J Radioanal Nucl Chem (2013) 295:717727

DOI 10.1007/s10967-012-1950-4

Adsorption of uranium(VI) by grapefruit peel in a fixed-bed

column: experiments and prediction of breakthrough curves
Weihua Zou Lei Zhao Lu Zhu

Received: 23 April 2012 / Published online: 25 July 2012

Akademiai Kiado, Budapest, Hungary 2012

Abstract Adsorbent, natural grapefruit peel (GFP) exhibit good efficacy to adsorb a highly toxic radioactive heavy
metal, uranium(VI). Through the fixed-bed column technique adsorption characteristics of uranium(VI) is observed
at different flow rate, bed depth, influent uranium(VI)
concentration and particle size of adsorbent. The results
showed that adsorption reached saturation faster with
increasing the flow rate and influent uranium(VI) concentration while it was the advantage of column adsorption
with the increase in the GFP bed. The data were fitted to
the Thomas model, the Yan model, the Clark model and the
mass transfer model by nonlinear regressive analysis.
When the flow rate was 8.0 mL min-1 and the influent
concentration of uranium(VI) was 90 mg L-1, the maximum adsorption quantity reached 104.1 mg g-1 according
to the Thomas model. The bed depth service time model
was applied to predict the service times with other flow rate
and initial concentration. The theoretical breakthrough
curve was compared with experimental breakthrough curve
profile in the dynamic process. The results showed that the
Yan model was better for the description of breakthrough
curves at the experimental conditions than the Thomas and
the Clark models. The saturated column was regenerated
by 0.05 mol L-1 hydrogen chloride solution and GFP
could be reused in uranium(VI) removal.

W. Zou (&)  L. Zhao

School of Chemical Engineering and Energy, Zhengzhou
University, 100# of Kexue Road, Zhengzhou 450001,
Peoples Republic of China
e-mail: whzou@zzu.edu.cn
L. Zhu
Department of Chemistry, Zhengzhou University, 100# of Kexue
Road, Zhengzhou 450001, Peoples Republic of China

Keywords Column adsorption  Grapefruit peel 

Uranium(VI)  Dynamic model

Introduction
Uranium is one of the most important heavy metals because
of its strategic importance in the energy field. Thus, excessive quantities of uranium have entered into environment
due to activities of nuclear industry. The toxic nature of the
radionuclides, even at trace levels, has been a public health
problem for many years [1, 2]. Thus, the removal of uranium
from wastewater is of great importance [3].
Adsorption technology is one of the effective methods
used to remove heavy metals from aqueous solutions and
agricultural wastes or by-products are considered to be the
most potential low-cost adsorbents for wastewater treatment
[47]. Up to now, different types of biomass have been utilized for adsorption of uranium(VI). They include rice straw,
olive cake, wood powder and wheat straw, etc. [710].
Grapefruit peel (GFP) is one of the valuable agriculture
biomass wastes, principally consisting of cellulose, pectin,
hemicellulose, lignin, chlorophyll pigments and other low
molecular weight hydro-carbons [11]. It is also found to
contain abundant carboxyl and hydroxyl functional groups,
thus making it a potential adsorbent material for several metals
through ion exchange and/or complexation mechanism. The
pattern of adsorption of ions onto GFP was attributable to the
active groups and bonds present on them [12]. These groups
may function as proton donors, hence deprotonated hydroxyl
and carboxyl groups may be involved in coordination with
positive ions. UO22? ions are positively charged and will
undergo attraction on approaching the anionic GFP structure.
On this basis, it is expected that an UO22? ion will have a
strong sorption affinity by GFP. Since GFP is a cheap,

123

718

W. Zou et al.

renewable, biodegradable and readily available material often

considered as waste [11, 12], its advantage over synthetic
materials such as polymers is enormous and contributes to the
actual trend of green chemistry.
In the previous paper, we have reported the adsorptive
removal of uranium(VI) by an GFP adsorbent in batch
method [12]. The adsorption characteristic obtained from
batch experiments is useful in providing fundamental
information about the effectiveness of the uranium(VI)/
GFP system. Batch adsorption provides certain preliminary
information such as pH for maximum adsorption, maximum initial uranium(VI) concentration, and approximate
time for adsorption of uranium(VI) ions as well as the
adsorption capacity of the adsorbent. All these information
are useful for fixed-bed studies.
Batch adsorption experiments are used easily in the
laboratory for the treatment of small volume of effluents,
but less convenient to use on industrial scale, where large
volumes of wastewater are continuously generated [13]. In
fixed-bed, the adsorbate is continuously in contact with a
given quantity of fresh adsorbent, thus providing the
required concentration gradients between adsorbent and
adsorbate for adsorption. During the flow of the wastewater
through the percolator, the wastewater is purified by
physicochemical processes. The design and theory of fixedbed adsorption systems focuses on establishing the shape of
the breakthrough curve and its velocity through the bed.
The performance of packed beds is described through the
concept of the breakthrough curve [13].
The aim of the present work is to explore the possibility
of utilizing GFP for the adsorptive removal of uranium(VI)
from wastewater in fixed-bed columns. The effect of such
factors such as the flow rate, influent concentration, bed
depth and particle size of adsorbent on uranium(VI)
adsorption by GFP bed column was investigated, respectively. The dynamic process of adsorption was modeled by
Thomas model, Yan model, Clark model, bed depth service
time (BDST) model and mass transfer model. Error analysis was carried out to test the adequacy and the accuracy
of the model equations. Regeneration studies were also
carried on the adsorbent.

