Precipitation Behavior of Salts in Supercritical Water: Experiments and Molecular Dynamics Simulations

Abstract

Supercritical water desalination (SCWD) shows great potential in the treatment of highsalt wastewater with zero liquid discharge. To investigate the salt precipitation behavior and mechanism in supercritical water, experiments and molecular dynamics simulations (MDs) were used to study the salting‐out process of different salts in supercritical water. The equilibrium concentrations of NaCl, KCl, CaCl2, Na2SO4, and Na2CO3 in supercritical water were experimentally measured. When the temperature exceeded 693 K, the salt equilibrium concentration measured in the experiment was less than 130 mg/L. The solubility decreased in the order of KCl > NaCl > CaCl2 > Na2SO4 > Na2CO3. To elucidate the effects of different cations and anions in supercritical water on salt dissolution and precipitation behavior, the potential energy, radial distribution function (RDF) and coordination number in the system were obtained via molecular dynamics simulation. Experimental and MD results showed that salt solubility has significant positive correlation with systemic potential energy and hydration number. MD results indicated that a small ionic radius, large ionic charge, and low hydration coordination number are favorable for inorganic salts to precipitate and crystallize since these factors can strengthen the interaction between free ions and salt clusters. Moreover, due to the formation of multilayer coordination structure, polyatomic ions can achieve a lower equilibrium concentration than that of the corresponding monatomic ions.