Dhaka Univ. J. Sci.

60(2): 185-189, 2012 (July)

Removal of Methylene Blue from Waste Water Using Activated Carbon Prepared from
Rice Husk
Mohammad Arifur Rahman, S. M. Ruhul Amin and A. M. Shafiqul Alam*
Department of Chemistry, University of Dhaka, Dhaka-1000, Bangladesh
Received on 01. 06. 2011. Accepted for Publication on 22. 02. 2012.

Abstract
The possible utilization of rice husk activated carbon as an adsorbent for the removal of methylene blue dye from aqueous
solutions has been investigated. In this study, activated carbons, prepared from low -cost rice husk by sulfuric acid and zinc
chloride activation, were used as the adsorbent for the removal of methylene blue, a basic dye, from aqueous solutions.
Effects of various experimental parameters, such as adsorbent dosage and particle size, initial dye concentration, pH and flow
rate were investigated in column process. The maximum uptakes of methylene blue by activated rice husk carbon at
optimized conditions (particle sizes: 140 m; Flow rate: 1.4 mL/min; pH: 10.0; initial volume of methylene blue: 50 mL and
initial concentration of methylene blue: 4.0 mg/L etc.) were found to 97.15%. The results indicate that activated carbon of
rice husk could be employed as low-cost alternatives to commercial activated carbon in waste water treatment for the
removal of basic dyes. This low cost and effective removal method may provide a promising solution for the removal of crystal violet dye
from wastewater.

Key words: Methylene blue, wastewater, activated carbon, rice husk.

I. Introduction In the present investigation, attempts have been made
to explore for the removal of methylene blue (MB)
About 15% of the total world production of dyes is lost
with activated carbon prepared from rice husk.
during the dyeing process and is released as liquid
effluents1. Color removal from such wastes is one of the II. Experimental
most difficult requirements, faced by the textile finishing,
Preparation of activated charcoal from rice husk
dye manufacturing, pulp and paper industries. Among the
various types of dye, various cationic dyes, including Rice husk was collected from Comilla district,
mythelene blue, are used in dye, paint production and Bangladesh. Then it was washed and oven dried. Then,
wool dyeing. Methylene blue is also used in part of the dried rice husk was soaked in concentrated
microbiology, surgery, diagnostics2,3 and as a sensitizer in H2SO4 in an amount sufficient to cover the raw
photo-oxidation of organic pollutants4. materials completely, mixed vigorously for 30 min, and
then left for 2 h. After mixing, the slurry was subjected
The effluent containing dyes are highly colored, resulting
to drying at 100C in an oven for 24h. Chemical
in major environmental problems. As international activation of the rice husk was performed with ZnCl2 as
environmental standards are becoming more stringent, well. Ten grams of rice husk was well mixed with 100
these colored wastes need treatment before disposal. mL of a concentrated solution that contained 10g of
Several methods for the removal of dyes have been ZnCl2. The mixing was performed at 50 C for 1h. After
developed. Physical methods, mainly adsorption on mixing, the slurry was also subjected to drying at 100
various supports, are the most frequently used5. Biological 0
C for 24 h. The resulting impregnated solids were
methods such as biodegradation have been proposed. placed in a beaker and heated to a temperature of 300
However, due to the low biodegradability of dyes, C under a nitrogen flow at a rate of 150cm3 min-1 STP
conventional biological waste water treatment processes at 100 C for 1h. The products were washed sequentially
are not very efficient for the treatment of dyeing wastes6. with 0.5M HCl, hot water, and finally cold distilled
Chemical treatment processes (ozonation and water to remove residual organic and mineral materials
chlorination) are more effective7, 8. The photocatalytic and then dried at 110C18. The physicochemical
degradation over solid support is an interesting recent characteristics of activated carbons prepared from rice
proposition9-11. M. Bielska et al. and S. Wang et al. husk was carbon; yield, 36%; ash content (3%);
studied the removal of methylene blue using micellar moisture content (4.28%); bulk density (0.84 g/mL);
enhanced ultrafiltration, fly ash and red mud and coal BET surface area (681m2/g); total pore volume
respectively12-15. However, adsorption is one of the (0.42cm3/g); mean pore radius (24.2 A) 18.
promising methods to remove the dye pollutants Preparation of methylene blue solution
from aqueous system completely16-17.It was,
therefore, thought worthwhile to develop highly About 0.1 g of methylene Blue (C16 H18 N3 SCl. 3 H2O) was
efficient and effective adsorbents for the removal taken in a 100 mL volumetric flask and diluted up to the mark
of dye from the textile effluents. by addition of deionized water. 0.5 mL of the stock solution

*Author for correspondence. [email protected]; [email protected];