(mg L-1), kTh is the Thomas rate constant (mL min-1

mg-1), q0 is the maximum uranium(VI) uptake per g of the
adsorbent (mg g-1), x is the amount of adsorbent in the
column (g), Q, the flow rate (mL min-1). The value of
Ct/C0 is the ratio of effluent and influent each uranium(VI)
concentrations. The value of t is breakthrough time (min,
t = Veff/Q, Veff is the volume of effluent solution).
The values of kTh and q0 can be determined from a plot
of Ct/C0 against t for a given flow rate using nonlinear
regression analysis as the values of Ct/C0 is within
0.050.90.

Models

The bed depth/service time analysis (BDST) model

The Thomas model

BDST is a simple model for predicting the relationship

between bed depth, Z (cm), and service time, t (min), in
terms of process concentrations and adsorption parameters. BDST model is based on the assumption that the
rate of adsorption is controlled by the surface reaction
between adsorbate and the unused capacity of the
adsorbent [17].
The values of breakthrough time obtained for various
bed heights used in this study were introduced into the

The expression by Thomas for an adsorption column is

given below [14]:
Ct
1

C0 1 expkTh q0 x=Q  kTh C0 t

where, Ct is the effluent uranium(VI) concentration

(mg L-1), C0 is the influent uranium(VI) concentration

123

The Yan model

The Yan model [15] is also used to describe the column
adsorption data. Use of this model can minimize the error
resulting from the use of the Thomas model, especially at
lower or higher time periods of the breakthrough curve.
The expression is given as:
Ct
1
1
a
C0
1 Qt
b

where a and b are the constants of the Yan model,

respectively. From value of b, the value of q0 can be
estimated using following equation [15]:
q0

bC0
x

The Clark model

Clark [16] defined a new simulation of breakthrough
curves. The model developed by Clark was based on the
use of a mass transfer concept in combination with the
Freundlich isotherm [16]:

1=n1
Ct
1

4
1 Aert
C0
From a plot of Ct/C0 against t at a given bed height and
flow rate using nonlinear regressive analysis, the values of
A and r can be obtained.

Adsorption of uranium(VI) by GFP in a fixed-bed column

719

BDST model. A linear relationship between bed depth and

service time given by Eq. (5) [17]:


N0
1
C0
t
Z
ln
1
5
Ka C0
C0 F
Ct
A plot of t vs. Z, should yield a straight line where N0
(mg L-1) and Ka (L mg-1 min-1), the adsorption capacity
and rate constant, respectively, can be evaluated.
A simplified form of the BDST Model is:
t aZ  b

where
a
b

N0
C0 F



1
C0
ln
1
Ka C0
Ct

The slope constant for a different flow rate can be directly

calculated by Eq. (8) [17]:
F
Q
a a 0a 0
F
Q
0

where a and F (cm min-1) is the old slope and influent

linear velocity and a0 and F0 (cm min-1) is the new slope
and influent linear velocity, respectively. As the column
used in experiment has the same diameter, the ratio of
original (F) and the new influent linear velocity (F0 ) and
original flow rate (Q) and the new flow rate (Q0 ) is equal. It
was assumed that the value of b does not change significantly by change in flow rates.
For other influent concentrations, the desired equation is
given by a new slope, and a new intercept given by following expression:
a0 a

b0

C0
C00

C0 ln
C00 ln

10


C00
0
Ct

1

C0
Ct

1


b

11

where b0 , b are the new and old intercept, respectively; C00

and C0 are the new and old influent concentration,
respectively. Ct0 is the effluent concentration at influent
concentration C00 and Ct is the effluent concentration at
influent concentration C0.
The mass transfer model
The data obtained from the batch adsorption isotherm can
be used to predict the theoretical breakthrough curve,
which can be well compared with the experimental
curve. The detailed calculations for the generation of the

experimental breakthrough curve from the equilibrium data

obtained from batch studies are as follows [18, 19]:
(1)

