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CSSR 06’07

THE REMOVAL OF BASIC DYE (METHYLENE BLUE) FROM AQUEOUS


SOLUTIONS BY ADSORPTION ON ACTIVATED CARBON
PREPARED FROM PALM OIL FIBRE

Fairus Muhamad Darus, Rusdin Laiman and Mohd Nizam Yusof


Department of Environmental Technology
Faculty of Applied Sciences, Universiti Teknologi MARA, Shah Alam

Abstract

Adsorption is as an alternative technology to remove colour from wastewater. In this


study, activated carbon, prepared from low cost palm oil fibre has been utilised as the
adsorbent for the removal of basic dyes from aqueous solution. A basic dye, Methylene
Blue has been used as the adsorbate. Experiments were conducted by varying several
parameters namely pH, adsorbent dose, initial concentration of dye and contact time.
Colour was effectively been removed at all selected pH, and the increase in activated
carbon dose showed an increase in the removal’s percentage. The percentage of colour
removal decreased with increasing of initial dye concentration. The adsorption equilibrium
for colour was reached after 90 minutes of contact time. The adsorption followed both
Langmuir and Freundlich isotherms. Results obtained indicate that palm oil fibre could be
employed as a low cost alternative to commercial activated carbon in wastewater
treatment for dye removal.

1. Introduction

Colour can be considered as the earliest pollutant to be detected in polluted water.


The extensive use of dyes, in both dye manufacturing and consuming industries create
significant problems due to the discharged of coloured wastewater. The presence of very
small amounts of dyes in water (less than 1 ppm for some dyes) is highly visible and
affects the quality of waterbodies (Banat et.al, 1996). Dyes can be divided into several
categories, based on their chemical nature whether anionic or cationic dye, and basic or
reactive dyes. The discharge of highly coloured industrial wastewater also contributes
appreciable concentrations of materials with highly biochemical oxygen demand (BOD)
and significant amount of suspended solids (Mckay, 1984).

Besides the effect to the environment, dyes can also cause deterioration in human’s
health. Some dyes are found to be toxic, mutagenic and carcinogenic (Chen et al., 2003).
Dyes released by the industries can get into the water bodies and eventually contaminate
the water supply system. Consumption of dye-polluted water can cause allergy reactions,
dermatitis, skin irritation, cancer and mutation both in babies (Garg et al., 2003) and
grown-ups. In addition, this problem can impact several vital activities such as fisheries,
livestock and agriculture since the polluted water is no longer suitable for their particular
use.

Many regulations have been enacted to regulate the effluent discharged by the industries.
These regulations aim to control and limit several parameters in the effluent wastewater.
Colour is one of the parameters concerned. For instance, the Environmental Quality
(Sewage and Industrial Effluents) Regulation, 1979, limits the colour present in the final
discharged by the industries to 10 Hazen for Standard A and 50 Hazen for Standard B
(Environmental Quality Act, 1974). Dyes discharged, mainly from textile industries, are

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often found exceeding these limits along with other parameters such as COD, BOD,
dissolved oxygen and total iron (Tan et al., 2000).

Removing colour from wastewater can be done via several methods namely chemical,
biological and physical (Walker et al., 1998; Chern et al., 2001; Namasivayam et al.,
2001a; Yang et al., 2001; Annadurai et al., 2002; Robinson et al., 2002b; Gupta et al.,
2003; Janos et al., 2003; Rozada et al., 2003). Chemical methods use coagulation or
flocculation combined with flotation and filtration, precipitation-flocculation, electro-
flotation, electrokinetic coagulation and ozonisation to remove colour. Biological colour
treatment utilizes fungi, bacteria or other biomass (either dead or alive) and is widely
accepted due to its economical advantage. This method however requires longer
treatment period.

Physical methods often applied are either using membrane filtration or adsorption
techniques. Among these two, adsorption has been found to be superior due to
advantages it offers in initial cost, flexibility and simplicity of design, ease of operation and
insensitivity to toxic pollutants. Generation of harmful substances also can be avoided by
applying this technique (Crini, 2006).

