Investigation of Selective Catalytic Reduction Impact on Mercury Speciation under Simulated NOx Emission Control Conditions

Abstract

Selective catalytic reduction (SCR) technology increasingly is being applied for controlling emissions of nitrogen oxides (NO_x) from coal-fired boilers. Some recent field and pilot studies suggest that the operation of SCR could affect the chemical form of mercury (Hg) in coal combustion flue gases. The speciation of Hg is an important factor influencing the control and environmental fate of Hg emissions from coal combustion. The vanadium and titanium oxides, used commonly in the vanadia-titania SCR catalyst for catalytic NO_x reduction, promote the formation of oxidized mercury (Hg²⁺).

The work reported in this paper focuses on the impact of SCR on elemental mercury (Hg⁰) oxidation. Bench-scale experiments were conducted to investigate Hg⁰ oxidation in the presence of simulated coal combustion flue gases and under SCR reaction conditions. Flue gas mixtures with different concentrations of hydrogen chloride (HCl) and sulfur dioxide (SO₂) for simulating the combustion of bituminous coals and subbituminous coals were tested in these experiments. The effects of HCl and SO₂ in the flue gases on Hg⁰ oxidation under SCR reaction conditions were studied. It was observed that HCl is the most critical flue gas component that causes conversion of Hg⁰ to Hg²⁺ under SCR reaction conditions. The importance of HCl for Hg⁰ oxidation found in the present study provides the scientific basis for the apparent coal-type dependence observed for Hg⁰ oxidation occurring across the SCR reactors in the field.     

Pilot-Scale Study of the Effect of Selective Catalytic Reduction Catalyst on Mercury Speciation in Illinois and Powder River Basin Coal Combustion Flue Gases

Abstract

A study was conducted to investigate the effect of selective catalytic reduction (SCR) catalyst on mercury (Hg) speciation in bituminous and subbituminous coal combustion flue gases. Three different Illinois Basin bituminous coals (from high to low sulfur [S] and chlorine [Cl]) and one Powder River Basin (PRB) subbituminous coal with very low S and very low Cl were tested in a pilot-scale combustor equipped with an SCR reactor for controlling nitrogen oxides (NO_x) emissions. The SCR catalyst induced high oxidation of elemental Hg (Hg⁰), decreasing the percentage of Hg⁰ at the outlet of the SCR to values <12% for the three Illinois coal tests. The PRB coal test indicated a low oxidation of Hg⁰ by the SCR catalyst, with the percentage of Hg⁰ decreasing from ～96% at the inlet of the reactor to ～80% at the outlet. The low Cl content of the PRB coal and corresponding low level of available flue gas Cl species were believed to be responsible for low SCR Hg oxidation for this coal type. The test results indicated a strong effect of coal type on the extent of Hg oxidation.     

Active methods of mercury removal from flue gases

Due to its adverse impact on health, as well as its global distribution, long atmospheric lifetime and propensity for deposition in the aquatic environment and in living tissue, the US Environmental Protection Agency (US EPA) has classified mercury and its compounds as a severe air quality threat. Such widespread presence of mercury in the environment originates from both natural and anthropogenic sources. Global anthropogenic emission of mercury is evaluated at 2000 Mg year⁻¹. According to the National Centre for Emissions Management (Pol. KOBiZE) report for 2014, Polish annual mercury emissions amount to approximately 10 Mg. Over 90% of mercury emissions in Poland originate from combustion of coal.

