Ce改性Fe-Mn/TiO2低温SCR脱硝催化剂硫中毒机理

以Ce改性Fe-Mn/TiO_2低温选择性催化还原(SCR)脱硝催化剂为研究对象,通过活性测试和一系列表征技术对其低温抗硫性能及中毒机理进行探究。实验结果表明:当烟气中通入SO_2体积分数在0.02%以下时,Fe_(0.1)Ce_(0.07)Mn_(0.4)/TiO_2催化剂呈现出良好的抗硫性,且停止通入SO_2时催化剂的脱硝活性可恢复至初始水平;当通入SO_2的体积分数增加至0.04%时,催化剂会发生不可逆失活。表征结果显示:(NH_4)_2SO_4在催化剂表面的沉积和活性组分锰氧化物的硫酸化(生成MnSO_4)是催化剂硫中毒的主要原因;中毒后的催化剂比表面积显著降低,氧化还原能力减弱;催化剂Lewis酸的酸性大幅度减弱是催化剂活性降低的重要原因。     

低温NH_3-SCR脱硝催化剂的研究现状与进展

高效催化剂的研制与开发是低温氨气选择性催化还原(NH_3-SCR)脱硝技术的核心。从活性组分(单一氧化物型、复合氧化物型)和载体(金属氧化物、碳基材料、分子筛)两方面详细介绍了低温NH_3-SCR催化剂,总结了其研究现状,并讨论了其抗水、抗硫性能及失活原因。指出在保证催化剂具有较高活性的同时提高其抗水、抗硫性能,是低温NH_3-SCR催化剂未来研究的重点。     

SCR烟气脱硝钛载催化剂的研究进展

综述了SCR烟气脱硝钛载催化剂的研究进行，重点介绍了国内外TiO2载体原料、钒基活性组分、非钒基活性组分以及催化剂失活原因等方面的研究进展。采用低成本工业级TiO2或偏钛酸作为载体，可开发出催化活性温度低、高抗硫中毒和稳定性高的SCR脱硝催化剂，这对我国NOx污染的治理具有重要意义。     

中等温度SCR脱硝催化剂在高硫、高钙条件下的适应性研究

介绍了在模拟高硫、高钙灰的试验烟气环境下,钒钛系中温SCR脱硝催化剂在NH3/NOx、SO2、空速、O2、H2O等参数变化时对脱硝效率的影响.试验还对催化剂的抗毒性能、再生性能进行了初步研究,可为工业化的催化剂选型提供参考.     

烟气脱硝低温选择性催化还原金属氧化物催化剂的研究进展

低温选择性催化还原(SCR)技术具有很高的脱硝效率。概述了低温SCR金属氧化物催化剂的制备方法和性能,分析了催化剂的失活原因和再生方法,探讨了催化反应的机理,并介绍了低温SCR技术在工业烟气脱硝中的应用案例。SCR催化剂未来的发展不仅要以低温下的高活性和高选择性为主要目的,还要考虑到催化剂的抗失活性能(如抗硫性和抗水稳定性)和操作温度范围,使其可广泛应用于不同的工况中,以满足我国日益提高的环保要求。     

脱硝催化剂的失活机理及其再生技术

采用SEM、XRD和XRF对电厂失活脱硝催化剂进行表征,探讨其失活原因和机理。结果表明:电厂脱硝催化剂失活的主要原因是活性组分V的流失及碱金属K、碱土金属Ca和As元素造成的催化剂中毒,烟气中飞灰的沉积也有一定的影响。经吹扫、水洗、酸洗和V负载再生,催化剂的各项物化性质基本恢复,NOx转化率基本达到新鲜催化剂的水平。水洗主要去除催化剂中的碱金属,酸洗主要去除As2O3,负载V补充催化剂活性组分。V再生催化剂在较高温度下的抗硫性能更好。     

Fe_2P_3-NM催化氧化CS_2的性能

采用催化氧化法治理含有机硫化物(以CS_2为例)的废气,研制了一种以天然丝光沸石为担体的非贵金属单组份Fe_2O_3催化剂。考察了Fe_2O_3催化剂的氧化活性及添加碱金属氧化物对它的影响,并通过对CS_2催化氧化反应途径的分析和考察,讨论了反应温度、空速、CS_2浓度对CS_2氧化效率的影响。     

