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American Journal of Applied Chemistry

2015; 3(3-1): 1-7


Published online November 19, 2014 (http://www.sciencepublishinggroup.com/j/ajac)
doi: 10.11648/j.ajac.s.2015030301.11
ISSN: 2330-8753 (Print); ISSN: 2330-8745 (Online)

Synthesis and characterization of nano-activated carbon


from el maghara coal, Sinai, Egypt to be utilized for
wastewater Purification
M. F. Elkady1, 2, *, M. M. Hussein3, M. M. Salama3
1
Chemical and Petrochemical Engineering Department, Egypt-Japan University of Science and Technology, New Borg El-Arab City,
Alexandria, Egypt
2
Fabrication Technology Department, Advanced Technology and New Materials and Research Institute (ATNMRI), City of Scientific Research
and Technological Applications, Alexandria, Egypt
3
Chemical Engineering Department, Faculty of Engineering, Alexandria, Egypt

Email address:
maroelkady@yahoo.com (M. F. Elkady)

To cite this article:


M. F. Elkady, M. M. Hussein, M. M. Salama. Synthesis and Characterization of Nano-Activated Carbon from El Maghara Coal, Sinai, Egypt to
be Utilized for Wastewater Purification. American Journal of Applied Chemistry. Special Issue: Nano-technology for Environmental Aspects.
Vol. 3, No. 3-1, 2015, pp. 1-7. doi: 10.11648/j.ajac.s.2015030301.11

Abstract: This study targeted to evaluate the availability of extraction the nano-activated carbon from el maghara coal that
represents as Jurassic coal deposits in the Maghara area, Sinai, Egypt to be utilized as adsorbent material for methyl orange dye
decontamination from polluted wastewater. Nano-activated carbon was prepared through the alkaline and acidic activation of el
maghara coal with potassium hydroxide and phosphoric acid respectively at different conditions such as activation temperature,
activation time and activating agent/ carbon ratio. The maximum removal for methyl orange with the extracted nano-activated
carbon was recorded to be 90%. This efficient nano-activated carbon was synthesized through the reaction of el maghara coal
with potassium hydroxide with 1:2 weight ratios for 90 minutes. Then the yielded powder material was carbonized at 600ºC for
90 minutes. The physical and chemical characteristics of raw coal and the most efficient extracted nano-activated carbon material
were examined using different techniques such as scanning electron microscopic and infrared spectroscopy analysis. The
different factors affecting the methyl orange treatment process onto the most efficient prepared material will be optimized using
the batch technique. The equilibrium time for dye sorption process onto the prepared nano-activated carbon was established at
120min. the improvement at both the agitation speed and the material dosage has positive effect on the dye sorption process. The
maghara coal was establish to be suitable resource for Nano-ctivated carbon extraction as an adsorbent after alkaline and thermal
activation of the raw el maghara coal for the removal of methyl orange dye from polluted industrial wastewater.

Keywords: Nano-Activated Carbon, Dyes Adsorption, Low Cost Adsorbents, Wastewater Treatment

1. Introduction
Dyes are widely used in industries such as textiles, rubber, carcinogenic and can cause severe damage to human beings,
paper, plastics, cosmetics etc. A large variety of dyestuffs is such as dysfunction of kidney, reproductive system, liver,
available. They can be conveniently classified according to brain and central nervous system [1,2].Treatment of dye-based
their type, which reflects their macroscopic behavior(acid, effluents is considered to be most challenging in the
basic, reactive, direct, disperse, sulphur and metallic dyes) and environmental fraternity and the industries, the recent
also according to their prevailing properties (porosity, surface stringent regulations compound the problem further .
area).Disposal of this colored water from dyeing industries Respecting to the large degree of organics present in these
into receiving water generally may be toxic to aquatic life. The molecules and the stability of modern dyes, conventional
dyes upset the biological activity in water bodies. They also biological treatment methods are ineffective for their removal
pose a problem because they may be mutagenic and [3, 4]. This led to the study of other effective methods.
2 M. F. Elkady et al.: Synthesis and Characterization of Nano-Activated Carbon from El Maghara Coal, Sinai, Egypt to be
Utilized for Wastewater Purification

