Membrane-assisted reactive crystallisation for the recovery of dissolved phosphorus in vivianite form from liquid effluents

Novel membrane crystallisation processes resolve the mixing challenge on conventional crystallisers, by providing fixed interfacial area over which supersaturation is controlled for nucleation. Moreover, the membrane surface is thought to reduce interfacial energy and encourage micromixing. In this regard, a novel membraneassisted reactive crystallisation (MARC) process was used in this work for the dissolved phosphorous recovery in form of vivianite crystals from a phosphate-rich solution by means of the dosing of iron (II). To characterise the role of the boundary layer in controlling nucleation, a batch lab-scale system was used for the crystallization tests, and different hydraulic conditions (Reynolds ranging from 105 to 395) and polymeric membranes were tested. The crystallisation process was influenced by the hydraulic conditions, in which a low liquid velocity led to a lower induction time and vivianite supersaturation, and therefore, higher nucleation rates. Membrane properties were characterised to establish their role in the modification of the critical free energy requirement for nucleation, and for the promotion of micromixing, as possible factors that can be used to modify nucleation kinetics. As result, the bulk induction time tended to decrease with the increase in membrane hydrophobicity, roughness, pore size and porosity. Spherical vivianite nanoparticles were always synthesised with a mean size around 35 nm and a narrow distribution independently of the hydraulic conditions and membrane used. Finally, the crystallisation kinetic conformed to a diffusion-dependent nucleation mechanism, in which higher residence times for mixing increased the ion collision probability for nucleation. Importantly, this study demonstrated that MARC is an attractive prospect for nutrient recovery from wastewaters where crystal nucleation can be easily controlled by setting the operational conditions and membrane properties, eliciting considerable process intensification over existing conventional crystalliser.