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1.
Predicting extents of mercury oxidation in coal-derived flue gases   总被引:1,自引:0,他引:1  
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.  相似文献   

2.
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 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.  相似文献   

3.
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 Hgp (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.  相似文献   


4.
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.  相似文献   

5.
Previous workers have shown that simultaneous SO2/NOX removal can be obtained in a dry scrubbing system with Ca(OH)2 promoted by an additive such as NaOH, and that fly ash and product recycle improve the reactivity of the solids toward SO2. To test SO2/NOX removal with fly ash and product recycle, bench-scale experiments with a packed bed reactor were performed at bag filter conditions. The most reactive solid for NOX removal was prepared by slurrying Ca(OH)2 with fly ash, CaSO3, and NaOH. The best conditions for NOX removal were the greatest temperature (125°C) and greatest concentrations of SO2 (1500 ppm) and O2 (20 percent). At the best conditions, NOX removed in 1 hour was 3-4 moles per 100 moles Ca(OH)2, compared to 5-10 moles SO2 removed per 100 moles Ca(OH)2. The best SO2 removal was obtained at the highest relative humidities/lowest temperatures (55% RH/ 65°C) with solids prepared by slurrying Ca(OH)2 with fly ash and NaOH. At these conditions, SO2 removed In 1 hour was 60-80 moles per 100 moles Ca(OH)2, compared to 0.5 to 1 moles NOX removed per 100 moles Ca(OH)2.  相似文献   

6.

Four different mixed fuels consisted of leather waste, coal, and sewage sludge were combusted in a lab-scale entrained flow fluidized bed furnace. The influence of blending ratio on emission characteristics of SO2, NOx, HCl, particulate matter (PM), heavy metals, and polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans (PCDD/Fs) was studied. Results showed that the mixing of coal with sewage sludge had a complex effect on the emission characteristics. On the one hand, with more sewage sludge blending in the mixed fuel, the acid gas pollutant (SO2, NOx) decreased a lot, and the recovery of volatile heavy metals (Cd, Pb) increased at the same time. Furthermore, the leaching toxicity of Cr in the fly ash and bottom ash went down below the national standard with the adding of sewage sludge. On the other hand, the mixing of sewage sludge which consisted of more ash content resulted in the increase of the PM emission. Moreover, the high content of Cu and chlorine in the sewage sludge can promote the formation of polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans (PCDD/Fs) when the fuel 3 and 4 were combusted. Most importantly, the concentration of toxic PCDD/Fs in the flue gas produced from fuel 3 and fuel 4 was successfully controlled down below 0.20 ng I-TEQ/Nm3 by the active carbon.

  相似文献   

7.
Abstract

The long-term stability of Hg in coal combustion byproducts (CCBs) was evaluated at ambient and near-ambient temperatures. Six CCB samples with atypically high levels of total Hg were selected for study assuming a greater potential for release of measurable amounts of Hg vapor. The samples selected included two fly ash samples from U.S. eastern bituminous coal, two fly ash samples from South African low-rank coal, one fly ash from Powder River Basin (PRB) subbituminous coal blended with petroleum coke, and one PRB subbituminous coal fly ash incorporated with flue gas desulfurization material.

Air scrubbed of Hg was passed through compacted 100-g aliquots of each sample at 1 mL/min and vented to a gold-coated quartz trap to collect released Hg vapor. The samples were maintained at ambient and near-ambient (37 °C) temperatures. All samples released low-picogram levels of Hg after 90 days. No pattern was evident to link the total Hg content to the rate of release of Hg vapor. An average of 0.030 pg Hg/g CCB/day was released from the samples, which equates to 2.2 x 10-8 lb Hg/ton CCB/year. If this were applied to a coal-fired power plant production of 200,000 tons of fly ash per year, there would be a maximum potential release of 0.0044 lb, or 2.00 g, of Hg per year. Experiments are continuing to determine long-term vapor release of Hg from CCBs. All samples have been set up in duplicate at ambient temperature with an improved apparatus to reevalu-ate results reported in this article.  相似文献   

8.
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.  相似文献   

9.
Abstract

For the past 22 years in the Netherlands, the behavior of Hg in coal-fired power plants has been studied extensively. Coal from all over the world is fired in Dutch power stations. First, the Hg concentrations in these coals were measured. Second, the fate of the Hg during combustion was established by performing mass balance studies. On average, 43 ± 30% of the Hg was present in the flue gases downstream of the electrostatic precipitator (ESP; dust collector). In individual cases, this figure can vary between 1 and 100%. Important parameters are the Cl content of the fuel and the flue gas temperature in the ESP. On average, 54 ± 24% of the gaseous Hg was removed in the wet flue-gas desulfurization (FGD) systems, which are present at all Dutch coal-power stations. In individual cases, this removal can vary between 8% (outlier) and 72%.

