拉萨市环境空气中NO2变化特征分析

选取用长光程差分光谱法监测的拉萨市2000年7月-2004年6月环境空气质量监测数据,分析了NO₂变化特征.结果表明:目前拉萨市ρ(NO₂)在<环境空气质量标准>(GB3095-1996)一级标准之内,但呈逐渐上升趋势.拉萨市ρ(NO₂)月均值呈明显的"U"字型分布规律,即1月和年末10-12月高,其他时间低;每年10月至次年1月,ρ(NO₂)月均值超过年均值,月均最高值均出现在12月;每日在8:00-12:00,20:00-24:00有2个高峰值区.汽车尾气、当地居民生活中的燃烧过程是目前拉萨市NO₂的主要产生源,特殊边界层气象条件影响拉萨市环境空气中ρ(NO₂)的变化规律.      

Influence of Geometry on the Mean Flow within Urban Street Canyons – A Comparison of Wind Tunnel Experiments and Numerical Simulations

A comparison between numerical simulations and wind tunnel modelling has been performed to examine the variation with streamwise aspect ratio (width/height, W/H) of the mean flow patterns in a street canyon. For this purpose a two-dimensional (2-D) cavity was subjected to a thick turbulent boundary layer flow perpendicular to its principal axis. Five different test cases, W/H = 0.3, 0.5, 0.7, 1.0 and 2.0, have been studied experimentally with flow measurements taken using pulsed-wire anemometry. The results show that the skimming flow regime, with a large vortex in the canyon, occurred for all the cases investigated. For the cavities with W/H 0.7 a weaker secondary circulation developed beneath the main vortex. The narrower the canyon, the smaller the wind speed close to the cavity ground, giving increasingly poor ventilation qualities. The corresponding numerical results were obtained with the Computational Fluid Dynamics (CFD) code CHENSI that uses the standard k- model. The intercomparison showed good agreement in terms of the gross features of the mean flow for all the geometries examined, although some detailed differences were observed.     

Seasonal variability of ambient NH3, NO, NO2 and SO2 over Delhi

We present the diurnal and seasonal variability of ambient NH3, NO, NO2 and SO2 over Delhi, India. Ambient NH3, NO and NO2 were measured continuously during winter, summer and autumn seasons using NH3- and NOx-analyzer, which operates by chemiluminescence method with a higher estimation e ciency (> 90%) than the chemical trap method (reproducibility 4.7%). Prominent diurnal, day-to-day and seasonal variations of ambient mixing ratio of NH3, NO, NO2 and SO2 were observed during the study period. Seasonal variation with higher mixing ratio in winter was observed for all measured trace gases except NO. Day-night variation of all measured trace gases observed was higher in winter in comparison with summer. Late morning increase in NO2 mixing ratio might be attributed to conversion of NO to NO2 with the interaction of O3.     

尖晶石型MnCo_2O_4催化剂的制备及SCR性能研究

用柠檬酸配位燃烧法制备了尖晶石复合金属氧化物MnCo2O4,使用X射线衍射仪、傅立叶红外分析仪对其进行了表征,并进一步在固定床反应器中考查了该催化剂的催化氧化、还原NO的性能以及SO2的影响。结果表明,所制备的MnCo2O4催化剂呈现典型的尖晶石结构,在300℃,空速20000h-1时,NO氧化率可以达到30%,而NH3催化还原NO的效率可达99.5%,但SO2对其还原性能有明显影响。     

贫燃条件Ag-Rh/CeO_2-ZrO_2-Al_2O_3协同催化C_3H_6选择性还原NO的原位红外研究

将Ag-Rh浸渍到共沉淀法合成的Ce-Zr-Al上,制备出Ag(0.04)-Rh(x)/Ce0.5Zr0.5O2-75%Al2O3系列催化剂,采用BET比表面积、X射线衍射光谱(XRD)和原位漫反射傅里叶变换红外光谱(DRIFTS)对催化剂进行表征,并探讨催化剂在贫燃条件下选择性还原NO的活性和反应机理.结果表明,Ag-Rh双组分催化剂的活性较单组分Ag、Rh催化剂的高.Rh负载量为0.7%(质量分数)时,NO转化率达最佳(90.3%),且反应的起燃温度低、活性温度范围宽(300～500℃).DRIFTS结果显示,Rh的添加不仅有利于催化剂表面NO的吸附,而且能促进Ag催化生成关键反应中间体—CO—NH—,进而显著提高NO的转化率.     

天津夏季低层大气O3和NO2浓度垂直分布

利用2007年8月8-24日天津255 m气象铁塔上连续17 d的ψ(O3)和ψ(NO2)及同期气象观测数据,分析了ψ(O3)和ψ(NO2)(以小时平均值计)的日变化和垂直分布规律及其与气象因子之间的关系.结果表明:天津市近地层ψ(O3)分布具有明显的日变化和垂直分布特征,昼夜差异显著;一般情况下,ψ(O3)日均值在220 m高度处最大,120 m处次之,40 m处最小;ψ(O3)与温度和风速呈正相关,而与相对湿度呈负相关.ψ(NO2)日变化多为双峰型,白天较低;ψ(NO2)垂直差异较小,夜间稳定层使NO2产生局地积累,低层大于高层;ψ(NO2)与温度和风速呈负相关,与相对湿度的关系比较复杂,白天呈正相关,夜间呈负相关.     

