Performance of multi-wall carbon nanotubes modified by chitosan and EDTA in the removal of Direct Blue 15 dye from aqueous solutions

Document Type : Original Article


1 Student Research Committee, Kurdistan University of Medical Sciences, Sanandaj, Iran

2 Environmental Health Research Center, Research Institute for Health Development, Kurdistan University of Medical Sciences, Sanandaj, Iran


Dyes are considered to be important pollutants in different industries (e.g., textile) and contain various organic materials with complicated structures. These compounds are mainly carcinogenic and toxic and less biodegradable when discharged into the environment. The present study aimed to investigate the performance of multi-wall carbon nanotubes (MWCNTs) modified by chitosan and EDTA in the removal of Direct Blue 15 dye from aqueous solutions. MWCNT was synthesized and characterized using the BET, zeta potential, DLS, SEM, and FTIR techniques. The effects of key parameters including pH, adsorbent dose, initial dye concentration, and contact time were also evaluated. The experimental data of the adsorption process were analyzed using the Langmuir and Freundlich models. With the increased contact time, the removal efficiency of the dye improved, while the increased pH, initial dye concentration, and adsorbent dose led to the reduced dye removal efficiency. With the optimum values of pH (=7), contact time (60 min), adsorbent dose (0.5 g/L), and initial dye concentration (60 mg/L), the maximum adsorption capacity was determined to be 114.42 mg/g. According to the results, the adsorption process using the modified MWCNT followed the Langmuir model and pseudo-second-order kinetics.


