Rhombohedral calcite precipitation from CO2-H2O-Ca(OH)2 slurry under supercritical and gas CO2 media

TL;DR

This study investigates the synthesis of fine calcite particles via hydrothermal carbonation of calcium hydroxide under supercritical and gaseous CO2 conditions, analyzing morphology, efficiency, and reaction kinetics for potential industrial applications.

Contribution

It demonstrates how different CO2 pressures and temperatures affect calcite particle morphology, carbonation efficiency, and reaction rates, providing insights for optimizing industrial CaCO3 production.

Findings

High CO2 pressure increases calcium carbonate precipitation rate.

Carbonation efficiency reaches approximately 95% under studied conditions.

Precipitated particles are sub-micrometric and micrometric in size.

Abstract

The formation of solid calcium carbonate (CaCO3) from aqueous solutions or slurries containing calcium and carbon dioxide (CO2) is a complex process of considerable importance in the ecological, geochemical and biological areas. Moreover, the demand for powdered CaCO3 has increased considerably recently in various fields of industry. The aim of this study was therefore to synthesize fine particles of calcite with controlled morphology by hydrothermal carbonation of calcium hydroxide at high CO2 pressure (initial PCO2=55 bar) and at moderate and high temperature (30 and 90 degrees C). The morphology of precipitated particles was identified by transmission electron microscopy (TEM/EDS) and scanning electron microscopy (SEM/EDS). In addition, an X-ray diffraction analysis was performed to investigate the carbonation efficiency and purity of the solid product. Carbonation of dispersed calcium hydroxide in the presence of supercritical (PT=90 bar, T=90 degrees C) or gaseous (PT=55 bar, T=30 degrees C) CO2 led to the precipitation of sub-micrometric isolated particles (<1$\mu$m) and micrometric agglomerates (<5$\mu$m) of calcite. For this study, the carbonation efficiency (Ca(OH)2-CaCO3 conversion) was not significantly affected by PT conditions after 24 h of reaction. In contrast, the initial rate of calcium carbonate precipitation increased from 4.3 mol/h in the "90bar-90 degrees C" system to 15.9 mol/h in the "55bar-30 degrees C" system. The use of high CO2 pressure may therefore be desirable for increasing the production rate of CaCO3, carbonation efficiency and purity, to approximately 48 kg/m3h, 95% and 96.3%, respectively in this study. The dissipated heat for this exothermic reaction was estimated by calorimetry to be -32 kJ/mol in the "90bar-90 degrees C" system and -42 kJ/mol in the "55bar-30 degrees C" system.