International Journal of Engineering & Technology IJET-IJENS Vol: 10 No: 06
Effect of preparation conditions of activated carbon
prepared from rice husk by ZnCl2 activation for
removal of Cu (II) from aqueous solution
Nasehir Khan E M Yahayaa, Muhamad Faizal Pakir Mohamed Latiffa, Ismail Abustana, Mohd Azmier Ahmadb,*
a
School of Civil Engineering, Engineering Campus, Universiti Sains Malaysia,
14300 Nibong Tebal, Penang, Malaysia
b
School of Chemical Engineering, Engineering Campus, Universiti Sains Malaysia,
14300 Nibong Tebal, Penang, Malaysia
Abstract - Rice husk based activated carbon (RHAC) were
prepared using chemical activation method which consisted of
zinc chloride (ZnCl2) treatment. The effects of activation
temperature, activation time and ZnCl2:char impregnation ratio
(IR) on RHAC yield and Cu (II) removal from aqueous solution
were investigated. Based on the central composite design (CCD),
two quadratic models were respectively developed to correlate
the preparation variables to the both responses. From the
analysis of variance (ANOVA), the significant factors on each
experimental design response were identified. The optimum
RHAC was obtained by using activation temperature of 500oC,
activation time of 1.71 h and IR of 1.04, which resulted RHAC
yield of 34.21% and Cu (II) removal of 33.92%.
Index Terms - Activated carbon, Central composite design, Cu
(II) removal, Optimization, Rice husk
I. INTRODUCTION
R ecently Cu (II) contamination presents a danger for living
species and ecological systems. Various Cu (II)
elimination techniques are available such as chemical
precipitation, ion exchange, solvent extraction, ultra filtration,
reverse osmosis, membrane filtration and adsorption. The
adsorption technique is found to be the simplest method for
Cu (II) removal due to its high efficiency and ease of
handling. Activated carbon as adsorbent is preferred in most
of the Cu (II) treatment from wastewater. However, the
manufacturing cost of commercial activated carbon is in fact
rather high. As such, there is a need to produce activated
carbon with high adsorption performance from alternative
material that is cheaper and readily available. From the
literature, many studies have been carried out to prepare low
cost activated carbons from agricultural wastes such as oil
palm empty fruit bunch [1], coconut husk [2] and rice straw
[3]. In this work, an attempt was made in preparing activated
carbon from rice husk. By utilizing rice husk into activated
carbon will decrease the cost of waste disposal and also
converted this waste into value-added product. Currently no
study has been done on optimization of the RHAC preparation
Manuscript received November 10, 2010. This work was supported by the
research grant from Universiti Sains Malaysia (Project number: 6035296 and
814021). Mohd Azmier Ahmad and Ismail Abustan are the members of Waste
Management Cluster of Universiti Sains Malaysia. Nasehir Khan E M Yahaya
and Muhamad Faizal Pakir Mohamed Latiff are postgraduate students
working on activated carbon. The correspondence author can be contacted via
e-mail: chazmier@eng.usm.my (M.A. Ahmad).
108506-2525 IJET-IJENS © December 2010 IJENS
27
conditions for Cu (II) removal using the response surface
methodology (RSM) approach. The effects of preparation
variables; activation temperature and activation time were
studied simultaneously to give a high RHAC yield and high
Cu (II) percentage removal from aqueous solution.
II. MATERIALS AND METHODS
A. Materials
Rice husk (RH) as precursor was obtained from the local
rice processing mill in Kepala Batas, Penang, Malaysia. Stock
solutions of Cu (II) was prepared by Cu(NO3)2.3H2O (Merck,
99% purity) in deionised distilled water. Deionized water was
used to prepare all solutions.
B. Preparation of activated carbon
RH was washed with water and subsequently dried at 105
o
C for 24 h to remove moisture content. The dried RH was
ground and sieved to a particle size of 1-2 mm before loading
it in a stainless steel vertical tubular reactor placed in a tube
furnace. Carbonization step was carried out at 400oC for 30
min under nitrogen (99.99%) flow at flow rate of 150 ml/min.
The char produced was mixed with ZnCl2 pellets at different
impregnation ratio (IR), calculated as below:
IR = WZnCl / Wchar (1)
2
where W ZnCl 2 is the dry weight (g) of ZnCl2 pellets and
is the dry weight (g) of char. Deionized water was then added
to dissolve all the ZnCl2 pellets. The activation step was done
using similar reactor as in carbonization step. Once the final
activation temperature was reached, the gas flow was switched
from nitrogen to CO2 at a flow rate of 150 ml/min for different
period of time. The activated product was then cooled to room
temperature under nitrogen flow. Then, the sample was
washed with hot deionized water and hydrochloric acid (0.1M)
until the pH of the washed solution reached 6.5-7.
C. Adsorption studies
For batch adsorption studies, 0.3 g of adsorbent were
mixed with 100 ml aqueous dye solutions of 50 mg/l initial
concentration in 13 sets of 250 ml Erlenmeyer flasks. The
mixture was agitated at 400 rpm at 30°C until equilibrium was
reached. The concentration of Cu (II) solution was determined
IJENS
 International Journal of Engineering & Technology IJET-IJENS Vol: 10 No: 06 28

