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P. Tarapitakcheevin, P. Weerayutsil, and K.

Khuanmar / GMSARN International Journal 7 (2013) 83 - 90

Adsorption of Acid Dye on Activated Carbon Prepared from


Water Hyacinth by Sodium Chloride Activation

Panupong Tarapitakcheevin, Panomchai Weerayutsil, and Kulyakorn Khuanmar

Abstract— The adsorption of acid dye (AB80) onto the prepared adsorbents from water hyacinth, Hyacinth Black
Carbon (HBC) and Hyacinth Activated Carbon (HAC), were investigated. Batch isotherm studies were carried out
under varying experimental conditions of contact time, temperature, and pH. The adsorption efficiency study was also
compared to the Commercial Activated Carbon (CAC). The study results indicated that the prepared adsorbents from
hyacinth, HBC and HAC, could be substantially used for the adsorption of acid dye (AB80) as compared with the
commercial activated carbon, CAC. The HAC also presented the comparable efficiency to CAC. Base on the Langmuir
isotherm, the monolayer adsorption capacity was determined to be 5.75, 56.50, and 100.00 mg/g for HBC, HAC, and
CAC, respectively. The RL values showed that all adsorbents were favourable for the adsorption of acid dye (AB80).
Base on Freundlich isotherms, the magnitudes of 1/n for Freundlich isotherms were revealed to lie between zero to one,
indicating that acid dye (AB80) is favorably adsorbed by all three adsorbents. The results of isotherm adsorption study
elucidated that HBC was fitted to Langmuir model with high correlation (R2) of 0.997 while HAC and CAC were well
fitted to Freundlich model with favorable correlation (R2) of 0.990 and 0.991, respectively.

Keywords— Adsorption, acid dye (AB80), water hyacinth, sodium chloride activation, activated carbon.

been recognized for the production of activated carbon


1. INTRODUCTION with high developed porosity. Furthermore, this
procedure leads to high yield by activating at low
Water hyacinth (Eichhornia crassipes) is a free-floating temperture as well [9]. Activating agents used in the
perennial aquatic plant and it was introduced to Thailand chemical process are normally KOH, NaOH, H3PO4,
in 1901 during the reign of King Rama V from Indonesia ZnCl2, Na3PO4, NaCl, KMnO4 for various raw materials
as ornamental plant. Nowadays, water hyacinth changed to yield for activated carbon [10]. Among of these
itself form the decorated flower to problematic weed due chemical agents, NaCl shows attractive property because
to its fast spread and congested growth (over 60 kg/m2). of inexpensive and non toxic.
The floating mats of water hyacinth obstruct navigation This study aimed to investigate the possibility of
and clog irrigation works. Although water hyacinth is activated cabon prepared from water hyacinth by
seen as a weed and worthless, there are many researches chemical activation using sodium chloride (NaCl) as an
reported its application for water tretment due to its activating agent for removal of color from acid dye in
dominant structure is fibrous tissue which is capable to aqueous solution.
be an adsorbent for pollutants removal from water [1-5].
Water pollution from textile industry is a challenge 2. MATERIALS AND METHODS
problem due to large volume of colored wastewater and
its low biodegradability. Effluents discharged from 2.1 Preparation of adsorbent
textile industry into recieving water might be toxic to
Water hyacinth was collected from Sritan Pond at Khon
aquatic life, and colored water reduce sunlight
Kaen University, Khon Kaen, Thailand. It was
transmission through water. Especially when even just
thoroughly washed to remove dirt particles and its
1.0 mg/L of dye concentration in water supply, it could
spongy inflated petioles (leaf stalks) and separated as a
be inappropriate for human consumption [6, 7].
piece to prepare for an adsorbent. Then it was dried in
Adsorption is an effective process for removal of
sunlight for a week and dried in an oven at 103 oC for 24
contaminants from wastewater. Activated carbon is the
hours. The dried material was burnt without oxygen at
most widely used as an adsorbent because of its
600 oC for 2 hours to obtain Hyacinth Black Carbon
advantage on high adsorption capacity for both organic
(HBC). To prepare hyacinth activated carbon (HAC),
and inorganic compounds. The adsorption capacity of
HBC was chemically activated using 1:1 of NaCl and
activated carbon is usually related to their specific
HBC by weight and followed by carbonization at 800 ๐C
surface area and porosity. In addition, the adsorption
property of activated carbon is found to strongly depend for 2 hours. Then, HAC was washed with distilled water
on the activation process [8]. Chemical activation has for several times. Both HBC and HAC were crushed to
pass a sieve with apertures of 125 µm and kept in an
airtight container for adsorption studies. To compare the
adsorption properties between prepared carbons and
Panupong Tarapitakcheevin, Panomchai Weerayutsil, and Commercial Activated Carbon (CAC), the powder
Kulyakorn Khuanmar (corresponding author) are with Department of
Environmental Engineering, Faculty of Engineering, Khon Kaen
activated charcoal Fluka 0512 supplied from Sigma
University, Khon Kaen 40002, Thailand. Email: kulyakorn@kku.ac.th. Aldrich was selected to use in this study.

