Available online at www.sciencedirect.

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Bioresource Technology 99 (2008) 1623–1629

Utilization of ground eggshell waste as an adsorbent for the removal

of dyes from aqueous solution
a,*
Wen-Tien Tsai , Kuo-Jong Hsien b, Hsin-Chieh Hsu b, Chien-Ming Lin b, Keng-Yu Lin b,
Chun-Hsiang Chiu b
a
Graduate Institute of Bioresources, National Pingtung University of Science and Technology, Pingtung 912, Taiwan
b
Department of Environmental Engineering and Science, Chia Nan University of Pharmacy and Science, Tainan 717, Taiwan

Received 5 February 2007; received in revised form 5 April 2007; accepted 5 April 2007
Available online 31 May 2007

Abstract

The adsorption of cationic basic blue 9 and anionic acid orange 51 from aqueous solution onto the calcified eggshell (ES) and its
ground eggshell powder (ESP) was carried out by varying the process parameters such as agitation speed, initial dye concentration,
adsorbent mass and temperature. The adsorption potential for basic blue 9 onto ESP is far lower than that for acid orange 51, mainly
due to the ionic interaction between the acid dye with the sulfonate groups and the positively charged sites on the surface of ESP. The
adsorption capacity of acid orange 51 onto ES is significantly smaller than that onto ESP, which is in line with their pore properties (i.e.,
1 vs. 21 m2/g). The experimental results showed that the adsorption process can be well described with a simple model, the pseudo-
second-order model. According to the equilibrium adsorption capacity from the fitting of pseudo-second order reaction model, it was
further found that the Freundlich model yields a somewhat better fit than the Langmuir model in the adsorption of acid orange 51 onto
ESP. In addition, an increase in adsorption temperature from 15 to 45 C significantly enhances the adsorption capacity of acid orange
51 onto ESP, revealing that the adsorption should be an endothermic or chemisorption process. From the results, it is feasible to utilize
the ground eggshell waste as an effective adsorbent for removal of anionic dye from aqueous solution.
 2007 Elsevier Ltd. All rights reserved.

Keywords: Calcified eggshell; Dye; Liquid-phase adsorption; Kinetic modeling; Bioresource utilization

1. Introduction nesium carbonate (1%), calcium phosphate (1%) and

The hen eggshell mainly consists of two regions: the mam-
millary matrix (i.e., eggshell membrane) consisting of inter-
woven protein fibers and spherical masses, and the spongy
matrix (i.e., calcified eggshell) made of interstitial calcite or
calcium carbonate crystals (Li-Chan et al., 1995). Notably,
numerous funnel-shaped pore canals with submicron-scaled
mouth are distributed on the surface of eggshell, forming
connection passages between the shell membrane and the
cuticle (a foamy layer of protein on the outer surface). The
chemical composition (by weight) of by-product eggshell
has been reported as follows: calcium carbonate (94%), mag-
*
Corresponding author. Tel.: +886 8 7703202; fax: +886 8 7740134.
E-mail address: wttsai@mail.npust.edu.tw (W.-T. Tsai).
organic matter (4%) (Stadelman, 2000). The by-product egg-
shell weighs approximately 10% of the total mass (ca. 60 g)
of hen egg (Stadelman, 2000), representing a significant
waste from the egg-derived products processor because it
was traditionally useless and commonly disposed of in land-
fills without any pretreatment. However, the waste manage-
ment was not a desirable practice in view of the
environmental odor from biodegradation. Because of its
high nutrition contents such as calcium, magnesium and
phosphorus (Tacon, 1982), the utilization of this food pro-
cessing by-product was usually reused as a fertilizer, soil
conditioner or an additive for animal feed (Christmas and
Harms, 1976). Due to its intrinsic pore structure in the calci-
fied eggshell and the amount in abundance, it is thus feasible
to grind the eggshell agrowaste in the preparation of fine

0960-8524/$ - see front matter  2007 Elsevier Ltd. All rights reserved.
doi:10.1016/j.biortech.2007.04.010
1624 W.-T. Tsai et al. / Bioresource Technology 99 (2008) 1623–1629
powders, which might pave the way for available materials
such as porous adsorbents.
