Reactive Crystallization Kinetics of K2SO4 from Picromerite-Based MgSO4 and KCl

In this work, the kinetic parameters, the degrees of initial supersaturation (S-0) and the profiles of supersaturation (S) were determined for the reactive crystallization of K2SO4 from picromerite (K(2)SO(4)(.)MgSO(4)(.)6H(2)O) and KCl. Different reaction temperatures between 5 and 45 degrees C were considered, and several process analytical techniques were applied. Along with the solution temperature, the crystal chord length distribution (CLD) was continuously followed by an FBRM probe, images of nucleation and growth events as well as the crystal morphology were captured, and the absorbance of the solution was measured via ATR-FTIR spectroscopy. In addition, the ion concentrations were analyzed. It was found that S-0 is inversely proportional to the reactive crystallization temperature in the K+, Mg2+/Cl-, SO42-//H2O system at 25 degrees C, where S-0 promotes nucleation and crystal growth of K2SO4 leading to a bimodal CLD. The CLD was converted to square-weighted chord lengths for each S-0 to determine the secondary nucleation rate (B), crystal growth rate (G), and suspension density (M-T). By correlation, from primary nucleation rate (B-b) and G with S-0, the empirical parameters b = 3.61 and g = 4.61 were obtained as the order of primary nucleation and growth, respectively. B versus G and M-T were correlated to the reaction temperature providing the rate constants of B and respective activation energy, E = 69.83 kJ center dot mol(-1). Finally, a general Equation was derived that describes B with parameters K-R = 13,810.8, i = 0.75 and j = 0.71. The K2SO4 crystals produced were of high purity, containing maximal 0.51 wt% Mg impurity, and were received with ~73% yield at 5 degrees C.