PRESENTED BY

SITI NADZIFAH BINTI GHAZALI

Degree of Bachelor of Science (Hons.) Chemistry

Faculty of Applied Sciences

Universiti Teknologi MARA

SUPERVISOR

MDM. ZURHANA BINTI MAT HUSSIN

INTRODUCTION

BACKGROUND OF STUDY

• Colored (dye) pollution is one of the contributors to the global problem

which is water pollution (Wang et al., 2011).

• Methylene Blue (MB) is widely use in industry and daily life (Rafatullah

et al., 2010).

• The presence of MB in wastewater gives harm to living organism

including human beings and gives a toxic effect to microorganisms

disease (Cazetta et al., 2011; Hameed and Ahmad, 2009).

Figure 1 : Chemical structure of MB

N

H3C

CH3

S

N

NCH3

CH3

+

BACKGROUND OF STUDY

• Adsorption has been found to be the most favorable technique due to its potential technique to remove dye (Wang et al., 2011).

• Chitosan is a natural amino polymer which was reported as one of the more preferable and common adsorbent in removing dye pollutants from the water body (Crini and Badot, 2008).

• The presence of amine and hydroxyl groups in chitosan makes chitosan to have strong adsorption ability towards heavy metal and dyes ( Kannamba et al., 2010)

Figure 2 : Chemical structure of chitosan

O O

OH

O

NH2

PROBLEMS STATEMENT • A few studies were done to treat Methylene Blue (MB) dyes in wastewater but

some of the treatment are not effective, not practical, and expensive and

sometimes produces toxic sludge which required another disposal technique

(Zhu et al., 2012).

• Adsorption of dyes was found to be effective and economical compared to the

use of other conversational techniques (Wang et al., 2011).

• Activated carbon was introduced in the past as the most effective adsorbent to

remove coloring materials (Vargas et al., 2011). However, activated carbon

requires high operating cost (Weng et al., 2009).

• Modified chitosan was proven in removing large amount of MB from waste

water (Wang et al., 2011; Liu et al., 2010; Huang et al., 2011).

• Alternatively, Xanthogentated-Modified Chitosan Microbeads was proposed

as the new alternative adsorbents used to improve the discharged water

conditions.

SIGNIFICANCE OF STUDY

• Through this study :

The feasibility of XMCM to remove MB in wastewater would

be revealed.

The chemical process and uptake rate of XMCM against MB

will be assessed and compared to other adsorbents. This will

provide knowledge of the best chitosan-based adsorbent

available in treating polluted wastewater.

OBJECTIVES

The intention of this research is to investigate the adsorption capacity of MB onto XMCM.

The specific objectives of this project include to :

i) To characterize XMCM by FTIR, pHslurry and pHzpc.

ii) To determine the effect of important physicochemical parameters such as adsorbent dosage and initial pH of MB solution that can affect adsorption efficiency of methylene blue.

iii) To determine the isotherm study based on isotherm model (Langmuir and Freundlich model).

LITERATURE

REVIEW

METHYLENE BLUE

Adsorbent

Maximum

adsorption

capacity

(mg/g)

References

Garlic peel 82.64 (Hameed & Ahmad ., 2009)

Activated carbon-flamboyant pods 874.68 (Vargas et al., 2008)

Sugar beet pulp 714.29 (Vučurović et al., 2012)

Activated carbons of coconut shell

produced by NaOH activation 916.26 (Cazetta et al., 2011)

NaOH-modified rejected tea (N-RT) 242.11 (Nasuha & Hameed, 2010)

Table 1 : Removal of MB by using various type of adsorbent

MB appears as a dark green powder and yields a blue solution when dissolved

in water (Hameed and El-Khaiary, 2008).

MB has strong adsorption characteristic onto solid with 668 nm maximum

absorption wavelength (Hameed and El-Khaiary, 2008).

MODIFIED CHITOSAN • Chitosan are not effective to remove MB (cationic dyes) unless

undergo some modification (Liu et al., 2010).

