Impact of Oxy-Fuel Conditions on Elemental Mercury Re-Emission in Wet Flue Gas Desulfurization Systems.

This study evaluates some of the variables that may influence mercury retention in wet flue gas desulfurization (WFGD) plants, focusing on oxy-coal combustion processes and differences when compared with atmospheres enriched in N2. The main drawback of using WFGD for mercury capture is the possibility of unwanted reduction of dissolved Hg(2+), leading to the re-emission of insoluble elemental mercury (Hg(0)), which decreases efficiency. To acquire a better understanding of the mercury re-emission reactions in WFGD systems, this work analyses different variables that influence the behavior of mercury in slurries obtained from two limestones, under an oxy-combustion atmosphere. The O2 supplied to the reactor, the influence of the pH, the concentration of mercury in the gas phase, and the enhancement of mercury in the slurry were the variables considered. The study was performed at laboratory scale, where possible reactions between the components in the scrubber can be individually evaluated. It was found that in an oxy-combustion atmosphere (mostly CO2), the re-emission of Hg(0) is lower than under a N2-enriched atmosphere, and the mercury is mainly retained as Hg(2+) in the liquid phase.

Effect of oxy-combustion flue gas on mercury oxidation.

This study evaluates the effect of the gases present in a typical oxy-coal combustion atmosphere on mercury speciation and compares it with the mercury speciation produced in conventional air combustion atmospheres. The work was performed at laboratory scale at 150 °C. It was found that the minor constituents (SO2, NOx, and HCl) significantly modify the percentages of Hg(2+) in the gas. The influence of these species on mercury oxidation was demostrated when they were tested individually and also when they were blended in different gas compositions, although the effect was different to the sum of their individual effects. Of the minor constituents, NOx were the main species involved in oxidation of mercury. Moreover, it was found that a large concentration of H2O vapor also plays an important role in mercury oxidation. Around 50% of the total mercury was oxidized in atmospheres with H2O vapor concentrations typical of oxy-combustion conditions. When the atmospheres have similar concentrations of SO2, NO, NO2, HCl, and H2O, the proportion of Hg(0)/Hg(2+) is similar regardless of whether CO2 (oxy-fuel combustion) or N2 (air combustion) are the main components of the gas.

Influence of limestone characteristics on mercury re-emission in WFGD systems.

This work evaluates the influence of the effect of the properties of limestones on their reactivity and the re-emission of mercury under typical wet scrubber conditions. The influence of the composition, particle size, and porosity of limestones on their reactivity and the effect of sorbent concentration, pH, redox potential, and the sulphite and iron content of the slurry on Hg(0) re-emission was assessed. A small particle size, a high porosity and a low magnesium content increased the high reactivity of the limestones. Moreover, it was found that the higher the reactivity of the sample the greater the amount of mercury captured in the scrubber. Although sulphite ions did not cause the re-emission of mercury from the suspensions of the gypsums, the limestones enriched in iron increased Hg(0) re-emission under low oxygen conditions. It was observed that the low pH values of the gypsum suspensions favored the cocapture of mercury because Fe(2+) formation was avoided. The partitioning of the mercury in the byproducts of the scrubber depended on the impurities of the limestones rather than on their particle size. No leaching of mercury from the gypsum samples occurred suggesting that mercury was either tightly bound to the impurities of the limestone or was transformed into insoluble mercury species.

The capture of oxidized mercury from simulated desulphurization aqueous solutions.

Elemental mercury in flue gases from coal combustion is difficult to control. However, oxidized mercury species are soluble in water and can be removed with a high degree of efficiency in wet flue gas desulphurization (WFGD) systems operating in coal combustion plants, provided that no re-emissions occur. In this article the mechanisms affecting the re-emission of oxidized mercury species in WFGD conditions via sulphite ions are discussed. The parameters studied include the operating temperature, the pH, the redox potential, the concentrations of mercury and oxygen in the flue gas and the concentration of reductive ions in the solution. The results show that temperature, pH and the concentration of mercury at the inlet of the WFGD systems are the most important factors affecting oxidized mercury removal. The results indicate that sulphite ions, not only contribute to the reduction of Hg(2+), but that they may also stabilize the mercury in the liquid fraction of the WFGD limestone slurry. Consequently, factors that increase the sulphite content in the slurry such as a low oxygen concentration promote the co-capture of mercury with sulphur.

Mercury occurrence and speciation in sediments from hard coal mining in Czechia.