Adsorption is major technique that used for dyes removal from reagents. The activation process was initiated in a 250-ml
wastewater [5]. It has many advantages over several other glass-stopper flask through mixing 2 g of the as-received coal
conventional treatment methods for wastewater treatment. with a solution consisting of 50 g of water and 4g of a
These include (i) less land area , (ii) lower sensitivity to diurnal chemical reagent. The flask was immersed in a
variation, (iii) not getting affected by toxic chemicals, (iv) constant-temperature shaker bath, with a shaker speed of 150
greater flexibility in the design and operation and (v) superior rpm. The mixing was performed at 80◦C and lasted for 2 h.
removal of organic contaminants [6]. After mixing, the coal slurry was subjected to vacuum drying
Activated carbon is the most widely used adsorbent for at 110◦C for 8h. The resulting chemical loaded samples were
this purpose because of its extended surface area, micro then carbonized in a horizontal cylindrical furnace.
porous structure, high adsorption capacity and high degree of Carbonization was carried out by heating the samples at 30◦C
surface reactivity. However, commercially available activated min from room temperature to carbonization temperatures in a
carbons are very expensive [7-9]. Therefore, studies are now range of 400–700◦C, followed by holding the samples at the
focusing on new natural adsorbents with low cost and local carbonization temperature for 90 minutes before cooling
availability, such as chitosan, bentonite, zeolite, clay minerals, under N2.
olive mill residue, flay ashes, coal, rice husk, waste tea leaves, After cooling the carbonized products that have been
peanut hull pellets and bio sorbents. This study targeted to treated with KOH and H3PO4 were subjected to washing by
evaluate the availability for activated carbon extraction from stirring with 250 ml of 0.5 N HCl solutions at 80◦C for 30 min,
el maghara coal to be utilized as adsorbent material for followed by filtration for powder separation. The acid-washed
methyl orange dye removal. The synthesis of high samples were then leached by mixing with 250 ml of distilled
performance activated carbons is feasible using maize talks water at 80◦C for several times until the pH value of the
and KOH activation. Note that recent studies have showed water–carbon mixture was between 6 –7. The leached
that it is possible to use natural wastes (e.g., egg shell products were then dried by vacuum at 110◦C for 8 h to give
residues) to produce alternative and low cost activating the nano-activated carbon products. For the samples treated
agents for improving the adsorption properties of activated with H3PO4, the washed solution was alkalized with NaOH
carbons for heavy metal removal [10]. Analysis of coal rank instead of the HCl and the samples were leached by distilled
parameters indicated that the maghara coal can be classified water to reach a pH value between 6 –7.
as medium volatile bituminous coal [11].The optimum
conditions of chemical activation for nano-activated carbon 2.2. Characterization of Synthesized Nano-Activated
production and the best condition for treatment of the Carbon
produced activated carbon were evaluated. In order to have a better understanding the difference in the
properties between the raw el Maghara coal and the prepared
2. Experimental nano-activated carbon, different physico-chemical
characterization techniques was examined. The Fourier
2.1. Chemical and Thermal Modification of El Maghara Transform Infrared spectrum (FTIR - 8400 S Shimadzu, Japan)
Coal was used in order to determine the chemical structural change
on the Maghara coal sample after the chemical and thermal
El Maghara coal was used as the starting raw material for activation. Furthermore, the Scanning Electron Microscope
nano-activated carbon production. The proximate and ultimate (SEM-JEOL JSM6360 LA, Japan) was used to study the
analyses of the raw coal are shown in table 1. Unless otherwise structural features of the carbon surface. The crystalline
specified, the particle sizes of the coal used for carbon structure of the prepared materials was established using XRD
preparation were within a range of 0.4–0.6mm. (X-ray powder diffractometry).
Table 1. The ultimate and proximate analysis of Maghara coal [12] 2.3. Batch Technique for Dye Decolonization Using the
Parameters Values (%) Prepared Materials
-Proximate analysis
Ash 4.12
In order to screen the efficiency of the different prepared
Moisture 2.65
samples after the chemical and thermal modifications, the
Volatile 50.6 batch technique was utilized for testing the material
Fixed carbon 40.00 performance for dye decontamination. The experiments were
-Ultimate analysis performed through mixing 0.25 g from the prepared material
Carbon 71.44 with 50 ml from M.O (methyl orange) solution in the
Hydrogen 6.62 concentration of 100 ppm in closed bottles. The mixture was
Oxygen (by diff) 9.1 stirred at room temperature (25±2) 0C for 2 hours at 200 rpm
Nitrogen 2.27 as determined from the pre-performed kinetic tests. The
Sulphur 3.8 percentage removal of dye was calculated using the following
relationship:
Chemical activation of el Maghara coal was performed
using potassium hydroxide and phosphoric acid as the Percentage removal % = {(Ci-Cf)/Ci}*100 (1)
American Journal of Applied Chemistry 2015; 3(3-1): 1-7 3

Where, Ci= initial dye concentration, Cf= final dye treatment process with the increase at the reactant ratio. So,
concentration. 2/1 weight ratio from the raw coal to the potassium hydroxide
The different factors affecting at the batch process for dye was recorded as the optimum reactant ratio at the reaction time
decontamination using the most efficient prepared material of 90min.
will be tested such as contact time, dye concentration and
material dosage.