1. Luo X, Zhan Y, Huang Y, Yang L, Tu X, Luo S. Removal of water-soluble acid dyes from water environment using a novel magnetic molecularly imprinted polymer. J Hazard Mater 2011; 187(1-3): 274-82.
2. Mckay G, Hadi M, Samadi MT, Rahmani AR,  Solaimany Aminabad M, Nazemi F. Adsorption of reactive dye from aqueous solutions by compost. Desalin Water Treat 2011; 28(1-3): 164-73.
3. Bulut Y, Aydın H. A kinetics and thermodynamics study of methylene blue adsorption on wheat shells. Desalination 2006; 194(1-3): 259-67.
4. Ghodsian M, Ayati B, Ganjidoust H. Determination of optimum amounts of effective parameters in reactive dyes removal using photocatalytic reactions by immobilized TiO2 nano particles on concrete surface. J Water Wastewater 2013; 24(3): 45-53. [In Persian]
5. Lima EC, Royer B, Vaghetti JC, Simon NM, Da Cunha BM, Pavan FA, et al. Application of Brazilian pine-fruit shell as a biosorbent to removal of reactive red 194 textile dye from aqueous solution: Kinetics and equilibrium study. J Hazard Mater 2008; 155(3): 536-50.
6. Vijayaraghavan K, Yun Y-S. Biosorption of C.I. Reactive Black 5 from aqueous solution using acid-treated biomass of brown seaweed Laminaria sp. Dyes Pigm 2008; 76(3): 726-32.
7. Punzi M, Anbalagan A, Börner RA, Svensson B-M, Jonstrup M, Mattiasson B. Degradation of a textile azo dye using biological treatment followed by photo-Fenton oxidation: Evaluation of toxicity and microbial community structure. Chem Eng J 2015; 270: 290-9.
8. Paździor K, Wrębiak J, Klepacz-Smółka A, Gmurek M, Bilińska L, Kos L, et al. Influence of ozonation and biodegradation on toxicity of industrial textile wastewater. J Environ Manage 2017; 195: 166-73.
9. Türgay O, Ersöz G, Atalay S, Forss J, Welander U. The treatment of azo dyes found in textile industry wastewater by anaerobic biological method and chemical oxidation. Sep Purif Technol 2011; 79(1): 26-33.
10. Liu M, Chen Q, Lu K, Huang W, Lü Z, Zhou C, et al. High efficient removal of dyes from aqueous solution through nanofiltration using diethanolamine-modified polyamide thin-film composite membrane. Sep Purif Technol 2017; 173: 135-43.
11. Mahvi AH, Ghanbarian M, Nasseri S, Khairi A. Mineralization and discoloration of textile wastewater by TiO2 nanoparticles. Desalination 2009; 239(1-3): 309-16.
12. Dehghani MH, Mesdaghinia AR, Nasseri S, Mahvi AH, Azam K. Application of SCR technology for degradation of reactive yellow dye in aqueous solution. Water Qual Res J Can 2008; 43(2-3): 183-187.
13. Kabra K, Chaudhary R, Sawhney RL. Treatment of hazardous organic and inorganic compounds through aqueous-phase photocatalysis: A review. Ind Eng Chem Res2004; 43(24): 7683-96.
14. Tsai WT, Chang CY, Wang SY, Chang CF, Chien SF, Sun HF. Cleaner production of carbon adsorbents by utilizing agricultural waste corn cob. Resour Conserv Recycl 2001; 32(1): 43-53.
15. Tseng R-L, Wu F-C, Juang R-S. Liquid-phase adsorption of dyes and phenols using pinewood-based activated carbons. Carbon 2003; 41(3): 487-95.
16. Yagub MT, Sen TK, Afroze S, Ang HM. Dye and its removal from aqueous solution by adsorption: A review. Adv Colloid Interface Sci 2014; 209: 172-84.
17. Malik PK. Dye removal from wastewater using activated carbon developed from sawdust: Adsorption equilibrium and kinetics. J Hazard Mater 2004; 113(1-3): 81-8.
18. Asouhidou DD, Triantafyllidis KS, Lazaridis NK, Matis KA, Kim S-S, Pinnavaia TJ. Sorption of reactive dyes from aqueous solutions by ordered hexagonal and disordered mesoporous carbons. Micropor Mesopor Mat 2009; 117(1-2): 257-67.
19. Jourvand M, Shams Khorramabadi G, Omidi Khaniabadi Y, Godini H, Nourmoradi H. Removal of methylene blue from aqueous solutions using modified clay. J Bas Res Med Sci 2015; 2(1): 32-41.
20. Chiou M-S, Li H-Y. Equilibrium and kinetic modeling of adsorption of reactive dye on cross-linked chitosan beads. J Hazard Mater 2002; 93(2): 233-48.
21. Wang XS, Zhou Y, Jiang Y, Sun C. The removal of basic dyes from aqueous solutions using agricultural by-products. J Hazard Mater 2008; 157(2-3): 374-85.
22. Bao Y, Zhang G. Study of adsorption characteristics of methylene blue onto activated carbon made by Salix psammophila. Energy Procedia 2012; 16: 1141-6.
23. Madrakian T, Afkhami A, Ahmadi M, Bagheri H. Removal of some cationic dyes from aqueous solutions using magnetic-modified multi-walled carbon nanotubes. J Hazard Mater 2011; 196: 109-14.
