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.     

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.     

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.     

Manganese-cerium oxide (MnOx-CeO2) catalysts supported by titanium-bearing blast furnace slag for selective catalytic reduction of nitric oxide with ammonia at low temperature

A series of manganese-cerium oxide (MnO_x-CeO₂) catalysts supported by Ti-bearing blast furnace slag were prepared by wet impregnation and used for low-temperature selective catalytic reduction (SCR) of NO with NH₃. The slag-based catalyst exhibited high nitrogen oxide removal (deNO_x) activity and wide effective temperature range. Under the condition of NO = 500 ppm, NH₃ = 500 ppm, O₂ = 7–8 vol%, and total flow rate = 1600 mL/min, the Mn-Ce/Slag catalyst exhibited a NO conversion higher than 95% in the range of 180–260 °C. The activity of Mn/Slag catalysts was greatly enhanced with the addition of CeO₂. The results indicated that Ti-bearing blast furnace slag had suitable phase composition as good support of SCR catalyst.

Implications: Ti-bearing blast furnace slag is a kind of industrial waste in China. Much slag was underused and piling up, which could cause many environmental issues, such as enormous waste of titanium and groundwater and soil contamination by heavy metals in leachates. The utilization of slag as the support of SCR catalyst will not only make use of solid waste but also cut down the NO_x emitted from power plant.     

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.     

Quick vaporization of sprayed sodium hypochlorite (NaClO(aq)) for simultaneous removal of nitrogen oxides (NOx), sulfur dioxide (SO2), and mercury (Hg0)

Sodium hypochlorite (NaClO) has been widely used as a chemical additive for enhancing nitrogen oxide (NO_x; NO + NO₂), sulfur dioxide (SO₂), and mercury (Hg⁰) removals in a wet scrubber. However, they are each uniquely dependent on NaClO_(aq) pH, hence making the simultaneous control difficult. In order to overcome this weakness, we sprayed low liquid-to-gas (L/G) ratio (0.1 L/Nm³) of NaClO_(aq) to vaporize quickly at 165 °C. Results have shown that the maximized NO_x, SO₂, and Hg⁰ removals can be achieved at the pH range between 4.0 and 6.0. When NO_x and Hg⁰ coexist with SO₂, in addition, their removals are significantly enhanced by reactions with solid and gaseous by-products such as NaClO_(s), NaClO_2(s), OClO, ClO, and Cl species, originated from the reaction between SO₂ and NaClO_(aq). We have also demonstrated the feasibility of this approach in the real flue gases of a combustion plant and observed 50%, 80%, and 60% of NO_x, SO₂, and Hg⁰ removals, respectively. These findings led us to conclude that the spray of NaClO_(aq) at a relatively high temperature at which the sprayed solution can vaporize quickly makes the simultaneous control of NO_x, SO₂, and Hg⁰ possible.

Implications: The simple spray of NaClO_(aq) at temperatures above 165 °C can cause the simultaneous removal of gaseous NO_x, SO₂, and Hg⁰ by its quick vaporization. Their maximized removals are achieved at the pH range between 4.0 and 6.0. NO_x and Hg⁰ removals are also enhanced by gaseous and solid intermediate products generated from the reaction of SO₂ with NaClO_(aq). The feasibility of this approach has been demonstrated in the real flue gases of a combustion plant.     

Adsorption properties of regenerative materials for removal of low concentration of toluene

A specific type of material, activated carbon fiber (ACF), was modified by SiO₂, and the final products ACF-x were obtained as ACF-12.5, ACF-20, ACF-40, and ACF-80 according to different dosages of tetraethoxysilane (TEOS). The modified material on the ACF surface had a significant and smooth cover layer with low content of silica from scanning electron microscope (SEM) image. The modified ACF-x showed the stronger hydrophobicity, thermal stability, and adsorption capacity, which had almost no effect in the presence of water vapor and no destruction in multiple cycles. ACF-20 was proven as the most efficient adsorbent in humid conditions. The dual-function system composed of the regenerative adsorbents and the combustion catalyst would be efficient in consecutive toluene adsorption/oxidation cycles, in which the combustion catalyst was prepared by the displacement reaction of H₂PtCl₆ with foam Ni. Therefore, the adsorption/catalytic oxidation could be a promising technique in the indoor air purification, especially in the case of very low volatile organic compound (VOC; toluene) concentration levels.

