Fine particulate-bound arsenic and selenium from coal-fired power plants: Formation, removal and bioaccessibility.

The arsenic (As) and selenium (Se) in fine particulate matter (PM10) have attracted increasing attentions due to their health effects. However, the emission control of fine particulate-bound arsenic and selenium (fine particulate-bound As/Se) from coal-fired power plants still faces various challenges. Understanding the formation and characteristics of fine particulate-bound As/Se is crucial for developing specific control technologies. This study clarifies the formation mechanism, removal characteristics, and inhalation bioaccessibility of fine particulate-bound As/Se from industrial coal-fired power plants through methods including aerosol generation, As/Se speciation determination, and in vitro bioaccessibility testing. The findings demonstrated that PM1 from pulverized coal-fired (PC) boilers was enriched with As/Se in terms of concentration and mass distribution. Instead, As/Se was mainly distributed in PM2.5-10 from circulating fluidized bed (CFB) boilers. Limestone injection in CFB boilers promoted As/Se enrichment in coarse PM. Fine particulate-bound As was mainly formed by chemical adsorption of As vapors by Ca-minerals, while the formation of fine particulate-bound Se was closely related to active Ca-minerals and Fe-minerals. Furthermore, Ca-bound As was easy to remove by electrostatic precipitator (ESP) and the removal of physically adsorbed SeO2(s) was difficult, which was caused by the specific resistivity of different mineral components. Importantly, finer particulate-bound As/Se posed higher inhalation bioaccessibility, following the order of PM1 ≥ PM1-2.5 > PM2.5-10. In particular, Ca-bound Se in fine PM owned high bioaccessibility. Based on these findings, measures were proposed to suppress the formation of fine particulate-bound As/Se in the furnace and/or strengthen its removal in the post-combustion stage.

Condensation and adsorption characteristics of gaseous selenium on coal-fired fly ash at low temperatures.

Gaseous selenium is of high saturated vapor pressure, making its retention in solid phases quite difficult during coal combustion. The selenium transformation from gaseous form into solid phases at low temperatures can be essential to control selenium emission. To understand the migration of SeO2 (g) on ash particles in the low-temperature zone, this study investigated the speciation of selenium in fly ash and simulated the physical retention of SeO2 (g) on fly ash. The results demonstrated that there was a large proportion of physically-bound Se in the fly ash of pulverized-coal-fired boiler (22.62 %-58.03%), while the content of physically-bound Se in fly ash of circulated fluidized-bed boiler was lower (∼6%). The physically-bound Se was formed through selenium condensation and physical adsorption. The decrease of temperature or the increase of cooling rate could promote the transformation of gaseous selenium to solid phase and the presence of HCl might suppress SeO2 transformation into Se in the condensation process. Meanwhile the compositions of fly ash had a great influence on the selenium adsorption process. Among typical coal-fired ash components, mullite showed the best performance in the selenium capture in the temperature range of 90-200 °C, contributing to the high content of physically-adsorbed selenium in PC fly ash. These findings provided new ideas for improving the removal rate of volatile selenium.

Migration and emission behavior of arsenic and selenium in a circulating fluidized bed power plant burning arsenic/selenium-enriched coal.

Arsenic (As) and selenium (Se) pollution caused by coal combustion is receiving increasing concerns. The environmental impacts of As/Se are determined not only by stack emission but also by leaching process from combustion byproducts. For a better control of As/Se emission from As/Se-enriched coal combustion, this study investigated the migration and emission behavior of As/Se in a circulating fluidized bed (CFB) power plant equipped with fabric filter (FF) and wet flue gas desulfurization (WFGD) system. The results demonstrated that arsenic was both enriched in bottom ash (41.4-47.6%) and fly ash (52.4-58.6%), while selenium was mainly captured by fly ash (73.9-83.4%). Limestone injection into furnace promoted As/Se retention in ash residues. Arsenic was mainly converted into arsenate in high-temperature regions and partly trapped in bottom ash as arsenite. In contrast, selenium capture mainly occurred in low-temperature flue gas by the formation of selenite, because of the poor thermal stability of most selenite. Triplet-tank method can totally remove arsenic in WFGD wastewater. And 18.4-58.7% of selenium was removed, resulting from the precipitation of Se4+ anions with highly soluble Se6+ anions remaining in wastewater. The concentrations of As and Se in the stack emission were 0.25-1.02 and 0.96-2.24 µg/m3, receptively. The CFB boiler equipped with FF + WFGD was shown to provide good control of the As/Se emission into the atmosphere. Leaching tests suggested that more attention should be paid to As leachability from fly ash/gypsum, and Se leachability from gypsum/sludge.