Process Optimization and Biosorption of Lead Using: Albizia Saman Leaf Powder
Process Optimization and Biosorption of Lead Using: Albizia Saman Leaf Powder
Process Optimization and Biosorption of Lead Using: Albizia Saman Leaf Powder
579-592
PROCESS OPTIMIZATION AND BIOSORPTION OF LEAD USING ALBIZIA SAMAN LEAF POWDER
Rao, P.J1, Kumari, R.S1,Babji J.S2, Naga Lakshmi, N.V.R3 and Raju, Ch.A.I.1*
2
Department of Chemical Engineering, Andhra University, Visakhapatnam 530 003 Department of Computer Science and Systems Engineering, Andhra University, Visakhapatnam 530 003 3 Department of Petroleum Engineering, GIET College of Engineering, Rajahmundry
ABSTRACT
Water pollution is one of the signs that humans have exceeded the limits and causing health problems for living beings on earth. The present paper comprises the optimization and biosorption of lead from aqueous solution using Albizia saman leaf powder as biosorbent. Single Step Optimization was considered for preliminary runs with the variables agitation time, biosorbent size, pH of the solution, initial concentration of the aqueous solution, dosage of biosorbent and temperature. The Central Composite Design (CCD) was used for final runs optimization using Response Surface Methodology (RSM). Results indicated that the optimum agitation time for biosorption of lead is 50 min. The increase in mass of biosorbent lead to increase in lead (pb) ion biosorption due to the increase in the number of active biosorption sites. Maximum percentage biosorption is observed at a pH of 6 and with particle size of 53 m. Experimental data were better described by pseudosecond-order model. The adsorption isotherm could be well fitted by the Langmuir equation followed by Freundlich and Temkin. Over and all, Albizia Saman leaf powder can be used as an effective natural biosorbent for the economic treatment of aqueous solutions containing lead.
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Final experimental runs for optimization were obtained through Response Surface Methodology from Design of Experiments (DoE) using STATISTICA software. The extent of biosorption of lead calculated at the preliminary optimum conditions is verified with the final runs for the optimum conditions.
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3.7 Isotherms 3.7.1 Langmuir isotherm Irving Langmuir developed an isotherm named as Langmuir isotherm, which is the most widely used simple twoparameter equation. Langmuir isotherm is drawn between Ce vs Ce/ qe shown in fig 7. The equation obtained is (Ce/qe) = 2.8729 Ce + 0.05929 with a good linearity (correlation coefficient, R2=0.9791) indicating strong binding of lead ions to the surface of albizia saman leaf powder. The separation factor (RL) of 0.9219 shows favorable biosorption (0< RL<1). Hence a maximum biosorption capacity of the Albizia saman leaf powder for lead is find to be 16.8656 mg/g by Langmuir isotherms at 303K (mass of biosorbent: 10 g/L) [17, 18]. 3.7.2 Freundlich isotherm Freundlich empirical adsorption isotherm equation can be applied in case of low and intermediate concentration ranges. Freundlich isotherm is drawn between log qe and log Ce, in fig. 8 The equation obtained is log qe = 0.6815 log Ce 0.2404. The resulting equation has a correlation coefficient of 0.9655. The n value in the above equations is 0.6815, satisfies the condition of 0<n<1 indicating favorable biosorption. Kf is 0.5748 mg/g [19]. 3.7.3 Temkin isotherm Temkin and Pyzhev isotherm equation describes the behavior of many adsorption systems on the heterogeneous surface. The present data are analysed according to the linear form of Temkin isotherm and the linear plot is shown in fig. 9 The equation obtained for lead biosorption is: q e = 3.1546 ln Ce -3.8813 with a correlation coefficient 0.9637. The best fit model is determined based on the linear regression correlation coefficient (R2) [20]. 3.8 Kinetics of biosorption Kinetic models are used to describe the order of biosorbate biosorbent interactions. Traditionally, the first order model of Lagergren finds wide application. In the case of biosorption preceded by diffusion through a boundary, the kinetics in most cases follows the first order rate equation of Lagergren [21]: (dqt/dt) = K1 (qe qt) where qe and qt are the amounts adsorbed at t, min and equilibrium time and Kad is the rate constant of the first order adsorption. The above equation can be presented as log (qe qt) = log qe (K1/2.303) t log (qe qt) = 0.02357 t 0.3027 ; R2 = 0.9620 Plot of log (qeqt) versus t gives a straight line for first order kinetics, facilitating the computation of biosorption rate constant (K1). If the experimental results do not follow the above equation, they differ in two important aspects: K1 (qe qt) does not represent the number of available adsorption sites and log q e is not equal to the intercept. In such cases, pseudo second order kinetic equation [22, 23]: (dqt/dt ) = K2 (qe qt)2 is applicable, where K2 is the second order rate constant. The other form of the above equation is: (t/qt) = (1/ K2qe2) + (1/qe) t (t/qt) = 0.6229 t + 1.1720; R2 = 0.9959 The pseudo second order model based on above equation, considers the rate-limiting step as the formation of chemisorptive bond involving sharing or exchange of electrons between the biosorbate and biosorbent. If the pseudo second order kinetics is applicable, the plot of (t/qt) versus t gives a linear relationship that allows computation of q e and K2. In the present study, the kinetics are investigated with 50 mL of aqueous solution (C 0= 20 mg/L) at 303 K with the interaction time intervals of 1 min to 50 min. Lagergren and pseudo plots for biosorption of lead with biosorbent size 53 m of Albizia saman leaf powder are drawn in figs. 10 & 11. As the correlation coefficient values for the pseudo second order kinetics is 0.99 which is better than first order kinetics (R2=0.962), very well describes the biosorption mechanism of lead using Albizia saman leaf powder. 