Methylene blue removal using modified chitosan beads Presented in IIEST, Shibpur, West Bengal.

1. National Conference on Sustainable Advanced Technologies for Environmental Management (SATEM-2017)
June 28-30, 2017
Paper No.71
Methylene Blue Removal: An Approach towards Sludge Management after Adsorption of
Cadmium onto Surfactant Modified Chitosan Beads
Preeti Pal# and Anjali Pal*
# School of Environmental Science and Engineering
* Department of Civil Engineering
Indian Institute of Technology, Kharagpur, West Bengal - 721302,
India.
Email: pal.preiti@iitkgp.ac.in; anjalipal@civil.iitkgp.ernet.in
1

2. 2
Chitosan SDS Cadmium Methylene blue
Introduction
•Chitin deacetylation
•Obtained from marine
waste
•Presence of –OH and –
NH2 groups make it feasible
modifications.
•Highly toxic, carcinogenic,
persistent metal
Used in
• PVC products
• Color pigments and
alloys
• Ni-Cd batteries
• Anticorrosion agent
Can affect
• Liver and kidney
• Respiratory system
• Skeletal system
Used to treat
methemoglobinemia (7-8
mg/kg) (Sikka et al., 2011)
Can cause
• Dizziness
• Mental confusion
• Headache
• Fever
• High blood pressure
•An anionic surfactant
Used in
• Cosmetics
• Pharmaceutical
• Food products
• Industrial cleaning
Can cause
• Skin and eye
irritation
Permissible limit is
0.003 mg/L (IS
10500:2012)
Tolerance limits for inland
surface waters and drinking
water- 1.0 mg/L (IS 10500:2012)

3. Preparation of surfactant modified beads (SMCS beads)
Cd2+ removal by SMCS beads (CdL-SMCS beads)
Methodology
Optimization of
adsorption parameters
Use of CdL-SMCS beads for removal of methylene blue (MB)
3

4. Figure: Schematic of the formation of CS beads and its modification with SDS for removal of Cd2+
to form CdL-SMCS beads followed by the adsorption of MB.
4
CS beads
SMCS beads
CdL-SMCS beads
MBL-SMCS beads
CS powder
Step 1
Step 2
Step 3
Step 4
Step-wise modification of CS beads
(Pal and Pal, 2017)

5. 0
100
200
300
400
10 20 50 100 250
qt(mg/g)
MB concentration (mg/L)
CS beads
CdL-SMCS beads
Figure: Evaluation of the CS and Cd2+ loaded SMCS beads (Cd loading = 125 mg/g) for removal of MB.
[MB]: 10-250 mg/L, adsorbent dose: 0.45g/L, time: 72 h, agitation speed: 100 rpm, temperature: 30oC.
Evaluation of the CS and CdL-SMCS beads for
removal of MB
5
Type of
adsorbent
[MB] (mg/L) *qt (mg/g)
CS beads 250 64.35
CdL-SMCS
beads
250 366.46
*qt = mg of adsorbate (MB) adsorbed on the
adsorbent (CdL-SMCS) in a given time

6. Selection of beads after Cd2+ loading
Figure: Effect of Cd2+ loading on removal of MB by CdL-SMCS beads. [MB]: 50 mg/L, dose: 0.45g/L, time:
72 h, agitation: 100 rpm, temperature: 30oC.
6
% R for MB qt (mg/g)
Cd2+ MB
98.86 124.86 219.68
0
10
20
30
40
50
60
70
80
90
100
0
50
100
150
200
250
10 20 30 50 100
%RemovalofMB
qt(mg/g)
Cd2+ concentration used for SMCS beads loading (mg/L)
qt (mg/g) for MB removal
qt (mg/g) for Cd2+ removal
% Removal (MB)

7. Effect of contact time on adsorption of MB on CdL-SMCS
beads
88.75
92.06
92.75
0
10
20
30
40
50
60
70
80
90
100
0 0.083 0.5 1 2 4 12 24 48 72 96
%RemovalofMB
Time (h)
Figure: Time dependency on removal of MB using CdL-SMCS beads. [MB]: 50 mg/L, dose: 0.45g/L,
agitation: 100 rpm, temperature: 30oC.
7
Time (h) % R of MB
48 88.75
72 92.06
96 92.75

8. Effect of adsorbent dose on adsorption of MB
0
50
100
150
200
250
300
350
400
450
500
50
60
70
80
90
100
0.09 0.225 0.45 0.675 0.9 1.35
qt(mg/g)
%RemovalofMB
Dose (g/L)
% Removal
Capacity (mg/g)
Figure: Effect of adsorbent dosage on removal of MB by CdL-SMCS beads. [MB]: 50 mg/L, time: 72 h,
agitation speed: 100 rpm, temperature: 30oC.
8
Dose (g/L) % R of MB
0.45 95.63
0.675 96.15

