A novel cyclic process using CaSO4/CaS pellets for converting sulfur dioxide to elemental sulfur without generating secondary pollutants: Part I. Feasibility and kinetics of the reduction of sulfur dioxide with calcium-sulfide pellets

Abstract

Certain new sulfide-smelting processes and coal-gasification processes generate high-strength sulfur dioxide streams, for which a new process for converting sulfur dioxide to elemental sulfur needs to be developed because no process exists that is generally and economically applicable to the treatment of such streams. A thermodynamic and experimental investigation to develop a new process for converting sulfur dioxide to elemental sulfur by a cyclic process involving calcium sulfide and calcium sulfate without generating secondary pollutants was carried out. In this process, the starting raw material, calcium sulfate, is reduced by a suitable reducing agent, such as hydrogen, to produce calcium sulfide, which is used to reduce sulfur dioxide to elemental sulfur vapor and calcium sulfate. The latter is, in turn, reduced to regenerate calcium sulfide. In this Part I, detailed experimental results are presented on the kinetics of the reaction between sulfur dioxide and calcium-sulfide pellets, which produces elemental sulfur and calcium sulfate. The experiments were carried out at temperatures between 1023 and 1088 K and sulfur-dioxide partial pressures between 9 and 60 kPa by the use of a thermogravimetric analysis (TGA) technique. The rate of this reaction was demonstrated by the conversion of 40 pct calcium-sulfide pellets obtained from the hydrogen reduction of fresh calcium sulfate in 10 minutes at 1073 K under a sulfur-dioxide partial pressure of 43 kPa. The reactivity decreased somewhat during the first three cycles but remained largely unchanged thereafter up to the tenth cycle. This characteristic of the pellets is important because the solids must be reusable for repeated cycles to avoid generating secondary pollutants. A pore-blocking model was found to fit the reaction rate. The reaction is first order with respect to sulfur-dioxide partial pressure and has an activation energy of 101 to 134 kJ/mol (24 to 32 kcal/mol) for calcium-sulfide pellets reacted and regenerated several different times. Sulfur dioxide-containing streams from certain sources, such as the regenerator off-gas from an integrated-gasification, combined-cycle, desulfurization unit and new sulfide-smelting plants, contain much higher partial pressures of SO2. In these cases, the rate of the first reaction is expected to be proportionally higher than in the test conditions reported in this article. The reduction kinetics of calcium-sulfate pellets with hydrogen gas is reported in the accompanying Part II.