 137 (2006) 1538–1544.
[8] A. Özer, G. Dursun, J. Hazard. Mater. 146 (2007) 262–269.
[9] I.D. Mall, V.C. Srivastava, N.K. Agarwall, M. Mishra, Chemosphere 61 (2005)
492–501.
[10] A.A. Attia, B.S. Girgis, N.A. Fathy, Dyes Pigments 76 (2008) 282–289.
[11] I.A.W. Tan, A.L. Ahmad, B.H. Hameed, Desalination 225 (2008) 13–28.
[12] G. McKay, J.F. Porter, G.R. Prasad, Water Air Soil Poll. 114 (1999) 423–438.
[13] T.G. Chuah, A. Jumasiah, S. Katayon, Desalination 175 (2005) 305–316.
[14] G. Annadurai, R.S. Juang, D.J. Lee, J. Hazard. Mater. B92 (2002) 263–274.
[15] V. Vadivelan, K.V. Kumar, J. Colloid Interface Sci. 286 (2005) 90–100.
257
[16] R.P. Han, Y.F. Wang, P. Han, J. Shi, J. Yang, Y.S. Lu, J. Hazard. Mater. 137 (2006)
550–557.
[17] K.G. Bhattacharyya, A. Sharma, Dyes Pigments 57 (2003) 211–222.
[18] K.G. Bhattacharyya, A. Sharma, J. Environ. Manage. 71 (2004) 217–229.
[19] P. Waranusantigul, P. Pokethitiyook, M. Kruatrachue, E.S. Upatham, Environ. Poll.
125 (2003) 385–392.
[20] P. Janoš, H. Buchtová, M. Ryznarová, Water Res. 37 (2003) 4938–4944.
[21] V. Ponnusami, S. Vikram, S.N. Srivastava, J. Hazard. Mater. 152 (2008) 276–286.
[22] J.Z. Yi, L.M. Zhang, Biores. Technol. 99 (2008) 2182–2186.
[23] M.I. El-Khaiary, J. Hazard. Mater. 147 (2007) 28–34.
[24] L. Wang, A. Wang, J. Hazard. Mater. 147 (2007) 979–985.
[25] K.V. Kumar, K. Porkodi, J. Hazard. Mater. 146 (2007) 214–226.
[26] R. Gong, S. Zhu, D. Zhang, J. Chen, S. Ni, R. Guan, Desalination 230 (2008) 220–228.
[27] A. Özer, G. Dursun, J. Hazard. Mater. 146 (2007) 262–269.
[28] B. Bestani, N. Benderdouche, B. Benstaali, M. Belhakem, A. Addou, Biores. Technol.
99 (2008) 8441–8444.
[29] F.A. Pavan, E.C. Lima, S.L.P. Dias, A.C. Mazzocato, J. Hazard. Mater. 150 (2008)
703–712.
[30] A.E. Omaja, Biochem. Eng. J. 40 (2008) 8–18.
[31] M. Zhao, P. Liu, Micropor. Mesopor. Mater. 112 (2008) 419–424.
[32] S. Karag z, T. Tay, S. Ucar, M. Erdem, Biores. Technol. 99 (2008) 6214–6222.
[33] A. Mittal, A. Malviya, D. Kaur, J. Mittal, L. Kurup, J. Hazard. Mater. 148 (2007)
229–240.
[34] P. Janoš, S. Coskun, V. Pilarova, J. Rejnek, Biores. Technol. 100 (2009) 1450–1453.
[35] Y. Zhi-yuan, J. China Univ, Min. Technol. 18 (2008) 437–440.
[36] K. Rastogi, J.N. Sahu, B.C. Meikap, M.N. Biswas, J. Hazard. Mater. 158 (2008)
531–540.
[37] V.C. Srivastava, I.D. Mall, I.M. Mishra, J. Hazard. Mater. 134 (2006) 257–267.
[38] W. Nakbanpote, B.A. Goodmanb, P. Thiravetyan, Colloids Surfaces A 304 (2007)
7–13.
[39] V.C. Srivastava, I.D. Mall, I.M. Mishra, Colloids Surfaces A 312 (2008) 172–184.
[40] K.S. Chou, J.C. Tsai, C.T. Lo, Biores. Technol. 78 (2001) 217–219.
[41] J.C. Saha, K. Dikshit, M. Byopadhyay, Comparative studies for selection
technologies for arsenic removal from drinking water BUET-UNU International
Workshop on Technologies for Arsenic Removal from Drinking Water,
Bangladesh, , 2001.
