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Removal of Cu(II) from aqueous solution using the rice husk

carbons prepared by the physical activation process

Jinghui Zhang, Hao Fu, Xiaoshu Lv, Jie Tang, Xinhua Xu*
Department of Environmental Engineering, Zhejiang University, Hangzhou 310027, PR China

article info abstract

Article history: The adsorption of Cu(II) from aqueous solution by carbons prepared from rice husk
Received 11 March 2010 through pyrolysis and steam activation was studied. The rice husk carbon was charac-
Received in revised form terized by Fourier transform infrared spectroscopy (FTIR) and scanning electron micros-
23 August 2010 copy (SEM), and its pore structure was also examined. After comparing different
Accepted 3 September 2010 characteristics of the carbons prepared under different conditions and their adsorption
abilities of Cu(II), the optimum temperature for pyrolysis and steam activation was chosen
Keywords: as 700 and 750
C, respectively, using 3% (V/V) steam as the best activation gas. It was
Carbon found that the Cu(II) adsorption on the rice husk derived carbons was pH and temperature
Rice husk dependent with an optimum pH value of 5.0, and an equilibrium time of 24 h. The
Characterization adsorption kinetics and isotherms of Cu(II) by the rice husk derived carbons were also
Adsorption investigated under four different temperatures, and good correlation coefficients were
Cu(II) obtained for the pseudo-second-order kinetic models, and the Langmuir isotherm model
fitted very well with the experimental data. The mean free energy E (kJ mol1) obtained in
the Dubinin-Radushkevitch (D-R) adsorption isortherm equation indicated a chemical ion-
exchange mechanism. Several thermodynamic parameters were also caculated to predict
the nature of adsorption process.
ª 2010 Elsevier Ltd. All rights reserved.

1. Introduction excessively large doses of Cu(II) by human may lead to severe

Water pollution due to toxic heavy metals is a serious problem
facing society today. Therefore, effective strategies for
removing heavy metal ions from water and various industrial
effluents have attracted considerable research and practical
interest [1]. As one of the important toxic heavy metals, copper
finds its way to the water stream from industries like electro-
plating, mining, electrical and electronics, iron and steel
production, the non-ferrous metal industry, the printing and
photographic industries and metalworking and finishing
processes [2,3]. Moreover, copper sulfate has been used in
eutrophic lakes to kill the algae since the early 1990s and is still
widely used today [4]. Trace amounts of copper are essential to
human and many other living species. However, the intake of
mucosal irritation, a central nervous system irritation, possible
necrotic changes in the liver and kidney, etc., and the recom-
mended maximum acceptable concentration of Cu(II) in
drinking water by the World Health Organization(WHO) is
1.5 mg L1 [5,6]. As per U.S. Environmental Protection Agency
(EPA) standards, the permissible limit of copper for industrial
effluents to be discharged to surface water is 0.25 mg L1 [7].
A variety of methods such as precipitation, adsorption,
evaporation, reverse osmosis and ion-exchange have been
employed to remove Cu(II) from wastewater, among which
adsorption with activated carbon is considered to be the best
technology for the removal of heavy metals except for its high
manufacturing cost [8,9]. In recent years, some researchers
have been searching for more cost-effective ways to obtain

