Synthesis and Characterization of Nano A
Synthesis and Characterization of Nano A
Synthesis and Characterization of Nano A
Email address:
maroelkady@yahoo.com (M. F. Elkady)
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.
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
(A)
Figure 4. Effect of carbonization temperature on methy
ethyl orange removal onto
the different prepared materials after the treatment with potassium hydroxide
(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)
(
(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
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
Chem Technol Biotechnol., vol. 61, pp. 307–17, 1994.
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
resultant powder at 600ºC for 90min. the different parameters materials", Water Air Soil Pollution, vol.29, pp. 273–83, 1986.
affecting the methyl dye removal onto the prepared [9] S. Khare, K. Panday, R. Srivastava, and V. Singh, "Removal of
nano-activated carbon using the batch technique was Victoria blue from aqueous solution by fly ash”, J Chem
optimized. The equilibrium dye sorption time was recorded at Technol Biotechnol., vol. 38, pp. 99–104, 1987.
120min. the optimum material dosage the record 92.4% dye [10] V. Hernández-Montoya, D.Mendoza-Castillo, A.
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.