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Factor Affecting Microwave Assisted Preparation of Activated Carbon from

Local Raw Materials

Article  in  International Letters of Chemistry Physics and Astronomy · February 2015

DOI: 10.18052/www.scipress.com/ILCPA.47.15

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International Letters of Chemistry, Physics and Astronomy Vol. 47 (2015) pp 15-23 Online: 2015-02-24
© (2015) SciPress Ltd., Switzerland
doi:10.18052/www.scipress.com/ILCPA.47.15

Factor Affecting Microwave Assisted Preparation

of Activated Carbon from Local Raw Materials

M. A. Elsayed*, O. A. Zalat
Egyptian Armed Forces, Cairo, Egypt
*E-mail address: [email protected]

ABSTRACT
This study illustrates the preparation of activated carbon (AC) from Corn Cob (CC) via
microwave assisted K2CO3 activation. The effect of operational parameters including chemical
impregnation ratio (0.25-1.25), microwave power (90 – 800 W) and irradiation time (1 – 9 min) on the
carbon yield and adsorption capability of derived Corn Cob Activated Carbon (CCAC) were
investigated. The results indicated that the optimum conditions were as follows: microwave power of
600W, microwave radiation time of 5 min and the impregnation ratio of K 2CO3 was 0.75 g/g. The
optimum conditions resulted in CCAC with a maximum adsorption capacity of 275.32 mg/g for MB
and carbon yield of 27.09%. The BET surface area, Langmuir surface area and total pore volume were
determined to be 765 m2/g, 834 m2/g and 0.43 cm3/g, respectively.

Keywords: Activated carbon; Chemical Activation; Adsorption; Methylene blue; Microwave Corn
Cob

1. INTRODUCTION

The removal of toxic dyes from dilute or concentrated solutions has received a great
deal of attention in the last few decades. In recent years, stringent statutory regulations have
been introduced to reduce the discharge of dyes to low level at source, particularly from
textile, paper, cosmetics and food processing industries. The discharge of effluents from these
industries contain large amount of dyes which is toxic to aquatic life [1] .
This has been partially achieved by minimization and recycling of existing resources.
With the increasing demand for cleaner water, attention has been focused on improvements to
existing treatments and the development of new techniques and materials [2, 3].
The discharge of dyes into natural water impedes light penetration and destroy the
biological processes [4]. In addition, many dyes are toxic to some organisms causing direct
destruction of aquatic communities. Some dyes can cause allergic dermatitis, skin irritation,
cancer and mutation in man [5]. Wastewaters from dyeing industries released into nearby land
or rivers without any treatment because the conventional treatment methods are not cost
effective in the Egypt context.
As dyes are designed to resist breakdown with time, exposure to sunlight, water, soap
and oxidizing agent, cannot be easily removed by conventional wastewater treatment
processes due to their complex structure and synthetic origins [2, 6, 7]. Adsorption techniques
to remove dyes from water have been widely used. It has been found to be an economical and
effective treatment method for removal of dyes due to its sludge free clean operation [2].

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16 Volume 47

Adsorption is one of the most effective methods and activated carbon is the preferred
adsorbent widely employed to treat wastewater containing different classes of dyes,
recognizing the economic drawback of commercial activated carbon [4, 8] .
Many investigators have studied the feasibility of using inexpensive alternative
materials like pearl millet husk, date pits, saw dust, buffing dust of leather industry, coir pith,
crude oil residue, tropical grass, olive stone, almond shells, pine bark, wool waste, coconut
shell etc., as carbonaceous precursors for the removal of dyes from water and wastewater [3,
5, 9-11].
In present work, activated carbon was prepared from Corn Cob by microwave assisted
K2CO3 activation. Corn Cob was chosen as a natural and a promising alternative due to its
abundance and its low cost commercial value. Effects of the radiation time, impregnation ratio
of K2CO3 to Corn Cob, radiation power on the adsorption capacity and yield of the activated
carbon were researched to determine the optimum preparation conditions.