On average, the fate of Hg entering the power station in the coal was as follows: <1% in the bottom ash, 49% in the pulverized fuel ash (ash collected in the ESP), 16.6% in the FGD gypsum, 9% in the sludge of the wastewater treatment plant, 0.04% in the effluent of the wastewater treatment plant, 0.07% in fly dust (leaving the stack), and 25% as gaseous Hg in the flue gases and emitted into the air. The distribution of Hg over the streams leaving the FGD depends strongly on the installation. On average, 75% of the Hg was removed, and the final concentration of Hg in the emitted flue gases of the Dutch power stations was only ~3 μg/mSTP 3 at 6% O2. During co-combustion with biomass, the removal of Hg was similar to that during 100% coal firing.

Speciation of Hg is a very important factor. An oxidized form (HgCl2) favors a high degree of removal. The conversion from Hg0 to HgCl2 is positively correlated with the Cl content of the fuel. A catalytic DENOX (SCR) favors the formation of oxidized Hg, and, in combination with a wet FGD, the total removal can be as high as 90%.  相似文献   

10.
This paper presents results of a survey of mercury concentrations in coal, ash, water, fly ash, and flue gas discharges from a 5.5 × 106 Ib/hr steam generator serving a 775 MW (net) turbine-generator set. Representative composite or grab samples were obtained for inlet coal and outlet ash and water. Stack samples were obtained for fly ash and mercury vapor emissions while the unit was operated at 660 MW (net) (85% of full load). Samples were analyzed by anodic stripping voltammetry, plasma emission spectroscopy, and neutron activation analysis to determine mercury concentration entering the furnace in the coal and leaving the furnace in the flue gas, fly ash, bottom and hopper ash, and water. Method inter-comparisons are discussed. A material balance for mercury has been calculated from fuel, ash, and stack gas flow rates. About 90% of the mercury in the coal is released and appears as vapor discharged in the stack gas while 10% remains in the residual ash. For a 700 MW (net) unit, about 5 lb/day of mercury vapor is released to the atmosphere.  相似文献   

11.
The Proposed New Environmental Quality (Clean Air) Regulation 201X (Draft), which replaces the Malaysia Environmental Quality (Clean Air) 1978, specifies limits to additional pollutants from power generation using fossil fuel. The new pollutants include Hg, HCl, and HF with limits of 0.03, 100, and 15 mg/N-m3 at 6% O2, respectively. These pollutants are normally present in very small concentrations (known as trace elements [TEs]), and hence are often neglected in environmental air quality monitoring in Malaysia. Following the enactment of the new regulation, it is now imperative to understand the TEs behavior and to assess the capability of the existing abatement technologies to comply with the new emission limits. This paper presents the comparison of TEs behavior of the most volatile (Hg, Cl, F) and less volatile (As, Be, Cd, Cr, Ni, Se, Pb) elements in subbituminous and bituminous coal and coal combustion products (CCP) (i.e., fly ash and bottom ash) from separate firing of subbituminous and bituminous coal in a coal-fired power plant in Malaysia. The effect of air pollution control devices configuration in removal of TEs was also investigated to evaluate the effectiveness of abatement technologies used in the plant. This study showed that subbituminous and bituminous coals and their CCPs have different TEs behavior. It is speculated that ash content could be a factor for such diverse behavior. In addition, the type of coal and the concentrations of TEs in feed coal were to some extent influenced by the emission of TEs in flue gas. The electrostatic precipitator (ESP) and seawater flue gas desulfurization (FGD) used in the studied coal-fired power plant were found effective in removing TEs in particulate and vapor form, respectively, as well as complying with the new specified emission limits.

Implications:Coals used by power plants in Peninsular Malaysia come from the same supplier (Tenaga Nasional Berhad Fuel Services), which is a subsidiary of the Malaysia electricity provider (Tenaga Nasional Berhad). Therefore, this study on trace elements behavior in a coal-fired power plant in Malaysia could represent emission from other plants in Peninsular Malaysia. By adhering to the current coal specifications and installation of electrostatic precipitator (ESP) and flue gas desulfurization, the plants could comply with the limits specified in the Malaysian Department of Environment (DOE) Scheduled Waste Guideline for bottom ash and fly ash and the Proposed New Environmental Quality (Clean Air) Regulation 201X (Draft).  相似文献   

12.
Wu HL  Lu SY  Yan JH  Li XD  Chen T 《Chemosphere》2011,84(3):361-367
The fly ash used in this study was collected from a bag filter in a medical waste rotary kiln incineration system, using lime and activated carbon injection followed by their collection as mixed fly ash. Experiments were conducted on fly ash in a quartz tube, heated in a laboratory-scale horizontal tube furnace, in order to study the effect of temperature and nitrogen flow rate on the removal of PCDD/Fs. Results indicated that in this study PCDD/Fs in the fly ash mostly were removed and desorbed very little into the flue gas under thermal treatment especially when the heating temperature was higher than 350 °C, and dechlorination and destruction reactions took important part in the removal of PCDD/Fs. However, in terms of flow rate, when flow rate was higher than 4 cm s−1, destruction efficiency of PCDD/Fs decreased dramatically and the main contributors were P5CDF, H6CDF and H7CDF desorbed to flue gas, the PCDD/Fs in the fly ash decreased with enhanced flow rate.  相似文献   