* Corresponding author. Tel.: þ86 571 87951239; fax: þ86 571 87952771.
E-mail address: xuxinhua@zju.edu.cn (X. Xu).
0961-9534/$ e see front matter ª 2010 Elsevier Ltd. All rights reserved.
doi:10.1016/j.biombioe.2010.09.002
 b i o m a s s a n d b i o e n e r g y 3 5 ( 2 0 1 1 ) 4 6 4 e4 7 2
the carbon. Since carbon can be produced theoretically from
any carbonaceous materials that are rich in element carbon
[10], some low-cost and easily-available agricultural by-prod-
ucts, such as peanut shell [11], rice husk [12], cassava peel [13],
sawdust [14], olive kernels [15] and wheat straw [16] have been
utilized as the precursors of activated carbon to remove heavy
metals. And more recently, some other new materials such as
algal bloom residue [17] and durian peel [18] have also been
explored in order to prepare activated carbon.
Rice husk, rich in carbon, is the major by-product of the
rice milling industry, accounting for almost 20% of the rice
production. The world annual output of rice husk is up to 80
million tons [19,20]. As rice plant is the main cereal crop in
China with an annual output of more than 180 million tons,
the production of rice husk is over 36 million tons. Despite its
large quantity, rice husk has mainly been used as an energy
resource or the raw material for manufacturing of paper and
cardboard in the world [10], there is still a great deal of it left,
burnt in-situ or discarded, posing some environment prob-
lems. And in China most of the rice husk is left in rural areas
or rice processing plants, with little utilized in the wine-
making industry and the smelting industry, and thus it
becomes the waste that is hard to deal with. As a conse-
quence, utilizing rice husk as the precursor to manufacture
carbon could not only alleviate problems of disposal and
management of waste agricultural by-products, but also
provide a high quality end product for pollutant treatment.
In this study, the physical activation method was adopted
to prepare the rice husk carbon, part of our intentions was to
avoid contributing further pollution to the environment. A
series of batch experiments were carried out to study the
adsorption behavior of Cu(II) from aqueous solution by carbon
derived from rice husk. The optimal preparation condition of
the carbon and its characteristics were investigated. The
adsorption capacity was studied as a function of the solution
pH, temperature, and contact time. Furthermore, in order to
understand the adsorption process, the kinetics, isotherms
and thermodynamics about Cu(II) adsorption by carbon
prepared in this study were also investigated.
2. Materials and methods
2.1. Adsorbent preparation
Rice husk, collected from a local farm in Huzhou, China, was
used as the precursor of the carbon which was investigated in
this study. The material was first washed with deionized water
to remove the impurities, and then dried in an oven at 40
C for
24 h. Approximately 15 g of dried rice husk was packed tightly
into the cylinder of the vacuum tube furnace (Hefei Kejing
Material Technology Co. Ltd., China), under inert nitrogen
atmosphere with the flow rate of 2.5 m3 h1, at a heating rate of
5
C min1 from room temperature up to the designated
pyrolysis temperature and keeping the final temperature for
0.5 h. As the vacuum tube furnace was equipped with an
intelligent temperature controller, the pyrolysis temperature
and the heating rate could be controlled after inputting the
right program. During the activation process, the activation
temperature was usually 50
C higher than the pyrolysis
465
temperature, and it was aerated with the activation gas con-
taining steam at a certain concentration while using nitrogen
as the carrier gas (2.5 m3 h1) for 1 h. Once the activation was
completed the activation gas was changed to nitrogen gas to
supply to the sample until it could be sealed in a container. In
this study, the carbon labeled with “RHA-700-750” means it
was prepared with the pyrolysis temperature of 700
C and the
activation temperature of 750
C, and “RH” indicates the rice
husk which was used to obtain the carbon.
2.2. Adsorbent characterization
The surface organic functional groups were investigated in
the region of 4000e400 cm1 by a Fourier transform infrared
spectrometer (Nicolet Nexus-670, America). Pore structure
characterization of the samples was performed with
a computer controlled automated porosimeter (Micromeritics
ASAP-2020, America) at 77 K. The specific surface areas were
calculated by using the BrunauereEmmetteTeller (BET)
equation [21]. Single point total pore volume was obtained
from the liquid volume of adsorbate at a relative pressure of
0.99. The t-plot method was used to calculate the micropore
volume [22]. Element analysis was conducted with an X-ray
energy dispersion spectrometer (Oxford INCA Energy 200,
Britain). Scanning electron micrographs were obtained with
two scanning electron microscopes (Hitachi TM-1010, Japan
and Jeol JSM-5610LV, Japan).
2.3. Chemicals
Unless mentioned otherwise, all chemicals used in this study
were purchased from the Sinopharm Chemical Reagent Co.,
Ltd, China. They were all of analytical grade, and were used as
received without further purification. The N2 gas (99.9%),
stored in the steel cylinder, was provided by Jingong Gas Co.,
Ltd, China. A stock solution of Cu(II) with a concentration of
1 g L1 was obtained by dissolving accurately weighed 0.1 g
metal copper (purity > 99.999%) in nitric acid and diluting it to
100 mL with deionized distilled water in a volumetric flask.
Adsorption solutions were prepared by diluting the stock
solution of Cu(II) to the desired concentrations with deionized
water, and before adding adsorbent into them, the pH value of
the solutions was adjusted using a digital pH meter (Mettler-
Toledo Instruments (Shanghai) Co. Ltd., China) with HNO3 and
NaOH.
2.4. Adsorption studies
Adsorption experiments were carried out in 250 mL Erlen-
meyer flasks containing a certain amount of carbon prepared
previously and a 100 mL solution with known concentration,
pH value and temperature. The flasks were shaken in
a constant temperature beaker (Shanghai Yihen Scientific
Instrument Co. Ltd., China) at 90 rpm. After a preset contact
time, the samples were all filtrated through 0.22 mm pore-size
filters. The concentration of the residual copper ions in the
filtrate was analyzed by an atomic absorption spectrometer
(Shimdzu AA-6300, Japan). The amount of copper ions adsor-
bed on the carbon was calculated from the difference between
the initial concentration of Cu(II) and the residual Cu(II)
466 b i o m a s s a n d b i o e n e r g y 3 5 ( 2 0 1 1 ) 4 6 4 e4 7 2