using a spectrophotometer (model DR 2010) at wavelength of
560 nm. The percentage removal at equilibrium was calculated
as follows:
C C
Removal % x 100 2
C
where Co and Ce are the liquid-phase Cu (II) concentrations at
initial state and at equilibrium (mg/l), respectively.
D. Activated carbon yield
The RHAC yield was calculated based on the following
equation:
w F.
Yield % x100 3
w The experimental data were analyzed using a statistical
where wc and wo are the dry weight of final activated carbon
(g) and the dry weight of precursor (g), respectively.
E. Design of experiments
In this work, a standard RSM design called central
composite design (CCD) was applied to study the variables for
preparing the activated carbon from RHAC. This method can
reduce the number of experimental trials needed to evaluate
multiple parameters and their interaction [2]. Generally, the
CCD consists of three kinds of runs which are the 2n factorial
runs, 2n axial runs and six center runs, where n is the number
of factors.
The RHAC was prepared using physiochemical activation
method. The variables studied are activation temperature (x1),
activation time (x2) and impregnation ratio (IR) (x3). These
three variables together with their respective ranges were
chosen based on literature and preliminary studies are reported
in Table 1.
Each response was used to develop an empirical model which
correlated the response to the three activated carbon
preparation variables using a second-degree polynomial
equation as given by (5):
5
where Y is the predicted response, bo the constant coefficient,
bi the linear coefficients, bij the interaction coefficients, bii the
quadratic coefficients and xi, xj are the coded values of the
activated carbon preparation variables.
Model fitting and statistical analysis
software Design Expert software version 6.0.6 (STAT-EASE
Inc., Minneapolis, USA) for regression analysis to fit the
second-degree polynomial equation and also for the evaluation
of the statistical significance of the equations developed.
G. Characterization of optimized RHAC
The surface morphology of the samples was examined
using a scanning electron microscope (JEOL, JSM-6460 LV,
Japan). Proximate analysis was carried out using
thermogravimetric analyser (Perkin Elmer TGA7, USA) and
elemental analysis was performed using Elemental Analyzer
(Perkin Elmer Series II 2400, USA). The surface area, pore
volume and average pore diameter of the RHAC were
determined by nitrogen adsorption isotherm at 77 K using
Micromeritics ASAP 2020 volumetric adsorption analyzer.
The surface area of the sample was determined using
Brunauer-Emmett-Teller (BET) equation. The total pore
volume was estimated to be the liquid volume of nitrogen at a
relative pressure of 0.98.