Implications: Exploring highly effective adsorptive materials with less expensive costs becomes an urgent issue in the indoor air protection. ACF-20 modified by SiO₂ with Pt/Ni catalysts shows stronger hydrophobicity, thermal stability, and adsorption capacity. This dual-function system composed of the regenerative materials and the combustion catalyst would be a promising technique in the indoor air purification, especially in the case of removal of very low concentration of toluene.     

Effect of the Mn oxidation state and lattice oxygen in Mn-based TiO2 catalysts on the low-temperature selective catalytic reduction of NO by NH3

TiO₂-supported manganese oxide catalysts formed using different calcination temperatures were prepared by using the wet-impregnation method and were investigated for their activity in the low-temperature selective catalytic reduction (SCR) of NO by NH₃ with respect to the Mn valence and lattice oxygen behavior. The surface and bulk properties of these catalysts were examined using Brunauer-Emmett-Teller (BET) surface area, X-ray diffraction (XRD), temperature-programmed reduction (TPR), and temperature-programmed desorption (TPD). Catalysts prepared using lower calcination temperatures, which contained Mn⁴⁺, displayed high SCR activity at low temperatures and possessed several acid sites and active oxygen. The TPD analysis determined that the Brönsted and Lewis acid sites in the Mn/TiO₂ catalysts were important for the low-temperature SCR at 80～160 and 200～350 °C, respectively. In addition, the available lattice oxygen was important for attaining high NO to NO₂ oxidation at low temperatures.

Implications: Recently, various Mn catalysts have been evaluated as SCR catalysts. However, there have been no studies on the relationship of adsorption and desorption properties and behavior of lattice oxygen according to the valence state for manganese oxides (MnO_x). Therefore, in this study, the catalysts were prepared by the wet-impregnation method at different calcination temperatures in order to show the difference of manganese oxidation state. These catalysts were then characterized using various physicochemical techniques, including BET, XRD, TPR, and TPD, to understand the structure, oxidation state, redox properties, and adsorption and desorption properties of the Mn/TiO₂ catalysts.     

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.     

Modeling of methane oxidation in landfill cover soil using an artificial neural network

Knowing the fraction of methane (CH₄) oxidized in landfill cover soils is an important step in estimating the total CH₄ emissions from any landfill. Predicting CH₄ oxidation in landfill cover soils is a difficult task because it is controlled by a number of biological and environmental factors. This study proposes an artificial neural network (ANN) approach using feedforward backpropagation to predict CH₄ oxidation in landfill cover soil in relation to air temperature, soil moisture content, oxygen (O₂) concentration at a depth of 10 cm in cover soil, and CH₄ concentration at the bottom of cover soil. The optimum ANN model giving the lowest mean square error (MSE) was configured from three layers, with 12 and 9 neurons at the first and the second hidden layers, respectively, log-sigmoid (logsig) transfer function at the hidden and output layers, and the Levenberg-Marquardt training algorithm. This study revealed that the ANN oxidation model can predict CH₄ oxidation with a MSE of 0.0082, a coefficient of determination (R ²) between the measured and predicted outputs of up to 0.937, and a model efficiency (E) of 0.8978. To conclude, further developments of the proposed ANN model are required to generalize and apply the model to other landfills with different cover soil properties.

Implications:

To date, no attempts have been made to predict the percent of CH₄ oxidation within landfill cover soils using an ANN. This paper presents modeling of CH₄ oxidation in landfill cover soil using ANN based on field measurements data under tropical climate conditions in Malaysia. The proposed ANN oxidation model can be used to predict the percentage of CH₄ oxidation from other landfills with similar climate conditions, cover soil texture, and other properties. The predicted value of CH₄ oxidation can be used in conjunction with the Intergovernmental Panel on Climate Change (IPCC) First Order Decay (FOD) model by landfill operators to accurately estimate total CH₄ emission and how much it contributes to global warming.     