Adsorbent Optimum

pH

Optimum

dosage (g)

qmax

(mg g-1)

Isotherm

model references

chitosan-g-poly (acrylic

acid) vermiculite

hydrogel

7 0.025 1685.56 Langmuir ( Liu et al.,

2010)

chitosan-g-poly acrylic

acid 5 0.05 1873 Langmuir

(Wang et

al., 2011) chitosan-g-poly (acrylic

acid) attapulgite

composite

5 0.05 1848 Langmuir

cross-linked succinyl

chitosan 8 0.02 298.02 Langmuir

(Huang et

al., 2011)

magnetic

chitosan/graphene

oxide

10.0 0.05 180.83 Langmuir (Fan et al.,

2012)

Table 2 : Removal of MB by using various type of modified chitosan

XANTHOGENATED • The principle of preparing cellulose xanthogenate has been clarified by Tan et

al. (2008) is shown in the following reaction:

• Cell-OH + NaOH → Cell-ONa + H2O

• CS2 + Cell-ONa → Cell-OCS2Na

• 2Cell-OCS2Na + Mg2+ → (Cell-OCS2)2Mg + 2Na+

• The purpose of adsorbent modification with xanthate (NaOH + CS2) is to improve the potential of adsorption capacity of adsorbent onto adsorbate(Chauhan and Sankararamakrishnan, 2008)

• Xanthate group have been chosen due to the presence of sulfur atoms (Chauhan and Sankararamakrishnan, 2008)

• sulphur and magnesium content in xanthogenates increase the adsorption capacities of xanthogenates on heavy metal (Cu2+) (Zhou et al., 2011), .

• The exchange of copper with magnesium also increases the adsorption of copper (Zhou et al., 2011),

METHODOLOGY

Sample Treatment

Characterization

FTIR pHslurry

pHzpc

Batch Mode Study

pH Dosage

Isotherm Study

Figure 3 : Flow chart of research methodology

Modifications of chitosan were performed by modifying the methods

used by (Kannamba et al., 2010; Wan Ngah et al., 2013; Zhou et al.,

2011).

RESULTS

AND

DISCUSSION

ADSOBENT CHARACTERIZATION

pHslurry = 9.91

pHzpc = 9.80

When the pH of adsorbate is greater than pHzpc, the surface of

adsorbent will carry negative charge and vice versa (Kamal et al.,

2010).

ADSORBENT CHARACTERIZATION

4000 3600 3200 2800 2400 2000 1800 1600 1400 1200 1000 800 650

cm-1

%T

CHITOSAN

XMCM

3273 2875

1744

1637

1560

1453

1375

1229

1147

1033

896

739

707

3187 1730

1654

1429

1225

1145 1035

865

848

739

706

Figure 4 : FTIR spectra of Chitosan before and after treatment

ADSORBENT CHARACTERIZATION

Functional group

Wavenumber cm-1

Before treatment

(Chitosan)

After

treatment

(XMCM)

overlapping of O-H and N-H stretching 3273 3187

C-H stretching 2875 2934

NH2 groups 1453 1445

C=S stretching 1429

C-O-C 1033 1034

Table 3 : Characterization of Chitosan before and after treatment

ADSORBENT CHARACTERIZATION

4000 3600 3200 2800 2400 2000 1800 1600 1400 1200 1000 800 650

cm-1

%T

T

XMCM

XMCM- MB

3190

1746

1546 1370 1228

1144

706

2934

3566

1638 1464

1038 891

739

3187 1730

1654

1445 1429

1225 1145

1034 865

848

739

706

3451 2941

Figure 5 : FTIR spectra of XMCM before and after MB loaded.

ADSORBENT CHARACTERIZATION

Functional group

Wavenumber cm-1

Before MB loaded

(XMCM)

After MB

loaded

(XMCM-MB)

overlapping of O-H and N-H stretching 3187 3189

C-H stretching 2934 2941

NH2 groups 1445 1463

C=S stretching 1429 1370

C-O-C 1034 1037

1017

Table 4 : Characterization of XMCM before and after MB loaded.