The purpose of this paper was to understand mercury behaviour during sub-bituminous coal and lignite combustion for flue gas purification in terms of reduction of emissions by active methods. The average mercury content in Polish sub-bituminous coal and lignite was 103.7 and 443.5 μg kg⁻¹. The concentration of mercury in flue gases emitted into the atmosphere was 5.3 μg m⁻³ for sub-bituminous coal and 17.5 μg m⁻³ for lignite. The study analysed six low-cost sorbents with the average achieved efficiency of mercury removal from 30.6 to 92.9% for sub-bituminous coal and 22.8 to 80.3% for lignite combustion. Also, the effect of coke dust grain size was examined for mercury sorptive properties. The fine fraction of coke dust (CD) adsorbed within 243–277 μg Hg kg⁻¹, while the largest fraction at only 95 μg Hg kg⁻¹. The CD fraction < 0.063 mm removed almost 92% of mercury during coal combustion, so the concentration of mercury in flue gas decreased from 5.3 to 0.4 μg Hg m⁻³. The same fraction of CD had removed 93% of mercury from lignite flue gas by reducing the concentration of mercury in the flow from 17.6 to 1.2 μg Hg m⁻³. The publication also presents the impact of photochemical oxidation of mercury on the effectiveness of Hg vapour removal during combustion of lignite. After physical oxidation of Hg in the flue gas, its effectiveness has increased twofold.

     

Top-down estimate of mercury emissions in China using four-dimensional variational data assimilation

An inverse modeling method using the four-dimensional variational data assimilation approach is developed to provide a top-down estimate of mercury emission inventory in China. The mercury observations on board the C130 aircraft during the Asian Pacific Regional Aerosol Characterization Experiment (ACE-Asia) campaign in April 2001 are assimilated into a regional chemical transport model, STEM. Using a 340 Mg of elemental mercury emitted in 1999, the assimilation results in an increase in Hg⁰ emissions for China to 1140 Mg in 2001. This is an upper limit amount of the elemental mercury required in China. The average emission-scaling factor is ∼3.4 in China. The spatial changes in the mercury emissions after the assimilation are also evaluated. The largest changes are estimated on the China north-east coastal areas and the areas of north-center China. The influences of the observation and inventory uncertainties and the initial and boundary conditions on the emission estimates are discussed. Increasing the boundary conditions of Hg from 1.2 to 1.5 ng m⁻³, results in a top-down estimate of Hg⁰ emissions for China of 718 Mg, and leads the average scaling factor from 3.4 to 2.1.     

Trends in anthropogenic mercury emissions estimated for South Africa during 2000–2006

Recent studies suggest an increase in mercury (Hg) emissions to the global environment, particularly as a result of anthropogenic activities. This has prompted many countries to complete Hg emission inventories, based on country-specific Hg sources. In this study, information on annual coal consumption and Hg-containing commodities produced in South Africa, was used to estimate Hg emissions during 2000–2006. Based on the information, the UNEP toolkit was used to estimate the amount of Hg released to air and general waste from each activity; using South Africa specific and toolkit based emission factors. In both atmospheric and solid waste releases, coal-fired power plants were estimated to be the largest contributors of Hg emissions, viz. 27.1 to 38.9 tonnes y^?1 in air, and 5.8 to 7.4 tonnes y^?1 in waste. Cement production was estimated to be the second largest atmospheric Hg emission contributor (2.2–3.9 tonnes y^?1), while coal gasification was estimated to be the second largest Hg contributor in terms of general waste releases (2.9–4.2 tonnes y^?1). Overall, there was an increase in total atmospheric Hg emissions from all activities, estimated at ca. 34 tonnes in 2000, to 50 tonnes in 2006, with some fluctuations between the years. Similarly, the total Hg emissions released to general waste was estimated to be 9 tonnes in 2000, with an increase to 12 tonnes in 2006.     

Local deposition of mercury in topsoils around coal-fired power plants: is it always true?

