International Journal of Engineering Trends and Technology (IJETT) – Volume 3 Issue 3 No 3 – May 2012
*Sr. Engineer Clear Tech Environmental Solution
**Asst. Professor Civil Engineering Department, Bharath University
***Assoc. Professor, Anna University Chennai
ABSTRACT
The effluent generated from textile industries, cosmetics, paper and food coloring industries contains dyestuffs. The entry of this effluent into river or any other surface water stream affects the biological activity of that system. BSW is identified to be an effective sorbent for the removal of AV 54 dye from aqueous solution. Dye containing waste water is a major environmental problem .The treatment method for the removal of dye is costly.
For this the use of low cost easily available adsorbent was studied. Sorption of Acid violet 54 on to Banana stalk waste was studied by varying the parameters like initial dye concentration, pH and sorbent dosage.
Dye biosorption was rapid up to 60 minutes and equilibrium was attained at 240 minutes after 60 minutes the removal rate was slow due to the decrease in the number of vacant sites. Also the uptake capacity decreases as the amount of sorbent dosage was increased this is due to the increase in the number of solute particles and as the pH varies the is a considerable change in the uptake capacity of the sorbent and all the dyes follow pseudo second order kinetics and also the data fit to Langmuir isotherm very well. colouring industries contains dyestuffs. The entry of this effluent into river or any other surface water stream affects the biological activity of that system.
Dyes can cause allergic dermatitis, skin irritation, cancer and mutation [1]. At present, it is estimated that more than 100000 commercially available over
7*10
5
tonnes of dyestuff produced annually [2, 3].
Most of which are difficult to biodegrade due to their complex aromatic molecular structure and synthetic origin [4]. These dyes may drastically affect photosynthetic phenomenon in aquatic life due to reduced light penetration [5, 6]. Among the various kinds of dyes available water-soluble and brightly colored acid and reactive dyes are the most problematic as they tend to pass through conventional decolorization systems unaffected [7, 8, 9].
1.1 CLASSIFICATION OF DYES:
Dyes are classified according to how they are used in the dyeing process.
Acid dyes:
1. INTRODUCTION
These are water soluble anionic dyes that are mainly applied to nitrogenous fibers such as silk, wool, nylon and modified acrylic fibers from acid or neutral baths.
Dyes are coloured substance used for the colouration of various substrates including paper, leather, fur, hair, foods, drugs, cosmetics waxes, greases, petroleum products, plastics and textile materials.
Synthetic dyes quickly replaced the traditional natural dyes. They cost less, they offered a vast range of new colors, and they imparted better properties upon the dyed materials. The effluent generated from textile industries, cosmetics, paper and food
Basic dyes:
These are water soluble cationic dyes that are mainly applied to acrylic fibers, but find some use for wool and silk. Basic dyes dissociate into anions and cations. Basic dyes are also used in the coloration of paper.
Azo dyes :
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International Journal of Engineering Trends and Technology (IJETT) – Volume 3 Issue 3 No 3 – May 2012
The azo compound class accounts for 60-70% of all dyes. They contain an azo group, -N=N-, which links two carbon atoms. Often, these carbons are part of aromatic systems, but this is not always the case. Most azo dyes contain only one azo group, but some contain two ( dis azo), three ( tris azo) or more
Vat dyes:
These are complex organic molecules that are insoluble in water but when their carbonyl groups are properly reduced in a solution of caustic soda and sodium hydrosulfite to the leuco, they exhibit an affinity for cellulosic fibers.
Reactive dyes:
These utilize a chromophore attached to a substitute that is capable of directly reacting with the fiber substrate. The covalent bonds that attach reactive dye to natural fibers make them among the most permanent of dyes. "Cold" reactive dyes, such as
Procion MX, Cibacron F, and Drimarene K, are very easy to use because the dye can be applied at room temperature. Reactive dyes are by far the best choice for dyeing cotton and other cellulose fibers.
Disperse dyes:
These are coloured organic compounds, which are only very slightly soluble in water and therefore dyeing is carried out with aqueous dispersion. These dyes are originally developed for the dyeing of cellulose acetate, and are substantially water insoluble.
Sulfur dyes:
These are compounds prepared by heating various nitrogeneous organic materials with sulphur, sodium sulphide or other sulphfurizing agents
1.2
TECHNOLOGIES FOR COLOUR
REMOVAL:
Wastewater containing dyes is very difficult to treat, since the dyes are recalcitrant organic molecules, resistant to aerobic digestion, and are stable to light. A synthetic dye in wastewater cannot be efficiently decolorized by traditional methods.
This is because of the high cost and disposal
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problems for treating dye wastewater at large scale in the textile and paper industries .The technologies for colour removal can be divided into three categories: biological, chemical and physical. All of them have advantages and drawbacks.
1.2.1 Physical methods:
Physical methods used in the colour removal includes the following,
1) Membrane – filtration processes (nanofiltration, reverse osmosis,Electro dialysis)
2) Adsorption Techniques.
Adsorption has been found to be superior to other techniques for water re-use in terms of initial cost, flexibility and simplicity of design, ease of operation and insensitivity to toxic pollutants.