An experimental equilibrium curve is drawn assuming various values of Ce (the value is equal to Ct) and
calculating the corresponding values of qe using the
best fit isotherm model obtained from the batch
results.
(2) An operating line is drawn, which was passing
through the original and end points obtained by
experimental equilibrium curve. The significance of
this operating line is that the data of the continuously
batch reactor and the data of the fixed-bed reactor are
identical at these two points, first at the initiation and
other at the exhaustion of the reaction.
(3) According to Weber, the rate of transfer of solute
from solution over a differential depth of column, dh,
is given by Eq. (12):
vdC Ka0 C  C dh
12

where v is the wastewater flow rate, Ka0 the overall mass

transfer coefficient, which includes the resistances offered
by film diffusion and pore diffusion and C* is the equilibrium
concentration of solute in solution corresponding to an
adsorbed concentration, qe. The term (C - C*) is the driving
force for adsorption and is equal to the distance between the
operating line and equilibrium curve at any given value of
qe. Integrating Eq. (12) and solving for the height of the
adsorption zone:
Z
v CE dC
hZ 0
13
Ka CB C  C 
For any value of h less than hZ, corresponding to a
concentration C between CB and CE, Eq. (13) can be
written as:
v
h 0
Ka

CB

dC
C  C

14

Dividing Eqs. (14) by (13) results in Eq. (15)

RC
dC=C  C 
h
V  VB
R CCBE


hZ
V
E  VB
dC=C  C

15

CB

where VB and VE are total volume of water treated till

breakthrough and up to exhaust point, respectively, and V
is the volume of water treated within VE for effluent
concentration C within CE. Dividing the values of
RC
R CE


CB dC=C  C by the value CB dC=C  C the term
(V - VB)/(VE - VB) was evaluated.
(4)

Now the plot of Ct/C0 versus (V - VB)/(VE - VB)

represents the theoretical breakthrough curve.

123

720

Error analysis
As different formulate used to calculate R2 values would
affect the accuracy more significantly during the linear
regressive analysis, the nonlinear regressive analysis can be
a better option in avoiding such errors [14, 20]. So the
parameters of different kinetic models were obtained using
nonlinear analysis according to least square of errors.
In order to confirm which model was better, error
analysis was performed. Relative mathematical formula of
SS is:
P
Ct =C0 c  Ct =C0 e 2
SS
16
N
where (Ct/C0)c is the ratio of effluent and influent uranium(VI) concentrations obtained from calculation according to dynamic models, and (Ct/C0)e is the ratio of effluent
and influent uranium(VI) concentrations obtained from
experiment, respectively; N is the number of the experimental point. In order to confirm the best fit isotherm for
the adsorption system, it is necessary to analyze the data
using SS, combined the values of determined coefficient
(R2).

W. Zou et al.

70 C inside a convection oven for 24 h. The dried GFPs

was crushed and sieved to obtain a particle size range of
1620, 2040 and 4060 mesh for future use.
Methods of adsorption studies
Column adsorption was operated in 1.10 cm diameter glass
column (weighted mass of GFP packed in column) at
298 K. The uranium(VI) solution was pumped from the
container to the fixed-bed with a peristaltic pump at a
specified flow rate. The pH of uranium(VI) solution was
adjusted to 5.0 by addition of 0.1 mol L-1 HNO3 or
0.1 mol L-1 NaOH solution, respectively. No other solutions were provided for additional ionic strength. Samples
of the effluent were collected at regular intervals and the
effluent concentrations were analyzed for the uranium(VI)
content. Upon column exhaustion, the adsorbed uranium(VI) from GFP were eluted by using 0.05 mol L-1
HCl solution. Usually, breakthrough and exhaustion were
defined as the phenomenon when effluent concentrations
were about 5 and 90 %, respectively.

Result and discussion

Experimental

Influence of operating conditions on column sorption

of uranium(VI)

Materials
The effect of bed depth on breakthrough curve
Reagents
All chemicals and reagents used for the study were analytical
grades, and all aqueous solutions were prepared in distilled
water. The stock solution of 1,000 mg L-1 uranium(VI) was
prepared by dissolving accurately weighted amount of
UO2(NO3)26H2O, while working solutions were obtained
by diluting the stock solution. The initial pH of the working
solution was adjusted by addition of HCl and NaOH solution.
Arsenazo III solution was prepared by dissolving 0.5 g of the
reagent in 1,000 mL of distilled water.
A simple and sensitive spectrophotometric method based
on coloured complexes with arsenazo III in an aqueous
medium was used for the determination of the uranium(VI)
ion concentration [21]. The concentration of uranium(VI)
ions in solution was determined spectrophotometrically by
absorbance measurements at kmax = 588 nm using a Shimadzu Brand UV-3000 spectrophotometer.

