New kinetic model for the rapid step of calcium oxide carbonation by carbon dioxide

International audienceCarbonation of solid calcium oxide by gaseous carbon dioxide was monitored by thermogravimetry (TG). A kinetic model of CaO carbonation is proposed in order to interpret the first rapid step of the reaction. By taking into account the existence of large induction period as well as the sigmoidal shape of the kinetic curves in this kinetic-controlled region, a surface nucleation and isotropic growth kinetic model based on a single nucleus per particle is proposed and the expressions of the fractional conversion and the reaction rate versus time are detailed. The induction period is found to have a linear variation with respect to temperature and to follow a power law with respect to CO2 partial pressure. The areic reactivity of growth decreases with temperature increase, and increases with CO2 partial pressure increase. A mechanism of CaCO3 growth is proposed to account for these results and to determine a dependence of the areic reactivity of growth on the temperature and the CO2 partial pressure

Impact of rock fabric, thermal behavior, and carbonate decomposition kinetics on quicklime industrial production and slaking reactivity

This paper deals with thermal analyses, burning trials and reactivity tests on 15 carbonate rocks, i.e., pure and impure carbonates, mud-supported and grain-supported limestones, crystalline marbles, and dolomites, used for the production of different lime products in industrial vertical shaft kilns worldwide. In particular, thermogravimetric and differential thermogravimetric analysis (TG–DTG) on massive (80–120 g) fine-grained (< 3.35 mm) samples allowed the extrapolation of the Arrhenius kinetic parameters, i.e., the (apparent) activation energy (Ea) and the pre-exponential or frequency factor (A). Other calcination parameters, i.e., the duration time, starting and ending calcination times and temperatures, and peaks of maximum calcination rate were also extrapolated in order to enhance their relationships with quicklime reactivity. Moreover, thermal analyses (TG–DTG–DTA) were repeated on powders (90 mg) using a more accurate analyzer to compare results. The study is completed by a thorough chemical–physical and mineralogical–petrographic characterization of carbonate rocks and derived burnt products. Results pointed out that medium-to-coarse crystalline materials, i.e., grain-supported limestones, diagenetic dolomites, and granoblastic marbles presented the highest activation energy, burnability and slaking reactivity. Conversely, microcrystalline carbonates with the highest micrite-to-sparite ratio, i.e., mud-supported limestones, and impure carbonates, enriched in quartz, clay minerals, and other subordinated non-carbonate impurities, presented the lowest activation energy, burnability, and slaking reactivity. This study also investigated the effect of BET-specific surface area and real density, depending on specific sintering tendency, on quicklime reactivity. Results from this multidisciplinary research activity put further constraints on carbonate rocks calcination kinetics and their suitability in the lime industry