83
P. Tarapitakcheevin, P. Weerayutsil, and K. Khuanmar / GMSARN International Journal 7 (2013) 83 - 90

2.2 Characterization of the activated carbons adjusting the pH of the solution with 0.1 M HCl and 0.1 M
NaOH solutions.
Adsorbent was characterized as a specific surface area
(SBET) by the conventional adsorption of N2 at 77 K 2.6 Adsorption isotherms
(Autosorb I MP, Quantachrome). The morphology of the
The adsorption isotherm studies were determined by
adsorbents, after being coated with gold, was
contacting a constant mass 0.1 g of adsorbent material
characterized by SEM (LEO SEM 1450VP, U.K.).
with a range of different concentrations of dye solutions
2.3 Preparation of dye solution from 5, 10, 20, 40, 60, 80, 120, 160, and 200 mg/L and
the solutions were adjusted to neutral pH. All
The adsorption studies were carried out with color of
experiments were conducted in 250 ml of glass bottle
Acid Blue 80. The acid dye (AB80) was used without
with working volume of 50 ml. The mixture of each
further purification. Acid Blue dye has an empirical
batch was constantly agitated by orbital shaker at speed
formula of C32H28N2Na2O8S2, molecular weight of
of 200 rpm and controlled temperature at 25 οC. After
678.68 g/mol, and its chemical structure of the acid dye
equilibrium time shaking, water samples were filtered
is shown in Fig.1. The dye solution of 1000 mg/L was
with filter disk 0.45 µm to remove the adsorbent and the
prepared from Acid Blue 80 (dye content 40 %) for
water samples were measured concentration by UV-Vis
single solution which was dissolved in heated deionized
Spectrophotometer. The experimental results were
water and made up to 1000 ml for the concentrated stock
evaluated in terms of fitting with Langmuir and
solution. The concentration of acid dye was analyzed by
Freundlich model.
Shimadzu-1601 UV-visible using the maximum UV
absorption (λmax) of acid dye solution that was fixed for
3. RESULTS AND DISCUSSION
measuring its color concentrations.
3.1 Characterization of adsorbents and adsorbate
The prepared adsorbents as Hyacinth Black Carbon
(HBC) and Hyacinth Activated Carbon (HAC),
characterized for the specific surface area (SBET) and
morphology are shown in Table 1. Specific surface areas
(SBET) of prepared adsorbents without and with activation
were found to be 158.22m2/g and 745.13m2/g,
respectively. Fluka 05120 selected as the representative
of Commercial Activated Carbon (CAC), with BET
results from other researchers reported that its surface
Fig. 1. The chemical structure of Acid Blue 80.
area is in the range of 788-1110 m2/g.