The breakthrough curves of the ratio between effluent and

influent concentration (Ct/Co) versus time for various bed
depth of 6.4, 9.6 and 12.6 cm (2.09, 2.99 and 3.84 g) at a
constant flow rate of 8 mL min-1 and uranium(VI) initial
concentration of 90 mg L-1 are shown in Fig. 1. From Fig. 1,
as the breakthrough time and exhaustion time increased with
the bed depth. The bed depth (adsorbent mass) increased,
uranium(VI) had more time to contact with GFP and this
resulted in higher removal efficiency of uranium(VI)ions in
column. So the higher bed column resulted in a decrease in the
effluent concentration at the same service time. The slope of
breakthrough curve decreased with increasing bed depth,
which resulted in a broadened mass transfer zone. High
adsorption capacity was observed at the highest bed depth due
to an increase in the surface of adsorbent, which provided
more binding sites for the adsorption [22, 23]. The adsorption
capacities are listed in Table 1.

Adsorbent preparation

The effect of flow rate on breakthrough curve

Grapefruit peels was selected and washed with water several times to remove ash and other contaminants. Then it
was washed with double distilled water and was dried at

The effect of flow rate on the adsorption of uranium(VI)

ions in the GFP column was investigated by changing the
flow rate from 5.8 to 10.3 mL min-1 at the bed depth of

123

Adsorption of uranium(VI) by GFP in a fixed-bed column

721

1.0

The effect of initial concentration on breakthrough curve

0.8

Initial uranium(VI) concentration of 60, 90 and 120

mg L-1 were used to study the column studies at flow rate
of 8 mL min-1 and Z = 9.6 cm. The change in the initial
uranium(VI) concentration had a significant effect on
breakthrough curve (Fig. 3). It is illustrated that the
breakthrough time slightly decreased with increasing initial
uranium(VI) concentration. At lower influent uranium(VI)
concentrations, breakthrough curves were dispersed and
breakthrough occurred slower. As influent concentration
increased, sharper breakthrough curves were obtained. This
can be explained by the fact that a lower concentration
gradient caused a slower transport due to a decrease in the
diffusion coefficient or mass transfer coefficient. The larger
the influent concentration, the steeper is the slope of
breakthrough curve and smaller is the breakthrough time.
These results demonstrate that the change of concentration
gradient affects the saturation rate and breakthrough time,
or in other words, the diffusion process is concentration
dependent [17]. The adsorption capacity was expected to
increase with increasing the influent concentration because
a high concentration difference provides a high driving
force for the adsorption process.

Ct/C0

0.6

0.4
6.4 cm
9.6 cm
12.6 cm
Thomas model fitted curve
Yan model fitted curve
Clark model fitted curve

0.2

0.0
0

300

600

900

1200

t/min

Fig. 1 Comparison of the experimental and predicted breakthrough

curves obtained at different bed depth according to the Thomas, the
Yan model and the Clark model

9.6 cm. The initial uranium(VI) concentration was hold

constant at 90 mg L-1. As seen in Fig. 2, the adsorption
arrived saturation faster with increasing flow rate. Breakthrough time reaching saturation was increased significantly with a decreased in the flow rate. The tendency
accorded with other research [18, 24]. When at a low rate
of inlet uranium(VI) had more time to contact with GFP
that resulted in higher removal of uranium(VI) ions in
column. The variation in the slope of the breakthrough
curve and adsorption capacity may be explained on the
basis of mass transfer fundamentals. At higher flow rate,
the rate of mass transfer gets increases, i.e. the amount of
uranium(VI) adsorbed onto unit bed height (mass transfer
zone) gets increased with increasing flow rate leading to
faster saturation at higher flow rate [24]. At a higher flow
rate, the adsorption capacity was lower due to insufficient
residence time of the solute in the column and diffusion of
the solute into the pores of the adsorbent, and therefore, the
solute left the column before equilibrium occurred.

The effect of particle size of GFP on breakthrough curve

The adsorption process of GFP was performed at various
particle sizes. Figure 4 showed the results of the experiments carried out at a flow rate of 8.0 mL min-1 for different particle sizes ranged from 1620 mesh to 4060 mesh.
The initial uranium(VI) concentration was 90 mg L-1.
It was observed from Fig. 4 that the column with a
larger adsorbent particle size had an earlier breakthrough,
and the slope of the breakthrough curve increased with a
decrease in particle sizes. The equilibrium adsorption
capacity (qe(exp)) increased significantly. The results may
be due to the fact that the adsorption is a surface

Table 1 Thomas parameters at different conditions

C0 (mg L-1)

Q (mL min-1)

Z cm
6.4

Particle size (mesh)

qe(exp) (mg g-1)

2040

108.4

q0 (mg g-1)

kTh (mL mg-1 min-1)