Comparison of titania nanotubes and titanium dioxide as supports of low-temperature selective catalytic reduction catalysts under sulfur dioxide poisoning

A series of iron–manganese oxide catalysts supported on TiO₂ and titanium nanotubes (TNTs) were studied for low temperature selective catalytic reduction (SCR) of NO with NH₃ in the presence of SO_2. The results showed that the specific surface area and the amount of Brønsted acid sites were highly correlated. The results also demonstrated that higher Mn⁴⁺/Mn³⁺ ratios and larger specific surface areas might be the main reasons for the excellent performance of MnFe-TNTs catalyst after SO₂ poisoning. The SO₂ poisoning effect could be minimized by reducing the GHSV, increasing the reaction temperature, or increasing the [NH₃]/[NO] molar ratio. The results also indicated that the formation of ammonium sulfate had a stronger effect on the NO conversion efficiency as compared to the formation of metal sulfate. Thus operating the low temperature SCR at above 230 ^oC to avoid the formation of ammonium sulfate would be the priority choice when SO₂ poisoning is a concerned issue.?Implications: Low-temperature selective catalytic reduction (SCR) has attracted increasing attention due to that it can reduce the energy consumption for the SCR process employed in industries such as steel plants and glass manufacturing plants. However, it also suffers from the sulfur dioxide (SO₂) poisoning problem. This study investigates the possibility of using titania nanotubes (TNTs) as the support of Mn/Fe bimetal oxide catalysts for low-temperature SCR to reduce the SO₂ poisoning. The results indicated that the MnFe-TNT catalyst can tolerate SO₂ for a longer time as compared with the MnFe-TiO₂ catalyst.     

燃煤烟气低温SCR脱硝中试研究

低温选择性催化还原(SCR)脱硝是国内外脱硝技术研发的热点,但目前主要集中在实验室小试范围,无法完全反映催化剂在实际烟气中的运行状况。在30 t/h循环流化床燃煤锅炉脱硫除尘装置后建设了2 000~5 000 m3/h的SCR脱硝中试装置,经系统研究发现,中试使用的蜂窝式催化剂对SO2和NO具有很强的吸附能力,且反应温度、喷氨速率和气体空速均会影响催化脱硝效率。为期5 d的连续运行实验结果表明,催化剂的脱硝效率一直稳定在30%~50%,并未发现明显的失活,这证明设计除雾除尘器、较大的混合器、混合器与反应器间较长的管路均有利于缓解催化剂因SO2、H2O和飞灰中的碱性金属导致的失活。     

Improving the activity of Mn/TiO2 catalysts through control of the pH and valence state of Mn during their preparation

In this study, the authors investigated the influence of the valence state of Mn on the efficacy of selective catalytic reduction using a Mn-based catalyst. The nitrogen oxides (NO_x) conversion rate of the catalyst was found to be dependent on the type of TiO₂ support employed and on the temperature, as the catalyst showed an excellent conversion of > 80% at a space velocity of 60,000 hr^?1 when the temperature was above 200 °C. Brunauer-Emmett-Teller, X-ray diffraction, and X-ray photoelectron spectroscopy analyses confirmed that catalyst displaying the highest activity contained the Mn⁴⁺ species and that its valence state was highly dependent on the pH during the catalyst preparation.

Implications Recently, various Mn catalysts have been evaluated as selective catalyst reduction (SCR) catalysts. However, in these previous studies, only the reaction characteristics and catalytic activity on the NH₃ SCR over Mn catalysts were evaluated. There have been no studies on the effect of pH during catalyst preparation. Therefore, in this study, the effect of pH during the catalyst preparation process was examined and a new application of the Mn catalysts was proposed based on the current findings.     

Effects of Sulfur Dioxide and Nitric Oxide on Mercury Oxidation and Reduction under Homogeneous Conditions

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.     