1.2.2 Chemical methods:
Chemical methods for colour removal are,
1. Coagulation
2. Flocculation combined with flotation and filtration
3. Precipitation-flocculation
4. Electro flotation
5. Electro kinetic coagulation
6. Conventional oxidation methods by using oxidizing agents (ozone),
Irradiation,
7. Electrochemical processes.
These chemical techniques are often expensive, and although the dyes are removed, accumulation of concentrated sludge creates a disposal problem.
1.2.3 Biological methods:
Biological treatment is the often the most economical alternatives when compared with other

International Journal of Engineering Trends and Technology (IJETT) – Volume 3 Issue 3 No 3 – May 2012 physical and chemical processes. Biodegradation methods such as fungal decolourization, microbial degradation, adsorption by (living or dead) microbial biomass and bioremediation systems are commonly applied to the treatment of industrial effluents because many microorganisms such as bacteria, yeasts, algae and fungi are able to accumulate and degrade different pollutant. However, their application is often restricted because of technical constraint. According to Bhattacharyya and Sharma,
(2003), biological treatment requires a large land area and is constrained by sensitivity toward diurnal variation as well as toxicity of some chemicals, and less flexibility in design and operation. Further, biological treatment is incapable of obtaining satisfactory colour elimination with current conventional biodegradation processes. Moreover, although many organic molecules are degraded, many others are recalcitrant due to their complex chemical structure and synthetic organic origin .In particular, due to their xenobiotic nature, azo dyes are not totally degraded.
BSW are disposed into landfills and rivers. Then it affects aquatic life. So the reuse of the BSW will be beneficial. The banana stalk is used as a pre cursor for the preparation of polyacrylamide grafted banana stalk having –COOH group for the removal of Co (II) from aqueous solutions [23]. The leaching from lignocellulosic materials can be decreased by washing of adsorbents prior to their usage, or modifying them in appropriate manner. If improvement in adsorption capacities of modified adsorbents was realized, it would compensate for the costs of additional processing. To improve a sorption ability of wood-derived materials and agricultural waste towards various kinds of organic pollutants, pretreatment procedures have been developed, including the treatment with mineral acids, bases, or their salts – HCl, NaOH, Na
2
CO
3
,Na
2
HPO
4 or H
2
SO
4
,
HNO
3
.
In this study, BSW was pretreated with
H
2
SO
4
and HNO
3
.Then raw BSW, H
2
SO
4
treated
BSW and HNO
3 treated BSW was used as a sorbent for the removal of AV 54 from aqueous solution.
Among the above mentioned methods, biosorption is considered to be relatively superior to other techniques because of low cost, simplicity of design, ease of operation, and ability to treat dyes in more concentrated form [10, 11].
1.3 Scope and Objective of the Present Work:
Removal of Acid violet 54 synthetic Dye solution by using Banana stalk waste as a sorbent.
Activated carbon is the most popular and widely used adsorbent, but there are certain problems with its use. It is expensive and the higher the quality the greater the cost. Furthermore, regeneration using solutions produces a small additional effluent, while regeneration by refractory technique results in a loss of adsorbent and its uptake capacity.
The Objectives of the Present Investigation are to study,

Effect of initial dye concentration

Effect of sorbent Dosage

Effect of pH
Therefore, there is a growing interest in using lowcost, easily available materials for the biosorption of dye colors [14]. These materials include orange peel
[15], rise husk [16, 17], coffee husk [18], soy meal hull [19], cone biomass [20], coconut husk [21] etc.
 Effect of temperature
 Sorption Kinetics
 Sorption Equilibrium.
The banana fruit stalk which accumulates in the agro-industrial yards, has no significant industrial and commercial uses, but contributes to serious environmental problems. The residual component of the banana plant contains holocellulose and lignin corresponding to 33 and 8.67% of the dry weight of the component, respectively [22]. Normally these
2. LITERATURE REVIEW
B.H. Hameed et al (2008) studied the Sorption equilibrium and kinetics of basic dye from aqueous solution using banana stalk waste. In this study they concluded that the BSW is an efficient sorbent for the
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International Journal of Engineering Trends and Technology (IJETT) – Volume 3 Issue 3 No 3 – May 2012 removal of MB from aqueous solution and it may be an alternative to more costly adsorbents such as activated carbon. The equilibrium data have been analyzed using Langmuir, Freundlich and Temkin isotherms. The Langmuir isotherm was demonstrated to provide the best correlation for the sorption of MB onto BSW sorbent. The maximum monolayer adsorption capacity of BSW was found to be 243.90 mg/g at 30 ◦C. The sorption kinetics of the MB onto the BSW is well described by the pseudo-second order model.
Cr (VI)-biosorbent was its reduction into Cr (III) and binding of the reduced-Cr (III). On the basis of this mechanism, a kinetic model equation was derived and described well both Cr (VI) and total Cr removal behaviors by the Cr (VI)-biosorbent in aqueous phase. In conclusion, the Cr(VI)-biosorbent must be a potent candidate to substitute for chemical reductants as well as adsorbents to treat Cr(VI)-containing wastewaters, and the process using it may be economic and environmentally friendly.
