Proceedings of the 19th IAHR-APD Congress 2014, Hanoi, Vietnam

ISBN xxx-xxxx-xx-x

ACTIVATED CARBON DERIVED FROM THE TROPICAL AGRICULTURAL WASTES (CORN COB,
RICE STRAW) AND ITS APPLICATION FOR TREATMENT OF THE INDUSTRIAL WASTEWATER
LAN T.N.PHAM(1), VAN T. NGUYEN(2)
1 Environmental Engineering Division, Water Resource University, Hanoi, Viet nam
Email: ngoclanmt@wru.edu.vn
2 Environmental Engineering Division, Water Resource University, Hanoi, Viet nam
Email: nguyenthivan528@gmail.com

ABSTRACT

Production of activated carbons (activated charcoal) from agricultural wastes is one of the good methods to solve the
environmental problems caused by burning and getting rid of the crop wastes: emission of CO 2 into the atmosphere - the
main reason of the global climate change, pollution of air and inhibition of the vision, etc... Besides, there is a great
economical value of recycling the corn cob and rice straw to produce activated carbons which have many applications for
treatment industrial wastewaters. In this study, a series of activated carbons experiments were done from the agricultural
waste corn cob and rice straw by the chemical activation using phosphoric acid, sulfuric acid, zinc chloride and potassium
hydroxide as activating agents. Many factors affecting the process have been studied such as the pyrolysis temperature,
soaking time and chemical treatment of the raw materials through the impregnation ratio of the production of adsorbent
in order to determine the optimal conditions. As the results, the important parameters in the chemical activation of corn
cob and rice straw with ZnCl2, KOH, H3PO4, H2SO4 are the impregnation ratio and the pyrolysis temperature. Under the
experimental conditions in the laboratory, the temperature of 350 oC for pyrolysis process and of 550oC for activation
during 120 minutes with phosphoric acid and sulfuric acid were found to be the optimal condition for producing high
surface area carbons in the range of 982-1234 m2/g. The activated carbons produced in this work were used as an excellent
sorbent to remove color and heavy metals: copper (Cu 2+), iron (Fe2+), zinc (Zn2+), Chromium trivalent (Cr3+) from various
wastewaters such as: as metal plating, mining, tanneries.
Keywords: activated carbons; agricultural wastes; pyrolysis; wastewater treatment; heavy metals

1. INTRODUCTION process (O.S. Amudaa,∗, A.A. Giwaa, I.A. Bellob,2007), in

Activated carbon is a well known material used in ever
increasing numbers of environmental application, in
environment protection, in water and wastewaters
treatment, in gas filters, etc (W.T.Tsai, 1998). Several
wastewaters in industry present certain hazards and
environmental problems. Colour and heavy metals in
water body, which goes into the environment, have
caused many harmful effect for the aquatic environment.
The metals are considered to be special because of their
persistency in the environment. At least 20 metals are
classified as toxic, and half of them are emitted into the
environment in quantities that pose risks to human health.
Adsorption is the ideal method because it is non specific
and the adequate activated carbon must exhibit a high
volume of micro pores of a variety of pore size to be able
to absorb a wide range of molecules, coupled with an
adequate proportion of meson and macro pores to
facilitate the access to the micro pores (M. Molina-Sabio, F.
Rodriguez-Reinoso, 2004). Activated carbons are the most
versatile and commonly used adsorbents because of their
extremely high surface areas and micro pore volume,
large adsorption capacities, fast adsorption kinetics, and
relative ease of regeneration.
Activated carbon can be produced theoretically from any
carbonaceous material rich in element carbon. Although
most of types of industrial activated carbons are produced
naturally from the carbonaceous material such as coal,
wood and coconut shell by some form of activation
the recent years, there is growing interest in the
production of activated carbons from agricultural by
products and residual waste. Agricultural by-products
available in large quantities are corn cob and rice straw.
The annual globe production of 800 million tons of corn
results in 240 million tons of corn cob while the estimated
annual word rice production is about 571 million tones
resulting in approximately 140 million tons of rice straw
available annually for utilization. Despite the wide
consumption of corn cob and rice straw as a fuel for mill
boilers, for electricity and steam generation, animal feed
or as a raw material for manufacture of paper and board,
the residues still remain as a surplus which poses a
disposal problem for mill owners (O. Ioannidou, A.
Zabaniotou, 2006).
Phosphoric acid and zinc chloride are used for the
activation of lingo cellulose materials, which have not
been carbonized previously; whereas metal compounds
such as potassium hydroxide are used for the activation of
coal precursors or chars. When compared to zinc chloride,
phosphoric acid is the most preferred because of the
environmental disadvantages associate with zinc chloride.
Problem of corrosion efficient chemical recovery is also
associated with choosing chemical activation. Moreover,
the carbons obtained using zinc chloride cannot be used in
pharmaceutical and food industries as it may contaminate
the product. Although potassium hydroxide develops
large micro porosity, yield of activated carbon
impregnated by potassium hydroxide is lower than those

