Mercury oxidation promoted by a selective catalytic reduction catalyst under simulated Powder River Basin coal combustion conditions

A bench-scale reactor consisting of a natural gas burner and an electrically heated reactor housing a selective catalytic reduction (SCR) catalyst was constructed for studying elemental mercury (Hg(o)) oxidation under SCR conditions. A low sulfur Powder River Basin (PRB) subbituminous coal combustion fly ash was injected into the entrained-flow reactor along with sulfur dioxide (SO2), nitrogen oxides (NOx), hydrogen chloride (HCl), and trace Hg(o). Concentrations of Hg(o) and total mercury (Hg) upstream and downstream of the SCR catalyst were measured using a Hg monitor. The effects of HCl concentration, SCR operating temperature, catalyst space velocity, and feed rate of PRB fly ash on Hg(o) oxidation were evaluated. It was observed that HCl provides the source of chlorine for Hg(o) oxidation under simulated PRB coal-fired SCR conditions. The decrease in Hg mass balance closure across the catalyst with decreasing HCl concentration suggests that transient Hg capture on the SCR catalyst occurred during the short test exposure periods and that the outlet speciation observed may not be representative of steady-state operation at longer exposure times. Increasing the space velocity and operating temperature of the SCR led to less Hg(o) oxidized. Introduction of PRB coal fly ash resulted in slightly decreased outlet oxidized mercury (Hg2+) as a percentage of total inlet Hg and correspondingly resulted in an incremental increase in Hg capture. The injection of ammonia (NH3) for NOx reduction by SCR was found to have a strong effect to decrease Hg oxidation. The observations suggest that Hg(o) oxidation may occur near the exit region of commercial SCR reactors. Passage of flue gas through SCR systems without NH3 injection, such as during the low-ozone season, may also impact Hg speciation and capture in the flue gas.     

Effects of sulfur dioxide and nitric oxide on mercury oxidation and reduction under homogeneous conditions

This paper is particularly related to elemental mercury (Hg0) oxidation and divalent mercury (Hg2+) reduction under simulated flue gas conditions in the presence of nitric oxide (NO) and sulfur dioxide (SO2). As a powerful oxidant and chlorinating reagent, Cl2 has the potential for Hg oxidation. However, the detailed mechanism for the interactions, especially among chlorine (Cl)-containing species, SO2, NO, as well as H2O, remains ambiguous. Research described in this paper therefore focused on the impacts of SO2 and NO on Hg0 oxidation and Hg2+ reduction with the intent of unraveling unrecognized interactions among Cl species, SO2, and NO most importantly in the presence of H2O. The experimental results demonstrated that SO2 and NO had pronounced inhibitory effects on Hg0 oxidation at high temperatures when H2O was also present in the gas blend. Such a demonstration was further confirmed by the reduction of Hg2+ back into its elemental form. Data revealed that SO2 and NO were capable of promoting homogeneous reduction of Hg2+ to Hg0 with H2O being present. However, the above inhibition or promotion disappeared under homogeneous conditions when H2O was removed from the gas blend.     

Gas-phase mercury reduction to measure total mercury in the flue gas of a coal-fired boiler

Gaseous elemental and total (elemental + oxidized) mercury (Hg) in the flue gas from a coal-fired boiler was measured by a modified ultraviolet (UV) spectrometer. Challenges to Hg measurement were the spectral interferences from other flue gas components and that UV measures only elemental Hg. To eliminate interference from flue gas components, a cartridge filled with gold-coated sand removed elemental Hg from a flue gas sample. The Hg-free flue gas was the reference gas, eliminating the spectral interferences. To measure total Hg by UV, oxidized Hg underwent a gas-phase, thermal-reduction in a quartz cell heated to 750 degrees C. Simultaneously, hydrogen was added to flash react with the oxygen present forming water vapor and preventing Hg re-oxidation as it exits the cell. Hg concentration results are in parts per billion by volume Hg at the flue gas oxygen concentration. The modified Hg analyzer and the Ontario Hydro method concurrently measured Hg at a field test site. Measurements were made at a 700-MW steam turbine plant with scrubber units and selective catalytic reduction. The flue gas sampled downstream of the selective catalytic reduction contained 2100 ppm SO2 and 75 ppm NOx. Total Hg measured by the Hg analyzer was within 20% of the Ontario Hydro results.     