This study examines Hg distribution in stream sediments impacted by hard coal mining in the Upper Silesian Coal Basin (USCB), Czechia. By means of a comparative analysis, geological samples and samples from stream sediments were used to carry out a comprehensive assessment of the effects of anthropogenic activities on Hg distribution and speciation. Total Hg (THg), total organic and inorganic carbons (TOC and TIC), and total sulphur (TS) were measured in the samples to reveal a potential relationship. In addition, THg and TS species were discussed in order to elucidate their mobility pattern in the environment. The results have shown that there are no correlations between THg, TS, and TOC indicating overlapping Hg sources attributed to industrial processes. Geological samples, particularly coal and associated sedimentary rocks, contained lower Hg concentrations compared to a variety of stream sediments. The main Hg species identified in the samples was a stable ß-HgS, which decreases its mobility in the riverine environment. It follows that Hg enrichment and speciation is linked to industrial processes, which are the main origin/cause for Hg enrichment and transformation. Minor proportions of HgO in some samples show Hg oxidation upon diagenesis, while HgCl2 is attributed to the chemical loads from the former coking plant.

Influence of SO3 on the MnOx/TiO2 SCR catalyst for elemental mercury removal and the function of Fe modification.

Elemental mercury (Hg0) is a highly hazardous pollutant of coal combustion. The low-temperature SCR catalyst of MnOx/TiO2 can efficiently remove Hg0 in coal-burning flue gas. Considering its sulfur sensitivity, the effect of SO3 on the catalytic efficiency of MnOx/TiO2 and Fe modified MnOx/TiO2 for Hg0 removal was investigated comprehensively for the first time. Characterizations of Hg-TPD and XPS were conducted to explore the catalytic mechanisms of Hg0 removal processes under different conditions. Hg0 removal efficiency of MnOx/TiO2 was inhibited irreversibly from 92% to approximately 60% with the addition of 50 ppm SO3 at 150 â„ƒ, which resulted from the transformation of Mn4+ and chemisorbed oxygen to MnSO4. The existence of H2O would intensify the inhibitory effect. The inhibition almost disappeared and even converted to promotion as the temperature increased to 250 â„ƒ and above. Fe modification on MnOx/TiO2 improved the Hg0 removal performance in the presence of SO3. The addition of SO3 caused only a slight inhibition of 1.9% on Hg0 removal efficiency of Fe modified MnOx/TiO2 in simulated coal-fired flue gas, and the efficiency maintained good stability during a 12 h experimental period. This work would be conducive to the future application of MnOx/TiO2 for synergistic Hg0 removal.

Study of boron behaviour in two Spanish coal combustion power plants.

A full-scale field study was carried out at two Spanish coal-fired power plants equipped with electrostatic precipitator (ESP) and wet flue gas desulfurisation (FGD) systems to investigate the distribution of boron in coals, solid by-products, wastewater streams and flue gases. The results were obtained from the simultaneous sampling of solid, liquid and gaseous streams and their subsequent analysis in two different laboratories for purposes of comparison. Although the final aim of this study was to evaluate the partitioning of boron in a (co-)combustion power plant, special attention was paid to the analytical procedure for boron determination. A sample preparation procedure was optimised for coal and combustion by-products to overcome some specific shortcomings of the currently used acid digestion methods. In addition boron mass balances and removal efficiencies in ESP and FGD devices were calculated. Mass balance closures between 83 and 149% were obtained. During coal combustion, 95% of the incoming boron was collected in the fly ashes. The use of petroleum coke as co-combustible produced a decrease in the removal efficiency of the ESP (87%). Nevertheless, more than 90% of the remaining gaseous boron was eliminated via the FGD in the wastewater discharged from the scrubber, thereby causing environmental problems.

The impact of saline mine water on fate of mineral elements and organic matter: The case study of the Upper Silesian Coal Basin.

The work presented here provides a complex environmental impact of sediments in vicinity to the area of the former Lazy coal mine site in the Upper Silesian Coal Basin (Czech Republic). The main aim of this work has been to determine the degree of contamination, to describe the organic matter, and to carry out sorption isotherms to see the size and distribution of pores in the monitored sediments that are the crucial parameters to assumption of removal mechanisms of elements carried in mine water. The results show that the greatest enrichment of Mn, Sr, Ba, and was in sediments of the first tens of meters from the mine water discharge sediments. Ba and Sr were precipitated as mineral barite and thus formed a dominant insoluble component in the river sediments, which were further carried by water flow towards the water reservoirs. Predominant amounts of fossil material and smaller quantities of carbonized and recent organic matter were altered by weathering and erosion processes. The coal materials have a relatively beneficial sorption capacity, which increases with the carbon content. The overburden waste should be considered for use in removing heavy metals in-situ.

Speciation of Cr and its leachability in coal by-products from spanish coal combustion plants.

This study evaluates the behaviour of total Cr and Cr (VI) during coal combustion in two Spanish power stations. The content and distribution of Cr in the feed coal and combustion wastes was determined and the Cr contents were normalized using enrichment factor indexes. The speciation of Cr in the fly ash fractions from the different hoppers of the electrostatic precipitators was established and the possibility that the Cr (VI) might lixiviate when ashes are disposed of at landfill sites was assessed. Differences in the distribution and behavior of Cr in the two power stations were observed. According to European directive 1999/31/CEE, soluble Cr(VI) in the fly ashes studied would be unlikely to pose an environmental or health risk when the ash is disposed of.