Mercury (Hg) is a toxic element that is emitted to the atmosphere through human activities, mainly fossil fuel combustion. Hg accumulations in soil are associated with atmospheric deposition, while coal-burning power plants remain the most important source of anthropogenic mercury emissions. In this study, we analyzed the Hg concentration in the topsoil of the Kozani–Ptolemais basin where four coal-fired power plants (4,065 MW) run to provide 50 % of electricity in Greece. The study aimed to investigate the extent of soil contamination by Hg using geostatistical techniques to evaluate the presumed Hg enrichment around the four power plants. Hg variability in agricultural soils was evaluated using 276 soil samples from 92 locations covering an area of 1,000 km². We were surprised to find a low Hg content in soil (range 1–59 μg kg^?1) and 50 % of samples with a concentration lower than 6 μg kg^?1. The influence of mercury emissions from the four coal-fired power plants on soil was poor or virtually nil. We associate this effect with low Hg contents in the coal (1.5–24.5 μg kg^?1) used in the combustion of these power plants (one of the most Hg-poor in the world). Despite anthropic activity in the area, we conclude that Hg content in the agricultural soils of the Kozani–Ptolemais basin is present in low concentrations.     

Distribution of mercury in the combustion products from coal-fired power plants in Guizhou,southwest China

Method 30B and the Ontario Hydro Method (OHM) were used to sample the mercury in the flue gas discharged from the seven power plants in Guizhou Province, southwest China. In order to investigate the mercury migration and transformation during coal combustion and pollution control process, the contents of mercury in coal samples, bottom ash, fly ash, and gypsum were measured. The mercury in the flue gas released into the atmosphere mainly existed in the form of Hg°. The precipitator shows a superior ability to remove Hg^p (particulate mercury) from flue gas. The removal efficiency of Hg²⁺ by wet flue gas desulfurization (WFGD) was significantly higher than that for the other two forms of mercury. The synergistic removal efficiency of mercury by the air pollution control devices (APCDs) installed in the studied power plants is 66.69–97.56%. The Hg mass balance for the tested seven coal-fired power plants varied from 72.87% to 109.67% during the sampling time. After flue gas flowing through APCDs, most of the mercury in coal was enriched in fly ash and gypsum, with only a small portion released into the atmosphere with the flue gas. The maximum discharge source of Hg for power plants was fly ash and gypsum instead of Hg emitted with flue gas through the chimney into the atmosphere. With the continuous upgrading of APCDs, more and more mercury will be enriched in fly ash and gypsum. Extra attention should be paid to the re-release of mercury from the reutilization of by-products from APCDs.

Implications: Method 30B and the Ontario Hydro Method (OHM) were used to test the mercury concentration in the flue gas discharged from seven power plants in Guizhou Province, China. The concentrations of mercury in coal samples, bottom ash, fly ash, and gypsum were also measured. By comparison of the mercury content of different products, we found that the maximum discharge source of Hg for power plants was fly ash and gypsum, instead of Hg emitted with flue gas through the chimney into the atmosphere. With the continuous upgrading of APCDs, more and more mercury will be enriched in fly ash and gypsum. Extra attention should be paid to the re-release of mercury from the reutilization of by-products from APCDs.     

The influence of ozone on atmospheric emissions of gaseous elemental mercury and reactive gaseous mercury from substrates

Experiments were performed to investigate the effect of ozone (O₃) on mercury (Hg) emission from a variety of Hg-bearing substrates. Substrates with Hg(II) as the dominant Hg phase exhibited a 1.7 to 51-fold increase in elemental Hg (Hg^o) flux and a 1.3 to 8.6-fold increase in reactive gaseous mercury (RGM) flux in the presence of O₃-enriched clean (50 ppb O₃; 8 substrates) and ambient air (up to ∼70 ppb O₃; 6 substrates), relative to clean air (oxidant and Hg free air). In contrast, Hg^o fluxes from two artificially Hg^o-amended substrates decreased by more than 75% during exposure to O₃-enriched clean air relative to clean air. Reactive gaseous mercury emissions from Hg^o-amended substrates increased immediately after exposure to O₃ but then decreased rapidly. These experimental results demonstrate that O₃ is very important in controlling Hg emissions from substrates. The chemical mechanisms that produced these trends are not known but potentially involve heterogenous reactions between O₃, the substrate, and Hg. Our experiments suggest they are not homogenous gas-phase reactions. Comparison of the influence of O₃ versus light on increasing Hg^o emissions from dry Hg(II)-bearing substrates demonstrated that they have a similar amount of influence although O₃ appeared to be slightly more dominant. Experiments using water-saturated substrates showed that the presence of high-substrate moisture content minimizes reactions between atmospheric O₃ and substrate-bound Hg. Using conservative calculations developed in this paper, we conclude that because O₃ concentrations have roughly doubled in the last 100 years, this could have increased Hg^o emissions from terrestrial substrates by 65–72%.     