3.9 Thermodynamics of biosorption The process of Biosorption is temperature dependant. In general, the temperature dependence is associated with three thermodynamic parameters namely change in enthalpy of biosorption (H), change in entropy of biosorption (S) and change in Gibbs free energy (G). The Vant Hoffs plots for the biosorption data obtained at initial concentrations of the lead are shown in fig. 12. The equation obtained is log qe / Ce = 0.41701(1/T) + 0.5921. The correlation coefficient is 0.9568. In the present study, the enthalpy change is H is 7.9845 J/mole is positive indicating that the biosorption is endothermic. The value of S is 11.3370 J/mole is also positive indicating the irreversibility of process, G is 3427.1334 J/mole is negative indicating the spontaneity of biosorption.
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3.10 Optimization of the selected parameters using CCD In order to determine an optimum condition for lead ions removal, the parameters having greater influence over the response are to be identified. In the present study, the relationship between four independent variables and percent of lead ions biosorption is fitted well with the quadratic model. The regression equation for the optimization of lead biosorption: % biosorption of lead (Y) is a function of the W (X1), Co (X2), pH (X3), and T (X4). Table1 presents the coded levels and Table 2 represents the variations in the corresponding coded values of four parameters and response based on experimental runs and predicted values proposed by CCD design. Y = 452.007 + 0.429 X1 + 0.369 X2 + 5.846 X3 + 3.347 X4 0.006X12 0.015X22 0.548 X32 0.006 X42 + 0.004 X1X2 0.010 X1X3 + 0.026 X2X3 + 0.002 X3X4 -------------------------------- (1) Interpretation of the regression analysis: The results of above regression model for Eq. (1) (in the form of analysis of variance ANOVA) are compiled in Table-3. In general, the Fischers F-statistics value (=MSmodel/MSerror), where MS (mean square) with a low probability P value indicates high significance of the regression model. The ANOVA of the regression model demonstrates that the model is highly significant, as is evident from the Fishers F-test (Fmodel = 33852) and a very low probability value (Pmodel > F=0.000000). More over, the computed F-value (F0.05 (14.15) = MSmodel/MSerror = 33852) is greater than that of the tabular Fvalue (F0.05 (14.15) tabulars = 2.42) at the 5% level, indicating that the treatment differences are significant. The significance of the regression coefficient of the parameter can be verified by the Students t-test as a tool, while P values signify the pattern of interaction among the factors. From the Table4, we can observe that, the larger the value of t and smaller the value of P, more significant is the corresponding coefficient term. By analyzing the t values and P values from Table-4, it is found that the X1, X2, X3, X4, X12 , X22 , X32 , X42 X1X2, X1X3, X1X4, X2X3, X2X4, X3X4 have high significance to explain the individual and interaction effect of biosorption variables on the biosorption of lead to predict the response. A positive sign of the coefficient represents a synergistic effect which means response (% biosorption of lead increases with the increase in effect, while a negative sign indicates an antagonistic effect which means response (% biosorption of lead) decreases with the increase in effect. The optimal set of conditions for maximum percentage biosorption of lead is pH = 6.0250, biosorption dosage (w) = 31.7191 g/L, initial lead concentration (C o) = 19.8996 mg/L and temperature = 304.0673 K. The extent of biosorption of lead calculated at these optimum conditions is 84.90612%. Fig. 13 shows the comparison between the % biosorption obtained through experiments and predicted. The correlation coefficient (R2) provides a measure of the models variability in the observed response values. The closer the R2 value to 1, the stronger the model is and it predicts the response better. In the present study the value of the regression coefficient (R 2 = 0.99997) indicates that 0.003% of the total variations are not satisfactorily explained by the model. The ANOVA Table-3 can be used to test the statistical significance of the ratio of mean square due to regression and mean square due to residual error. Figs. 15 to 20 were represented as a function of two factors at a time, holding other factors fixed at zero level for the Interaction effects of biosorption variables.
