adsorption of methylene blue onto xanthogenated modified chitosan microbeads


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Methylene Blue (MB) is thiazine dyes that widely use to color product in many industry such as textile, printing, leather, cosmetic and paper. Xanthogenated-Modified Chitosan Microbeads (XMCM) is use to observe the new alternative adsorbent in removing MB from water body through adsorption process. The interactions between MB and functional group in XMCM were confirmed by Fourier Transform Infrared (FT-IR) spectra. Several parameters that influence adsorption ability such as the effect of adsorbent dosage of XMCM and the effect of initial pH of MB aqueous solution were studied. This study were done at optimum condition which is at pH 4 of initial pH of MB solution, 0.01 g of initial XMCM dosage, 6 hours stirring time and temperature of (30 ± 2 ℃). The adsorption data fit well Langmuir model more than Freundlich model. Based on Langmuir model, the maximum monolayer adsorption capacity of MB was 21.62 mg g-1 which indicated that XMCM can be a new alternative adsorbent for removing MB.

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adsorption of methylene blue onto xanthogenated modified chitosan microbeads

  1. 1. 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
  3. 3. 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 N CH3 CH3 +
  4. 4. 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
  5. 5. 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.
  6. 6. 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.
  7. 7. 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).
  9. 9. 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).
  10. 10. 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
  11. 11. 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),
  13. 13. 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).
  15. 15. 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).
  16. 16. 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
  17. 17. 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
  18. 18. 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.
  19. 19. 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
  20. 20. 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).
  21. 21. 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),
  22. 22. 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.
  23. 23. 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)
  24. 24. ISOTHERM MODELS Figure 10 : Freundlich isothermFigure 9 : Langmuir isotherm
  25. 25. 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
  27. 27. 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
  28. 28. 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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