Airborne Emissions of Mercury from Municipal Solid Waste. I: New Measurements from Six Operating Landfills in Florida

Abstract

Mercury-bearing material enters municipal landfills from a wide array of sources, including fluorescent lights, batteries, electrical switches, thermometers, and general waste; however, the fate of mercury (Hg) in landfills has not been widely studied. Using automated flux chambers and downwind atmospheric sampling, we quantified the primary pathways of Hg vapor releases to the atmosphere at six municipal landfill operations in Florida. These pathways included landfill gas (LFG) releases from active vent systems, passive emissions from landfill surface covers, and emissions from daily activities at each working face (WF). We spiked the WF at two sites with known Hg sources; these were readily detected downwind, and were used to test our emission modeling approaches. Gaseous elemental mercury (Hg⁰) was released to the atmosphere at readily detectable rates from all sources measured; rates ranged from ～1–10 ng m^?2 hr^?1 over aged landfill cover, from ～8–20 mg/hr from LFG flares (LFG included Hg⁰ at μg/m³ concentrations), and from ～200–400 mg/hr at the WF. These fluxes exceed our earlier published estimates. Attempts to identify specific Hg sources in excavated and sorted waste indicated few readily identifiable sources; because of effective mixing and diffusion of Hg⁰, the entire waste mass acts as a source. We estimate that atmospheric Hg releases from municipal landfill operations in the state of Florida are on the order of 10–50 kg/yr, substantially larger than our original estimates, but still a small fraction of current overall anthropogenic losses.     

Evaluation of mercury emissions to the atmosphere from coal combustion,China

Mercury emissions from the coal smoke is the main source of anthropogenic discharge and mercury pollution in atmosphere. The calculated total amount of mercury emissions of China in 1995 is approximately 213.8 tonnes, which accounts for c. 5% of estimated total global discharge of 4000 tonnes in the same period. From 1978 to 1995, total coal consumption increased fourfold. Based on these data it is estimated that the mercury emissions will increase at a rate of 5% a year, and the predicted emissions will be 273 tonnes in China in 2000. Controlling and solving mercury emissions from coal combustion are among the most important environmental tasks facing China.     

Differential partitioning and speciation of Hg in wet FGD facilities of two Spanish PCC power plants

This paper evaluates the speciation and partitioning of mercury in two Spanish pulverised coal combustion power plants (PP1 and PP2), equipped with wet limestone-based flue gas desulphurisation facilities (FGD) operating with forced oxidation and re-circulation of FGD water streams. These plants are fed with coal (PP1) and coal/pet-coke blends (PP2) with different mercury contents. The behaviour, partitioning and speciation of Hg were found to be similar during the combustion processes but different in the FGD systems of the two power plants. A high proportion (86-88%) of Hg escaped the electrostatic precipitator in gaseous form, Hg²⁺ being the predominant mercury species (68-86%) to enter the FGD. At this point, a relatively high total Hg retention (72% and 65%) was achieved in the PP1 and PP2 (2007) FGD facilities respectively. However, during the second sampling campaign for PP2 (2008), the mercury removal achieved by the FGD was much lower (26%). Lab-scale tests point to liquid/gas ratio as the main parameter affecting oxidised mercury capture in the scrubber. The partitioning of the gaseous mercury reaching the FGD system in the wastes and by-products differed. In the low mercury input power plant (PP1) most of the mercury (67%) was associated with the FGD gypsum. Moreover in PP2 a significant proportion of the gaseous mercury reaching the FGD system remained in the aqueous phase (45%) in the 2007 sampling campaign while most of it escaped in 2008 (74%). This may be attributed to the scrubber operating conditions and the different composition and chemistry of the scrubber solution probably due to the use of an additive.     

