Influence of HCl on oxidation of gaseous elemental mercury by dielectric barrier discharge process

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.     

Removal of gaseous elemental mercury by dielectric barrier discharge

The removal of elemental mercury (Hg(0)) with the reactive species produced from dielectric barrier discharge (DBD) was studied. The effects of the operating parameters, such as the applied voltage, residence time, initial concentration and co-existence of other pollutants, were investigated. The removal of Hg(0) was significantly promoted by an increase in the applied voltage of the DBD reactor system. The presence of NO gas decreased the Hg(0) removal efficiency within the range of input powers tested compared to the case of Hg(0)-only due to the competition for ozone between Hg(0) and NO gas in the DBD reactor.     

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.     

Removing and recovering gas-phase elemental mercury by Cu(x)Co(3-x)O(4) (0.75< or = x < or =2.25) in the presence of sulphur compounds

The Hg(0) oxidation ability and reusability of Cu(x)Co(3-x)O(4) were investigated in an attempt to improve SO(2) anti-poisoning ability of metal oxide and produce more economic and effective sorbents for the control of Hg(0) emission from combustion processes. The influence of copper content on Cu(x)Co(3-x)O(4)'s (0.75< or = x < or =2.25) oxidation ability of Hg(0) in the presence of SO(2) was investigated. According to the X-ray diffraction, Brunauer-Emmett-Teller (BET) and mass balance analysis on mercury, we found that Cu(1.5)Co(1.5)O(4) showed the highest S(BET) and best Hg(0) oxidation ability. With continuous increase of x from 0.75 to 2.25, Cu(x)Co(3-x)O(4)'s SO(2) anti-poisoning ability increased. The analysis results of the X-ray photoelectron spectroscopy manifested that the adsorptive mercury species on spent Cu(1.5)Co(1.5)O(4) was HgO. The spent Cu(1.5)Co(1.5)O(4) could be regenerated by thermal decomposition at 673K and regenerated Cu(1.5)Co(1.5)O(4) showed higher Hg(0) oxidation ability due to Hg-doping. Regenerated enrichment Hg(0) was collected using activated carbon at an ambient temperature to eliminate the secondary pollution.     

Oxidation of elemental mercury using atmospheric pressure non-thermal plasma

The oxidation of gas phase elemental mercury (Hg0) by atmospheric pressure non-thermal plasma has been investigated at room temperature, employing both dielectric barrier discharge (DBD) of the gas mixture of Hg0 and injection of ozone (O3) into the gas mixture of Hg0. Results have shown that the oxidative efficiencies of Hg0 by DBD and the injection of O3 are 59% and 93%, respectively, with energy consumption of 23.7 J L(-1). This combined approach has indicated that O3 plays a decisive role in the oxidation of gas phase Hg0. Also the oxidation of Hg0 by injecting O3 into the gas mixture of Hg0 proceeds with better efficiency than DBD of the gas mixture of Hg0. These results have been explained by the incorporation of the competitive reaction pathways between the formation of HgO by O3 and the decomposition of HgO back to Hg0 in the plasma environment.     

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.     

Pilot-scale study of the effect of selective catalytic reduction catalyst on mercury speciation in Illinois and Powder River Basin coal combustion flue gases

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.     

A predictive mechanism for mercury oxidation on selective catalytic reduction catalysts under coal-derived flue gas

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.     

Structural effect of the in situ generated titania on its ability to oxidize and capture the gas-phase elemental mercury

Structural effect of the in situ generated TiO(2) sorbent particle was examined for its ability to capture elemental mercury under UV irradiation in a simulated combustion flue gas. Titania particles were prepared by thermal gas-phase oxidation of Titanium (IV) isopropoxide (TTIP) using a high temperature electric furnace reactor. The structural characteristics of the in situ generated TiO(2) at various synthesis temperatures were investigated; size distribution and the geometric mean diameter were measured using a scanning mobility particle sizer, while fractal dimension and radius of gyration were evaluated from the transmission electron microscopy images. Results from the Hg(0) capture experiment show that with increasing titania synthesis temperature, the overall aggregate size increases and the morphology becomes more open-structured to gas-phase Hg(0) and UV light, resulting in the improved mercury removal capability.     