Wastewater containing a variety of dyes was often dis-
charged in aqueous effluents from dyestuff manufacturing,
dyeing and textile industries. Its physical processes for
removal of dyes from effluents may be divided into two
main categories: adsorption and membrane separation
(Slokar and Majcen-Le Marechal, 1998; Vandevivere
et al., 1998; Hao et al., 2000). Adsorption is generally con-
sidered to be an effective method for quickly lowering the
concentration of dissolved dyes in an effluent. In this
regard, activated carbon has been evaluated extensively
for the removal of color resulting from the different classes
of dyes, and is now the most widely used adsorbent for
dyes. However, the adsorption using carbon adsorbent still
remains an expensive process due to the high cost in the use
of activated carbon and the difficulty in the regeneration of
spent activated carbon (Reife and Freeman, 1996). For this
reason, there is growing interest in utilizing biomass
wastes/alternatives to activated carbon as low-cost adsor-
bents (Pollard et al., 1992; Allen, 1996; Bailey et al.,
1999; Gupta and Ali, 2002; Babel and Kurniawan, 2003).
Based on the bioresource recycling, the proposal of reus-
ing hen eggshell as adsorbents has slightly increased in
recent years. Chojnacka (2005) studied the sorption of
Cr(III) ions from aqueous solutions using crushed hen egg-
shells (on an average of about 100 lm) as a low-cost sor-
bent, finding that it had a relatively high sorption
capacity as compared to other sorbents. Vijayaraghavan
et al. (2005) investigated an up-flow column packed with
crushed eggshell (on an average of about 0.767 mm) for
removal of copper ions from aqueous solutions, indicating
the sorption characteristics of the eggshell as a function of
bed height and flow rate. Otun et al. (2006) reported
removal of metal(II) ions (i.e., Pb, Ni and Cd) from aque-
ous solutions using powdered eggshell with particle size
63 lm, revealed that the adsorption capacities of metal(II)
ions obtained from the isotherm experiments followed the
sequence: Pb > Ni > Cd. In the previous paper (Tsai
et al., 2006), we carried out the chemical and physical char-
acterizations of crushed hen eggshell particles (not ground),
indicating that they are basically characteristic of ‘‘nonpo-
rous’’ materials with BET surface area of ca. 1.0 m2/g, and
also strongly associated with the presence of carbonate
minerals from the Fourier transform infrared (FTIR) spec-
tra. In addition, its adsorption capacity could only intake
the cationic dye (i.e., methylene blue) of less than 1.0 mg/
g in aqueous solutions.
Taking into account the add-on utilization of eggshell
particle, it is necessary to fabricate more fine powder by
the size reduction method because the properties (e.g., sur-
face area) of powder material mainly depend on its particle
size, particle shape and porosity (Lowell et al., 2004). It is
well known that the grinding or milling of granular mate-
rial can cause not only a reduction in particle size but also
a structural change, resulting in a reduction of the crystal-
linity (Filio et al., 1994). In the present work, the planetary
ball mill was used to comminute the calcified eggshell in the
preparation of fine powder, which was applied to be an effi-
cient adsorbent in the adsorption of cationic and anionic
dyes (i.e., basic blue 9 and acid orange 51, respectively)
from aqueous solutions. Thus, the main objects of this
paper were to (i) compare the ability of ground eggshell
powder (denoted as ESP) to remove basic blue 9 and acid
orange 51 by adsorption, and further elucidate this result
on the basis of interaction between the dye molecule and
the adsorption site on the surface of adsorbent; (ii) make
a comparison between the performances of the starting cal-
cified eggshell (ES) and the ground eggshell powder (ESP)
as adsorbents to remove one preferable dye from aqueous
solutions; (iii) evaluate the usefulness of simple pseudo-sec-
ond-order model for the adsorption kinetics of one prefer-
able dye onto ESP from aqueous solutions; (iv) determine
the applicability of common isotherm models (i.e., Lang-
muir and Freundlich) based on the adsorption capacities
from the fittings of the adsorption rate model.