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%biosorption of lead
75
70
65 % biosorption of lead 60
90 88 86
1.60
% biosorption of lead
84 82 80 78 76 74 72 70 40 60 80 100 120
Biosorbent size m
80
2.0
% biosorption of lead
65
60
1.4
1.2
55 1 2 3 4 5 6 7 8 9
1.0
pH of aqueous solution
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metal uptake
metal uptake
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80
12
% biosorption of lead
0 200
86
1.8
% Biosorption of lead
80
86
0.58
% biosorption of lead
0.56
0.54
0.52
310
320
0.50 330
Temperature, K
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metal uptake
83
Metal uptake
metal uptake
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Ce/qe gm/L
C
4
/q e
C 29 .87 =2
,r 92 92 .05 +0 e
91 .97 =0
2 0 10 20 30 40 50 60 70 80
Ce
1.2
0.8
0.6
q log
0.4
Ce log 15 .68 =0
log qe
,r 04 24 -0.
55 .96 =0
0.2
0.0 0.4 0.6 0.8 1.0 1.2 1.4 1.6 1.8 2.0
log Ce
-2
.15 46
lnC
e- -3 .
88 13 ,r2 =0 .96 37
qe
ln Ce
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-1.4
-1.0
log (qe-qt)
-0.8
( log
-0.6
q e-
= q) t
7 35 02 -0.
,r 27 30 -0.
20 .96 =0
-0.4
-0.2
0.0 0 10 20 30 40 50
t, min
35 30 25 20
t/qt
15
= t/q t
10 5 0
9 22 0.6
, 20 .17 t+1
59 99 2 0. r=
Dp= 53 m W = 10 g/L T =303 K pH =6.0 C0=20 mg/L
10
20
30
40
50
60
t, min
-0.65
log
-0.75
q/ e C
e =-0
.41
70 (1
logqe/Ce
/ t)
+0 .59
-0.80
-0.85
21 ,
r2 =
0.9
56
-0.90
1/t x 103min
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Fig. 15 Surface contour plot for the effects of dosage and initial concentration of lead on % biosorption
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Fig. 16 Surface contour plot for the effects of dosage and pH on % biosorption of lead
Fig. 17 Surface contour plot for the effects of dosage & Temperature on % biosorption of lead
Fig. 18 Surface contour plot for the effects of initial concentration and pH on % biosorption of lead
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Fig. 19 Surface contour plot for the effects of initial concentration and Temperature on % biosorption of lead
Fig. 20 Surface contour plot for the effects of pH and Temperature on % biosorption of lead
TABLE1 Levels of different process variables in coded and un-coded form for % biosorption of lead using Albizia saman leaf powder
Var Name -2 X1 Biosorbent dosage, w, g/L Initial concentration, Co, mg/L pH of aqueous solution Temperature, T, K 10 Range and levels -1 20 0 30 1 40 2 50
X2
10
15
20
25
30
X3 X4
4 283
5 293
6 303
7 313
8 323
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TABLE2 Results from CCD for lead biosorption by Albizia saman leaf powder
Runs 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 X1, W -1.00 -1.00 -1.00 -1.00 -1.00 -1.00 -1.00 -1.00 1.00 1.00 1.00 1.00 1.00 1.00 1.00 1.00 -1.00 2.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 X2, Co -1.00 -1.00 -1.00 -1.00 1.00 1.00 1.00 1.00 -1.00 -1.00 -1.00 -1.00 1.00 1.00 1.00 1.00 0.00 0.00 -2.00 2.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 X3, pH -1.00 -1.00 1.00 1.00 -1.00 -1.00 1.00 1.00 -1.00 -1.00 1.00 1.00 -1.00 -1.00 1.00 1.00 0.00 0.00 0.00 0.00 -2.00 2.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 X4, T -1.00 1.00 -1.00 1.00 -1.00 1.00 -1.00 1.00 -1.00 1.00 -1.00 1.00 -1.00 1.00 -1.00 1.00 0.00 0.00 0.00 0.00 0.00 0.00 -2.00 2.00 0.00 0.00 0.00 0.00 0.00 0.00 Experimental 82.70 82.98 82.72 83.06 81.94 82.16 82.44 82.76 82.96 83.14 82.54 82.80 83.04 83.18 83.16 83.36 82.04 82.92 83.50 83.28 82.60 82.78 82.44 82.92 84.88 84.88 84.88 84.88 84.88 84.88 Predicted 82.70 82.98 82.71 83.05 81.93 82.15 82.44 82.75 82.96 83.13 82.54 82.80 83.04 83.18 83.15 83.36 82.04 82.91 83.49 83.28 82.59 82.78 82.43 82.92 84.88 84.88 84.88 84.88 84.88 84.88