1
activated carbon with zinc chloride or phosphoric acid,
and at high temperature, the carbon content is less than
fixed activated carbon in initial precursor. The presence of
metallic potassium will intercalate to the carbon matrix,
yielding lower yield of activated carbon, less than the
carbon content of the raw material.
The objective of this work is: (1) to produce a new bio-
sorbent from corn cob and rice straw having
simultaneously high BET (Brunauer–Emmett–Teller)
surface area and excellent cationic sorption capacity, with
the highest possible carbon yield and (2) to investigate the
application of this new sorbent in getting rid of the colour
and cationic metal in several wastewater industries.
2. METHODOLOGY
The logical research framework
450, 500 and the retention times of 60, 90, 120, 150 minutes
were examined.
3.2 Application for treatment of the industrial wastewater
Activated carbon from corn cob and rice straw has the
high surface areas. Its application for treatment of the
industrial wastewater: Textile, Tanning, and plating metal
have been done. Pollution parameters such as Cr,
Fe,…and color were determined using an DR5000
Spectrophotometer (HACH Co., USA) based on Standard
Methods (APHA). Batch adsorption experiments were
carried out at room temperature by shaking a series of
bottles containing the desired dose of adsorbent with a
predetermined concentration of heavy metal solution.
Samples were withdrawn at different time intervals.
The percentage of removal of heavy metal from solution
was calculated by the following equation:
𝐶𝑜 − 𝐶𝑖
% 𝒓𝒆𝒎𝒐𝒗𝒂𝒍 = × 100
𝐶𝑜

4. RESULTS AND DISCUSSION

4.1 Some images of produced activated carbon in different

conditions.

