International Journal of Environmental Science and Development, Vol. 5, No.

2, April 2014

Preparation of Activated Carbon Derived from Rice Husk

by Simple Carbonization and Chemical Activation for
Using as Gasoline Adsorbent
Arunrat Cheenmatchaya and Sukjit Kungwankunakorn

 Latiflorus [5], mangosteen shell [6], oil plam shell [7] and
Abstract—Rice from Thailand is the top ranking of the world. jackfruit shell [8] have been studied for preparation of
The by-product of rice manufacturing is rice husk, which its activated carbon because of their proper properties. Thus, a
usefulness is not fully attempt. The aims of research are to make possible solving of rice husk is converting it into value-added
value-added activated carbons of rice husk and to study the
optimum conditions for gasoline adsorption using these
activated carbon used as adsorbents. In other words, the
activated carbons as adsorbents. All samples were analyzed for expensive commercial activated carbon will be reduced.
gasoline adsorption by gas chromatograph-mass spectrometry Normally, the manufacturing of activated carbons involves
(GC-MS). The activated carbon of rice husk, which activated by two major processes, carbonization of raw carbonaceous
H3PO4 at temperature of 450 ° C, has the highest adsorption materials in an inert atmosphere and activation of the
capacity. According to gasoline adsorption study, the optimum carbonized product. The activation process can be divided by
conditions were 0.1 g of activated carbon, 70 ° C of adsorption
two types; physical activation and chemical activation.
temperature and 30 minutes of adsorption time. Physical
characterization of the activated carbon obtained was However, chemical activation is widely applied because of its
performed by scanning electron microscopy (SEM). The results lower activation temperature and higher product yield
present that the activated carbon of rice husk possesses a high compared with physical activation [2]. With many earlier
apparent surface area (SBET = 336.35 m2/g). They thus studies, the activated carbons from agricultural wastes were
encourage the use of activated carbon of rice husk as an always studied on its characteristic and adsorption efficiency.
adsorbent for the qualitative analysis of gasoline in order to Many indicators such as iodine [2], methylene blue [2],
apply for gasoline sampling in arson case and to reduce the
analysis cost from commercial adsorbent. congo red [1] and metal ions such as cadmium [9] were used
to determine adsorption efficiency.
Index Terms—Rice husk, activated carbon, gasoline, The aims of this work were to utilize rice husk, agricultural
adsorption. waste, for the preparation of activated carbon by either
carbonization or chemical activation using H3PO4 as an
activating agent. The carbonized rice husk and chemical
I. INTRODUCTION activated rice husk were applied to use as gasoline adsorbents
Rice is regarded as main food of Thai people for a long for adsorption efficiency determination. In this work, SEM
time. Beside domestic consumption, rice is a major technique and BET theory were employed to determine the
agricultural product that extremely high exportation value. In physical characterization of studied adsorbent for the purpose
rice manufacturing, rice husk is the by-product from paddy of noncommercial adsorbents developing for gasoline
grinding. So far, rice husk has been successfully used as fuel sampling in forensic science.
in many industrial factories and used as biomass fuel in
electricity generating [1] because of its low humidity and
simple operation. Not only rice husk, their charcoal that II. EXPERIMENTAL
obtained from combustion step is also versatile. Both rice A. Material
husk and rice husk charcoal have major components namely,
Rice husk was collected from rice mill in Lamphun
carbon and silica. They have been found to be suitable
Province, Thailand. In this study, gasoline was selected to be
materials owing to their high carbon and silica and low ash
an adsorbate as it was found in arson scene frequently. Due to
contents. Consequently, they are determined to be the
low flash point and availability, gasoline was a good
precursors used for the production of activated carbon that
accelerant. Gasohol 95 was obtained from petrol station in
commonly used as adsorbents. Activated carbons have
Lamphun Province, Thailand.
exceptional adsorption properties because of their high
surface area, large adsorption capacity and fast adsorption B. Instrumentations
kinetics [2]. From previous studies, many agricultural wastes All samples were analyzed by gas chromatograph-mass
such as Jatropha curcas fruit shell [2], coconut shell [3], corn spectrometry (Agilent 6850-5973N, U.S.A.) which is used in
cob [4], Dendrocalamus asper Baker and Dendrocalamus the entire experiment. The HP-5ms column (Agilent, U.S.A.)
was employed. The injector port was set at 150 ° C and the
Manuscript received August 15, 2013; revised September 27, 2013. This carrier gas used was He at a constant flow of 1.0 mL/min. The
work was supported by the Institute for the Promotion of Teaching Science
and Technology (IPST). split ratio was 200:1 and the electron impact mode was
The authors are with the Chemistry Department, Chiang Mai University, applied for MS operation, choosing 70 eV as the electron
Chiangmai, Thailand (e-mail: arunrat_chem@ hotmail.com, energies, while the ion source temperature was set at 230 °C.
ksukjit@hotmail.com).

