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.     

The electrochemical selective reduction of NO using CoSe2@CNTs hybrid

Converting the NO from gaseous pollutant into NH₄ ⁺ through electrocatalytical reduction using cost-effective materials holds great promise for pollutant purifying and resources recycling. In this work, we developed a highly selective and stable catalyst CoSe₂ nanoparticle hybridized with carbon nanotubes (CoSe₂@CNTs). The CoSe₂@CNTs hybrid catalysts performed an extraordinary high selectivity for NH₄ ⁺ formation in NO electroreduction with minimal N₂O production and H₂ evolution. The specific spatial structure of CoSe₂ is conductive to the predominant formation of N-H bond between the N from adsorbed NO and H and inhibition of N-N formation from adjacent adsorbed NO. It was also the first time to convert the coordinated NO into NH₄ ⁺ using non-noble metal catalysis. Moreover, the original concept of employing CoSe₂ as eletrocatalyst for NO hydrogenation presented in this work can broaden horizons and provide new dimensions in the design of new highly efficient catalysts for NH₄ ⁺ synthesis in aqueous solution.

     

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.     

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。     

Superior Pillared Clay Catalysts for Selective Catalytic Reduction of Nitrogen Oxides for Power Plant Emission Control

ABSTRACT

Fe³+-, Cr³+-, Cu²+-, Mn²+-, Co²+-, and Ni²+-exchanged Al₂O₃-pillared interlayer clay (PILC) or TiO₂-PILC catalysts are investigated for the selective catalytic reduction (SCR) of nitric oxide by ammonia in the presence of excess oxygen. Fe³+-exchanged pillared clay is found to be the most active. The catalytic activity of Fe-TiO₂-PILC could be further improved by the addition of a small amount of cerium ions or cerium oxide. H₂O and SO₂ increase both the activity and the product selectivity to N₂. The maximum activity on the Ce-Fe-TiO₂-PILC is more than 3 times as active as that on a vanadium catalyst. Moreover, compared to the V₂O₅-WO₃/TiO₂ catalyst, the Fe-TiO₂-PILC catalysts show higher N₂/N₂O product selectivities and substantially lower activities (by ~85%) for SO₂ oxidation to SO₃ under the same reaction conditions. A 100-hr run in the presence of H₂O and SO₂ for the CeO₂/Fe-TiO₂-PILC catalyst showed no decrease in activity.     

Deactivation of the Vanadia Catalyst in the Selective Catalytic Reduction Process

Results are summarized of a comprehensive study of the effects on the SCR process of all major possible poisons encountered in the combustion gases from U.S. coals. A general rule evolved from this study Is that the effect of the additive on the catalyst activity Is directly related to the basicity of the additive; poisoning Is caused by the basicity. Quantitative effects are presented, while a qualitative summary is given as follows: strong poisons-alkali metal oxides; weak poisons-oxides of alkaline earth metals, arsenic, lead phosphorus and chlorides of strong alkaline metals. SO₂ is a promoter due to its acidity. HCI, although acidic, reacts with both NH₃ (forming NH₄CI) and V₂O₅ (forming VCI₂ and VCI₃) and consequently strongly deactivates the SCR reaction.

A summary is also given for a theoretical and experimental study of the monolithic honeycomb reactor using both undoped and poison-doped catalysts. The results showed that the reactor performance can be predicted directly from the intrinsic catalyst activity through a model.     

改进钒基SCR脱硝催化剂的抗碱金属中毒性能

以锐钛矿型二氧化钛和钛钨粉(5%WO3-TiO2)为载体,制备了系列钒和钨负载量不同的钒钛催化剂,考察碱金属和碱土金属(钾、钠和钙)对催化剂在氨选择性催化还原(NH3-SCR)氮氧化物反应中催化活性的影响。钾、钠和钙对钒钛催化剂的中毒影响大小顺序为钾钠钙。提高钒钛催化剂中钒的含量可显著提高催化剂的SCR活性和抗碱金属中毒性能,但高钒负载量(4.5%V2O5)造成催化剂氮气选择性明显下降,氧化亚氮生成显著增加。钨的添加有利于提高钒钛催化剂的低温活性和抗碱金属中毒性能,对氮气选择性无明显影响。     

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.     