186 Mohammad Arifur Rahman, S. M. Ruhul Amin and A. M. Shafiqul Alam

was pipetted out in a 250 mL volumetric flask and the III. Results and Discussion
volume was adjusted by addition of deionized water. The
Optimization of particle size
resulting concentration of the solution was 2.0 mg/L.
Similarly 4.0, 6.0 and 8.0 mg/L dye solutions were Effect of particle sizes on removal of methylene blue was
prepared by pepetting out 1.0, 1.5 and 2.0 mL of the stock investigated. Column adsorption experiments were carried out
solution respectively in a number of separate 250 mL for the removal of methylene blue from aqueous solution
using three particle sizes 140 m, (141-355) m and (356-
volumetric flasks.
425) m. The results are shown in Fig. 1. It shows that
Analysis of crystal violet solution removal efficiency of methylene blue was decreased with
increasing particle size of AC (activated carbon). About
Crystal violet solution was analysed by using UV-Visible
94.10% of methylene blue was removed with particle size 140
spectrometer (UV-160A, Shimadzu, Japan) at a m, whereas 92.30% removal efficiency was found with
wavelength of 665.0 nm. particle size 141-355m and 90.20% with particle size 356-
Preparation of column 425 m. From the above findings, it is clear that methylene
blue removal efficiency increases with decreasing particle
For the treatment of single adsorbent, firstly glass wool size. Therefore particle size 140m was chosen for next
was inserted into the column which acted as a support for experiments. The removal efficiency increasing with
the adsorbent. The soaked adsorbent with water was decreasing particle size is was probably due to the fact that,
poured into column and the water was then allowed to with the decrease of particle size, the surface areas of the
pass through the column. In this way dissolved materials adsorbents were increased, which provide greater number of
and coloured substances were washed out form the sites for adsorption.
adsorbent. Further few milliliter of deionized water was
added to complete removal of these unwanted substances. 96

This water was then drained out 95

94
Adsorption and analytical procedures
Removal efficiency (%)

93
The adsorption experiments were carried out in columns 92
that were equipped with a stopper for controlling the 91
column elute flow rate (treatment rate) as represented in
90
figure 1. Adsorption factors including the amount of each
89
adsorbent (2.0-6.0) g, particle size (90-425) m, treatment
88
flow rate (1.0-2.2) mL/min, initial sample concentration
(2- 1000) mg/L, and pH (1-12) were evaluated. After the 87

pH had been adjusted to the desired value with HCl and 86

<140 141-355 356-425
NaOH solutions, the sample solution (50 mL) was passed
Particlesize(m)
through the adsorption column at a given flow rate. The
treatment flow rates of 1.4 mL/min correspond to Fig. 1. Effect of particle size on the removal of methylene blue by
retention times of, 109 s, 58 s and 29 s, respectively. The adsorption on acid activated carbon. Initial MB concentration: 4
mg/L; Amount of AC: 2 g; Volume of methylene blue solution: 50
packing density of the treatment column was 0.32 g/cm3. mL; Flow rate 0.6 mL /min.
The flow rate was kept constant by controlling the stopper
valve. The removal treatment was performed at ambient Optimization of amount of adsorbent
temperature. The number of experiments for the removal The effect of the amount of adsorbents on the removal of
of methylene blue was greater than five. The removal methylene blue was investigated. For all the experiments,
(adsorption) efficiency was calculated using the equation: initial concentration of methylene blue solution was kept
constant at 4 mg/L, initial volume was 50 mL and particle size
Removal efficiency (%) = [(C0-Ce)/C0] x 100 was 140 m. The results were depicted in Fig. 2 shows that
Where, C0 = Concentration of methylene blue in the removal efficiency was increased sharply with increasing
sample solution before treatment amount of activated carbon up to 3.0 g. Then removal
efficiencies were not changed significantly with increasing
Ce= Concentration of methylene blue in the sample amount of adsorbent. It shows that removal efficiency was
solution after treatment. 74.36% when the amount was 2.00 g. For 3.00 g, it was
93.70% and 97.15% for 4.00 g.
Removal of methylene blue from waste water using activated carbon prepared from rice husk 187

Optimization of initial concentration

100 Removal efficiency is greatly depended on the initial
90 concentration of solution of adsorbate. For the evaluation of
the effect of initial concentration, 50 mL solution of different
Removal efficiency (%)

80

70 initial concentrations was treated onto the adsorbent. Initial

60
concentration was varied from 2 mg/L to 8 mg/L. The results
50
were illustrated in Fig. 4.
40

30
100
20
98
10

Removal efficiency (%)

1 2 3 4 5 96
Amount of adsorbent (g)
94

Fig. 2. Effect of adsorbent amount on the removal of methylene 92

blue by adsorption on acid activated carbon. Initial MB 90
concentration: 4 mg/L; particle size: 140 m; Volume of
88
methylene blue solution: 50 mL; Flow rate 0.6 mL /min.
86
That is adsorption efficiency increased due to the
84
increased number of adsorption sites. Therefore, removal
efficiency reached in equilibrium with the amount of 3.0 g 82

of activated carbon. 2 4 6 8 10

Optimization of flow rate Concentration (mg/L)