aldehydes, lactones and carboxyl groups [23]. However, the

-1
803 cm
-1

-1

-1
2920 cm
band around 1700 cm1 is not significant either in RHA-400-

1600 cm

465 cm
-1
1090 cm
450 sample or in sample RHA-700-750, this suggests that the
-1

a
3431 cm
carbonyl-containing groups are not only little in the rice husk
and the carbon obtained from it but also very temperature
sensitive. The band around 1600 cm1 is ascribed to aromatic
ring or C]C stretching vibration, demonstrating the carbon-
ization of the precursor [20], and it can be seen in both
samples of RH and RHA-400-450, moreover, the relative

-1
1700 cm
intensity of the band increased in the RHA-400-450 compared
b with that of RH, suggesting the evolution of carbonization
process. Nevertheless, this band was not found in sample
RHA-700-750, and this might be caused by the high prepara-
c tion temperature. The significant bands around 803 cm1 and
465 cm1 of all the samples were due to the existence of the
silica which accounts for a large percentage in the rice husk,
4000 3000 2000 1500 1000 500 as well as in the carbon derived from it.
-1
wave number(cm )
3.1.2. Pore structure characterization
Fig. 1 e FTIR spectra of (a) rice husk, (b) RHA-400-450, and
The specific surface areas were calculated by using the BET
(c) RHA-700-750.
equation. The volume of the mesopore was calculated by
subtracting micropore volume obtained by the t-plot method
from the single point total volume. The BET theory is an
concentration in the solution. The calculation equation is as extension of the Langmuir theory, which is a theory for
follows: monolayer molecular adsorption, to multilayer adsorption.
The resulting BET equation is expressed as follows [21]:
VðC0  Ct Þ
Qt ¼ (1)

W 1 c1 P 1
¼ þ (2)
where Qt is the amount of Cu(II) adsorbed by the carbon(mg Cu v½ðP0 =PÞ  1 vm c P0 vm c
(II)/g carbon), C0 and Ct are the initial Cu(II) concentration and
where P and P0 are the equilibrium and the saturation pres-
the Cu(II) concentration at time t in the solution(mg L1), V is
sure of adsorbates at the temperature of adsorption, respec-
the volume of the Cu(II) solution (L), and W is the weight of
tively, v is the adsorbed gas quality, and vm is the monolayer
carbon added into the solution (g).
adsorbed gas quality, and c is the BET constant.
The values of vm and c can be obtained from linear
regression, and the specific surface area can be calculated
3. Results and discussion from the following equation:

3.1. Characteristics of adsorbent ðvm NsÞ

SBET;total ¼ (3)
V
3.1.1. Fourier transform infrared spectroscopy analysis
FTIR analysis was performed in this study to investigate the Stotal
SBET ¼ (4)
a
surface functional groups on the RHA-700-750. The wide band
of the samples at around 3431 cm1 is ascribed to OeH where N is the Avogadro’s constant, s is the adsorption cross
stretching mode of hydroxyl groups or adsorbed water (Fig. 1). section, V is the molar volume of the adsorbent gas, and a is
The band observed around 2920 cm1 is attributed to CeH the molar mass of the adsorbed species.
stretching vibration of eCH2, and with the increasing prepa- It can be seen from Table 1 that with the preparation
ration temperature, it could be seen that the relative intensity temperature going up, the BET surface area of the samples
of the band decreased, indicating a loss of the functional increased. Furthermore, the difference in the BET surface
groups eCH2 in the carbon prepared at higher temperatures. A area between the RHA-700-750 and RHA-600-650 was more
small band near 1700 cm1 is found in the sample of RH, significant, compared with that between RHA-600-650 and
which is assigned to the C]O stretching vibration of ketones, RHA-500-550. These could also be observed in the total pore

