Effects of WOx modification on the activity, adsorption and redox properties of CeO2 catalyst for NOx reduction with ammonia

A series of WO₃/CeO₂ (WOx/CeO₂) catalysts were synthesized by wet impregnation of ammonium metatungstate on a CeO₂ support. The resulting solid acid catalysts were characterized by X-ray diffraction (XRD), UV-Vis spectroscopy (UV-Vis), Raman spectroscopy (Raman), in-situ Fourier transform infrared spectroscopy (in-situ FT-IR) of ammonia adsorption, NH₃-TPD, H₂ temperature-programmed reduction (H₂-TPR), NH₃/NO oxidation and activity measurements for NOx reduction by NH₃ (NH₃-SCR). The results show that polytungstate (WOx) species are the main species of tungsten oxide on the surface of ceria. The addition of tungsten oxide enhances the Brönsted acidity of ceria catalysts remarkably and decreases the amount of surface oxygen on ceria, with strong interaction between CeO₂ and WOx. As a result, the N₂ selectivity of NH₃ oxidation and NH₃-SCR at high temperatures (> 300℃) is enhanced. Therefore, a wide working temperature window in which NOx conversion exceeds 80% (NOx conversion > 80%) from 200 to 450℃, is achieved over 10 wt.% WOx/CeO₂ catalyst. A tentative model of the NH₃-SCR reaction route on WOx/CeO₂ catalysts is presented.     

Activity and hydrothermal stability of CeO2–ZrO2–WO3 for the selective catalytic reduction of NOx with NH3

A series of CeO_2–ZrO_2–WO_3(CZW)catalysts prepared by a hydrothermal synthesis method showed excellent catalytic activity for selective catalytic reduction(SCR)of NO with NH_3 over a wide temperature of 150–550°C.The effect of hydrothermal treatment of CZW catalysts on SCR activity was investigated in the presence of 10% H_2O.The fresh catalyst showed above 90% NO_x conversion at 201–459°C,which is applicable to diesel exhaust NO_x purification(200–440°C).The SCR activity results indicated that hydrothermal aging decreased the SCR activity of CZW at low temperatures(below 300°C),while the activity was notably enhanced at high temperature(above 450°C).The aged CZW catalyst(hydrothermal aging at 700°C for 8 hr)showed almost 80% NO_x conversion at 229–550°C,while the V_2O_5–WO_3/TiO_2 catalyst presented above 80% NO_x conversion at 308–370°C.The effect of structural changes,acidity,and redox properties of CZW on the SCR activity was investigated.The results indicated that the excellent hydrothermal stability of CZW was mainly due to the CeO_2–ZrO_2 solid solution,amorphous WO_3 phase and optimal acidity.In addition,the formation of WO_3 clusters increased in size as the hydrothermal aging temperature increased,resulting in the collapse of structure,which could further affect the acidity and redox properties.     

The influence of long term trends in pollutant emissions on deposition of sulphur and nitrogen and exceedance of critical loads in the United Kingdom

In the United Kingdom, as with other European countries, land-based emissions of NO_x and SO₂ have fallen significantly over the last few decades. SO₂ emissions fell from a peak of 3185 Gg S in 1970 to 344 Gg S in 2005 and are forecast by business-as-usual emissions scenarios to fall to 172 Gg by 2020. NO_x emissions were at a maximum of 951 Gg N in 1970 and fell to 378 by 2005 with a further decrease to 243 Gg N forecast by 2020. These large changes in emissions have not been matched by emissions changes for NH₃ which decreased from 315 Gg N in 1990 to 259 in 2005 and are forecast to fall to 222 by 2020. The Fine Resolution Atmospheric Multi-pollutant Exchange model (FRAME) has been applied to model the spatial distribution of sulphur and nitrogen deposition over the United Kingdom during a 15-year time period (1990–2005) and compared with measured deposition of sulphate, nitrate and ammonium from the national monitoring network. Wet deposition of nitrogen and sulphur was found to decrease more slowly than the emissions reductions rate. This is attributed to a number of factors including increases in emissions from international shipping and changing rates of atmospheric oxidation. The modelled time series was extended to a 50-year period from 1970 to 2020. The modelled deposition of SO_x, NO_y and NH_x to the UK was found to fall by 87%, 52% and 25% during this period. The percentage area of sensitive habitats in the United Kingdom for which critical loads are exceeded is estimated to fall from 85% in 1970 to 37% in 2020 for acidic deposition and from 73% to 49% for nutrient nitrogen deposition. The significant reduction in land emissions of SO₂ and NO_x focuses further attention in controlling emissions from international shipping. Future policies to control emissions of ammonia from agriculture will be required to effect further significant reductions in nitrogen deposition.     

