REMOVAL OF CADMIUM USING COCOS NUCIFARA.

L: EQUILIBRIUM AND KINETIC STUDIES

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ABSTRACT:
This investigation comprises the equilibrium and kinetics on biosorption of Cadmium ions from aqueous solutions using `Coconut husk powder in a batch process. The results indicate that biosorption of Cadmium is increased with an increase in adsorbent dosage and decrease in adsorbent size. A significant increase in percentage removal of Cadmium is observed as pH value is increased from 1 to 7 and the percentage removal is decreases beyond pH 7. Increased initial concentration of Cadmium in the aqueous solution results in lower percentage of biosorption. Freundlich and Langmuir isotherm models describe the present data very well indicating favourable biosorption. The biosorption follows pseudo-secondorder kinetics.

Key words: Adsorption, Isotherms, Kinetics of Cadmium adsorption 1. INTRODUCTION

Rapid industrialization generating large quantities of liquid effluents with varying quantities heavy metals. Cadmium is one among them and is toxic when it is present in small quantities. The effluent based cadmium take different roots for its dispersion including fish, algae and other aquatic flora and fauna. Removal of this metal is vary much essential. Several studies have been conducted with varying degree of success. Toxic heavy metals include cadmium, mercury, silver, lead, tin, and chromium, although several nutrient metals, notably zinc, copper and nickel, can also be toxic at elevated concentrations. Waste water of industrial and domestic, if not properly managed, is responsible for severe damage to the environment and adversely affecting the health of the people. In recent years, increasing attention has been placed on removal of toxic metals from industrial wastewaters, not only for pollution control aspect but also to enable the reuse of water and toxic materials themselves in some cases. The industries where toxic metals are found in the effluent are shown in Table-I. Among these heavy metals, Cadmium represents major hazardous waste in the environment. Cadmium can be taken into the body through the pulmonary system from contaminated air or cigarette smoke or via the digestive system through water or food contamination from plant Cadmium uptake. Cadmium can cause problem such as hypertension, emphysema, renal cancer, and prostrate cancer and kidney disease. Several processes are available for the removal of cadmium from industrial effluents. These include adsorption, bio-sorption with organisms like bacteria, yeast, or algae, precipitation, filtration through lime stone beds, ion exchange, reverse osmosis, evaporation, and electrodialysis The present investigation looks into a specific process, for the removal of toxic heavy metal, cadmium by adsorption using an economically viable low cost adsorbent developed from an easily, freely and abundantly available Coconut Husk Powder.

2. MATERIALS AND METHODS

The matured Coconut Husk Powder is collected from Visakhapatnam region. They are dried at room temperature in a shade followed by oven at 110 0C till the constant weight of the sample is attained. The resulting husk is sieved to different size fractions using Rotap sieve shaker. The size fractions are 53, 75,106 and 212m are preserved in glass bottles for use as adsorbent.

2.1 Metal solution

3CdSO48H2O is used in the preparation of cadmium stock solution. All the required solutions are prepared with double-distilled water. 2.132gm of 3CdSO 48H2O is dissolved in 1L of distilled water to produce 1000 mg/l of cadmium stock solution. Samples of different concentrations of Copper are prepared from this stock solution by appropriate dilutions. 81ml of 1000mg/l cadmium stock solution is taken in a 1000 ml volumetric flask and is made up to the mark with distilled water.

2.2 Analysis
These samples are analyzed in Atomic Adsorption Spectroscopy (AAS) at 326.1nm to obtain final concentrations of Cadmium. The same experimental procedure is repeated with other adsorbent sizes varied as 75, 106 and 212m.

3. RESULTS AND DISCUSSION 3.1Effect of agitation time:

Agitation time has influence on metal uptake. Percentage copper removed was calculated by the expression [(Co-Ct)/Co] * 100. Time versus concentration of metal in solution data is obtained. The percentage removal of cadmium against the agitation time was shown in figures 1 for different dosages (0.5, 1.0, 1.5 and 2.0gm). The % adsorption is found to increase upto 50 min and there after, negligible increase in percentage adsorption is noticed with agitation time. It is noticed that the rate of adsorption is fast in the initial stages because adequate surface area of the adsorbent is available for the adsorption of Cadmium. As time increases, more amount of Cadmium gets adsorbed onto the surface of the adsorbent and the surface area available for adsorption decreases. The adsorbate, normally, forms a thin one molecule thick layer over the surface. When this monomolecular layer covers the surface, the adsorbent capacity is exhausted. The maximum percentage of adsorption is attained at 50 min of agitation. The percentage removal of cadmium becomes almost constant after 50 min. indicating the attainment of the equilibrium. Therefore all other experiments are conducted at this agitation time.