2.4 Effect of contact time Table 1. Physical properties of adsorbents


The effect of contact time of three adsorbents (HBC, Total
Surface Mean
HAC, and CAC) was investigated at 20 mg/L initial pore References
Samples area radius
concentration of dye solution. A constant mass 0.1 g of volume
(m2/g) (nm)
adsorbent materials was mixed with a 50 ml dye solution (ml/g)
at neutral pH. The mixture of each batch was constantly HBC 158.22 0.098 2.48 This work
agitated as a function of time by orbital shaker at speed HAC 745.13 0.558 2.99 This work
of 200 rpm and controlled temperature 25 οC. At various CAC 1110 - - [11]
time intervals (5, 10, 15, 20, 30, 40, 50, 60, 90, 120, 180, 930 - - [12]
240, 300, and 360 minutes), samples were taken and 788 0.74 - [13]
filtered with filter disk 0.45 µm to remove the adsorbent,
then the dye concentrations were measured by UV-Vis
Spectrophotometer.
2.5 Effect of temperature and pH
The effects of temperature and pH on the amount of dye
solution on three adsorbents (HBC, HAC, and CAC)
were examined at 60 mg/L initial concentration of dye
solution. A constant mass 0.1 g of adsorbent materials
was mixed with a 50 ml dye solution and 200 rpm
agitation speed for 6 hours. The effect of temperature
study, different adsorption temperatures for each batch of
the experiment was controlled from 20-50 ๐C. The effect
of the solution pH on the adsorption of dye solution was
examined at the controlled temperature of 25 ๐C. The
solution pH range was adjusted between 2 and 10 by

84
P. Tarapitakcheevin, P. Weerayutsil, and K. Khuanmar / GMSARN International Journal 7 (2013) 83 - 90

0.8
(a) HBC with magnification 500X

A bsor banc e
0.6
0.4
0.2
0
450 500 550 600 650 700 750

Wavelength (nm)
Fig. 3. Absorption spectra for Acid Blue 80 solution.

3.2 Effect of contact time


Various contact time intervals of experiments were
performed to optimize the adsorption time at an initial
(b) HAC with magnification 500X
dye concentration of 20 mg/L. The contact time effect of
dyes adsorption is presented in Fig.4. The percentage of
dye removal by adsorption on HBC, HAC, and CAC
were found that HBC shown efficiency of dye removal
28.21 % at the equilibrium of 120 minutes, while HAC
and CAC presented favorable removal efficiency of
92.88 % and 97.39 % with the optimum contact time 240
minutes and 40 minutes respectively [15]. Although the
HAC and CAC were identified as activated carbon with
high surface area, HAC consumed longer time than CAC
to achieve the optimum adsorption. This might be due to
the surface area and uniformity of pore structure of HAC
is less than CAC which is produced for commercial
activated carbon.
1
0
0

(c) CAC with magnification 2000X [14]


8
0

Fig. 2. Scanning electron micrograph (SEM) of (a) HBC, (b)

H H C
B A A
C C C
HAC, and (c) CAC %
( )
6
0

l
The morphology examinations of adsorbent particles a
v
o
using the scanning electron microscopy (SEM) images m
4
0

e
are shown in Fig.2 (a)-(c). Fig 2 (a) presents the SEM R
e
image for HBC, indicating the surface texture was rough y
2
0

D
and irregular. The SEM image for HAC shown in Fig 2
(b), reveal the texture having the pores within the
0
0

5
0

1
0
0

1
5
0

2
0
0

2
5
0

3
0
0

3
5
0

4
0
0

adsorbent particles with highly heterogeneous and


T
i
m
e
,
m
i
n

honeycomb shape gabs with different sizes. The


commercial adsorbent texture image shown in Fig 2 (c)
indicate that CAC appearing to have numbers of
microporous structure which offers more adsorption Fig. 4. Effect of contact time of dye removal by HBC, HAC
sites. It also indicated that CAC having a good and CAC
possibility for dye to be trapped and adsorbed into these
pore more than HBC and HAC. 3.3 Effect of pH
The scanning wavelength was observed to locate the
maximum absorbance of acid dye (AB80) by The pH medium is an important factor in the adsorption
Spectrophotometer. The absorption spectra illustrates in process since it controls the magnitude of electrostatic
Fig.3. The spectra indicated two peaks of λmax that were charges. At a high pH solution, the positive charge at the
584 and 625 nm, so the higher absorbance was selected. solution interface decrease and the adsorbent surface
appears for negative charges. Therefore, the adsorption
The fixed wavelength at λmax 625 nm was used for
measuring concentrations of dye solution for all of cationic dye increases while adsorption of anionic dye
experiments. decreases. In contrast, at a low pH solution, the positive
charges on the solution interface increase and the
adsorbent surface appears for positive charges, which
results for an increase in anionic dye adsorption and
decrease in cationic dye adsorption [7, 16, 17].