R2

SS

95.5 3.5

0.082 0.006

0.9671

0.0023

90

8.0

90

8.0

9.6

2040

111.0

104.1 1.9

0.061 0.003

0.9856

0.0012

90
120

8.0
8.0

12.6
9.6

2040
2040

133.1
122.0

116.3 1.8
111.3 2.4

0.055 0.003
0.054 0.003

0.9814
0.9866

0.0019
0.0012

60

8.0

9.6

2040

101.1

88.2 1.6

0.076 0.003

0.9804

0.0018

90

5.8

9.6

2040

136.2

124.7 1.6

0.044 0.002

0.9860

0.0013

90

10.3

9.6

2040

103.9

91.7 2.8

0.088 0.006

0.9764

0.0020

90

8.0

9.6

4060

127.6

121.9 1.2

0.093 0.004

0.9927

0.0008

90

8.0

9.6

1620

95.1

85.1 2.4

0.060 0.003

0.9733

0.0019

123

722

phenomenon and the extent of adsorption is expected to be

proportional to the specific surface. So effective surface
area increase as particle size decreases and as a consequence, the saturation adsorption per unit mass of adsorbent increases.

Evaluation of breakthrough curves

In order to describe the fixed-bed column behavior and to
scale it up for industrial applications, five models, Thomas,
Yan, Clark, mass transfer and BDST were used to fit the
experimental data in the column.

W. Zou et al.

increased, the value of a, b and q0 increased. While with

the flow rate increasing, the value of a, b and q0 decreased.
The bed capacity q0 increased while the value of a and
b decreased with the influent concentration increasing. As
the particle size of GFP increases, the value of q0 decreases
but the values of a and b decreased. The all values of q0 in
Table 2 are smaller than those in Table 1.
The comparison of the experimental points and predicted curves according to the Yan model are also shown in
Figs. 1, 2, 3, and 4 at different experimental conditions.
The experimental breakthrough curves were significantly
close to those predicted by the Yan model. So the correlation between the experimental and predicted values using
the Yan model conformed significantly.

Application of the Thomas model

Application of the Yan model

The Yan model constants (a and b) and the values of q0 are
listed in Table 2 using nonlinear regressive analysis. From
Table 2, they were fitted higher determined coefficients
(R2) ranging from 0.9902 to 0.9993 and lower values of SS
(less than 9.5 9 10-3). From Table 2, as the bed depth

123

1.0

0.8

Ct/C0

0.6

0.4
-1

10.3 mL min
-1
8.3 mL min
-1
5.8 mL min
Thomas model fitted curve
Yan model fitted curve
Clark model fitted curve

0.2

0.0
0

300

600

900

1200

1500

t/min

Fig. 2 Comparison of the experimental and predicted breakthrough

curves obtained at different flow rate according to the Thomas, the
Yan model and the Clark model

1.0

0.8

0.6

Ct/C0

The column data were fitted to the Thomas model to

determine the Thomas rate constant (kTh) and maximum
solid-phase concentration (q0). The determined coefficients
and relative constants were obtained using non-linear
regression analysis according to Eq. (1) and the results are
listed in Table 1. The values of SS (less than 0.0023) at
various conditions are also listed in Table 1. From Table 1,
it is seen that values of determined coefficients (R2) range
from 0.9671 to 0.9927. From Table 1, as the influent
concentration increased, the value of q0 increased but the
value of kTh decrease. The reason is that the driving force
for adsorption is the concentration difference between
uranium(VI) ions on the adsorbent and uranium(VI) ions in
the solution [14]. Thus, the high driving force due to the
higher uranium(VI) concentration resulted in better column
performance. The bed capacity q0 decreased while the
value of kTh increased with the flow rate increasing. With
the bed volume increasing, the value of q0 decreased. As
the particle size of GFP increases, the value of q0 and kTh
decreases. So higher flow rate and lower influent concentration have a disadvantage for the adsorption of uranium(VI) on the GFP column.
The predicted curves at various experimental conditions
according to the Thomas model are shown in Figs. 1, 2, 3
and 4, respectively. It was clear from the figures that there
was a good agreement between the experimental points and
predicted normalized concentration. The Thomas model is
suitable for adsorption processes where the external and
internal diffusions will not be the limiting step [14].

0.4

-1

120 mg L
-1
90 mg L
-1
60 mg L
Thomas model fitted curve
Yan model fitted curve
Clark model fitted curve

0.2

0.0
0

300

600

900

1200

t/min

Fig. 3 Comparison of the experimental and predicted breakthrough

curves obtained at different concentration according to the Thomas,
the Yan model and the Clark model

Adsorption of uranium(VI) by GFP in a fixed-bed column

723

0.8

in the column. Therefore, the batch system may provide

better interaction between uranium(VI) and adsorbent than
the column system.