Control of mercury vapor emissions from combustion flue gas

GOAL, SCOPE AND BACKGROUND: Mercury (Hg) emission from combustion flue gas is a significant environmental concern due to its toxicity and high volatility. A number of the research efforts have been carried out in the past decade exploiting mercury emission, monitoring and control from combustion flue gases. Most recently, increasing activities are focused on evaluating the behavior of mercury in coal combustion systems and developing novel Hg control technologies. This is partly due to the new regulatory requirement on mercury emissions from coal-fired combustors to be enacted under the U.S. Title III of the 1990 Clean Air Act Amendments. The aim of this review work is to better understand the state-of-the-art technologies of flue gas mercury control and identify the gaps of knowledge hence areas for further opportunities in research and development. MAIN FEATURES: This paper examines mercury behaviors in combustion systems through a comprehensive review of the available literature. About 70 published papers and reports were cited and studied. RESULTS AND DISCUSSION: This paper summarizes the mechanisms of formation of mercury containing compounds during combustion, its speciation and reaction in flue gas, as well as subsequent mobilization in the environment. It also provides a review of the current techniques designed for real-time, continuous emission monitoring (CEM) for mercury. Most importantly, current flue gas mercury control technologies are reviewed while activated carbon adsorption, a technology that offers the greatest potential for the control of gas-phase mercury emissions, is highlighted. CONCLUSIONS AND RECOMMENDATIONS: Although much progress has been achieved in the last decade, techniques developed for the monitoring and control of mercury from combustion flue gases are not yet mature and gaps in knowledge exist for further advancement. More R&D efforts are required for the effective control of Hg emissions and the main focuses are identified.     

Airborne Emissions of Mercury from Municipal Solid Waste. II: Potential Losses of Airborne Mercury before Landfill

Abstract

Waste distribution and compaction at the working face of municipal waste landfills releases mercury vapor (Hg⁰) to the atmosphere, as does the flaring of landfill gas. Waste storage and processing before its addition to the landfill also has the potential to release Hg⁰ to the air if it is initially present or formed by chemical reduction of Hg^II to Hg⁰ within collected waste. We measured the release of Hg vapor to the atmosphere during dumpster and transfer station activities and waste storage before landfilling at a municipal landfill operation in central Florida. We also quantified the potential contribution of specific Hg-bearing wastes, including mercury (Hg) thermometers and fluorescent bulbs, and searched for primary Hg sources in sorted wastes at three different landfills. Surprisingly large fluxes were estimated for Hg losses at transfer facilities (～100 mg/hr) and from dumpsters in the field (～30 mg/hr for 1,000 dumpsters), suggesting that Hg emissions occurring before landfilling may constitute a significant fraction of the total emission from the disposal/landfill cycle and a need for more measurements on these sources. Reducing conditions of landfill burial were obviously not needed to generate strong Hg⁰ signals, indicating that much of the Hg was already present in a metallic (Hg⁰) form. Attempts to identify specific Hg sources in excavated and sorted waste indicated few readily identifiable sources; because of effective mixing and diffusion of Hg⁰, the entire waste mass acts as a source. Broken fluorescent bulbs and thermometers in dumpsters emitted Hg⁰ at 10 to >100 μg/hr and continued to act as near constant sources for several days.     