Table 1 e The pore structure properties of the carbon derived from rice husk at different preparation temperatures.
Sample SBET (m2 g1) Vtotal (cm3 g1) Vmicro (cm3 g1) Vmeso (cm3 g1) Vmicro/Vtotal (%) Vmeso/Vtotal (%)

RHA-500-550 146.7 0.1034 0.0566 0.0468 54.73 45.27

RHA-600-650 168.8 0.1145 0.0670 0.0475 58.52 41.48
RHA-700-750 231.7 0.1466 0.0980 0.0485 66.89 33.11
 b i o m a s s a n d b i o e n e r g y 3 5 ( 2 0 1 1 ) 4 6 4 e4 7 2
Table 2 e The pore structure properties of the carbon prepared with different amounts of steam in the activation gas.
Sample SBET (m2 g1) Vtotal (cm3 g1) Vmicro (cm3 g1)
RHA-700-750 (0%) 155.1 0.1047
RHA-700-750 (3%) 231.7 0.1466
RHA-700-750 (6%) 244.3 0.1556
volume of the samples that pore evolution was more evident
with the preparation temperature increasing from 600e650
C
to 700e750
C. The simultaneous increase of the micropore
and mesopore volume suggests that new pore creation and
pore widening happened at the same time, however, the
decreasing percentage of the mesopore volume with
increasing temperature also indicates that the rate of pore
creation exceeded that of pore widening [24].
The effect of the amount of the activation gas on the pore
structure was also investigated by varying the steam
percentage in the activation gas from 0 to 6% (V/V). As is
shown in Table 2 that compared with the sample treated
without steam, the BET surface areas and pore volumes of the
carbon treated with activation gas of 3% (V/V) and 6% (V/V)
steam were much larger, which could be explained by the fact
that in the process of pyrolysis with N2, moisture and volatile
matters were removed from the material, and with the
oxidizing agent applied the porosity by gasification would
develop [25]. When the amount of steam increased, an
increase in the BET surface area and pore volume could be
observed, however, the decreasing contribution of the
micropore volume to the total one from 66.89% to 65.70%
suggests that the pore widening effect dominated the pore-
opening effect with more steam involved, for there were
a larger amount of oxidizing agent reacting with carbon in the
sample according to the equation shown below:
CðsÞ þ H2 OðgÞ/COðgÞ þ H2 ðgÞ (5)
3.1.3. Elemental analysis
The results obtained by elemental analysis show that the
contents of three main elements present on the outer surface
of RH were different from those on the inner surface, and this
was also observed in the sample of RHA-700-750 (Table 3).
Furthermore, the outer surface of all the samples has higher
contents of oxygen and silicon, but lower content of carbon.
After comparing the elemental compositions of rice husk and
RHA-700-750, it was evident that after the treatment the
content of carbon decreased on the outer and inner surfaces,
however, more carbon was lost on the outer surface for the
reason that the outer surface might be in full contact with the
activation gas which led to more carbon being oxidized. There
Table 3 e The weight contents of three main elements
existing in the samples.
Samples C (%) O (%) Si (%)
Rice husk (outer surface) 37.93 48.88 13.20
RHA-700-750 (outer surface) 15.33 56.31 28.36
Rice husk (inner surface) 43.60 46.34 10.06
RHA-700-750 (inner surface) 37.29 43.34 19.37
467
Vmeso (cm3 g1) Vmicro/Vtotal (%) Vmeso/Vtotal (%)
0.0648 0.0399 61.89 38.11
0.0980 0.0485 66.89 33.11
0.1023 0.0534 65.70 34.30
was more oxygen on the outer surface after the treatment
while less was found on the inner surface, most likely because
more activation agents reacted with the compounds on the
outer surface, and the outer surface possessed more oxygen-
containing surface functional groups.
3.1.4. Surface morphology
The SEM micrographs of rice husk, carbon and carbon that
treated with Cu(II) aqueous solution are shown in Fig. 2. It can
be seen that the outer surface of carbon RHA-700-750 prepared
by pyrolysis under N2 and activation with steam has been
corroded, as indicated by the gaps on the corrugated outer
epidermis which are wider compared with those on the outer
surface of the rice husk (as shown in Fig. 2(b)). Also it can be
seen from Fig. 2(c) that the inner surface of RHA-700-750 was
much rougher than that of rice husk (Fig. 2(d)), indicating the
erosion caused by the reaction between oxidizing agent and
carbon in the precursor. Fig. 2(e) shows the section of the
RHA-700-750 and the formation of many pores can be
observed inside it, which has been confirmed by the pore
characterization before. After treated with Cu(II) aqueous
solution, it can be observed from Fig. 2(f) that most of the
cupric salt were accumulated on the section of the carbon
because of the pore structure formed within.
3.2. Effect of preparation condition
During the investigation of the optimal preparation conditions
of the carbon derived from rice husk, carbon prepared under
different conditions were added into the solution of which the
initial concentration, pH value and temperature were
64 mg L1, 5.0 and 30
C, respectively, with the doses varying
from 0.1 g to 0.7 g. The optimal temperature and the amount
of steam for carbon preparation were determined on the basis
of the amount of Cu(II) removed by carbon prepared under
different conditions.
The Cu(II) adsorption efficiencies of carbon prepared under
different pyrolysis and activation temperatures are shown in
Fig. 3(a). The amount of steam in the activation gas was 3% (V/V).
It is obvious that as the pyrolysis and activation temperature
went up, the Cu(II) removal ability improved with the sequence
of RHA-800-850 > RHA-700-750 > RHA-600-650 > RHA-500-
550 > RHA-400-450. This could be explained by the higher
microporosity obtained at higher carbonization temperature
[26]. Furthermore, it could be observed that when the pyrolysis
and activation temperatures increased from 600
C and 650
C to
700
C and 750
C, the removal efficiencies increased signifi-
cantly, which could correlate well with the obvious increase of
the BET surface area and total pore volume. Nevertheless, the
difference of the Cu(II) removal percentage between RHA-800-
850 and RHA-700-750 was slight compared with that between
RHA-600-650 and RHA-700-750. Thus, considering the
468 b i o m a s s a n d b i o e n e r g y 3 5 ( 2 0 1 1 ) 4 6 4 e4 7 2