DOI: 10.7763/IJESD.2014.V5.472 171

 International Journal of Environmental Science and Development, Vol. 5, No. 2, April 2014

The solvent delay was 1.30 min. The details of the program determined based on adsorbent mass balance using equation;
used in GC-MS analysis were as follows: the initial
temperature of the GC oven is 100 °
C and hold for 2 min. The (Co - Ce )V
qe = (2)
temperature was increased from 100 to 200 ° C at a rate of 20 M
°C/min and hold at 200 °C. The total run time was 8.30 min.
where Co and Ce are the initial and equilibrium concentrations
C. Carbonization of Rice Husk of the gasoline (mg/L), respectively, V is the volume of the
The 20 g of rice husk samples were carbonized at 200 and dichloromethane (L) and M is the mass of adsorbent used (g)
400 °C for 1 hr in a muffle furnace (Barnstead, IA U.S.A.) in [11].
order to produce charcoal. The sample was crushed with
blender and sieved to a size smaller than 850 µm to obtain the
IV. RESULTS AND DISCUSSION
charcoal of rice husk (CRH).
A. Type of Adsorbent
D. Chemical Activation of Rice Husk
The 100 g of rice husk was subjected impregnation in 1
dm3 of 3 molar H3PO4 at 80 ° C for 3 hr. After that, it was
cleaned with DI water until its pH value was 7. The sample
was dried at 100 ° C for 24 hr. The 22 g of dried samples were
carbonized at 450 and 700 ° C for 2 hr in a muffle furnace
(Barnstead, IA U.S.A.). The charcoal was crushed and sieved
to a size smaller than 850 µm to obtain the activated carbon of
rice husk (ACRH).

III. OPTIMUM GASOLINE ADSORPTION CONDITIONS FOR

ACTIVATED CARBON OF RICE HUSK
Some parameters which had effect on the gasoline
adsorption for activated carbon of rice husk namely type of
adsorbent (CRH200, CRH400, ACRH450 and ACRH700),
amount of adsorbent (0.05-0.4 g), adsorption temperature
(60-90 ° C) and adsorption time (10 min-24 hr) were studied
to determine the optimal conditions for gasoline adsorption.
For adsorption and desorption procedures, activated
carbons of rice husk were filled in tea bags and hung in the
containers. The containers contained soil that spiked with 10
µg/mL gasoline. The samples were took to the oven
(Memmert, Germany) at given adsorption temperature for
given adsorption time. After that, dichloromethane was used
as solvent desorber for analysis of gasoline by GC-MS
technique.
Microstructure of the samples was examined using a
scanning electron microscopy (Jeol JSM-5410LV, Japan).
In this work, gasoline adsorption efficiency of activated
carbon of rice husk was considered by various equations for
each parameter.
A. The Relative Signal Value
To make the comparison of adsorption efficiency of
investigated adsorbents easier, the relative signal value was
calculated;

The relative signal value = x 100 (1)

y

where x is the mean signal value for the compound and

investigated adsorbent; y is the mean signal value for the
same compound and adsorbent that turn out to be more
effective with relation to this compound [10].
B. The Equilibrium Adsorption Capacity (qe)
For the study of amount of adsorbent, adsorption
temperature and adsorption time, the equilibrium adsorption Fig. 1. Representative chromatograms comparing the amount of gasoline for
capacities (qe) of the activated carbon of rice husk were CRH200 (a), CRH400 (b), ACRH450 (c) and ACRH700 (d).

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Examples of obtained chromatograms are shown in Fig. 1.

The 5 characteristic peaks of gasoline as listed in Table I
were investigated [12]. Evaluating the adsorption efficiency
of the 4 types of adsorbent for these compounds allows one to
estimate their suitability for the analysis of gasoline.

TABLE I: THE 5 CHARACTERISTIC PEAKS OF GASOLINE

Number Name Retention time (min) Formula
1 Toluene 1.803 C7H8
2 Ethylbenzene 2.133 C8H10
3 Xylene 2.171 C8H10
4 O-xylene 2.301 C8H10
5 3-ethyltoluene 2.690 C9H12