北京夏季SO_2-NO_2-O_3的DOAS观测结果及变化特征

利用实施北京市奥运空气质量保障计划"北京市与周边地区空气污染物的输送、转化及北京市空气质量目标研究"项目的有利时机,2006年8月对北京城区空气污染物进行加强观测。文章利用SO2、NO2和O3等污染气体的差分吸收光谱仪(DOAS)的观测数据,初步分析这些污染气体的变化特征,得到了一些有价值的结果:2006年8月空气质量总体较好,但NO2和O3小时平均浓度有时超标;北京8月份主导风向是东南风,空气对流活动及降水可明显降低大气中的污染物浓度;NO2污染主要来自局地污染源排放,O3污染来自光化学反应和大气输送;DOAS观测结果与北京市环境保护局发布的空气污染指数间具有比较好的一致性。     

Effects of support acidity on the reaction mechanisms of selective catalytic reduction of NO by CH4 in excess oxygen

The reaction mechanisms of selective catalytic reduction (SCR) of nitric oxide (NO) by methane (CH₄) over solid superacid-based catalysts were proposed and testified by DRIFTS studies on transient reaction as well as by kinetic models. Catalysts derived from different supports would lead to different reaction pathways, and the acidity of solid superacid played an important role in determining the reaction mechanisms and the catalytic activities. Higher ratios of Br?nsted acid sites to Lewis acid sites would lead to stronger oxidation of methane and then could facilitate the step of methane activation. Strong Br?nsted acid sites would not necessarily lead to better catalytic performance, however, since the active surface NO_y species and the corresponding reaction routes were determined by the overall acidity strength of the support. The reaction routes where NO₂ moiety was engaged as an important intermediate involved moderate oxidation of methane, the rate of which could determine the overall activity. The reaction involving NO moiety was likely to be determined by the step of reduction of NO. Therefore, to enhance the SCR activity of solid superacid catalysts, reactions between appropriate couples of active NO_y species and activated hydrocarbon intermediates should be realized by modification of the support acidity.     

A comparative investigation of NdSrCu1-xCoxO4-σ and Sm1:8Ce0:2Cu1-xCoxO4-σ(x: 0-0.4) for NO decomposition

A series of single-phase T-structured NdSrCu1??xCoxO4?? with oxygen vacancies and T0-structured Sm1:8Ce0:2Cu1??xCoxO4?? (x: 0–0.4) with oxygen excess were prepared using ultrasound-assisted citric acid complexing method, and characterized by means of techniques such as thermogravimetric analysis and NO temperature-programmed desorption (NO-TPD). The catalytic activities of these materials were evaluated for the decomposition of NO. It was found that the NdSrCu1??xCoxO4?? catalysts were of oxygen vacancies whereas the Sm1:8Ce0:2Cu1??xCoxO4?? ones possessed excessive oxygen (i.e., over-stoichiometric oxygen); with a rise in Co doping level, the oxygen vacancy density of NdSrCu1??xCoxO4?? decreased while the over-stoichiometric oxygen amount of Sm1:8Ce0:2Cu1??xCoxO4?? increased. The NO-TPD results revealed that NO could be activated much easier over the oxygen-deficient perovskite-like oxides than over the oxygen-excessive perovskite-like oxides, with the NdSrCuO3:702 catalyst showing the best e ciency in activating NO molecules. Under the conditions of 1.0% NO/helium, 2800 hr??1, and 600–900°C, the catalytic activity of NO decomposition followed the order of NdSrCuO3:702 > NdSrCu0:8Co0:2O3:736 > NdSrCu0:6Co0:4O3:789 > Sm1:8Ce0:2Cu0:6Co0:4O4:187 > Sm1:8Ce0:2Cu0:8Co0:2O4:104 > Sm1:8Ce0:2CuO4:045, in concord with the sequence of decreasing oxygen vacancy or oxygen excess density. Based on the results, we concluded that the higher oxygen vacancy density and the stronger Cu3+/Cu2+ redox ability of NdSrCu1??xCoxO4?? account for the easier activation of NO and consequently improve the catalytic activity of NO decomposition over the catalysts.     

青海湖区域背景点夏季大气NO2，SO2 和O3 浓度变化规律

利用ECOTECH 公司系列气体监测仪,对青海湖区域背景点夏季的大气污染物的变化规 律及其和气象因素之间的关系进行了分析。结果表明,夏季三种气体中NO₂ 浓度较低,平均值 为2.30×10^-9,其日内变化呈现单峰形式,日较差非常小;SO₂ 浓度较高,平均值达到20.82×10^-9, 波幅变化较大, 其日内变化表现的较不规则;O₃ 浓度夏季平均值高达57.63×10^-9,日变化呈现单 谷形态,早晨7:00-8:00 达到最低值;三种污染物均在凌晨或午夜达到高值。和气象因子的相关 分析表明,NO₂ 静风情况下浓度较低,主要污染源为西北及东北方向的公路及铁路机动车排放; SO₂ 主要来源于当地生物质燃烧排放,同时东南风向时其浓度增高;静风时O₃ 浓度最高,其受 风向影响较小。