The effect of the treatment flow rate on the removal of

methylene blue was investigated. It is presented in Fig. 3. Fig. 4. Effect of initial concentration on the removal of methylene
It could be clearly understood from the figure that blue by adsorption on activated carbon. Amount of adsorbent: 3g;
particle size: 140 m; Volume of methylene blue solution: 50 mL;
removal efficiency decreases with increasing flow rate.
flow rate: 1.0 mL/min.
About 98.43% of methylene blue was removed at flow
rate 1.0 mL/min, where as 96.81% of methylene blue was It shows that removal efficiency was decreased with
removed at flow rate 1.4 mL/min and similarly 91.86% of increasing of initial concentrations, although the amount of
methylene blue was removed at flow rate 1.8 mL/min. total methylene blue accumulation increased. The total
These phenomena might be due to the fact that when the
accumulation of methylene blue increased with increasing
flow rate was slow methylene blue in the sample solution
got more contact time with the active surface of the initial concentration was probably due to more contact of
adsorbents. However flow rate 1.4 mL/min was chosen adsorbent sites with methylene blue. The removal efficiency
for the next experiments because it makes the removal decreased with increasing adsorbate concentration in the
process faster. solution. From this experiment it was observed that about 99%
methylene blue was removed using 2 mg/L. In addition,
100
98.5% methylene blue was removed at initial concentration 4
95
mg/L. For initial concentration 6 mg/L removal efficiency was
Removal efficiency (%)

89.81%. Therefore, initial concentration 4 mg/L was chosen

90 for the next method optimization work. At low concentration,
85
most of methylene blue in the sample solution might contact
with active sites of adsorbent and when the concentration is
80 increased all methylene blue species will not be available to
75
contact with the active surface due to active sites are already
filled up.
70
1.0 1.2 1.4 1.6 1.8 2.0 2.2 Optimization of initial volume
Flow rate (mL/min)
It is desired to obtain the optimum condition for the
Fig. 3. Effect of flow rate on the removal of methylene blue by development of a noble method for a methylene blue removal.
adsorption on acid activated carbon. Initial MB concentration: 4 It is also required to investigate the effect of initial volume.
mg/L; amount of adsorbent:2g; particle size: 140 m; Volume
of methylene blue solution: 50 mL.
Different initial volumes with optimized concentration of 4
mg/L were treated onto activated carbon prepared from rice
188 Mohammad Arifur Rahman, S. M. Ruhul Amin and A. M. Shafiqul Alam

husk. It shows that removal efficiency decreases with Table1. Removal and Desorption of Methylene Blue from
increase of initial volume. The removal efficiency was the waste water by the Developed Method*
100% when the volume of methylene blue solution was Sampl pH Initial MB Final MB Removal Desorpti
50.0 mL. For initial volume 100 mL, the removal e no concentrati concentrati (%) on (%)
on (mg/L) on (mg/L)
efficiency was 98.70% and for 150 mL, the removal
efficiency was 80.16% and similarly decreased for 1 7.49 2.28 0.22 87.50 85
successive higher initial volumes. This removal efficiency 2 7.5 2.20 0.21 87.40 84
decreases probably due to increased contact of adsorbate 3 7.45 2.02 0.20 87.00 85
with available sites of adsorbent.
*Amount of activated rice husk: 3.0 g; Particle size : <140 m;
Effect of pH on the removal of methylene blue Flow rate: 1.4 mL/min; Desorption: 4 M NaOH, 100 mL;
Standing time: 20 minute
Fig. 5 indicates the effect of pH on the removal of
methylene blue in the presence of activated carbon. When The concentration of methylene blue in the treated sample
initial pH of the dye solution was increased from 3 to 11, water could be lowered to 0.22 mg/L. Desorption of
the percentage removal increased from lower to higher. methylene blue from the activated carbon was also studied.
The desorption efficiency of 100 mL MB solution was 85%
The increasing trend of removal of the methylene blue
with 4 M NaOH. These results indicate that the adsorbed
with increasing pH is dependent on the nature of the methylene blue could be recovered from the surface of
adsorbent. At lower pH, the percentage of the removal of activated carbon.
methylene blue was 40%. Interestingly, at higher pH, the
Probable removal mechanism
trend of the removal was increased.
It is known that ionic dyes upon dissolution release colored
dye anions/cations into solution. The adsorption of these
100
charged dye groups onto the adsorbent surface is primarily
influenced by the surface charge of the adsorbent which is in
90
turn influenced by the solution pH. Methylene blue is a basic
Removal efficiency (%)

dye. In water it produces cation (C+) and reduced ions (CH+).

80 If the solution pH is above the zero point of charge the
negative charge density on the surface of the activated carbon
70 increases, which favors the sorption of basic (cationic) dyes18.
In addition, the basic dye will become protonated in the acidic
60 medium and the positive charge density would be located
more on the dye molecules at low pH results the lower uptake.
50 IV. Conclusion

40
From the results of this study it may be concluded that the
2 3 4 5 6 7 8 9 10 11 12 utilization of activated carbon prepared from rice husk
pH materials in a column system may offer a practical mean for
an effective treatment of wastewater contaminated with
Fig. 5. Effect of pH on the removal of methylene blue by methylene blue. Further investigation is required to study the
adsorption on acid activated carbon. Amount of adsorbent: 3 g; removal mechanism of methylene blue by activated carbon.
particle size: 140 m; Volume of methylene blue solution: 50
mL; flow rate: 1.0 mL/min. ------------------
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Table 1.
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