2. Methods
2.1. Materials
The raw precursor used in this research was a calcified
hen eggshell as described previously (Tsai et al., 2006). Its
powdered form was performed by a tumbling (planetary)
ball mill (Model: PM 100; Retsch Co., Germany) at the fol-
lowing conditions: rotational speed of 400 rpm, grinding
time of 30 min, and precursor mass of 1.0 g. The median
size and BET surface area of resulting ground eggshell
powder were determined to be approximately 15 lm and
21 m2/g, respectively. To examine the functional groups
on the surface of the ground eggshell powder, its Fourier
transform infrared spectroscopy (FTIR) was also carried
out by using a FTIR spectrometer (Model: System 2000;
Perkin–Elmer Co., USA). Its observable peaks at about
710, 870, 1425, 1800, 2515, and 2900 cm1 are strongly
associated with the presence of calcium carbonate (Aldrich,
1997), also showing that it seemed to be no chemical
change in comparison with that in the starting eggshell
(Tsai et al., 2006). Two different dyestuffs were used as
adsorbates in the study, including basic blue 9 (i.e., methy-
lene blue) and acid orange 51, purchased from Katayama
Chemical Co. (Osaka, Japan) and Aldrich Chemical Co.
(Milwaukee, USA). All dyestuffs were directly used without
any further purification. The characteristics of the selected
dyes was listed in Table 1.
2.2. Adsorption studies
Prior to the determination of residual dye concentration
in the aqueous solutions, a calibration curve of each dye
was preliminarily carried out to calculate the dye amount
adsorbed by the eggshells. The standard solutions having
five or six different dye concentrations were first prepared
and measured using UV/VIS spectrophotometer (Model:
 W.-T. Tsai et al. / Bioresource Technology 99 (2008) 1623–1629
Table 1
Characteristics of selected dyestuffs used as adsorbates in this work
Dyestuff (CAS registry no.) C.I. number Commercial name
Basic blue 9 (7220-79-3) C.I. 52015 Methylene blue
Acid organic 51 (8003-88-1) C.I. 26550 – 50
a
Determined by the Hitachi UV/VIS Spectrophotometer U-2001 over a range from 190 to 1100 nm.
U-2001; Hitachi Co., Japan) to obtain the maximum absor-
bance at 661 nm and 455 nm for basic blue 9 and acid
organic 51, respectively. Then, the maximum absorbance
of each dye was correlated with an available range of dye
concentrations, indicating a high correlation (R2  0.999).
As a result, the residual concentration of the dye samples
can be determined and the adsorbed dye amount can be
further calculated according to the data on the initial dye
concentration and residual dye concentration.
All the experiments of adsorption studies were carried out
in a ca. 3-dm3 stirred batch adsorption apparatus with four
baffles as similarly described in our previous studies (Tsai
et al., 2004, 2005a,b). All the dye solutions were prepared
with de-ionized water. The effect of agitation speed at 200,
400 and 600 rpm on the adsorption uptake was first tested.
The results, which were described later, showed that it
seemed to be negligible at above 400 rpm. Thus, the adsorp-
tion uptake of the adsorbent under the initial dye concentra-
tion of 30 mg dm3, mixing rate of 400 rpm, temperature of
25 C, pH of 7.0, and dosage of 0.5 g 2.0 dm3 was first
investigated for the purpose of studying the adsorbability
of basic blue 9 and acid orange 51 by the ground eggshell
powder. Base on the former results, one experiment was car-
ried out to make a comparison between the performances of
the starting calcified eggshell and the ground eggshell pow-
der as adsorbents to remove one preferable dye from aque-
ous solutions at the same adsorption conditions.
From the results described above, the ground eggshell
powder was further used to study the variation of adsorp-
tion at various agitation speeds (i.e., 200–600 rpm), initial
dye concentrations (i.e., 10–50 mg dm3), adsorbent dos-
age (i.e., 0.5–1.5 g dm3), and temperature (i.e., 15–
45 C). The sampling method and determination of dye
concentration in aqueous solution were also identical to
the previous studies (Tsai et al., 2004, 2005a,b). In order
to evaluate the statistical significance of data in the kinetic
experiments, a preliminary experiment was also repeated
under identical conditions (i.e., initial dye concentration
of 30 mg dm3, mixing rate of 400 rpm, temperature of
25 C, pH of 7.0 and dosage of 0.5 g 2.0 dm3), showing
that the reproducibility of the measurements is within 9%
in the adsorption experiments.