Predicting extents of mercury oxidation in coal-derived flue gases

The proposed mercury (Hg) oxidation mechanism consists of a 168-step gas phase mechanism that accounts for interaction among all important flue gas species and a heterogeneous oxidation mechanism on unburned carbon (UBC) particles, similar to established chemistry for dioxin production under comparable conditions. The mechanism was incorporated into a gas cleaning system simulator to predict the proportions of elemental and oxidized Hg species in the flue gases, given relevant coal properties (C/H/O/N/S/Cl/Hg), flue gas composition (O2, H2O, HCl), emissions (NO(X), SO(X), CO), the recovery of fly ash, fly ash loss-on-ignition (LOI), and a thermal history. Predictions are validated without parameter adjustments against datasets from lab-scale and from pilot-scale coal furnaces at 1 and 29 MWt. Collectively, the evaluations cover 16 coals representing ranks from sub-bituminous through high-volatile bituminous, including cases with Cl2 and CaCl2 injection. The predictions are, therefore, validated over virtually the entire domain of Cl-species concentrations and UBC levels of commercial interest. Additional predictions identify the most important operating conditions in the furnace and gas cleaning system, including stoichiometric ratio, NO(X), LOI, and residence time, as well as the most important coal properties, including coal-Cl.     

Simultaneous absorption of NO and SO2 into hexamminecobalt(II)/iodide solution

An innovative catalyst system has been developed to simultaneously remove NO and SO2 from combustion flue gas. Such catalyst system may be introduced to the scrubbing solution using ammonia solution to accomplish sequential absorption and catalytic oxidation of both NO and SO2 in the same reactor. When the catalyst system is utilized for removing NO and SO2 from the flue gas, Co(NH3)(6)2+ ions act as the catalyst and I- as the co-catalyst. Dissolved oxygen, in equilibrium with the residual oxygen in the flue gas, is the oxidant. The overall removal process is further enhanced by UV irradiation at 365 nm. More than 95% of NO is removed at a feed concentration of 250-900 ppm, and nearly 100% of SO2 is removed at a feed concentration of 800-2500 ppm. The sulfur dioxide co-existing in the flue gas is beneficial to NO absorption into hexamminecobalt(II)/iodide solution. NO and SO2 can be converted to ammonium sulfate and ammonium nitrate that can be used as fertilizer materials. The process described here demonstrates the feasibility of removing SO2 and NO simultaneously only by retrofitting the existing wet ammonia flue-gas-desulfurization (FGD) scrubbers.     

Medium-Sulfur Coal and Fly Ash Resistivity

Electric generating plants burning medium-sulfur coal need a way to predict when ESP performance will be limited by high electrical resistivity of the collected fly ash. The main uncertainty in mathematical predictions of fly ash resistivity lies in the marginal effect of naturally occurring SO₃ vapor in the flue gas. This paper results from a project to expand the data base of SO₃/SO₂ concentrations and fly ash resistivities measured in utility fly ash precipitators. Complete data sets are presented from three plants in the Southern Company electric system. In situ resistivity data are compared with laboratory measurements and with two different mathematical predictions of resistivity based on coal and ash analyses. The revised version of the resistivity predictor gives results in good agreement with resistivity values measured both in situ and in the laboratory.     

Natural desulfurization in coal-fired units using Greek lignite

This paper analyzes the natural desulfurization process taking place in coal-fired units using Greek lignite. The dry scrubbing capability of Greek lignite appears to be extremely high under special conditions, which can make it possible for the units to operate within the legislative limits of sulfur dioxide (SO2) emissions. According to this study on several lignite-fired power stations in northern Greece, it was found that sulfur oxide emissions depend on coal rank, sulfur content, and calorific value. On the other hand, SO2 emission is inversely proportional to the parameter gammaCO2(max), which is equal to the maximum carbon dioxide (CO2) content by volume of dry flue gas under stoichiometric combustion. The desulfurization efficiency is positively correlated to the molar ratio of decomposed calcium carbonate to sulfur and negatively correlated to the free calcium oxide content of fly ash.     

