Fabrication of chitosan microspheres for efficient adsorption of methyl orange

doi:10.1016/j.cjche.2017.08.015

Abstract

Abstract: In this article, morphology, structure and size controllable chitosan microspheres with high mechanical strength were synthesized by microfluidic technology combining chemical crosslinking and used as an adsorbent for methyl orange. The synthesized adsorbents were characterized using scanning electron microscopy (SEM), Fourier transform infrared spectroscopy (FTIR), and an Energy Dispersive Spectrometer (EDS). The effect of pH revealed that the adsorption process depended on pH and the pH variation of methyl orange solution after adsorption indicated that adsorption capacity was affected through the associated role of chitosan nature and pH variation. Experimental results suggested that the as-prepared chitosan microspheres were controlled within a narrow size distribution (coefficients of variation is 1.81%), whose adsorption capacity reached to 207 mg·g^-1 and mechanical strength was suitable to resist forces. In addition, the adsorption isotherm was well fitted with the Langmuir model, and the adsorption kinetic was best described by the pseudo-second-order kinetic model. The high performance microfluidic-synthesized chitosan microspheres have promising potentials in the applications of removing dyes from wastewater.

Key words: Microfluidic technology, Chitosan microspheres, Adsorption, Methyl orange

摘要： In this article, morphology, structure and size controllable chitosan microspheres with high mechanical strength were synthesized by microfluidic technology combining chemical crosslinking and used as an adsorbent for methyl orange. The synthesized adsorbents were characterized using scanning electron microscopy (SEM), Fourier transform infrared spectroscopy (FTIR), and an Energy Dispersive Spectrometer (EDS). The effect of pH revealed that the adsorption process depended on pH and the pH variation of methyl orange solution after adsorption indicated that adsorption capacity was affected through the associated role of chitosan nature and pH variation. Experimental results suggested that the as-prepared chitosan microspheres were controlled within a narrow size distribution (coefficients of variation is 1.81%), whose adsorption capacity reached to 207 mg·g^-1 and mechanical strength was suitable to resist forces. In addition, the adsorption isotherm was well fitted with the Langmuir model, and the adsorption kinetic was best described by the pseudo-second-order kinetic model. The high performance microfluidic-synthesized chitosan microspheres have promising potentials in the applications of removing dyes from wastewater.

关键词: Microfluidic technology, Chitosan microspheres, Adsorption, Methyl orange

Linlin Zhai, Zhishan Bai, Yong Zhu, Bingjie Wang, Wenqiang Luo. Fabrication of chitosan microspheres for efficient adsorption of methyl orange[J]. Chin.J.Chem.Eng., 2018, 26(3): 657-666.

Linlin Zhai, Zhishan Bai, Yong Zhu, Bingjie Wang, Wenqiang Luo. Fabrication of chitosan microspheres for efficient adsorption of methyl orange[J]. Chinese Journal of Chemical Engineering, 2018, 26(3): 657-666.

References

[1] V.K. Gupta, R. Kumar, A. Nayak, T.A. Saleh, M.A. Barakat, Adsorptive removal of dyes from aqueous solution onto carbon nanotubes:A review, Adv. Colloid Interf. Sci. 193-194(2013) 24-34.

[2] S.A. Hassanzadeh-Tabrizi, M.M. Motlagh, S. Salahshour, Synthesis of ZnO/CuO nanocomposite immobilized on γ-Al₂O₃ and application for removal of methyl orange, Appl. Surf. Sci. 384(2016) 237-243.

[3] H.Y. Zhu, R. Jiang, J. Yao, F.Q. Fu, J.B. Li, Novel ZnO/Zn-Cr hydrotalcite-like anionic clay as a high-performance and recyclable material for efficient photocatalytic removal of organic dye under simulated solar irradiation, Res. Chem. Intermed. 42(2015) 1-14.

[4] P. Sharma, H. Kaur, M. Sharma, V. Sahore, A review on applicability of naturally available adsorbents for the removal of hazardous dyes from aqueous waste, Environ. Monit. Assess. 183(2011) 151-195.