NOx Removal with Combined Selective Catalytic Reduction and Selective Noncatalytic Reduction: Pilot-Scale Test Results

Pilot-scale tests were conducted to develop a combined nitrogen oxide (NO_x) reduction technology using both selective catalytic reduction (SCR) and selective noncatalytic reduction (SNCR). A commercially available vanadium- and titanium-based composite honeycomb catalyst and enhanced urea (NH₂CONH₂) were used with a natural-gas-fired furnace at a NO_x concentration of 110 ppm. Changes in SNCR chemical injection temperature and stoichiometry led to varying levels of post-furnace ammonia (NH₃), which acts as the reductant feed to the downstream SCR catalyst. The urea-based chemical could routinely achieve SNCR plus SCR total NO_x reductions of 85 percent with less than 3 ppm NH₃ slip at reductant/NO_x stoichiometries ranging from about 1.5 to 2.5 and SCR space velocities of 18,000 to 32,000 h^?1. This pilot-scale research has shown that SNCR and SCR can be integrated to achieve high NO_x removal. SNCR provides high temperature reduction of NO_x followed by further removal of NO_x and minimization of NH₃ slip by a significantly downsized (high-space velocity) SCR.     

Selective Reduction of Nitrogen Oxides In Combustion Flue Gases

The body of Information presented in this paper is directed to those Individuals concerned with the removal of NO_x in combustion flue gases. A catalytic process for the selective reduction of nitrogen oxides by ammonia has been investigated. Efforts were made toward the development of catalysts resistant to SO_x poisoning. Nitrogen oxides were reduced over various metal oxide catalysts in the presence or absence of SO_x(SO₂ and SO₃). Catalysts consisting of oxides of base metals (for example, Fe₂O₃) were easily poisoned by SO₃, forming sulfates of the base metals. A series of catalysts which are not susceptible to the SO_x poisoning has been developed. The catalysts possess a high activity and selectivity over a wide range of temperatures, 250—450°C. The catalysts were tested in a pilot plant which treated a flue gas containing 110-150 ppm NO_x, 660-750 ppm SO₂, and 40-90 ppm SO₃. The pilot plant was operated at 350°C and at a space velocity of 10,000 h^-1. The removal of nitrogen oxides was more than 90% for several months.

A mechanism of the NO-NH₃ reaction has also been investigated. It is found that NO reacts with NH₃ at a 1:1 mole ratio in the presence of oxygen and the reaction is completely inhibited by the absence of oxygen. The experimental data show that the NO-NH₃ reaction in the presence of oxygen is represented byNO + NH₃ + 1/4 O₂ = N₂ + 3/2 H₂O.     

Catalytic destruction of pentachlorobenzene in simulated flue gas by a V2O5-WO3/TiO2 catalyst

Pentachlorobenzene (PeCB) in simulated flue gas was destructed by a commercial V₂O₅-WO₃/TiO₂ catalyst in this study. The effects of reaction temperature, oxygen concentration, space velocity and some co-existing pollutants on PeCB conversion were investigated. Furthermore, a possible mechanism for the oxidation of PeCB over the vanadium oxide on the catalysts was proposed. Results show that the increase of gas hourly space velocity (GHSV) and the decrease of operating temperature both resulted in the decrease of PeCB removal over the catalyst, while the effect of the oxygen content in the range of 5-20% (v/v) on PeCB conversion was negligible. PeCB decomposition could be obviously affected by the denitration reactions under the conditions because of the positive effect of NO but negative effect of NH₃. The introduction of SO₂ caused the catalyst poisoning, probably due to the sulfur-containing species formed and deposited on the catalyst surface. The PeCB molecules were first adsorbed on the catalyst surface, and then oxidized into the non-aromatic acyclic intermediates, low chlorinated aromatics and maleic anhydride.     