The importance of the location of sodium chlorite application in a multipollutant flue gas cleaning system

In this study, removing sulfur dioxide (SO2), nitrogen oxides (NO(x)), and mercury (Hg) from simulated flue gas was investigated in two laboratory-sized bubbling reactors that simulated an oxidizing reactor (where the NO and Hg(0) oxidation reactions are expected to occur) and a wet limestone scrubber, respectively. A sodium chlorite solution was used as the oxidizing agent. The sodium chlorite solution was an effective additive that enhanced the NO(x), Hg, and SO2 capture from the flue gas. Furthermore, it was discovered that the location of the sodium chlorite application (before, in, or after the wet scrubber) greatly influences which pollutants are removed and the amount removed. This effect is related to the chemical conditions (pH, absence/presence of particular gases) that are present at different positions throughout the flue gas cleaning system profile. The research results indicated that there is a potential to achieve nearly zero SO2, NO(x), and Hg emissions (complete SO2, NO, and Hg removals and -90% of NO(x) absorption from initial values of 1500 ppmv of SO2, 200 ppmv of NO(x), and 206 microg/m3 of Hg(0)) from the flue gas when sodium chlorite was applied before the wet limestone scrubber. However applying the oxidizer after the wet limestone scrubber was the most effective configuration for Hg and NO(x) control for extremely low chlorite concentrations (below 0.002 M) and therefore appears to be the best configuration for Hg control or as an additional step in NO(x) recleaning (after other NO(x) control facilities). The multipollutant scrubber, into which the chlorite was injected simultaneously with the calcium carbonate slurry, appeared to be the least expensive solution (when consider only capital cost), but exhibited the lowest NO(x) absorption at -50%. The bench-scale test results presented can be used to develop performance predictions for a full- or pilot-scale multipollutant flue gas cleaning system equipped with wet flue gas desulfurization scrubber.     

降解SO_2功能菌的16S rRAN基因测序及降解特性

用低浓度SO2诱导驯化方法获得高效脱硫菌群,并用分离培养与16S rRNA基因测序技术相结合的方法鉴定菌群种属,分析驯化过程中种群结构的动态变化,同时研究分离纯菌种的脱硫性能。结果表明,从诱导驯化7 d和14 d菌液中分别分离出23株菌和22株菌,16S rRNA序列分析发现这些菌归属于13个种,其中有6个种（Rhodococcus erythropolis、Pseudomonas putida、Microbacterium oxydans、Sphingomonas koreensis、Acinetobacter junii、Acinetobacter johnsonii）对SO2-3有较强的降解能力,并在持续驯化过程中稳定的生长传代,降解产物以硫酸根为主,还有极少量的单质硫。与含混合菌的驯化菌液降解SO2-3的能力相比,单一脱硫菌的脱硫性能较弱。脱硫功能菌株及其基本特性的研究为微生物处理SO2烟气提供了丰富的菌源信息和理论基础。     

Eliminating Reheat from Existing FGD Systems

The Clean Air Act Amendments of the early 1970_s required coal burning utilities to reduce their emissions of sulfur dioxide. Lime or limestone based wet systems were employed for flue gas desulfurization (FGD). These systems reduced flue gas temperatures to below acid dew point conditions. Concerned about the prospect of ductwork exposed to a saturated, acid-rich environment, most utilities turned to stack gas reheat (SGR) to increase flue gas temperatures. By 1980, 82 percent of all FGD facilities employed SGR. Today there are about 130 FGD systems of which 101 employ some form of stack gas reheat.     