Atmospheric emissions of mercury from Australian point sources

The UN Global Mercury Assessment (GMA) estimates that atmospheric emissions of mercury from Australian stationary combustion sources were 97.0 tonnes for the year of 1995. This is more than 90% of the estimated emissions from stationary combustion for the whole of North America, and seems abnormally high for a country with a population of around 20 million, in spite of the fact that most of Australia's stationary energy supply is provided by coal. It is also significantly larger than previous estimates of mercury emissions from Australian sources. New estimates of Australian mercury emissions from stationary energy sources, based on both a top down and bottom up approach, are presented. These estimates can be reconciled for black coal fired power stations, but suggest that the bottom up approach (the Australian National Pollutant Inventory) significantly under-estimates emissions from brown coal fired plant, if mercury capture efficiencies in these plants are low, as observed for lignite-fired plant. The major uncertainties in these estimates are the coal mercury content in coals burnt in Australian power stations, and the mercury capture efficiency in particulate control devices used at these stations. Based on these estimates, Australian emissions of mercury from stationary energy are currently 2–8 tonnes/year, significantly lower than the GMA estimate.     

Mercury contamination in vicinity of secondary copper smelters in Fuyang, Zhejiang Province, China: Levels and contamination in topsoils

In the present study, we aim to investigate the extent of soil contamination by Hg, particularly by anthropogenic Hg, and tentatively estimate the total Hg (Hg_T) accumulation in topsoils (0-15 cm) in Fuyang, Zhejiang Province—a secondary Cu smelter of China. The results show that the levels of soil Hg in the vicinity of the smelters have been substantially elevated following local smelting activities. The spatial distribution of soil Hg in this area reveals a rapid decrease as the distance from the smelter reaches 1.5 km, which is probably due to the quick deposition process of particulate Hg and reactive gaseous Hg emitted from the smelters. The total accumulation of Hg_T in the topsoils of the study area of 10.9 km² is approximately 365-561 kg and of which 346-543 kg might be contributed by anthropogenic emission alone with an annual emission of 17.3-27.2 kg Hg to the topsoils.     

Investigation of selective catalytic reduction impact on mercury speciation under simulated NOx emission control conditions

Selective catalytic reduction (SCR) technology increasingly is being applied for controlling emissions of nitrogen oxides (NOx) from coal-fired boilers. Some recent field and pilot studies suggest that the operation of SCR could affect the chemical form of mercury (Hg) in coal combustion flue gases. The speciation of Hg is an important factor influencing the control and environmental fate of Hg emissions from coal combustion. The vanadium and titanium oxides, used commonly in the vanadia-titania SCR catalyst for catalytic NOx reduction, promote the formation of oxidized mercury (Hg2+). The work reported in this paper focuses on the impact of SCR on elemental mercury (Hg0) oxidation. Bench-scale experiments were conducted to investigate Hg0 oxidation in the presence of simulated coal combustion flue gases and under SCR reaction conditions. Flue gas mixtures with different concentrations of hydrogen chloride (HCl) and sulfur dioxide (SO2) for simulating the combustion of bituminous coals and subbituminous coals were tested in these experiments. The effects of HCl and SO2 in the flue gases on Hg0 oxidation under SCR reaction conditions were studied. It was observed that HCl is the most critical flue gas component that causes conversion of Hg0 to Hg2+ under SCR reaction conditions. The importance of HCl for Hg0 oxidation found in the present study provides the scientific basis for the apparent coal-type dependence observed for Hg0 oxidation occurring across the SCR reactors in the field.     

Emissions of PCDD/F from uncontrolled, domestic waste burning

Emissions of polychlorinated dibenzodioxin and dibenzofuran (PCDD/F) result from inefficiencies of combustion processes, most typically waste combustion. Uncontrolled combustion, such as occurs during so-called "backyard burning" of domestic waste, may therefore produce optimal conditions for formation and emission of PCDD/F. However, few assessments of PCDD/F emissions are available from these sources. This work describes the first known comprehensive assessment of PCDD/F emissions from uncontrolled, domestic waste burning. Emissions were copious, but highly variable, ranging over several orders of magnitude. The potential for emissions appears to be related primarily to combustion parameters and concentrations of various gas-phase species, the latter which may be affected by changes in waste composition, waste orientation, and/or combustion conditions.     