3.2 Effect of adsorbent size:

The variations in percentage removal of cadmium from the aqueous solution with particle size (53m, 75m, 106m and 212m) are obtained at different adsorbent dosages- namely at 0.5, 1.0, 1.5 and 2.0gm. The results are drawn as figure 2 as percentage removal of cadmium versus adsorbent size. The percentage removal of cadmium is increased as the adsorbent particle size decreased. This phenomenon is expected, as the size of the particle decreases, surface area of the adsorbent increases, thereby the number of active sites on the adsorbent are more and better exposed to the adsorbate.

3.3Effect of adsorbent dosage:

The percentage removal of cadmium is drawn against adsorbent dosage for

different adsorbent sizes (53m, 75m, 106m and 212m) and shown in figure 3. It is evident from the plots that the percentage removal of metal from the aqueous phase increases with increase in the adsorbent dosage. For the adsorbent size 53m, percentage removal of cadmium increases from 72.84% to 91.98%, as dosage is increased from 0.5 to 2.0 gm. Such behavior is obvious because the number of active sites available for metal removal would be more as the amount of the adsorbent increases.

3.4Effect of initial concentration of cadmium in the aqueous solution:

A graph is drawn as the percentage removal of cadmium versus initial concentration of cadmium and is shown in fig.4. The percentage removal of cadmium is decreased from 93.48% to 86.17% as the initial concentration of cadmium in the aqueous solution increases from 23 mg/l to 188 mg/l. Such behavior can be attributed to the increase in the amount of adsorbate to the unchanging number of available active sites on the adsorbent (since the amount of adsorbent is kept constant.

3.5Effect of pH of the aqueous solution:

pH influences the surface charge of the adsorbent, the degree of ionization and the adsorbate. So pH is an important factor controlling the process of adsorption. It is shown in fig 5. In the present investigation, adsorption data are obtained in the pH range of 1 to 14 for cadmium initial concentration of 81 mg/l and 2 gm of adsorbent dosage, 53m size adsorbent. The effect of pH of aqueous solution on percentage removal of cadmium is drawn and shown in figure 8. The percentage removal of metal is increased from 69.14%to 93.83% as pH is increased from 1 to 7. The percentage removal is decreased from 83.95% to 70.99% as pH increases from 8 to 14. In the present investigation, the maximum percentage removal of cadmium is obtained for 2 gm of 53m size adsorbent at equilibrium. The principal driving force for metal ion adsorption is the electrostatic interaction (i.e) attraction between adsorbent and adsorbate. The greater the interaction, adsorption of heavy metal will be more. With an increase in interaction, the cadmium ions replace H+ ions bound to the adsorbent for forming part of the surface functional groups such as OH, COOH etc.

4. EQUILIBRIUM STUDIES 4.1Freundlich isotherm for adsorption of cadmium:

The Freundlich relationship is an empirical equilibrium relationship. It does not indicate a finite uptake capacity of the adsorbent and can thus only be applied in case of low and intermediate concentration ranges. However, it is easier to handle mathematically as it is a simple relationship. The freundlich isotherm is given by qe = Kf Cen ---(3) Taking logarithms on both sides, we get logqe = logKf + n logCe ---(4) Where Kf and n are known as Freundlich constants obtainable from the plots of logqe versus log Ce on the basis of the linear form of the equation (4)Freundlich isotherm is drawn between log Ce and log qe shown in figure 6. The resulting lines have the correlation coefficient of 0.9862. The following equations are obtained from the plot drawn in fig.10.

log qe = 0.6880log Ce 0.3368 at 303K The slopes (n) of the above equations are varied between 0.6880. The n value satisfies the condition of 0< n< 1 indicating favorable adsorption.

