The widespread use of nanofiltration and electrodialysis membrane processes is slowed down by the difficulties in predicting the membrane performances for treating streams of variable ionic compositions. Correlations between ion hydration properties and solute transfer can help to overcome this drawback. This research aims to investigate the correlation between theoretically evaluated hydration properties of major ions in solution and experimental values of neutral organic solute fluxes. In particular, ion hydration energies, coordination and hydration number and the average ion-water distance of Na⁺, Ca²⁺, Mg²⁺, Cl⁻ and SO₄²⁻ were calculated at a high quantum mechanics level and compared with experimental sugar fluxes previously reported. The properties computed by simple and not computationally expensive models were validated with information from the literature. This work discusses the correlation between the hydration energies of ions and fluxes of three saccharides, measured through nanofiltration and ionic-exchange membranes. In nanofiltration, the sugar flux increases with the presence of ions of increasing hydration energy. Instead, inverse linear correlations were found between the hydration energy and the sugar fluxes through ion exchange membranes. Finally, an empirical model is proposed for a rough evaluation of the variation in sugar fluxes as function of hydration energy for the ion exchange membranes in diffusion experiments.

The increasing number of investigations on the use of electrodialysis (ED) in bio-refinery requires a better understanding and tools to evaluate and describe the transfer of charged organic solutes. This study focuses, as an example, on the selective transfer of acetate, butyrate, and chloride (used as a reference), characterized by using permselectivity. It is shown that permselectivity between two anions does not depend on the total ion concentration, neither on the ion proportions, current intensity, or time nor on the presence of an additional compound. Therefore, it is demonstrated that permselectivity can be used to model the evolution of the stream composition during ED, even at high demineralization rates. Indeed, a very good agreement is found between experimental and calculated values. This study and the application of permselectivity as a tool, as developed in this paper, could be highly valuable for a wide range of applications in electrodialysis.

In this study, nanofiltration experiments using synthetic solutions containing acetate, butyrate, and lactate are carried out to assess the impact of the feed composition, i.e., feed concentration and feed proportions, on the separation factor of couples of solutes in binary and ternary solutions. In binary solutions, no influence of the solute proportions in the feed was pointed out, whatever the couple of solutes. The separation factor of acetate/butyrate and acetate/lactate was found to decrease with increasing feed concentration, while that of lactate/butyrate remained constant. The separation factors of acetate/lactate and lactate/butyrate were identical in ternary solutions compared to binary ones, showing no impact of the addition of the third solute. In ternary solutions, the presence of lactate decreased the separation factor of acetate/butyrate, but this decrease was not influenced by the proportion of lactate.