Beruflich Dokumente
Kultur Dokumente
Desalination
j o u r n a l h o m e p a g e : w w w. e l s ev i e r. c o m / l o c a t e / d e s a l
Center of Eco-materials and Green Chemistry, Lanzhou Institute of Chemical Physics, Chinese Academy of Sciences, Lanzhou, 730000, China
Graduate University of the Chinese Academy of Sciences, Beijing 100049, China
a r t i c l e
i n f o
Article history:
Received 10 April 2010
Accepted 22 June 2010
Available online 17 July 2010
Keywords:
Starch
Sodium humate
Hydrogel
Cu2+ adsorption
Complexation
a b s t r a c t
A series of starch-g-poly(acrylic acid)/sodium humate (St-g-PAA/SH) hydrogels were prepared and used to
adsorb Cu2+ from the aqueous solution. The batch adsorption experiments were carried out by varying
contact times (090 min), initial Cu2+ concentration (0.0030.02 mol/L), and pH values (2.05.0). The
effects of ion strength (5, 10 mmol/L NaCl) and competitive ion (5, 10 mmol/L Pb(NO3)2) on the adsorption
capacity were investigated. The results indicated that the addition of 5% SH into St-g-PAA polymeric
networks could not only improve the initial adsorption rate and nal adsorption capacity for Cu2+, but also
make a remarkable contribution to regeneration ability. St-g-PAA/SH hydrogels exhibited high adsorption
capacity within a wide pH range and the adsorption data could be well described by the pseudo-secondorder kinetic model and Langmuir isotherm model. FTIR spectra before and after adsorption of Cu2+ on the
hydrogels revealed that complexation was considered as the main adsorption mechanism.
2010 Elsevier B.V. All rights reserved.
1. Introduction
Adsorption is a conventional but important separation process and
has been used widely in the chemical, biological, analytical, and
environmental elds [13]. In most cases, the adsorbents have large
internal porosities to ensure adequate surface area for adsorption.
However, the diffusion limitations within the particles lead to
decreases in the adsorption rate and the available capacity [4]. So, it
is interesting to develop a novel adsorbent with a small diffusion
resistance and a high adsorption capacity.
Polymeric hydrogels are crosslinked three-dimensional network
structure of hydrophilic homopolymers or copolymers [57]. Due to
the super-hydrophilicity characteristics, they can swell quickly in the
aqueous solution, which is benecial for shortening the time to reach
the adsorption equilibrium [8]. Polymeric hydrogels can be prepared
with different functional groups such as carboxylic acid, amine,
hydroxyl, amidoxime and sulfonic acid groups. These groups attached
onto the polymeric networks can be tailored easily for a specic
application. Owing to higher adsorption rate and adsorption capacity,
polymer hydrogels can provide many advantages as a novel type, fastresponsive, and high-capacity adsorbent materials in an adsorption
process [9,10].
With the development of polymer hydrogels, an incorporation of
biodegradable, environmentally friendly polysaccharide, such as
starch [1113] cellulose [14,15] or chitosan [16,17], into the polymer
are also excellent adsorbents for Cu2+, in this study, a series of starchg-poly(acrylic acid)/sodium humate (St-g-PAA/SH) hydrogels were
prepared and used as adsorbents for Cu2+ adsorption from aqueous
solution. The parameters inuencing the adsorption capacity of the
hydrogel, such as SH content, initial pH values of solution, contact
time and initial Cu2+ concentration were investigated. The effects of
competitive cation of Pb2+ were evaluated and the adsorption
mechanism of Cu2+ onto St-g-PAA/SH was also discussed.