3. Results and Discussion


Respecting to the preparation of nano-activated carbon
from Maghara coal through the coal activation principally
consists of two consecutive steps which are impregnation of a
chemical reagent followed by carbonization. The
experimental results are discussed separately as follows.
3.1. Influence of the Chemical Modification Process onto
the Dye Decontamination Efficiency of the Prepared
Materials
(a) (b) (c)
The influence of both the reactants weight ratios and the Figure 2. Effect of Reagent /coal ratio on methyl orange removal onto the
carbonization temperatures either for alkaline or acidic different prepared materials after the treatment with KOH at 600 0C.
treatment will be tested onto the performance of the produced
materials for methyl orange dye decolorization process. 3.1.2. Effect of the Carbonization Temperature onto the
Material Performance
3.1.1. Effect of the Reactant Weight Ratios onto the As an attempt to enhance the performance of the different
Material Performance prepared materials produced from both the alkaline and the
The influence of the different alkaline and acidic reactants acidic chemical modification processes, the carbonization
ratio using potassium hydroxide and phosphoric acid temperature of these materials will be varied in the range
respectively on the percentage dye removal of the produced (400-600ºC) to determine the most proper carbonization
materials was monitored to determine the optimum reactant temperature that yield the highly efficient material for dye
ratios with the type of the chemical reaction. For the acidic decolorization. Regarding to the acidic treatment, it was
chemical modification, Fig.1 investigates that the increase at indicated from Fig.3 that there is a slight improvement at the
both the reaction time and the reactant weight ratios has dye decolorization from 30% to 70% as the carbonization
positive effects on the dye decolorization efficiency of the temperature increased from 400 to 700 ºC at the high reactant
produced materials. ratios from the raw coal to the phosphoric acid.

Figure 1. Effect of Reagent /coal ratio on methyl orange removal onto the
different prepared materials after the treatment with phosphoric acid at 600
0
C.
Figure 3. Effect of carbonization temperature on methyl orange removal onto
However, this improvement at the dye decolorization the different prepared materials after the treatment with phosphoric acid
efficiency of the prepared materials with the increase at both
For the equivalent ratios from the raw coal to the
the reaction time and the reactant weight ratios was scaled up
phosphoric acid (1:1), the dye percentage decolorization
in the case of the alkaline treatment. It was evident from fig.2
increased from 10 to 40%. This improvement at the dye
that the methyl orange decolorization process improves as the
decolorization is comparatively low compared with the
potassium hydroxide to raw coal ratio increases especially for
alkaline activation process. It was indicated from Fig. 4 that
the alkaline treatment that takes place for short reaction
the increment at the carbonization temperature from 400 to
periods. As the alkaline treatment period increases
700 ºC increases the percentage dye removal from 5% to
above90min, there is no significant improvement at the dye
4 M. F. Elkady et al.: Synthesis andd Characterization
Cha of Nano-Activated Carbon from El Maghara
hara Co
Coal, Sinai, Egypt to be
Utilized for Wastewater Purification

around 90% for the high alkaline to raww cool


coo ratio above 1:1. stretching vibration modee of hhydroxyl functional groups.
So, the predetermined optimum reactant ant ratio
rat of 2/1 weight These surface functional group
groups can serve as active sites
ratio from the raw coal to the potassium ssium hydroxide was where chemical transformations
ations occur via surface reactions.
confirmed as the most efficient alkalinealine activation ratio. These results illustrated that tthe most efficient prepared
Moreover, the optimum carbonization ion ttemperature was material represented as activated
ivated carbon [14].
detected at 6000C for the alkaline potassium
ssium treatment [13].

