Treatment of synthetic wastewater containing Cr(VI) using novel magnetic nanocomposite of Chitosan/EDTA/CeZnO under UV irradiation

Document Type : Research Article


1 Civil engineering department, Faculty of Engineering, Civil Engineering Department, Kharazmi University

2 civil engineering department, Faculty of Engineering, Civil Engineering Department, Kharazmi University

3 Faculty of Chemistry, Tehran University


Because of the increasing use of chromium in various industries, water pollution with chromium has become a significant problem. Hexavalent chromium (Cr (VI)) is known as a toxic substance for aquatic organisms, animals and humans and as a carcinogen, so it is very important to treat this type of wastewater. In the present study, a new magnetic nanocomposite EDTA/Chitosan/CeZnO (MEC-CeZnO) was synthesized and used to remove heavy metal ions of Cr (VI) from an aqueous solution. The morphology, structure, and properties of the new MEC-CeZnO magnetic nanocomposite were identified by SEM, EDX, and XRD methods and the effect of various parameters such as initial pH, contact time and initial Cr (VI) concentration on system efficiency was investigated. The results showed that MEC-CeZnO nanoparticles with an average diameter of less than 45 nm, had the best performance of Cr (VI) regeneration at an input concentration of 10 mg/L, pH of 3 and retention time equal to 180 minutes. Also, process kinetic studies showed that the results of Cr (VI) reduction process follow the second-order kinetic model. Finally, the reusability of nanocomposites was tested in 5 cycles; the results showed high efficiency of 90% of nanocomposites in the reduction of metal ions.


