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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
Textile industry, intensive
used of water. Wastewater
consists of harmful and toxic
chemical such as dye
Water pollution
3
Adsorption
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+
+
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+
+
+
+
+
+
+
+
+ +
+
+
+
+
+ Adsorbate (MB)
- Adsorbent (SB)
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-
--
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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)
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-)
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)
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.
Research
Methodology
Design
Methodologies
qe =
𝑪𝒊 − 𝑪𝒆 × 𝑽
𝑾
10
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)
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)
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%
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).
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
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.
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).
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%
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
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.
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).
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.
Recommendations
23
Pretreated
Cetylpyridinium
bromide
To remove methyl
orange
Factors
Temperature
pH
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.
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.
Acknowledgement
26
My sincere appreciation and
special thanks to my
supervisor
Dr. Nik Ahmad Nizam Nik Malek
27

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wongshiting BME presentation

  • 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
  • 2. Textile industry, intensive used of water. Wastewater consists of harmful and toxic chemical such as dye Water pollution
  • 3. 3 Adsorption - + + + + + + + + + + + + + + + + + + Adsorbate (MB) - Adsorbent (SB) - - -- - - - - - - - - - - - - - - - - - - - - -
  • 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.
  • 9. Methodologies qe = 𝑪𝒊 − 𝑪𝒆 × 𝑽 𝑾
  • 10. 10
  • 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.
  • 26. Acknowledgement 26 My sincere appreciation and special thanks to my supervisor Dr. Nik Ahmad Nizam Nik Malek
  • 27. 27

Notas do Editor

  1. Pollute environment if left untreated
  2. 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.
  3. 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
  4. 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).
  5. 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.
  6. demonstrates the deviation of standard deviation of actual from predicted values generated by Design Expert 6.0.4 Software.
  7. 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).