J.P. Gaur et al (2008) studied the Kinetic and isotherm modeling of lead (II) sorption onto some waste plant materials. Most of the tested plant materials could rapidly sorbs Pb(II) from solution with >90% sorption occurring within 10 min. Pb(II) sorption attained maxima at pH 4 (peepul leaves, mango leaves, rice stem and coir fibers) or 5 (grass, tea leaves, banana peels, teak saw dust, peanut hulls and rice husk). Peepul leaves sorbed Pb(II) maximally followed in decreasing order by banana peels, peanut hulls, coir fibers, rice stem, teak saw dust, tea leaves, mango leaves, rice husk and grass clippings. Lagergren pseudo-first-order and -secondorder reaction models were in good agreement with the time course data of Pb(II) sorption by various tested plant materials at varying concentrations of metal and biomass. But, the latter model showed greater fitness. Furthermore, external diffusion, rather than intra-particle diffusion, was the dominant mechanism for Pb(II) sorption by all the test plant materials.
S. Hashemian et al(2008) studied the Sorption of acid red 138 from aqueous solutions onto rice bran. They concluded that The optimum reaction time, at a speed of 30 rpm, is 60 min and at initial pH of 2 and at room temperature, AR 138 was removed more effectively. The isothermal data for biosorption followed the Langmuir and Freundlich models.
3. MATERIALS AND METHODS
3.1 CHEMICALS:
The dye used in this work was obtained from the
Department Of Textile Technology, A.C.College of
Technology
3.2 PREPARATION OF SORBENT:
Jong Moon Park et al (2008) studied the
Development of a new Cr (VI)-biosorbent from agricultural biowaste. Slow Cr (VI) reduction rate by biomaterials at less acidic pH could be solved by screening a new efficient biomaterial, banana skin, which has been considered as an useless agricultural waste. Low removal efficiency of total Cr by the biomaterial could be solved by immobilizing it within
Ca-alginate bead. Finally, a new Cr (VI)-biosorbent was developed in this study, and showed very fast rate and high efficiency of Cr (VI) and total Cr removals. Mechanism of Cr (VI) Biosorption by the
The sorbent (banana stalk waste) used in this work was collected from farmland in karur. The BSW was washed with distilled water to remove the surface adhered particles and water-soluble materials.
Then it was sliced, spread on trays and oven dried at
60
◦
C for 48 hours. The dried slices were ground and sieved in a 60 mesh size sieve and the underflow was stored in plastic bottle for further use. No other chemical or physical treatments were used prior to adsorption experiments.
3.3 PREPARATION OF ACID TREATED
SORBENT:
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International Journal of Engineering Trends and Technology (IJETT) – Volume 3 Issue 3 No 3 – May 2012
For pretreatment of an adsorbent, about 20 gm of the adsorbent was taken in a 250 mL capacity glass beaker (Borosil, India) and the adsorbent slurry was stirred with magnetic stirrer at a slow speed (60–80 rpm) for 15 min to remove suspended and washable contaminants. The adsorbent was washed twice with
100 mL of distilled water with slow stirring for 5 min each, kept in oven for 4 h at a temperature of 150◦C to remove any volatile materials present within the pores of the grain. After cooling, the adsorbent was kept in a dry container. To prepare acid treated adsorbent, distilled water washed wasted activated carbon was kept immersed overnight in 200 mL of
1N acid solution in a 250 mL glass beaker (Borosil,
India). Sulfuric acid and nitric acid were employed for the acid treatment. The adsorbent was then washed with distilled water several times to get the conductivity of washed water about 4 μ S/cm and pH in between 6.8–7.2. Then it was kept in an oven at a temperature 150◦C for 4 h to remove any volatile materials present within the pores of the grains. After cooling, sieved adsorbent was properly stored [13].
3.4 CHARACTERIZATION OF SORBENT:
Scanning electron microscopy (SEM) analysis was carried out on the BSW to study its surface texture before adsorption. Fourier transform infrared
(FTIR) analysis was applied on the BSW to determine the surface functional groups, by using
FTIR spectroscope where the spectra were recorded from 4000 to 400 cm
−1
.
3.5 STRUCTURE OF DYE:
Fig 3.1. Structure of Acid violet 54
3.6 PREPARATION OF DYE SOLUTION:
A 1000 ppm stock solution of dye was prepared by dissolving 1g of Acid violet 54 dye in 1 L of distilled water. This stock solution was used for further studies.
3.7 EFFECT OF INITIAL CONCENTRATION:
Adsorption experiments were carried out by adding a fixed amount of raw BSW sorbent 0.5 g into 100 ml of different initial concentrations such as 50,100,150 and 200 ppm of dye solution. The initial and equilibrium dye concentrations were determined by absorbance measurement using colorimeter at 54 filter range. It was then computed to dye concentration using standard calibration curve. For the acid treated sorbent viz, H
2
SO
4
treated BSW,
HNO
3
treated BSW same procedure was followed as above.
3.8 EFFECT OF SORBENT DOSAGE:
A 50ppm dye solution was prepared from the stock solution and the different amount of sorbent was added (0.1, 0.2, 0.3, 0.4, 0.5, 0.6 g) to the 100 ml of dye solution and the system is kept in a shaker for the equilibrium time of 270 minutes. Then the dye concentration was measured with time interval of
60,120,180,240 and 270 minutes. For the acid treated sorbent viz, .H
2
SO
4
treated BSW, HNO
3
treated BSW same procedure was followed as above.But the equilibrium time for H
2
SO
4
treated BSW and HNO
3 treated BSW was 240 minutes.