0.6

Application of the Clark model

Ct/C0

1.0

0.4
40-60 mesh
20-40 mesh
16-20 mesh
Thomas model fitted curve
Yan model fitted curve
Clark model fitted curve

0.2

0.0
0

200

400

600

800

1000

t/min

Fig. 4 Comparison of the experimental and predicted breakthrough

curves obtained at different particle size of adsorbent according to the
Thomas, the Yan model and the Clark model

The amount of uranium(VI) adsorbed on the GFP column was approximately 104.1 and 94.1 mg g-1 at the
initial uranium(VI) concentration of 90 mg L-1, flow rate
of 8 mL min-1 and bed depth of 9.6 cm, which calculated
according to the Thomas and the Yan model, respectively.
The maximum adsorption capacity (qm) of GFP was also
investigated in a batch experiment with a variable initial
uranium(VI) concentration. Using the Langmuir model, the
qm was calculated to be 140.8 mg g-1 adsorbent. This
means that the capacity of column system in this study was
lower than that of batch system. In the batch process, the
adsorption reached equilibrium in 90 min [12], while the
time of these column studies was less than 10 min.
Therefore, the studied flow rate might not provide sufficient contact time for uranium(VI) to distribute throughout
all surface area of the adsorbent. It is also difficult to
control the column conditions in order to obtain the maximum loading of uranium(VI), because the flow disturbances, channeling effects, and clogging are easily occurred

In our previous study [12], the Freundlich constants of

1/n were obtained in a batch experiment. The value of
1/n (0.336) calculated according to Freundlich model at
298 K was used to calculate the parameters in the Clark
model. The values of A and r in the Clark model were
determined using Eq. (4) by nonlinear regression analysis
and are shown in Table 3. As seen in Table 3, as both flow
rate and influent dye concentration increased, the values of
r increased. However, the values of r decreased when the
bed depth and particle size of adsorbent increased. Plotting
Ct/C0 against t according to Eq. (4) also gave the breakthrough curves predicted by the Clark model (also shown
in Figs. 1, 2, 3, and 4). From the experimental results and
data regression, the model proposed by the Clark model
provided good correlation on the effects of bed depth,
influent uranium(VI) concentration, flow rate and particle
size of adsorbent.
Comparison of the Thomas, the Yan and the Clark
models
Among the Thomas, the Yan and the Clark models, the
values of R2 from the Yan model and the Thomas model
are higher than that of the Clark model. The value of error
(SS) for the Yan was lowest for a given experimental
condition, while it was the largest for the Clark model. At
all conditions examined, the predicted breakthrough curves
from the Yan model showed reasonably better agreement
with the experimental curves than the Thomas and Clark
models. At the lower and high time of breakthrough curves,
the fitted curves of the Clark model were far from experimental points. Thus, it was concluded that the Yan model

Table 2 Yan parameters at different conditions

C0 (mg L-1)

Q (mL min-1)

Z cm

Particle size
(mesh)

b (mL)

q0 (mg g-1)

R2

SS

90

8.0

6.4

2040

1.96 0.06

1938.5 32.2

83.5 1.4

0.9950

0.00043

90

8.0

9.6

2040

2.25 0.08

3126.9 51.9

94.1 1.6

0.9902

0.00080

90

8.0

12.6

2040

2.95 0.03

4644.9 15.3

108.9 0.4

0.9993

0.00005

120

8.0

9.6

2040

2.11 0.10

2477.9 53.3

99.4 2.1

0.9895

0.00095

60

8.0

9.6

2040

2.33 0.05

3990.1 37.4

80.1 0.8

0.9960

0.00037

90

5.8

9.6

2040

2.64 0.04

3846.6 23.4

115.8 0.7

0.9974

0.00040

90

10.3

9.6

2040

2.16 0.06

2701.3 38.8

81.3 1.2

0.9962

0.00039

90

8.0

9.6

4060

4.09 0.06

3909.4 14.6

117.7 0.4

0.9991

0.00011

90

8.0

9.6

1620

1.84 0.06

2460.1 43.6

74.0 1.3

0.9917

0.00058

123

724

W. Zou et al.

Table 3 Clark parameters at different conditions

C0 (mg L-1)

Q (mL min-1)

Z cm

Particle size (mesh)

r 9 103

R2

SS

90

8.0

6.4

2040

46.0 14.4

9.63 0.93

0.9488

0.0044

90

8.0

9.6

2040

71.8 15.9

7.16 0.44

0.9721

0.0024

90

8.0

12.6

2040

193.9 58.9

6.58 0.44

0.9640

0.0044

120

8.0

9.6

2040

63.3 15.5

8.56 0.62

0.9720

0.0025

60

8.0

9.6

2040

85.7 20.6

5.95 0.38

0.9637

0.0044

90

5.8

9.6

2040

139.7 31.1

5.25 0.28

0.9707

0.0026

90

10.3

9.6

2040

73.1 24.2

10.52 0.96

0.9591

0.0037

90

8.0

9.6

4060

1066.3 436.1

11.41 0.76

0.9812

0.0022

90

8.0

9.6

1620

36.3 8.38

6.91 0.52

0.9563

0.0031

1000
Ct /C0=0.20

800

Ct /C0=0.55

t/min

Ct /C0=0.75

600

400

200

0
6

10

12

14

Z/cm
Fig. 5 Iso-removal lines for breakthroughs of 0.20, 0.55 and 0.75,
respectively, for different bed depths

was better to predict the uranium(VI)/GFP column

adsorption than the Thomas and Clark model. Several
researchers studied the metal removal by adsorption in the
column mode, and found that that the column kinetics
could be described more adequately by the Yan model than
by the Thomas model [15, 25, 26]. Our study on uranium(VI) removal in column adsorption had similar results.
Application of the BDST model