Heterogeneous mercury reaction chemistry on activated carbon

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.     

滤料负载粉尘层对气态汞脱除性能的实验研究

通过不同性能纤维滤料负载燃煤飞灰粉尘层,来模拟袋式除尘器滤袋表面粉尘附着层,进而研究袋滤器用不同性能纤维滤料和粉尘附着层对燃煤烟气中Hg0的联合脱除性能。在固定床实验系统上分别进行了不同纤维滤料和燃煤飞灰粉尘层,以及经实验优选得到的华博特滤料负载燃煤飞灰粉尘层脱除燃煤烟气中Hg0的实验研究。结果表明,燃煤飞灰粉尘层和华博特滤料对Hg0分别有一定的脱除作用,脱除效率可达35%和42.5%,它们对Hg0的脱除是物理吸附和化学吸附共同作用的结果;同时,华博特滤料负载燃煤飞灰粉尘层对Hg0的联合脱除效率受到吸附反应温度、入口汞浓度和烟气停留时间等因素的影响,最佳脱汞率可达64.4%;吸附反应温度越高,脱除效率越低;烟气停留时间越大,脱除效率越高;入口汞浓度的提高并不一定提高华博特滤料负载飞灰粉尘层的脱汞效果。     

A mechanistic model for mercury capture with in situ-generated titania particles: role of water vapor

A mechanistic model to predict the capture of gas-phase mercury (Hg) species using in situ-generated titania nanosize particles activated by UV irradiation is developed. The model is an extension of a recently reported model for photochemical reactions by Almquist and Biswas that accounts for the rates of electron-hole pair generation, the adsorption of the compound to be oxidized, and the adsorption of water vapor. The role of water vapor in the removal efficiency of Hg was investigated to evaluate the rates of Hg oxidation at different water vapor concentrations. As the water vapor concentration is increased, more hydroxy radical species are generated on the surface of the titania particle, increasing the number of active sites for the photooxidation and capture of Hg. At very high water vapor concentrations, competitive adsorption is expected to be important and reduce the number of sites available for photooxidation of Hg. The predictions of the developed phenomenological model agreed well with the measured Hg oxidation rates in this study and with the data on oxidation of organic compounds reported in the literature.     

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.     

A study of gas-phase mercury speciation using detailed chemical kinetics.

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.     

Uptake of atmospheric mercury by deionized water and aqueous solutions of inorganic salts at acidic,neutral and alkaline pH

Mercury (Hg) is well known as a toxic environmental pollutant that is among the most highly bioconcentrated trace metals in the human food chain. The atmosphere is one of the most important media for the environmental cycling of mercury, since it not only receives mercury emitted from natural sources such as volcanoes and soil and water surfaces but also from anthropogenic sources such as fossil fuel combustion, mining and metal smelting. Although atmospheric mercury exists in different physical and chemical forms, as much as 90% can occur as elemental vapour Hg0, depending on the geographic location and time of year. Atmospheric mercury can be deposited to aquatic ecosystems through both wet (rain or snow) and dry (vapour adsorption and particulate deposition) processes. The purpose of the present study was to measure, under laboratory conditions, the rate of deposition of gaseous, elemental mercury (Hg0) to deionized water and to solutions of inorganic salt species of varying ionic strengths with a pH range of 2-12. In deionized water the highest deposition rates occurred at both low (pH 2) and high (pH 12). The addition of different species of salt of various concentrations for the most part had only slight effects on the absorption and retention of atmospheric Hg0. The low pH solutions of various salt concentrations and the high pH solutions of high salt concentrations tested in this study generally showed a greater tendency to absorb and retain atmospheric Hg0 than those at a pH closer to neutral.     

