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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 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 (NOX, SOX, 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, NOX, LOI, and residence time, as well as the most important coal properties, including coal-Cl.  相似文献   

3.
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.  相似文献   

4.
Ko KB  Byun Y  Cho M  Namkung W  Shin DN  Koh DJ  Kim KT 《Chemosphere》2008,71(9):1674-1682
The influence of HCl on the oxidation of gaseous elemental mercury (Hg0) has been investigated using a dielectric barrier discharge (DBD) plasma process, where the temperature of the plasma reactor and the composition of gas mixtures of HCl, H2O, NO, and O2 in N2 balance have been varied. We observe that Cl atoms and Cl2 molecules, created by the DBD process, play important roles in the oxidation of Hg0 to HgCl2. The addition of H2O to the gas mixture of HCl in N2 accelerates the oxidation of Hg0, although no appreciable effect of H2O alone on the oxidation of Hg0 has been observed. The increase of the reaction temperature in the presence of HCl results in the reduction of Hg0 oxidation efficiency probably due to the deterioration of the heterogeneous chemical reaction of Hg0 with chlorinated species on the reactor wall. The presence of NO shows an inhibitory effect on the oxidation of Hg0 under DBD of 16% O2 in N2, indicating that NO acts as an O and O3 scavenger. At the composition of Hg0 (280 microg m(-3)), HCl (25 ppm), NO (204 ppm), O2 (16%) and N2 (balance) and temperature 90 degrees C, we obtain the nearly complete oxidation of Hg0 at a specific energy density of 8 J l(-1). These results lead us to suggest that the DBD process can be viable for the treatment of mercury released from coal-fired power plants.  相似文献   

5.
The laser photolysis/laser induced fluorescence (LP/LIF) technique has been applied to studies of gas-phase mercury (Hg) chlorination. Mercury (I) chloride (HgCl) was been detected via LIF at 272 nm from reactions of elemental Hg with Cl atoms generated from the 193 nm photolysis of carbon tetrachloride. While the formation of HgCl was too fast to be observed on millisecond time scales, the kinetics of the consumption of HgCl have been determined at temperatures characteristic of post-combustion conditions. Rate coefficients and Arrhenius parameters for the reaction of HgCl with Cl2, HCl and Cl atoms were determined. The reaction of HgCl with Cl2 was the fastest reaction studied, while the reaction of HgCl with HCl was the only reaction to show any measurable temperature dependence. Estimates of the rate coefficient for the reaction Hg + Cl --> HgCl were determined using a modeling approach. Comparisons of these new measurements with model predictions are discussed.  相似文献   

6.
A study of gas-phase mercury speciation using detailed chemical kinetics.   总被引:5,自引:0,他引:5  
Mercury speciation in combustion-generated flue gas was modeled using a detailed chemical mechanism consisting of 60 reactions and 21 species. This speciation model accounts for the chlorination and oxidation of key flue-gas components, including elemental mercury (Hg0). Results indicated that the performance of the model is very sensitive to temperature. Starting with pure HCl, for lower reactor temperatures (less than approximately 630 degrees C), the model produced only trace amounts of atomic and molecular chlorine (Cl and Cl2), leading to a drastic underprediction of Hg chlorination compared with experimental data. For higher reactor temperatures, model predictions were in good accord with experimental data. For conditions that produce an excess of Cl and Cl2 relative to Hg, chlorination of Hg is determined by the competing influences of the initiation step, Hg + Cl = HgCl, and the Cl recombination reaction, 2Cl = Cl2. If the Cl recombination reaction is faster, Hg chlorination will eventually be dictated by the slower pathway Hg + Cl2 = HgCl2.  相似文献   

7.
Valdés H  Zaror CA 《Chemosphere》2006,65(7):1131-1136
Ozone oxidation combined with activated carbon adsorption (O(3)/AC) has recently started to be developed as a single process for water and wastewater treatment. While a number of aspects of aqueous ozone decomposition are well understood, the importance and relationship between aqueous ozone decomposition and organic contaminant degradation in the presence of activated carbon is still not clear. This study focuses on determining the contribution of homogeneous and heterogeneous reactions to organic contaminants removal in O(3)/AC system. Benzothiazole (BT) was selected as a target organic pollutant due to its environmental concern. A reactor system based on a differential circular flow reactor composed by a 19 cm(3) activated carbon fixed bed column and 1 dm(3) storage tank was used. Ozone was produced from pure and dry oxygen using an Ozocav ozone generator rated at 5 g O(3)h(-1). Experimental results show that BT removal rate was proportional to activated carbon dosage. Activated carbon surface contribution to BT oxidation reactions with ozone, increased with pH in absence of radical scavengers. The radical reaction contribution within the pH range 2-11 accounted for 67-83% for BT removal in O(3)/AC simultaneous treatment. Results suggest that at pH higher than the pH of the point of zero charge of the activated carbon dissociated acid groups such as carboxylic acid anhydrides and carboxylic acids present on activated carbon surface could be responsible for the observed increase in the ozone decomposition reaction rate. A simplified mechanism and a kinetic scheme representing the contribution of homogeneous and heterogeneous reactions on BT ozonation in the presence of activated carbon is proposed.  相似文献   