Many types of sorbent are available for sorption. However, activated carbon is found to be
the most popular adsorbent. Commercial activated carbons were prepared from various
sources such as charred bone, wood and incomplete combustion of gases. Yet, it is quite
expensive and ineffective against disperse and vat dyes. Therefore, many studies were
carried out to vary the sources of raw material which can be activated. Wastes from agro-
based industries are of attention mainly because of their abundance. Production of
activated carbon from this source may reduce the cost of wastewater treatment, and at
the same time open new market for low-cost agricultural by-product.

In this study, waste fibre generated from oil palm mill has been chosen as the raw material
to be activated. The availability of this source together with its characteristics has made
palm oil fibre a suitable choice to be activated. The result of this study is hoped to provide
useful information on the efficiency of activated carbon prepared from palm oil fibre for
colour removal.

2. Methodology

2.1 Preparation of activated carbon from palm oil fibre

300g of sun-dried palm oil fibre was mixed with concentrated H2SO4 (17.5M) (1:2
v/w) and left to dry at room temperature for 24 hours. Dried material was put into an oven,
heated at 180oC for 24 hours. The samples were then allowed to cool at room
temperature in an inert atmosphere. The product resulting from the activation step was
blended in order to form a granular activated carbon and washed with 3M NaOH per 100
g of product. The carbon product then was vacuum-filtered through Whatman 2 V filter
paper and washed repeatedly with distilled water to remove all traces of the acid and
alkali i.e until the pH of the rinsed water was constant. The product was wet-screed and
dried at 80°C overnight.

2.2 Aqueous solution

Stock solution of Methylene Blue (1000 mg/l) was prepared and diluted to the
required initial concentration. Adsorption experiments were carried out at room
temperature.

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2.3 Adsorption experiments

The initial and final concentrations of Methylene Blue were determined by


measuring at 663 nm using spectrophotometer. 100 ml of Methylene Blue solution with
required dose of activated carbon was shaken 200 rpm. The initial pH of the solutions was
adjusted to the required value (range: 3-9) by adding 1M NaOH or 1M H2SO4 solution.
Experimental variables considered were (i) different initial concentration of dye; (ii) pH; (iii)
adsorbent dose and (iv) contact time between adsorbent and dye solution.

2.4 Separation techniques

For separation between adsorbent and solution, the sample was centrifuged at
200 rpm at predetermined times. The supernatant was measured using UV-
spectrophotometer at 663 nm to determine the percentage of colour removed.

2.5 Analysis of the data

Data was analysed by calculating the percentage removal of dye and the amount
adsorbed (in mg/g) using equations below:

Percentage removal = 100 (Ci . Cf) / Ci


Amount adsorbed (qe) = (Ci . Cf) / m

where Ci and Cf are initial and final concentration (in mg/L) of dye respectively,
and m is the mass of activated carbon (in mg/L).

Deionised water was used for each series of experiments as controls. The average values
of duplicates run were obtained and analysed.

The adsorption data was analysed with the help of the following linear forms of Freundlich
and Langmuir isotherms:

Freundlich Isotherms: log qe = log kf + (1/n) log Ce

Langmuir Isotherms: (Ce/qe) = (1/Qob) + (Ce/Qo)

where;

log kf = the adsorption capacity,


1/n = an indictor of adsorption effectiveness,
qe = amount of dye adsorbed per unit mass of adsorbent (in
mg/g)
Ce = the equilibrium concentration of dye (in mg/L),

Qo and b were the Langmuir constants, which measures of monolayer (maximum)


adsorption capacity (in mg/g) and energy of adsorption (in g/L), respectively. The values
of Freundlich and Langmuir parameters were obtained from the linear correlations
between the values of:

i) log qe and log Ce (Freundlich)

ii) (Ce/ qe) and Ce (Langmuir)

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The observed statistically significant (at 95% confidence level) linear relationships as
evidence by r-values (close to unity) indicate the capability of these two adsorption
isotherms. Other essential characteristics of the Langmuir isotherms can be described by
a separation factor RL; defined by the following equation:

RL = 1/(1 + b Ci)

Where;
Ci = initial concentration of dye (in ppm or mg/L) and
b = the Langmuir constant (in g/L).

