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.     

Experimental and modeling study of the effect of CO and H2 on the urea DeNO(x) process in a 150kW laboratory reactor

An experimental and modeling investigation has been performed to study the effect of process additives, H2 and CO on NO(x) removal from flue gases by a selective non-catalytic reduction process using urea as a reducing agent. Experiments were performed with a flow reactor in which flue gas was generated by the combustion of propane in air at 3% excess oxygen and the desired levels of initial NO(x) (500ppm) were achieved by doping the flame with ammonia. Experiments were performed throughout the temperature range of interest, i.e. from 850 to 1200 degrees C for investigation of the effects of the process additives on the performance of aqueous urea DeNO(x). Subsequently, computational kinetic modeling with SENKIN code was performed to analyze the performance of urea providing a direct comparison of modeling prediction with experimental measurements. With CO addition, a downwards shift of 215 degrees C in the peak reduction temperature from 1125 to 910 degrees C was observed during the experimentation while the kinetic modeling suggests it to be 150 degrees C, i.e. from 1020 to 870 degrees C. The addition of H2 impairs the peak NO(x) reduction but suggests a low temperature application of the process. A downward shift of 250 degrees C in the peak reduction temperature, from 1020 to 770 degrees C, was observed during kinetic modeling studies. The kinetic modeling shows a good qualitative agreement with the experimental observations and reveals additional information about the process.     

TiO2 nanotube-supported cu as the catalyst for selective NO reduction with NH3

Catalyst supports composed of titanate nanotubes were prepared from hydrothermal treatment on TiO2 nanoparticles in NaOH followed by HCl washing. The nanotubes exhibited well-defined TiO2 anatase phase after calcination at 400 degrees C. The nanotube aggregates and other commercially available TiO2 nanoparticles, all with surface areas >300 m(2)/g, were impregnated with Cu and examined in selective catalytic reduction of NO with NH3. In catalyst preparation, the nanotubes were found to be more thermally stable than nanoparticles, withstanding agglomeration at elevated temperatures. The Cu species supported on the nanotubes showed a higher catalytic activity than those supported on the nanoparticles. Analysis with temperature programmed reduction, X-ray photoelectron spectroscopy, and NO adsorption reflected that the layered-titanate feature of the tube wall was advantageous for even distribution of the Cu species, thus leading to the high-catalytic activity of the tubular Cu/TiO2 catalyst.     

NO removal by reducing agents and additives in the selective non-catalytic reduction (SNCR) process

The effect of the additives on the selective non-catalytic reduction (SNCR) reaction has been determined in a three-stage laboratory scale reactor. The optimum reaction temperature is lowered and the reaction temperature window is widened with increasing concentrations of the gas additives (CO, CH4). The optimum reaction temperature is lowered and the maximum NO removal efficiency decreases with increasing the concentration of alcohol additives (CH3OH, C2H5OH). The addition of phenol lowers the optimum reaction temperature about 100-150 degrees C similar to that of the toluene addition. The volatile organic compounds (VOCs: C6H5OH, C7H8) can be utilized in the SNCR process to enhance NO reduction and removed at the same time. A previously proposed simple kinetic model can successfully apply the NO reduction by NH3 and the present additives.     

还原剂对Ag/Al2O3催化剂上NO还原的影响

在富氧条件下,研究了CH4、C3H8、C 3H6、C8H18、CH 3OH、C2H5OH,以及C3H6与CH3OH、C3H6与C2H5OH组合作还原剂时,在Ag/Al2O3催化剂上NO的还原活性.结果表明,不同碳氢化合物还原NO的活性温度存在较大的差异.SO2的存在会导致CH3OH还原NO的活性提高,而其他碳氢化合物还原NO的活性降低.随着还原剂浓度提高,NOx转化率增大,不过,过高的还原剂浓度对NO还原不利.组合使用CH3OH与C3H6或C2H5OH与C3H6作为还原剂,能显著拓宽活性温度范围.     