2.1. Materials
Starch (St, Hua'ou Starch Co., Ltd., Inner Mongoulia, China) was
derived from potato. Acrylic acid (AA, chemically pure, Shanghai
Wulian Chemical Factory, Shanghai, China) was distilled under
reduced pressure before use. Ammonium persulfate (APS, analytical
grade, Xi'an Chemical Reagent Factory, Xi'an, China) was recrystallized from water before use. N,N-methylenebisacrylamide (MBA,
chemically pure, Shanghai Chemical Reagent Corp., Shanghai, China)
was used as purchased. Sodium humate (SH, Shuanglong Humic Acid
Co., Ltd., Xinjiang, China) was milled and passed through a 320-mesh
screen prior to use. Other agents used were all analytical grade and all
solutions were prepared with distilled water.
2.2. Preparation of St-g-PAA/SH hydrogels
St-g-PAA/SH hydrogels were prepared according to our previous
reports [27]. 1.44 g St and 30 mL of distilled water were put in a
250 mL four-necked ask equipped with a stirrer, a condenser, a
thermometer, and a nitrogen line. The slurry was gelatinized at 95 C
for 30 min and cooled down to 60 C, while 0.049 g of APS was added.
After 15 min, the mixture containing 10 mL of distilled water, 10.08 g
AA with 60% neutralization degree, 0.01 g MBA and a certain amount
of SH was added dropwise into the ask. The reaction was performed
at 70 C for 3 h and the resulting product was put into 400 mL alcohol
and then dried at 70 C to a constant weight. The adsorbent used for
test had a particle size in the range of 4080 mesh.
2.3. Adsorption and analysis
Adsorption experiments were carried out by agitating 50 mg of
hydrogel with 25 mL Cu2+ ion solution in a shaker at 30 C/120 rpm.
The samples were withdrawn from the asks at predetermined time
intervals and analyzed for Cu2+ content by atomic absorption
spectrometry. The adsorption capacity of the hydrogel for Cu2+ was
calculated through the following equation:
CoCeV
m
q=
171
172
k1
t
2:303
t
1
t
=
+
qt
qe
k2 qe 2
3.2. pH-dependence
It is well known that the changes in pH values of an external
solution can inuence the adsorption behaviors of a metal ion by an
adsorbent. Indeed, pH affects the transition metal speciation and the
charge of functional groups in the polymer hydrogels. Fig. 2 shows the
effects of solution pH on the adsorption capacity of St-g-PAA/SH for
Cu2+. It can be seen that the adsorption capacities of the hydrogels
with different SH content show a rapid increase when pH is increased
from 2.0 to 2.7, beyond which a gradual increase in the adsorption
capacity is observed. St-g-PAA/SH is an ionic polymer matrix and its
surface charge is essentially affected by changing the pH values. At the
lower pH values, the carboxylate anions present in polymeric
networks are converted to protonated form, which can hinder the
interaction of St-g-PAA/SH with metal ion, by which the adsorption
capacities for Cu2+ decrease appreciably. Conversely, at the higher pH
values, more ionized carboxylic groups will be available, thereby
increasing interaction between positively charged Cu2+ and negatively charged carboxylate groups and causing an increase in Cu2+
adsorption. Nevertheless, little changes in the adsorption capacities
are observed when the pH values lie between 4.0 and 5.0. In this
study, the pH value of 0.02 mol/L Cu2+ solution prepared freshly is
determined to be 4.68 and thus the original pH value of Cu2+ solution
is not necessary to be adjusted for further study.
3.3. Adsorption isotherms for Cu2+
As shown in Fig. 3, the amount of Cu2+ adsorbed increases with an
increase in the initial Cu2+ concentration and remains nearly constant
after the initial Cu2+ concentration reaches 0.01 mol/L. In addition, it
can be observed from Fig. 3 that at lower initial Cu2+ concentration
(0.005 mol/L), St-g-PAA/SH shows a higher adsorption capacity for
Cu2+ compared with St-g-PAA regardless of the content of SH in the
hydrogel. Therefore, it can be concluded that the introduction of SH
into the polymer hydrogel is more benecial for the improvement of
adsorption capacity at lower Cu2+ concentration.
