Академический Документы
Профессиональный Документы
Культура Документы
www.elsevier.com/locate/jcis
Abstract
Batch experiments were carried out for the sorption of methylene blue onto rice husk particles. The operating variables studied were initial
solution pH, initial dye concentration, adsorbent concentration, and contact time. Equilibrium data were fitted to the Freundlich and Langmuir
isotherm equations and the equilibrium data were found to be well represented by the Langmuir isotherm equation. The monolayer sorption
capacity of rice husks for methylene blue sorption was found to be 40.5833 mg/g at room temperature (32 C). The sorption was analyzed
using pseudo-first-order and pseudo-second-order kinetic models and the sorption kinetics was found to follow a pseudo-second-order kinetic
model. Also the applicability of pseudo second order in modeling the kinetic data was also discussed. The sorption process was found to be
controlled by both surface and pore diffusion with surface diffusion at the earlier stages followed by pore diffusion at the later stages. The
average external mass transfer coefficient and intraparticle diffusion coefficient was found to be 0.01133 min1 and 0.695358 mg/g min0.5 .
Analysis of sorption data using a Boyd plot confirms that external mass transfer is the rate limiting step in the sorption process. The effective
diffusion coefficient, Di was calculated using the Boyd constant and was found to be 5.05 1004 cm2 /s for an initial dye concentration of
50 mg/L. A single-stage batch-adsorber design of the adsorption of methylene blue onto rice husk has been studied based on the Langmuir
isotherm equation.
2005 Elsevier Inc. All rights reserved.
Keywords: Sorption; Rice husk; Methylene blue; Kinetics; Equilibrium; Mechanism; Process design
1. Introduction
Color is a visible pollutant and the presence of even a
very minute amount of coloring substance makes it undesirable due to its appearance. The removal of color from
dye-bearing effluents is a major problem due to the difficulty in treating such wastewaters by conventional treatment
methods. The most commonly used methods for color removal are biological oxidation and chemical precipitation.
However, these processes are effective and economic only in
the case where the solute concentrations are relatively high.
Most industries use dyes and pigments to color their products [1]. Most dye-containing effluents from various industrial branches are discharged into the river streams mainly
* Corresponding author.
from dye manufacturing and textile finishing industries. Currently the sorption technique is proved to be an effective
and attractive process for the treatment of these dye-bearing
wastewaters [25]. Also this method will become inexpensive, if the sorbent material used is of cheaper cost and does
not require any expensive additional pretreatment step. In the
present study rice husks, an agro-based waste material have
been used as adsorbent for the removal of methylene blue
from its aqueous solution. Methylene blue is selected as a
model compound in order to evaluate the capacity of rice
husk for the removal of dye (methylene blue) from its aqueous solutions. Methylene blue has wider applications, which
include coloring paper, temporary hair colorant, dyeing cottons, wools, and coating for paper stock. Though methylene
blue is not strongly hazardous, it can cause some harmful effects. Acute exposure to methylene blue will cause increased
heart rate, vomiting, shock, Heinz body formation, cyanosis,
V. Vadivelan, K.V. Kumar / Journal of Colloid and Interface Science 286 (2005) 90100
91
jaundice, quadriplegia, and tissue necrosis in humans. Previously several researchers had proved several low-cost materials such as pear millet husk carbon [6], brown coal fly
ash [7], rice husk [8], hair [8], cotton waste [8], bark [8],
perlite [9], raw kaolin [10], pure kaolin [10], calcined raw
kaoline [10], calcined pure kaoline [10], NaOH-treated raw
kaolin [10], coir pith [11], guava seed-activated carbon [12],
iron humate [7], neem sawdust [13], and clay [14] for the
removal of methylene blue from its aqueous solutions. Previously McKay et al. [8] reported on the removal of methylene
blue by rice husks. However, the kinetic aspects involved
in the sorption process were not discussed. In the present
study rice husks have been used as an adsorbent for the removal of methylene blue from its aqueous solutions. The dye
methylene blue is selected as a model compound in order
to evaluate the capability of rice husks to remove dye from
wastewaters. Also the sorption of methylene blue at solid
liquid interfaces has been studied extensively under equilibrium conditions. Further the kinetics and the mechanistic
steps involved in the sorption process were evaluated at different initial methylene blue concentrations. A single-stage
batch sorber has been designed for the removal of methylene
by rice husks based on the equilibrium data obtained.