低温NH3-SCR催化剂抗水抗硫性能研究进展

针对低温氨选择性催化还原(NH₃-SCR)催化剂易因烟气中水蒸气和SO₂中毒的问题,从制备方法、载体类型、结构形貌调控3个方面综述了提高低温NH₃-SCR催化剂抗水抗硫性能的方法,深入探讨了催化剂结构形貌与其抗水抗硫性能之间的关系,详细介绍了低温NH₃-SCR催化剂设计和制备的新思路,并指出,今后应加强低温NH₃-SCR催化剂结构和形貌调控方面的研究。     

烟气HC-SCR脱硝技术的研究进展

近年来提出的碳氢化合物选择性催化还原NO技术引起了国内外研究工作者的关注，已成为近年SCR研究的热点。概述了贵金属、金属氧化物和分子筛催化剂选择性催化还原脱除NOx的研究进展，并对该技术下一步的研究进行了展望。     

TiO2基新型硫回收催化剂的活性评价和工业应用

介绍了ＬＳ－９０１ ＴｉＯ２基新型硫回收催化剂的特点及工业应用情况。该催化剂与传统的ＬＳ－８１１ Ａｌ２Ｏ３基催化剂相比,具有更高的克劳斯反应活性和水解反应活性、更强的抗“漏氧”中毒能力,在硫回收装置上应用,可明显提高硫回收率并减少ＳＯ２排放量,具有明显的经济效益和环境效益。     

Fluxes of NO3-, NH4+, NO,NO2, and N2O in an Old Danish Beech Forest

The fluxes of the major nitrogen compounds havebeen investigated in many ecosystem studies over the world.However, only in few studies has attention been drawn to theimportance of the fluxes of minor gaseous nitrogen compoundsto complete the nitrogen cycle. In Denmark a detailed study onthe nitrogen cycle in an old beech forest has been implementedin 1997 at Gyrstinge near Sorø, Zealand. The study includesthe fluxes of the gases NO, N₂O and water mediatedtransport of NO₃ ^- and NH₄ ⁺. Measurementsof the fluxes of the gaseous compounds are performed withmicro-meteorological methods (eddy-correlation and gradient)and with chambers. Water mediated fluxes encompass rain,throughfall, stem-flow and leaching from the root zone. Thehydrological model is verified by TDR measurements. The findings show that the total water mediated N input tothe forest floor with throughfall and stemflow was 25.6 kg Nha^-1 yr ^-1, and open field wet deposition withprecipitation was 19.0 kg N ha^-1 yr ^-1. The internalcycling of N in the ecosystem measured as turnover oflitterfall and plant uptake was 100 kg N ha^-1 yr ^-1and 14 kg N ha^-1 yr ^-1, respectively. The fluxes ofthe gaseous N compounds NO and N₂O were of minorimportance for the total N turnover in the forest, NO_xemission being <1 kg N ha^-1 yr ^-1 and N₂Oemission from the soil being 0.5 kg N ha^-1 yr ^-1 withno significant difference between wet and dry soils.Concentrations of NO₃ ^- and NH₄ ⁺ in thesoil solution beneath the rooting zone are very small andconsequently the N leaching is almost negligible. It isconcluded that the nitrogen mass balance of this old beechforest ecosystem mainly is controlled by the input by dry andwet deposition and a large internal N cycle with a fast litterturnover. The nitrogen input tothe forest ecosystem which currently exceeds the critical loadby 5 kg N ha^-1 yr ^-1is mainly accumulated in the soil and no significant nitrateleaching is occurring.     

Atmospheric Deposition of Reactive Nitrogen on Turf Grassland in Central Japan: Comparison of the Contribution of Wet and Dry Deposition

The atmospheric deposition of reactive nitrogen on turf grassland in Tsukuba, central Japan, was investigated from July 2003 to December 2004. The target components were ammonium, nitrate, and nitrite ions for wet deposition and gaseous ammonia, nitric and nitrous acids, and particulate ammonium, nitrate, and nitrite for dry deposition. Organic nitrogen was also evaluated by subtracting the amount of inorganic nitrogen from total nitrogen. A wet-only sampler and filter holders were used to collect precipitation and the atmospheric components, respectively. An inferential method was applied to calculate the dry deposition velocity of gases and particles, which involved the effects of surface wetness and ammonia volatilization through stomata on the dry deposition velocity. The mean fraction of the monthly wet to total deposition was different among chemical species; 37, 77, and 1% for ammoniacal, nitrate-, and nitrite-nitrogen, respectively. The annual deposition of inorganic nitrogen in 2004 was 47 and 48 mmol m⁻² yr⁻¹ for wet and dry deposition, respectively; 51% of atmospheric deposition was contributed by dry deposition. The annual wet deposition in 2004 was 20, 27, and 0.07 mmol m⁻² yr⁻¹, and the annual dry deposition in 2004 was 35, 7.4, and 5.4 mmol m⁻² yr⁻¹ for ammoniacal, nitrate-, and nitrite-nitrogen, respectively. Ammoniacal nitrogen was the most important reactive nitrogen because of its remarkable contribution to both wet and dry deposition. The median ratio of the organic nitrogen concentration to total nitrogen was 9.8, 17, and 15% for precipitation, gases, and particles, respectively.     