3.9. Effect of pH:
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International Journal of Engineering Trends and Technology (IJETT) – Volume 3 Issue 3 No 3 – May 2012
The effect of pH on equilibrium uptake capacity of raw BSW was measured by adding a fixed amount of sorbent (0.5 g) into 100 ml of dye solution having different pH such as 2, 4,6,8,10,12 of dye solution.
The pH of the dye solution is varied by using 0.1N
H
2
SO
4
for acidic pH and 0.1 NaOH for basic pH. The initial and equilibrium dye concentrations were determined by absorbance measurement using colorimeter at 54 filter range. It was then computed to dye concentration using a calibration curve. For the acid treated sorbent viz, .H
2
SO
4
treated BSW,
HNO
3
treated BSW same procedure was followed as above.
3.10 Effect of Temperature:
Adsorption studies were carried out by adding 0.5 g of adsorbent in to 100 ml of 50ppm solution at 30,
40, and 50 ±1
◦
C for raw BSW. The initial and equilibrium dye concentrations were determined by absorbance measurement using colorimeter at 54 filter range. It was then computed to dye concentration using a calibration curve. For the acid treated sorbent viz, .H
2
SO
4
treated BSW, HNO
3 treated BSW same procedure was followed as above.
4. RESULTS AND DISCUSSION
4.1 Effect of initial concentration
To investigate the effect of initial dye concentration on equilibrium uptake capacity of BSW, batch biosorption experiments were carried out for different initial concentrations of AV 54 ranging from 50 mg/L to 200 mg/Lat room temperature. From the
Fig 4.1(a),(b),(c) It was observed that the percentage of dye removal was decreased with increase in the concentration of dye solution from 50 mg/L to 200 mg/L., but the amount of dye adsorbed increased with increase in the dye concentration. The percentage removal of AV 54 was decreased from
84.11% to 66.07%.for Biosorption of AV 54 by raw
BSW, 90.03215% to 69.78588% and 88.42444% to
67.68% for Biosorption of AV 54 by H
2
SO
4
treated
BSW,HNO
3 treated BSW respectively
100
90
80
70
60
50
40
30
20
10
0
0
60
50
40
30
20
10
0
90
80
70
0 200
Time (mins)
400
(a)
100 200
Time (min)
(b)
300
50 mg/l
100 mg/l
150 mg/l
200 mg/l
50 mg/l
100 mg/l
150 mg/l
200 mg/l
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International Journal of Engineering Trends and Technology (IJETT) – Volume 3 Issue 3 No 3 – May 2012
30
20
10
0
60
50
40
100
90
80
70
0
50 m g/l
100 m g/l
150 m g/l
200 m g/l
100
80
60
40
20
0
0 0.2
0.4
Sorbent dosage (g)
0.6
0.8
Raw BSW
H2SO4 Treated BSW
HNO3 Treated BSW
100 200
Tim e (m in)
300
(c)
Fig 4.1. Effect of Initial concentration of biosorption of AV 54 by (a) Raw BSW (b) H
2
SO
4 treated BSW and (c) HNO
3 treated BSW
It also showed that the biosorption of dye in the first
60 minutes was rapid and after that biosorption rate decreased gradually. The biosorption rate attains the equilibrium at 4 h and 30 minutes for biosorption of
AV 54 by Raw BSW, 4 hours for both H
2
SO
4
treated
BSW and HNO
3 treated BSW for the initial concentration of 50 mg/L to 200 mg/L Biosorption of
AV 54 by various sorbents such as bagasse charcoal, brick kiln ash, cement kiln ash, cow dung charcoal, groundnut shell charcoal, used tea leaves charcoal and wheat straw charcoal was studied [24].
4.2. Effect of Sorbent Dosage:
The effect of sorbent dosage on equilibrium uptake capacity of BSW is shown in Fig 4.2. From the Fig
4.2 It was evident that the amount of dye adsorbed varied with the sorbent concentration and that removal increased with an increase in sorbent dosage.
After the equilibrium time of biosorption, the percentage removal of AV 54 increased from 42.08% to 85.20%, 46.62% to 91.63% and 43.40% to
90.03215% for Raw BSW, H
2
SO
4
treated BSW and
HNO
3 treated BSW respectively with an increase in sorbent dosage from 1g L
−1
to 6 g L
-1
.
Fig 4.2. Effect of Sorbent dosage biosorption of
AV 54 by Raw BSW,H
2
SO
4
treated BSW and
HNO
3 treated BSW
The resulting effect can be easily explained by an increase in surface area (more availability of active biosorption sites) with the increase in sorbent mass.
The amount of dye adsorbed per unit mass of sorbent decreased with increasing sorbent mass, due to the reduction in effective surface area.
4.3. Effect of pH:
The effect of initial pH on sorption of AV 54 by
BSW was studied at 50 mg/L AV 54 initial concentration at room temperature shown in Fig 4.3.
From this figure, the maximum sorption of AV 54 was obtained at pH 2.The maximum sorption capacity for AV 54 onto BSW biosorption could be largely related to a significant electrostatic attractions existing between the surfaces of BSW and AV 54 since the number of negatively charged sites increases while positively charged sites decrease on the biosorbent surface as the solution pH increases and for pH 4 to 10 it remained nearly constant. For pH 12, there is a sudden decrease in sorption this is due to competition between the excess hydroxyl ions and the negatively charged dye ions for the biosorption sites.