Emissions of N2O and NH3, and nitrogen leaching from direct seeded rice under different tillage practices in central China

Tillage practices affect the fate of fertilizer nitrogen (N) through influencing transformations of N, but few studies have examined N₂O and NH₃ emissions, and N leaching from different rice tillage systems. Thus the objective of this study was to assess N₂O emission, NH₃ volatilization and N leaching from direct seeded rice in conventional tillage (CT) and no-tillage (NT) production systems in the subtropical region of China during the 2008 and 2009 rice growing seasons. Treatments were established following a split-plot design of a randomized complete block with tillage practices as the main plot and N fertilizer level as the sub-plot treatment, and there were four treatments: NT + no fertilizer (NT0), CT + no fertilizer (CT0), NT + compound fertilizer (NTC) and CT + compound fertilizer (CTC), respectively. Results showed that N fertilization significantly increased (p < 0.01) N₂O emissions, NH₃ volatilization and N leaching from rice fields in both years. In general, there was no significant difference in N₂O emissions and NH₃ volatilization between NT0 and CT0 in both years, while NTC had significantly higher (p < 0.05) N₂O emissions and NH₃ volatilization compared to CTC. Over the two rice growing seasons, NTC showed 32% and 47% higher N₂O emissions, and 29% and 52% higher NH₃ losses than CTC. Higher (p < 0.05) N₂O emissions from NTC than CTC were presumably due to higher soil organic C and greater denitrification. Total N and NO₃^? concentrations were higher (p < 0.05) in CTC than NTC, but larger volumes of percolation water in NTC than CTC resulted in no significant difference in leakage of total N and NO₃^?. Hence, application of N fertilizer in combination with NT appeared to be ineffective in reducing N losses from N fertilizer in paddy fields.     

Comparison of absorption rates and absorption capacity of ammonia solvents with MEA and MDEA aqueous blends for CO2 capture

In this work we present the experimental results of absorption rates and absorption capacity for the CO₂ absorption by ammonia (NH₃) aqueous solutions. Experiments are carried out in a thermoregulated Lewis-type cell reactor and are achieved in temperature and concentration ranges of 278–303 K and 2–5wt.% NH₃ respectively. The obtained values for absorption kinetic rates and absorption capacity are compared with those available for alkanolamine solvents, commonly used to absorb CO₂. In order to achieve this comparison, data available in studies about alkanolamine solvents at 303–333 K and 5–50wt.% for alkanolamines solutions were considered. Results show that CO₂ absorption by NH₃ is faster than the one carried out by MDEA, except for 2wt.% NH₃ at 288 K. At 278 K and using aqueous solutions of 3wt.% NH₃, the absorption rate is almost identical to the one reached with MDEA solvent. The highest absorption capacity, also compared with alkanolamine solution, is reached with aqueous solutions of 5wt.% NH₃ at 278 K and 303 K.     

Effect of Ce doping of TiO2 support on NH3-SCR activity over V2O5-WO3/CeO2-TiO2 catalyst

CeO2–TiO2composite supports with different Ce/Ti molar ratios were prepared by a homogeneous precipitation method, and V2O5–WO3/CeO2–TiO2catalysts for the selective catalytic reduction（SCR） of NOx with NH3 were prepared by an incipient-wetness impregnation method. These catalysts were characterized by means of BET, XRD, UV–Vis,Raman and XPS techniques. The results showed that the catalytic activity of V2O5–WO3/TiO2 was greatly enhanced by Ce doping（molar ratio of Ce/Ti = 1/10） in the TiO2 support.The catalysts that were predominantly anatase TiO2 showed better catalytic performance than the catalysts that were predominantly fluorite CeO2. The Ce additive could enhance the surface adsorbed oxygen and accelerate the SCR reaction. The effects of O2 concentration, ratio of NH3/NO, space velocity and SO2 on the catalytic activity were also investigated. The presence of oxygen played an important role in NO reduction. The optimal ratio of NH3/NO was 1/1 and the catalyst had good resistance to SO2 poisoning.     