Characterization of adsorbents: Physical characterization

of rice straw and corn cob activated carbon.
Determine the total surface BET (m2/g) for four sample of
activated carbon from rice straw and corn cod. Impregnated raw material with chemical
3. DESIGN OF THE EXPERIMENTAL MODEL
3.1 Preparation of activated carbon
First of all, raw materials of activated carbon were
acquired by collecting corn cob and rice straw from field
in the last harvest, then they were removed and
subsequently cleaned by removing the carpel fibers and
washing several times with distilled water to remove
impurities. The precursors were then dried at 105oC for 4
hours Raw materials are burned because of high temperature:
500, 600,700oC without chemical
Chemical activation method using phosphoric acid,
sulphuric acid, zinc chloride and potassium hydroxide to
activated the raw materials. 30 g of raw material was
impregnated by certain amount of 5-10 weight in
percentage with occasional stirring. The resulting slurry
was then kept in a desiccator overnight.
A sample of 30 g of raw material was mixed with the
chemical reagent in a glass beaker at a ratio of reagent to
raw material sample of 0.1, 0.25, 0.5, 0.75 and 1
(weight/weight). Distilled water was added at a quantity
amounting to 10 times of the total weight of the mixture.
Physical characteristics of activated carbon
The mixture was then stirred and heated to become
homogenized and impregnated at a temperature of 85oC
until a thick uniform paste was obtained. A sample of wet
material after impregnating (remain about 75% moisture)
was weighed before placing it on the top of the metal
mesh filter inside the reactor. Part of the remaining paste
was used to determine the moisture content.
In this work, the effect of impregnating agents such as
ZnCl2, KOH, H3PO4, H2SO4, on the carbon surface area
was investigated, at a ratio of reagent to raw material
sample of 0.1, 0.25, 0.5, 0.75 and 1 (w/w). Activation was
performed at the different temperatures of 300, 350, 400,
2
Table 1. Samples of the activated carbon prepared at the
optimal conditions
BET
Raw Yield surface
materials (%) area Images
(m2/g)
M1 57 1078**
M2 55 928**
M3 61 1234**
M4
M1, M2,M3 samples are shown in Table 4
4.2 Effect of activation condition to the quality of the
activated carbon
Chemical, temperature, impregnated time, and some
other factors were examined and the qualification of
activated carbon were determined by the surface areas
(BET, m2/g) and sorption capacity. If chemical activation
is essentially considered as a reaction between the raw
precursor and the chemicals it is clear that concentration,
temperature and activation time determines the extent of
reaction. However, such reaction cannot proceed to the
completion because of the destructive precursor.
Consequently, it is important to select a range of
experimental conditions in which the first reactants reacts
with the precursor during the impregnation step,
producing a partial modification of the botanic texture and
later during the heat treatment either alters the
carbonisation process in respect to the unimpregnated
precursor or directly reacts with the carbon. The optimal
conditions selected within this range will lead to the
carbon formation with the maximum uniform micro-
porosity.
Under these conditions, the carbon is more similar to a
char and the carbon that are formed in the above process
will exhibit a heterogeneous micro-porosity or even meso-
porosity. The optimum degree of activation is a function
of each chemical and it can be observed in the plots for the
evolution of micro-porosity. For the four activating agents
studied here: ZnCl2, H3PO4 and KOH, H2SO4 such
optimum conditions lead to the activated carbons with
surface area of pores have ranged from 0.7-1234m2/g (see
Table 2).
Table 2. Description of the BET surface area of the
produced activated carbons with the raw material
impregnation under different chemical treatments.
SBET(m2/g) At SBET(m2/g) at
Sample Reference [1]
the first step the second step
420-1917[2-
M1 1.1329* 1078**
Steps KOH]
M2 0.70296* 928** 420-1917
M3 113.5889* 1234** 420-1917
M4 - 1124 420-1917
(*) Experimental results of the single–stage production of
activated carbon (AC) from straw and corn cob using
H3PO4 and H2SO4 as reagents. (**) Experimental results of
the two–stage production of activated carbon: the
optimum conditions for producing the activated carbon
was obtained at 550oC for 120 min and AC has a surface
area of 1234m2/g.
These products were used in experiments of treating the
color in the textile industrial wastewater. The results
shown that approximately 98%, 90% and 90% of color
removal efficiencies were achieved within 1h by the
commercial AC, the wood charcoal and coconut shell
respectively.
The yield of the resulting activated carbons is in the range
of 20-36%, listed in Table 3. The yield was observed to
decrease slightly at higher pyprolysis temperature, which
is possibly attributed to the volatilization of tar products
derived from the ligno-cellulosic components of raw
material.
Surface areas of the AC obtained from the chemical
pretreatment of both corn cob and rice straw materials
with H2SO4 of 5% were always above 800m2/g.
4.3 Performance of the activated carbon production
The produced yield is usually defined by a difference of a
final weight of the completely produced activated carbon
and the initial weight of raw material then divided by the
initial weight of raw material, both on a dry basic (Devarly
Prahas, Y. Kartika, 2008). Table. 3 shows the yield of
activated carbon prepared from corn cob and rice straw at
different activation temperature and impregnation ratio.
As indicated in Table.3, the yields of activated carbon
obtained in this study are in the range of 17.0 – 40.4 %.
These figures are similar to the results obtained by other
studies (W.T.Tsai, C. Y. Chang & S. L. Lee,1998; R. Li, Z.P.
Zhong, B.S. Jin, A.J. Zheng, 2012; Randal L. Shogrena,
2011) i.e.: 31.9-42.3 % for activated carbon from jackfruit
peel, 27.0-30.4 % for activated carbon from corn cob, and
18.0-76.0% for some agricultural residues.
3
 Table 3. Summary of properties of the produced AC in char per 1L absorbed wastwater (Kennedy et. al. Devarly
different experiments Prahas, Y. Kartika, N. Ismadji, 2008) tested the phenol
adsorption on AC prepared from rice husk in a two-stage
Activation Impregnation Yield Shape of
Experiment process using 5 % of H3PO4, 5 % of H2SO4 as the
condition ratio (%) properties
impregnating agents.
Pyrolyzed/
500oC, 150 burn-off char
1 1% 17-30
min with soaking
KOH & ZnCl2
Pyrolyzed char
500oC, 150
2 5% 18-35 with soaking
min
KOH ZnCl2
Pyrolyzed char
500oC, 150
3 10% 20-40 with soaking
min
KOH, ZnCl2

