RESUMO
Despite the growing interest in pulsed electric field modes in membrane separation processes, there are currently not many works devoted to studying the effect of the surface properties and composition of ion-exchange membranes on their efficiency in these modes. In this paper, we have shown the effect of increasing mass transfer using different kinds of ion-exchange membranes (heterogeneous and homogeneous with smooth, undulated, and rough surfaces) during electrodialysis in the pulsed electric field modes at underlimiting and overlimiting currents. It was found that the maximum increment in the average current is achieved when the average potential corresponds to the right-hand edge of the limiting current plateau of the voltammetric curve, i.e., at the maximum resistance of the system in the DC mode. For the first time, the development of electroconvective vortices was visualized in pulsed electric field modes and it was experimentally shown that even at relatively low frequencies, a non-uniform concentration field is preserved at the time of a pause, which stimulates the rapid development of electroconvection when pulses are switched on again. In the case of relatively high pulse frequencies, the electroconvective vortices formed during a pulse lapse do not completely decay during a pause; they only slightly decrease in size.
RESUMO
Electrodialysis (ED) with ion-exchange membranes is a promising method for the extraction of phosphates from municipal and other wastewater in order to obtain cheap mineral fertilizers. Phosphorus is transported through an anion-exchange membrane (AEM) by anions of phosphoric acid. However, which phosphoric acid anions carry the phosphorus in the membrane and the boundary solution, that is, the mechanism of phosphorus transport, is not yet clear. Some authors report an unexpectedly low current efficiency of this process and high energy consumption. In this paper, we report the partial currents of H2PO4-, HPO42-, and PO43- through Neosepta AMX and Fujifilm AEM Type X membranes, as well as the partial currents of H2PO4- and H+ ions through a depleted diffusion layer of a 0.02 M NaH2PO4 feed solution measured as functions of the applied potential difference across the membrane under study. It was shown that the fraction of the current transported by anions through AEMs depend on the total current density/potential difference. This was due to the fact that the pH of the internal solution in the membrane increases with the growing current due to the increasing concentration polarization (a lower electrolyte concentration at the membrane surface leads to higher pH shift in the membrane). The HPO42- ions contributed to the charge transfer even when a low current passed through the membrane; with an increasing current, the contribution of the HPO42- ions grew, and when the current was about 2.5 ilimLev (ilimLev was the theoretical limiting current density), the PO43- ions started to carry the charge through the membrane. However, in the feed solution, the pH was 4.6 and only H2PO4- ions were present. When H2PO4- ions entered the membrane, a part of them transformed into doubly and triply charged anions; the H+ ions were released in this transformation and returned to the depleted diffusion layer. Thus, the phosphorus total flux, jP (equal to the sum of the fluxes of all phosphorus-bearing species) was limited by the H2PO4- transport from the bulk of feed solution to the membrane surface. The value of jP was close to ilimLev/F (F is the Faraday constant). A slight excess of jP over ilimLev/F was observed, which is due to the electroconvection and exaltation effects. The visualization showed that electroconvection in the studied systems was essentially weaker than in systems with strong electrolytes, such as NaCl.