The results obtained are presented graphically. Fig. 2

presents the relative signal values of 4 types of adsorbent.
The uncertainty of the obtained relative signal values was
calculated on the basis of the standard derivation of means.
For CRH200, all of these compounds except
3-ethyltoluene was hardly adsorbed. Because CRH200 has
unsuitable physical properties due to its low carbonization
temperature, which used to produce the charcoal.
The results in Fig. 2 showed that ACRH450 turned out to
be more effective for the adsorption of gasoline than others.
SEM photographs in Fig. 3 show that the ACRH450
adsorbent (c) gives the texture with heterogeneous surface
and a variety of randomly distributed pore size. Furthermore,
it composes of an irregular and highly porous surface,
indicating relatively high surface area. This result can be
support by BET surface area of ACRH450 which is 336.35
m2/g.
Therefore, the ACRH450 adsorbent was chosen as the
optimum condition for further experiments.
B. Amount of Adsorbent
Theoretically, with increase of amount of adsorbent, the
adsorption became more intensive due to more amount
resulting in an increased surface area which was considered
to be the most important factor for adsorption. However,
when considering the qe value that based on adsorbent mass
balance, the results showed that unless the toluene
compound, the qe values of 0.05 and 0.1 g of adsorbent were
nearly the same. Ethylbenzene and 3-ethyltoluene which
could remain after extinguishment as reported previously
[13] were used to determine the conclusion.

Fig. 2. The bar graphs illustrate the effectiveness of CRH200, CRH400, Fig. 3. SEM photographs of CRH200 (a), CRH400 (b), ACRH450 (c) and
ACRH450 and ACRH700 in the adsorption of gasoline. ACRH700 (d).

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From the results as shown in Fig. 4, it illustrated that the D. Adsorption Time
highest qe values of ethylbenzene and 3-ethyltoluene were For the study on adsorption time, the results showed that
obtained when using 0.1 g of adsorbent. Thus, 0.1 g of increasing in adsorption time significantly decreased in qe
adsorbent was chosen as the optimum amount of adsorbent. value, which related to the results of adsorption temperature.
C. Adsorption Temperature This was due to the desorption, which might occur with the
high vapor density substance such as gasoline, rate of
The effect of adsorption temperature on qe value is
desorption at long adsorption time was higher than that at
illustrated in Fig. 5. It was shown that increasing in the
short adsorption time, then the possibility of gasoline leak
adsorption temperature resulted in the decreasing in qe value.
would be occurred.
This trend is expected because gasoline which had high vapor
As shown in Fig. 6, the qe value of 10 min, the shortest
density could evaporate more with high temperature, so the
time in this study, was not the most suitable condition among
adsorbent could not adsorb well.
the investigated adsorption times. The reason is that 10 min
The results present that instead of 60 ° C, 70 ° C is the
was insufficient for evaporation and adsorption of gasoline in
suitable temperature for gasoline adsorption because it gave
a container. A small amount of gasoline was adsorbed during
the highest qe value of ethylbenzene and 3-ethyltoluene. The
this period. Consequently, the optimum adsorption time for
adsorption temperature at 60 ° C could not be adequate for
gasoline adsorption was 30 min.
ethylbenzene and 3-ethyltoluene that had a high boiling In this study, the amounts of gasoline detected by GC-MS
point. Although 3-ethyltoluene had the highest qe value at 80 that represented in term of qe values were much lower than
°C, the standard deviation that observed from the error bar in spiked amount due to their volatile property. However, this
the graph has shown that the variance of qe value has a wide study focused on the qualitative analysis that can be used to
range. This is why 70 ° C seems to be the most proper identify gasoline in arson cases. So, the activated carbon of
adsorption temperature for activated carbon of rice husk. rice husk which could adsorb gasoline and show all 5
characteristic peaks deserved to be the gasoline adsorbent.

V. CONCLUSION
The value-added activated carbon of rice husk can be
produced by simple carbonization-chemical activation.
Carbonization at 450 ° C for 2 hr and using H3PO4 as an
activating agent was a suitable process. Under these optimum
conditions, BET surface area of the activated carbon of rice
husk was 336.35 m2/g. The adsorption efficiency of activated
carbon of rice husk which has the highest gasoline adsorption
was obtained when using 0.1 g of ACRH450 as adsorbent at
Fig. 4. The bar graphs illustrate the qe values of various amounts of 70 ° C adsorption temperature for 30 min of adsorption time.
adsorbent. Since the activated carbon of rice husk is high surface area
and gasoline adsorption capacity, therefore, it can be
employed as noncommercial adsorbent and considered as an
alternative one to commercial adsorbent. For further research,
these optimum conditions for gasoline adsorption using
activated carbon of rice husk as adsorbent will be used for the
study of residual gasoline detection in soil samples as
duplicated evidence in arson scenes.

ACKNOWLEDGMENT
The authors acknowledge stimulating discussions with the
group of Sukjit’s laboratory on the topics reported in this
Fig. 5. The bar graphs illustrate the qe values of various adsorption
temperatures.
study.

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