Sorption of copper ions from aqueous solutions by highly dispersed cobalt ferrite and zinc ferrite
Abstract
Magnetic materials are highly demanded in sorption technologies of separation and purification of substances due to possibility of their fast and effective magnetic separation by external magnetic field for further use and regeneration. Nanoparticles of metal ferrites (MeFe2O4) are considered perspective to fabricate new magnetic sorbents as their magnetic susceptibility and physical-chemical properties can be tuned using different synthesis methods. Present work establishes kinetic and equilibrium characteristics of sorption extraction of copper ions from aqueous solutions by samples of nanodispersed powders of cobalt ferrite (Co-F) and zinc ferrite (Zn-F) synthesized by a citrate burning method. Specific surface area and porosity of samples was characterized by nitrogen adsorption-desorption isotherms. Sorption capacity of materials was determined in aqueous solutions of 0.005-0.075 N CuSO4 by varying time of sorption (0÷120 min), рН=2÷5, mass of sorbent at temperature of t=20оС. Quantitative analysis of solutions was done by photocolorimetric method. Magnetic properties of sorbents were qualitatively assessed by action of Nd-magnet on aqueous dispersions of ferrites. Experimental isotherms of nitrogen adsorption-desorption by samples of ferrites observed sigmoid shape corresponding to II type of IUPAC classification and a narrow loop of hysteresis caused by the presence of secondary mesopores in the materials. The specific surface area and pore volume of the samples were 26 m2/g (Zn-F), 16 m2/g (Co-F) and 0,106 cm3/g (Zn-F), 0,094 cm3/g (Co-F) respectively, while the pore diameter was 5.9 nm (Zn-F) and 21.4 nm (Co-F). The kinetic curves of Cu2+ ions sorption revealed that adsorption equilibrium in the system sorbent-solution established during 10 (Co-F) – 40 (Zn-F) min and lead to twice higher values of zinc ferrite sorption capacity as one for cobalt ferrite. The pseudo-second order kinetics model adequately (R2=0.93÷0.99) described the sorption process on ferrites. The calculated values of the rate constant (k2) indicated a lower rate of sorption of Cu2+ ions by zinc ferrite sample as compared to cobalt ferrite that can be caused by the diverse nature of sorption sites at ferrites surface due to different distribution of cations in the crystal lattice of normal (zinc ferrite) and inverse (cobalt ferrite) spinel. The isotherms of copper ions adsorption were described by models of Langmuir, Freundlich and BET. The best fit of experimental isotherms for zinc and cobalt ferrites were found within the frames of Freundlich and BET models. The models parameters evidenced at a higher affinity towards a sorbate and favorable conditions of sorption for the case of zinc ferrite in contrast to cobalt ferrite as well as the tendency of sorbents to polymolecular sorption of copper ions in the range of medium and high solution concentrations. At pH<3 sorption of Cu2+ by Co-F samples decreased, while it passed through the maximum at pH=3 that testified to a simultaneous sorption of hydroxonium along with Cu2+ as well as to a distinct charge of the ferrites surface. The sorption capacity of sorbents retained for five to six (zinc ferrite) and three to four (cobalt ferrite) sorption cycles without regeneration. After regeneration of spent sorbents with 0.1 М HCl, zinc ferrite sorbent renewed and maintained its capacity constant, while cobalt ferrite sorbent loosed its capacity. The application of Nd magnet resulted in complete magnetic separation of cobalt ferrite and partial separation in the case of zinc ferrite sorbent.
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