Effect of NOx control processes on mercury speciation in utility flue gas

The speciation of Hg in coal-fired flue gas can be important in determining the ultimate Hg emissions as well as potential control options for the utility. The effects of NOx control processes, such as selective catalytic reduction (SCR) and selective non-catalytic reduction (SNCR), on Hg speciation are not well understood but may impact emissions of Hg. EPRI has investigated the reactions of Hg in flue gas at conditions expected for some NOx control processes. This paper describes the methodology used to investigate these reactions in actual flue gas at several power plants. Results have indicated that some commercial SCR catalysts are capable of oxidizing elemental Hg in flue gas obtained from the inlets of SCR or air heater units. Results are affected by various flue gas and operating parameters. The effect of flue gas composition, including the presence of NH3, has been evaluated. The influence of NH3 on fly ash Hg reactions also is being investigated.     

Effect of Flue Dust on the Vanadium Oxide Catalyst Utilized by the Contact Oxidation Process

Concepts for controlling SO₂ from fossil fuels can be separated into two main categories: (1) Residual and vacuum gas oil desulfurization and (2) Flue gas desulfurization. The Kiyoura-T.I.T. process confines itself to the desulfurization of flue gas. It employs vandium oxide as a catalyst which oxidizes the sulfur dioxide to trioxide, followed by a gaseous phase reaction of ammonia. The end product, ammonium sulfate is removed by an electrostatic precipitator. (The details were presented at annual meetings of APCA in 1966 and 1967 as 1 and II.) Flue gas is passed through cyclone and dust filter to remove dust. Under normal operating conditions almost all of the dust is removed at the filters. The author carried out experiments to determine whether there was any effect on the activity of the catalyst, assuming that a portion of the dust escapes into the stream along the flue. It has been generally accepted that in fuel oil firing steam power plants, about 100 mg./nm³ of dust including carbon, hydrocarbon, and ash are normally contained in the flue stream. The carbon and hydrocarbon is oxidized readily at the filters and exists only as ash. An amount of ash equivalent to the amount assumed to have settled on the catalyst over a period of 3–12 months, was placed on the catalyst, and experiments were carried out. The SO₂ conversion efficiency was measured and found to be over 93%. The results showed that at the actual operational temperature of 450°C, ash had practically no effect at all.     

Electric Utility Applications Of Fabric Filters

Encouraged by the successes attained with fly ash control by fabric filters in Pennsylvania Power & Light and Colorado Ute, other utilities are installing, planning, and/or considering baghouses as a practical and economical means for controlling emissions from the burning of low sulfur coals. Where deposits of alkaline reagents (i.e. nahcolite) are available, some power plants are also considering a process for dry scrubbing SO₂ from the flue gas. By introducing such reagents with the emission ahead of the fabric collector, both partlculates and SO₂ are removed.     

Emissions of sulfur trioxide from coal-fired power plants

Emissions of sulfur trioxide (SO3) are a key component of plume opacity and acid deposition. Consequently, these emissions need to be low enough to not cause opacity violations and acid deposition. Generally, a small fraction of sulfur (S) in coal is converted to SO3 in coal-fired combustion devices such as electric utility boilers. The emissions of SO3 from such a boiler depend on coal S content, combustion conditions, flue gas characteristics, and air pollution devices being used. It is well known that the catalyst used in the selective catalytic reduction (SCR) technology for nitrogen oxides control oxidizes a small fraction of sulfur dioxide in the flue gas to SO3. The extent of this oxidation depends on the catalyst formulation and SCR operating conditions. Gas-phase SO3 and sulfuric acid, on being quenched in plant equipment (e.g., air preheater and wet scrubber), result in fine acidic mist, which can cause increased plume opacity and undesirable emissions. Recently, such effects have been observed at plants firing high-S coal and equipped with SCR systems and wet scrubbers. This paper investigates the factors that affect acidic mist production in coal-fired electric utility boilers and discusses approaches for mitigating emission of this mist.     

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.     

Performance Standards in Zoning

Burning of western low sulfur coal, to reduce sulfur oxide emissions, has resulted in decreased electrostatic precipi-tator collection efficiencies. In an effort to restore pre-cipitator performance a flue gas conditioning program was established by the company. This paper is a brief history of Commonwealth Edison Company’s experience with sulfur trioxide as a flue gas conditioning agent. Testing at State Line Station has proven that sulfur trioxide conditioning can effectively be used to improve precipitator performance when burning low sulfur coals. Although the first phase of the conditioning program is not completed, information has been gained which is being used as a basis in design and evaluation of future systems.     