3. Results and discussion
3.1. Adsorbability of two different dyes
In the present study, the adsorption characteristics of
two different dyes, basic blue 9 (one of cationic dyes) and
1625
a
Purity (%) Formula fw kmax (nm)
95 C16H18ClN3S 319.86 661
C36H28N6O11S3 860.81 455
acid orange 51 (one of anionic dyes), using the ground egg-
shell powder were investigated as to their effect upon its
removal from aqueous solution. The plots of residual dye
concentration vs. time in each of the adsorption systems
were depicted in Fig. 1. It can be seen that preliminary
investigations on the adsorption removal by the ground
eggshell powder have indicated that the process occurs
for acid orange 51, not in the case for basic blue 9. The
decrease in residual concentration of acid orange 51 meant
the increase in the amount adsorbed as a function of time
until the adsorption of the anionic dye approached to
remain constant, implying that adsorption equilibrium
has been reached. After the lapse of ca. 2 h, a gradual
approach to the limiting adsorption was observed. Evi-
dently, the adsorption removal (10%) of basic blue 9 on
the ground eggshell powder was far lower than that
(60%) of acid orange 51. The adsorbabilty of the dye
adsorbate thus followed the sequence: acid orange
51 > basic blue 9. It was observed that the adsorption
behavior in order of favorability seemed to be parallel to
the molecular weights and molecular sizes of the dyes as
indicated in Table 1, showing that the London (dispersion)
forces derived from the adsorption potential could still
pose a significant role in encountering the interaction
between the cationic dye (i.e., basic blue 9) and the ground
eggshell powder at the neutral condition.
35
30
25
Ct (mg/L)
20
15
10
5 Basic blue 9
Acid orange 51
0
0 30 60 90 120 150
Time (min)
Fig. 1. Plots of residual dye concentration versus time onto the ground
eggshell powder [adsorption conditions: initial dye concentra-
tion = 30 mg dm3, adsorbent dosage = 0.5 g 2.0 dm3, pH = 7.0, agita-
tion rate = 400 rpm, and temperature = 25 C; Symbols: experimental
data, full and dotted lines: calculated from the pseudo-second-order
equation].
1626 W.-T. Tsai et al. / Bioresource Technology 99 (2008) 1623–1629
3.2. Adsorption characteristics of acid orange 51 onto ES
and ESP
Adsorption studies of acid orange 51 onto the starting
eggshell (ES) and the ground eggshell powder (ESP) were
carried out at initial dye concentration of 30 g dm3, adsor-
bent dosage of 0.5 g 2.0 dm3, agitation rate of 400 rpm,
pH of 7.0, and temperature of 25 C. Fig. 2 showed plots
comparing the experimental adsorption data for these
two adsorbents. There are two noteworthy features from
the results in Fig. 2.
1. The optimum period for the dye adsorption onto the
adsorbent can be observed by looking at the variances
on its residual concentration after adding the adsorbent.
As shown in Fig. 2, preliminary investigations on the
adsorption rate by these two adsorbent have indicated
that the process occurs rapidly at an early stage. After
the lapse of 120 min, a gradual approach to the limiting
adsorption was observed. Therefore, the optimum agita-
tion period for removal of acid orange 51 from aqueous
solution is about 120 min in the adsorption system.
2. The adsorption capacity of acid orange 51 onto the
starting eggshell (ES) are significantly smaller than that
onto the ground eggshell powder (ESP), suggesting that
the latter with a relatively high surface area (i.e., 21 vs.
1 m2/g) will be more effective than the former for
removal of acid organic 51 from aqueous solution.