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International Journal of Engineering Trends and Technology (IJETT) – Volume 3 Issue 3 No 3 – May 2012
50
40
30
20
10
0
0
100
90
80
70
60
5 pH
10 15
Fig 4.3 Effect of pH biosorption of AV 54 by Raw
BSW, H
2
SO
4
treated BSW and HNO
3 treated
BSW
4.4 Effect of Temperature:
The effect of temperature on equilibrium uptake capacity of BSW was carried out for 30, 40, and
50±1
0
C.The equilibrium uptake capacity was decreased as temperature increase from 30 to 50
0
C for the dye concentration of 50 mg/L at an equilibrium time of 4 h and 30 minutes for raw BSW and 4 hour for both H
2
SO
4
treated BSW and HNO
3 treated BSW. Decrease in the Biosorption capacity shows that it was a kinetically controlling process. So the Biosorption of AV 54 on to BSW was controlled by exothermic process.
Raw
BSW
H2SO4
Treated
BSW
HNO3
Treated
BSW
100
90
80
70
60
50
40
30
20
10
0
20
Raw BSW
H2SO4
Treated
BSW
HNO3
Treated
BSW
30 40
Temperature (
0
C)
50 60
Fig 4.4 Effect of temperature biosorption of AV 54
Raw BSW, H
2
SO
4
treated BSW and HNO
3 treated
BSW
4.4.1. Thermodynamic Parameters:
The free energy change (∆G 0
) enthalpy change ( ∆H ◦) and entropy change ( ∆S ◦) were determined in order to evaluate the effect of temperature on MB biosorption by coffee husks. The Gibbs free energy was evaluated as
∆G
0 = − RT ln K (1)
Where ∆G ◦ is the standard Gibbs free energy change
(J), R is the universal gas constant (8.314 J mol−1
K−1),
T is the absolute temperature (K) and K is the apparent equilibrium constant, defined as
K

C ad, e
C e (2)
Where C e and C ad,e correspond to the equilibrium concentration of AV 54 on the solution and on the sorbent, respectively.
Enthalpy ( ∆H ◦) and entropy ( ∆S ◦) values can be obtained from the slope and intercept of a van’t Hoff equation of ∆G 0
versus T
∆G
0
= ∆H ◦-T ∆S ◦ - (3)
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International Journal of Engineering Trends and Technology (IJETT) – Volume 3 Issue 3 No 3 – May 2012
-2500
-3000
-3500
-4000
-4500
0
-500
300
-1000
-1500
-2000
0
300
-1000
-2000
-3000
-4000
-5000
-6000
-7000
0
300
-1000
-2000
-3000
-4000
-5000
-6000
305
305
305
310
(a)
310
Temperature (K)
(b)
310
315
Temperature (k)
315
315
320
320
320
(c)
325
325
Fig 4.5 Free energy plot of biosorption of AV 54 by (a) Raw BSW (b) H
2
SO
4
treated BSW and (c)
HNO
3 treated BSW
4.5. Sorption Isotherms:
The biosorption data were analyzed with the biosorption isotherm models, namely Langmuir, and
Freundlich. The Langmuir biosorption model [25] is based on the assumption that maximum biosorption corresponds to a saturated monolayer of solute molecules on the sorbent surface.
4.5.1. Langmuir Isotherm model:
The expression of the Langmuir model is given by the following equation
0 e
1 + bC e (4)
325
Where, q e
(mg/g) and C e
(mg/L) are the amount of adsorbed dye per unit mass of sorbent and unadsorbed dye concentration in solution at equilibrium, respectively.Q
0
is the maximum amount of the adsorbed dye per unit mass of sorbent to form a complete monolayer on the surface bound at high
C e
(mg/g), and b (L/mg) is a constant related to the affinity of the binding sites.
The linear form of the Langmuir equation is written as follows
C e
/q e
= 1/Q
0 b+ C e
/ Q
0
(5)
The linear plot of specific biosorption (C e
/q e
) against the equilibrium concentration (C e
) (Fig 4.6) shows that the biosorption obeys the Langmuir model. The
Langmuir constants Q
0
and b were determined from the slope and intercept of the plot and are presented in Table 4.1.
Temperature(k)
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International Journal of Engineering Trends and Technology (IJETT) – Volume 3 Issue 3 No 3 – May 2012
2
1.5
1
0.5
3
2.5
0
0 20 40 c e
(mg/L)
60 80
Raw BSW
H2SO4 Treated BSW
HNO3 Treated BSW
The Freundlich model [27] is an empirical equation that assumes heterogeneous biosorption due to the diversity of biosorption sites.
The Freundlich equation is expressed as q e
= K
F
C e
1/n
(7)
Where K
F
(mg/g (L/mg)
1/n
) is roughly an indicator of the biosorption capacity and 1/n is the biosorption intensity. The magnitude of the exponent, 1/ n , gives an indication of the favorability of biosorption.
Values of n > 1 represent favorable biosorption conditions. [28, 29]
Equation may also be written in the logarithmic form as ln q e
= ln K
F
+(1/n) ln C e
(8)
Values of K
F
and n are calculated from the intercept and slope of the plot and are listed in Table 4.1.