Polarity effect of pulsed corona discharge for the oxidation of gaseous elemental mercury

The effect of polarity on the oxidation of Hg⁰ was examined in the presence of O₂ via a pulsed corona discharge (PCD). The experimental result showed no difference in the energy yield of Hg⁰ oxidation at both positive and negative PCDs (∼8 μg Hg W h⁻¹ at following conditions: total flow rate = 2 L min⁻¹ (Hg⁰ = 50 μg N m⁻³, O₂ = 10%, and N₂ balance), temperature = 150 °C, and specific energy density = 5-15 W h N m⁻³). This suggests that the positive PCD process used to control gaseous air pollutants may play an essential key role in Hg⁰ oxidation because it consumes enough energy (∼15 W h N m⁻³) but an electrical precipitator could not because it consumes less energy (∼0.3 W h N m⁻³) to oxidize Hg⁰.     

Unregulated greenhouse gas and ammonia emissions from current technology heavy-duty vehicles

The study presents the measurement of carbonyl, BTEX (benzene, toluene, ethyl benzene, and xylene), ammonia, elemental/organic carbon (EC/OC), and greenhouse gas emissions from modern heavy-duty diesel and natural gas vehicles. Vehicles from different vocations that included goods movement, refuse trucks, and transit buses were tested on driving cycles representative of their duty cycle. The natural gas vehicle technologies included the stoichiometric engine platform equipped with a three-way catalyst and a diesel-like dual-fuel high-pressure direct-injection technology equipped with a diesel particulate filter (DPF) and a selective catalytic reduction (SCR). The diesel vehicles were equipped with a DPF and SCR. Results of the study show that the BTEX emissions were below detection limits for both diesel and natural gas vehicles, while carbonyl emissions were observed during cold start and low-temperature operations of the natural gas vehicles. Ammonia emissions of about 1 g/mile were observed from the stoichiometric natural gas vehicles equipped with TWC over all the driving cycles. The tailpipe GWP of the stoichiometric natural gas goods movement application was 7% lower than DPF and SCR equipped diesel. In the case of a refuse truck application the stoichiometric natural gas engine exhibited 22% lower GWP than a diesel vehicle. Tailpipe methane emissions contribute to less than 6% of the total GHG emissions.

Implications: Modern heavy-duty diesel and natural gas engines are equipped with multiple after-treatment systems and complex control strategies aimed at meeting both the performance standards for the end user and meeting stringent U.S. Environmental Protection Agency (EPA) emissions regulation. Compared to older technology diesel and natural gas engines, modern engines and after-treatment technology have reduced unregulated emissions to levels close to detection limits. However, brief periods of inefficiencies related to low exhaust thermal energy have been shown to increase both carbonyl and nitrous oxide emissions.     

Size Distribution of Particles That May Contribute to Soiling of Material Surfaces

ABSTRACT

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

IMPLICATIONS Recently, NMO and manganese oxide have been reported as SCR catalysts. They usually have only reported the reaction characteristics and catalytic activity on the NH₃ SCR over NMO or manganese/metal oxide catalysts. There are no studies about the effect of addition of V to NMO. Therefore, this study investigates the catalytic activity and reaction characteristics on the NH₃ SCR over NMO and V/NMO, and a new application is proposed based on the conclusions of this study.     

Characteristics of penicillin bacterial residue

A hybrid selective noncatalytic reduction/selective catalytic reduction (SNCR/SCR) system that uses two types of technology, low-temperature SCR process and SNCR process, was designed to develop nitrogen oxide (NO_x) reduction technology. SCR was conducted with space velocity (SV) = 2400 hr^?1 and hybrid SNCR/SCR with SV = 6000 hr^?1, since the study focused on reducing the amount of catalyst and both achieved 98% NO_x reduction efficiency. Characteristics of NO_x reduction by NH₃ were studied for low-temperature SCR system at 150 °C using Mn-V₂O₅/TiO₂ catalyst. Mn-added V₂O₅/TiO₂ catalyst was produced, and selective catalyst reduction of NO_x by NH₃ was experimented. NO_x reduction rate according to added Mn content in Mn-V₂O₅/TiO₂ catalyst was studied with varying conditions of reaction temperature, normalized stoichiometric ratio (NSR), SV, and O₂ concentration. In the catalyst experiment according to V₂O₅ concentration, 1 wt.% V₂O₅ catalyst showed the highest NO_x reduction rate: 98% reduction at temperature window of 200~250 °C. As a promoter of the V₂O₅ catalyst, 5 wt.% Mn was added, and the catalyst showed 47~90% higher efficiency even with low temperatures, 100~200 °C. Mn-V₂O₅/TiO₂ catalyst, prepared by adding 5 wt.% Mn in V₂O₅/TiO₂ catalyst, showed increments of catalyst activation at 150 °C as well as NO_x reduction. Mn-V₂O₅/TiO₂ catalyst showed 8% higher rate for NO_x reduction compared with V₂O₅/TiO₂ catalyst in 150 °C SCR. Thus, (5 wt.%)Mn-(1 wt.%)V₂O₅/TiO₂ catalyst was applied in SCR of hybrid SNCR/SCR system of low temperature at 150 °C. Low-temperature SCR hybrid SNCR/SCR (150 °C) system and hybrid SNCR/SCR (350 °C) showed 91~95% total reduction rate with conditions of SV = 2400~6000 hr^?1 SCR and 850~1050 °C SNCR, NSR = 1.5~2.0, and 5% O₂. Hybrid SNCR/SCR (150 °C) system proved to be more effective than the hybrid SNCR/SCR (350 °C) system at low temperature.