85
P. Tarapitakcheevin, P. Weerayutsil, and K. Khuanmar / GMSARN International Journal 7 (2013) 83 - 90

According to the general rule, the percentage of

1
0
0
anionic dyes adsorption removal will increase at low pH
solution, while the percentage of dye removal will

8
0
decrease at high pH solution. An investigation of the
effect of pH adsorption of acid dye was carried out at pH
%

( )
6
0
range of 2-10 for 240 minutes. The experimental results
l

H H C
B A A
C C C
illustrated that there was no significant variation in the a
v
o

4
0
amount of solute adsorbed on CAC. The adsorption on m
HAC slightly decreased as increasing pH. Notably, the e
R
adsorption on HBC significantly decreased as increasing e
y

2
0
pH as shown in Fig.5. D
The adsorption of both activated carbons, CAC and

0
HAC, seem not to be affected by the charges in the pH of

1
0
the solution. Similar results were reported for the

p
H
activated carbon adsorption of tannery dye on which is
classified as an acidic dye [18] and Acid Blue (AB25)
[16]. An explanation of this behavior might be the Fig. 5. Effect of pH on acid dye (AB80) adsorption by HBC,
presence of both negatively and positively charge HAC, and CAC.
function groups in the dye molecules. At low pH

1
0
0
solution, more hydrogen ions (H+) are in the solution
making the adsorbent surface more positive, thereby
increasing electrostatic attraction between the negative
8
charge SO3- anion of the dye and the activated adsorbent. 0
Likewise, at high pH, most favorable adsorption %
6
0
( )

H H C
B A A
C C C
occurred due to interaction of amines groups of Acid l
a
v
Blue (AB80). It is possibly to conclude that both acidic o
4
0

and basic solutions present remarkable adsorption of acid m


e
dye on activated carbon which has more active sites R
e
2
0

(high surface area) due to the presence of both positive y


D
and negative groups on Acid Blue (AB80) structure. This
substance structure is also known as amphoteric
2
0

3
0

4 ,
0

5
0
substance [16].
T
e
m
p
e
r
a
t
u
r
e
An explanation of HBC adsorption behavior which has C o

lower active sites (low surface area) than others


adsorbents, its adsorption followed the general rule. That
was a lower adsorption of acid dye at higher pH value Fig. 6. Effect of temperature on acid dye (AB80)
while a higher adsorption occurred at lower pH value. adsorption by HBC, HAC, and CAC

3.4 Effect of Temperature According to the experimental result, the adsorption


The effect of temperature on the equilibrium of adsorption capacity increased with increasing temperature, so the
of AB80 on HBC, HAC, and CAC was carried out at adsorption was an endothermic process. Because the
various temperatures including 20, 30, 40, and 50 ๐C. The diffusion process was an endothermic process, the
increasing adsorption of dye with temperature might due
result of this effect is given in Fig. 6. The adsorption of
to the enhance rate of intraparticle of diffusion of the
acid dye (AB80) on three adsorbents trended to increase as
adsorbate. Besides, increasing temperature might also
increasing temperature. Especially, HAC and CAC present
produce a swelling effect within the internal structure of
a likely increased adsorption capacity at temperature
carbons enabling more dye molecules diffuse into carbon
beyond 40 ๐C.
[8, 19, 20].
3.5 Adsorption Isotherms
Equilibrium study on adsorption is necessary to establish
the most appropriate correlation for the adsorption
isotherms. Because the adsorption isotherms not only
describe how adsorbates interact with adsorbents but also
are basic requirements for design and operation of
adsorption systems. The most widely used isotherm
equation for the modeling of the adsorption data is
Langmuir and Freundlich model [21].

