RI 8540 The Chemical Reactions of Sulfur in the Citrate Process for Flue Gas Desulfurization

The Bureau of Mines performed chemical research to elaborate details of sulfur chemistry pertaining to the citrate flue gas desulfurization process in which sulfur dioxide (SO2), absorbed (as bisulfite ion) in a buffered sodium citrate solution, is reduced by hydrogen sulfide (H2S) according to the overall reaction 2H2S + HSO3 + H+ ? 3S + 3H20. The rate-limiting step in the process was shown to be the reduction by H2S of thiosulfate (S2031-) that is formed as an intermediate. Pseudo first-order kinetic measurements were made at room temperature to retard the reaction sufficiently that adequate analysis was possible. These measurements showed the rates of the following net processes to be -d [S02]/dt (pH 4.5) = (0.409±0.050)min-1 [S02]; d [S2032-]/dt (pH 4.5) = (0.199±0.017)min-1 [S02]; -d [S2032-]/dt (pH 4.0) = (0.0437±0.0265)min-1 [S2032-]~1; -dH2S/dt (pH 3.9) = (21.6±3.0) mmoles/min-atm [H2S]g1.4, where [H2S]g is the partial pressure of H2S in the gas phase, in atmospheres, and the rate describes the consumption of H2S, in millimoles per minute; d[S]/dt (pH 4.0) = (38.0±3.4)min-1 [H2S]1, where [H2S] is the concentration of H2S in solution. Hydrogen ion consumption during the slow phase of regeneration was shown to occur at (2.1±0.5) times he rate of thiosulfate consumption, which is interpreted as evidence for the following as the rate-limiting reaction: 2H2S + S2032- + 2H+ ? 4S + 3H20 A scheme consisting of five sequential general reactions is proposed to account for sulfur formation.