Implications:?NO_x control is very important, since they are the part of greenhouse gases as well as the cause of acid rain and ozone hole. A technology, so-called hybrid SNCR/SCR process, was tested using Mn-V₂O₅/TiO₂ monolithic catalyst for NO_x reduction, and the method is promising. The results of this study would provide some ideas to parties such as policy makers, environmental engineers, and so on.     

Revisiting nitrous acid (HONO) emission from on-road vehicles: A tunnel study with a mixed fleet

Nitrous acid (HONO) is an important precursor of OH radicals in the atmosphere. In urban areas, emissions from vehicles are the main source of air pollutants, including reactive nitrogen. Previously reported emission ratios of HONO (HONO/NO_x) from vehicles were measured in the late 1990s and need to be updated due to the significant changes in emission control technologies. We measured the emission ratio of a fleet of vehicles (38% diesel on average) from March 11 to 21, 2015, in a road tunnel in Hong Kong. The emission ratio of 1.24% (±0.35%) obtained is greater than the commonly adopted 0.8% or 0.3%. The elevated emission ratio is found to be related to the presence of vehicles equipped with diesel particle filters (DPFs). Positive correlation between HONO and black carbon (BC) shows that HONO and BC were emitted together, while the lack of correlation or even anticorrelation between HONO/NO_x and BC indicates that the BC-mediated conversion of NO₂ to HONO in the dark was insignificant in the immediate vicinity of the emission sources.

Implications: Vehicular emission is a key source for HONO in the urban atmosphere. However, the most commonly used emission ratio HONO/NO_x in modeling studies was measured more than 15 years ago. Our tunnel study suggests that a mixed fleet nowadays has a higher emission ratio, possibly because of the diesel particle filter (DPF) retrofit program and the growing share of Euro IV or more advanced diesel vehicles. Our study also provides new insight into the role of black carbon in HONO formation from vehicles.     

Research and proposal on selective catalytic reduction reactor optimization for industrial boiler

The advanced computational fluid dynamics (CFD) software STAR-CCM+ was used to simulate a denitrification (De-NOx) project for a boiler in this paper, and the simulation result was verified based on a physical model. Two selective catalytic reduction (SCR) reactors were developed: reactor 1 was optimized and reactor 2 was developed based on reactor 1. Various indicators, including gas flow field, ammonia concentration distribution, temperature distribution, gas incident angle, and system pressure drop were analyzed. The analysis indicated that reactor 2 was of outstanding performance and could simplify developing greatly. Ammonia injection grid (AIG), the core component of the reactor, was studied; three AIGs were developed and their performances were compared and analyzed. The result indicated that AIG 3 was of the best performance. The technical indicators were proposed for SCR reactor based on the study.

Implications: Flow filed distribution, gas incident angle, and temperature distribution are subjected to SCR reactor shape to a great extent, and reactor 2 proposed in this paper was of outstanding performance; ammonia concentration distribution is subjected to ammonia injection grid (AIG) shape, and AIG 3 could meet the technical indicator of ammonia concentration without mounting ammonia mixer. The developments above on the reactor and the AIG are both of great application value and social efficiency.