Fig. 2 e SEM micrographs of (a) the outer surface of RHA-700-750, (b) the outer surface of rice husk, (c) the inner surface of
RHA-700-750, (d) the inner surface of rice husk, (e) the section of RHA-700-750, and (f) RHA-700-750 treated with Cu(II)
aqueous solution.

adsorption ability and energy consumption, 700
C and 750
C
were chosen as the optimal pyrolysis and activation tempera-
ture for the carbon preparation from rice husk.
Fig. 3(b) shows the influence of the amount of steam in the
activation gas on the Cu(II) removal efficiency. It is evident
that compared with carbon treated without steam, those
treated with activation gas of 3% (V/V) and 6% (V/V) steam had
much higher Cu(II) adsorption efficiencies. However, with
more steam involved in the activation gas from 3% to 6%, Cu
(II) was adsorbed less from aqueous solution. It is speculated
from the data of pore structure characterization that with
more steam involved in the activation of the carbon, pore
widening effect dominated the pore-opening effect for there
were a larger amount of oxidizing agent reacting with the
carbon in the sample, resulting in a decrease of micropore
percentage, and thus the adsorption ability of Cu(II) declined.
As a consequence, carbon prepared with activation gas of 3%
steam was used in our subsequent study.
3.3. Effect of pH
The effect of initial pH on the Cu(II) adsorption was investi-
gated over a pH range of 3.0e6.0. The variation of the amounts
of Cu(II) adsorbed by 4 g L1 carbon from 100 mL aqueous
solution of 64 mg L1 at the 30
C is shown in Fig. 4. It could be
observed that when the initial pH of the Cu(II) aqueous
 b i o m a s s a n d b i o e n e r g y 3 5 ( 2 0 1 1 ) 4 6 4 e4 7 2 469

a 100
16

14
80
Adsorption efficiency (%)

12

10
60

Qt (mg g )
-1
8
40
6
RHA-400-450
RHA-500-550 4
20 RHA-600-650
RHA-700-750
2
RHA-800-850
0
0
0.1 0.2 0.3 0.4 0.5 0.6 0.7
3.0 3.5 4.0 4.5 5.0 5.5 6.0
Adsorbent dosage (g)
Solution pH

b 100 Fig. 4 e Effect of initial pH on the Cu(II) adsorption

(V, 100 mL; C0, 64 mg LL1; pH, 3.0e6.0; T, 30
C; contact
time, 24 h; adsorbent dose, 0.4 g).
80
Adsorption efficiency (%)

60 acidity, pH 5.0 was selected as the optimum value for con-

ducting further experiment.