2. Experimental
2.1. Materials
The rice husk used in the present investigation was obtained from local rice mills. The collected materials were
then washed with distilled water for several times to remove
all the dirt particles. The washing process was continued till
the wash water contains no color. The washed materials were
then dried in a hot air oven at 60 C for 24 h. The dried materials were then ground using a domestic mixer. The ground
materials were then sieved to constant particle sizes of +60
to 85 mesh. The materials were then stored in plastic bottles for use.
2.2.1. Effect of pH
The effect of pH on the amount of color removal was analyzed over the pH range from 3 to 8. The pH was adjusted
using 0.1 N NaOH and 0.1 N HCl solutions. In this study
50 mL of dye solution of 100 mg/L was agitated with 0.03 g
of rice husk using water-bath shakers at room temperature
(32 C). Agitation was made for 48 h which is more than
sufficient to reach equilibrium at a constant agitation speed
of 95 strokes/min. The samples were then centrifuged and
the left out concentration in the supernatant solution was analyzed using a UV spectrophotometer (Deep Vision 301 E)
by monitoring the absorbance changes at a wavelength of
maximum absorbance (665 nm).
(C0 Ce )V
(1)
,
M
where C0 (mg/L) and Ce (mg/L) are the concentration in
the solution at time t = 0 and at equilibrium time t, V is
the volume of solution treated (L), and M is the amount of
biomass added (g). From Fig. 1, it was observed that the
solution pH affects the amount of dye adsorbed. The dye
uptake was found to increase with increasing pH and it increases from 43.333 to 80.791 mg/g for an increase in pH
from 3 to 8. Several reasons may be attributed to dye sorption
behavior of the sorbent relative to solution pH. The surface
of rice husks may contain a large number of active sites and
the solute (dye ions) uptake can be related to the active sites
qe =
92
V. Vadivelan, K.V. Kumar / Journal of Colloid and Interface Science 286 (2005) 90100
Fig. 2. Effect of adsorbent mass (C0 , 100 mg/L; V , 50 mL; pH, 8; temperature, 32 C).
V. Vadivelan, K.V. Kumar / Journal of Colloid and Interface Science 286 (2005) 90100
Fig. 3. Adsorption kinetics for methylene blue onto rice husk (C0 ,
100 mg/L; V , 1 L; M, 4 g; pH, 8; agitation speed, 800 rev min1 ).
93
K1 (min1 )
r12
50
70
100
0.0249
0.02772
0.04515
0.996096
0.989395
0.992677
K1 t
.
2.303
(3)
r 2 = 1.
(4)
Further from Table 1, it was observed that correlation coefficients were higher for all ranges of initial dye concentrations studied (50 to 100 mg/L). This shows the applicability
94
V. Vadivelan, K.V. Kumar / Journal of Colloid and Interface Science 286 (2005) 90100
(6)
(7)
(8)
Thus the rate constant K2 , initial sorption rate h, and predicted qe can be calculated from the plot of t/q versus time
t using Eq. (7).
Fig. 5 shows the plot between t/q versus time t. The initial sorption rate h, pseudo-second-order-rate constant K2 ,
amount of dye adsorbed at equilibrium qe , and the corresponding linear regression correlation coefficient r22 values
are given in Table 2. From Table 2 it was observed that the
r22 values were found to be higher than that of r12 at all initial dye concentrations. Also the r22 values were found to
be in the range of 0.995985 to 0.999136. The higher values r22 values confirm that the sorption process follows a
pseudo-second-order mechanism. Also this suggests the assumption behind the pseudo-second-order model that the
dye uptake process is due to chemisorption [18]. Chemical
sorption can occur by the polar functional groups of lignin,
which include alcohols, aldehydes, ketones, acids, phenolic hydroxides, and ethers as chemical bonding agents [18].
