Study of calcium carbonate and sulfate co-precipitation

• CaCO3 and sulfate co-precipitation was investigated in this paper.
• Co-precipitation kinetics were studied by monitoring different parameters.
• CaCO3 germination followed by gypsum (and vice-versa) precipitation was studied.
• The influence of co-precipitation ions was also investigated.

Co-precipitation of mineral based salts in scaling is still not well understood and/or thermodynamically well defined in the water industry. This study focuses on investigating calcium carbonate (CaCO3) and sulfate mixed precipitation in scaling which is commonly observed in industrial water treatment processes including seawater desalination either by thermal-based or membrane-based processes. Co-precipitation kinetics were studied carefully by monitoring several parameters simultaneously measured, including: pH, calcium and alkalinity concentrations as well as quartz microbalance responses. The CaCO3 germination in mixed precipitation was found to be different than that of simple precipitation. Indeed, the co-precipitation of CaCO3 germination time was not anymore related to supersaturation as in a simple homogenous precipitation, but was significantly reduced when the gypsum crystals appeared first. On the other hand, the calcium sulfate crystals appear to reduce the energetic barrier of CaCO3 nucleation and lead to its precipitation by activating heterogeneous germination. However, the presence of CaCO3 crystals does not seem to have any significant effect on gypsum precipitation. IR spectroscopy and the Scanning Electronic Microscopy (SEM) were used to identify the nature of scales structures. Gypsum was found to be the dominant precipitate while calcite and especially vaterite were found at lower proportions. These analyses showed also that gypsum crystals promote calcite crystallization to the detriment of other forms.