3.3. Adsorption kinetics
Due to the fast decrease in residual dye (i.e., acid orange
51) concentration at a short time scale, implying that the
35
30
25
Ct (mg/L)
20
15
10
5 ES
ESP
0 Pseudo-second-order parameters for the adsorption of acid orange 51
0 30 60 90 120 150
Time (min)
Fig. 2. Plots of residual acid orange 51 concentration versus time onto the
starting eggshell (ES) and the ground eggshell powder (ESP) [adsorption
conditions: initial dye concentration = 30 mg dm3, adsorbent dos-
age = 0.5 g 2.0 dm3, pH = 7.0, agitation rate = 400 rpm, and tempera-
ture = 25 C; symbols: experimental data, full and dotted lines: calculated
from the pseudo-second-order equation].
strong adsorption interaction between the positive charge
on the surface of the ground eggshell powder (ESP) and
the anionic dye compound, a simple kinetic analysis of
adsorption, pseudo-second-order equation (Ho and
McKay, 1998), was thus used to fit experimental data in
the present work as reported previously (Tsai et al., 2004,
2005a,b). Its linear form can be denoted as follows:
t=qt ¼ 1=ðkq2e Þ þ ð1=qe Þt ð1Þ
where k is the rate constant of pseudo-second-order
adsorption (g mg1 min1), qe and qt are the amount
(mg g1) of the acid dye adsorbed at equilibrium and time
t, respectively. Rate parameters, k and qe, can be directly
obtained from the intercept and slope of the plot of (t/qt)
against t. The equilibrium concentration (i.e., Ce) can be
further calculated based on the mass balance concept as
the value of qe has been obtained from the fitting of Eq. (1).
3.3.1. Effect of agitation speed
The effect of agitation speed on the dye adsorption at the
adsorbent dosage of 0.5 g 2.0 dm3, initial dye concentra-
tion of 30 mg dm3, pH of 7.0, and temperature of
25.0 C is listed in Table 2. The correlation between the
experiments with the theoretical results is excellent. The
data in Table 2 indicate that the adsorption capacity (i.e.,
qe) significantly increases as the agitation speed increased
from 200 rpm to 400 rpm. On the other hand, the experi-
mental errors between the agitation speeds of 400 and
600 rpm are within 10%, showing that the effect of agita-
tion seemed to be negligible at above 400 rpm. This effect
can be attributed to the increase in turbulence and the
decrease in boundary layer thickness around the adsorbent
particles as a result of increase in the degree of mixing
(Weber and DiGiano, 1996). This result was also in agree-
ment with those of Al-Qodah (2000) and Ho et al. (2001)
for the adsorption of dye onto activated clay and shale
oil ash, respectively.
3.3.2. Effect of initial concentration
The kinetic data obtained from a series of batch adsorp-
tion studies have been analyzed using the pseudo-second-
order model under different initial dye concentrations at
the adsorbent dosage of 0.5 g 2.0 dm3, mixing speed of
400 rpm, pH of 7.0, and temperature of 25.0 C. The fitted
k and qe values and correlation coefficients for acid orange
51 are given in Table 3, showing that an increase in the ini-
Table 2
onto ESP at various agitation ratesa
Agitation rate (rpm) k (g mg1 min1) qe (mg g1) R2
200 0.00619 58.82 0.9920
400 0.00829 71.94 0.9997
600 0.00541 78.74 0.9964
a
Adsorption conditions: initial concentration = 30 mg dm3, dos-
age = 0.5 g 2.0 dm3, pH = 7.0, and temperature = 25 C.
 W.-T. Tsai et al. / Bioresource Technology 99 (2008) 1623–1629
Table 3
Pseudo-second-order parameters for the adsorption of acid orange 51
onto ESP at various initial concentrationsa
Initial concentration k (g mg1 min1) qe (mg g1)
(mg dm3)
10 0.01596 28.74
20 0.00907 52.63
30 0.00829 71.94
40 0.00525 93.46
50 0.00307 112.36
a
Adsorption conditions: adsorbent dosage = 0.5 g 2.0 dm3, agitation
rate = 400 rpm, pH = 7.0, and temperature = 25 C.
tial dye concentration from 10 to 50 mg dm3 produces an
increase in the adsorption capacities of the acid dye. It is
also seen that the kinetic modeling of the acid adsorption
onto the ground eggshell powder well follows this model
with the correlation coefficients of higher than 0.995 for
all the system in the present work. From the results in
Table 3, it is further found that the variations of rate con-
stant (i.e., k) seem to have a decreasing trend with initial
dye concentration increased, which is consistent with those
by Ho et al. (2001). The result could be attributed to the
amount of adsorption sites have been determined by a
given adsorbent dosage. This indicates that the adsorption
rate will increase with an increased initial dye concentra-
tion mainly due to the increase in the mass transfer from
the concentration gradient, but the concentration effect will
inversely impact on its adsorption frequency which is indic-
ative of the adsorption rate constant because of the limited
adsorption sites available for the uptake of adsorbate.
