1. BIOSORPTION STUDIES OF METHYLENE BLUE
BY SUGARCANE BAGASSE USING TWO
FACTORIAL DESIGN AND RESPONSE SURFACE
METHODOLOGY.
NAME: WONG SHI TING
IC: 900204-01-6412
SUPERVISOR: DR. NIK AHMAD NIZAM NIK MALEK
4. Adsorption
4
Adsorption method has been getting a big attention for the
elimination and recovery of dyes because it has been proven to
be
Efficient
Inexpensive
Ease of operation for the treatment of
effluents bearing dyes
Does not result in the formation of harmful
substances (Ahmad, 2009)
5. Sugarcane Bagasse
5
Sugarcane bagasse is anionic material because of the present of
lignocellulosic materials .
Consist of 3 main components polymers- cellulose, lignin, and
hemicellulose.
Negative charge in their hydroxyl group (OH-)
6. 66
Products Malaysia Indonesia India Mexico Nigeria Philippines
Coconut 459640 21565700 10148000 1004710 236700 15667600
Oil palm 84842000 86000000 - 292499 8500000 516115
Rice
paddy
2510000 64398900 133700000 263028 3402590 16266400
Sugarcane 700000 26500000 285029000 49492700 1412070 22932800
Table 1.0 Agricultural production in some countries (Ton/ year) (Salleh et al., 2011)
7. Objectives
7
To characterize sugarcane bagasse
(SB) powder with Fourier Transform
Infrared (FTIR) spectroscopy.
To characterize sugarcane bagasse
(SB) powder with Fourier Transform
Infrared (FTIR) spectroscopy
To study the biosorption of
methylene blue on SB using response
surface methodology.
11. Characterization of Sugarcane Bagasse
by FT-IR Spectroscopy
11
Figure 1.0 FTIR spectrums of sugarcane bagasse
Indicating a dominant xylan of the hemicellulose (Bian et al., 2012)
12. Two- Level Factorial Design
12
Table 2.0: Analysis of variance (ANOVA) for selected factorial
model influenced adsorption of methylene blue by sugarcane bagasse
Source Sum of
Square
DF Mean Square F Value a
Prob > F
Model 2795.43 10 279.54 3748.61 < 0.0001
A 1.80 1 1.80 24.10 < 0.0001
B 744.25 1 744.25 9980.23 < 0.0001
C 4.14 1 4.14 55.56 < 0.0001
D 1941.53 1 1941.53 26035.47 < 0.0001
Curvature 45.60 1 45.60 611.45 < 0.0001
R-Squared 0.9989
Adj R-Squard 0.9986
The “Pred R-Squared” of 0.9981 is in reasonable agreement with the
“Adj R-Squared” of 0.9986.
*Values of p less than 0.05 indicate that the model terms are significant.
*(A= contact time, B=initial MB concentration, C= shaking rate, D= adsorbent dosage)
13. Two- Level Factorial Design
13
Figure 2.0 Factors that significantly influenced the adsorption capacity of sugarcane
bagasse toward methylene blue analyzed using 2-Level-Factorial Design
Predicted
Experimental value
(qe)= 22.25mg/g
91%
14. Effect of Initial Methylene Blue
Concentration
14
Higher concentration of MB is needed in order to
achieve highest adsorption capacity.
Adsorption capacity increase from 10.47 to
34.67 mg/g when initial dye concentration
increased from 25 to 100 mg/L (Reddy et al.,
2012).
Dye concentration was the most significant
factor in term of adsorption capacity (Rehman
et al., 2012).
15. Effect of Contact Time & Adsorbent
Dosage
15
As the contact time increases, the rate of
adsorption decrease depending on the
chemical characteristics on the surface
(Anupam et al., 2011)
The percentage removal of MB
increased with the increase in adsorbent
dosage, but the adsorption density (qe)
of MB decreased with increase in
adsorbent dosage (Uddin et al., 2009) .
16. 16
Effect of Shaking Rate
The higher the shaking rate, the
higher the contact between the
adsorbent and the adsorbate lead to
increase in adsorption capacity.
17. Response Surface Methodology (RSM)
Central Composite Design (CCD)
17
Figure 3.0 Response surface plot of adsorption at equilibrium
(qe) of methylene blue on sugarcane bagasse from model
equation: effect of shaking rate and contact time
A large number of empty surface
sites are available for the
adsorption during the initial
stage, and after a period of time,
the remaining free surface site
are difficult to be occupied due to
repulsive forces between the
solute molecules on the solid and
bulk phases (Guimarães
Gusmão et al., 2012).
