Solidification/stabilization of flue gas desulfurization brine and coal fly ash for heavy metals and chloride immobilization: Effects of S/S conditions and zero-valent-iron pretreatment.

Effective management of flue-gas-desulfurization (FGD) wastewater and coal-combustion-residues (CCRs) are major challenges in the coal-fired power industry. The zero-liquid-discharge (ZLD) method of combining FGD brines and CCRs in solidification/stabilization (S/S) is promising due to its potential of treating both wastes in the same process. This study evaluated the performance of such a ZLD method for immobilizing heavy metals (Se, As, Cd and Cr) and chloride in FGD wastewater and/or CCRs. Effects of different coal fly ash (bituminous (BCFA) and sub-bituminous (SCFA)), activating agent (Portland cement (PC) and lime) and pretreatment of brines by zero valent iron (ZVI) on the S/S process were evaluated. Short-term and long-term leaching tests were conducted to evaluate performance of the S/S solids in pollutant retainment. The pre-treatment of FGD brine by ZVI enhanced the retainment of heavy metals when BCFA was used, but not when SCFA was used since it already performed quite well without ZVI pretreatment. Quantitative X-ray diffraction and scanning electron microscopy analyses strongly indicated the formation of Friedel's salt, Ca2Al(OH)6(Cl,OH)·2H2O, is critical in the retainment of heavy metals and chloride. SCFA contained higher lime and reactive aluminate contents than BCFA; thus, S/S solids made with SCFA contained higher amounts of Friedel's salt.

Removal of heavy metals by aged zero-valent iron from flue-gas-desulfurization brine under high salt and temperature conditions.

To achieve zero liquid discharge, the flue-gas-desulfurization (FGD) wastewater at coal-fired power plants can be concentrated into brine through thermal evaporation to maximize water reuse; however, the hot brine generated requires further treatment prior to disposal. To address this need, this study investigates the performance of aged, micron-sized zero-valent iron (ZVI) for heavy metal removal in simulated and real FGD hot brines, which was scarcely studied previously. The effects of temperature, pH, total dissolved solids, ZVI dosage, major cations, nitrate and sulfate on the reactivity of ZVI in the brines were evaluated. Among many factors, higher temperature and Mg2+ exert the dominant influence. At 80 °C, almost 100% of arsenate (1 mg/L) and chromate (1 mg/L) can be removed in <5 min using 4.17 g/L of ZVI in simulated brines, while selenate (25 mg/L) and cadmium (5 mg/L) can be completely removed within 30 min. Mg2+ ions naturally present in FGD brines account for the depassivation of aged ZVI. X-ray diffraction results suggest that green rust is the reactive intermediate for selenate and cadmium removal. Overall, this study demonstrates that ZVI is an effective material for removing heavy metals in hot FGD brines generated through thermal evaporation at power plants.