4.2Langmuir isotherm for adsorption of cadmium:

Since the chemical forces fall off very rapidly with distance, it is probable that chemisorption does not extend beyond a single layer of adsorbate on the surface of the solid. It can be anticipated as first pointed out by Langmuir that chemisorbed adsorbate layers may be only one molecule thick. The Langmuir isotherm is the most widely used two-parameter equation. The relationship is of a hyperbolic type form: qe/qm= bCe / (1+bCe) --- (5) Where Ce is the concentration of the adsorbate at equilibrium, qe is the amount adsorbed at equilibrium per unit mass of the adsorbent, qm is the maximum amount adsorbed per unit mass of the adsorbent and b is the coefficient related to affinity. Equation (5) can be rearranged as (Ce/qe) = 1/bqm + Ce/qm --- (6) From the plots between (Ce/qe) and Ce, we can calculate the slope (1/qm) and the intercept (1/b). Further analysis of the Langmuir equation is made on the basis of separation factor, RL defined as RL = 1/(1+bCe) 0< RL<1 RL > 1 RL = 1 RL = 0 indicates indicates indicates indicates Favorable adsorption Unfavorable adsorption Linear adsorption Irreversible adsorption --- (7)

Langmuir isotherms drawn in figure 7 have good linearity (correlation coefficient, R~ 0.9856) indicating strong binding of cadmium ions to the surface of Coconut husk powder. The separation factor (RL), obtained is 0.7167 shows favourable adsorption. The following equation obtained from fig.7. (Ce /qe) = 0.1562Ce + 2.57 at 303K The isotherm constants for cadmium Coconut husk powder interactions at 303K, t = 50min, Co = 81mg/l, dp = 53m and w = 2gm are shown in Table-1.

5. KINETICS OF ADSORPTION
The order of adsorbate adsorbent interaction has been described by using various kinetic models. Traditionally, the pseudo first order model derived by Lagergren finds wide application. On the other hand, several authors have shown that pseudo second order kinetics can also describe these interactions very well in certain specific cases. In the case of adsorption preceded by diffusion through a boundary, the kinetics in most cases follows the pseudo first order rate of equation of Lagergren and graph is shown in fig 8. (dqt/dt) = Kad (qe qt) --- (8) Where qe and qt are the amounts adsorbed at t, min and at equilibrium and Kad is the rate constant of the pseudo first order adsorption process. Equation (8) is then written as (dqt / (qe qt)) = Kad dt --- (9)

After applying the initial condition qt = 0 at t = 0 and integration, we get log (qe qt) = log qe (Kad/2.303) t --- (10) Plot of log (qe qt) vs t gives a straight line for first order kinetics, which allows computation of the adsorption rate constant, Kad. If the experimental results do not follow equations (8) and (10), they differ in two important aspects: Kad (qe qt) then does not represent the number of available adsorption sites and log qe is not equal to the intercept of the plot of log (qe qt) against t.In such cases, pseudo second order kinetics, given by (dqt/dt ) = K (qe qt)2 --- (11) is applicable, where K is the second order rate constant and its shown in fig 9. The plots (t/qt) versus t for the present data are indicated in figs.15, 16, 17 and 18. The linearity of the plots (R=0.999) confirms the suitability of pseudo second order rate equation. The following second order rate equations are obtained from the graphs: From fig.15, the following pseudo second order rate equations are obtained. For w = 0.5, 1.0, 1.5 and 2.0gm of dp = 53m (1) (t/qt) = 0.1678t + 0.1891 (2) (t/qt) = 0.3147t + 0.2640 (3) (t/qt) = 0.4501t + 0.4377 (4) (t/qt) = 0.5304t + 0.6529

6.

CONCLUSIONS

The following conclusions are drawn from the studies 1. The optimum agitation time for the metal adsorption is 50 minutes. 2. The percentage removal of cadmium from the aqueous solution increases with a decrease in the particle size of the adsorbent. 3. The percentage removal of cadmium from aqueous solution is augmented with increase in weight of the adsorbent. 4. Higher the concentration of cadmium in the aqueous solution, the percentage removal of cadmium from the aqueous solution is decreased. 5. Percentage removal of cadmium from the aqueous solution is increased significantly with increase in pH value from 1 to 7 and removal decreases for pH beyond 7. 6. In the range of variables studied, percentage removal is increased from 50.62 % to 91.98 %. 7. The data are well represented by Freundlich and Langmuir isotherms indicating favorable adsorption of cadmium by the adsorbent. 8. The kinetic studies show that the adsorption of cadmium is better described by pseudo- second- order kinetics.

