A Predictive Mechanism for Mercury Oxidation on Selective Catalytic Reduction Catalysts under Coal-Derived Flue Gas

Abstract

This paper introduces a predictive mechanism for elemental mercury (Hg⁰) 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 Hg⁰ 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 Hg⁰ oxidation behavior on SCRs: that hydrochloric acid (HCl) competes for surface sites with NH₃ and that Hg⁰ contacts these chlorinated sites either from the gas phase or as a weakly adsorbed species. This mechanism explicitly accounts for the inhibition of Hg⁰ 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 Hg⁰ oxidation. But once NH₃ has been consumed, the Hg⁰ 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 Hg⁰ oxidation.

This mechanism accurately interprets the reported tendencies for greater extents of Hg⁰ oxidation on honeycomb monoliths with smaller channel pitches and hotter temperatures and the tendency for lower extents of Hg⁰ oxidation for hotter temperatures on plate monoliths. The mechanism also depicts the inhibition of Hg⁰ 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 Hg⁰ 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.     

Analytical management of SCR catalyst lifetimes and multipollutant performance

Selective catalytic reduction (SCR) catalysts are deactivated by several mineral and metallic trace elements at highly variable rates determined by fuel quality and furnace firing conditions. With a loss in activity, NO is reduced over a longer inlet length of the SCR monolith, which leaves a shorter trailing section to sustain the most favorable conditions to oxidize Hg⁰ and SO₂. Since virtually no operating SCR was designed for Hg oxidation and since different monoliths are routinely combined as layers in particular units, the Hg oxidation performance of any SCR fleet is largely unmanaged. The analysis in this paper directly relates a measurement or manufacturer’s forecast on the deterioration in NO reduction with age to corresponding estimates for oxidation of Hg⁰. It accommodates any number of catalyst layers with grossly different properties, including materials from different manufacturers and different ages. In this paper, the analysis is applied to 16 full-scale SCRs in the Southern Company fleet to demonstrate that catalyst deactivation disrupts even the most prominent connections among the Hg⁰ oxidation performance of commercial SCRs and the behavior of fresh catalysts at lab, pilot, and even full scale.

Implications: Catalyst deactivation confounds even the most prominent connections among the Hg⁰ oxidation performance of commercial SCRs and the behavior of fresh catalyst at lab, pilot, and even full scale. The halogen dependence has been emphasized throughout the literature on catalytic Hg⁰ oxidation, based on a large database on fresh catalysts. But for deactivated catalysts in commercial SCRs, the number of layers is much more indicative of the Hg⁰ oxidation performance, in that SCRs with four layers perform better than those with three layers, and so on. The new qualified conclusion is that Hg⁰ oxidation is greater for progressively greater HCl concentrations only among SCRs with the same number of layers, even for an assortment of catalyst design specifications and operating conditions.     

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.     

Oxidation of mercury across selective catalytic reduction catalysts in coal-fired power plants

A kinetic model for predicting the amount of mercury (Hg) oxidation across selective catalytic reduction (SCR) systems in coal-fired power plants was developed and tested. The model incorporated the effects of diffusion within the porous SCR catalyst and the competition between ammonia and Hg for active sites on the catalyst. Laboratory data on Hg oxidation in simulated flue gas and slipstream data on Hg oxidation in flue gas from power plants were modeled. The model provided good fits to the data for eight different catalysts, both plate and monolith, across a temperature range of 280-420 degrees C, with space velocities varying from 1900 to 5000 hr(-1). Space velocity, temperature, hydrochloric acid content of the flue gas, ratio of ammonia to nitric oxide, and catalyst design all affected Hg oxidation across the SCR catalyst. The model can be used to predict the impact of coal properties, catalyst design, and operating conditions on Hg oxidation across SCRs.     

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.     

The impact of wet flue gas desulfurization scrubbing on mercury emissions from coal-fired power stations

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.     

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

Abstract

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

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

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.     

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.     

Characterization and reactivity of natural manganese ore catalysts in the selective catalytic oxidation of ammonia to nitrogen

Natural manganese ore (NMO) catalysts were characterized and tested in the selective catalytic oxidation of ammonia to nitrogen oxides under dilute conditions. Also, the oxidation of ammonia (NH(3)) was carried out using pure MnO(2), Mn(2)O(3) for comparing with the activity. It is found that the activity of NMO was similar to that of MnO(2) at low temperature below 150 degrees C but above this temperature, the activity of these catalysts showed the difference. In the course of NH(3) oxidation, N(2), NO, N(2)O and H(2)O were produced. But the quantity of NO(2) produced in this experiment was negligible. At temperature below 250 degrees C, selectivity into N(2) from NH(3) oxidation was in the order, NMO > MnO(2) > Mn(2)O(3). This is the reverse of activity of these manganese oxides. Also the characterization of NH(3) oxidation was proposed and supported by the effect of space velocity, inlet O(2) and NH(3) concentration. The increase of space velocity remarkably influenced not only the conversion but also selectivity into N(2). The higher the reaction temperature was, the higher the effect of inlet O(2) and NH(3) concentration on the reaction rate was. By introducing NO during NH(3) oxidation reaction, the possibility of NMO as selective catalytic reduction catalyst at low temperature was studied and showed positive results.     