Effect of NOx Control Processes on Mercury Speciation in Utility Flue Gas

Abstract

The speciation of Hg in coal-fired flue gas can be important in determining the ultimate Hg emissions as well as potential control options for the utility. The effects of NO_x control processes, such as selective catalytic reduction (SCR) and selective non-catalytic reduction (SNCR), on Hg speciation are not well understood but may impact emissions of Hg. EPRI has investigated the reactions of Hg in flue gas at conditions expected for some NO_x control processes. This paper describes the methodology used to investigate these reactions in actual flue gas at several power plants. Results have indicated that some commercial SCR catalysts are capable of oxidizing elemental Hg in flue gas obtained from the inlets of SCR or air heater units. Results are affected by various flue gas and operating parameters. The effect of flue gas composition, including the presence of NH₃, has been evaluated. The influence of NH₃ on fly ash Hg reactions also is being investigated.     

Joint US/USSR Test Program for Reducing Fly Ash Resistivity

An electrostatic precipitator preceded by a wet scrubber was tested at the Reftinskaya Power Station. The unit collects a high resistivity fly ash from the combustion of low sulfur Ekibastuz coal. The operating parameters of the precipitator were measured as well as the mass emissions and the in-situ electrical resistivity of the fly ash. Density, particle size distribution, electrical resistivity, and chemical composition were determined for collected samples of the fly ash. The fly ash was also characterized by x-ray diffraction and scanning electron microscopy. When a centrifugal wet wall scrubber was installed ahead of the electrostatic precipitator, the temperature of the flue gas entering the precipitator was decreased and the moisture content increased. The electrical resistivity of the fly ash was attenuated a decade, but not enough to overcome the adverse effects of back corona in the precipitator. Lowering the flue gas temperature to about 85°C by the addition of a venturi scrubber ahead of the centrifugal scrubber reduced the electrical resistivity of the fly ash another decade and allowed the operation of the precipitator without back corona.     

Reduction of combustion by-products in WTE plants: O2 enrichment of underfire air in the MARTIN SYNCOM process

The SYNCOM process involves oxygen enrichment of underfire air, recirculation of flue gas and a combustion control system using infrared thermography of the waste layer on the grate. At the demonstration plant in Coburg, operational reliability and plant availability using SYNCOM could be proven under real disposal conditions with a waste throughput of 7 t/h. Oxygen enrichment of the underfire air promotes the destruction of pollutants due to the high oxygen partial pressures and temperatures. This is then reflected in very low residual amounts of organic combustion by-products in the bottom ash and flue gas from the SYNCOM unit. The flue gas concentrations of organic pollutants are reduced, as compared with conventional operation, by over 35% (for CO, total hydrocarbons and PCDD/F) at the boiler outlet. As the flue gas flow is reduced by oxygen enrichment and flue gas recirculation, the resulting reduction in terms of kg of pollutant per Mg of waste is even higher. In the bottom ash, the level of organic residues is reduced, by 45% in the case of loss on ignition and by 55% in the case of TOC and dioxins (I-TE of PCDD/F). This is due to the higher oxygen partial pressures and the fuel bed temperature which is increased by 135 to 1200 degrees C. Other important features of the process include more intense sintering and thus improved immobilization of the bottom ash, as well as reduced flue gas and fly ash flows.     

粉煤灰烧制陶粒过程中二氧化硫的释放规律与形成机理

研究了粉煤灰烧制陶粒过程中烟气二氧化硫的释放规律,同时对烧结前后粉煤灰与陶粒中不同形态硫含量和硫平衡进行了分析,探讨了烟气中二氧化硫的来源和转化机理.结果表明,烟气中约55％的二氧化硫来源于硫酸盐的还原,其余主要来自有机硫燃烧和亚硫酸盐的分解.烧制每千克陶粒所产生的二氧化硫量约为7.8g.高温烧结过程中粉煤灰球内形成的还原性气氛导致了粉煤灰中硫酸盐向二氧化硫的还原转化.