9. Figure: Effect of MB concentration on its removal by CdL-SMCS beads. [MB]: 10-250 mg/L, dose:
0.45g/L, time: 72 h, agitation speed: 100 rpm. The photograph showing (a) SMCS beads, (b) CdL-SMCS
beads, (c) 10 mg/L MB loaded beads (d) 50 mg/L MB loaded beads.
Effect of MB concentration on % removal efficiency of
CdL-SMCS beads
9

10. Model Pseudo first order Pseudo second order
Equation of linear fit
line
Ln (qe-qt) =-0.0009x + 3.6812 t/qt = 0.0097x + 0.4675
R2 0.8785 0.999
qe (mg/g) 39.69 103.09
Constant (k) kS1 =9.0×10-4 (min−1) kS2=2.0×10-4 (g mg−1 min−1)
-1
0
1
2
3
4
5
0
10
20
30
40
50
60
0 2000 4000 6000
Ln(qe-qt)
t/qt
Time (min)
Pseudo second order curve fitting
Pseudo first order curve fitting
(a)
Kinetic study for adsorption of MB on to CdL-SMCS beads
Figure: Kinetics on MB removal by CdL-SMCS beads. (a) The fitting of pseudo first order and pseudo second order model, and (b)
plot of qt vs. t for experimental data and calculated values of qe (based on the pseudo-second order model). [MB]: 50 mg/L, dose:
0.45g/L, time: 72 h, agitation: 100 rpm, temperature: 30oC.
Table: Pseudo first order and pseudo second order rate constants of MB adsorption onto the CdL-SMCS beads.
10
0
20
40
60
80
100
120
0 1000 2000 3000 4000 5000 6000
qt(mg/g)
Time (min)
qt calculated
qt experimental
(b)

11. 0.00
0.10
0.20
0.30
0.40
0.50
0 50 100 150
Ce/qe(g/L)
Ce (mg/L)
(a)
0
1
2
3
4
5
6
7
-2 0 2 4 6
Ln(qe)
Ln (Ce)
(b)
Figure: Langmuir (a) and Freundlich (b) adsorption isotherm model for removal of MB using CdL-SMCS beads. [MB]: 10-
250 mg/L, dose: 0.45g/L, time: 72 h, agitation: 100 rpm, temperature: 30oC.
Equilibrium adsorption isotherm study on MB removal by
CdL-SMCS beads
11
Model Parameters Values
Langmuir isotherm model
Equation Ce/qe = 0.002Ce + 0.062
qmax (mg/g) (Maximum
adsorption capacity)
500.0
KL 0.0323
R2 0.922
Freundlich isotherm model
Equation lnqe = 0.516 lnCe + 3.342
kf [(mg/g)(L/mg)1/n] (constant
related to adsorption
capacity)
28.76
1/n (adsorption intensity) 0.516
R2 0.985
Table: Adsorption isotherm model equations, values of isotherm constants and their corresponding R2 values.

12. Wavenumbers
(cm-1)
Characteristic
band
Reference
1604 C=C [Ramaraju et al., 2014]
1539 C=C of aromatic
compound
[Ramaraju et al., 2014]
1337 CH3 (of MB) [Xiong et al., 2010]
1014 C-O stretching [Gottipati et al., 2010]
890 -NH2
[Akinyeye et al., 2016]
808 -C-H- [Qutub et al., 2016]
Interpretation of the peaks obtained by the FTIR spectra of the CdL-SMCS and
MBL-SMCS beads.
FTIR analysis of MB loaded CdL-SMCS beads (MBL-SMCS) and
CdL-SMCS beads
12

13. • Surfactant-modified chitosan (SMCS) beads were successfully prepared.
• SMCS beads were able to remove Cd2+ from aqueous solutions.
• CdL-SMCS loaded beads (124.86 mg/g) successfully removed MB from aqueous
solution.
• Optimized dose= 0.45 g/L.
• Contact time= 72 h
• Agitation speed= 100 rpm at 30oC
• The material (SMCS beads) is broadly suitable for the removal of positively
charged pollutants.
• Adsorption followed Freundlich isotherm, which confirms the multilayer adsorption.
• Langmuir adsorption capacity obtained was 500.0 mg/g.
• Kinetic data complied with pseudo-second order model.
• CS beads used successively for the removal of SDS, Cd2+, and MB.
Conclusions
13

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14 References

15. Thankyou