Main Subjects

[1] N.N. Thinh, P.T.B. Hanh, L.T.T. Ha, L.N. Anh, T.V. Hoang, V.D. Hoang, L.H. Dang, N.V. Khoi, T.D. Lam, Magnetic chitosan nanoparticles for removal of Cr(VI) from aqueous solution, Materials Science and Engineering: C, 33(3) (2013) 1214-1218.
[2] P. Gopi Krishna, M. Gladis, U. Rambabu, T. Prasada Rao, G. Naidu, Preconcentrative Separation of Chromium(VI) Species from Chromium(III) by Coprecipitation of Its Ethyl Xanthate Complex onto Naphthalene, Talanta, 63 (2004) 541-546.
[3] C. Das, P. Patel, S. De, S. Dasgupta, Treatment of tanning effluent using nanofiltration followed by reverse osmosis, Separation and Purification Technology, 50 (2006) 291-299.
[4] N. Kongsricharoern, C. Polprasert, Chromium removal by a bipolar electro-chemical precipitation process, Water Science and Technology, 34(9) (1996) 109-116.
[5] B. Alizadeh, M. Delnavaz, A. Shakeri, Removal of Cd(ӀӀ) and phenol using novel cross-linked magnetic EDTA/chitosan/TiO2 nanocomposite, Carbohydrate Polymers, 181 (2018) 675-683.
[6] E.S. Abdel-Halim, S.S. Al-Deyab, Hydrogel from crosslinked polyacrylamide/guar gum graft copolymer for sorption of hexavalent chromium ion, Carbohydrate Polymers, 86(3) (2011) 1306-1312.
[7] J. Liu, C. Wang, J. Shi, H. Liu, Y. Tong, Aqueous Cr(VI) reduction by electrodeposited zero-valent iron at neutral pH: Acceleration by organic matters, Journal of Hazardous Materials, 163(1) (2009) 370-375.
[8] R. Güell, E. Anticó, V. Salvadó, C. Fontàs, Efficient hollow fiber supported liquid membrane system for the removal and preconcentration of Cr(VI) at trace levels, Separation and Purification Technology, 62(2) (2008) 389-393.
[9] T. Sardohan, E. Kir, A. Gulec, Y. Cengeloglu, Removal of Cr(III) and Cr(VI) through the plasma modified and unmodified ion-exchange membranes, Separation and Purification Technology, 74(1) (2010) 14-20.
[10] L. Fan, C. Luo, Z. Lv, F. Lu, H. Qiu, Preparation of magnetic modified chitosan and adsorption of Zn2+ from aqueous solutions, Colloids and surfaces. B, Biointerfaces, 88 (2011) 574-581.
[11] W.S. Wan Ngah, L.C. Teong, M.A.K.M. Hanafiah, Adsorption of dyes and heavy metal ions by chitosan composites: A review, Carbohydrate Polymers, 83(4) (2011) 1446-1456.
[12] M. Sheydaei, M. Fattahi, L. Ghalamchi, V. Vatanpour, Systematic comparison of sono-synthesized Ce-, La- and Ho-doped ZnO nanoparticles and using the optimum catalyst in a visible light assisted continuous sono-photocatalytic membrane reactor, Ultrasonics Sonochemistry, 56 (2019) 361-371.
[13] S. Gokila, T. Gomathi, S. P.N, A. Sukumaran, Removal of the heavy metal ion chromiuim(VI) using Chitosan and Alginate nanocomposites, International Journal of Biological Macromolecules, 104 (2017) 1459-1468.
[14] R. Nithya, T. Gomathi, S. P.N, J. Venkatesan, A. Sukumaran, S.J. Kim, Removal of Cr(VI) from aqueous solution using chitosan-g-poly(butyl acrylate)/silica gel nanocomposite, International Journal of Biological Macromolecules, 87 (2016) 545-554.
[15] E. Repo, J.K. Warchol, T.A. Kurniawan, M.E.T. Sillanpää, Adsorption of Co(II) and Ni(II) by EDTA- and/or DTPA-modified chitosan: Kinetic and equilibrium modeling, Chemical Engineering Journal, 161(1) (2010) 73-82.
[16] X. Chen, W. Zhang, X. Luo, F. Zhao, Y. Li, R. li, Z. Li, Efficient removal and environmentally benign detoxification of Cr(VI) in aqueous solutions by Zr(IV) cross-linking chitosan magnetic microspheres, Chemosphere, 185, (2017) 991-1000.
[17] M.H. Dehghani, B. Heibati, A. Asadi, I. Tyagi, S. Agarwal, V.K. Gupta, Reduction of noxious Cr(VI) ion to Cr(III) ion in aqueous solutions using H2O2 and UV/H2O systems, Journal of Industrial and Engineering Chemistry, 33 (2016) 197-200.
[18] A.T. Le, S.-Y. Pung, S. Sreekantan, A. Matsuda, D.P. Huynh, Mechanisms of removal of heavy metal ions by ZnO particles, Heliyon, 5(4) (2019) e01440.
[19] F. Zhao, E. Repo, M. Sillanpää, Y. Meng, D. Yin, W. Tang, Green Synthesis of Magnetic EDTA- and/or DTPA-Cross-Linked Chitosan Adsorbents for Highly Efficient Removal of Metals, Industrial & Engineering Chemistry Research, 54(4), (2015) 1271-1281.
[20] M. Haghighi, F. Rahmani, R. Dehghani, A. Mazaheri Tehrani, M. Miranzadeh, Photocatalytic reduction of Cr (VI) in aqueous solution over ZnO/ HZSM-5 nanocomposite: Optimization of ZnO loading and process conditions, Desalination and water treatment, 58 (2017) 168-180.
[21] M. Naimi-Joubani, M. Shirzad-Siboni, J.-K. Yang, M. Gholami, M. Farzadkia, Photocatalytic reduction of hexavalent chromium with illuminated ZnO/TiO2 composite, Journal of Industrial and Engineering Chemistry, 22 (2015) 317-323.
[22] U. Alam, A. Khan, D. Bahnemann, M. Muneer, Synthesis of Co doped ZnWO4 for simultaneous oxidation of RhB and reduction of Cr(VI) under UV-light irradiation, Journal of Environmental Chemical Engineering, 6(4) (2018) 4885-4898.
[23] A. Mohagheghian, K. Ayagh, K. Godini, M. Shirzad-Siboni, Enhanced photocatalytic activity of Fe3O4-WO3-APTES for azo dye removal from aqueous solutions in the presence of visible irradiation, Particulate Science and Technology, 37 (2018) 1-13.
[24] M. Rezaei, S. Salem, Photocatalytic activity enhancement of anatase–graphene nanocomposite for methylene removal: Degradation and kinetics, Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy, 167 (2016) 41-49.
[25] R. Mu, Z. Xu, L. Li, Y. Shao, H. Wan, S. Zheng, On the photocatalytic properties of elongated TiO2 nanoparticles for phenol degradation and Cr(VI) reduction, Journal of Hazardous Materials, 176(1) (2010) 495-502.