From Table 2, it was also observed that the initial sorption rate h, pseudo-second-order-rate constant K2 , and the
equilibrium sorption capacity are increased with increase in
initial dye concentration. A similar observation was previously reported by Ho [18] for copper ions onto tree fern
adsorbent. The corresponding linear plots of K2 , h, and qe
can be expressed as a function of C0 for methylene blue
as
K2 = 0.0002C0 0.00533,
h = 0.011262C0 0.30005,
r 2 = 0.922848,
r = 0.922848,
2
(9)
(10)
Table 2
Pseudo-second-order rate constant for the sorption of methylene blue onto
rice husk
C0 (mg/L)
K2 (g/mg min)
h (mg/g min)
qe, predicted
(mg)
r22
50
70
100
0.003224
0.011075
0.0137
0.181647
0.623958
0.771878
11.29793
14.60515
19.28963
0.996964
0.999136
0.995985
(11)
V. Vadivelan, K.V. Kumar / Journal of Colloid and Interface Science 286 (2005) 90100
95
Table 3
Predicted pseudo-first-order equation for the sorption of methylene blue
onto rice husk
C0 (mg/L)
Predicted Lagergren I
order equation
50
q = 7.7345 7.7345
0.0249t
70
q = 12.7345 12.7345
0.02772t
100
q = 16.01482 16.01482
0.04515t
exp
exp
exp
Table 4
Predicted second-order equation for the sorption of methylene blue onto
rice husk
C0 (mg/L)
Predicted Lagergren I
order equation
70
t
q = 0.181647+t/11.29793
t
q = 0.623958+t/14.60515
100
t
q = 0.771878+t/19.28963
50
Fig. 7. Predicted q values for different initial dye concentrations (conditions: pH, 8; rpm, 800 rev min1 ; temperature, 32 C; V /X, 1 L/4 g).
t
.
(K2 qe2 ) + (1/qe )t
(12)
The predicted pseudo-second-order kinetic expression at different initial dye concentrations are given in Table 4.
The q values predicted from Lagergren pseudo-first-order
kinetics and Ho pseudo-second-order kinetics are shown in
Fig. 6. From Fig. 6, it was observed that for the entire sorption period, pseudo-second-order expression better predicts
the sorption kinetics than the pseudo-first-order model. This
1/n
qe = Kf Ce ,
(14)
96
V. Vadivelan, K.V. Kumar / Journal of Colloid and Interface Science 286 (2005) 90100
q0 KL Ce
,
(15)
1 + KL Ce
where Kf and n are Freundlich constants related to sorption
capacity and sorption intensity of adsorbents. The value of n
falling in the range of 110 indicates favorable sorption. The
linearized form of Freundlich and Langmuir can be written
as follows:
Langmuir,
qe =
(16)
(17)
Thus the Freundlich constant Kf and n can be calculated from the intercept and slope of plot between log qe and
log Ce . Similarly the Langmuir constants q0 and KL were
calculated from the slope of plot between Ce /qe versus Ce .
The predicted Freundlich and Langmuir isotherm equation
for methylene blue onto rice husk particles useful for design
calculations are given by Eqs. (18) and (19), respectively:
qe = 8.628196Ce0.382809 ,
(18)
5.590999Ce
.
qe =
(19)
1 + 0.13776Ce
Fig. 7 shows the Freundlich and Langmuir curve for methylene blue onto rice husk at a constant solution temperature of 32 C along with the experimental data. The Freundlich and Langmuir curves in Fig. 8 were generated using
Eqs. (18) and (19). From Fig. 8 it was observed that the
equilibrium data were very well represented by the Langmuir isotherm equation when compared to the Freundlich
equation. The sorption equilibrium data fit Freundlich and
Langmuir equations with a correlation coefficient value of
0.968246 and 0.984986, respectively. The best fit of equilibrium data in the Langmuir isotherm expression confirms the
monolayer coverage of methylene blue onto rice husk particles. The calculated Freundlich and Langmuir isotherm constants, predicted Freundlich and Langmuir equations, and
their corresponding linear regression correlation coefficient
values at 32 C are given in Table 5. From Table 5, it was
observed that the maximum sorption capacity of rice husk
particles for methylene blue was found to be 40.5833 mg/g.