18. RSM CCD - Optimum Conditions
18
Figure 4.0 Optimum conditions for the optimization of the adsorption
of methylene blue on sugarcane bagasse
Predicted
Experimental
Value, qe = 26.58
mg/g
93%93%
19. Comparison with Previous works
19
Adsorbent Adsorption
capacity (mg/g)
References
Sugarcane bagasse 26.58 This work
NaOH- treated raw kaolin 16.34 (Ghosh and Bhattacharyya,
2002)
NaOH- treated pure kaolin 20.49 (Ghosh and Bhattacharyya,
2002)
Beech sawdust pretreated
with CaCl2
13.02 (Batzias and Sidiras, 2004)
Fly ash 5.57 (Kumar et al., 2005)
Glass fiber 2.24 (Chakrabarti and Dutta, 2005)
Sugar extracted spent rice
biomass
8.13 (Rehman et al., 2012)
Cashew nut shell 5.31 (Kumar et al., 2011)
Natural rice husk 19.77 (Zou et al., 2011)
Table 3.0: Comparison of adsorption capacity of various adsorbent for methylene blue
20. Validation of the Models
20
Figure 5.0 Plot of outlier T versus run number
No occurrences of abnormal
runs in the experiment
which results in response
depart far from the predicted
value.
21. FT-IR Spectroscopy- After Adsorption
Process
21
Figure 6.0 FTIR spectra of methylene blue, sugarcane
bagasse, and sugarcane bagasse after adsorption
The shift of the 3362.07
cm-1 to 3361.56 cm-1
suggests the attachment
of MB dye on –OH.
New bands at 816.77
cm-1 and 790.81 cm-1
were ascribed to
wagging vibration of C-
H in aromatic ring of
MB and appeared in the
spectra of SB after
adsorption.
(Liu et al., 2012).
22. Conclusions
22
Through the FTIR analysis, formation of electrostatic
attraction dominated the adsorption process.
Two-level factorial design Four factors are
significant in influencing the SB adsorption capacity
toward MB.
RSM Adsorption capacity of SB is 26.58 mg/g.
24. References
24
1. Ahmad, R. (2009). Studies on adsorption of crystal violet dye from aqueous solution onto
coniferous pinus bark powder (CPBP). Journal of Hazardous Materials, 171, 767-773.
2. Salleh, M. A. M., Mahmoud, D. K., Karim, W. A. W. A. and Idris, A. (2011). Cationic and
anionic dye adsorption by agricultural solid wastes: A comprehensive review. Desalination,
280, 1-13.
3. Bian, J., Peng, F., Peng, X.-P., Xu, F., Sun, R.-C. and Kennedy, J. F. (2012). Isolation of
hemicelluloses from sugarcane bagasse at different temperatures: Structure and properties.
Carbohydrate Polymers, 88, 638-645.
4. Reddy, S., Sivaramakrishna, L. and Varada Reddy, A. (2012). The use of an agricultural
waste material, Jujuba seeds for the removal of anionic dye (Congo red) from aqueous
medium. Journal of Hazardous Materials, 203, 118-127.
5. Rehman, M. S. U., Kim, I. and Han, J.-I. (2012). Adsorption of methylene blue dye from
aqueous solution by sugar extracted spent rice biomass. Carbohydrate Polymers.
25. References
25
6. Anupam, K., Dutta, S., Bhattacharjee, C. and Datta, S. (2011). Adsorptive removal of
chromium (VI) from aqueous solution over powdered activated carbon: Optimisation
through response surface methodology. Chemical Engineering Journal, 173, 135-143.
7. Uddin, M. T., Islam, M. A., Mahmud, S. and Rukanuzzaman, M. (2009). Adsorptive
removal of methylene blue by tea waste. Journal of Hazardous Materials, 164, 53-60.
8. Guimarães Gusmão, K. A., Alves Gurgel, L. V., Sacramento Melo, T. M. and Gil, L. F.
(2012). Application of succinylated sugarcane bagasse as adsorbent to remove methylene
blue and gentian violet from aqueous solutions–Kinetic and equilibrium studies. Dyes
and Pigments, 92, 967-974.
9. Liu, Y., Wang, J., Zheng, Y. and Wang, A. (2012). Adsorption of methylene blue by
kapok fiber treated by sodium chlorite optimized with response surface methodology.
Chemical Engineering Journal, 184, 248-255.
Agricultural and industrial sectors dispose a huge amount of untreated waste, which may lead to various type of pollution and result in damage of ecosystem.
qe (24.52 mg/g) at this condition matches very well with the experimental value (22.25 mg/g). The experimental value is 91% of the predicted value
The dye uptake is rapid for the first 65 min and thereafter it proceeds at a slower rate and finally attains saturation. At this point, the amount of adsorbed dye reached a dynamic equilibrium state with the amount of dye in solution (Hameed et al., 2007).
The adsorption at equilibrium of methylene blue by sugarcane bagasse resulted as 26.58 mg/g, which is 93% of the predicted value.
This crested a big gap of 4.33 mg/g with 2- factorial design, which means the adsorption condition is being optimized.
demonstrates the deviation of standard deviation of actual from predicted values generated by Design Expert 6.0.4 Software.
The information indicated that the formation of hydrogen bond between surface of the SB and aromatic ring of MB molecules and electrostatic attraction dominated the adsorption process (Liu et al., 2012).