The characteristics of separation factors can be referred in Table 1.

Table 1:The characteristics of separation factor, RL

RL value Nature of adsorption


process

RL > 1 Unfavourable
RL = 1 Linear
0 < RL < 1 Favourable
RL = 0 Irreversible

3. Result and discussion

3.1 Effect of pH on dye removal in aqueous solution

The effect of pH on the amount of adsorption was studied by varying the initial pH
of dye solution and keeping the other process parameters as constant. The experiments
were carried out at different pH (pH 3 – 9) for different dye concentration (50, 70 and 100
mg/L) and constant carbon dosage of 2.0 g. The results are shown in Figure 1. The data
indicates that the colour removal using activated carbon prepared from palm oil fiber is pH
independent.

50 mg/l 70 mg/l 100 mg/l


Amount Removal (%)

100.0
99.5
99.0
98.5
98.0
97.5
3 4 5 6 7 8 9
pH

Figure 1: Effect of pH on dye removal using activated carbon prepared from palm oil fibre
(dose = 2 g, temp = 27 ± 1 oC, time: 120 min, particle size: < 105 µm)

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3.2 Effect of different initial dye concentration

The removal of dye increased with increase in initial dye concentration (Figure 2).
The amount of dye removed increased when initial dye concentration is increased from 50
mg/L to 100 mg/L with 99.5% and 99.4% for 1 and 2 g adsorbent dose respectively. It is
clear that the removal of dye was dependent on the concentration of dye. These results
are comparable to other similar previous studies (Kannan and Meenakshisundaram, 2002;
Namasivayam et al., 2001a; 2001b).

1g 2g
Amount Removal (%)

100.0

99.5

99.0

98.5

98.0
50 60 70 80 90 100
Initial Dye Concentration (m g/L)

Figure 2: Effect of different initial dye concentration on dye removal using


activated carbon prepared from palm oil fibre
o
(pH = 7.2, temp = 27 ± 1 C, time: 120 min, particle size: < 105 µm)

3.3 Effect of adsorbent dose and contact time

The effect of adsorbent dose on the amount of dye adsorbed is shown in Figure 3.
The removal percentage increases when the adsorbent dose increased from (0.2-2.0
g/100 ml) at 50, 70 and 100 mg/L dye concentration. Varying the adsorbent mass may
affect the porosity of the adsorbent suspension. A larger mass of adsorbent could adsorb
larger amount of dyes due to the availability of more surface area of the adsorbent
(Namasivayam et al., 1996; 2001a; 2001b).

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50 mg/l 70 mg/l 100 mg/l

Amount Removal (%)


120.0
100.0
80.0
60.0
40.0
20.0
0.0
0.2 0.4 0.8 1.2 1.6 2
Adsorbent Dose (g)

Figure 3: Effect of adsorbent dose on dye removal using activated carbon prepared from palm oil
fibre
o
(pH = 7.2, temp = 27 ± 1 C, time: 120 min, particle size: < 105 µm)

The colour’s removal percentage increases with the increase of contact time and remains
constant after a particular time as shown in Figure 4. Removal of dyes increased rapidly in
the beginning but then slowed down until it reaches the equilibrium time. The equilibrium
times for all different initial dye concentration were reached after 90 min treatment. After
reaching the equilibrium the adsorbate species normally forms a surface layer, which is
only one molecule thick, on the surface of the adsorbent which prevent further attachment
of dyes molecule to it (Kannan and Meenakshisundaram, 2002).

50 mg/l 70 mg/l 100 mg/l

100.0
Amount Removal (%)

98.0

96.0

94.0

92.0

90.0
30 60 90 120 150 180
Contact Tim e (m inute)

Figure 4: Effect of contact time on dye removal using activated carbon


prepared from palm oil fibre
o
(dose = 2.0 g, pH = 7.2, temp = 27 ± 1 C, particle size: < 105 µm)

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3.4 Adsorption isotherms

Adsorption data for a wide range of adsorbate concentration and adsorbent doses
have been analyzed using Langmuir and Freundlich isotherms in order to find the
adsorption capacity of activated carbon prepared from palm oil fibre (Figure 5 and 6).

