Modeling solid–liquid equilibrium of NH4Cl‐MgCl2‐H2O system and its application to recovery of NH4Cl in MgO production

A new method to recover NH₄Cl from NH₄Cl‐rich aqueous solutions generated in the magnesia (MgO) production is developed on the basis of modeling the solid–liquid equilibrium (SLE) for the NH₄Cl‐MgCl₂‐H₂O system with the Pitzer model embedded in Aspen Plus? platform. The SLE values for the ternary system were determined from 278.15 to 348.15 K. The new standard‐state chemical potentials of NH₄Cl and MgCl₂·6H₂O were judicially obtained. The resulting equilibrium constants were used to determine new interaction parameters for the NH₄Cl‐H₂O and MgCl₂‐H₂O systems. These new parameters, together with the mixing parameters determined from correlating the experimental values, were used to correlate the equilibrium constant for NH₄MgCl₃·6H₂O, which plays a key role in NH₄Cl recovery. The results could extend SLE calculation for the NH₄Cl‐MgCl₂‐H₂O system from 278.15 to 388.15 K, satisfying the process identification and simulation requirement involved in the recovery process. The phase‐equilibrium diagram generated by modeling was illustrated to identify the process alternatives for recovering NH₄Cl. The resulting course to recover NH₄Cl by three fractional crystallization operations was finally proved feasible. © 2010 American Institute of Chemical Engineers AIChE J, 2011.