13.
The long-term stability of Hg in coal combustion by-products (CCBs) was evaluated at ambient and near-ambient temperatures. Six CCB samples with atypically high levels of total Hg were selected for study assuming a greater potential for release of measurable amounts of Hg vapor. The samples selected included two fly ash samples from U.S. eastern bituminous coal, two fly ash samples from South African low-rank coal, one fly ash from Powder River Basin (PRB) subbituminous coal blended with petroleum coke, and one PRB subbituminous coal fly ash incorporated with flue gas desulfurization material. Air scrubbed of Hg was passed through compacted 100-g aliquots of each sample at 1 mL/min and vented to a gold-coated quartz trap to collect released Hg vapor. The samples were maintained at ambient and near-ambient (37 degrees C) temperatures. All samples released low-picogram levels of Hg after 90 days. No pattern was evident to link the total Hg content to the rate of release of Hg vapor. An average of 0.030 pg Hg/g CCB/day was released from the samples, which equates to 2.2 x 10(-8) lb Hg/ton CCB/year. If this were applied to a coal-fired power plant production of 200,000 tons of fly ash per year, there would be a maximum potential release of 0.0044 lb, or 2.00 g, of Hg per year. Experiments are continuing to determine long-term vapor release of Hg from CCBs. All samples have been set up in duplicate at ambient temperature with an improved apparatus to reevaluate results reported in this article.  相似文献   

14.
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 approximately 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.  相似文献   

15.
This paper evaluates an elementary reaction mechanism for Hg0 oxidation in coal-derived exhausts consisting of a previously formulated homogeneous mechanism with 102 steps and a new three-step heterogeneous mechanism for unburned carbon (UBC) particles. Model predictions were evaluated with the extents of Hg oxidation monitored in the exhausts from a pilot-scale coal flame fired with five different coals. Exhaust conditions in the tests were very similar to those in full-scale systems. The predictions were quantitatively consistent with the reported coal-quality impacts over the full range of residence times. The role of Cl atoms in the homogeneous mechanism is hereby supplanted with carbon sites that have been chlorinated by HCl. The large storage capacity of carbon for Cl provided a source of Cl for Hg oxidation over a broad temperature range, so initiation was not problematic. Super-equilibrium levels of Cl atoms were not required, so Hg was predicted to oxidize in systems with realistic quench rates. Whereas many fundamental aspects of the heterogeneous chemistry remain uncertain, the information needed to characterize Hg oxidation in coal-derived exhausts is now evident: complete gas compositions (CO, hydrocarbons, H2O, O2 NOx, SOx), UBC properties (size, total surface area), and the ash partitioning throughout the exhaust system are required.  相似文献   

16.
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.  相似文献   

17.
The nitrogen oxides (NOx) reduction technology by combustion modification which has economic benefits as a method of controlling NOx emitted in the combustion process, has recently been receiving a lot of attention. Especially, the moderate or intense low oxygen dilution (MILD) combustion which applied high temperature flue gas recirculation has been confirmed for its effectiveness with regard to solid fuel as well. MILD combustion is affected by the flue gas recirculation ratio and the composition of recirculation gas, so its NOx reduction efficiency is determined by them. In order to investigate the influence of factors which determine the reduction efficiency of NOx in MILD coal combustion, this study changed the flow rate and concentration of nitrogen (N2), carbon dioxide (CO2) and steam (H2O) which simulate the recirculation gas during the MILD coal combustion using our lab-scale drop tube furnace and performed the combustion experiment. As a result, its influence by the composition of recirculation gas was insignificant and it was shown that flue gas recirculation ratio influences the change of NOx concentration greatly. Implications: We investigated the influence of factors determining the nitrogen oxides (NOx) reduction efficiency in MILD coal combustion, which applied high-temperature flue gas recirculation. Using a lab-scale drop tube furnace and simulated recirculation gas, we conducted combustion testing changing the recirculation gas conditions. We found that the flue gas recirculation ratio influences the reduction of NOx emissions the most.  相似文献   

18.
Abstract

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.  相似文献   

19.
ABSTRACT

This paper presents a technique for the complete, simultaneous decomposition of CO2, SO2, and NOx, as well as the simultaneous removal of fly ash by ultra-high voltage pulse activation. Ultra-high voltage narrow pulse is used to make the gases in the reactor become active molecules, which are then dissociated into nonpoisonous gas molecules and solid particles under the control of a directional reaction model. By using a sufficient charge and a strong electric field, the fly ash can be removed. It becomes the carrier of C and S, and its efficiency is 99.5%. Owing to the action of catalyst B (using Ni as the mother's body), the activation energy of CO2, SO2, and NOx gases is reduced in great magnitude, and their removal efficiency can reach 75~90% at normal pressure and 180 °C.  相似文献   

20.
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.  相似文献   

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