2. EXPERIMENTAL WORK

a. Materials and methods

Corn Cob (CC), an agricultural waste, was the precursor used in the present study. The
raw precursor was washed exhaustively with distilled water to remove adhering dirt from the
surface. Dried CC was cut, crushed, and screened to a particle size of 1–2 mm. The
carbonization process was carried out by loading 100 g of dried precursor into a modified
muffle furnace, under N2 gas flow (150 cm3/min) and heated up to a carbonization
temperature of 700 ◦C, at the heating rate of 10 ◦C/min. The char produced was mixed with
K2CO3 pellets with different impregnation ratio (IR), defined as:

(1)

where and are the dry weight of K2CO3 pellets (g) and Corn Cob (CC) (g).
A modified microwave oven with continuous output power and a frequency of 2.45
GHz was applied for the activation step. Nitrogen flow was used to purge air in the reactor
before microwave heating and it continued to flow during the cooling stage. The oven has a
power controller to select different power levels from 1 to 5 which is corresponding to 90,
180, 360, 600 and 800 W and a timer for various exposure times at a set microwave power
level. The activated samples were washed sequentially with deionized water and 0.1 M
hydrochloric acid until the pH of the washing solution reached 6–7. The yield was calculated
as the ratio of the dry weight of resultant activated carbon to the weight of the raw precursor.

b. Methylene Blue adsorption equilibrium experiments

The batch adsorption experiments were undertaken in a set of 250 mL Erlenmeyer

flasks containing 0.20 g of adsorbent and 200 ml of dye solutions within the initial
concentration range
of 50 – 500 mg/L. The mixture was agitated at 120 rpm and 25 ◦C until the equilibrium was
reached. The concentration of methylene blue (MB) dye solution was determined using
Agilant UV-Vis Cary 60 PC scan double beam recording spectrophotometer using (1) cm
glass cells at 668 nm.
The amount of adsorption at time t, Qt (mg/g) was calculated using the following formula
 International Letters of Chemistry, Physics and Astronomy Vol. 47 17

(2)

where Ct (mg/L) is the liquid concentration of dye at any time, C0 (mg/L) is the initial
concentration of the dye in solution. V is the volume of the solution (L) and W is the mass of
dye adsorbent (g). The amount of equilibrium adsorption Qe (mg/g) was calculated using the
formula.

(3)

where C0 and Ce (mg/L) are the liquid concentrations of dye initially and at equilibrium.

c. Characterization of Corn Cob activated carbon (CCAC)

The specific surface areas of AC produced by the optimum conditions as well as the
carbonized char were determined by the BET method using nitrogen as the adsorbate at 77K
utilizing the commonly used Autosorb instrument. Prior to the measurements, the samples
were out gassed at 300°C under nitrogen for at least 12h. Nitrogen adsorption isotherms of
AC and char were tested over a relative pressure (P/P0) range from 10-7 to 1. The total pore
volumes were estimated to be the equivalent liquid volume of the adsorbate (N2) at a relative
pressure of 0.99. The BET surface of the samples was calculated by the Brunauer-Emmett-
Teller (BET) equation.
Chemical characterization of functional groups was detected by Fourier transform
infrared spectrometer (FTIR-100, Perkin Elmer) in the scanning range of 4000–400 cm−1. The
adsorbent and potassium bromide (KBr) were dried in an oven and then ground together in a
ratio of 20:1 (KBr:AC) for FTIR measurement using disc sample method.

3. RESULTS AND DISCUSSION

3.1. Preparation of CCAC

3.1.1. Effect of chemical impregnation ratio

Effect of chemical impregnation ratio (IR) on the carbon yield and adsorption uptake of
MB was evaluated at the microwave power of 360W and irradiation time of 5 min. It was
found from Fig. 1 that increasing IR from 0.25 to 0.75 showed an enhancement of carbon
yield from 25.12 to 40.34%. Beyond the value, further increase in IR leads to a gradual
decrease of carbon yield. Similarly, increasing IR from 0.25 to 0.75 indicated an increase of
adsorption uptake from 120.31 to 250.79 mg/g, and then steadily decreased. The best
adsorption uptake and carbon yield of CCAC were obtained at the K2CO3/char ratio of 0.75.
The development of porosity by K2CO3 activation was associated with gasification reaction
with the formation of potassium, potassium carbonate and hydrogen [11]. When IR was lower
than 0.75, the carbons on the active sites reacted partially lowering the adsorption uptake and
carbon yield. As IR increased, it was assumed that metallic potassium formed during the
gasification process would diffuse into the interior of char matrix contributing to the
development of new porosities. Correspondingly, the adsorption uptake was further enhanced
[12]. When the ratio had reached to its optimum value, the active sites on the carbons had
18 Volume 47

reacted completely and the adsorption uptake had reached its maximum amount. Beyond the
optimum value, the catalytic oxidation entailed the widening of mesoporous structures and
carbon burn off [12].