Estimation and characterization of PCDD/Fs, dl-PCBs, PCNs, HxCBz and PeCBz emissions from magnesium metallurgy facilities in China

Magnesium production is considered to be one potential source of unintentional persistent organic pollutants (unintentional POPs). However, studies on the emissions of unintentional POPs from magnesium metallurgy are still lacking. Emissions of unintentional POPs, such as polychlorinated dibenzo-p-dioxins/dibenzofurans (PCDD/Fs), dioxin-like polychlorinated biphenyls (dl-PCBs), polychlorinated naphthalenes (PCNs), hexachlorobenzene (HxCBz) and pentachlorobenzene (PeCBz) are covered under the Stockholm Convention. In this study, these emissions were investigated through a magnesium smelting process. Stack gas and fly ash samples from a typical magnesium plant in China were collected and analyzed to estimate the emissions of unintentional POPs from magnesium metallurgy. Emissions factors of 412 ng TEQ t⁻¹ for PCDD/Fs, 18.6 ng TEQ t⁻¹ for dl-PCBs, 3329 μg t⁻¹ for PCNs, 820 μg t⁻¹ for HxCBz, and 1326 μg t⁻¹ for PeCBz were obtained in 2009. Annual emissions from magnesium metallurgy in China were estimated to be 0.46 g WHO-TEQ for PCDD/Fs and dl-PCBs, 1651 g for PCNs, 403 g for HxCBz and 653 g for PeCBz, respectively.     

A New Method to Assess Mercury Emissions: A Study of Three Coal-Fired Electric-Generating Power Station Configurations

Abstract

U.S. Environmental Protection Agency (EPA) Method 7473 for the analysis of mercury (Hg) by thermal decomposition, amalgamation, and atomic absorption spectroscopy has proved successful for use in Hg assessment at coal-fired power stations. In an analysis time of ～5 min per sample, this instrumental methodology can directly analyze total Hg—with no discrete sample preparation—in the solid matrices associated with a coal-fired power plant, including coal, fly ash, bottom ash, and flue gas desulfurization (FGD) material. This analysis technique was used to investigate Hg capture by coal combustion byproducts (CCBs) in three different coal-fired power plant configurations. Hg capture and associated emissions were estimated by partial mass balance. The station equipped with an FGD system demonstrated 68% capture on FGD material and an emissions estimate of 18% (11 kg/yr) of total Hg input. The power plant equipped with low oxides of nitrogen burners and an electrostatic precipitator (ESP) retained 43% on the fly ash and emitted 57% (51 kg/yr). The station equipped with conventional burners and an ESP retained less than 1% on the fly ash, emitting an estimated 99% (88 kg/yr) of Hg. Estimated Hg emissions demonstrate good agreement with EPA data for the power stations investigated.     

Surface Compositions of Carbon Sorbents Exposed to Simulated Low-Rank Coal Flue Gases

Abstract

Bench-scale testing of elemental mercury (Hg⁰) sorption on selected activated carbon sorbents was conducted to develop a better understanding of the interaction among the sorbent, flue gas constituents, and Hg⁰. The results of the fixed-bed testing under simulated lignite combustion flue gas composition for activated carbons showed some initial breakthrough followed by increased mercury (Hg) capture for up to ～4.8 hr. After breakthrough, the Hg in the effluent stream was primarily in an oxidized form (>90%). Aliquots of selected activated carbons were exposed to simulated flue gas containing Hg⁰ vapor for varying time intervals to explore surface chemistry changes as the initial breakthrough, Hg capture, and oxidation occurred. The samples were analyzed by X-ray photoelectron spectroscopy to determine changes in the abundance and forms of sulfur, chlorine, oxygen, and nitrogen moieties as a result of interactions of flue gas components on the activated carbon surface during the sorption process. The data are best explained by a competition between the bound hydrogen chloride (HCl) and increasing sulfur [S(VI)] for a basic carbon binding site. Because loss of HCl is also coincident with Hg breakthrough or loss of the divalent Hg ion (Hg²⁺), the competition of Hg²⁺ with S(VI) on the basic carbon site is also implied. Thus, the role of the acid gases in Hg capture and release can be explained.