4.0
Ce/qe (mg/g)

3.0

2.0

1.0 y = 0.0399x + 0.0735


R2 = 0.9986
0.0
0 20 40 60 80 100
Ce (m g/L)
Figure 5 : Langmuir isotherms for the removal of Methylene Blue by adsorption of activated carbon
prepared from palm oil fibre

1.5

1.0
log qe

0.5 y = 0.1825x + 0.8669


R2 = 0.823
0.0
0.0 0.5 1.0 1.5 2.0 2.5
log ce
Figure 6: Freundlich isotherms for the removal of Methylene Blue by adsorption of
activated carbon prepared from palm oil fibre

The linear plots of Langmuir isotherms will determine whether the activated carbon
prepared from palm oil fiber can be used as low cost adsorbent by calculating the
separation factor RL by using Langmuir equation. The linear graph of Langmuir isotherms
also represents the correlation coefficient and the value of intercept that is interpreted in
Table 2. The linear plots of log qe and log Ce show the strength of adsorption capacity.

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Table 2: The Langmuir and Freundlich parameters of adsorption isotherms

Dye Langmuir isotherm Freundlich isotherm


Qo b Correlation RL Intercept Slope Correlation
coefficient (kf) (1/n) coefficient
(r) (r)
Methylene 26.65 0.005 0.9986 0.8000 0.8669 5.479 0.8230
blue

The applicability of the Langmuir isotherm with the RL values showed to be in the range of
0-1 indicates that the adsorption process is favourable as low cost adsorbents. According
to Choy et al., (1999), Namasivayam et al., (2001a, 2001b, 2002), Tsai et al., (2001),
Rozada et al., (2003) and Wong et al., (2004), Langmuir isotherms based on the
assumption that maximum adsorption corresponds to saturated monolayer of dye
molecules on the adsorbent surface. The energy of adsorption is constant and there is no
transmigration of adsorbate in the plane of the surface of activated carbons.

The Freundlich isotherm describes equilibrium on a heterogeneous surface where energy


of the adsorption was not equivalent for all adsorption sites, thus allowing multi-layer
adsorption. The larger the value of adsorption capacity, kf , the higher the adsorption. The
more heterogeneous the surface will bring the 1/n value closer to zero (Tsai et al., 2001;
Azira et al., 2004). Values of kf and n were calculated from the slope and intercept of the
Freundlich plots respectively.

The magnitude of the exponent ‘n’ gives an indication of the favourability and kf the
capacity of the adsorbent/adsorbate system. Result from this experiment shows the n
values ranging between 1 and 10, indicating beneficial adsorption. Comparison of
Langmuir and Freundlich isotherms between previous studies and the present study can
be referred in Table 3.

Table 3: Langmuir and Freundlich isotherms of activated carbon prepared from various
material

Activated Langmuir isotherm Freundlich isotherm Reference


carbon RL B Intercept Slope
(kf) (1/n)
Palm oil 0.8000 0.005 0.8669 5.479 This work
fiber
Bamboo 0.083 0.120 0.683b 0.514b Kannan et al.,
dust 2001

Coconut 0.001 0.091 0.620b 0.677b


shell

Groundnut 0.072 0.128 0.698b 0.524b


shell
a a
Coir pith 0.62 5.17 Namasivayam
et al., 2001
Dye: Methylene Blue
a
Langmuir isotherm was not followed
b
Freundlich isotherm was not followed

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4. Conclusion

The results of present study show activated carbon prepared from low cost palm oil fibre
have suitable adsorption capacity in removing Methylene Blue from its aqueous solution.
The adsorption is highly dependent on contact time, adsorbent dose and adsorbate
concentration. Adsorption trends are found to follow both Freundlich and Langmuir
isotherms.

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