Graphs:

95
100

dp, m Co, mg/l 90 53 75 106 212 81 81 81 81

V, ml 50 50 50 50

t, min pH 50 50 50 50 4.1 4.1 4.1 4.1

% Removal of Cadmium

90

% Removal of Cadmium

85

80

80

70 W ,gm Co, mg p pH /l l W (gm) Co (mg/L) dV, m d p, m pH 60 0.5 1.0 1.5 2.0 81 81 81 81 50 50 50 50 53 53 53 53 4.1 4.1 4.1 4.1

75

70

65
50 0 20 40 60 80 100 120 140

0.4

0.6

0.8

1.0

1.2

1.4

1.6

1.8

2.0

2.2

Agitation tim , t (m e in)

Adsorbent Dosage , W (gm)

Fig 1 Effe of ag tion tim on pe nta ere ova of Ca ium . ct ita e rce g m l dm
120 W, gms Co, mg/l V, ml pH 0.5 1.0 1.5 2.0 81 81 81 81 50 50 50 50 4.1 4.1 4.1 4.1

Fig 3 Effect of adsorbent dosage on percentage removal of Cadmium

96

110

% Removal of Cadmium

94

W, gms 2.0

dpp,m 53

pH 4.1

% Removal of Cadmium

100

92

90

90

80

Co, ppm W, gms

88

dp

84

2.0

53

70

86

60 40 60 80 100 120 140 160 180 200 220

84 0 20

Adsorbent Size (m)

Initial concentration of Aqueous Solution (mg/l)

40

60

80

100

120

140

160

180

200

Fig 2. Effect of adsorbent size on percentage removal of Cadmioum

Fig 4 Effect of initial concentration of aqueous solution on . percentage removal of CAdmium

0.0
100 95

-0.2 -0.4 -0.6

lo g( qe -

r2 =0 .981
qt )=

Co, ppm W, gms 81 2.0

dp p,m 53

% Removal of Cadmium

log (qe - qt )

90 85 80 75 70 65 0 2 4

-0.8 -1.0 -1.2 -1.4 -1.6 -1.8

Co, ppm W, gms 81 2.0 dp p,m 53

-0 .32 41 t-

0.2 09 5

pH 4.1

pH of the Aqueous Solution

10

12

14

16

10

20

30

40

50

Agitation time , t ,(min)

Fig 5 Effect of pH of the aqueous solution on . pe rcentage removal of cadmium

Fig 8. First order kinetics for adsorption of Cadmium

Co, ppm W, gms 84 2.0

dpp,m 53

pH 5.76

70
0.8

W, gms C o, mg/l 0.5 1.0 1.5 2.0 81 81 81 81

V , ml m pH dp, 50 50 50 50 53 53 53 53

T, K 4.1 4.1 4.1 4.1 303 377 303 0.4 303 501t + 4 . 303 0 t= t/q 40 0.26 7t + .314 =0 t/qt
891 t +0.1 0.1678 t/qt =

60 50
C og 0l 88 0.6 =

0.6

r =0 86 .9 2

t / qt (gm - min / mg)

0.4

68 .33 -0 e

40 30 20 10 0
2

log qe

0.2

qe log

r = 0.999
t t/q

t+ 04 .53 =0

9 52 0.6

0.0

W, gms 2.0

dpp,m 53

pH 4.1

Co, ppm W, gms 84 2.0 Co, ppm W, gms 84 2.0 Co, ppm W, gms 84 2.0 Co, ppm W, gms 84 2.0 Co, ppm W, gms 84 2.0 Co, ppm W, gms 84 2.0 Co, ppm W, gms 53 dpp,m 53 dpp,m 53 dpp,m 53 dpp,m 53 dpp,m

dpp,m

pH

53 dpp,m

pH 5.76

-0.2

pH 5.76

pH 5.76

pH 5.76

-0.4 0.0 0.2 0.4 0.6 0.8 1.0 1.2 1.4 1.6

pH 5.76

log Ce Fig 6 Freundlich isotherm for adsorption of Cadimum w.r.t concentration . using Coconut husk powder

20
84

84 4 0 2.0 Co, ppm W, gms 2.0

6 0 53 dpp,m

80 pH 5.76

pH 5.76

10 0

12 0

140

84 2.0 Co, ppm W, gms

dp m A gitation53 pH 5.76, (min) time , t

p,

53

5.76

Fig 9. Second order kinetics for adsorption of Cadmium

6 r2 = 0.9856
e 2C 56 0.1

.57 +2

Ce / qe (gm/L)

/ Ce

= qe

4
W, gms dpp,m 53 pH 4.1

2.0

2 0 5 10 15 20 25 30

Ce (mg/L)

Fig7. Langmuir isotherm for adsorption of Cadmium w.r.t concentration using Coconut husk powder

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