Atmospheric concentrations of ammonia and ammonium at an agricultural site in the southeast United States

In this study, we present ∼1 yr (October 1998–September 1999) of 12-hour mean ammonia (NH₃), ammonium (NH₄⁺), hydrochloric acid (HCl), chloride (Cl⁻), nitrate (NO₃⁻), nitric acid (HNO₃), nitrous acid (HONO), sulfate (SO₄²⁻), and sulfur dioxide (SO₂) concentrations measured at an agricultural site in North Carolina's Coastal Plain region. Mean gas concentrations were 0.46, 1.21, 0.54, 5.55, and 4.15 μg m⁻³ for HCl, HNO₃, HONO, NH₃, and SO₂, respectively. Mean aerosol concentrations were 1.44, 1.23, 0.08, and 3.37 μg m⁻³ for NH₄⁺, NO₃⁻, Cl⁻, and SO₄²⁻, respectively. Ammonia, NH₄⁺, HNO₃, and SO₄²⁻ exhibit higher concentrations during the summer, while higher SO₂ concentrations occur during winter. A meteorology-based multivariate regression model using temperature, wind speed, and wind direction explains 76% of the variation in 12-hour mean NH₃ concentrations (n=601). Ammonia concentration increases exponentially with temperature, which explains the majority of variation (54%) in 12-hour mean NH₃ concentrations. Dependence of NH₃ concentration on wind direction suggests a local source influence. Ammonia accounts for >70% of NH_x (NH_x=NH₃+NH₄⁺) during all seasons. Ammonium nitrate and sulfate aerosol formation does not appear to be NH₃ limited. Sulfate is primarily associated ammonium sulfate, rather than bisulfate, except during the winter when the ratio of NO₃⁻–NH₄⁺ is ∼0.66. The annual average NO₃⁻–NH₄⁺ ratio is ∼0.25.     

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.     

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.     

Photochemical model performance for PM2.5 sulfate,nitrate, ammonium,and precursor species SO2, HNO3, and NH3 at background monitor locations in the central and eastern United States

Health studies have shown premature death is statistically associated with exposure to particulate matter <2.5 μm in diameter (PM2.5). The United States Environmental Protection Agency requires all States with PM2.5 non-attainment counties or with sources contributing to visibility impairment at Class I areas to submit an emissions control plan. These emission control plans will likely focus on reducing emissions of sulfur oxides and nitrogen oxides, which form two of the largest chemical components of PM2.5 in the eastern United States: ammonium sulfate and ammonium nitrate. Emission control strategies are simulated using three-dimensional Eulerian photochemical transport models.A monitor study was established using one urban (Detroit) and nine rural locations in the central and eastern United States to simultaneously measure PM2.5 sulfate ion (SO₄²⁻), nitrate ion (NO₃⁻), ammonium ion (NH₄⁺), and precursor species sulfur dioxide (SO₂), nitric acid (HNO₃), and ammonia (NH₃). This monitor study provides a unique opportunity to assess how well the modeling system predicts the spatial and temporal variability of important precursor species and co-located PM2.5 ions, which is not well characterized in the central and eastern United States.The modeling system performs well at estimating the PM2.5 species, but does not perform quite as well for the precursor species. Ammonia is under-predicted in the coldest months, nitric acid tends to be over-predicted in the summer months, and sulfur dioxide appears to be systematically over-predicted. Several indicators of PM2.5 ammonium sulfate and ammonium nitrate formation and chemical composition are estimated with the ambient data and photochemical model output. PM2.5 sulfate ion is usually not fully neutralized to ammonium sulfate in ambient measurements and is usually fully neutralized in model estimates. The model and ambient estimates agree that the ammonia study monitors tend to be nitric acid limited for PM2.5 nitrate formation. Regulatory strategies in this part of the country should focus on reductions in NO_X rather than ammonia to control PM2.5 ammonium nitrate.     

