In systems for utilizing seawater resources based on the desalination and salt production process, to prevent scaling in reverse osmosis (RO) and electrodialysis (ED) units, the calcium (Ca) recovery and upgrading method was studied. From the viewpoint of solubility of Ca salts, the synthesis of calcium carbonate (CaCO
3) by reactive crystallization between the dissolved Ca
2+ in seawater/brine and carbon dioxide (CO
2) can be considered as an effective separation/recovery method. Moreover, the obtained CaCO
3 is able to upgrade to hydroxyl apatite (HAP) with treatment of phosphoric acid and hydroxide. In this paper, as a two-stage process of Ca
2+ recovery, CaCO
3 generation using the dissolved Ca
2+ ion in the brine solution and CO
2 bubbles, and conversion to HAP were examined. Additionally, in order to simplify and facilitate the process, the one-stage process of HAP generation, including treatment of phosphoric acid and hydroxide, was also investigated. The experimental results in a two-stage process were as follows: 1) when CO
2 bubbles were continuously supplied to the brine solution, only CaCO
3 was crystallized; 2) aragonite fine particles were produced by minimizing bubble size; 3) the suspended CaCO
3 particles in the solution were almost converted to HAP by treatment of phosphoric acid and hydroxide at solution pH of 7.0; furthermore, 4) when the brine solution was treated with phosphoric acid and hydroxide, HAP was generated in the range over 4.7 of solution pH; and 5) the generation rate and crystallinity of HAP increased with an increase in solution pH.
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