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.     

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.     

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.     

A mechanism for mercury oxidation in coat-derived exhausts

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.     

Effects of NO2 and SO2 on selective catalytic reduction of nitrogen oxides by ammonia

The selective catalytic reduction (SCR) characteristics of NO and NO(2) over V(2)O(5)-WO(3)-MnO(2)/TiO(2) catalyst using ammonia as a reducing agent have been determined in a fixed-bed reactor at 200-400 degrees C. The presence of NO(2) enhances the SCR activity at lower temperatures and the optimum ratio of NO(2)/NO(x) is found to be 0.5. During the SCR reactions, there are some side reactions occurred such as ammonia oxidation and N(2)O formation. At higher temperatures, the selective catalytic oxidation of ammonia and the nitrous oxide formation compete with the SCR reactions. The denitrification (DeNO(x)) conversion decreases at lower temperatures but it increases at higher temperatures with increasing SO(2) concentration. The presence of SO(2) in the feeds inhibits N(2)O formation.     

MnOx／Al-SBA-15催化剂低温NH3选择性催化还原NO的原位红外研究

用原位红外分别进行了MnOx／Al-SBA-15催化剂上NH3和NO＋O2的吸附态和瞬态实验以及NH3＋NO＋02反应的稳态实验。结果表明,催化剂上存在着L酸位和B酸位,NH3吸附在催化剂上形成配位态的NH3和NH4＋,配位态的NH3能脱氢形成-NH2活性中间态。NO＋O2在催化剂上吸附形成硝酸盐类、硝基类和亚硝酸盐类。将NO＋O2通入预吸附NH3的催化剂中时,表面的配位态的NH3、NH4＋和-NH2都会减少直至消失,SCR反应显著。而将NH3通人预吸附NO＋O2的催化剂中时,只有硝基类和亚硝酸盐类减少,硝酸盐类基本不发生变化,SCR反应微弱。NH3＋NO＋O2稳态反应中,催化剂表面稳定存在着NH4＋和硝酸盐类,SCR反应显著。     

SCR performance on a hydrogen reformer furnace

In late 1993, Air Products and Chemicals, Inc. began operating a new steam-methane reformer at the Tosco Refining Co.'s Avon refinery in Martinez, CA, to provide hydrogen and steam to the refinery under a long-term supply agreement. The hydrogen plant--owned, operated, and maintained by Air Products--includes a selective catalytic reduction (SCR) unit on the reformer-furnace flue gas for environmental control. SCR is a commercially proven process capable of abating emissions of nitrogen oxides (NOx) to extremely low levels; however, documented experience in a refinery setting has been limited. This paper discusses performance of the SCR, primarily during its first two years of operation; it incorporates theory and prior research findings sufficient to understand the relationship between key system variables and SCR performance. Test results demonstrate that NOx, ammonia (NH3) slip, and carbon monoxide (CO) emissions are in compliance with permit limits. NOx removal efficiency is nearly linear with the inlet NH3:NOx molar ratio up to almost 90% NOx conversion, where ammonia slip begins to rise steeply. The stoichiometric reaction ratio of NH3 to NOx is close to the theoretical 1.0. Catalyst life is estimated at four years, in line with published figures for SCR catalysts in clean-gas service.     

Ti-Ce-Zr-Ox复合脱硝催化剂的制备及其性能研究

采用共混法制备了Ti-Ce-Zr-Ox复合脱硝催化剂TiCe0.1Zr0.1O2.4,运用X射线衍射、氮气物理吸附、扫描电镜等表征手段,分别对该催化剂的晶型、表面积、孔分布及结构形貌进行了分析,同时考察了反应温度、空速、水蒸气和SO2对该催化剂NH3选择性催化还原NO的影响.结果表明,TiCe0.1Zr0.1O2.4催...     

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.     

A study on the reaction characteristics of vanadium-impregnated natural manganese oxide in ammonia selective catalytic reduction

This study investigated the effect of adding vanadium (V) to natural manganese oxide (NMO) in ammonia (NH3) selective catalytic reduction (SCR). The addition of V to NMO decreased the catalytic activity at low temperatures by blocking the active site. However, the enhancement of catalytic activity was achieved by controlling NH3 oxidation at high temperatures. From the NH3 temperature programmed desorption and oxygen on/off test, it was confirmed that the amount of Lewis acid site and active lattice oxygen of the catalyst affects the catalytic performance at low temperature.