Size effect of Pt nanoparticles in acid-assisted soot oxidation in the presence of NO

Pt/Al₂ O₃ catalysts with mean Pt particle size ranged from 2.7 to 7.1 nm were synthesized by chemical reduction method,and the sulfated counterparts were prepared by impregnation of sulfuric acid.The turnover frequency of platinum for soot oxidation under loose contact conditions in a feed flow containing NO and O₂ are positively correlated with the size of platinum.The sulfated Pt/Al₂ O₃ exhibits higher catalytic activity for soot oxidation...     

Protecting the photosynthetic performance of snap bean under free air ozone exposure

Tropospheric ozone(O_3) is a major air pollutant and causes serious injury to vegetation. To protect sensitive plants from O_3 damage, several agrochemicals have been assessed,including cytokinin(e.g., kinetin, KIN) and ethylenediurea(EDU) with cytokinin-like activity.In higher plant, leaves are primarily injured by O_3 and protective agrochemicals are often applied by leaf spraying. To our knowledge, the mitigating abilities of EDU and KIN have not been compared directly in a realistic setup. In the present research, impacts of elevated O3(2 × ambient O_3, 24 hr per day, for 8 days) on an O_3 sensitive line(S156) of snap bean(Phaseolus vulgaris), which is often used for biomonitoring O_3 pollution, were studied in a free air controlled exposure system. The day before starting the O_3 exposure, plants were sprayed with a solution of EDU(300 ppm), KIN(1 mmol/L) or distilled water, to compare their protective abilities. The results demonstrated that 2 × ambient O_3 inhibited net photosynthetic rate and stomatal conductance, increased the minimal fluorescence yield of the dark-adapted state, decreased the maximal quantum yield of PSII photochemistry, and led to visible injury. KIN and EDU alleviated the reduction of the photosynthetic performance, and visible injury under O_3 fumigation. The plants sprayed with EDU showed greater ability to mitigate the O_3 damage than those sprayed with KIN. Chlorophyll fluorescence imaging may have detected more precisely the differences in O_3 response across the leaf than the conventional fluorometer.     

V2O5/TiO2催化剂中毒机理的试验研究

选择性催化还原(SCR)催化剂是SCR烟气脱硝技术的核心,是整个SCR系统脱硝效率和经济性的决定因素.本文工作的主要研究思路是以钒钛SCR催化剂为研究对象,研究了H2O和SO2,以及相同含量下K、Na、Ca、Pb的氧化物对钒钛催化剂NO转化率的影响.H2O的存在会抑制V2O5/TiO2催化剂脱硝活性,而SO2在一定程度上促进(V2O5/TiO2)催化剂的SCR脱硝反应,提高NO转化率;碱金属K对钒钛催化剂的钝化作用都是最强,K2O和Na2O的掺入会抑制钒钛催化剂上V2O5的还原能力,而CaO和PbO的掺入对钒钛催化剂上V2O5的还原能力影响较小.     

Promotional effect of Si-doped V2O5/TiO2 for selective catalytic reduction of NOx by NH3

TiO2 supports doped with different amounts of Si were prepared by a sol-gel method, and 1 wt% vanadia (V2O5) loaded on Si-doped TiO2 was obtained by an impregnation method. The mole ratio of Si/Ti was 0.2, NOx conversion exceeds 94% at 300℃ and GHSV of 41,324 hr-1 , which is about 20% higher than pure V2O5/TiO2 . The catalysts were characterized by XRD, BET, TEM, FT-IR, NH3-TPD, XPS, H2-TPR, Raman and in situ DRIFTS. The results of FT-IR and XPS indicated that Si was doped into the TiO2 lattice successfully and a solid solution was obtained. V2O5 active component could be dispersed well on the support with the increasing of surface area of the catalyst, which was confirmed by Raman and XRD results. Above all, the numbers of acid sites (especially the Br nsted-acid) and oxidation properties were enhanced for Si-doped V2O5/TiO2 catalysts, which improved the deNOx catalytic activity.     