TABLE 1 III. RESULTS AND DISCUSSION

INDEPENDENT VARIABLES AND THEIR CODED LEVELS
Coded variable levels A. Development of regression model equation
Variables (factors) Code
-α -1 0 +1 +α
Activation temperature, oC x1 431.82 500 600 700 768.18
Table 2 shows the complete design matrixes together with
Activation time, h x2 0.12 0.6 1.3 2.0 2.48 both the response values obtained from the experimental work.
Impregnation ratio (IR) x3 0.10 0.6 1.3 2.0 2.50 Run 5-20 at the center point were conducted to determine the
experimental error and the reproducibility of the data. The
For each categorical variable, a 23 full factorial CCD for the RHAC yield and the percentage of Cu (II) removal were found
three variables, consisting of 8 factorial points, 6 axial points to range from 20.19 to 35.27% and 13.33 to 31.33%,
and 6 replicates at the center points were employed, indicating respectively. According to the sequential model sum of
that altogether 20 experiments for this procedure for the squares, the models were selected based on the highest order
precursor are calculated from (4): polynomials where the additional terms were significant. For
both responses, two quadratic models were the best model to
2 2n n 2 2‫٭‬3 6 20 (4) correlate the data to the responses as suggested by the
software. The final empirical formula models for the RHAC
where N is the total number of experiments required. yield (Y1) and Cu (II) removal (Y2) in terms of coded factors
The center points are used to determine the experimental are represented by (5) and (6), respectively.
error and the reproducibility of the data. The axial points are
located at (±α, 0, 0), (0, ±α, 0) and (0, 0, ±α) where α is the Y1= 26.20 – 4.21x1 – 1.23x2 - 0.26x3 + 0.54x12 – 0.061x22 +
distance of the axial point from center and makes the design 0.19x32 + 0.59x1x2 + 0.026x1x3 –0.20x2x3 (5)
rotatable. In this study, the α value was fixed at 1.682
Y2 = 27.81 – 3.79x1 + 1.46x2 – 0.45x3 – 3.48x12 –2.26x22 –
(rotatable). The experimental sequence was randomized in
0.45x32 – 3.9x1x2 – 0.45x1x3 + 0.6x2x3 (6)
order to minimize the effects of the uncontrolled factor. The
two responses were RHAC yield (Y1) and Cu (II) removal (Y2).

108506-2525 IJET-IJENS © December 2010 IJENS

IJENS
 International Journal of Engineering & Technology IJET-IJENS Vol: 10 No: 06 29