Entrained-flow adsorption of mercury using activated carbon

Bench-scale experiments were conducted in a flow reactor to simulate entrained-flow capture of elemental mercury (Hg0) by activated carbon. Adsorption of Hg0 by several commercial activated carbons was examined at different C:Hg ratios (by weight) (350:1-29,000:1), particle sizes (4-44 microns), Hg0 concentrations (44, 86, and 124 ppb), and temperatures (23-250 degrees C). Increasing the C:Hg ratio from 2100:1 to 11,000:1 resulted in an increase in removal from 11 to 30% for particle sizes of 4-8 microns and a residence time of 6.5 sec. Mercury capture increased with a decrease in particle size. At 100 degrees C and an Hg0 concentration of 86 ppb, a 20% Hg0 reduction was obtained with 4- to 8-micron particles, compared with only a 7% reduction for 24- to 44-micron particles. Mercury uptake decreased with an increase in temperature over a range of 21-150 degrees C. Only a small amount of the Hg0 uptake capacity is being utilized (less than 1%) at such short residence times. Increasing the residence time over a range of 3.8-13 sec did not increase adsorption for a lignite-based carbon; however, increasing the time from 3.6 to 12 sec resulted in higher Hg0 removal for a bituminous-based carbon.     

Heterogeneous and homogeneous catalytic ozonation of benzothiazole promoted by activated carbon: kinetic approach

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.     

Comparison of mercury chemistry models

Five mercury (Hg) chemistry models are compared using the same data set for model initialisation. All five models include gas-phase oxidation of Hg(0) to Hg(II) (except for one model), fast reduction–oxidation aqueous reactions between Hg(0) and Hg(II), and adsorption of Hg(II) species to soot particles within droplets. However, the models differ in their detailed treatments of these processes. Consequently, the 48-h simulations reveal similarities but also significant discrepancies among the models. For the simulation that included all Hg species (i.e., Hg(0), Hg(II) and Hg(p)) as well as soot in the initial conditions, the maximum simulated Hg(II) aqueous concentrations ranged from 55 to 148 ng l⁻¹ whereas the minimum concentrations ranged from 20 to 110 ng l⁻¹. These results suggest that further experimental work is critically needed to reduce the current uncertainties in the formulation of Hg chemistry models.     

Hg reactions in the presence of chlorine species: homogeneous gas phase and heterogeneous gas-solid phase

The kinetics of Hg chlorination (with HCl) was studied using a flow reactor system with an online Hg analyzer, and speciation sampling using a set of impingers. Kinetic parameters, such as reaction order (alpha), overall rate constant (k'), and activation energy (Ea), were estimated based on the simple overall reaction pathway. The reaction order with respect to C(Hg), k', and Ea were found to be 1.55, 5.07 x 10(-2) exp(-1939.68/T) [(microg/m3)(-055)(s)(-1)]. and 16.13 [kJ/ mol], respectively. The effect of chlorine species (HCl, CH2Cl2) on the in situ Hg capture method previously developed (28) was also investigated. The efficiency of capture of Hg by this in situ method was higher than 98% in the presence of chlorine species. Furthermore, under certain conditions, the presence of chlorine enhanced the removal of elemental Hg by additional gas-phase oxidation.     

Performance of Copper Chloride-Impregnated Sorbents on Mercury Vapor Control in an Entrained-Flow Reactor System

Abstract

An entrained-flow system has been designed and constructed to simulate in-flight mercury (Hg) capture by sorbent injection in ducts of coal-fired utility plants. The test conditions of 1.2-sec residence time, 140 °C gas temperature, 6.7 m/sec (22 ft/sec) gas velocity, and 0–0.24 g/m³ (0–15 lbs of sorbent per 1 million actual cubic feet of flue gas [lb/MMacf]) sorbent injection rates were chosen to simulate conditions in the ducts. Four kinds of sorbents were used in this study. Darco Hg-LH served as a benchmark sorbent with which Hg control capability of other sorbents could be compared. Also, Darco-FGD was used as a representative raw activated carbon sorbent. Two different copper chloride-impregnated sorbents were developed in our laboratory and tested in the entrained-flow system to examine the possibility of using these sorbents at coal-fired power plants. The test results showed that one of the copper chloride sorbents has remarkable elemental mercury (Hg⁰) oxidation capability, and the other sorbent demonstrated a better performance in Hg removal than Darco Hg-LH.