Adsorption properties and equilibrium data, commonly known as
adsorption isotherms, describe how pollutants interact with adsorbent materials and so, are critical in optimizing the use of adsorbents.
Then, it is important to establish the most appropriate correlation for
the equilibrium curve. In this study, two typical isotherms were used
for tting the experimental data:
Langmuir equation :
Ce
1
C
=
+ e
qmb
qe
qm
4
1
log Ce
n
Table 1
Estimated adsorption kinetic parameters for Cu2+ adsorption.
SH/
%
Pseudo-rst-order model
qe, exp (mmol/g)
k1 (min 1)
R2
Pseudo-second-order model
qe, cal (mmol/g)
k2 (g/mmol/min 1)
h (mmol/g/min)
R2
0
5
10
15
20
2.76
2.80
2.72
2.69
2.61
1.87
2.87
2.99
2.51
2.10
0.1059
0.3777
0.3081
0.2278
0.09604
0.9001
0.9566
0.9766
0.9961
0.9393
2.76
2.80
2.72
2.69
2.61
2.77
2.87
2.83
2.79
2.75
0.1642
0.3120
0.1413
0.1665
0.07951
1.256
2.563
1.135
1.294
0.602
0.9980
0.9993
0.9976
0.9996
0.9984
173
Table 2
Estimated adsorption isotherm parameters for Cu2+ adsorption.
SH/
%
0
5
10
15
20
Langmuir model
qm
2.80
2.83
2.75
2.73
2.63
Freundlich model
b
3
7.14 10
7.07 103
1.21 104
6.11 103
7.60 103
R2
R2
0.9992
0.9996
0.9995
0.9994
0.9998
3.18
3.10
2.95
3.05
2.90
34.1
41.8
62.5
37.6
41.3
0.9286
0.9928
0.8199
0.8533
0.8415
2+
2+
Table 3
Comparison of the adsorption capacities of Cu2+ onto different adsorbents.
Adsorbents
qm (mmol/g)
Reference
0.17
0.40
0.70
1.04
1.12
1.64-1.81
2.80
2.83
[30]
[31]
[32]
[33]
[34]
[35]
This work
This work
174
Fig. 4. Effects of ion strength and coexisting competitive ion on the adsorption capacity
(initial Cu2+ concentration, 0.02 mol/L; contact time, 60 min; pH, original; temperature, 303 K; agitation speed, 120 rpm; and adsorbent dose, 50 mg/25 mL).
eeCOOH eeCOO + H
eeCOO + Cu
2 +
2 +
eeCOO Cu
Fig. 5. FTIR spectra of (a) St-g-PAA, (b) St-g-PAA/5% SH, (c) St-g-PAA/10% SH, (d) St-gPAA/15% SH, (e) St-g-PAA/20% SH after the adsorption and (f) St-g-PAA/20% SH before
the adsorption.
4. Conclusions
In this study, a series of hydrogels containing St and SH were
developed and used to adsorb Cu2+ from the aqueous solution. The
results indicate that 5% addition of SH into St-g-PAA can increase the
initial adsorption rate, improve the nal adsorption capacity and
benet for the regeneration ratio. This kind of hydrogel shows a
higher adsorption capacity with a pH range of 2.75.0 and the
addition of NaCl has no appreciable effects on the adsorption capacity.
The adsorbent material displays an excellent reusable ability for Cu2+
adsorption and after the forth adsorptiondesorption cycle, the
adsorption capacity for Cu2+ shows only a slight decrease compared
with the initial one. The adsorption kinetics data can be described by
the pseudo-second-order model, and the adsorption isotherm agrees
well with the Langmuir model. During the whole adsorption process,
complexation interaction is the governed adsorption mechanism.
Acknowledgements
The authors thank the joint support by the National Natural
Science Foundation of China (No. 20877077) and Science and
Technology Support Project of Gansu Provincial Science and Technology Department (No. 0804GKCA03A).
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