8.
This paper introduces a predictive mechanism for elemental mercury (Hg(o)) oxidation on selective catalytic reduction (SCR) catalysts in coal-fired utility gas cleaning systems, given the ammonia (NH3)/nitric oxide (NO) ratio and concentrations of Hg(o) and HCl at the monolith inlet, the monolith pitch and channel shape, and the SCR temperature and space velocity. A simple premise connects the established mechanism for catalytic NO reduction to the Hg(o) oxidation behavior on SCRs: that hydrochloric acid (HCl) competes for surface sites with NH3 and that Hg(o) contacts these chlorinated sites either from the gas phase or as a weakly adsorbed species. This mechanism explicitly accounts for the inhibition of Hg(o) oxidation by NH3, so that the monolith sustains two chemically distinct regions. In the inlet region, strong NH3 adsorption minimizes the coverage of chlorinated surface sites, so NO reduction inhibits Hg(o) oxidation. But once NH3 has been consumed, the Hg(o) oxidation rate rapidly accelerates, even while the HCl concentration in the gas phase is uniform. Factors that shorten the length of the NO reduction region, such as smaller channel pitches and converting from square to circular channels, and factors that enhance surface chlorination, such as higher inlet HCl concentrations and lower NH3/NO ratios, promote Hg(o) oxidation. This mechanism accurately interprets the reported tendencies for greater extents of Hg(o) oxidation on honeycomb monoliths with smaller channel pitches and hotter temperatures and the tendency for lower extents of Hg(o) oxidation for hotter temperatures on plate monoliths. The mechanism also depicts the inhibition of Hg(o) oxidation by NH3 for NH3/NO ratios from zero to 0.9. Perhaps most important for practical applications, the mechanism reproduces the reported extents of Hg(o) oxidation on a single catalyst for four coals that generated HCl concentrations from 8 to 241 ppm, which covers the entire range encountered in the U.S. utility industry. Similar performance is also demonstrated for full-scale SCRs with diverse coal types and operating conditions.  相似文献   

9.
The mass transfer of naphthalene vapor to water droplets in air was studied in the presence of ozone (O3) in the gas phase. A falling droplet reactor with water droplets of diameters 55, 91, and 182 microm was used for the study. O3 reacted with naphthalene at the air-water interface, thereby decreasing the mass transfer resistance and increasing the rate of uptake of naphthalene into the droplet. A Langmuir-Hinshelwood reaction mechanism at the air-water interface satisfactorily described the surface reaction. The first-order surface reaction rate constant, ks, increased with decreasing droplet size. Three organic intermediates were identified in the aqueous phase as a result of ozonation of naphthalene at the surface of the droplet indicating both peroxidic and nonperoxidic routes for ozonation. The presence of an organic carbon surrogate (fulvic acid) increased both the partition constant of naphthalene and the surface reaction rate of O3. The heterogeneous oxidation of naphthalene by O3 on the droplet was 15 times faster than the homogeneous oxidation by O3 in the bulk air phase, whereas it was only 0.08 times the homogeneous gas-phase oxidation by hydroxyl radicals under atmospheric conditions.  相似文献   

10.
This article introduces a predictive capability for Hg retention in any Ca-based wet flue gas desulfurization (FGD) scrubber, given mercury (Hg) speciation at the FGD inlet, the flue gas composition, and the sulphur dioxide (SO2) capture efficiency. A preliminary statistical analysis of data from 17 full-scale wet FGDs connects flue gas compositions, the extents of Hg oxidation at FGD inlets, and Hg retention efficiencies. These connections clearly signal that solution chemistry within the FGD determines Hg retention. A more thorough analysis based on thermochemical equilibrium yields highly accurate predictions for total Hg retention with no parameter adjustments. For the most reliable data, the predictions were within measurement uncertainties for both limestone and Mg/lime systems operating in both forced and natural oxidation mode. With the U.S. Environmental Protection Agency's (EPA) Information Collection Request (ICR) database, the quantitative performance was almost as good for the most modern FGDs, which probably conform to the very high SO2 absorption efficiencies assumed in the calculations. The large discrepancies for older FGDs are tentatively attributed to the unspecified SO2 capture efficiencies and operating temperatures and to the possible elimination of HCl in prescrubbers. The equilibrium calculations suggest that Hg retention is most sensitive to inlet HCl and O2 levels and the FGD temperature; weakly dependent on SO2 capture efficiency; and insensitive to HgCl2, NO, CA:S ratio, slurry dilution level in limestone FGDs, and MgSO3 levels in Mg/lime systems. Consequently, systems with prescrubbers to eliminate HCl probably retain less Hg than fully integrated FGDs. The analysis also predicts re-emission of Hg(O) but only for inlet O2 levels that are much lower than those in full-scale FGDs.  相似文献   

