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Sorption Studies of Methylene Blue on Silica Gel

Article  in  International Journal of Chemical Engineering and Applications · January 2010

DOI: 10.7763/IJCEA.2010.V1.59

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 International Journal of Chemical Engineering and Applications, Vol. 1, No. 4, December 2010
ISSN: 2010-0221

Sorption Studies of Methylene Blue on Silica Gel

R.W.Gaikwad and S.A.Misal

Abstract—The removal of methylene blue (a basic dye) from added to it .The pH of the solution was adjusted to a desired
its aqueous solution by adsorption on silica gel has been carried value using HCL & NaoH. After pH adjustment the
out. It has been noted that low adsorbate concentration, low temperature of the solution was also adjusted at the end of
temperature and basic medium favor the removal of the dye. A
reaction time. The solution was filtered through the whatman
95.2% removal of the methylene blue was achieved at 25
mg/liter dose, 35OC & at pH 10.The kinetics studies were made filter paper No.42 and the filtrate was taken to analyses the
using the model suggested by Langergren. The rate constants dye present in the solution by UV spectrophotometer
were found to be 1.22/min for 30OC and 6.58/min for 35OC. The (systronics-118) at 665 nm. In order to have a clear picture of
equilibrium data fits well in the Langmuir and Freundlich the effect of different parameters on the adsorption of dye,
model of adsorption. Effect of temperature was studied. Fixed the experiments were carried out at different initial
bed studies were made in a glass column. It was found that at
concentrations, dosages, pH, and different temperatures.
1.6cm of adsorbent bed height, 97.6% removal was possible.
The adsorption capacity of silica gel has been estimated as 195 During the uptakes of dye from the solution by adsorption
mg/liter in fixed bed study. process, two factors namely; concentration of dye in the
solution and time of contact between adsorbate and adsorbent
Index Terms—basic dye, textile wastewater, adsorption, phases, play an important role. A rapid transport of adsorbate
silica gel, capacity. cuts through the equilibrium period. The time taken to attain
the equilibrium is important to predict the efficiency and the
I. INTRODUCTION feasibility of the adsorbent. The experiments were conducted
The removal of colour from textile wastewater is one of the at two different initial concentrations of dye i.e. 25mg/liter &
major environmental problems because of the treatment of 12.5 mg/liter of solution. The amount of adsorbent is kept
such water by conventional methods. Colored waters are also fixed at 500 mg & at room temperature i.e.20OC with a pH 8.
objectionable on aesthetic ground for drinking and other Adsorption at Different Adsorbent Doses: -The
municipal as well as agriculture purpose[1],[2],[3].Many experiment was carried out to observe the effect of different
colored effluents are composed of non-biologically amount of adsorbent on the adsorption of dye on silica gel.
oxidisable organic components because of the molecular size Moreover the experiment was conducted for two
and structure of the dyestuffs. The increasingly tighter concentration of dye solution i.e. 25mg/liter & 12.5 mg/liter
legislation of effluent discharges in most countries will bring to observe comparative study of the two. The experimental
new developments, resulting in considerably smaller amount procedure was same as described earlier and the total time of
of effluents [4]. Adsorption is a physico-chemical process experiment was 10 min. The temperature was fixed at 20OC
which offers great potential for treating effluents containing ( ± 5OC) & pH 8.
undesirable components and render them safe and Adsorption at Different pH Values: -The aim of the
reusable.[5],[6],[7],[8].The feasibility of using silica gel for experiment was to find out a suitable pH range for the
adsorption of a methylyne blue has been tested in this study. maximum efficiency of the removal process. The experiment
The major advantage of an adsorption system for water was carried out for two different concentration of the dye i.e.
pollution control, are low investment in terms of both initial 25 mg/liter and 12 .5 mg/liter of solution for each
and land cost, simple design easy operation and no effect by concentration of solution, the temperature was maintained at
toxic harmful substance [9]. Adsorption offers an attractive 20OC ( ± 5OC) . The pH was adjusted by adding 1N HCL or
method of treatment for producing high quality colorless NaoH as desired.
effluents. It is important to study the dependence of initial Adsorption at Different Temperature: -Temperature
and final concentration of the adsobate on the contact time has significant effect on the process of adsorption. Physical
with the adsorbent under several operating conditions. adsorption is always an exothermic process and hence any
Various low cost material such as, bagasse pith [10], Fullers increases in temperature do not favor the extent of adsorption.
earth [11], Activated carbon [12], Ash cinder [13], Coconut Therefore at higher temperature silica gel proved to be good
husk [14], Aquatic Plants [15] have been investigated with adsorbent. The decrease in adsorption density is attributed to
varying degrees of success. the weakening of adsorptive forces between the adsobate and
The present investigation reports on the use of silica gel to adsorbent and also between the adjacent sites of adsorbed
adsorb the dye-methylene blue from aqueous solution in a phase. Time rate adsorption studies were carried out at a
batch and column study. particular initial concentration of dye solution at 25mg/liter
and 12.5 mg/liter and at a particular pH value of 8 of the
II. MATERIALS AND METHODS solution; with total time of the experiment 10 minutes at
Stock solution of dye was prepared by dissolving 200mg different temperatures 35oC, 45oC, 55oC, 60oC & 65oC.
of dye/liter of double distillated water was taken in a 250 ml Kinetic Study: - Kinetic studies have been carried out by
beaker and a known quantity of adsorbent i.e. Silica gel was using Freundlich, Langmuir and Langergren equations.