3.3.3. Effect of adsorbent dosage
The effect of varying the ground eggshell powder dosage
on acid orange 51 adsorption at the initial concentration of
30 mg dm3, pH of 7.0, agitation rate of 400 rpm, and tem-
perature of 25 C has been carried out. The values of k and
qe for the adsorption system are listed in Table 4. Evi-
dently, the correlation between the experimental and theo-
retical results is also good. From the results in Table 4, it is
suggested that the adsorption frequency increases at the
same initial dye concentration and the rate constant, k,
thus increased at a larger value as the adsorbent dosage
increases. However, the adsorbability diminished as the
adsorbent dosage was increased, resulting in that the
amount of the acid dye adsorbed per unit mass of ground
eggshell powder (i.e., adsorption capacity) decreased with
an increasing amount of adsorbent added. This leads to
Table 4
Pseudo-second-order parameters for the adsorption of acid orange 51
onto ESP at various adsorbent dosagesa
Adsorbent dosage (g dm3) k (g mg1 min1) qe (mg g1)
0.5 0.00829 71.94
1.0 0.00897 45.45
1.5 0.01785 32.15
a
Adsorption conditions: initial concentration = 30 mg dm3, pH = 7.0,
agitation rate = 400 rpm, and temperature = 25 C.
1627
make a suggestion that, in order to obtain the optimal
adsorbent dosage, higher dye concentrations should be
tested in conjunction with appropriate adsorbent dosage.
R2
3.3.4. Effect of adsorption temperature
0.9987
0.9982 The variations of qt vs. t at various temperatures under
0.9997 the adsorbent dosage of 0.5 g 2.0 dm3, initial dye concen-
0.9989 tration of 30 mg dm3, mixing speed of 400 rpm, and pH of
0.9968 7.0 still confirm to fit the pseudo-second-order model with
high correlation coefficients (>0.99). The values of model
parameters (i.e., k and qe) for different temperatures have
been calculated from Eq. (3) and the results are given in
Table 5, revealing that the fitted adsorption capacity at
equilibrium (i.e., qe) increased with increasing temperature.
For example, the values of qe increase from 42.92 mg g1 at
15 C to 84.03 mg g1 at 45 C. The observations were in
line with those observed by Low et al. (1996) for carbon-
ized SBE and basic blue 3 and methylene blue (i.e., basic
blue 9), by Ghosh and Bhattacharyya (2003) for kaolinite
and methylene blue, by Dogan and Alkan (2003) for perlite
and methyl violet (i.e., basic violet 1), and also by Tsai et al.
(2005a) for regenerated bleaching earth and ethyl violet
(i.e., basic violet 4). Based on the results of the effect of
temperature on the fitting adsorption capacity, the main
mode for the adsorption of acid dye onto the ground egg-
shell was speculated to be strong dispersion forces and thus
led to significant attraction between the dye molecule and
the ground eggshell particle, which should be an endother-
mic or chemisorption process, showing that the amount of
dye adsorbate adsorbed onto adsorbent increases with rais-
ing adsorption temperature.
3.4. Adsorption isotherm
Two common isotherm equations have been applied to
model the isotherms in the present study: the Langmuir
and the Freundlich models (Al Duri, 1996).
Langmuir : qe ¼ qm K L C e =ð1 þ K L C e Þ ð2Þ
Freundlich : qe ¼ K F C e1=n ð3Þ
In Eq. (2), Ce and qe are the concentration (mg dm3) and
amount (mg g1) of acid orange 51 adsorbed at equilib-
rium, respectively, KL is a direct measure of the intensity
of the adsorption process (dm3 mg1), and qm is a constant
relating to the surface area occupied by a monolayer of
Table 5
Pseudo-second-order parameters for the adsorption of acid orange 51
onto ESP at various initial temperaturea
Initial temperature (C) k (g mg1 min1) qe (mg g1) R2
R2
15 0.01324 42.92 0.9988
0.9997 25 0.00829 71.94 0.9997
0.9976 35 0.00893 80.00 0.9990
0.9990 45 0.01242 84.03 0.9995
a
Adsorption conditions: dosage = 0.5 g 2.0 dm3, initial concentra-
tion = 30 mg dm3, agitation rate = 400 rpm, and pH = 7.0.