The GaNE programme in a global perspective

This paper provides the background to this special issue, outlining the extent to which the global atmospheric nitrogen cycle has been modified by human activity and outlining the range of effects. The global total emissions of reduced and oxidized nitrogen, amount to 124 Tg N, and exceed those from natural sources (34 Tg N) by almost a factor of four showing the extent to which anthropogenic activity has taken over the global N cycle. Of the 124 Tg N, 70 Tg N is emitted in the oxidized form, largely as NO and 70% of which results directly from anthropogenic activity. The remaining 54 Tg N is emitted as NH₃, (66% anthropogenic). The enhanced nitrogen emissions are associated with a range of local, regional and global issues including, acidification, eutrophication, climate change, human health and tropospheric O₃. The paper also places the Global Nitrogen Enrichment (GaNE) research programme in the UK in a wider perspective.     

Influence of sewage inputs and fish farm effluents on dissolved nitrogen species in a chalk river

Nitrate, ammonium and dissolved organic nitrogen (DON) concentrations were measured in the lower reaches of the River Test in Hampshire to assess the impact of two effluent point sources. An 18-month survey from July 2001 to December 2002 was carried out at locations above and below fish farm inputs and a sewage effluent outfall. The concentration of nitrate exceeded 400 M at the four sites on all sample dates. A consistent increase in ammonium concentration was measured downstream of the fish farm, but not the sewage effluent input. DON samples collected downstream of the fish farm did not show a consistent increase in concentration, compared with the upstream sampling location, whereas the sewage effluent input at Romsey was a point source of DON to the River Test with a mean increase of 15 M. Nitrate was the major component of dissolved nitrogen in this aquifer-fed chalk-bed river system, with up to 10% being DON and ammonium comprising <1%.     

湛江电力公司氮氧化物减排措施

介绍了湛江电力公司4×300 MW燃煤发电机组减排氮氧化物实施的技术。     

Critical Loads Exceedances in Germany and their Dependence on the Scale of Input Data

Critical load exceedances have been used as an effects-related parameter for guiding international air emission control negotiations. High-resolution critical load data are combined with low-resolution deposition data.This article shows that doing so systematicallyunderestimates `true' critical load exceedances as obtainedfrom combining critical load and deposition data of identicalhigh spatial resolution. 95th percentile critical loadexceedances in EMEP grids based on high resolution depositiondata are 60 and 150% higher (mean values for nutrientnitrogen and acidity, respectively) than critical loadexceedances based on the low resolution EMEP depositionmodel. The latter are used in international negotiations. Differences in individual EMEP grid squares vary betweeninsignificantly different from zero and 340%, depending onregional deposition and critical load characteristics andcritical load types (nutrient nitrogen versus acidity).Exceedances based on high-resolution deposition values arealso compared to EMEP grid averages of these values forforests only. This comparison excludes the effect ofsystematically higher depositions to forests. Still, thescale difference of (averaged, low-resolution) deposition and(high-resolution) critical loads data yields underestimatesof the 95th percentiles by on average ca. 20%.These systematic errors due to the scale dependence should beborne in mind when interpreting effects of internationalemission control measures.     

Winter and Spring Thaw Measurements of N2O,NO and NOx Fluxes using a Micrometeorological Method

The impact of nitrogen fertilizers on gaseous emissions duringwinter and spring-thaw is not well understood and was the objective of this research. Using a micrometeorological method,N₂O, NO and NO_x fluxes from ryegrass were measured from November 1997 to March 1998. Three different mineralfertilizers were applied in November: urea (U), slow-release urea(SRU) and ammonium nitrate (AN). N₂O emissions during the winter were small, increasing significantly in March. Total losses of N₂O-N were significantly higher from SRU and U plots, with winter N₂O emissions accounting for 50% of annual losses. Nitric oxide fluxes from all plots weresmall during the measurement period (<0.9 ng N m^-2 s^-1). The NO fluxes from U and AN fertilized plots were significantly higher than from SRU and control plots. NO₂ fluxes were always negative (–6 ng N m^-2 s^-1)indicating deposition, but decreased to –2 ng N m^-2s^-1 when snow was present on the soil surface. Our resultsindicate that the form of inorganic N applied has an effect on NO+ N₂O emissions but not on NO₂ fluxes.Sponsored by CAPES – Brasília, Brazil     