342
 International Journal of Chemical Engineering and Applications, Vol. 1, No. 4, December 2010
ISSN: 2010-0221

Langmuir Model: - The equation is 96

95
X b ( x / m ) Ce
= (1) 94
M 1 + bCe 93

%Removal
92

Where b is an adsorption coefficient. 91

25gm/liter
90
Freundlich Model: -The linear plot of the Langmuir 12.5gm/liter
89
adsorption model suggested the application of the model for 88
the investigated system. 87
The equation is 86
1 2 3 4 5 6 7 8
KC 1 / n
X = (2) Tim e in Min.
M
Fig.1. Adsorption For Different Initial Concentration on
Silica Gel
here
X =Amount of solute adsorbed
Effect of Different Dosages on Adsorption of Methylene
M = Weight of adsorbent
Blue on Silica Gel: -
C = Concentration of solute remaining in solution after
Initially the rate of adsorption increases as dosage
adsorption is complete.
increases but after the dose of 600 mg/liter, the rate of
K and n = Constant that must be evaluated for each solute
adsorption does not increase i.e. it remains constant as shown
and temperature.
in figure 2.
Langergren's Model: - Kinetic modeling for the removal
 
of methylyne blue by silica gel has been carried out by
lageregen’s equation.

Log (qe − q ) = Logq e −

Kad
*t (3)
% Removal

95
2.303
90
Where qe & q = Amounts of dye adsorbed at equilibrium and
at time t respectively. 85
Kad = Rate constant for the adsorption of dye. 1 2 3 4 5 6 7 8
Column Studies: Column studies were conducted using
Dosage in gram
down flow technique. A column of 15-mm diameter was
prepared. Initial concentration of 200-mg/liter solution was
passed through the column. Glass wool was kept at the Fig.2. Effect of Different Dosage of Silica Gel on
bottom of the column to avoid the loss of adsorbent with the Adsorption
flow of dye solution. Methylyne blue solution was fed into
the column at 5ml/min. To determine exhaustive capacity, Effect of pH on Adsorption of Methylyne Blue on Silica
fraction of effluent was collected from the bottom of the Gel: -
column. The process was continued until the amount of dye As the pH increases, the removal of dye also increases. For
in the effluent was same as that in the feed. the good rate of adsorption higher pH is favorable. Figure 3
has shown the change in the rate of adsorptions due to change
in pH. In the range of pH 8 to 10, maximum removal is
III. RESULTS AND DISCUSSION possible.
Effect of Different Initial Concentration and Fixed Dose on  
Adsorption of Methylene Blue on Silica Gel:-
Initially the rate of adsorption increases due to different in 100
90
bulk flow and when equilibrium is established the nature of 80
the graph become a straight line as there is decrease in mass 70
% Removal

60
transfer as shown in figure 1. The equilibrium time is 4 50
minutes. The time taken to attain equilibrium is independent 40
of the concentration. It was found that 93% removal for 25 30 pH1 pH3 pH6
20
mg/liter of dye solution & 94.6% removal for 12.5 mg/liter of pH8 pH10
10
dye solution occur. 0
2 4 6 10 15
Time in Minutes
Fig. 3.Effect of pH on Adsorption of Methylene Blue

Effect of Temperature on Adsorption of Methylene Blue on

Silica Gel:-
As temperature increases the removal decreases, since it is
343
 International Journal of Chemical Engineering and Applications, Vol. 1, No. 4, December 2010
ISSN: 2010-0221

an exothermic phenomenon. Figure 4 shows the rate of The straight line is shown in figure 7 and figure 8
adsorption with the change in temperature. The optimum indicates the validity of Lageragrens equation and suggests
temperature for maximum removal was found to be 350C for that the removal of methylyene blue follow first order
the finest removal of dye. kinetics. The rate constant K for the process is also calculated
and found to be 1.22/min for 30 oC and 6.58 /min for 35 oC.
 
 

100
80 0.2
% Re m o val

60 0.1
40 Time(min)
0
20 1 2 3

Log(qe-q)
-0.1
0
35 45 55 60 65 -0.2
Temperature in Centigrade -0.3
-0.4
Fig.4. Effect of Temperature on Adsorption of Methylene
Blue -0.5
Adsorption Dynamics: -0.6
Freundlich Model: -The sorption data also follows the
Fig.7. Adsorption Dynamics by Langergren
linear path as shown in figure 5. Thus the applicability of the for pH 1 and temperature 30 C.
Freundlich model is justified.
 
