Limestone Dissolution in Flue Gas Scrubbing: Effect of Sulfite

Batch limestone dissolution experiments were carried out in a pH stat apparatus at 55°C with CO2 sparging and dissolved sulfite. Particle size distribution, utilization, sulfite in solution, limestone type, and the approach to calcite equilibrium were all found to contribute to the limestone reactivity. In the absence of sulfite, limestone dissolution was controlled solely by mass transfer. For a given stone under mass transfer control, film thickness was found to be independent of pH. The dissolution rate in the presence of sulfite was controlled by a combined surface kinetics/mass transfer regime. SEM micrographs supported this conclusion. A surface rate correlation was developed which accounted for observed inhibition by an inverse dependence on calcium sulfite concentration at the limestone surface. While the form of the rate expression was applicable to all stones, the surface rate constant was stone dependent. A computer code which accounted for mass transfer with surface kinetics was tested against experimental observations of four limestone types. Changes in pH and the concentrations of calcium, carbonate, sulfite, sulfate, and adipic acid were accurately modeled.