Methylene Blue uptake Carbon Yield

260 45
Methylene Blue (MB) adsorption capacity (mg/g)

240
40
220

Carbon Yield (%)

200
35

180

30
160

140
25
120

100 20
0.2 0.4 0.6 0.8 1 1.2 1.4

Chemical Impregnation Ratio (IR)

Figure 1. Effects of chemical impregnation ratio on the carbon yield and MB adsorption uptake.
(preparation conditions: microwave power = 360W; radiation time = 5 min).

Identical results were observed by Foo and Hameed from the KOH activation of fruit
residue (biodiesel industry solid residue). Their results showed that the diffusion of metallic
potassium formed during the gasification process widens the exit pores and creates new pores.
The adsorption capacity, therefore, increased from 132.74 to 253.44 mg/g by augmenting the
impregnation ratio from 0.25 to 1.00 (wt%) at a microwave power level of 600 W and an
activation time of 7 min. At the optimum impregnation ratio, the carbons on the active sites
reacted completely with the KOH and the adsorption capacity was maximized [13].

3.1.2. Effect of microwave power

Effect of microwave power on the adsorption uptake and carbon yield was investigated
at the IR of 0.75 and irradiation time of 5 min. Fig. 2. Under low microwave power of 90 and
180 W, the pore structure was not adequately developed, and the adsorption uptake is slightly
increased however the carbon yield is decreased, indicating no continual reaction between the
char and activating agent. At higher microwave power of 360 and 600 W, the adsorption
uptake was drastically increased, mainly attributed to the combined effect of internal and
volumetric heating widening the existing pores. Meanwhile, the loss rate of carbon increased
proportional to the microwave power level, possibly due to the fierce reaction at higher
thermal radiation which resulted in greater weight loss of the carbon sample. At high radiation
power of 800 W, over gasification might occur with detrimental impact of reducing surface
area and porosity, thus the adsorption uptake and carbon yield were progressively decreased.
 International Letters of Chemistry, Physics and Astronomy Vol. 47 19

Methylene Blue uptake Carbon Yield

300 38
Methylene Blue (MB) adsorption capacity (mg/g)
36

250
34

Carbon Yield (%)

32
200
30

28
150

26

100 24
0 200 400 600 800 1000

Microwave power (W)

Figure 2. Effects of microwave power on the carbon yield and adsorption uptake (preparation
conditions: chemical impregnation ratio=0.75; radiation time=5 min).

3.1.3. Effect of radiation time

Microwave radiation time is another decisive factor affecting the adsorption uptake and
carbon yield. Effect of radiation time was conducted at the IR of 0.75 and microwave input
power of 600W (Fig. 3). Generally, prolonging radiation time from 1 to 5 min exhibited an
enhancement of adsorption uptake from 175.99mg/g to 265.05 mg/g, and beyond the limit,
the adsorption uptake was slightly decreased. Meanwhile, the loss rate of carbon was found
increased proportional to the radiation time. The result implied that prolonging radiation time
promoted an acceleration of energy, which in turn increased the reaction rates, thus developed
the internal porosity of the CCAC. The best conditions were inferred at the IR of 0.75,
microwave power of 600W and irradiation of 6 min. Beyond this condition, further heat
treatment might produce local hotspots, which considerably destroyed the pore walls between
the adjacent pores. This work resulted in higher adsorption uptake as compared previous
studies [10].
20 Volume 47

Methylene Blue uptake Carbon Yield

280 45
Methylene Blue (MB) adsorption capacity (mg/g)

260
40

240

Carbon Yield (%)

35

220

30
200

25
180

160 20
0 2 4 6 8 10
Radiation time (min)

Figure 3. Effects of radiation time on the carbon yield and adsorption uptake (preparation conditions:
chemical impregnation ratio=0.75; microwave power=600W).