40
3.4. Effect of temperature

activation without steam

20
0 24 h under the temperatures of 30
C, 35
C, 40
C and 45
C,
0.1 0.2 0.3 0.4
Adsorbent dosage (g)
Fig. 3 e Effects of (a) different pyrolysis and activation
temperatures and (b) the amount of steam in the activation
gas on Cu(II) adsorption (V, 100 mL; C0, 64 mg LL1; pH, 5.0;
T, 30
C; contact time, 1.5 h).
solution increased from 3.0 to 4.0, there was a sharp increase
of the amount of Cu(II) adsorbed on the carbon from
3.93 mg L1 to 9.57 mg L1, and then more Cu(II) would be
removed with the increasing pH until it reached 5.5, however,
a slight decrease of the Cu(II) removal could be seen with the
pH changing from 5.5 to 6.0. This phenomenon is possibly due
to the fact that at lower pH values, H3Oþ ions compete with
the metal ions for the exchange sites in the adsorbent [27],
activation with 3% (V/V) steam
In order to evaluate the effect of the temperature on the Cu(II)
activation with 6% (V/V) steam adsorption by the rice husk derived carbon, the experiments
were carried out at regular time intervals from 10 min up to
0.5 0.6 0.7
respectively, and the pH value of the solution with Cu(II)
concentration at 64 mg L1 was adjusted to 5.0. Fig. 5 illus-
trates the relationship between the temperature and the
amount of Cu(II) ions adsorbed by the carbon at an initial Cu(II)
concentration of 64 mg L1 as a function of time. It can be
observed from the figure that the equilibrium time under four
temperatures of 25
C, 30
C, 35
C and 40
C was about 24 h,
and the amount of Cu(II) ions removed by the carbon at the
equilibrium time varied from 12.51 mg L1 to 15.78 mg L1
18
16
14
12
Qt (mg g )
-1

when there is an increase in the pH, the concentration of the 10

H3Oþ ions decreases, and more Cu(II) ions can react with the
8 o
25 C
carbon, nevertheless, with the pH value further increasing, o
30 C
the Cu(II) species existing in the solution predominantly 6 o
35 C
would change from Cu2þ to Cu(OH)2 gradually, causing o
40 C
precipitation. In our experiment it was also found that after 4
120 min the pH value of 100 mL deonized water added with
2
0.4 g carbon would increase from 6.79 to 9.90, indicating the 0 5 10 15 20 25
high alkali concentration in the carbon derived from rice husk.
Time (h)
Thus, considering the effect of initial pH on the Cu(II) removal
and the high alkalinity of the carbon as well as the fact that Fig. 5 e Effect of temperature on the Cu(II) adsorption
wastewater containing heavy metals is usually showing weak (V, 100 mL; C0, 64 mg LL1; pH, 5.0; adsorbent dose, 0.4 g).
470 b i o m a s s a n d b i o e n e r g y 3 5 ( 2 0 1 1 ) 4 6 4 e4 7 2

Table 4 e Adsorption kinetic constants and correlation coefficients for adsorption of Cu(II) at different temperatures.
Temperature (
C) Qe,exp (mg g1) Pseudo-first-kinetic model Pseudo-second-kinetic model
1 1
Qe,cal (mg g ) K1 (min ) r2
Qe,cal (mg g1) K2 (g mg1 min1) r2

25 12.51 10.76 1.0293 0.730 12.94 0.0630 0.995

30 14.32 12.64 1.0320 0.793 14.64 0.0677 0.997
35 14.29 12.88 0.9610 0.858 14.68 0.0673 0.999
40 15.78 14.22 1.4543 0.859 15.95 0.0906 0.999