Ammonia and nitrous oxide emissions following land application of high and low nitrogen pig manures to winter wheat at three growth stages

Nitrous oxide (N₂O) and ammonia (NH₃) emissions from surface applied high (HN) and low (LN) nitrogen pig manures were measured under field conditions. Manures were band-spread to a winter wheat crop at three growth stages—mid-tillering, stem elongation and flag leaf emergence. The N₂O flux rates were measured using the static chamber technique while NH₃ volatilisation was assessed using a micrometeorological mass balance technique with passive flux samplers. The N₂O emissions were episodic in nature with flux rates observed ranging from 2.8 to 31.5 g N₂O–N ha^?1 day^?1 (P < 0.001). Higher N₂O emissions generally occurred after rainfall events. Highest N₂O losses were observed from the HN treatment with LN manure use decreasing emissions by 18% (P < 0.03). The NH₃ volatilisation rates were highest within 1 h of manure application with 95% of emissions occurring within 24 h (P < 0.001). Cumulative N loss was highest at mid-tillering as low crop canopy cover and increased wind-speeds enhanced NH₃ loss (P < 0.001). Highest emissions were measured from the HN manure (P < 0.03). Total ammoniacal N loss ranged from 6 to 11%. Crop N uptake and grain yield were unaffected by application timing or manure type. Therefore, the use of LN manures decreased gaseous emissions of N₂O and NH₃ without any adverse effects on crop performance.     

Effects of O3/Cl2 disinfection on corrosion and opportunistic pathogens growth in drinking water distribution systems

The effects of O_3/Cl_2 disinfection on corrosion and the growth of opportunistic pathogens in drinking water distribution systems were studied using annular reactors(ARs).The corrosion process and most probable number(MPN) analysis indicated that the higher content of iron-oxidizing bacteria and iron-reducing bacteria in biofilms of the AR treated with O_3/Cl_2 induced higher Fe_3O_4 formation in corrosion scales.These corrosion scales became more stable than the ones that formed in the AR treated with Cl_2 alone.O_3/Cl_2 disinfection inhibited corrosion and iron release efficiently by changing the content of corrosion-related bacteria.Moreover,ozone disinfection inactivated or damaged the opportunistic pathogens due to its strong oxidizing properties.The damaged bacteria resulting from initial ozone treatment were inactivated by the subsequent chlorine disinfection.Compared with the AR treated with Cl_2 alone,the opportunistic pathogens M.avium and L.pneumophila were not detectable in effluents of the AR treated with O_3/Cl_2,and decreased to(4.60 ± 0.14) and(3.09 ± 0.12) log10(gene copies/g corrosion scales) in biofilms,respectively.The amoeba counts were also lower in the AR treated with O_3/Cl_2.Therefore,O_3/C_l2 disinfection can effectively control opportunistic pathogens in effluents and biofilms of an AR used as a model for a drinking water distribution system.     

Selective catalytic reduction of nitrogen oxides over a modified silicoaluminophosphate commercial zeolite

Nitrogen oxides(NO_x:NO,NO_2)are a concern due to their adverse health effects.Diesel engine transport sector is the major emitter of NO_x.The regulations have been strengthened and to comply with them,one of the two methods commonly used is the selective catalytic reduction of NO_xby NH_3(NH_3-SCR),NH_3being supplied by the in-situ hydrolysis of urea.Efficiency and durability of the catalyst for this process are highly required.Durability is evaluated by hydrothermal treatment of the catalysts at temperature above 800°C.In this study,very active catalysts for the NH_3-SCR of NO_xwere prepared by using a silicoaluminophosphate commercial zeolite as copper host structure.Characterizations by X-ray diffraction(XRD),scanning electron microscopy(SEM)and temperature programmed desorption of ammonia(NH_3-TPD)showed that this commercial zeolite was hydrothermally stable up to 850°C and,was able to retain some structural properties up to950°C.After hydrothermal treatment at 850°C,the NO_xreduction efficiency into NH_3-SCR depends on the copper content.The catalyst with a copper content of 1.25 wt.%was the most active.The difference in activity was much more important when using NO than the fast NO/NO_2reaction mixture.     