Char keep of
material’s shape,
400oC, 120 KOH &
4 24-31 don’t break,
min ZnCl2 50%
have typical of
activated carbon
Figure. 1. Effect of activation temperature on the adsorption
colour of basic dye
Keep of
material’s Color removal that is absorbed by the activated carbons
original shape, produced from agricultural residuals at different
400oC, 120 KOH &
5 27-36 don’t break, temperatures is presented in Fig. 1. The activating agent
min ZnCl2 100%
have typical of
was H3PO4 of 5%, the results indicated that an increase in
activated carbon
temperature resulted in an increase of the colour
absorbed. The carbons with the highest colour absorbed
which were obtained at 350oC.
Table. 2 depicts the effect of the activation temperature
and impregnation ratio on yield of activated carbon. This There is the similar between the effect of activation
figure shows that the carbon yield was found to increase temperatures to the adsorption colour of basic dye of two
with the increasing of impregnation ratio with KOH, activated carbons that impregnating with H3PO4 and
ZnCl2 and there are some differences in trend of change H2SO4
characteristics between the acid reagent and KOH or
ZnCl2.

Impregnation ratio is another critical factor that affects the

quality of the carbon. From Fig in Table 3. it is obvious
that yield of carbon decreases as the impregnation ratio
increases. Here the surplus phophoric acid will promote
gasification of char and increase the level of loss of
carbons in the different forms. The same result was also
observed by other researchers (R. Li, Z.P. Zhong, B.S. Jin,
A.J. Zheng, 2012; W.T.Tsai, C. Y. Chang & S. L. Lee, 1998)

Table 4. Summary of optimal condition for activation of various

agricultural by products
Raw Particle Carbonization Activation Chemical Figure. 2. Effect of activation chemicals on the colour adsorption
Sample
material size condition condition treatment of basic dyes
Rice 350oC, 120 550oC, 120 H3PO4
M1 1-2 cm
straw min min 5%, Figure 2 shows that in the same activation condition, the
Corn 350oC, 120 550oC, 120 H2SO4 activated carbon that are produced from the rice straw
M2 1-2 cm
cob min min 5%, has higher adsorption capability than that from the corn
Rice 350oC, 120 550oC, 120 H2SO4 cob. However, both of H3PO4 and H2SO4 demonstrate
M3 1-2 cm
straw min min 5%,
their efficiency in the activation. Rice straw AC exhibited a
Coconut
higher adsorption capacity compared to the corn cob AC.
M4* shell Power

M4*: The commercial AC from coconut shell compared

with three samples M1, M2, M3 in this study.
Using the above AC samples for the treatment of colour in
the textile wastewater and this color was determined by
spectrophotometric method with the HACH DR5000
device (measuring at a wave length of 456 nm). Similar
results were obtained by Ozkaya, who studied the
adsorption and desorption of colour of dye using the
commercial activated carbon with the amount of 10mg of
4
Figure. 3. Effect of activation time on the colour adsorption of Figure 6. Sorption of heavy metal from the dye wastewater by
basic dyes preparation activated carbons