with the temperature increasing from 25
C to 40
C. The and temperature were 0.4 g, 5.0 and 30
C, then the widely used
change of 26.14% caused by a 20
C temperature increase Langmuir isotherm [32] and Freundlich isotherm [33] were
indicates Cu(II) ion adsorption by the carbon obtained in our applied to analyze experimental data. And the Dubinin-
experiments was affected significantly by the temperature. Radushkevich (D-R) isotherm [34] was also used in this study.
The Langmuir equation can be expressed as:
3.5. Adsorption kinetics
Qm KL Ce
Qe ¼ (8)
1 þ KL Ce
In this study adsorption kinetics was investigated by fitting
the experimental data with the pseudo-first-order kinetic where Qe and Ce are the amount of Cu(II) ions absorbed
model and pseudo-second-order kinetic model under four (mg g1) at equilibrium and the equilibrium concentration of
different temperatures. The integral form of pseudo-first- Cu(II) ions (mg L1) in the solution; Qm and KL are Langmuir
order kinetic model can be expressed as follows [28]: constants, which are the adsorption capacity (mg g1) and
  energy of adsorption (L mg1).
Qt ¼ Qe 1  eK1 t (6) The Freundlich isotherm can be represented by the
where Qe and Qt are the amount of Cu(II) ions absorbed (mg g ) 1 following equation:
at equilibrium and time t, respectively; and K1 is the rate
Qe ¼ KF Ce1=n (9)
constant of pseudo-first-order kinetic model(g mg1 min1).
The pseudo-second-order kinetic model can be presented where Qe and Ce are the amount of Cu(II) ions absorbed
by the integral equation [29]: (mg g1) at equilibrium and the equilibrium concentration of
Cu(II) ions (mg L1) in the solution; and KF and 1/n indicate the
t
Qt ¼ (7) adsorption capacity (mg g1) of the adsorbent and the
1 t
þ adsorption intensity.
K2 Qe2 Qe
The D-R isotherm can be described as follows:
where Qe and Qt are the amount of Cu(II) ions absorbed (mg g1)
ln Qe ¼ ln Qm  b32 (10)
at equilibrium and time t, respectively; and K2 is the rate
constant of pseudo-second-order kinetic model (g mg1 min1).
1
The kinetics parameters obtained by using non-linear E ¼ pffiffiffiffiffiffi (11)
2b
regression are listed in Table 4. Fig. 6 illustrates the two kinetic
models at the temperature of 30
C. It can be seen from both where b is a constant related to the mean free energy of
Table 4 and Fig. 6 that compared with pseudo-first-order adsorption per mole of the adsorbate (mol2 kJ2) and E is the
model, the pseudo-second-order model fitted the experi-
mental data better with the correlation coefficients (r2) values 16
under four temperatures all above 0.995 and the calculated Qe
14
very close to the experimental values. Also some literatures
have reported that the adsorption of Cu(II) on the carbon 12
derived from some biomass follows the pseudo-second-order
model, which is based on the consumption that chemisorp- 10
Qt (mg g )

tion is the rate-limiting step with the electron sharing and

-1

8
exchanging between adsorbent and adsorbate [2,30].
o
Experimental data at 30 C
6
3.6. Adsorption isotherms pseudo- first- order fit
4 pseudo- second- order fit
Adsorption isotherms are important in predictive modeling the
2
procedures for designing the adsorption system, because the
adsorption capacity of a quantitative of adsorbent could be 0
described, making the selection of appropriate adsorbent and 0 5 10 15 20 25
determination of adsorbent dosage feasible [31]. In our equilib-
Time (h)
rium experiments, the initial Cu(II) concentrations varying from
8 to 384 mg L1 have been involved and the experiments were Fig. 6 e Adsorption kinetics of Cu(II) on carbon derived
conducted under the conditions that the carbon dose, pH value from rice husk at 30
C.
 b i o m a s s a n d b i o e n e r g y 3 5 ( 2 0 1 1 ) 4 6 4 e4 7 2 471

Table 5 e Adsorption isotherm constants and correlation coefficients for adsorption of Cu(II) at different temperatures.
Temperature (
C) Langmuir isotherm Freundlich isotherm D-R isotherm
1 1 1 1
Qm (mg g ) KL (l mg ) r2
KF (mg g ) n 2
r Qm (mg g ) E (kJ mol1) r2

25 21.01 0.250 0.998 6.049 3.943 0.861 36.47 14.7 0.917

30 21.88 0.154 0.995 4.626 3.179 0.885 38.6 13.3 0.903
35 23.09 0.116 0.995 5.512 3.730 0.908 36.77 14.3 0.936
40 25.25 0.152 0.998 6.329 3.782 0.905 40.22 14.6 0.923