(A)
Figure 4. Effect of carbonization temperature on methy
ethyl orange removal onto
the different prepared materials after the treatment with potassium hydroxide

3.2. Characterization of the Most Efficient


ient P
Prepared
Material

The crystalline, chemical and morpholog


hological structures of
the most efficient prepared material that
at recorded
reco the highest
dye decontamination will be examined to be b compared with
the raw Maghara cool using XRD, FTIR R and SEM. Firstly the
chemical structures of the raw cool was as co
compared with the
efficient prepared sample using FTIR, Fig. ((5 a, b) shows the
FTIR spectra of the two samples. It wass indic
indicated that the raw
coal sample exhibited noticeable IR R bands
ban below 1700
cm‾¹and between 2750 and 3250 cm‾¹. m‾¹. The
T broad band
represented at approximately 1200 cm‾¹may
cm‾¹m due to the (B)
overlapping of C–O–C stretching, C–O O stretching
stre and O–H Figure 5. FTIR spectrums of raw maghara
ma cool (A) and the prepared
bending modes of alcoholic, phenolic and carboxylic
ca groups. activated carbon (B)
The band at 1600 cm‾¹is assignedd to C═C stretching
conjugated with another C═C bond, an aromatic
arom nucleus, or a In order to confirm itss crystalline
crys structure, the XRD
C═O bond. It has been reported that at the C═C stretching spectrum of the prepared sample
ample was compared with the raw
frequently occurs at approximately 1600 cm‾¹for cool and investigated at Fig.
g. (6a, b).
carbonaceous materials .The bands att around
aroun 2900 cm‾¹are
assigned to alkyl groups such as –CH3,, ═CH2 and –CH2CH3.
The weak band at around 3500 cm‾¹cann assiassigned to the O–H

(A)
America
merican Journal of Applied Chemistry 2015; 3(3-1): 1-7 5

(B)
Figure 6. XRD spect
pectrums of raw maghara cool (A) and the prepared activated carbon
on (B)
(

The XRD spectrums showed the crystallin


stalline structure of the The surface of the primary Magahara
Ma cool was constricted,
carbon layers for the raw coal and activated
vated carbon.
c There are comprising mainly macro and mesopores without a deeper
two broad diffraction peaks around 2θ = 26º26 and 42 º in each pore structure. Conversely, the th image of the produced
spectrum, that corresponding to the planes
lanes of orientations of activated carbon displayed a well pronounced porosity, with a
(002) and (100), respectively. It is general
enerally expected that series of irregular cavitiesies distributed
di over the surface.
increasing the pre-carbonization temperatu
perature promotes the Moreover, noticeable nano-siz size spherical particles were
growth of the graphitic micro-crystallites and sharpens at the indicated as a light spots at the m
material surface that represents
XRD peaks of the produced activated carbon
rbon compared
c with the the morphology structure of the prepared activated carbon.
raw cool as indicated from Fig.6. So, thee XRD results confirm The average diameter of these particles was about 70nm.
the FTIR observations to confirm that hat the
th most efficient Comparison of the surface morphologies
morp verified substantial
prepared material represented as an activated
vated carbon
c [14]. changes occasioned by both the chemical and thermal
In order to identify the morphological
al structures
stru of the raw modification process [15]. Accordingly,
Acc the most efficient
Magahara cool and the most efficient prepared
prepar material after prepared material is activated
tivated carbon and produced at
the chemical and thermal modification process,
proce SEM images nano-scale.
for both the raw cool and the produced activ
activated carbon were
investigated at Figure 7. 3.3. Batch Technique for Dyee Decolonization
D Using the
Prepared Nano-Activated
ed CCarbon

In order to optimize the methyl


m orange dye treatment
process using the most efficie
efficient prepared nano-activated
carbon, the different main facto
factors affecting in the treatment
process will be examined.
3.3.1. Effect of Contact Time
The effect of contact timee on th
the percentage removal of MO
dye onto the prepared nano-activ
activated carbon was investigated
at Fig. 8. The percentage removal
remo of dye was rapid in the
beginning and the rate of removal
remov of MO was higher, due to
the availability of more thann required
requ number of active sites on
(A)
the surface of carbons and becomes
becom slower at the later stages
of contact time, due to the decreas
ecreased or lesser number of active
sites. The equilibrium timee for theth dye sorption process onto
the prepared material was 120mi
120min.