Fig. 5), the related constants of BDST according to the

slopes and intercepts of lines are listed in Table 4,
respectively. From Table 4, as the value of Ct/C0 increased,
the adsorption capacity of the bed per unit bed volume, N0,
increased. From the values of R2, the validity of the BDST
model for the present system is demonstrated. The BDST
model constants can be helpful to scale-up the process for
other flow rates and concentration without further experimental runs.
The BDST equation obtained at a flow rate of
8.0 mL min-1 and influent concentration 90 mg L-1 was
used to predict the adsorbent performance at other flow rates
(5.8 mL min-1) and influent concentration (120 mg L-1),
respectively. The predicted time (tcal) and experimental time
(texp) are shown in Table 5. The percent values of error (E)
between theory (tcal) and experiment (texp) were also listed in
Table 5. From Table 5, values of E were lower and good
prediction has been found for the case of changed feed
concentration and flow rate at Ct/C0 = 0.20, 0.55 and 0.75
Thus, model and the constants evaluated can be used to
design columns over a range of feasible flow rates and
concentrations at Ct/C0 = 0.20 0.55, 0.75, respectively.
These results indicate that the equation can be used to predict
adsorption performance at other operation conditions for
adsorption of uranium(VI) onto GFP column.
Mass transfer model based on batch isotherm studies
to the experimental data

The adsorption capacity (N0) and rate constant (Ka) can

be obtained through the BDST model. From the lines of
t - Z at values of Ct/C0 (0.20, 0.55 and 0.75) (shown in

According to mass transfer model, the date obtained from

the batch isotherm studies can be used to predict the

Table 4 Calculated constants of the BDST model for the adsorption of uranium(VI) onto GFP
Ct/C0

a (min cm-1)

b (min)

0.20

40.2 7.3

159.8 71.7

0.964

0.55

56.5 1.7

78.5 17.2

-0.284

0.75

67.8 1.5

11.1 15.1

5.13 0.11

123

Ka (L mg-1 min-1) 9 104

-11.0

N0 9 103 (mg L-1)

SD

3.04 0.55

0.9840

31.864

4.27 0.13

0.9995

7.937

0.9997

6.715

Adsorption of uranium(VI) by GFP in a fixed-bed column

725

Table 5 Predicted breakthrough time based on the BDST constants

for a new flow rate or new influent concentration (Z = 9.6 cm)

1.0

E (%)b

0.8

Ct/C0

a0

b0

tcal (min)

texp (min)

Q0 = 5.8 mL min-1, C0 = 90 mg L-1

55.4

159.8

372

0.55

77.9

78.5

669

750

10.8

0.75

93.5

11.1

887

1,000

11.3

-1

Q = 8.0 mL min ,

C00

= 120 mg L

380

5.3

0.6

Ct/C0

0.20

0.4

-1

0.20

30.2

119.9

170

150

13.3

0.55

42.4

58.9

348

360

3.3

0.75

50.9

8.3

480

520

7.7

0.2

Z = 5.4 cm
experimental breakthrough curve
theoretical breakthrough curve

0.0

c
E te t
te  100 %

-0.2

0.0

0.2

0.4

0.6

0.8

1.0

1.2

(V-VB)/(VE-VB)
1.0

0.8

0.6

Ct/C0

theoretical breakthrough curve, which can be compared

with the experimental breakthrough curve. Evaluating the
result from fitting the batch experimental data to the
Langmuir, Freundlich, RedlichPeterson and KobleCorrigan isotherm [12], it was showed that KobleCorrigan
isotherm (R2 = 0.9887) provided a best fitness compared
to others (Langmuir 0.9839, Freundlich 0.8938, Redlich
Peterson 0.9884). So the KobleCorrigan isotherm was
used to generate the theoretical breakthrough curve. Figure 6 showed the theoretical breakthrough curves compared with the experimental breakthrough curves which
relevant to 5.4, 9.6 and 12.6 cm bed depth, respectively.
The two curves followed the same trend with small differences. Therefore, KobleCorrigan isotherm constants
found from the batch experimental data can be used to
predict the breakthrough in fixed-bed system for uranium(VI) adsorption onto GFP.