A comprehensive evaluation of the influence of air combustion and oxy-fuel combustion flue gas constituents on Hg(0) re-emission in WFGD systems.

This paper evaluates the influence of the main constituents of flue gases from coal combustion (CO2, O2, N2 and water vapor), in air and oxy-fuel combustion conditions on the re-emission of Hg(0) in wet scrubbers. It was observed that the concentration of water vapor does not affect the re-emission of mercury, whereas O2 and CO2 have a notable influence. High concentrations of O2 in the flue gas prevent the re-emission of Hg(0) due to the reaction of oxygen with the metals present in low oxidation states. High concentrations of CO2, which cause a decrease in the pH and the redox potential of gypsum slurries, reduce the amount of Hg(0) that is re-emitted. As a consequence, the high content of CO2 in oxy-fuel combustion may decrease the re-emission of Hg(0) due to the solubility of CO2 in the suspension and the decrease in the pH. It was also found that O2 affects the stabilization of Hg(2+) species in gypsum slurries. The results of this study confirm that the amount of metals present in limestone as well as the redox potential and pH of the slurries in wet desulphurization plants need to be strictly controlled to reduce Hg(0) re-emissions from power plants operating under oxy-fuel combustion conditions.

Regenerable sorbents for mercury capture in simulated coal combustion flue gas.

This work demonstrates that regenerable sorbents containing nano-particles of gold dispersed on an activated carbon are efficient and long-life materials for capturing mercury species from coal combustion flue gases. These sorbents can be used in such a way that the high investment entailed in their preparation will be compensated for by the recovery of all valuable materials. The characteristics of the support and dispersion of gold in the carbon surface influence the efficiency and lifetime of the sorbents. The main factor that determines the retention of mercury and the regeneration of the sorbent is the presence of reactive gases that enhance mercury retention capacity. The capture of mercury is a consequence of two mechanisms: (i) the retention of elemental mercury by amalgamation with gold and (ii) the retention of oxidized mercury on the activated carbon support. These sorbents were specifically designed for retaining the mercury remaining in gas phase after the desulfurization units in coal power plants.

Arsenic and selenium capture by fly ashes at low temperature.

Arsenic and selenium compounds may be emitted to the environment during coal conversion processes, although some compounds are retained in the fly ashes, in different proportions depending on the characteristics of the ashes and process conditions. The possibility of optimizing the conditions to achieve better trace element retention appears to be an attractive, economical option for reducing toxic emissions. This approach requires a good knowledge of fly ash characteristics and a thorough understanding of the capture mechanism involved in the retention. In this work the ability of two fly ashes, one produced in pulverized coal combustion and the other in fluidized bed combustion, to retain arsenic and selenium compounds from the gas phase in coal combustion and coal gasification atmospheres was investigated. To explore the possible simultaneous retention of mercury, the influence of the unburned coal particle content was also evaluated. Retention capacities between 2 and 22 mg g(-1) were obtained under different conditions. The unburned coal particle content in the fly ash samples does not significantly modify retention capacities.

Using Wet-FGD systems for mercury removal.

A plan to control mercury emissions to the atmosphere and to establish mercury emission limits has recently been elaborated by the European Commission, making it necessary to devise an efficient and cost effective mercury removal technology. Towards this end wet flue gas desulfurization units appear as a promising option for multi-pollutant control. However, more investigation on mercury removal and a greater mercury removal efficiency are required to achieve this objective. In the present work scrubber chemistry and the application of various solid additives to enhance mercury removal in wet scrubbers is evaluated. The results obtained show a significant correlation between mercury removal efficiency and the pH of the scrubber slurry and SO2 concentration. A weaker correlation was observed between oxygen or slurry concentration and removal efficiency. Finally several solid oxides were found to be effective additives for enhancing mercury capture in wet scrubbers.

Retention of arsenic and selenium compounds using limestone in a coal gasification flue gas.

Volatile arsenic and selenium compounds present in coals may cause environmental problems during coal combustion and gasification. A possible way to avoid such problems may be the use of solid sorbents capable of retaining these elements from flue gases in gas cleaning systems. Lime and limestone are materials that are extensively employed for the capture of sulfur during coal processing. Moreover, they have also proven to have good retention characteristics for arsenic and selenium during combustion. The aim of this work was to ascertain whether this sorbent is also useful for retaining arsenic and selenium species in gases produced in coal gasification. The study was carried out in a laboratory-scale reactor in which the sorbent was employed as a fixed bed, using synthetic gas mixtures. In these conditions, retention capacities for arsenic may reach 17 mg g(-1) in a gasification atmosphere free of H2S, whereas the presence of H2S implies a significant decrease in arsenic retention. In the case of selenium, H2S does not influence retention which may reach 65 mg g(-1). Post-retention sorbent characterization, thermal stability, and water solubility tests have shown that chemical reaction is one of the mechanisms responsible for the capture of arsenic and selenium, with Ca(AsO2)2 and CaSe being the main compounds formed.