Fig 4.6 The langmuir isotherm for biosorption of
AV 54
The essential characteristics of the Langmuir isotherm can be expressed in terms of a dimensionless constant separation factor R
L
that is given by the following equation [26]:
R
L

1
1
 bQ
0
(6)
Where C
0
(mg/L), is the highest initial concentration of adsorbate and b is Langmuir constant. The parameter R
L
indicates the nature of the shape of the isotherm accordingly:
R
L
> 1 unfavorable biosorption,
0< R
L
< 1 favorable biosorption,
R
L
= 0 irreversible biosorption,
R
L
= 1 linear biosorption
The values of R
L
in the present investigation have been found to be 0.354336, 0.311391 and 0.324427 for biosorption of AV 54 by Raw BSW, H
2
SO
4 treated BSW and HNO
3 treated BSW respectively at room temperature indicating that the biosorption of
AV 54 on BSW is favorable.
4.5.2 The Freundlich isotherm model:
3
2.5
2
1.5
4.5
4
3.5
1
0.5
0
0 1 2 ln c e
(mg/L)
3 4 5
Raw BSW
H2SO4 Treated BSW
HNO3 Treated BSW
Fig 4.7 The Freundlich isotherm for biosorption of
AV 54
The Langmuir, Freundlich biosorption constants evaluated from the isotherms at room temperature with the correlation coefficients is listed in Table 1.
As seen from the table, very high regression correlation coefficient (0.99) was shown by the
Langmuir model. This indicates that the Langmuir model was very suitable for describing the sorption
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International Journal of Engineering Trends and Technology (IJETT) – Volume 3 Issue 3 No 3 – May 2012 equilibrium of AV 54 by the BSW sorbent. The maximum capacity Q
0 determined from the Langmuir isotherm defines the total capacity of the biosorbent for the dye as 36.496 mg/g, 38.46154 mg/g, and
37.17472 mg/g for Raw BSW, H
2
SO
4
treated BSW and HNO
3 treated BSW respectively.
The fact that the Langmuir isotherm fits the experimental data very well may be due to the homogenous distribution of active sites on the BSW surface; since the Langmuir equation assumes that the surface is homogenous. Table 4.1 also shows that the n value is greater than 1 which indicates favorable biosorption
Table 4.1langmuir and freundlich isotherm
4.6 Sorption kinetics:
In order to investigate the mechanism of the sorption of AV 54 onto BSW, the pseudo-first-order, pseudosecond-order kinetic model and intra particle diffusion model were applied to the experimental data.
4.6.1 Pseudo - first order kinetic model
Lagergren proposed a method for biosorption analysis which is the pseudo-first-order kinetic equation of Lagergren [30] in the form:
dq t
/d t
= k1(q e
− q t
) (9)
Integrating this for the boundary conditions t=0 to t = t and q t
=0 to q t
= q t
, gives l log (q e
− q t
) = log q e
− k
1
/2.303 ( t) (10)
Where K
F
(mg/g (L/mg)
1/n
) is roughly an indicator of the biosorption capacity and 1/n is the biosorption intensity
The value of the biosorption rate constant (k
1
) for AV
54 sorption by BSW was determined from the plot of log (q e
−q t
) against t. The parameters of pseudo-firstorder model are summarized in Table 4.2, 4.3, 4.4 for biosorption of AV 54 by Raw BSW H
2
SO
4
treated
BSW and HNO
3 treated BSW .In many cases the first-order equation of Lagergren does not fit well to the whole range of contact time and is generally applicable over the initial stage of the biosorption processes [31]. Although the correlation coefficients,
R
2
, for the application of the pseudo-first-order model are reasonably high in some cases, the calculated q e is not equal to experimental q e
, suggesting the biosorption of AV 54 on BSW is not likely to be a pseudo-first-order for the initial concentrations examined.
Isotherm Raw
BSW
Langmuir
Q
0
R
2
R
L
Freundlich
K f
(mg/g(L/g)
1/n n
R
2
0.9993
H
2
SO
4
Treated
BSW
HNO
3
Treated
BSW
0.354336 0.311391 0.324427
1.089206 1.358511 1.357036
0.8334
0.9984
0.8575
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0.9952
0.8824

International Journal of Engineering Trends and Technology (IJETT) – Volume 3 Issue 3 No 3 – May 2012
1
0
-1
0
-2
-3
-4
-5
-6
3
2
2
1.5
1
0.5
0
-0.5
0 200
50 mg/l
100 mg/l
150 mg/l
200 mg/l
400
4
-6
-8
2
0
-2
0
-4
100 200 300
50 mg/l
100 mg/l
150 mg/l
200 mg/l
100 200
Time (min)
(a)
300
50 mg/l
100 mg/l
150 mg/l
200 mg/l
(c)
Fig 4.8 The pseudo first order kinetic model of biosorption of AV 54 by (a) Raw BSW (b) H
2
SO
4 treated BSW and (c) HNO
3 treated BSW
4.6.2 The pseudo-second-order kinetic model:
The pseudo-second-order equation based on equilibrium Biosorption [29] is expressed as t/q t
= 1/k
2 q
2 e+ 1/q e t (11)
Where k
2
(g/mg min) is the pseudo-second-order rate constant determined from the plot of t/q t versus t, as shown in Fig 10.