Figure 6 has shown that almost all samples of the

produced activated carbons has a good adsorption
capacity for Cu(II), Fe(III), Zn(II) ions from the dye
wastewater. And in Figure 6, the adsorption of copper
from the metal plating wastewater by activated carbons
produced from rice straw and corn cob has been carried
out in diffirent conditions. The highest adsorption can
reach to 95-100% for Cu(II).

Figure.4. The adsorption of colour onto activated carbons

produced from rice straw and corn cob

A similar trend was observed by Emad N.El Qada et. al.

when the activated carbon prepared from tropical
agricultural was used to remove dye from aqueous
solution. The same effects were obtained for the
adsorption of colour of dye onto ACs produced from rice
straw and corn cob.
Figure 7. Sorption of copper from the metal plating wastewater
by preparation activated carbons

The equilibrium soild phase concentration, q (mg/g) was

then calculated according to the following equation:
𝑉
𝑞= (𝐶 − 𝐶𝑒 )
𝑚 𝑖
Where Ci and Ce are the initial and equilibrium metal
concentration, respectively (mg/l), V the volume of
solution (l) and m is the mass of adsorbent (g)

Figure. 5. The colour sorbed onto activated carbons: M1, M2, M3,
M4 after 10 mins and 60 mins

The adsorption of colour in four samples: M1, M2, M3,

M4 were shown in Figure 5, the highest adsorption
capacity was reached after 10 minutes and 60 minutes.
There is a uniform in colour adsorption of all 4 AC
samples.

Figure.8. Sorption of chrome from the tanning wastewater by

produced activated carbons

5
 Corn Cob at 350oC, 2h, H3PO4 10% (Double – stage
N1
chemical activation)
Corn Cob at 350oC, 2h, H2SO4 10% (Double – stage
N2
chemical activation)
Straw rice at 350oC, 2h, H3PO4 5% (Singgle-stage
R1
chemical activation )
Rice straw 350oC, 2h, H2SO4 5% (Singgle-stage
R2
chemical activation )
Rice straw 350oC, 2h, H2SO4 5% (Double – stage
R3
chemical activation)
Figure 8 shows that, the activated carbons produced from
rice straw and corn cob such as N1, N2, R1, R2, R3 also
suitable to treatment Cr(III) with high concentration from
the tanning wastewater.
4.4 Economic efficiency
Using the agricultural wastes producing the activated
carbon bring the economic benefit not just for its cheap
and available material but also be an economical
adsorbent material for removal of heavy metal from some
industrial wastewaters: textile, tanning and plating and a
great treatment performance has been achieved. Besides,
the costs for treatment of the agricultural solid wastes as
well as for reducing the release of CO2 into the
atmosphere are considered to be reduced significantly.
5. CONCLUSION
In conclusion, the chemical activation method was used to
produced the activated carbons from agricultural wastes:
corn cob and rice straw. The experiments have shown that
H2SO4 and H3PO4 acids are efficient in the process of
producing the activated carbon. The study has found out
that the optimal conditions during the implementation
are: the impregnation ratio of 5% and soaking time of 120
min were found to be the optimal conditions for
producing the high surface area carbons (i.e. 1234 m2/g).
In all studies, rice straw AC exhibited a higher adsorption
capacity as compared with the corn cob AC and with the
commercial ones. ACs were demonstrated to have
excellent efficiency in the removal of colour and some
heavy metals in some kinds of industrial wastewater.
Under the experimental conditions investigated, the
resulting activated carbons are found as the micro-porous
materials. From the results, the resulting activated carbons
have been used to effectively treat the dye wastewater,
tanning wastewater, plating wastewater water, industrial
gas and indoor air environmental due to their high
adsorption capacities.
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