11.
Abstract

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.  相似文献   

12.
Byun Y  Koh DJ  Shin DN 《Chemosphere》2011,83(1):69-75
The removal mechanism of elementary mercury (Hg(0)) by non-thermal plasma (NTP) has been investigated, where dielectric barrier discharge and O(3) injection methods as oxidation techniques are employed, together with the analysis of mercury species deposited on the reactor surface using temperature-programmed desorption and dissociation (TPDD) and scanning electron microscopy-energy dispersive spectroscopy. The removal of Hg(0) by NTP is found to be time-dependent and proceed through three domains; the Hg(0) concentration just slightly decreases as soon as NTP is initiated and then becomes constant for several minutes (Region 1), thereafter starts to decrease rapidly for 1h (Region 2) and, after passing fall-off region, very slowly decreases for about 4h (Region 3). The deposited mercury species on the reactor surface were conglomerated like islands, rather than dispersed uniformly, and their ratio of Hg(0) to O composition is observed to be 1:2. Additionally, the new peak in TPDD spectra observed in the region of 260-380°C is proposed as HgO(3). These results lead us to conclude that the deposited mercury species by NTP have extra O atoms to oxidize the adsorbed Hg(0), resulting in the acceleration of removal rate as the oxidation of Hg(0) proceeds.  相似文献   

13.
Photo-oxidation of cork manufacturing wastewater   总被引:7,自引:0,他引:7  
Several photo-activated processes have been investigated for oxidation of a cork manufacturing wastewater. A comparative activity study is made between different homogeneous (H2O2/UV-Vis and H2O2/Fe2+/UV-Vis) and heterogeneous (TiO2/UV-Vis and TiO2/H2O2/UV-Vis) systems, with degradation performances being evaluated in terms of total organic carbon (TOC) removal. Results obtained in a batch photo-reactor show that photo-catalysis with TiO2 is not suitable for this kind of wastewater while the H2O2/UV-Vis oxidation process, for which the effect of some operating conditions was investigated, allows to remove 39% of TOC after 4 h of operation (for C(H2O2)=0.59 M, pH=10 and T=35 degrees C). The combined photo-activated process, i.e., using both TiO2 and H2O2, yields an overall TOC decrease of 46% (for C(TiO2)=1.0 gl(-1)). The photo-Fenton process proved to be the most efficient, proceeds at a much higher oxidation rate and allows to achieve 66% mineralization in just 10 min of reaction time (for C(H2O2)=0.31 M, T=30 degrees C, Fe2+:H2O2=0.12 (mol) and pH=3.2).  相似文献   

14.
Atmospheric Mercury Depletion Events (AMDE) occur in Arctic and Antarctic regions during polar sunrise. During AMDE, reactive gaseous Hg is rapidly formed through in-situ oxidation of gaseous Hg0 by halogens, notably atomic Br and radical BrO. This leads to high Hg deposition fluxes yet an unknown fraction of deposited Hg is reemitted to the atmosphere through subsequent photo-reduction, so that the net deposition flux related to AMDE is not well constrained. Here, Hg and halogens were measured in lichens hanging in tree branches around Hudson Bay where AMDE were reported. Hg concentrations are strongly correlated to halogen elements Br, Cl and I (r2 of 0.91, 0.76, 0.81) and decrease with distance from Hudson Bay. We interpret this trend as the result of AMDE, supported by a 1D numerical Br and BrO oxidation model for Hg0. Organic carbon normalized Hg contents of down-core lake sediments reported in the literature also show a decreasing trend away from Hudson Bay. Combined observations suggest that at least 50% of Hg deposited during AMDE is reemitted to the atmosphere. Finally, the latitudinal Hg gradient observed in lake sediments suggests that AMDE were active in the Hudson Bay area during the last 90 to 200 years.  相似文献   