Therefore, the main functional groups that participate in

adsorption process onto XMCM were amino and sulfur

EQUATION OF ION EXCHANGE

• CTS-OH + NaOH → CTS-ONa+ + H2O

• CS2 + Cell-ONa+ → CTS-OCS2Na+

• CTS-OCS2Na+ + Mg2+ → (CTS-OCS2)2Mg2+ + 2Na+

• (CTS-OCS2)2Mg2+ + 2MB+→ 2(CTS-OCS2MB+) + Mg2+

• CTS-NH2 + MB+ → CTS-NH2MB+

Equation was modified by referring equation given by Tan et al. (2008) and

Chauhan et al. (2008).

ADSORBANCE DOSAGE

Figure 6 : Effect of adsorbent dosage on adsorption of MB onto XMCM

The increase in the adsorption of MB with the adsorbent dosage can be

associated with the increase of surface area and the sorption sites. (Özer et al..,

2007),

The decreases of the effective surface area explained the reduction in

adsorption capacity. (Özer et al.., 2007),

OPTIMUM PH OF ADSORBATE

Figure 7 : Effect of initial pH of MB aqueous

Chemical reaction between the dye molecules and adsorbent also affects the

adsorption capacity (Han et al., (2011).

Therefore, the experiment was carried out at pH 4 because the adsorption

capacity of XMCM decreased at the pH higher than pH 4.

ISOTHERM MODELS

Figure 8 : General adsorption isotherm plot of MB onto XMCM (adsorbent

weight: 0.01 g, pH: 4, volume: 50 mL, shaking speed: 120 rpm,

temperature: 30 ± 2 "℃" , initial MB concentration: 10 -70 mg L-1,

equilibrium time: 6 hours)

The isotherm plot shape provides information regarding the interaction

between adsorbate with adsorbent ( Kamal et al., 2010)

ISOTHERM MODELS

Figure 10 : Freundlich isotherm Figure 9 : Langmuir isotherm

SUMMARY OF ISOTHERM

MODEL DATA

Langmuir

Freundlich

qmax

(mg g-1)

b

(L mg-1) R2 KF n R2

21.62 0.13 0.9885 1.15 1.29 0.9351

Table 5 : Summary of Isotherm model data

CONCLUSION

AND

RECOMENDATION

CONCLUSSION

Adsorbent Optimum

pH

Optimum

dosage (g)

qmax

(mg g-1)

Isotherm

model references

N-benzyl mono-

and disulfonate

derivatives of chitosan

3 N/A 219.1 Langmuir (Crini et al.,

2008)

chitosan-g-poly (acrylic

acid) vermiculite

hydrogel

7 0.025 1685.56 Langmuir (Liu et al.,

2010)

cross-linked succinyl

chitosan 8 0.02 298.02 Langmuir

(Huang et

al., 2011)

magnetic

chitosan/graphene

oxide

10 0.05 180.83 Langmuir (Fan et al.,

2012)

Xanthogenated-

Modified Chitosan

Microbeads

4 0.01 21.62 Langmuir This study

Table 6: Removal of MB by using various type of modofied chitosan

the main functional groups that participate in adsorption process onto

XMCM were amino and sulfur

RECOMMENDATIONS

There are two probabilities that could be tested in the future :

whether there is a method to be utilized in preserving the OH group

while chitosan modification takes place, or

use of other chemical during the process of chitosan modification.

XMCM be used as an adsorbent to anionic dyes

Removal MB with modified chitosan with xanthate and hydrogel in order

to introduce

sulfur atoms (xanthation)

some ionic functional group (in hydrogel) inter alia; sulfonic acid,

hydroxyl, amine and carboxylic acid groups (Liu et al., 2010)

hydrogel able to adsorb and retain water and solute molecule

because it is has high porous structures and water content which

allow solute to diffuse through hydrogel structure (Liu et al., 2010).

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