Guo and Lua [14] used a different microwave power level and activation time to
investigate the effects of these variables on the properties of AC. At low microwave power
levels of 80, 150 and 300 W with an exposure time of 60 min, the microwave radiation has no
effect on the density and total porosity of the prepared AC. No reaction occurs between the
char and the agent at the lower power levels, but at the high microwave power levels of 450
and 750 W, the total pore volume increased progressively with increasing microwave
radiation time. They attained an increase of 20.9% in the total porosity of the AC by
increasing the exposure time from 5 min to 1 h at the microwave power level of 750 W. The
pores created during carbonization would, therefore, be enlarged by a combination of the
effects of continual carbonization and the carbon–CO2 reaction. New pores will be created
and formed by increasing the reaction time.

3.2. Textural and surface characterization of CCAC

Detailed characteristics of the porosities of CCAC and that of carbonized char were
summarized in Table 1. The total pore volume was estimated by converting the amount of N 2
gas adsorbed at a relative pressure of 0.95 to equivalent liquid volume of the adsorbate (N2).
The mesopore volume was determined by subtracting micropore volume from the total pore
volume. From Table 1, it was evident that the micrpores of CCAC account about 72% of the
total pore volume, with a well developed porous structure. The micropore volume, external
surface area and micropore surface area that deduced from the t-method were tabulated in the
same table. In the present study, it can be found that the BET surface area, Langmuir surface
 International Letters of Chemistry, Physics and Astronomy Vol. 47 21

area, and total pore volume of CCAC were greatly improved compared to char, implying
development of additional pores during the microwave irradiation stage [15-17].

Table 1. Porosity structures of CCAC and carbonized char.

Properties CCAC Carbonized char

BET surface area (m2/g) 765 507
Micropore surface area (m2/g) 682 436
External surface area (m2/g) 534 380
Langmuir surface area (m2/g) 834 567
Total pore volume (cm3/g) 0.43 0.32
Micropore volume (cm3/g) 0.31 0.26
Mesopore volume (cm3/g) 0.12 0.06
Average pore size (Å) 25.3 22.1

The FT-IR spectra of the carbonized chare and CCAC were shown in Fig. 4. It is seen
that the absorbance bands were observed to have peaks at 3441.6, 2352.5, 2336.6, 1627.7,
1604.0, 1346.6, 1120.8, 1053.3 cm−1. Most of these bands have been reported by other
investigators for different carbon materials. The band at around 3441.6 cm−1 can be assigned
to the –OH stretching vibration mode of hydroxyl functional groups[9]. The bands located at
about 2352.6 and 2336.6 cm−1 are attributed to the C≡C stretching [18]. The peak at 1627.7
cm−1 and 1604.0 cm−1 were the characteristics of the C-O stretching vibration of lactonic and
carbonyl groups[14]. The peaks occurring at 1346.5, 1120.8 and 1053.3cm−1 are all ascribed
to oxygen functionalities such as highly conjugated C-O stretching, C-O stretching in
carboxylic groups, and carboxylate moieties[17].

Figure 4. FTIR spectrum of the Corn Cob Activated Carbon (CCAC) and the carbonized char.
22 Volume 47

4. CONCLUSION

Activated carbons with well-developed microporosity and high surface areas can be
manufactured from agricultural waste (corn cob) using microwave assisted chemical
activation by K2CO3. Experimental results showed that microwave heating could shorten the
processing period, and remarkably, produce a high-quality activated carbon. CCAC prepared
by microwave assisted K2CO3 activation attained maximum BET surface area as 765.75 m2/g,
total pore volume as 0.43 cm3/g and a high contribution of micropores as 72% at IR of 0.75,
microwave power of 600 W and irradiation time of 5 min. These best conditions resulted in
activated carbon with a maximum adsorption capacity of 275.32 mg/g for MB and carbon
yield of 27.09%, respectively.

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( Received 01 January 2015; accepted 16 January 2015 )

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Factor Affecting Microwave Assisted Preparation of Activated Carbon from Local Raw Materials
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