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Impact of surface properties of cation-exchange membranes on the formation of Ca2+ and Mg2+ containing scales during electrodialysis of their aqueous solutions

Abstract : Scaling on the surface and in the bulk of ion-exchange membranes is a considerable locker for electrodialysis. The scale reduces the effective surface area of the membrane and leads to additional resistance to the mass transfer and solution flow.Three cation-exchange membranes are used in this study: a heterogeneous commercial MK-40 membrane and two of its modifications. The MK-40/Nafion membrane is obtained by mechanical coating the MK-40 membrane surface with a homogeneous ion-conductive Nafion® film. Modification of the MK-40/PANI membrane is carried out by polyaniline synthesis on the membrane surface. The solutions used in the study are 0.02 and 0.04 mol/L CaCl2 and MgCl2 solutions, as well as the solution, imitating the mineral composition of milk, concentrated 3 times. The visualization of the membrane surface is made using optical and scanning electron microscopy. The elemental analysis of the scale on the membrane surface is made by X-ray analysis. The hydrophobic-hydrophilic balance of the membrane surface is estimated by the contact angle measurements. To characterize the cation transport through and the water splitting rate, chronopotentiometry and voltammetry methods are used, pH measurement of the diluate solution is conducted at the same time.It is shown that the relatively high hydrophobicity of the membrane surface, its electrical and geometric heterogeneity, create conditions for the development of electroconvection. The electroconvection intensity in the case of MK-40/Nafion is significantly higher, and in the case of MK-40/PANI is lower in comparison with that of the unmodified membrane. Electroconvection vortexes cause the mixing of the solution at the membrane surface in a 10 µm thick layer. This effect significantly increases mass transfer in intensive current modes and prevents or reduces the scaling process, as well as reduces the water splitting rate at the membrane surface. The rate of electroconvection essentially depends on the counterion hydration degree, it increases with increasing the counterion Stokes radius. The rate of the scale formation on the membrane surface is determined by the slope of the chronopotentiogramme. The formation of Mg(OH)2, Ca(OH)2 and CaCO3 scales is observed. It is experimentally established that the scaling rate on the surface of MK-40/Nafion is smaller, and on the surface of the MK-40/PANI is larger in comparison with the MK-40 membrane. The scaling rate is significantly reduced when the pulsed electric current mode is applied. Such mode allows the reduction of the potential drop more than twice and achievement of a quasi steady-state because an unstable periodically crumbling scale occurs
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Submitted on : Thursday, April 5, 2018 - 12:30:22 PM
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Marina Andreeva. Impact of surface properties of cation-exchange membranes on the formation of Ca2+ and Mg2+ containing scales during electrodialysis of their aqueous solutions. Chemical and Process Engineering. Université Paris-Est; Kuban State agrarian university, 2017. English. ⟨NNT : 2017PESC1018⟩. ⟨tel-01759303⟩

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