(B)
Figure 8. Effect of contact time on the MO dye sorption process onto the
Figure 7. SEM images of raw maghara cooll (A)
(A and the prepared
prepared nano-activated carbon
nano-activated carbon (B)
6 M. F. Elkady et al.: Synthesis and Characterization of Nano-Activated Carbon from El Maghara Coal, Sinai, Egypt to be
Utilized for Wastewater Purification

3.3.2. Effect of Mixing Speed 10 ppm to 150 ppm. This results is owing to the lack occur at
Figure 9 indicated that the improvement at the mixing speed the available active sites for the dye sorption onto the prepared
from 0 rpm to 250rpm increase the percentage dye removal nano-activated carbon at high initial dye concentration [17].
from 35% to 90%. This enhancement in the dye sorption
process was due to the increase at the diffusion rate between
the dye and the particles of the nano-activated carbon.

Figure 11. Effect of initial dye concentration on the MO dye sorption process
Figure 9. Effect of mixing speed on the MO dye sorption process onto the
onto the prepared nano-activated carbon
prepared nano-activated carbon
3.3.5. Effect of Solution pH
3.3.3. Effect of Material Dosage
Solution pH affects adsorption by regulating the adsorbents
The effect of dose of adsorbent on the percentage removal
surface charge as well as degree of ionization of adsorbates
of MO dye was investigated at the equilibrium dye sorption
present in the solution. The effect of pH was conducted
time of 120min and the maximum agitation speed of 250rpm
varying the pH of dye solutions from 2 to 12 with an initial
and the results shown at Fig. 10.The percentage removal of
concentration of 10 mg/L, as shown in Fig. 12. A significant
MO increased with the increase in dose of the prepared
enhancement was noticeable at the dye removal onto the
nano-activated carbon. These results may be due to the
prepared nano-activated carbon at pH value of 7. Lower
increase in availability of surface active sites available for dye
adsorption at strong acidic pH is due to the protonation of MO
hosting onto the adsorbent material [16]. Moreover, it was
and high mobility oh H3O+ ions competing with the dye ions
indicated from the figure that the optimum dosage from the
for the adsorption sites [16]. At higher pH, the nano-activated
prepared nano-activated carbon was recorded at 0.25g/L.
carbon may become negatively charged and the formation of
where after this dosage the increase at the percentage dye
electric double layer changes its polarity, consequently dye
removal is not detectable compared with the increment at the
uptake decreases.
material dosage.

Figure 12. Effect of solution pH on the MO dye sorption process onto the
Figure 10. Effect of material dosage on the MO dye sorption process onto the
prepared nano-activated carbon
prepared nano-activated carbon

3.3.4. Effect of Initial Dye Concentration 4. Conclusion


The effect of initial methyl orange concentration (10
ppm–150 ppm) on the removal efficiency using the Nano-activated carbon was successfully prepared from
predetermined optimum amount from the prepared waste carbon source of Maghara cool presents at the Sinai
nano-activated carbon of 0.25g was showed in Fig. 11. As Desert in Egypt using simple chemical and thermal
seen from results, the sorption yield of dye was decreased with modification process. It was evident from scanning electron
increasing the initial dye concentration over the studied range microscopic analysis that the external surface of the prepared
especially for the higher studied dye concentrations above 50 material after the chemical and thermal treatment that it had
ppm. Where the removal efficiency at 120min decreased from large cavities compared with the raw cool and produced with
92.7% to 50.5% as the MO dye concentration increased from high porosity. Both XRD and FTIR confirm the chemical and
American Journal of Applied Chemistry 2015; 3(3-1): 1-7 7

crystalline structure of the prepared nano-activated carbon. [7] B. Singh, and N. Rawat, "Comparative sorption equilibrium
The optimum treatment conditions that attain the most studies of toxic phenols on fly ash and impregnated fly ash", J
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efficient prepared nano-activated carbon material was
recorded through the alkaline chemical treatment of the raw [8] G. McKay, G. Prasad, and P. Mowli, “Equilibrium studies for
cool using potassium hydroxide followed by carbonization the the adsorption of dyestuff from aqueous solutions by low cost
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removal within the equilibrium time was recorded at 0.25g/L. Bonilla-Petriciolet, M. Montes-Morán, and M. Pérez-Cruz,
the increment and decrement at the pH solution value around 7 "Role of the pericarp of Carya illinoinensis as biosorbent and as
declines the dye sorption process onto the prepared activated precursor of activated carbon for the removal of lead and acid
carbon. blue 25in aqueous solutions", Journal of Analytical and
Applied Pyrolysis, vol. 92, pp. 143-151, 2011.

[11] H. Baioumy, "Mineralogical and Geochemical


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