Model
24.3289
14
1.737778
33852.82
0.0000
Error
0.00077
15
0.0000513
Total
24.32967
Df- degree of freedom; SS- sum of squares; F- factor F; P- probability. R2=0.99997; R2 (adj):0.99994
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Table4 Estimated regression coefficients for the lead biosorption onto Albizia saman leaf powder
Terms Mean/Intercept Dosage, w, g/L (L) Dosage, w, g/L (Q) Conc, Co, mg/L (L) Conc, Co, mg/L (Q) pH (L) pH (Q) Temperature, T, K (L) Temperature, T, K (Q) 1L by 2L 1L by 3L 1L by 4L 2L by 3L 2L by 4L 3L by 4L Regression coefficient -452.007 0.429 -0.006 0.369 -0.015 5.846 -0.548 3.347 -0.006 0.004 -0.010 -0.000 0.026 -0.000 0.002 Standard error of the coefficient 1.335753 0.005629 0.000014 0.011310 0.000055 0.057298 0.001365 0.008391 0.000014 0.000036 0.000179 0.000018 0.000357 0.000036 0.000179 t-value -338.391 76.293 -439.689 32.663 -273.032 102.035 -401.230 398.867 -403.061 120.992 -58.048 -13.288 72.036 -6.294 10.491 P-value 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 0.000014 0.000000
5. CONCLUSION
Both Preliminary and finals experimental runs are carried out to find out the equilibrium, isotherms, kinetics and thermodynamic parameters for biosorption of lead from an aqueous solution using Albizia saman leaf powder. The analysis of the experimental and theoretical data results in the conclusions that the equilibrium agitation time for lead biosorption is 50 minutes. The % biosorption of lead from an aqueous solution increased from 72.12 to 79.45 % with a decrease in the particle size of the biosorbent from 152 to 53 m and increases from 77.14 to 83.78 % with increase in biosorbent dosage from 10 to 30 g/L. With an increase in the initial concentration of lead in the aqueous solution (20 to 180 mg/L), the percentage biosorption of lead from the aqueous solution is decreased from 77.12 to 58.68 %. Percentage biosorption of lead from the aqueous solution increased significantly with increase in pH from 2 to 6 (58.42 to 77.18 %). Hereafter, percentage biosorption decreases for further increase in pH from 6 to 8 (77.18 to 69.42 %). The maximum uptake capacity of 16.8656 mg/g is obtained at a temperature of 303 K. The present study involves the use of statistical experimental design to optimize process conditions for maximal biosorption of lead from aqueous solution using CCD involving RSM. The maximum biosorption of lead (84.90612 %) onto Albizia saman leaf powder is observed when the processing parameters are set as follows: pH = 6.0250, w = 31.7191 g/L, Co = 19.8996 mg/L and T = 304.0673 K. The kinetic studies showed that the biosorption of lead is better described by pseudo second order kinetics. The thermodynamic data depicted that % biosorption of lead increased with increase in temperature up to some extent.
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