催化法脱除NO_x的研究进展

如何有效地脱除氮氧化物是目前空气污染治理的一个重点和难点 ,催化还原和催化分解是目前研究得较多的脱除氮氧化物方法。本文从催化剂创新和催化反应体系的发展等方面对上述过程研究、应用情况进行了总结 ,并根据作者的认识进行了适当的评述。     

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.     

Removal of nitric oxide in a biotrickling filter under thermophilic condition using Chelatococcus daeguensis

The development of a thermophilic biotrickling filter (BTF) system to inoculate a newly isolated strain of Chelatococcus daeguensis TAD1 for the effective treatment of nitric oxide (NO) is described. A bench-scale BTF was run under high concentrations of NO and 8% O2 in thermophilic aerobic environment. A novel aerobic denitrifier Chelatococcus daeguensis TAD1 was isolated from the biofilm of an on-site biotrickling filter and it showed a denitrifying capability of 96.1% nitrate removal rate in a 24 h period in aerobic environment at 50 degrees C, with no nitrite accumulation. The inlet NO concentration fluctuated between approximately 133.9 and 669.6 mg m-3 and kept on a steady NOx removal rate above 80% in an oxygen stream of 8%. The BTF system was able to consistently remove 80-93.7% NO when the inlet NO was 535.7 mg m-3 in an oxygen stream of 2-20%. The biological removal efficiency of NO at 50 degrees C is higher than that at 25 degrees C, suggesting that the aerobic denitrifier TAD1 display well denitrification performance under thermophilic condition. Starvation for 2, 4 and 8 days resulted in the re-acclimation times of Chelatococcus daeguensis TAD1 ranging between 4 and 16 hours. A longer recovery time than that for weekend shutdown will be required when a longer starvation occurs. The results presented here demonstrate the feasibility of biotrickling filter for the thermophilic removal of NOx from gas streams. Implications: A novel denitrifier Chelatococcus daeguensis TAD1 was isolated from an on-site biotrickling filter in aerobic environment at 50 degrees C. To date, C. daeguensis has not been previously reported to be an aerobic denitrifier. In this study, a thermophilic biotrickling filter system inoculated with Chelatococcus daeguensis TADI for treatment of nitric oxide is developed. In coal-fired power plants, influent flue gas stream for nitrogen oxides (NOx) removal typically exhibit temperatures between 50 and 60 degrees C. Traditionally, cooling gases to below 40 degrees C prior to biological treatment is inevitable, which is costly. Therefore, the application ofthermophilic microorganisms for the removal of nitric oxide (NO) at this temperature range would offer great savings and would greatly extend the applicability ofbiofilters and biotrickling filters. Until now there has not been any study published about thermophilic biological treatment of NO under aerobic condition.     

Experimental and modeling study of the effect of CH(4) and pulverized coal on selective non-catalytic reduction process

The reduction of nitric oxide using ammonia combined with methane and pulverized coal additives has been studied in a drop tube furnace reactor. Simulated flue gas with 1000ppm NO(x) and 3.4% excess oxygen was generated by cylinder gas. Experiments were performed in the temperature range of 700-1200 degrees C to investigate the effects of additives on the DeNO(x) performance. Subsequently, a kinetic mechanism was modified and validated based on experimental results, and a computational kinetic modeling with CHEMKIN was conducted to analyze the secondary pollutants. For both methane and pulverized coal additives, the temperature window is shifted towards lower temperatures. The appropriate reaction temperature is shifted to about 900 and 800 degrees C, respectively with 1000ppm methane and 0.051gmin(-1) pulverized lignite coal. The addition of methane and pulverized coal widens the temperature window towards lower temperature suggesting a low temperature application of the process. Furthermore, selective non-catalytic reduction (SNCR) reaction rate is accelerated evidently with additives and the residence time to complete the reaction is shortened distinctly. NO(x) reduction efficiency with 80% is achieved in about 0.3s without additive at 1000 degrees C. However, it is achieved in only about 0.2s with 100ppm methane as additive, and only 0.07 and 0.05s are needed respectively for the cases of 500 and 1000ppm methane. The modified kinetic modeling agrees well with the experimental results and reveals additional information about the process. Investigation on the byproducts where NO(2) and N(2)O were analyzed by modeling and the others were investigated by experimental means indicates that emissions would not increase with methane and pulverized coal additions in SNCR process and the efficacious temperature range of SNCR reaction is widened approximately with 100 degrees C.     

