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.

Modeling Study of Selenium Migration Behavior in Wet Flue Gas Desulfurization Spray Towers.

Wet flue gas desulfurization (WFGD) system is the core equipment for removing SO2 from coal-fired power plants, and it also has an important synergistic effect on the removal of selenium. However, the removal efficiency of Se across WFGD systems is not as expected, and it varies greatly in different coal-fired units (12.5-96%). In this study, a mathematical model was established to quantitatively describe the selenium migration behavior in WFGD spray towers, including the conversion of gaseous selenium to particulate selenium and the capture of gaseous SeO2 and particles by droplets. The calculation results show that the behavior of selenium in the spray tower can be divided into three stages: preparation, condensation, and removal. The condensation stage significantly affected the selenium distribution and its total removal efficiency. Furthermore, five factors which may affect the selenium behavior were investigated. Among them, the inlet particle size distribution and the droplet temperature had great impacts on the outlet selenium concentration, which may be the reason for the unstable selenium removal efficiencies. This study can help in understanding the migration process of selenium in WFGD spray towers and provide some guidance for the development of specific selenium control technologies.

Kinetic analyses and synergistic effects of CO2 co-gasification of low sulphur petroleum coke and biomass wastes.

This study presents thermogravimetric analyses (TGA) of CO2 co-gasification of petroleum coke with low sulphur (PC) and various types of biomass wastes including agricultural (rice husk (RH), rice stalk (RS) and cotton straw (CS)) and by-product wastes (saw dust (SD) and sugar cane bagasse (SCB)). Their reactivities, synergistic effect and kinetics were studied and compared in detail. The homogeneous model (HM) and shrinking core models (SCM) were applied to estimate the kinetic parameters. The results indicated that obvious synergistic effect was observed during the co-gasification of the blends. The PC gasification reactivity was significantly improved by the addition of biomass wastes. The model of R2 was found to be most suitable for the co-gasification. The activation energy of PC was decrease from 293.72 kJ/mol to117.04 kJ/mol by the addition of SD. The co-gasification of PC and biomass waste is a promising way for the efficient utilization of PC and biomass wastes.

Comparison of CaO's effect on the fate of heavy metals during thermal treatment of two typical types of MSWI fly ashes in China.

Both grate and fluidized bed incinerators are widely used for MSW incineration in China. CaO addition for removing hazardous emissions from MSWI flue gas changes the characteristics of fly ash and affects the thermal behavior of heavy metals when the ash is reheated. In the present work, two types of MSWI fly ashes, sampled from both grate and fluidized bed incinerators respectively, were thermal treated at 1023-1323 K and the fate of heavy metals was observed. The results show that both of the fly ashes were rich in Ca and Ca-compounds were the main alkaline matter which strongly affected the leaching behavior of heavy metals. Ca was mostly in the forms of Ca(OH)2 and CaCO3 in the fly ash from grate incinerator in which nascent fly ash particles were covered by Ca-compounds. In contrast, the content of Ca was lower in the fly ash from fluidized bed incinerator and Ca was mostly in the form of CaSO4. Chemical reactions among Ca-compounds caused particle agglomeration in thermal treated fly ash from grate incinerator, restraining the heavy metals volatilization. In thermal treated fly ash from fluidized bed incinerator, Ca was converted into aluminosilicates especially at 1323 K which enhanced heavy metals immobilization, decreasing their volatile fractions as well as leaching concentrations. Particle agglomeration hardly affected the leaching behavior of heavy metals. However, it suppressed the leachable-CaCrO4 formation and lowered Cr leaching concentration.

CO2 co-gasification of lower sulphur petroleum coke and sugar cane bagasse via TG-FTIR analysis technique.

This study investigates the non-isothermal mechanism and kinetic behaviour of gasification of a lower sulphur petroleum coke, sugar cane bagasse and blends under carbon dioxide atmosphere conditions using the thermogravimetric analyser (TGA). The gas products were measured online with coupled Fourier transform infrared spectroscopy (FTIR). The achieved results explored that the sugar cane bagasse and blend gasification happened in two steps: at (<500 °C) the volatiles are released, and at (>700 °C) char gasification occurred, whereas the lower sulphur petroleum coke presented only one char gasification stage at (>800 °C). Significant interactions were observed in the whole process. Some solid-state mechanisms were studied by the Coats-Redfern method in order to observe the mechanisms responsible for the gasification of samples. The results show that the chemical first order reaction is the best responsible mechanism for whole process. The main released gases are CO2, CO, CH4, HCOOH, C6H5OH and CH3COOH.