Investigation of precipitation selectivity and particle size concentration dependences in supercritical antisolvent method via online supercritical fluid chromatography

Abstract

Supercritical antisolvent (SAS) precipitation technique, although being versatile and ecologically friendly, suffers from the lack of convenient methods for necessary thermodynamic parameters measurement. Recently we have proposed a method for solubility measurement in binary fluids based on an online hyphenation of supercritical antisolvent method and supercritical fluid chromatography (SAS-SFC). In this paper, we demonstrate the applicability of this method to the investigation of both selective precipitation from solution and particle size tuning in SAS using lower dicarboxylic acids as model objects. Measured solubility values adequately reflect selective crystallization from solution. SAS precipitation was observed only for those components, which concentration was above solubility in CO2-solvent mixture as predicted by SAS-SFC method. Also, concentration dependences of particle size plotted in supersaturation coordinates instead of direct concentration in initial solution give additional insight into crystallization behaviour in SAS.