1628 W.-T. Tsai et al. / Bioresource Technology 99 (2008) 1623–1629
150
120
90
qe (mg/g)
60
Langmuir
30
Freundlich
Experimental data
0 high surface area (i.e., 21 vs. 1 m2/g) will be more effec-
0 10 20 30 40
Ce (mg/L)
Fig. 3. Adsorption isotherm of acid orange 51 in aqueous solutions onto
the ground eggshell powder at 25 C [adsorption conditions: adsorbent
dosage = 0.5 g 2.0 dm3, agitation speed = 400 rpm, and pH = 7.0;
Symbols d: experimental data, full lines: calculated from the Freundlich
model, dotted lines: calculated from the Langmuir model].
adsorbate, reflecting the adsorption capacity (mg g1).
Based on the data of qe from the fittings of the pseudo-sec-
ond-order adsorption rate model, qm and KL can be deter-
mined from its slope and intercept from a typical plot of
1/qe vs. 1/Ce. In Eq. (3), KF is a constant for the system,
related to the bonding energy. KF can be defined as adsorp-
tion or distribution coefficient and represents the general
capacity of acid orange 51 adsorbed onto adsorbents for
a unit equilibrium concentration (i.e., Ce = 1 mg dm3).
The slope 1/n, ranging between 0 and 1, is a measure for
the adsorption intensity or surface heterogeneity.
The results of the Langmuir and the Freundlich iso-
therms fitted by using the data of adsorption capacity from
the regression of Eq. (1) at 25 C are shown in Fig. 3. It was
indicated that the Freundlich model obviously yields a
somewhat better fit than the Langmuir model, as reflected
with correlation coefficients (R2) of 0.978 vs. 0.953. The
adsorption isotherms reveal that the ground eggshell pow-
der can uptake 113.6 mg g1 in relatively low concentration
of the acid dye in aqueous medium. Also, the value of 1/n in
the Freundlich model is significantly less than unity indicat-
ing a favorable adsorption system. By comparing the mono-
layer saturation adsorption capacity (i.e., 113.6 mg g1)
with the data (i.e., 8.5 mg g1) obtained by the previous
study (Tsai et al., 2004), the equilibrium adsorption capac-
ities are not in accordance with the order of BET surface
areas (i.e., 21 vs. 245 m2 g1), implying that the acid orange
51 could be adsorbed largely and strongly on the ground
eggshell powder, somewhat less on the activated bleaching
earth in that its surface is negatively charged.
4. Conclusion
The calcified eggshell and its ground powder used as
adsorbents for removal of two different dyestuffs, namely,
basic blue 9 and acid orange 51, from aqueous solutions
have been studied. The following conclusions can be
drawn:
• The adsorption potential for basic blue 9 onto the
ground eggshell powder (ESP) is far lower than that
for acid orange 51. It was observed that the adsorption
behavior in order of favorability seemed to be parallel to
the molecular weights and molecular sizes of the dyes.
• The adsorption capacity of acid orange 51 onto the cal-
cified eggshell is significantly smaller than that onto its
ground form, suggesting that the latter with a relatively
tive than the former for removal of the acid dye from
aqueous solution.
• The adsorption kinetics of acid orange 51 onto the
ground eggshell powder can be well described by a sim-
ple model, namely, pseudo-second-order model. The
kinetic parameters thus obtained from the fittings of
the model are dependent on agitation speed, initial dye
concentration, adsorbent dosage and adsorption
temperature.
• An increase in adsorption temperature from 15 to 45 C
significantly enhances the adsorption capacity of acid
orange 51 onto the ground eggshell powder, revealing
that the adsorption should be endothermic or chemi-
sorption in nature.
• From the analysis of the isotherm data obtained from
the fittings of the pseudo-second-order model, the Fre-
undlich model yields a somewhat better fit than the
Langmuir model in the adsorption of acid orange 51
onto the ground eggshell powder.
References
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