The role of mixing on the kinetics of nucleation and crystal growth in membrane distillation crystallisation

While mixing is considered critical in membrane distillation crystallisation, an explicit link between mixing and crystallisation mechanisms has yet to be made. This study therefore used in-line nucleation detection to determine induction time and metastable zone width, as a method to characterise the independent roles of interfacial boundary layer mixing and bulk crystalliser mixing on the kinetics of nucleation and crystal growth in membrane distillation crystallisation. Interfacial boundary layer mixing was investigated by changing Reynolds number (Re, 1300-2050), where an increase in Re also increased flux. This increased supersaturation within the boundary layer, shortened induction time, and was correlated to a higher nucleation rate. The high nucleation rates introduced smaller crystal sizes, which is an effect that can be correlated to classical nucleation theory. Mixing within the crystalliser did not modify the interfacial supersaturation at nucleation (ReN 1562-18741). However, a decrease in induction time was observed when transitioning from lower to higher mixing, which may arise from the improved distribution of the supersaturated feed within the crystalliser. The effect of crystalliser mixing was also evident on crystal growth, where larger crystals were produced at higher crystalliser stirrer speeds due to improved diffusion-controlled growth. This study therefore demonstrates that bulk and interfacial mixing can be collectively used to control crystallisation by decoupling conditions that determine nucleation and crystal growth. Morphological assessment was subsequently undertaken that evidenced how dendritic breeding and wider secondary nucleation mechanisms that dominate crystal growth at high levels of supersaturation can be mitigated through mixing. Membrane crystallisation offers a scalable geometry in which we demonstrate mixing to facilitate good control over crystal growth which is more difficult to realise in existing evaporative crystalliser design.