0.2

Z = 9.6 cm
experimental breakthrough curve
theoretical breakthrough curve

0.0
-0.2

0.0

0.2

0.4

0.6

0.8

1.0

1.2

(V-VB)/(VE-VB)
1.0

0.8

Desorption of uranium(VI) and regeneration of GFP

0.6

Ct/C0

To make the process more effective and economically

feasible, sorbent regeneration and uranium(VI) recovery
must be evaluated. A simple test was carried out to see
whether the columns could be chemically regenerated. The
exhausted fixed-bed column was regenerated by passing
0.01 mol L-1 HCl, 0.05 mol L-1 HCl and 0.05 mol L-1
NaHCO3 solution with a flow rate of 2 mL min-1 downwards through the bed, respectively. In a previous paper,
batch studies showed that a 0.05 mol L-1 HCl solution
allows desorption of uranium(VI) and regeneration of GFP
[12]. This can be correlated to the fact that in acid solutions
the electrostatic interaction between GFP and uranium(VI)
becomes much weaker and the adsorbed uranium(VI) ions
leaves the adsorption sites of GFP. Figure 7 illustrated the
elution curve of uranium(VI) from GFP with three
desorbing agents. The elution curves obtained in all cases
exhibit a similar trend. The concentration of the effluent

0.4

0.4

0.2

Z = 12.6 cm
experimental breakthrough curve
theoretical breakthrough curve

0.0
-0.2

0.0

0.2

0.4

0.6

0.8

1.0

1.2

(V-VB)/(VE-VB)

Fig. 6 Measured and predicted breakthrough curve according to the

mass transfer model (Z = 6.4, 9.6 and 12.6 cm; Q = 8 mL min-1;
C0 = 90 mg L-1)

uranium(VI) is very high at the beginning of the desorption

process, and then drops quickly to a very low level. The
maximum concentrations of uranium(VI) are 11,230 mg L-1

123

726

W. Zou et al.

2GFP  COOH UO2

2 ! GFP  COO2 UO2
2H

12000

18

Conclusion

8000

-1

C/(mg L )

10000

6000

-1

0.05 mol L HCl

-1
0.01 mol L HCl
-1
0.05 mol L NaHCO3

4000
2000

On the basis of the experimental results of this investigation, the following conclusions can be drawn:
(1)

0
0

40

80

120

160

200

(2)

t/min

Fig. 7 Desorption curves of uranium(VI) through a packed bed of

GFP

for 0.05 mol L-1 HCl, 8,538 mg L-1 for 0.01 mol L-1 HCl,
and 6,509 mg L-1 for 0.05 mol L-1 NaHCO3. The solution
of 0.05 mol L-1 HCl was the most effective desorbing agent
among the eluting agents, so it was selected as the desorbing
agent.
This cycle of adsorptiondesorption was repeated three
times to evaluate the efficacy of the regenerated GFP to readsorb more uranium(VI) It was found that the regenerated
GFP column could be utilized for three cycles until completely exhausted. The result showed that more than 80 %
of adsorbed uranium(VI) could be recovered back in
solution by a solution using 0.05 mol L-1 HCl. The
wastage percent of GFP was less than 10 % after three
biosorptiondesorption cycles. Hence, it was proved that
the regeneration and reuse of GFP was an economical and
efficient method for removal of uranium(VI) from water.
From the results of desorption and regeneration using
HCl solution, ion exchange was an important mechanism
of uranium(VI) adsorption onto GFP [12, 27]. Because
there was negative charge of hydroxyl group (-OH) and
carboxyl group (-COO-) on the surface of GFP, but
uranium(VI) existed in solution were positive. This suggests that the one mechanism for the adsorption behavior
of uranium(VI) onto GFP be electrostatic interactions
between surface carboxylic groups of adsorbent and
cationic form of uranium(VI). In addition, GFP can
adsorb cation through ion exchange, or complexation, or
by a combination of both processes. In a cation
exchange mechanism, H? will be released from the -OH
and -COOH bonds from GFP, meanwhile cationic uranium(VI) will be adsorbed onto the active sites of the
adsorbent. The possible reactions are showed blow:

2GFP  OH UO2
2 ! GFP  O2 UO2 2H

17

123

(3)

(4)

(5)

This study showed that GFP was an effective

adsorbent for removal of uranium(VI) from aqueous
solution.
The adsorption of uranium(VI) was strongly dependent on bed depth, the initial uranium(VI) concentration, the flow rate and particle size of GFP.
At all experimental condition, the whole breakthrough process can be described by Thomas, Yan
and Clark model. The Yan model is better used to
predict the breakthrough curves than the Thomas and
Clark model.
The mass transfer model could provide a good
agreement between the experimental breakthrough
curve and theoretical breakthrough curve.
Uranium(VI) ions were easily desorbed from GFP
column using 0.05 mol L-1 HCl solution and the
GFP column can be reused to remove uranium(VI)
from aqueous efficiently.

Acknowledgments This work was supported by the Education

Department of Henan Province in China (No. 2010A610003) and
Henan Science and Technology Department in China (No.
122300410163).

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