8
6
LnX/M

4
2 0.8
0
0.6
0 0.2 0.4 0.6 0.8 1 1.2 1.4 1.6
0.4
Log(qe-q)

LnC
Fig.5. Freundlich Isotherm
0.2
Time(min)
0
1 2 3 4
-0.2

Langmuir Model: The linear plot of the Langmuir -0.4

adsorption model suggested the application of the model for
Fig.8. Adsorption dynamics by Langergren
the investigated system shown in figure 6.
for pH 2 and temperature 35 C.
 

0.8 Effect of Bed Heights on Removal of Methylyne Blue:

0.6 -Studies on removal of methylene blue at different bed
1/q e

0.4 heights are shown in figure 9. From the figure, it can be

revealed that for 200mg/ltr solution, after 1.6 cm of bed
0.2
height, removal of dye gets stabilized and are 97.6 %
0
0 4.5 8.77 12.98 17.27 21.27
1/Ce

Fig.6. Langmuir Isotherm

Langergren's model: - Kinetic modeling for the removal

of methylene blue by silica gel has been carried out by
Langergren’s equation.

344
 International Journal of Chemical Engineering and Applications, Vol. 1, No. 4, December 2010
ISSN: 2010-0221

  fixed bed study. The parameters studied would be helpful to

the engineers in designing the large-scale plants.

REFERENCES
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98 research”, Proc. 1st Int. conf. Water pollt. Res., New York, Pergamon
Press, 2, PN. 231-236.
% Removal

97 [2] Mukherjee K. K. (1996), “Environmental pollution and health

Hazards- Causes and control in India”, 1st Edition, Galgotia Press, New
96 Delhi, PN. 55-57.
95 [3] Sunil K.K. (1987), “Removal of Victoria Blue from aqueous solution
by Flyash”, Jr. Chem. Tech. Biotech.,38, PN. 99-104.
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93 carbon in fluidized Beds”,Chem.Engg.Res.Des.,61, PN.29-36.
[5] Gupta G.S., G.Prasad and V.N.Singh (1987), “Mordant Blue –13
0.5 0.75 1 1.25 1.6 1.75 removal from aqueous solution by fly ash –I(Equilibrium and rate
Column Height process studies),” Asian Env., PN. 29-30.
[6] GuptaG.S.G.Prasad and V.N.Singh (1988a),“Removal of colour from
Fig.9. Rem oval of Methylene Blue at different Height of wastewater by sorption for water reuse,” Env. Sci. Health A23,
the Colum n PN.205-217.
[7] Gupta G.S., G.Prasad and V.N.Singh (1988b), “Removal of chrome
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PN.13-24.
[8] Annadurai and Krishnan (1996),“Adsorption of basic dye using
Fixed bed Column Study for Adsorption of Dye: chitin,” Ind. Jr. of Environ. Protection, 16(6), PN. 444-449.
The column study was conducted having initial [9] Annadurai and Krishnan (1997), “ Batch kinetic studies of adsorption
concentration of 200-mg/lit and pH 8.The parameters of of reactive dye using chitosan”, Ind. Jr. of Environ. Protection, 17 (5),
study are given in the table 1.The breakthrough curve PN: 328-333.
[10] Nassar M. M. and El. Geundis, (1991), “Comparative cost of colour
obtained is shown in figure 10. The breakthrough and removal from textile effluents using natural adsorbents”, J. Chem. Tech.
exhaustion (ultimate) capacities of the adsorbent were Biotechnol.50, PN. 257-274.
calculated as 170-mg/lit and 195-mg/lit respectively. [11] Makay G, Otterburn M. S. and Aga J. A. (1985), “ Fullers Earth and
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methylene blue dye to its desirable limit. Maximum removal [13] Li Guolin, Zhao, Quinglianj (1991), “Dying wastewater treatment by
of methylyne blue has been obtained in the range of pH 8 to ash cinder”, Water Sci. Tec., 24(50), PN.215-220.
[14] Low K. S. and Lee C.K. (1990), “ The removal of cationic dyes by
10 and at a temperature of 35OC. The capacity of adsorption hydrilla verticillata”, Environ. Tech., 14, PN.115-124.
of silica gel is estimated as 195 mg/liter in the batch study. [15] Low K. S. Lee C.K. and Heng L.L. (1994), “Sorption of basic dyes by
The breakthrough and ultimate adsorption capacities are hydrilla verticillata, Environ. Tech., 14, PN.115-124.
estimated as 170-mg/lit and 195-mg/liter respectively in the

250
Concentration

200

150

100

50

0
100

200

300

400

500

600

700

800

900

1000

1050

1100

1150

1200

1250

1300

1350

1400

1450

1500

1550

1600

Volume of Effulent

Fig.10. Break Through Curve

345

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