15.
Experimental and theory-based investigations have been carried out on the oxidation and adsorption mechanism of mercury (Hg) on brominated activated carbon (AC). Air containing parts per billion concentrations of Hg was passed over a packed-bed reactor with varying sorbent materials at 140 and 30 degrees C. Through X-ray photoelectron spectroscopy surface characterization studies it was found that Hg adsorption is primarily associated with bromine (Br) on the surface, but that it may be possible for surface-bound oxygen (O) to play a role in determining the stability of adsorbed Hg. In addition to surface characterization experiments, the interaction of Hg with brominated AC was studied using plane-wave density functional theory. Various configurations of hydrogen, O, Br, and Hg on the zigzag edge sites of graphene were investigated, and although Hg-Br complexes were found to be stable on the surface, the most stable configurations found were those with Hg adjacent to O. The Hg-carbon (C) bond length ranged from 2.26 to 2.34 A and is approximately 0.1 A shorter when O is a nearest-neighbor atom rather than a next-nearest neighbor, resulting in increased stability of the given configuration and overall tighter Hg-C binding. Through a density of states analysis, Hg was found to gain electron density in the six p-states after adsorption and was found to donate electron density from the five s-states, thereby leading to an oxidized surface-bound Hg complex.  相似文献   

16.
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 (NOx) 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 approximately 96% at the inlet of the reactor to approximately 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.  相似文献   

17.
The adsorptive interactions of Hg(II) with gibbsite-rich soils (hereafter SOIL-g) were modeled by 1-pK surface complexation theory using charge distribution multi-site ion competition model (CD MUSIC) incorporating basic Stern layer model (BSM) to account for electrostatic effects. The model calibrations were performed for the experimental data of synthetic gibbsite-Hg(II) adsorption. When [NaNO(3)] > or = 0.01M, the Hg(II) adsorption density values, of gibbsite, Gamma(Hg(II)), showed a negligible variation with ionic strength. However, Gamma(Hg(II)) values show a marked variation with the [Cl(-)]. When [Cl(-)] > or = 0.01M, the Gamma(Hg(II)) values showed a significant reduction with the pH. The Hg(II) adsorption behavior in NaNO(3) was modeled assuming homogeneous solid surface. The introduction of high affinity sites, i.e., >Al(s)OH at a low concentration (typically about 0.045 sites nm(-2)) is required to model Hg(II) adsorption in NaCl. According to IR spectroscopic data, the bauxitic soil (SOIL-g) is characterized by gibbsite and bayerite. These mineral phases were not treated discretely in modeling of Hg(II) and soil interactions. The CD MUSIC/BSM model combination can be used to model Hg(II) adsorption on bauxitic soil. The role of organic matter seems to play a role on Hg(II) binding when pH>8. The Hg(II) adsorption in the presence of excess Cl(-) ions required the selection of high affinity sites in modeling.  相似文献   

18.
The photodegradation of monuron (3-(4-chlorophenyl)-1,1-dimethylurea) in aqueous solutions under simulated solar irradiation has been conducted by different advanced oxidation processes (UV/H(2)O(2), UV/H(2)O(2)/Fe(2+), UV/H(2)O(2)/TiO(2), UV/TiO(2), dark H(2)O(2)/Fe(3+)). The degradation rates were always higher for the homogeneous catalysis in photo-Fenton reactions (UV/H(2)O(2)/Fe(2+)) compared to the heterogeneous photocatalytic systems (TiO(2)/UV and UV/H(2)O(2)/TiO(2)). Optimal concentrations of Fe(2+) and H(2)O(2) for the abatement of the herbicide in the photo-Fenton system were found to be 1 mM Fe(II) and 10 mM H(2)O(2). Several intermediary products were identified using large volume injection micro-liquid chromatography with UV detection (mu-LC-UV), mu-LC-MS and GC-MS techniques and a degradation mechanism has been proposed.  相似文献   

19.
The issue of investigations in this study was an application of heterogeneous Fenton-type catalyst, Fe-exchanged zeolite FeZSM5, for the minimization of phenol and overall organic content in the model wastewater. Applied treatment systems included variation of heterogeneous and homogeneous Fenton-type catalyst with and without the assistance of UV irradiation, FeZSM5/H2O2, Fe2+/H2O2/NH4ZSM5, Fe3+/H2O2/NH4ZSM5, UV/FeZSM5/H2O2, UV/Fe2+/H2O2/NH4ZSM5 and UV/Fe3+/H2O2/NH4ZSM5. Processes efficiency was evaluated on the basis of phenol removal, mineralization extent, H2O2 consumption and concentration of iron ions in the bulk after the treatment. By all applied systems, complete phenol removal was achieved in less than 30 min of treatment time. Systems including heterogeneous Fenton-type catalyst showed somewhat lower mineralization efficiency in comparison to the corresponding systems applying homogeneous Fenton-type catalysts and the addition of synthetic zeolite NH4ZSM5. Significantly lower concentration of iron ions in the bulk after the treatment could give these systems, particularly UV/FeZSM5/H2O2, a great advantage over the homogeneous Fenton-type systems.  相似文献   

20.
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 (NOx) 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.  相似文献   

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