A Chronology of Nitrogen Deposition in the UK Between 1900 and 2000

Measurements of the concentrations of nitrogen compounds in air and precipitation in the UK have been made since the mid-19th century, but no networks operating to common protocols and having traceable analytical procedures were established until the 1950s. From 1986 onwards, a high-quality network of sampling stations for precipitation chemistry was established across the UK. In the following decade, monitoring networks provided measurement of NO₂, NH₃, HNO₃ and a satisfactory understanding of the dry deposition process for these gases allowed dry deposition to be quantified. Maps of N deposition for oxidized and reduced compounds at a spatial scale of 5 km × 5 km are available from 1986 to 2000. Between 1950 and 1985, the more limited measurements, beginning with those of the European Air Chemistry Network (EACN) provide a reasonable basis to estimate wet deposition of NO ₃ ^– –N and NH ₄ ⁺ –N. For the first half of the century, estimates of deposition were scaled with emissions assuming a constant relationship between emission and deposition for each of the components of the wet and dry deposition budget at the country scale. Emissions of oxidized N, which dominated total nitrogen emissions throughout the century, increased from 312 kt N annually in 1900 to a peak of 787 kt for the decade 1980–1990 and then declined to 460 kt in 2000. Emissions of reduced N, largely from coal combustion were about 168 kt N in 1900, increasing to a peak of 263 kt N in 2000 and by now dominated by agricultural sources. Reduced N dominated the deposition budget at the country scale, increasing from 163 kt N in 1900 to 211 kt N in 2000, while deposition of oxidized N was 66 kt N in 1900 and 191 kt N in 2000. Over the century, 68 Mt (Tg) of fixed N was emitted within the UK, 78% as NO _x , while 29 Mt of nitrogen was deposited (43% of emissions), equivalent to 1.2 t N ha^–1, on average, with 60% in the reduced form. Deposition to semi-natural ecosystems is approximately 15 Tg N, equivalent to between 1 and 5 t N ha^–1, over the century and appears to be accumulating in soil. The N deposition over the century is similar in magnitude to the total soil N inventory in surface horizons.     

氮氧化物防治技术在台湾之应用及管制策略

主要探讨台湾过去二十年来,在治理氮氧化物(NOx)排放方面所作的努力,包括NOx防治技术的引进与开发,以及管制策略的制定.在防治技术的引进与开发方面,主要以在使用化石燃料的发电厂加装SCR(触媒除硝法)设备为主,此外,老的热电厂亦有加装SNCR(选择性非触媒还原法)以及采用再燃烧技术来抑制NOx的排放.进一步探讨了台湾使用的这些NOx防治技术的优缺点以及所获得的经验.在NOx管制策略的制定方面,可分为1995年以前所制定的《空气污染防制法》;1995年以后,基于污染者付费的原则,以及为了鼓励工业及发电厂加装高效率NOx污染防治设备,进一步制定《空气污染防制费收费办法》.此后,台湾固定污染源所排放的NOx已大为改善.     

Controls on Leaching of N Species in Upland Moorland Catchments

Spatial and temporal changes in mobility of N species have been studied for three UK upland river networks, the Etherow in the South Pennines, the Nether Beck in the Lake District and the Dee in NE Scotland. The catchments are subject to N deposition at 35.1, 22.0 and 10.8–15.6 kg N ha^–1 yr^–1, respectively. TheNH ₄ ⁺ leaching appears to be predominantly regulated by flowpath in more polluted upland catchments. It is greatest where water draining acidified peaty soils contributes more to total discharge. Soluble organic matter may provide the dominant counter anion. In the Etherowand Dee catchments, which are dominated by acid mineral and organic soils, at high discharge NO ₃ ^– also appears to be associated with greater input of water from acidified soils. In contrast, for the Nether Beck, higher NO ₃ ^– concentrations are associated with tributaries draining soils contributingwater with higher alkalinity, suggesting nitrification is important. For the Etherow and Dee, dissolved organic N (DON) appears to originate predominantly from acidified, peaty soils. Spiking experiments with peat soil from the Etherow catchment confirmed the limited capacity of these soils to utilize inorganic N inputs, favouring equilibration with NH ₄ ⁺ inputs and leaching losses of inorganic N throughout the year.