以堇青石蜂窝陶瓷为载体的新型钒氧化物脱氮催化剂研究

以TiO₂/Al₂O₃/堇青石蜂窝陶瓷为载体,以V₂O₅-MoO₃-WO₃为活性组分,用于氨法选择性催化还原烟气中NO的新型催化剂,并对该催化剂的活性性能和微观结构进行了评价和表征.同时,将该催化剂的活性性能与其它几种活性组分相同但载体、制备方法、结构不同的催化剂进行了对比.对比结果表明,该新型催化剂能取得最好的选择性催化还原氮氧化物催化性能BET、FT IR、XPS表征实验结果表明,其高催化活性得益于大比表面积及大孔体积,而TiO₂/Al₂O₃/堇青石蜂窝陶瓷载体及其制备方法对获得好的催化剂构型起了至关重要的作用.     

Methane,nitrous oxide and ammonia emissions during storage and after application of dairy cattle slurry and influence of slurry treatment

Slurries are a significant source of CH₄, NH₃ and N₂O emissions to the atmosphere. The research project aimed at quantifying CH₄, NH₃ and N₂O emissions from liquid manure stores and after manure application under field conditions. The influence of the manure treatment options “no treatment”, “slurry separation”, “anaerobic digestion”, “slurry aeration” and “straw cover” on the emission level was investigated. Approximately 10 m³ of differently treated slurry were stored in pilot scale slurry tanks. Emissions were followed for c. 80 days. After the storage period, slurries were applied to permanent grassland. Greenhouse gas emissions from slurry were mainly caused by methane emissions during storage and by nitrous oxide emissions after field application of manures. Mitigation of GHG emissions can be achieved by a reduction in slurry dry matter and easily degradable organic matter content. Ammonia emissions mainly occurred after field application. Untreated slurry emitted 226.8 g NH₃ m⁻³ and 92.4 kg CO₂ eq. m⁻³ (storage and field application). Slurry separation (liquid fraction and composting of the solid fraction) resulted in NH₃ losses of 402.9 g m⁻³ and GHG losses of 58.5 kg CO₂ eq. m⁻³. Anaerobic digestion was a very effective means to reduce GHG emissions. 37.9 kg CO₂ eq. m⁻³ were lost. NH₃ emissions were similar to those from untreated slurry. Covering the slurry store with a layer of chopped straw instead of a wooden cover increased NH₃ emissions to 320.4 g m⁻³ and GHG emissions to 119.7 kg CO₂ eq. m⁻³. Slurry aeration nearly doubled NH₃ emissions compared to untreated slurry. GHG emissions were reduced to 53.3 kg CO₂ eq. m⁻³.     

Toluene decomposition performance and NOx by-product formation during a DBD-catalyst process

Characteristics of toluene decomposition and formation of nitrogen oxide (NOx) by-products were investigated in a dielectric barrier discharge (DBD) reactor with/without catalyst at room temperature and atmospheric pressure. Four kinds of metal oxides, i.e., manganese oxide (MnOx), iron oxide (FeOx), cobalt oxide (CoOx) and copper oxide (CuO), supported on Al₂O₃/nickel foam, were used as catalysts. It was found that introducing catalysts could improve toluene removal efficiency, promote decomposition of by-product ozone and enhance CO₂ selectivity. In addition, NOx was suppressed with the decrease of specific energy density (SED) and the increase of humidity, gas flow rate and toluene concentration, or catalyst introduction. Among the four kinds of catalysts, the CuO catalyst showed the best performance in NOx suppression. The MnOx catalyst exhibited the lowest concentration of O₃ and highest CO₂ selectivity but the highest concentration of NOx. A possible pathway for NOx production in DBD was discussed. The contributions of oxygen active species and hydroxyl radicals are dominant in NOx suppression.     