mean free energy of adsorption per mole of the adsorbate
(kJ mol1). Qm is the saturation capacity in theory, and 3 is
Polanyi potential, which equals to RTln(1 þ 1/Ce), and R
(J mol1 K1) and T (K) are the gas constant and the absolute
temperature, respectively.
The adsorption constants and correlation coefficients
obtained by using non-linear regression are presented in Table
5, and Langmuir, Freundlich and D-R isotherm curves at the
temperature of 30
C are shown in Fig. 7. The Langmuir
isotherm best described the experimental data, which is
apparent from the values of correlation coefficient (r2) under
25, 30, 35 and 40
C that they are all much higher than those of
Freundlich model and D-R model, implying the surface
homogeneity of the adsorbent. It also can be concluded from
the high values of Qm that the adsorption of Cu(II) on carbon
obtained in our experiment is an effective way to remove Cu(II)
ions from aqueous solution. However, as the D-R isotherm is
not based on the assumptions that the surface is homogeneous
or the adsorption potential is constant, it is more general than
Langmuir isotherm. The values of E obtained in D-R model
were found to be higher than 14 kJ mol1, indicating the
adsorption process may be a chemical ion-exchange process,
since the magnitude of E between 8 and 16 kJ mol1 corre-
sponds to a chemical ion-exchange process while the value of
E < 8 kJ mol1 represents a physical nature process [35].
3.7. Adsorption thermodynamics
The thermodynamic parameters can be evaluated from the
variation of the thermodynamic equilibrium constant K0 with
30
25
the change in temperature [36]. The K0 is defined as follows for
the adsorption reactions:
as vs Qe
K0 ¼ ¼ (12)
ae ve Ce
where as and ae are the activity of adsorbed Cu(II) ions and the
activity of Cu(II) ions in the solution at equilibrium, vs and ve
are the activity coefficient of adsorbed Cu(II) ions and the
activity coefficient of Cu(II) ions in the solution at equilibrium,
respectively. As the Cu(II) ions concentration in the solution
decreases and approaches to 0, K0 can be got by plotting
a straight line of ln(Qe/Ce) versus Qe based on a least-square
analysis, and then extrapolating Qe to 0, the intercept with the
vertical axis is the value of K0.
The free energy change (DG0), enthalpy change (DH0), and
entropy change (DS0) were determined by the following
equations:
DG0 ¼ RTln K0 (13)
TDS0
DG0 ¼ DH0  (14)
R
where R is the gas constant (8.314 J mol1 L1), and T is the
absolute temperature (K). The DH0 and DS0 can be obtained by
plotting DG0 versus T.
It can be seen that the value of DG0 was 3.42, 2.52, 3.18,
3.52 kJ mol1 at four different temperatures, respectively, and
the value of DS0 was 100 J mol1 K1, indicating the adsorption
process was spontaneous with a high affinity for Cu(II) ions
[37]. The positive value of DH0 at 27.86 kJ mol1 reveals the
adsorption process of Cu(II) ions by the carbon prepared was
endothermic, which was supported by the increasing adsorp-
tion of Cu(II) ions with the increase of the temperature.

20 4. Conclusions
Qe (mg g )

Carbon prepared from rice husk using physical activation

-1

15
method was utilized to adsorb Cu(II) from aqueous solution. In
o the preparation process of carbon, 700 and 750
C were chosen
10 Experimental data at 30 C
as the optimal pyrolysis and activation temperature, with 3%
Langmuir fit
(V/V) steam as the best kind of activation gas. The Cu(II)
5 Freundlich fit
adsorption on the rice husk derived carbon was pH dependent,
D-R fit and higher temperature favored the adsorption. The adsorp-
0 tion process followed a pseudo-second-order kinetic model,
0 50 100 150 200 250 300 and the Langmuir model fitted very well with the adsorption
Ce (mg L )
-1 isotherm data, with high values of maximum adsorption
capacity implying the rice husk derived carbon could serve as
Fig. 7 e Adsorption isotherms of Cu(II) on carbon derived an effective adsorbent for Cu(II) removal from aqueous solu-
from rice husk at 30
C. tion. The mean free energy E (kJ mol1) obtained in the D-R
472 b i o m a s s a n d b i o e n e r g y 3 5 ( 2 0 1 1 ) 4 6 4 e4 7 2
isortherm indicated a chemical ion-exchange mechanism. The
negative value of DG0 at four different temperatures and the
positive value of DS0 suggest the adsorption process was
spontaneous with a high affinity for Cu(II) ions, while the
positive value of DH0 at 27.86 kJ mol1 reveals the adsorption
process of Cu(II) ions in this study was endothermic.
Acknowledgments
This research was supported by the National Water Pollution
Control and Management Project of China (No. 2008ZX07101-
006) and the Science and Technology Project of Zhejiang
Province, PR China (No. 2009C33120).
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