SCR脱硝蜂窝陶瓷催化剂载体的制备

以二氧化钛、氧化铝作为主要原料,通过柱塞式挤压成型法制备了0.15 m×0.15 m×1 m规格的蜂窝陶瓷催化剂载体。通过对不同原料组成的载体性能对比,研究了各配方组分对载体性能的影响。为了提高载体活性,在21号配方的基础上加入A、B 2种商用造孔剂,考察了不同造孔剂的造孔性能。考察了蜂窝陶瓷载体负载催化剂后选择性催化还原(SCR)NO的活性,结果负载催化剂后的载体21a的在300℃时NO转化率达到最大96.5%。     

Catalytic effects by metal oxides on the formation and degradation of chlorinated aromatic compounds in fly ash

Polychlorinated benzenes, dibenzo-p-dioxins (PCDD), and dibenzofurans (PCDF) may be formed below the combustion temperature in fly ash from municipal solid waste incinerators (MSWI). Copper catalyzes this formation, possibly by the Deacon reaction. Many other elements are also Deacon catalysts or promoters, and here we report results from a statistically designed experiment with 15 metal oxides added to fly ash and heated at 300 degrees C for 2h in an air atmosphere. A resolution IV fractional factorial design with four replicates was completed in 36 runs with the oxides of magnesium, yttrium, titanium, vanadium, niobium, chromium, molybdenum, tungsten, manganese, iron, cobalt, nickel, copper, zinc, and tin. All samples were analyzed for chlorinated benzenes and the results were evaluated by analysis of variance. The addition of copper significantly increased the amounts of the chlorinated benzenes, while cobalt, chromium and vanadium decreased the net formation. The oxides of zinc and iron seemed to have a slightly positive and negative effect respectively. The findings in this study seem to corroborate our previously reported results regarding the different catalytic effects of copper and chromium, and lack of a significant effect by nickel. Besides chromium, it also identifies cobalt and vanadium as potent catalysts for oxidative degradation of the chlorinated aromatic compounds found in MSWI fly ash.     

Formate species in the low-temperature oxidation of dimethyl ether

The oxidation of dimethyl ether (DME, 340 ppm in 10% O2) has been studied experimentally in an atmospheric pressure laminar flow reactor in the temperature range from 240 degrees C to 700 degrees C for residence times in the range 2-4 s. The influence of nitric oxide additions up to 620 ppm to the feed gases has also been investigated. Products of reaction were determined by FTIR. In the absence of NO, reaction is first detected at about 260 degrees C. The products in the low-temperature region include formaldehyde (HCHO), and formic acid (HCOOH). The addition of NO leads to the appearance of methyl formate (CH3OCHO). While the overall behaviour of the system can be explained qualitatively in terms of typical low-temperature hydrocarbon ignition, recently published chemical kinetic models for DME ignition do not allow for the formation of these formate species. We find no experimental evidence for the formation of hydroperoxymethyl formate (HPMF, HOOCH2OCHO) which is predicted by the models to be a significant stable intermediate at temperatures below 350 degrees C. Since both formic acid and methyl formate have potentially harmful health effects, these observations may have significant implications for use of DME as a diesel fuel.     