Time (min)
(b)
40
35
30
25
20
15
10
5
0
0 200
400
50 mg/l
100 mg/l
150 mg/l
200 mg/l
(a)
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International Journal of Engineering Trends and Technology (IJETT) – Volume 3 Issue 3 No 3 – May 2012
35
30
25
20
15
10
5
0
35
30
25
20
15
10
5
0
0
0 100 200 300
Time (min)
(b)
50 mg/l
100 mg/l
150 mg/l
200 mg/l
50 mg/l
100 mg/l
150 mg/l
200 mg/l
The q e
and k
2
can be calculated from the slopes and intercepts of the plots t/qt versus t. The second-order rate constants values are shown in Table 4.2, 4.3, 4.4 for biosorption of AV 54 by Raw BSW H
2
SO
4 treated BSW and HNO
3 treated BSW. It can be seen from Table 4.2, 4.3, 4.4 that the coefficients for the pseudo-first-order kinetic model obtained at all the studied concentrations were low. Also the theoretical q e values found from the pseudo-first-order kinetic model did not give reasonable values. This suggests that this sorption system is not a first-order. The calculated q e
values agree very well with the experimental values for the case of pseudo-secondorder kinetics, and a regression coefficient of above
0.98 shows that the model can be applied for the entire biosorption process and confirms the chemisorption of AV 54 onto BSW. From Table 2, it was observed that the pseudo-second-order rate constant (k
2
) decreased with increased initial concentration.
Table 4.2. Pseudo - first and Pseudo - second order kinetic model for biosorption of AV 54 by
Raw BSW:
200
Time (min)
400
(c)
Fig 4.9
The pseudo second order kinetic model of biosorption of AV 54 by (a) Raw BSW (b) H
2
SO
4 treated BSW and (b) HNO
3 treated BSW
Initi al con c
Qe,ex p
(mg/g
)
Pseudo first order kinetic model
Pseudo second order kinetic model
K
1
(L/ min) q
(mg/g
) e,cal
R
2
K
2
(g/mg.m
in) q e,cal
(mg/g
)
R
2
50
100
150
200
8.888
16.50
7
22.85
7
0.0089
8
0.0112
8
0.0472
1
3.976 0.650
4
0.01168
10.02
9 0.856
8
0.00324
0.00165
110.3
3
0.00104
0.646
9
22.94 27.93
6 0.0124
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3
0.982
5
9.250
6
17.54
3
24.57
0
30.95
9
0.995
4
0.991
3
0.988
3
0.981
1

Initi al con c. p
International Journal of Engineering Trends and Technology (IJETT) – Volume 3 Issue 3 No 3 – May 2012 kinetic model kinetic model
(mg/g
)
K
1
(L/ min) q e,cal
(mg/g
)
R
2
K
2
(g/mg.
min) q e,cal
(mg/g
)
R
2 the larger the value of C the greater the boundary layer effect.
50 8.730
1
100
150
16.19
0
200
22.38
0
0.053
8
0.055
7
0.047
2
26.66
6
0.011
9
49.15
8
0.655
1
0.0117
5
9.225
0
0.993
6
121.1
4
113.5
2
0.648
4
0.651
7
23.61 0.987
2
0.0032
2
17.60
5
0.0016
5
0.0010
9
24.57
0
30.21
1
0.986
7
3
Initi
0.985
al con
0.972
c
8
Qe,ex p
(mg/g
)
Pseudo first order kinetic model
Pseudo second order kinetic model
K
1
(L/mi n) q e,cal
(mg/g)
R
2
K
2
(g/mg.m
in) q e,cal
(mg/g)
R
2
50 8.571 0.0076
Table 4. 3 Pseudo - first and Pseudo - second order kinetic model for biosorption of AV54 by
H
2
SO
4
treated BSW
5.122
10.269
16.195
19.943
0.838
6
0.934
4
0.931
4
0.952
4
0.00369
0.00171
0.00117
9.107 0.988
8
16.835
24.154
0.985
8
0.0009 28.985
0.987
4
0.986
6
Table 4.4 Pseudo - first and Pseudo - second order kinetic model for biosorption of AV54 by
HNO
3
BSW
100 15.55
5
150
21.90
7
200
26.03
7
0.0094
0.0112
0.0117
4.7 Intraparticle diffusion:
The intraparticle diffusion model which refers to the theory proposed by Weber and Morris is thus tested to identify the diffusion mechanism [32]. According to this theory: q t
= k i t
1/2
+C (12)
Where k i is the intraparticle diffusion rate constant
(mg/g min
1/2
) and C (mg/g) is a constant that gives an idea about the thickness of the boundary layer, i.e.,
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International Journal of Engineering Trends and Technology (IJETT) – Volume 3 Issue 3 No 3 – May 2012
35
30
25
20
15
10
5
0
0
20
15
10
5
0
35
30
25
0
10
0.5
0.5
t
1/2
(a)
10
(min
1/2
(b)
)
20
50 mg/l
100 mg/l
150 mg/l
200 mg/l
35
30
25
20
15
10
5
0
0
50 mg/l
100 mg/l
150 mg/l
200 mg/l
20
10
1/2
1/2
20
(c)
Fig 4.10 Plots for evaluating intraparticle diffusion rate constant for biosorption of AV 54 by (a) Raw BSW (b) H
2
SO
4
treated BSW and (c)
HNO
3 treated BSW.