[5] T.A. Gadallah, S. Kato, S. Satokawa, T. Kojima, Treatment of synthetic dyes wastewater utilizing a magnetically separable photocatalyst (TiO₂/SiO₂/Fe₃O₄):Parametric and kinetic studies, Desalination 244(2009) 1-11.

[6] H.Y. Zhu, R. Jiang, Y.Q. Fu, J.H. Jiang, L. Xiao, G.M. Zeng, Preparation, characterization and dye adsorption properties of γ-Fe₂O₃/SiO₂/chitosan composite, Appl. Surf. Sci. 258(2011) 1337-1344.

[7] E. Brillas, C.A. Martinez-Huitle, Decontamination of wastewaters containing synthetic organic dyes by electrochemical methods. An updated review, Appl. Catal. B Environ. 87(2009) 105-145.

[8] S. Hosseini, M.A. Khan, M.R. Malekbala, W. Cheah, T.S.Y. Choong, Carbon coated monolith, a mesoporous material for the removal of methyl orange from aqueous phase:Adsorption and desorption studies, Chem. Eng. J. 171(2011) 1124-1131.

[9] F. Foroughi, S.A. Hassanzadeh-Tabrizi, J. Amighian, A. Saffar-Teluri, A designed magnetic CoFe₂O₄-hydroxyapatite core-shell nanocomposite for Zn(Ⅱ) removal with high efficiency, Ceram. Int. 41(2015) 6844-6850.

[10] M.L. Yola, T. Eren, N. Atar, S. Wang, Adsorptive and photocatalytic removal of reactive dyes by silver nanoparticle-colemanite ore waste, Chem. Eng. J. 242(2014) 333-340.

[11] J.A. Gonzalez, M.E. Villanueva, L.L. Piehl, G.J. Copello, Development of a chitin/graphene oxide hybrid composite for the removal of pollutant dyes:Adsorption and desorption study, Chem. Eng. J. 280(2015) 41-48.

[12] K.S. Sudheer, Enhancement of visible light photocatalytic activity of CdO modified ZnO nanohybrid particles, J. Photochem. Photobiol. B Biol. 142(2014) 1-7.

[13] M. Gui, L.E. Ormsbee, D. Bhattacharyya, Reactive functionalized membranes for polychlorinated biphenyl degradation, Ind. Eng. Chem. Res. 52(2013) 10430-10440.

[14] H.P. Chao, C.K. Lee, L.C. Juang, Y.L. Han, Sorption of organic compounds, oxyanions, and heavy metal ions on surfactant modified titanate nanotubes, Ind. Eng. Chem. Res. 52(2013) 9843-9850.

[15] I. Khosravi, M. Yazdanbakhsh, M. Eftekhar, Z. Haddadi, Fabrication of nano Delafossite LiCo_0.5Fe_0.5O₂ as the new adsorbent in efficient removal of reactive blue 5 from aqueous solutions, Mater. Res. Bull. 48(2013) 2213-2219.

[16] M. Yazdanbakhsh, I. Khosravi, E.K. Goharshadi, A. Youssefi, Fabrication of nanospinel ZnCr₂O₄ using sol-gel method and its application on removal of azo dye from aqueous solution, J. Hazard. Mater. 184(2010) 684-689.

[17] K.Y. Shin, J.Y. Hong, J. Jang, Heavy metal ion adsorption behavior in nitrogen-doped magnetic carbon nanoparticles:isotherms and kinetic study, J. Hazard. Mater. 190(2011) 36-44.

[18] B. Bi, L. Xu, B. Xu, X. Liu, Heteropoly blue-intercalated layered double hydroxides for cationic dye removal from aqueous media, Appl. Clay Sci. 54(2011) 242-247.

[19] S.K. Shukla, A.K. Mishra, O.A. Arotiba, B.B. Mamba, Chitosan-based nanomaterials:A state-of-the-art review, Int. J. Biol. Macromol. 59(2013) 46-58.