Evaluation of Cu-PPHs as active catalysts for the SCR process to control NOx emissions from heavy duty diesel vehicles

Copper based catalysts supported on mesoporous materials, which were in turn based on a surfactant expanded zirconium phosphate for the formation of silica galleries in the interlayer space, were prepared by the impregnation method. They were then characterised and tested in the selective catalytic reduction of NO with ammonia as active catalysts for the control of the NOx emissions from heavy duty vehicles. Copper catalysts displayed a high catalytic performance, even in the presence of 14% (v/v) of H2O and 100 ppm of SO2. They also displayed improved catalytic behaviour when compared to a CuZSM5 catalyst.     

A review of the catalysts used in the reduction of NO by CO for gas purification

The reduction of NO by the CO produced by incomplete combustion in the flue gas can remove CO and NO simultaneously and economically. However, there are some problems and challenges in the industrial application which limit the application of this process. In this work, noble metal catalysts and transition metal catalysts used in the reduction of NO by CO in recent years are systematically reviewed, emphasizing the research progress on Ir-based catalysts and Cu-based catalysts with prospective applications. The effects of catalyst support, additives, pretreatment methods, and physicochemical properties of catalysts on catalytic activity are summarized. In addition, the effects of atmosphere conditions on the catalytic activity are discussed. Several kinds of reaction mechanisms are proposed for noble metal catalysts and transition metal catalysts. Ir-based catalysts have an excellent activity for NO reduction by CO in the presence of O₂. Cu-based bimetallic catalysts show better catalytic performance in the absence of O₂, in that the adsorption and dissociation of NO can occur on both oxygen vacancies and metal sites. Finally, the potential problems existing in the application of the reduction of NO by CO in industrial flue gas are analyzed and some promising solutions are put forward through this review.

     

Preparation of the Mn/Co mixed oxide catalysts for low-temperature CO oxidation reaction

The Mn/Co mixed powders with various Mn/Co molar ratios were prepared by the coprecipitation method and used in low-temperature CO oxidation. The physicochemical characteristics of these powders were characterized using the Brunauer-Emmett-Teller (BET), X-ray diffraction (XRD), temperature-programmed reduction (TPR), and scanning electron microscopy (SEM) analyses. The results demonstrated that the Mn/Co molar ratio significantly affected both the textural and catalytic properties and the sample with a Mn/Co = 1:1 possessed a BET area of 123.7 m²g⁻¹ with a small mean pore size of 6.44 nm. The catalytic results revealed that the pure cobalt and manganese catalysts possessed the low catalytic activity and the pure Co catalyst is not active at temperatures lower than 140 °C. The highest catalytic activity was observed for the catalyst with a Mn/Co = 1. The obtained results showed that the incorporation of Pd into the Mn/Co catalyst significantly enhanced the catalytic activity for oxidation of carbon monoxide and the highest CO conversion was observed for the catalyst with 1 wt.% Pd and this catalyst exhibited a CO conversion of 100% at 80 ^°C.

     

新型MnOx/CNTs催化剂低温选择性催化还原NO

采用等体积浸渍法制备了MnOx/CNTs催化剂,用于低温NH3选择性催化还原（SCR）NO的实验。使用BET,FT-IR,TEM和XRD对催化剂进行表征,结果表明：碳纳米管经混酸超声分散,增加了羧基活性基团,锰氧化物颗粒分布较均匀。在模拟烟气条件下,考察了催化剂的MnOx负载量、煅烧温度及质量和烟气流速比（W/F）对NO脱除率的影响。煅烧温度为773 K,MnOx负载量为10%时,NO脱除率达到98.56%;W/F为2-3 mg/（mL·min^-1）时NO的脱除率更高。     

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.     

