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

In this work, the kinetic parameters, the degrees of initial supersaturation (S0) and the profiles of supersaturation (S) were determined for the reactive crystallization of K2SO4 from picromerite (K2SO4.MgSO4.6H2O) and KCl. Different reaction temperatures between 5 and 45 °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 S0 is inversely proportional to the reactive crystallization temperature in the K+, Mg2+/Cl−, SO42−//H2O system at 25 °C, where S0 promotes nucleation and crystal growth of K2SO4 leading to a bimodal CLD. The CLD was converted to square-weighted chord lengths for each S0 to determine the secondary nucleation rate (B), crystal growth rate (G), and suspension density (MT). By correlation, from primary nucleation rate (Bb) and G with S0, 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 MT were correlated to the reaction temperature providing the rate constants of B and respective activation energy, E = 69.83 kJ∙mol−1. Finally, a general Equation was derived that describes B with parameters KR = 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 °C.

An Ultrasound Tomography Method for Monitoring CO2 Capture Process Involving Stirring and CaCO3 Precipitation

In this work, an ultrasound computed tomography (USCT) system was employed to investigate the fast-kinetic reactive crystallization process of calcium carbonate. USCT measurements and reconstruction provided key insights into the bulk particle distribution inside the stirred tank reactor and could be used to estimate the settling rate and settling time of the particles. To establish the utility of the USCT system for dynamical crystallization processes, first, the experimental imaging tasks were carried out with the stirred solid beads, as well as the feeding and stirring of the CaCO3 crystals. The feeding region, the mixing process, and the particles settling time could be detected from USCT data. Reactive crystallization experiments for CO2 capture were then conducted. Moreover, there was further potential for quantitative characterization of the suspension density in this process. USCT-based reconstructions were investigated for several experimental scenarios and operating conditions. This study demonstrates a real-time monitoring and fault detection application of USCT for reactive crystallization processes. As a robust noninvasive and nonintrusive tool, real-time signal analysis and reconstruction can be beneficial in the development of monitoring and control systems with real-world applications for crystallization processes. A diverse range of experimental studies shown here demonstrate the versatility of the USCT system in process application, hoping to unlock the commercial and industrial utility of the USCT devices.