86
P. Tarapitakcheevin, P. Weerayutsil, and K. Khuanmar / GMSARN International Journal 7 (2013) 83 - 90

Table 2. Langmuir Isotherm constants for HBC, HAC, and

4
0

H
B
C
CAC

y
=
0
.
1
7
4
x
+
1
.
6
9
7
3
0

R
R2 RL*
=
0
.
9
9
7
2
Adsorbents qm KL
(mg/g) (L/mg)
HBC 5.75 0.10 0.997 0.05-0.67
2
0

q
/e
e HAC 56.50 0.09 0.964 0.05-0.69
C CAC 100.00 0.15 0.940 0.03-0.57
* RL indicates the shape of isotherm [22].
1
0

RL > 1 Unfavorable
RL = 1 Linear
0

0< RL <1 Favorable


0

5
0

1
0
0

1
5
0

2
0
0
RL = 0 Irreversible
C
e

3.5.1 Langmuir Isotherm


(a) HBC Langmuir equation model is valid for monolayer
adsorption onto the adsorbent surface that reflects the
limiting adsorption capacity. The model equation is
2
.
0

H
A
C

given by Eq (1).
y
=
0
.
0
1
7
x
+
0
.
1
9
4
1
.
5

R
=
0
.
9
6
4
2
1
.
0

q
/e
e where qm and KL are Langmuir parameters related to
C maximum adsorption capacity (mg/g) and free energy of
adsorption (L/mg), respectively. Ce is the equilibrium
0
.
5

concentration in the aqueous solution, X is the amount of


adsorbate (mg), M is the mass of adsorbent (g), and qe is
0
.
0

the equilibrium adsorption capacity of the adsorbent


0

2
0

4
0

6
0

8
0

1
0
0

(mg/g). The linearlized form of Langmuir equation can


C

be written as Eq (2) and (3).


e

(b) HAC
0
.
4

C
A
C
y
=
0
.
0
1
0
x
+
0
.
0
6
6

The Langmuir constant qm and KL can be calculated by


R
=
0
.
9
4
0
0
.
3

plotting Ce/qe versus Ce as shown in Fig. 7 (a)-(c). The


isotherms of HBC, HAC, and CAC were found to be
linear. Table 2 shows Langmuir Isotherm constants for
0
.
2

qe
/ three adsorbents. The maximum sorption capacity of
e
C
HBC, HAC, and CAC for AB80 was found to be 5.75,
0
.
1

56.50, and 100.00 mg/g, respectively. Nevertheless, the


correlation coefficient of HBC was extremely higher
than HAC and CAC. This was confirmed that the
0
.
0

equilibrium adsorption data of HBC was well fitted to


0

1
0

1
5

2
0

2
5

3
0

Langmuir model and its behavior also demonstrated that


C

the formation of monolayer coverage of dye molecule on


e

the outer surface of HBC. Furthermore, Langmuir


(c) CAC equation can be expressed in term of a dimensionless
separation factor (KL). This factor is defined as Eq. (4)
Fig. 7. Langmuir isotherm for acid dye (AB80) adsorption and the calculated values are depicted for the adsorption
onto (a) HBC, (b) HAC, and (c) CAC. processes that are favorable or unfavorable for Langmuir
model.

87
P. Tarapitakcheevin, P. Weerayutsil, and K. Khuanmar / GMSARN International Journal 7 (2013) 83 - 90

where RL is a dimensionless separation factor, C0 is the Table 3. Freundlich Isotherm constants for HBC, HAC,
initial solution concentration and KL is Langmuir and CAC
constant (L/mg). Table 2 shows the calculate RL values
of HBC, HAC, and CAC. The values were in the range Adsorbents KF 1/n R2
of 0-1 which confirmed the favorable adsorption of (L/mg)
AB80 on the adsorbents. HBC 1.05 0.352 0.907
HAC 6.77 0.480 0.990
1
.
0