TABLE 2 x3 2 0.52 1 0.52 1.26 0.2878

EXPERIMENTAL DESIGN MATRIX FOR PREPARATION OF RHAC x1 x2 2.77 1 2.77 6.74 0.0266
Variables Response x1 x3 0.0055 1 0.0055 0.013 0.9101
Activation Activation RHAC Cu (II) x2 x3 0.33 1 0.33 0.81 0.3899
Run IR,
temp, x1 time, yield, Y1 removal,
x3
(⁰C) x2 (h) (%) Y2 (%) From the ANOVA for Cu (II) removal as shown in Table
1 500.00 0.60 0.6 32.42 21.99 4, the model F-value of 6.76 and Prob. > F of 0.0031 revealed
2 700.00 0.60 0.6 23.99 23.50
3 500.00 2.00 0.6 29.89 35.42 that the model was significant. In this case, x1, x12, x22 and x1x2
4 700.00 2.00 0.6 22.16 15.56 were significant model terms whereas x2, x3, x32, x1x3 and x2x3
5 500.00 0.60 2.0 33.12 21.27 were insignificant to the response. From the statistical results
6 700.00 0.60 2.0 23.14 15.21 obtained, it was shown that the above models were adequate to
7 500.00 2.00 2.0 28.12 31.33
8 700.00 2.00 2.0 22.15 15.44 predict the RHAC yield and Cu (II) removal within the range
9 431.82 1.30 1.3 35.27 20.17 of variables studied.
10 768.18 1.30 1.3 20.19 13.33
11 600.00 0.12 1.3 27.94 18.97 TABLE 4
12 600.00 2.48 1.3 24.12 21.43 ANOVA FOR CU (II) REMOVAL OF RHAC
13 600.00 1.30 0.1 27.24 23.21 Sum of Degree of Mean F
14 600.00 1.3 2.5 26.24 27.44 Source Prob > F
squares freedom square value
15 600.00 1.3 1.3 27.12 28.31 Model 582.72 9 64.75 6.76 0.0031
16 600.00 1.3 1.3 26.15 27.15 x1 196.50 1 196.50 20.50 0.0011
17 600.00 1.3 1.3 25.22 28.45 x2 29.05 1 29.05 3.03 0.1123
18 600.00 1.3 1.3 25.99 28.11 x3 2.73 1 2.73 0.28 0.6052
19 600.00 1.3 1.3 26.33 27.24 x1 2 174.73 1 174.73 18.23 0.0016
20 600.00 1.3 1.3 26.42 27.99 x2 2 73.76 1 73.76 7.70 0.0196
x3 2 2.92 1 2.92 0.30 0.5929
The coefficient with one factor represent the effect of the x1 x2 121.68 1 121.68 12.70 0.0052
particular factor, while the coefficients with two factors and x1 x3 1.62 1 1.62 0.17 0.6896
those with second-order terms represent the interaction x2 x3 2.88 1 2.88 0.30 0.5956
between two factors and quadratic effect, respectively. The
quality of the models developed was evaluated based on the C. RHAC yield
correlation coefficients, R2 value. In fact, the models
Referring to Table 3, the activation temperature and time
developed seems to be the best at low standard deviation and
were found to be significant on the response for RHAC yield,
high R2 statistics which is closer to unity as it will give
with activation temperature imposing the greatest effect on it.
predicted value closer to the actual value for the responses [4].
The IR showed insignificant effect on this response. Fig. 1
In this experiment, the R2 values for (6) and (7) were 0.985
illustrates the effect of activation temperature and activation
and 0.885, respectively. This indicated that 98.5 and 88.5% of
time on the RHAC yield, with IR fixed at zero level (IR=1.3).
the total variation in the RHAC yield and Cu (II) removal,
respectively were attributed to the experimental variables
studied. Both R2 values were considered high, indicating that
the predicted values for RHAC yield and Cu (II) removal
would be more accurate and closer to its actual value.
B. Analysis of variance
The ANOVA of the regression model demonstrates that
the model is highly significant as evident from the calculated
F-value and a very low probability value. If the value of Prob.
> F less than 0.05, the model terms are considered as
significant [5]. The ANOVA for the quadratic model for
RHAC yield is listed in Table 3. The model F-value of 73.29
and Prob. > F of less than 0.0001 implied that this model was
significant. In this cases, x1, x2, x12 and x1x2 were significant
model terms whereas x3, x22, x32, x1x3 and x2x3 were Fig. 1. Three-dimensional response surface plot of RHAC yield (Effect of
insignificant to the response. activation temperature and activation time, IR = 1.3).

TABLE 3 The carbon yield was found to decrease with increasing

ANOVA FOR RESPONSE SURFACE QUADRATIC MODEL FOR RHAC
activation temperature and activation time. The highest yield
YIELD
Sum of Degree of Mean F was obtained when both variables were at the minimum point
Source Prob > F within the range studied. This result was in agreement with the
squares freedom square value
Model 271.23 9 30.14 73.29 <0.0001 work done by Ahmad et al. [4] which found that activation
x1 241.85 1 241.85 588.18 <0.0001 temperature play an important role on the yield of activated
x2 20.60 1 20.60 50.11 <0.0001
x3 0.96 1 0.96 2.32 0.1585
carbon prepared by rattan sawdust whereas activation time did
x1 2 4.20 1 4.20 10.21 0.0096 not show much effect on the carbon yield. Overall weight loss
x2 2
0.054 1 0.054 0.13 0.7239 was found to increase with increasing temperature, resulting in