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.     

Role of ammonia chemistry and coarse mode aerosols in global climatological inorganic aerosol distributions

We use an inorganic aerosol thermodynamic equilibrium model in a three-dimensional chemical transport model to understand the roles of ammonia chemistry and natural aerosols on the global distribution of aerosols. The thermodynamic equilibrium model partitions gas-phase precursors among modeled aerosol species self-consistently with ambient relative humidity and natural and anthropogenic aerosol emissions during the 1990s.Model simulations show that accounting for aerosol inorganic thermodynamic equilibrium, ammonia chemistry and dust and sea-salt aerosols improve agreement with observed SO₄, NO₃, and NH₄ aerosols especially at North American sites. This study shows that the presence of sea salt, dust aerosol and ammonia chemistry significantly increases sulfate over polluted continental regions. In all regions and seasons, representation of ammonia chemistry is required to obtain reasonable agreement between modeled and observed sulfate and nitrate concentrations. Observed and modeled correlations of sulfate and nitrate with ammonium confirm that the sulfate and nitrate are strongly coupled with ammonium. SO₄ concentrations over East China peak in winter, while North American SO₄ peaks in summer. Seasonal variations of NO₃ and SO₄ are the same in East China. In North America, the seasonal variation is much stronger for NO₃ than SO₄ and peaks in winter.Natural sea salt and dust aerosol significantly alter the regional distributions of other aerosols in three main ways. First, they increase sulfate formation by 10–70% in polluted areas. Second, they increase modeled nitrate over oceans and reduce nitrate over Northern hemisphere continents. Third, they reduce ammonium formation over oceans and increase ammonium over Northern Hemisphere continents. Comparisons of SO₄, NO₃ and NH₄ deposition between pre-industrial, present, and year 2100 scenarios show that the present NO₃ and NH₄ deposition are twice pre-industrial deposition and present SO₄ deposition is almost five times pre-industrial deposition.     

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.     

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.     

The water-soluble ionic composition of PM2.5 in Shanghai and Beijing,China

A year-long field study to characterize the ionic species in PM2.5 was carried out in Shanghai and Beijing, China, in 1999–2000. Weekly samples of PM2.5 were collected using a special low flow rate (0.4 l min⁻¹) sampler. In Shanghai, SO₄²⁻ NO₃⁻ and NH₄⁺ were the dominant ionic species, which accounted for 46%, 18% and 17% of the total mass of ions, respectively. Local SO₂ emissions were an important source of SO₄²⁻ in PM2.5 because the SO₄²⁻ concentration was correlated with the SO₂ concentration (r=0.66). The relatively stable SO₄²⁻/SO₂ mass ratio over a large range of temperatures suggests that gas-phase oxidation of SO₂ played a minor role in the formation of SO₄²⁻. The sum of SO₄²⁻ and NO₃⁻ was highly correlated with NH₄⁺ (r=0.96), but insufficient ammonium was present to totally neutralize the aerosol. In Beijing, SO₄²⁻, NO₃⁻ and NH₄⁺ were also the dominant ionic species, constituting 44%, 25% and 16% of the total mass of water-soluble ions, respectively. Local SO₂ emissions were an important source of SO₄²⁻ in the winter since SO₄²⁻ was correlated with SO₂ (r=0.83). The low-mass SO₄²⁻/SO₂ ratio (0.27) during winter, which had low humidity, suggests that gas-phase oxidation of SO₂ was a major route of sulfate formation. In the summer, however, much higher mass ratios of SO₄²⁻/SO₂ (5.6) were observed and were ascribed to in-cloud sulfate formation. The annual average ratio of NO₃⁻/SO₄²⁻ was 0.4 and 0.6 in Shanghai and in Beijing, respectively, suggesting that stationary emissions were still a dominant source in these two cities.