CAC 12.39 0.617 0.991


H
B
C
y
=
0
.
3
5
2
x
+
0
.
0
2
4

3.5.2 Freundlich Isotherm


0
.
8

R
=
0
.
9
0
7
2

The Freundlich model is an empirical equation based on


0
.
6

adsorption on the heterogeneous surface and describes


reversible adsorption. The adsorption is not restricted to
qe
g the formation of the monolayer. Likewise, the Freundlich
0
.
4

o
l equation predicts that the dye concentration on the
adsorbent will increase so long as there is an increased in
0
.
2

the dye concentration in the liquid phase [23]. The empirical


equation is given as Eq (5).
0
.
0
0
.
0

0
.
5

1
.
0

1
.
5

2
.
0

2
.
5
l
o
g
C
e

where KF and n are the Freundlich constants that indicate


(a) HBC adsorption capacity and adsorption intensity,
respectively. The linearized form of Freundlich isotherm
can be written as Eq (6).
2
.
0

H
A
C
y
=
0
.
4
8
0
x
+
0
.
8
3
0
1
.
5

R
=
0
.
9
9
0
2

The value of KF and 1/n can be calculated by plotting


logqe versus logCe as shown in Fig. 8 (a)-(c). The
1
.
0

qe logarithmic plots show the deviation from linearity on


g the Freundlich linear plot for HBC while HAC and CAC
o
l
were well fitted to the experimental data. Table 3 shows
0
.
5

the Freundlich adsorption isotherm constant and


correlation coefficients. The values of KF indicate the
degree of the binding capacity between the adsorbent and
0
.
0-

dye molecules. Thus, the high degree of KF implies that


1
.
0

-
0
.
5

0
.
0

0
.
5

1
.
0

1
.
5

2
.
0

2
.
5
l
o
g
C

the affinity between the adsorbent and dye molecules is


e

also high [24]. From the experimental data, the constant


KF of HBC, HAC, and CAC for AB80 were found to be
(b) HAC 1.05, 6.77, and 12.39 L/mg, respectively. Likewise the
magnitudes of 1/n for Freundlich isotherms were
2
.
0

revealed to lie between zero to one, indicating that acid


C
A
C

dye (AB80) is favorably adsorbed by all the adsorbents


y
=
0
.
6
1
7
x
+
1
.
0
9
3

[6].
1
.
5

R
=
0
.
9
9
1
2

4. CONCLUSION
1
.
0

qe The study results elucidated that the prepared adsorbents


g
o
l from hyacinth, HBC and HAC, could be effectively used
0
.
5

as an adsorbent for the adsorption of acid dye (AB80).


The efficiency of HAC also showed the comparable
efficiency to the commercial activated carbon, CAC. The
0
.
0

adsorption is an endothermic process due to the


-
1
.
0

-
0
.
5

0
.
0

0
.
5

1
.
0

1
.
5

2
.
0

2
.
5

adsorption capacity increases with increasing


l
o
g
C

temperature and the adsorption favours acidic pH. The


e

isotherm adsorption study elucidated that HBC was fitted


(c) CAC to Langmuir model with high correlation (R2) of 0.997
Fig. 8. Freundlich isotherm for acid dye (AB80) adsorption while HAC and CAC were well fitted to Freundlich
onto (a) HBC, (b) HAC, and (c) CAC model with favorable correlation (R2) of 0.990 and

88
P. Tarapitakcheevin, P. Weerayutsil, and K. Khuanmar / GMSARN International Journal 7 (2013) 83 - 90

0.991, respectively. International Journal of Hydrogen Energy 2007,


32:3320-3326.
ACKNOWLEDGMENT [13] Suelves I, Pinilla JL, Lazaro MJ, Moliner R.
This research was financially supported by the National Carbonaceous materials as catalysts for
Center of Excellent for Environmental and Hazardous decomposition of methane. Chemical Engineering
Waste Management and Research Center for Journal 2008, 140:432-438.
Environmental and Hazardous Substance Management. [14] Temyarasilp P. Preparation and characterization of
activated carbon from Dendrocalamus asper Backer
and Dendrocalamus Latiflorus. Thailand: Kasetsart
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