[42] I. Langmuir, J. Am. Chem. Soc. 40 (1918) 1361–1403.
[43] H.M.F. Freundlich, Z. Phys. Chem. 57A (1906) 385–470.
[44] T.W. Weber, R.K. Chakraborti, J. Am. Inst. Chem. Eng. 20 (1974) 228–238.
[45] K.R. Hall, L.C. Eagleton, A. Acrivers, T. Vermenlem, Ind. Eng. Chem. Res. 5 (1966)
212–223.
[46] N.C. Filho, E.C. Venancio, M.F. Barriquello, A.A. Hechenleitner, E.A.G. Pineda,
Ecletica Quim. Sao Paulo 32 (2007) 63–70.
[47] F. Rozada, L.F. Calvo, A.I. Garcia, J. Martin-Villacorta, M. Otero, Biores. Technol. 87
(2003) 221–230.
[48] A. Gürses, S. Karaca, C. Dogar, R. Bayrak, M. Acikyildiz, M. Yalcin, J. Colloid
Interface, Sci. 269 (2004) 310–314.
[49] A. Aygün, S. Yenisoy-Karakaş, I. Duman, Micropor. Mesopor. Mater. 66 (2003)
189–195.
[50] C. Namasivayam, S. Sumithra, J. Environ. Manage. 74 (2005) 207–215.
[51] F.A. Batzias, D.K. Sidiras, J. Hazard. Mater. B114 (2004) 167–174.
[52] D. Ghosh, K.G. Bhattacharyya, Appl. Clay Sci. 20 (2002) 295–300.
[53] F.A. Pavan, Y. Gushikem, A.C. Mazzoczto, S.L.P. Dias, E.C. Lima, Dyes Pigments 72
(2007) 256–266.
[54] F. Banat, S. Al-Asheh, L. Al-Makhadmeh, Process Biochem. 39 (2003) 193–202.
[55] N. Al-Bastaki, F. Banat, Resour. Conserv. Recycl. 41 (2004) 103–113.
[56] S. Karaca, A. Gürses, R. Bayrak, Energy Convers. Manage. 45 (2004) 1693–1704.
[57] F.A. Pavan, E.C. Lima, S.L.P. Dias, A.C. Mazzocata, J. Hazard. Mater. 150 (2008)
703–712.
[58] V.K. Garg, M. Amita, R. Kumar, R. Gupta, Dyes Pigments 63 (2004) 243–250.
[59] M.T. Uddin, M.A. Islam, S. Mahmud, M. Rukanuzzaman, J. Hazard. Mater. 164
(2008) 53–60.
[60] A.L. Ahmad, M.M. Loh, J.A. Aziz, Dyes Pigments 75 (2007) 263–272.
[61] V. Ponnusami, R. Madhuram, V. Krithika, S.N. Srivastva, Chem. Eng. J. 140 (2008)
609–613.
[62] S.P. Raghuvanshi, R. Singh, C.P. Kaushik, Appl. Ecol. Environ. Res. 2 (2004) 35–43.
[63] M. Otero, F. Rozada, L.F. Calvo, A.I. García, A. Morán, Biochem. Eng. J. 15 (2003)
59–68.
[64] K. Kadirvelu, M. Kavipriya, C. Karthika, M. Radhika, N. Vennilamani, S. Pattabhi,
Biores. Technol. 87 (2003) 129–132.
[65] B.H. Hameed, A.A. Ahmad, J. Hazard. Mater. 164 (2009) 870–875.
[66] K.V. Kumar, A. Kumrana, Biochem. Eng. J. 27 (2005) 83–93.
[67] N. Kannan, M.M. Sundaram, Dyes Pigments 51 (2001) 25–40.
[68] M.A. Al-Ghouti, M.A.M. Khraisheh, S.J. Allen, M.N. Ahmad, J. Environ. Manage. 69
(2003) 229–238.
[69] K. Okada, N. Yamamoto, Y. Kameshima, A. Yasumori, J. Colloid Interface Sci. 262
(2003) 194–199.
[70] A.A. Attia, B.S. Girgis, N.A. Fathy, Dyes Pigments 76 (2008) 282–289.
[71] B. Royer, N.F. Cardoso, E.C. Lima, J.C.P. Vaghetti, N.M. Simon, T. Calvete, R.C. Veses,
J. Hazard. Mater. 164 (2009) 1213–1222.
[72] R. Tseng, F. Wu, R. Juang, Carbon 41 (2003) 487–495.
[73] R. Tseng, J. Hazard. Mater. 147 (2007) 1020–1027.