The qm values show that the sorption capacity of rice husk
particles was highly comparable to the sorption capacities of
some other low-cost adsorbent materials for methylene blue.
The essential characteristics of the Langmuir isotherm
can be expressed in terms of dimensionless constant separation factor or equilibrium parameter, RL , given by [20]
RL = 1/(1 + KL C0 ).
(20)
Type of isotherm
RL > 1
RL = 1
0 < RL < 1
RL = 0
Unfavorable
Linear
Favorable
Irreversible
Fig. 8. Equilibrium curve for the sorption of methylene blue onto rice husk
at 32 C (V , 50 mL; M, 0.06 g; pH, 8; agitation speed, 95 stroke min1 ).
From a mechanistic viewpoint to interpret the experimental data, prediction of the rate-limiting step is an important
factor to be considered in the sorption process [21]. Though
kinetic and equilibrium isotherm studies help to identify the
sorption process, predicting the mechanisms is required for
design purposes. For a solid liquid sorption process, the
solute transfer is usually characterized by either external
Table 5
Equilibrium constants for methylene blue onto rice husk at 32 C
Temperature
( C)
32
40.5883
KL
r2
Kf (mg/g)(L/g)
1/n
r2
0.137766
0.984986
8.628196
0.36289
0.968246
V. Vadivelan, K.V. Kumar / Journal of Colloid and Interface Science 286 (2005) 90100
mass transfer (boundary layer diffusion) or intraparticle diffusion or both. The sorption dynamics can be described by
the following three consecutive steps which are as follows:
Transport of the solute from bulk solution through liquid
film to the adsorbent exterior surface;
Solute diffusion into the pore of adsorbent except for a
small quantity of sorption on the external surface; parallel to this is the intraparticle transport mechanism of the
surface diffusion;
Sorption of solute on the interior surfaces of the pores
and capillary spaces of the adsorbent.
The last step is considered to be an equilibrium reaction.
Of the three steps, the third step is assumed to be rapid and
considered to be negligible. The overall rate of sorption will
be controlled by the slowest step, which would be either
film diffusion or pore diffusion. However, the controlling
step might be distributed between intraparticle and external
transport mechanisms. Whatever the case, external diffusion
will be involved in the sorption process. The sorption of
methylene blue onto rice husk particles may be controlled
due to film diffusion at earlier stages and as the adsorbent
particles are loaded with dye ions, the sorption process may
be controlled due to intraparticle diffusion. But for design
purposes, it is necessary to calculate the slowest step involved in the sorption process. For the sorption process, the
external mass transfer controls the sorption process for the
systems that have poor mixing, dilute concentration of adsorbate, small particle sizes of adsorbent, and higher affinity
of adsorbate for adsorbent. Whereas the intraparticle diffusion will control the sorption process for a system with good
97
(21)
(mg/g min0.5 )
98
V. Vadivelan, K.V. Kumar / Journal of Colloid and Interface Science 286 (2005) 90100
Fig. 10. Intraparticle diffusion plot for methylene blue onto rice husk (C0 ,
100 mg/L; V , 1 L; M, 4 g; pH, 8; agitation speed, 800 rev min1 ).
(22)
3.6. Design of batch sorption from isotherm data
and
F = q/q0 ,
(23)
where q0 is the amount of methylene blue adsorbed at infinite time (mg/g) and q represents the amount of dye adsorbed at any time t (min), F represents the fraction of solute
adsorbed at any time t, and Bt is a mathematical function
of F .
Substituting Eq. (23) in (22), Eq. (22) simplifies to
1 F = (6/ 2 ) exp(Bt)
(24)
or
Bt = 0.4977 ln(1 F ).
(25)
The Bt values at different contact times can be calculated using Eq. (25). The calculated Bt values were plotted against
time t as shown in Fig. 11. Fig. 11 is used to identify whether
external transport or intraparticle transport control the rate of
sorption [1,21,25]. From Fig. 11, it was observed that the
plots were linear but do not pass through the origin confirming that, for the studied initial dye concentration, external mass transport mainly governs the sorption process
[1,21,25]. The calculated B values were used to calculate
the effective diffusion coefficient, Di (cm2 /s) using the relation [26]
B = 2 Di /r 2 ,
(26)
V. Vadivelan, K.V. Kumar / Journal of Colloid and Interface Science 286 (2005) 90100
99
written as
V (C0 C1 ) = M(q0 q1 ) = Mq1 .