The Southeastern Aerosol Research and Characterization Study, part 3: continuous measurements of fine particulate matter mass and composition

Deployment of continuous analyzers in the Southeastern Aerosol Research and Characterization Study (SEARCH) network began in 1998 and continues today as new technologies are developed. Measurement of fine particulate matter (PM2.5) mass is performed using a dried, 30 degrees C tapered element oscillating microbalance (TEOM). TEOM measurements are complemented by observations of light scattering by nephelometry. Measurements of major constituents include: (1) SO4(2-) via reduction to SO2; (2) NH4+ and NO3- via respective catalytic oxidation and reduction to NO, (3) black carbon (BC) by optical absorption, (4) total carbon by combustion to CO2, and (5) organic carbon by difference between the latter two measurements. Several illustrative examples of continuous data from the SEARCH network are presented. A distinctive composite annual average diurnal pattern is observed for PM2.5 mass, nitrate, and BC, likely indicating the influence of traffic-related emissions, growth, and break up of the boundary layer and formation of ammonium nitrate. Examination of PM2.5 components indicates the need to better understand the continuous composition of the unmeasured "other" category, because it contributes a significant fraction to total mass during periods of high PM2.5 loading. Selected episodes are presented to illustrate applications of SEARCH data. An SO2 conversion rate of 0.2%/hr is derived from an observation of a plume from a coal-fired power plant during early spring, and the importance of local, rural sources of NH3 to the formation of ammonium nitrate in particulate matter (PM) is demonstrated.     

Catalytic reduction of NO on copper/MCM-41 studied by in situ EXAFS and XANES

Speciation of copper in the channels of MCM-41 during reduction of NO with CO at 473-773 K was studied by in situ extended X-ray absorption fine structural (EXAFS) and X-ray absorption near edge structural (XANES) spectroscopies in the present work. The component fitted (in situ) XANES spectra of the catalyst showed that about 72% of metallic copper (Cu(0)) in MCM-41 was oxidized to higher oxidation state coppers (Cu(II) (46%) and Cu(I) (26%)) during the NO reduction process (at 473 K). By EXAFS, we also found that in the NO reduction process, oxygen was inserted into the metallic copper matrix and led to a formation of the copper oxide species with a Cu-O bond distance of 1.93 A which was greater than that of the model compound Cu(2)O (typically 1.86 A). At 573-673 K, mainly Cu(II) was found in the channels of MCM-41. Nevertheless, at a higher temperature (e.g., 773 K), about 61% Cu(I), 31% Cu(II), and 8% Cu(O) with averaged Cu-Cu and Cu-O bond distances of 3.04 and 1.88 A, respectively were observed, that might account for the high selectivity-to-decomposition (S/D) ratios for yields of N(2) and CO(2) in the catalytic reduction of NO with CO.     

Removal of ammonia solutions used in catalytic wet oxidation processes

Ammonia (NH(3)) is an important product used in the chemical industry, and is common place in industrial wastewater. Industrial wastewater containing ammonia is generally either toxic or has concentrations or temperatures such that direct biological treatment is unfeasible. This investigation used aqueous solutions containing more of ammonia for catalytic liquid-phase oxidation in a trickle-bed reactor (TBR) based on Cu/La/Ce composite catalysts, prepared by co-precipitation of Cu(NO(3))(2), La(NO(3))(2), and Ce(NO(3))(3) at 7:2:1 molar concentrations. The experimental results indicated that the ammonia conversion of the wet oxidation in the presence of the Cu/La/Ce composite catalysts was determined by the Cu/La/Ce catalyst. Minimal ammonia was removed from the solution by the wet oxidation in the absence of any catalyst, while approximately 91% ammonia removal was achieved by wet oxidation over the Cu/La/Ce catalyst at 230 degrees C with oxygen partial pressure of 2.0 MPa. Furthermore, the effluent streams were conducted at a liquid hourly space velocity of under 9 h(-1) in the wet catalytic processes, and a reaction pathway was found linking the oxidizing ammonia to nitric oxide, nitrogen and water. The solution contained by-products, including nitrates and nitrites. Nitrite selectivity was minimized and ammonia removal maximized when the feed ammonia solution had a pH of around 12.0.