Zero liquid discharge strategies for industrial wastewater treatment have become prominent in recent years. When evaporative simultaneous crystallization is applied, knowledge about the particle crystallization mechanisms and morphology are important to ease solids downstream handling and for recovery of their valuable components. In this work, batch simultaneous crystallization of sodium chloride (NaCl) and calcium sulphate hemihydrate (CaSO4.0.5H2O) from aqueous solution was studied. It was found that CaSO4.0.5H2O is not an effective substrate for NaCl heterogeneous nucleation, but agglomerates with NaCl particles instead. CaSO4.0.5H2O particles on the surface of NaCl crystals sterically hamper agglomeration of NaCl particles with each other and, for a sufficiently high CaSO4.0.5H2O seed load, cover the NaCl crystals so that NaCl supersaturation rises, inducing NaCl primary nucleation. Simultaneous crystallization of CaSO4.0.5H2O and NaCl yields a satisfactory product for downstream handling even for high CaSO4.0.5H2O content in the crystallizer. However, seeding with CaSO4.0.5H2O is not recommended as it reduces the mean size and increases product size dispersion. NaCl seeding may be considered if it is desirable to separate CaSO4.0.5H2O from NaCl downstream the crystallizer by size classification, as it favors CaSO4.0.5H2O to build up in product sizes of 200 μm and below.
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