108506-2525 IJET-IJENS © December 2010 IJENS

IJENS
 International Journal of Engineering & Technology IJET-IJENS Vol: 10 No: 06 30

decreasing yield at high temperature [5]. The weight loss was and experimental results of RHAC yield and Cu (II) removal
due to devolatilization of the precursors, primary to increase obtained at optimum conditions are listed in Table 5.
of the pore development and create new pores, as a result of
intensifying dehydration and elimination reactions [6]. As TABLE 5: MODEL VALIDATION
temperature increases, the C-ZnCl2 and C-CO2 reaction rate Act.  Act. IR, RHAC yield (%) Cu (II) removal (%)
temp., time, x3 Err. Err.
were increase as well, leading towards decrease in carbon x1 (oC) x2 (h)
Pred. Act.
(%)
Pred. Act.
(%)
yield [7]. 500 1.71 1.04 35.27 34.21 3.00 35.42 33.92 4.23

D. Cu (II) removal The optimum RHAC was obtained by using activation

Based on the F-value as shown in Table 4, the activation
temperature was found to has significant effects on the Cu (II)
removal. The quadratic effects of activation temperature and
activation time as well as the interaction effects between these
two variables were considered moderate. Fig. 2 shows the
three-dimensional response surfaces which was constructed to
show the interaction effects of the activation temperature and
activation time on the Cu (II) removal. For this plot, the IR
was fixed at zero level (IR=1.3). The Cu (II) removal
generally increased with increase in the two variables studied.
The results obtained were in aggrement with the work done by
Sudaryanto et al. [8] which reported that activation
temperature gave significant effect on the pore structure of
activated carbon produced from casava peel.
temperature, activation time and IR of 500oC, 1.71 h and 1.04,
respectively. The optimum activated carbon showed RHAC
yield of 34.21% and Cu (II) removal of 33.92%. It was
observed that the experimental values obtained were in good
agreement with the values predicted from the models, with
relatively small errors between the predicted and the actual
values, which was only 3.00% and 4.23% for RHAC yield and
Cu (II) removal, respectively.
F. Characterization of optimized RHAC
Figs. 3(a) and (b), respectively show the SEM images of
the raw RH and RHAC. The precursor’s surface textures were
rough, uneven, undulating and very little pores were presence
as observed in other biomass [2,4].

Fig. 2. Three-dimensional response surface plot of Cu (II) removal (Effect

of activation temperature and activation time, IR = 1.3).

E. Process optimization
One of the main aims of this study was to find the
optimum process parameters which activated carbons
produced should have a high RHAC yield and a high Cu (II)
removal. However, it is difficult to optimize both these
responses under the same condition because the interest region
of factors is different. When adsorption performance
increases, carbon yield will decrease and vice versa.
Therefore, the function of desirability was applied using
Design-Expert software in order to compromise between these Fig. 3. SEM micrographs; (a) raw RH and (b) RHAC (500x)
two responses.
In the optimization analysis, the target criteria was set as After activation process, almost homogeneous type pores
maximum values for the two responses of RHAC yield and Cu structure were distributed on the surface of the RHAC as
(II) removal while the values of the three variables were set in shown in Fig. 3(b). This result revealed that the activation
the ranges being studied. The experimental conditions with the process of ZnCl2 was effective in creating well-developed
highest desirability were selected to be verified. The predicted pores, resulting to large surface area activated carbon with
good mesoporous structure. Similar observations were

108506-2525 IJET-IJENS © December 2010 IJENS

IJENS
 International Journal of Engineering & Technology IJET-IJENS Vol: 10 No: 06 31