[20] H. Zhao, J. Xu, W. Lan, T. Wang, G. Luo, Microfluidic production of porous chitosan/silica hybrid microspheres and its Cu(Ⅱ) adsorption performance, Chem. Eng. J. 229(2013) 82-89.

[21] J. Filipovic-Grcic, B. Perissutti, M. Moneghini, D. Voinovich, A. Martinac, I. Jalsenjak, Spray-dried carbamazepine-loaded chitosan and HPMC microspheres:Preparation and characterisation, J. Pharm. Pharmacol. 55(2003) 921-931.

[22] H. Peng, H. Xiong, J. Li, M. Xie, Y. Liu, C. Bai, L. Chen, Vanillin cross-linked chitosan microspheres for controlled release of resveratrol, Food Chem. 121(2010) 23-28.

[23] M. Vakili, M. Rafatullah, B. Salamatinia, A.Z. Abdullah, M.H. Ibrahim, K.B. Tan, Z. Gholami, P. Amouzgar, Application of chitosan and its derivatives as adsorbents for dye removal from water and wastewater:A review, Carbohydr. Polym. 113(2014) 115-130.

[24] A. Gamage, F. Shahidi, Use of chitosan for the removal of metal ion contaminants and proteins from water, Food Chem. 104(2007) 989-996.

[25] Z. Dong, H. Xu, Z. Bai, H. Wang, L. Zhang, X. Luo, Z. Tang, R. Luque, J. Xuan, Microfluidic synthesis of high-performance monodispersed chitosan microparticles for methyl orange adsorption, RSC Adv. 5(2015) 78352-78360.

[26] C.H. Yang, K.S. Huang, P.W. Lin, Y.C. Lin, Using a cross-flow microfluidic chip and external crosslinking reaction for monodisperse TPP-chitosan microparticles, Sensors Actuators B Chem. 124(2007) 510-516.

[27] J.H. Xu, S.W. Li, C. Tostado, W.J. Lan, G.S. Luo, Preparation of monodispersed chitosan microspheres and in situ encapsulation of BSA in a co-axial microfluidic device, Biomed. Microdevices 11(2009) 243-249.

[28] J.H. Xu, S.W. Li, J. Tan, G.S. Luo, Correlations of Droplet Formation in T-junction Microfluidic Devices:From Squeezing to Dripping, Pantheon Books, 2008.

[29] W.J. Lan, S.W. Li, J.H. Xu, G.S. Luo, Rapid measurement of fluid viscosity using coflowing in a co-axial microfluidic device, Microfluid. Nanofluid. 8(2010) 687-693.

[30] M.V. Subbaiah, D.S. Kim, Adsorption of methyl orange from aqueous solution by aminated pumpkin seed powder:kinetics, isotherms, and thermodynamic studies, Ecotoxicol. Environ. Saf. 128(2016) 109-117.

[31] Z. Zhou, F. Jiang, T.C. Lee, T. Yue, Two-step preparation of nano-scaled magnetic chitosan particles using Triton X-100 reversed-phase water-in-oil microemulsion system, J. Alloys Compd. 581(2013) 843-848.

[32] Y.G. Ko, S.S. Shin, U.S. Choi, S.P. Yong, J.W. Woo, Gelation of chitin and chitosan dispersed suspensions under electric field:Effect of degree of deacetylation, ACS Appl. Mater. Interfaces 3(2011) 1289.

[33] N.S. Kumar, M. Suguna, M.V. Subbaiah, A.S. Reddy, N.P. Kumar, A. Krishnaiah, Adsorption of phenolic compounds from aqueous solutions onto chitosan-coated perlite beads as biosorbent, Ind. Eng. Chem. Res. 49(2010) 9238-9247.

[34] T.V. Toledo, Preparation and evaluation of magnetic chitosan particles modified with ethylenediamine and Fe(Ⅲ) for the removal of Cr(VI) from aqueous solutions, Quim. Nova 37(2014) 327-329.

