To develop a utilization system for seawater resources based on the salt production process, a method for recovery and upgrading of Ca and Mg from the concentrated brine discharge of a salt manufacturer in Japan was examined. From a salt solubility viewpoint, the synthesis of the carbonates by reactive crystallization between the dissolved Ca
2+ and Mg
2+ ions in concentrated brine and CO
2 can be considered as an effective separation/recovery method. In this study, the production regions of the Ca and Mg carbonates were classified according to the solution pH and temperature (
TS) during reactive crystallization from concentrated brine, using the gas–liquid interfaces surrounding the CO
2 fine bubbles. In the regions near the minute gas–liquid interfaces, the local increase in the Ca
2+, Mg
2+, and CO
32- concentrations was caused by the electric charge on the fine bubble surface and the acceleration of CO
2 mass transfer as a result of a reduction in the bubble diameter. Additionally, at high solution pH and
TS values of the concentrated brine, the production of Ca and Mg carbonates could be controlled because of the variation in the local supersaturation, i.e., the concentration difference between the gas–liquid interfaces and bulk solution. This was attained by changing the local concentrations of the Ca
2+, Mg
2+, and CO
32- ions at the gas–liquid interfaces and the Ca and Mg carbonate solubilities in the bulk solution. At the pH range 5.3–8.3 and
TS range 278–348 K, CO
2 fine bubbles with an average diameter of 40 μm were continuously supplied to concentrated brine derived from salt manufacture discharge. The Ca and Mg carbonates crystallized within a reaction time of 60 min. Consequently, CaMg(CO
3)
2 was crystallized at the pH range 5.3–6.8 and
TS range 278–298 K with high selectivity. Aragonite form CaCO
3 was preferentially produced at
TS >333 K and the pH values 5.3 and 6.0. At solution pH values >7.8 and constant
TS 298 K, Mg(OH)
2 was precipitated as a by-product together with CaMg(CO
3)
2 and aragonite form CaCO
3.
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