不同硅铝比Fe-ZSM-5催化剂对氧化亚氮催化分解性能的研究

以不同硅铝比的H-ZSM-5分子筛为载体,采用离子交换法和化学气相沉积法制备Fe-ZSM-5催化剂,并用XRD、BET、TEM、UV-vis和NH3-TPD等表征手段对催化剂进行分析,研究催化剂中铁的存在状态.结果表明,分子筛的硅铝比影响铁在分子筛中的分布形态,化学气相沉积法和热离子交换法制得硅铝比为25的Fe-ZSM-5-25分子筛催化剂上均匀地分布着粒径为8 nm左右的纳米氧化铁颗粒,并且Fe-ZSM-5-25分子筛催化剂比Fe-ZSM-5-300更容易形成Fe3+x O y团簇.制得的Fe-ZSM-5分子筛催化剂催化分解氧化亚氮(N2O),结果表明,相同的制备方法,硅铝比小的Fe-ZSM-5-25催化剂对N2O分解活性更好;相同硅铝比的Fe-ZSM-5催化剂,采用化学气相沉积法制得的对N2O分解活性最好.另外,O2的存在对Fe-ZSM-5上N2O催化分解活性有抑制作用,而NO对N2O催化分解活性展示了一定的正效应.最后,经过100 h的连续反应,Fe-ZSM-5催化剂依然能够保持催化活性.     

Effect of Cu loading content on the catalytic performance of Cu-USY catalysts for selective catalytic reduction of NO with NH3

Series of Cu-USY zeolite catalyst with different Cu loading content were synthesized through simple impregnation method. The obtained catalysts were subjected to selective catalytic reduction of NO_x with NH₃ (NH₃-SCR) performance evaluation, structural/chemical characterizations such as X-ray diffraction (XRD), N₂ adsorption/desorption, H₂ temperature-programmed reduction (H₂-TPR), NH₃ temperature-programmed desorption (NH₃-TPD) as well as detailed in situ diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) experiments including CO adsorption, NH₃ adsorption and NO+O₂ in situ reactions. Results show that Cu-USY with proper Cu loading (in this work 5Cu-USY with 5 wt.% Cu) could be promising candidates with highly efficient NH₃-SCR catalytic performance, relatively low byproduct formation and excellent hydrothermal stability, although its SO₂ poisoning tolerability needs alleviation. Further characterizations reveal that such catalytic advantages can be attributed to both active cu species and surface acid centers evolution modulated by Cu loading. On one hand, Cu species in the super cages of zeolites increases with higher Cu content and being more conducive for NH₃-SCR reactivity. On the other hand, higher Cu loading leads to depletion of Brønsted acid centers and simultaneous formation of abundant Lewis acid centers, which facilitates NH₄NO₃ reduction via NH₃ adsorbed on Lewis acid centers, thus improving SCR reactivity. However, Cu over-introduction leads to formation of surface highly dispersed CuO_x, causing unfavorable NH₃ oxidation and inferior N₂ selectivity.     

Catalyst for NOx removal in nitric-acid plant gaseous effluents

The behaviour of a V₂O₅WO₃TiO₂ phosphorated catalyst, in the Selective Catalytic Reduction (SCR) of equimolar NO + NO₂ mixtures, is studied in order to analyse the possibility of its industrial utilization for the treatment of nitric-acid plant stack gases. With this new catalyst, an NO_x conversion higher than 90% molar can be achieved, the ammonia concentration at the exit gas being lower than that required to form ammonium salts, throughout the temperature range of commercial interest: 250–450°C, at a relatively high space velocity (GHSV ⩽ 40000 h⁻¹ NC). The effect of several operating variables such as oxygen concentration and NO₂/NO molar ratio in the feed is also discussed.     

超声辅助法制备新型FeMOR分子筛催化NOx还原反应性能研究

采用超声辅助浸渍法成功合成了高铁含量的Fe MOR-5%-UL催化剂,并且测试其催化还原NO性能.研究发现在超声辅助条件下浸渍制得的催化剂可以引入更高比例的离子交换位上的孤立的Fe~(3+),这些铁离子具有更强的NO还原活性,因此超声辅助浸渍法制备的催化剂催化性能显著高于传统的离子交换法和浸渍法.其中活性最高的FeMOR-5%-UL催化剂在添加SO_2等多种气氛时,催化活性下降不显著.并且在持续100 h的汽车尾气条件下进行的稳定性实验中,FeMOR-5%-UL的催化活性没有明显下降.FeMOR-5%-UL的优异的催化活性和稳定性非常具有应用前景和研究价值.