(27)
Fig. 13. Adsorbent mass (M) against volume of solution treated (L).
and q1 qe .
(28)
Since the sorption isotherm studies confirm that the equilibrium data for methylene blue onto rice husk particle fitted
well in a Langmuir isotherm, a Langmuir isotherm equation
can be used for q1 in equation batch adsorber design.
Equation (23) can be rearranged as
(C0 Ce ) C0 Ce C0 Ce
M
=
=
= qK C .
0 L e
V
q1
qe
(29)
1+KL Ce
4. Conclusion
1. The present study shows that the rice husk, an agrobased waste biomaterial can be used as an adsorbent for
the removal of methylene blue from its aqueous solutions.
2. The amount of dye sorbed was found to vary with initial
solution pH, adsorbent dose, and contact time.
3. The amount of dye uptake (mg/g) was found to increase
with increase in solution concentration and contact time
and found to decrease with increase in adsorbent dosage.
References
[1] V.K. Gupta, I. Ali, M.D. Suhas, J. Colloid Interface Sci. 265 (2003)
257.
[2] Y.S. Ho, G. McKay, Can. J. Chem. Eng. 76 (1998) 822.
[3] G.M. Walker, L. Hansen, J.A. Hanna, S.J. Allen, Water Res. 37 (2003)
2081.
[4] G. McKay, S.J. Allen, I.F. McConvey, J. Colloid Interface Sci. 323
(1981) 323.
[5] S.J. Allen, G. McKay, Can. J. Chem. Eng. 58 (1980) 521.
[6] B.S. Inbaraj, K. Selvarani, N. Sulochana, J. Sci. Ind. Res. 61 (2002)
971.
[7] P. Jano, Environ. Sci. Technol. 37 (2003) 5792.
[8] G. McKay, J.F. Porter, G.R. Prasad, Water Air Soil Pollut. 114 (1999)
423.
[9] M. Dogan, M. Alkan, J. Colloid Interface Sci. 267 (2003) 32.
[10] D. Gosh, G. Bhattacharya, Appl. Clay Sci. 20 (2002) 295.
[11] C. Namasiayam, M.D. Kumar, K. Selvi, R.A. Begum, T. Vanathi, R.T.
Yamuna, Biomass Bioenergy 21 (2001) 477.
[12] I.A. Rahman, B. Saad, Malaysian J. Chem. 5 (2003) 8.
[13] S.D. Khattri, M.K. Singh, Water Air Soil Pollut. 120 (2000) 283.
Dogar, R. Bayrak, M. Acikyildiz, M. Yalcin,
[14] A. Grses, S. Karaca, C.
J. Colloid Interface Sci. 269 (2004) 310.
[15] I.D. Mall, S.N. Upadhyay, Indian J. Environ. Health 40 (2) (1998) 177.
100
V. Vadivelan, K.V. Kumar / Journal of Colloid and Interface Science 286 (2005) 90100
[16] S.K. Khare, K.K. Panday, R.M. Srivatsava, V.N. Singh, J. Chem. Technol. Biotechnol. 38 (1987) 99.
[17] R. Sivaraj, C. Namasivayam, K. Kadirvelu, Waste Manage. 21 (2001)
105.
[18] Y.S. Ho, Water Res. 37 (2003) 2323.
[19] S. Ismadji, S.K. Bhatia, Can. J. Chem. Eng. 78 (2000) 892.
[20] G. McKay, J. Chem. Technol. Biotechnol. 32 (1982) 759.
[21] M. Sarkar, P.K. Acharya, B. Battacharya, J. Colloid Interface Sci. 266
(2003) 28.
[22] N.A. Fernadez, E. Chacin, E. Gutierrez, N. Alastre, Bioresource Technol. 54 (1995) 111.