Effect of current density, concentration of ternary electrolyte and type of cations on the monovalent ion selectivity of surface-sulfonated graft anion-exchange membranes: modelling and experiment

The dependence of monovalent-ion selectivity of surface-sulfonated anion exchange membranes (s-AEMs) on the electrodialysis (ED) desalination current density, the concentration of equimolar ternary electrolyte (XCl + X2SO4) in the total concentration range 0.04–0.2 M, and the type of cations (X = H, Cs, Na) has been studied. The membrane current-voltage characteristics and values of the diffusion permeability coefficients in electrolyte solutions and their mixtures were measured. It was shown that Cl/SO4-selectivity coefficients (PCl|SO4) increase along with current density, reaching maximum values at the limiting current density (Ilim). The PCl|SO4 maximum value of 5.5 was achieved for the s-AEM-18 membrane in the ED-desalination of equimolar ternary electrolytes NaCl/Na2SO4, and CsCl/Cs2SO4 (total salt concentration 0.04 M) at 1.4 and 2.4 mA cm−2 current densities, respectively. At the overlimiting currents, the splitting of water and the decrease of Cl/SO4-selectivity were observed. The obtained experimental results are interpreted using simplified mass transfer and numerical simulations in the framework of Nernst-Planck-Poisson equations implemented in the COMSOL® Multiphysics software. The model represents the modified membrane as an asymmetric bipolar membrane with two diffusion boundary layers (DBL) in electrolyte solutions on both sides of the membrane interface. The model includes the water splitting at the bipolar boundary and the chemical equilibrium between sulfate and hydrogen sulfate ions. The numerical simulations qualitatively predict the behaviour of s-AEMs membranes when the abovementioned conditions change.