50 mg/l
100 mg/l
150 mg/l
200 mg/l
If the Weber–Morris plot [33] of q t versus t
0.5 gives a straight line, then the sorption process is controlled by intraparticle diffusion only. The ki and C can be calculated from slope and intercept of the plots q t versus t
0.5
.The intraparticle diffusion rate constants values are shown in Table 3. It can be seen from
Fig11. That the regression was 0.93. Plots for evaluating intraparticle diffusion rate constant for sorption of AV 54 onto BSW.Fig.11. But the plot did not pass through the origin, suggesting that biosorption involved intraparticle diffusion, but that was not the only rate-controlling step. Other kinetic models may control the biosorption rate. This finding is similar to that made in previous work on AV 54 biosorption.
Table 4.5 Intraparticle diffusion constants for different initial AV 54 concentration biosorption of AV 54 by Raw BSW:
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International Journal of Engineering Trends and Technology (IJETT) – Volume 3 Issue 3 No 3 – May 2012
Table 4.6 Intraparticle diffusion constants for different initial AV 54 concentration for biosorption of AV54 by H
2
SO
4
treated BSW
Table 4.7 Intraparticle diffusion constants for different initial AV 54 concentration for biosorption of AV54 by HNO
3
BSW
4.8 SEM and FTIR of BSW:
The surface structure of BSW was analyzed by SEM before AV 54 biosorption. The textural structure examination of BSW particles can be observed from the SEM photographs. This figure reveals that the
Initial concentratio n (mg/L)
50
100
150
Initial
(mg/L)
50 ki
(mg/g min
1/2
)
C
0.450
2
1.526
7 q e,cal
(mg/g)
9.32439
3
R
2
0.922
8
0.848
7
2.238
4
16.9383
2
0.933
2
1.232
9
2.981
5
24.3359
5
0.936
5 ki C
3.280
3 q e,cal
R
2
0.936
8 1 min
1/2
)
3
0.4649 2.5868 2.5868 0.835
100 0.9301 3.5337 3.5337 0.9119
150 1.3442 3.6821 3.6821 0.9453 pores within the BSW particles are highly heterogeneous.
The FTIR spectrum of BSW (BSW) was obtained to
Initial concentration
(mg/L) ki (mg/g min
1/2
)
C q e,cal
(mg/g)
R
2
50 0.4547 2.2542 2.2542 0.8834
100
150
0.9138 2.8367 2.8367
1.3167 2.9751 2.9751
0.9455
0.954
200 1.6037 2.4395 2.4395 identify the functional groups in BSW. The FTIR spectrum had showed the following bands.,
3500-3400 cm
-1
: O-H stretch
2900-3000 cm
-1
: C-H stretch
1700-1600 cm
-1
: C=C stretch
1300-1400 cm
-1
: C-(CH
3
)
2
1106.17 cm
-1
: C-O stretch
1062.51 cm
-1
: C-O-C stretch
666.44 cm
-1
: C-OH stretch
0.9606
200 1.7377 2.6867 2.6867 0.9677
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International Journal of Engineering Trends and Technology (IJETT) – Volume 3 Issue 3 No 3 – May 2012
Fig 4.11 FTIR spectrum of Raw BSW (b)
(a)
(c)
Fig 4.12 Scanning electron microscope of (a) Raw
BSW (b) H
2
SO
4
treated BSW and (c) HNO
3 treated BSW. (Before adsorption)
5.CONCLUSION
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International Journal of Engineering Trends and Technology (IJETT) – Volume 3 Issue 3 No 3 – May 2012
BSW is identified to be an effective sorbent for the removal of AV 54 dye from aqueous solution. The biosorption is highly dependent on various operating parameters like; initial dye concentration, contact time, and sorbent dosage. The percentage of
Biosorption decreases from about 84.112 to 66.075,
90.03215% to 69.78588% and 88.42444% to 67.68% for Biosorption of AV 54 by H
2
SO
4
treated BSW,
HNO
3 treated BSW respectively as the initial dye concentrations increases from 50 mg/L to 200 mg/L at the end of the equilibrium time. The percentage biosorption increases from 42.08 % to 85.209%,
46.6273% to 91.6398 % and 43.408% to 90.032 % for for Biosorption of AV 54 by H
2
SO
4
treated BSW,
HNO
3 treated BSW respectively as the sorbent dosage increases from 0.1 g to 0.6 g for 50 mg/L. the dye uptake was maximum at pH 2.The sorption of
AV 54 onto BSW was controlled by exothermic process. The equilibrium data were analyzed using
Langmuir and Freundlich isotherm. The experimental data were best correlated by Langmuir isotherm. The maximum monolayer biosorption capacity of BSW was found to be 36.496 mg/g, 38.46154 mg/g, and
37.17472 mg/g for Raw BSW, H
2
SO
4
treated BSW and HNO
3 treated BSW respectively at room temperature. The sorption kinetics of AV 54 onto
BSW is well described by pseudo second order kinetics. The thermodynamic parameters were determined.
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