reported by other researchers in their work of preparing

activated carbons from oil palm empty fruit bunch [1], REFERENCES
coconut shells [2], rattan sawdust [4] and mangosteen peel.
Tables 6 and 7 respectively present the proximate and [1] B.H. Hameed, I.A.W. Tan, A.L. Ahmad, “Preparation of
elemental analysis of raw RH and RHAC samples. After oil palm empty fruit bunch-based activated carbon for
undergoing activation process, the volatile matter content of removal of 2,4,6-trichlorophenol: Optimization using
the precursor decreases significantly whereas the fixed carbon response surface methodology”, J. Hazard. Mater., 164,
content increases. This might be due to pyrolytic effect at high 2009, 1316-1324.
temperature where most of the organic substances have been [2] I.A.W. Tan, A.L. Ahmad, B.H. Hameed, “Optimization of
degraded and discharged both as gas and liquid tars leaving a preparation conditions for activated carbons from coconut
material with high carbon purity. A reduction of hydrogen husk using response surface methodology”, Chem. Eng. J.,
content to a value less than 1% was due to the organic 137 (2008), 462-470.
molecular chains ruptured after undergoing activation process [3] A.H. Basta, V. Fierro, H. El-Saied, A. Celzard, “2-Steps
[10]. KOH activation of rice straw: An efficient method for
preparing high-performance activated carbons”,
TABLE 6 Bioresource Technol., 100, 2009, 3941-3947.
PROXIMATE ANALYSIS
[4] A.A. Ahmad, B.H. Hameed, A.L. Ahmad, “Removal of
Sample Proximate analysis (%)
Moisture Volatile Fixed Carbon Ash disperse dye from aqueous solution using waste-derived
Raw RH 4.2 58.0 21.7 16.1 activated carbon: Optimization study”, J. Hazard. Mater.,
RHAC 2.1 19.9 63.2 24.8 170, 2009, 612-619.
[5] J.N. Sahu, J. Acharya, B.C. Meikap, “Optimization of
TABLE 7
ELEMENTAL ANALYSIS
production conditions for activated carbons from Tamarind
Sample Elemental analysis (%) wood by zinc chloride using response surface
C H N othersa methodology”, Bioresource Technol., 10, 2010, 1974-
Raw RH 38.1 8.3 0.8 52.8 1982.
RHAC 78.2 4.7 0.6 16.5 [6] D. Adinata, W.M.A. Wan Daud, M.K. Aroua, “Preparation
*Estimated by difference
and characterization of activated carbon from palm shell by
chemical activation with K2CO3”, Bioresource Technol.,
The BET surface area, total pore volume and average pore
98, 2007, 145-149.
diameter of the RHAC were found to be 604.34 m2/g, 0.41
[7] A.C. Lua, T. Yang, “Effect of activation temperature on
cm3/g and 2.75 nm, respectively. The average pore diameter of
the textural and chemical properties of potassoium
2.75 nm indicates that the RHAC prepared was in the
hydroxide activated carbons”, J. Anal. Appl. Pyrol., 76
mesopores region. The chemical activation process has
2004, 96-102.
contributed to the high surface area and total pore volume of
[8] Y. Sudaryanto, S.B. Hartono, W. Irawaty, H. Hindarso, S.
the RHAC.
Ismadji, “High surface area activated carbons from olive-
seed waste residue”, Micropor. Mesopor. Mater., 82, 2006,
IV. CONCLUSIONS 79-85.
RSM was successfully used to investigate the effects of [9] M.A. Ahmad, R. Alrozi, “Optimization of preparation
preparation variables on the RHAC yield and percentage of Cu conditions for mangosteen peel-based activated carbons for
(II) removal. Two quadratic models were developed to the removal of Remazol Brilliant Blue R using response
correlate the preparation variables to the two responses. surface methodology”, Chem. Eng. J., 165, 2010, 883-890.
Activation temperature was found to be the most significant [10] J.M. Salman, B.H. Hameed, “Effect of preparation
effect on both responses. In contrast, the IR was insignificant conditions of oil palm fronds activated carbon on
on both responses. The optimum RHAC was obtained by adsorption of bentazon from aqueous solutions”, J.
using activation temperature, activation time and IR of 500oC, Hazard. Mater. 175, 2010, 133-137.
1.71 h and 1.04, respectively, resulting in RHAC yield of
34.21% and Cu (II) removal of 33.92%. The RHAC prepared
demonstrated high surface area and well-developed porosity.

108506-2525 IJET-IJENS © December 2010 IJENS

IJENS