Abstract

To advance dimethyl ether-driven fractional crystallization (DME-FC), a more sustainable method of water treatment and mineral recovery, a range of chemical equilibria were measured. These include varying concentrations of miscible organic solvents (MOS) used to experimentally measure the solvent-induced solid-liquid equilibrium (SLE) of calcium sulfate (CaSO4) in water. Seven MOS, including dimethyl ether (DME), acetonitrile (MeCN), 1,4-dioxane, tetrahydrofuran (THF), acetone, ethanol, and diethylamine, were screened to establish trends associated with molecular volume, functional groups, and physical properties. The effect of MOS on CaSO4 removal differed at concentrations <0.15 mol fraction MOS; MOS with greater molecular volume (THF, 1,4-dioxane, and diethylamine) induced greater CaSO4 precipitation on a per mole basis. The solvent-induced SLE for all MOS converged between 0.15 and 0.2 mol fraction MOS, reaching a CaSO4 concentration consistent with a water to MOS hydration ratio of 5:1 to 6:1, which may correspond to the solvent generating a solution-based pseudo-clathrate structure with continuity within the solution. Solution pseudo-clathrate structures provide a mechanistic basis for DME-FC.

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