[35] S. Peng, H. Meng, Y. Ouyang, J. Chang, Nanoporous magnetic cellulose-chitosan composite microspheres:preparation, characterization, and application for Cu(Ⅱ) adsorption, Ind. Eng. Chem. Res. 53(2014) 2106-2113.

[36] V. Nair, A. Panigrahy, R. Vinu, Development of novel chitosan-lignin composites for adsorption of dyes and metal ions from wastewater, Chem. Eng. J. 254(2014) 491-502.

[37] S. Zhang, Y. Zhou, W. Nie, L. Song, T. Zhang, Preparation of uniform magnetic chitosan microcapsules and their application in adsorbing copper ion(Ⅱ) and chromium ion(Ⅲ), Ind. Eng. Chem. Res. 51(2012) 14099-14106.

[38] X. Tang, D. Niu, C. Bi, B. Shen, Hg²⁺ adsorption from a low-concentration aqueous solution on chitosan beads modified by combining polyamination with Hg²⁺-imprinted technologies, Ind. Eng. Chem. Res. 52(2013) 13120-13127.

[39] S. Saravanan, S. Nethala, S. Pattnaik, A. Tripathi, A. Moorthi, N. Selvamurugan, Preparation, characterization and antimicrobial activity of a bio-composite scaffold containing chitosan/nano-hydroxyapatite/nano-silver for bone tissue engineering, Int. J. Biol. Macromol. 49(2011) 188-193.

[40] H. Ren, Z. Gao, D. Wu, J. Jiang, Y. Sun, C. Luo, Efficient Pb(Ⅱ) removal using sodium alginate-carboxymethyl cellulose gel beads:preparation, characterization, and adsorption mechanism, Carbohydr. Polym. 137(2016) 402-409.

[41] O. Duman, S. Tunc, T.G. Polat, B.K. Bozoglan, Synthesis of magnetic oxidized multiwalled carbon nanotube-κ-carrageenan-Fe₃O₄ nanocomposite adsorbent and its application in cationic Methylene Blue dye adsorption, Carbohydr. Polym. 147(2016) 79-88.

[42] M.M. El-Zawahry, F. Abdelghaffar, R.A. Abdelghaffar, A.G. Hassabo, Equilibrium and kinetic models on the adsorption of Reactive Black 5 from aqueous solution using Eichhornia crassipes/chitosan composite, Carbohydr. Polym. 136(2015) 507-515.

[43] S. Duan, R. Tang, Z. Xue, X. Zhang, Y. Zhao, W. Zhang, J. Zhang, B. Wang, S. Zeng, D. Sun, Effective removal of Pb(Ⅱ) using magnetic Co_0.6Fe_2.4O₄ micro-particles as the adsorbent:synthesis and study on the kinetic and thermodynamic behaviors for its adsorption, Colloids Surf. A Physicochem. Eng. Asp. 469(2015) 211-223.

[44] H. Tajizadegan, O. Torabi, A. Heidary, M.H. Golabgir, A. Jamshidi, Study of methyl orange adsorption properties on ZnO-Al₂O₃ nanocomposite adsorbent particles, Desalin. Water Treat. 57(2015) 1-11.

[45] M. Costa, Effective removal of Cu (Ⅱ) ions from aqueous solution by aminofunctionalized magnetic nanoparticles, J. Hazard. Mater. 184(2010) 392-399.

[46] J. Fan, Z. Zhao, W. Liu, Y. Xue, Y. Shu, Solvothermal synthesis of different phase N-TiO₂ and their kinetics, isotherm and thermodynamic studies on the adsorption of methyl orange, J. Colloid Interface Sci. 470(2016) 229-236.

[47] M. Shariati-Rad, M. Irandoust, S. Amri, M. Feyzi, F. Ja'Fari, Magnetic solid phase adsorption, preconcentration and determination of methyl orange in water samples using silica coated magnetic nanoparticles and central composite design, Int. Nano Lett. 4(2014) 91-101.