24. Lin D, Xing B. Adsorption of phenolic compounds by carbon nanotubes: Role of aromaticity and substitution of hydroxyl groups. Environ Sci Technol 2008; 42(19): 7254-9.
25. Crini G, Badot P-M. Application of chitosan, a natural aminopolysaccharide, for dye removal from aqueous solutions by adsorption processes using batch studies: A review of recent literature. Prog Polym Sci 2008; 33(4): 399-447.
26. Moniruzzaman M, Winey KI. Polymer nanocomposites containing carbon nanotubes. Macromolecules 2006; 39(16): 5194-205.
27. Zhang L, Luo H, Liu P, Fang W, Geng J. A novel modified graphene oxide/chitosan composite used as an adsorbent for Cr (VI) in aqueous solutions. Int J Biol Macromol 2016; 87: 586-96.
28. Saroj S, Kumar K, Pareek N, Prasad R, Singh R. Biodegradation of azo dyes Acid Red 183, Direct Blue 15 and Direct Red 75 by the isolate Penicillium oxalicum SAR-3. Chemosphere 2014; 107: 240-8.
29. Asfaram A, Fathi MR. Removal of direct red 12B dye from aqueous solutions by wheat straw: Isotherms, kinetics and thermodynamic studies. J Color Sci Technol 2013; 7(3): 223-35. [In Persian]
30. Zare MA, Emadi M, Iranpoor M, Bazargan Lari R. Batch adsorption and removal of Methylene Blue (MB) from wastewater using Tassel as a cheap bioadsorbent.  J New Mater 2014; 4(16): 81-98. [In Persian]
31. Das R, Bee Abd Hamid S, Eaqub Ali M, Ramakrishna S, Yongzhi W. Carbon nanotubes characterization by X-ray powder diffraction–A review. Curr Nanosci 2015; 11(1): 23-35.
32. Saudagar P, Dubey VK. Carbon nanotube based betulin formulation shows better efficacy against Leishmania parasite. Parasitol Int 2014; 63(6): 772-6.
33. Li Y, Du Q, Liu T, Peng X, Wang J, Sun J, et al. Comparative study of methylene blue dye adsorption onto activated carbon, graphene oxide, and carbon nanotubes. Chem Eng Res Des 2013; 91(2): 361-8.
34. Yao Y, Bing H, Feifei X, Xiaofeng C. Equilibrium and kinetic studies of methyl orange adsorption on multiwalled carbon nanotubes. Chem Eng J 2011; 170(1): 82-9.
35. Maleki A, Mahvi AH, Rezaee R, Davari B. Removal of reactive blue 19 using natural and modified zeolites. Iran J Health & Environ 2013; 5(4): 519-30. [In Persian]
36. Bazrafshan E, Kord Mostafapour F, Hosseini AR, Raksh Khorshid A, Mahvi AH. Decolorisation of reactive red 120 dye by using single-walled carbon nanotubes in aqueous solutions. J Chem 2012; 2013.
37. Ghaneian MT, Momtaz M, Dehvari M. An investigation of the efficacy of Cuttlefish bone powder in the removal of Reactive Blue 19 dye from aqueous solutions: Equilibrium and isotherm studies. J Community Health Res 2012; 1(2): 68-78.
38. Elwakeel KZ. Removal of Reactive Black 5 from aqueous solutions using magnetic chitosan resins. J Hazard Mater 2009; 167(1-3): 383-92.
39. Duan J, Liu R, Chen T, Zhang B, Liu J. Halloysite nanotube-Fe3O4 composite for removal of methyl violet from aqueous solutions. Desalination 2012; 293: 46-52.
40. Rahmani AR, Asgari G, Farrokhi M, Shirzad siboni M. Removal of reactive black 5 (RB5) dye from aqueous solution using adsorption onto strongly basic anion exchange resin: Equilibrium and kinetic study. Iran J Health & Environ 2013; 5(4): 509-18. [In Persian]
41. Luo P, Zhao Y, Zhang B, Liu J, Yang Y, Liu J. Study on the adsorption of neutral red from aqueous solution onto halloysite nanotubes. Water Res 2010; 44(5): 1489-97.
42. Shirmardi M, Mesdaghinia A, Mahvi AH, Nasseri S, Nabizadeh R. Kinetics and equilibrium studies on adsorption of acid red 18 (Azo-Dye) using multiwall carbon nanotubes (MWCNTs) from aqueous solution. E-J Chem 2012, 9(4): 2371-83.
43. Malakootian M, Yaghmaeian K, Momenzadeh R. Performance Evaluation of inorganic adsorbent Leca-modified of HCl for the removal of anionic surfactant from wastewater. Sci J Ilam Univ Medic Sci 2015; 23(4): 168-80. [In Persian]
44. Kuo C-Y, Wu C-H, Wu J-Y. Adsorption of direct dyes from aqueous solutions by carbon nanotubes: Determination of equilibrium, kinetics and thermodynamics parameters. J Colloid Interface Sci 2008; 327(2): 308-15.
45. Amin NK. Removal of direct blue-106 dye from aqueous solution using new activated carbons developed from pomegranate peel: Adsorption equilibrium and kinetics. J Hazard Mater 2009; 165(1-3): 52-62.