Solid-liquid phase equilibrium and thermodynamic model of ternary system (NH4+ //SO42−, H2PO4−–H2O) from 313.15 to 343.15 K

A tremendous amount of wastewater containing ammonium salts, mainly NH₄H₂PO₄ and (NH₄)₂SO₄, has been produced in the production of cathode material of lithium iron phosphate (LFP). However, as an important basis for salt separation, the solid–liquid phase equilibrium (SLPE) of these two salts has been investigated by few studies. In this study, SLPE of the ternary system (NH₄⁺ //SO₄²⁻, H₂PO₄⁻–H₂O) from 313.15 K to 343.15 K at 101.2 kPa were investigated by isothermal dissolution method, and the corresponding physicochemical properties (density, viscosity, and pH) of saturated solution were measured. The phase diagram is composed of one invariant point, two univariant curves, and two single-salt crystallization fields for NH₄H₂PO₄ and (NH₄)₂SO₄. Comparing the phase diagrams from 263.15 K to 343.15 K, it is obvious that two single-salt crystallization fields shrink with increasing temperature. And the area reduction of NH₄H₂PO₄ in two salts is more significant. When the temperature drops below 268.15 K, the ice crystallization field would appear. Neither single-salt solid solution, hydrous salt nor double salt was found in the whole temperature range. Furthermore, Pitzer model was successfully applied to describe the SLPE of the ternary system at temperatures from 273.15 K to 343.15 K. The lacking Pitzer-model parameters of mixed electrolytes (θ_SO4-H2PO4 and ψ_{NH4-SO4-H2PO4}) were calculated, and the temperature coefficients of model parameters and dissolution equilibrium constant were obtained. The importance of this study is that it supplies basic data and theoretical references for the separation and resource utilization of two ammonium salts from wastewater in the LFP batteries industry.