焙烧温度对Fe2O3/SAPO-34催化剂低温NH3选择性催化还原NO性能的影响

采用尿素沉淀法制备了一系列Fe_2O_3/SAPO-34催化剂,考察了催化剂焙烧温度(200、300、400、500℃)对低温NH_3选择性催化还原(NH_3-SCR)NO性能的影响,并利用X射线衍射(XRD)、N_2吸附-脱附、原子吸收光谱(AAS)、场发射扫描电镜(FE-SEM)、X射线光电子能谱(XPS)、H_2程序升温还原(H_2-TPR)、NH_3程序升温脱附(NH_3-TPD)等多种手段对催化剂的表面结构和物理化学性质进行表征分析.XRD和FE-SEM分析表明,在较低的焙烧温度(400℃)下,铁物种能够高度均匀地负载在SAPO-34表面上.NH_3-TPD和H_2-TPR分析表明,高分散状态的Fe_2O_3使催化剂暴露出更多的强酸位和活性位,有利于提高催化剂的NH_3吸附和活化能力及氧化还原性能,从而使催化剂呈现出更高的低温SCR活性.BET和XPS分析表明,在较低的焙烧温度下,Fe_2O_3/SAPO-34催化剂具有更大的比表面积和更高的化学吸附氧比例,促进NO氧化为中间产物NO_2,从而加快低温SCR反应的进行.活性测试结果表明,300℃焙烧的Fe_2O_3/SAPO-34催化剂具有最佳的低温活性和较强的抗硫抗水性能,在空速为40000 h~(-1)的条件下,且反应温度为190~240℃时,NO转化率达90%以上且N_2选择性接近100%.     

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。     

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.     

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.     

扩散法测定沈阳市环境空气中的二氧化氮

被动式个体采样器（passive personal sampler）是基于气体分子扩散或渗透原理,采集空气中气态或蒸汽态污染物的一种采样方法,它不使用任何电源和抽气动力,是一种无泵采样器,可连续采样,并可作为环境空气质量评价的监测。国内外开展室内被动式扩散采样器的研究和应用的文章很多,并逐步应用于室内环境空气的监测方面,特别是对人体健康的影响评价。但是,在使用中要特别注意风速对气体污染物的采样速率的影响,为此文章介绍了利用中国预防医学科学院环境卫生监测所研制的室内分子扩散采样器[1],并自制挡风筒,使分子扩散采样器暴露在一个恒定的风速环境中,排除风速对采样速率的影响,应用于室外环境监测沈阳市环境空气中的二氧化氮的方法。经实验室性能评价能够满足实验室测试的要求,并经有动力的溶液吸收管法现场对比测试,两种测试结果一致。为室外环境监测二氧化氮提供了一个经济、准确,有实用价值的采样方法。     

Simultaneous removal of NO and SO2 from dry gas stream using non-thermal plasma

In order to investigate the feasibility of sequential removal NO and SO_2 using non-thermal plasma and adsorbent simultaneously,the removal of NO and SO_2 from dry gas stream(NO/SO_2/N_2/O_2)with very little O_2 using non-thermal plasma was investigated using a coaxial dielectric barrier discharge.Comparative experiments were carried out in the dry gas stream with and without Ar respectively at O_2 concentration of 0.1%.The results showed that NO could be removed remarkably and it would be enhanced in the presence of Ar in the dry gas stream.It seems that SO_2 could not be removed unless there is Ar in the dry gas stream.The mechanism of removal of NO and SO_2 in the dry gas stream was discussed.     

砍伐干扰对华北落叶松林下土壤有效氮含量空间异质性的影响

为揭示砍伐干扰对森林土壤有效氮(NO3--N和NH4+-N)含量空间异质性的影响,并为进一步认识森林生态系统N素循环及森林系统结构和功能提供基础依据.选取华北落叶松砍伐干扰林分(样地A)和未砍伐干扰林分(样地B),采用基于地统计学中区域化变量理论的格局分析方法.对样地林下土壤(0～30cm)有效氮含量的空间异质性特征进...     

蜂窝式MnO_x/PG-CC催化剂的制备及低温选择性催化还原法脱硝性能

采用悬浮浆液法将凹凸棒石(PG)涂覆于堇青石蜂窝陶瓷(CC)基体上,制取PG-CC涂层载体,利用过饱和浸渍法负载MnOx制备MnOx/PG-CC催化剂应用于柴油车尾气SCR脱硝.考察了制备条件对催化剂低温SCR活性的影响,采用BET、SEM-EDS、XRD手段对催化剂的理化性质进行了分析表征,探讨了催化剂结构特性与活性间的构效关系.研究发现,堇青石基体经PG涂层后,对活性组分的一次负载量显著增加,由3%增至13%,对应的催化剂低温脱硝活性显著提高,在100℃脱硝活性由10%提高到78%.结果分析表明,堇青石基体经PG涂层后比表面积大幅度增加,可以承载更高的活性组分,且活性组分具有更好的分散性,从而使得催化剂的活性点增加;另一方面,PG涂层催化剂具有更高的表面Mn4+/Mn3+价态比,更有利于催化剂的低温选择性催化还原法(SCR)活性.活性组分Mn Ox与PG涂层之间的协同作用是导致催化剂低温SCR脱硝活性得以提升的关键因素.研究结果表明,通过对堇青石蜂窝基体进行凹凸棒石涂层后采用浸渍法负载锰氧化物,可制备出具有较高低温SCR活性的蜂窝式模块催化剂.     

Role of NO in Hg oxidation over a commercial selective catalytic reduction catalyst V2O5–WO3/TiO2

Experiments were conducted in a fixed-bed reactor that contained a commercial catalyst, V₂O₅–WO₃/TiO₂, to investigate mercury oxidation in the presence of NO and O₂. Mercury oxidation was improved by NO, and the efficiency was increased by simultaneously adding NO and O₂. With NO and O₂ pretreatment at 350°C, the catalyst exhibited higher catalytic activity for Hg⁰ oxidation, whereas NO pretreatment did not exert a noticeable effect. Decreasing the reaction temperature boosted the performance of the catalyst treated with NO and O₂. Although NO promoted Hg⁰ oxidation at the very beginning, excessive NO counteracted this effect. The results show that NO plays different roles in Hg⁰ oxidation; NO in the gaseous phase may directly react with the adsorbed Hg⁰, but excessive NO hinders Hg⁰ adsorption. The adsorbed NO was converted into active nitrogen species (e.g., NO₂) with oxygen, which facilitated the adsorption and oxidation of Hg⁰. Hg⁰ was oxidized by NO mainly by the Eley–Rideal mechanism. The Hg⁰ temperature-programmed desorption experiment showed that weakly adsorbed mercury species were converted to strongly bound ones in the presence of NO and O₂.