富氧条件下Ag/Al2O3和Cu/Al2O3组合催化剂催化C3H6选择性还原Nox的性能

 在全自动催化剂活性评价装置上,考察了富氧条件下Ag/Al2O3和Cu/Al2O3两种催化剂上催化丙烯还原NOx的活性. 在实验温度范围(200～650 ℃)内,Ag/Al2O3具有 优异的催化丙烯选择性还原NOx的活性,但同时有大量副产物CO形成. Cu/Al2O3选择性催化丙烯还原NOx的活性不高,却能有效促进CO的氧化. 在无水条件,Ag/Al2O3-Cu/Al2O3组合体系具有与Ag/Al2O3相似的脱除NOx活性,同时使CO在300 ℃以后几乎完全转化. 在10%水蒸气存在的情况下,Ag/Al2O3-Cu/Al2O3组合催化剂脱除NOx的活性下降,但水蒸气对CO转化率的影响不大.     

催化剂低温NH3选择催化还原NO的研究

研究了碳纳米管担载的五氧化二钒（V₂O₅/CNTs）催化剂上NO低温选择催化还原反应（SCR）。与活性炭载体的催化剂作了对比,结果显示,在负载低含量V₂O₅时碳纳米管较活性炭显示了更好的催化能力,而且在SO₂存在下,催化性能有更大幅度的提高。暂态反应实验显示,V₂O₅/CNTs 催化剂上NO选择催化还原反应遵循Eley Rideal机理,即反应发生于吸附态的NH₃和气相或弱吸附的NO之间。     

新型铬锰复合氧化物低温选择性催化氨还原NOx

采用柠檬酸法合成了一系列铬锰复合氧化物催化剂,利用X射线衍射及X射线光电子能谱研究了催化剂活性相态,并考察了铬锰摩尔比对反应活性的影响. 结果表明,该体系在有氧条件下氨低温选择性催化还原氮氧化物反应中显示出优异的活性,其中Cr(0.4)-MnOx催化剂具有最佳低温催化活性,在空速 30 000 h-1和120 ℃条件下, NOx转化率达98.5%, N2选择性达100%. 在MnOx中添加Cr后形成了CrMn1.5O4晶相, 该相态在低温选择性催化还原NOx过程中起重要作用.     

Mechanism of the Selective Catalytic Reduction of NOx with NH3 over W-Doped Fe/TiO2 Catalyst

The W-doped Fe/TiO2 catalyst prepared by an impregnation method exhibited a good NH3-selective cata- lytic reduction（SCR） activity and N2 selectivity with broad operation temperature window. The interaction between Fe and W could increase the amount of surface chemisorbed oxygen, and thus enhances the low temperature SCR activity by facilitating the fast SCR of 2NH3＋NO＋NO2 →2N2＋3H2O. The NH3-SCR reaction mechanism over the W-Fe/TiO2 was fully investigated via in situ diffuse reflectance infrared Fourier transform spectroscopy（in situ DRIFTS）. In the low temperature range（〈250 ℃）, the reactive surface species were mainly coordinated NH3, ionic NH~ and adsorbed NO2 species, and the SCR mainly followed the Langmuir-Hinshelwood mechanism, during which the adsorbed NO2 species became the important active sites. In the high temperature range（〉250 ℃）, the reactive surface species were mainly NH2, and the SCR mainly followed the Eley-Rideal mechanism, during which the for- mation of NH2NO intermediate species after H-abstraction of NH3 was the rate-determining step.     

NO_x在Pt及其合金表面吸附的第一性原理模拟研究

本研究通过密度泛函理论(DFT)模拟氮氧化物(NO_X)在Pt及Pt/(Au,Rh)合金slab模型(111)表面的吸附行为,计算其吸附能与结合能.对比NO和NO_2的实验结果,表明合金元素的添加,可能使Pt(111)对NO_X的吸附能力和选择性发生变化,其中Au元素表面置换使得总吸附能力下降,但更容易吸附NO_2; Rh元素表面置换则使得总吸附能力提高,且更容易吸附NO.     

MnOx/SAPO-11催化剂的制备、表征及其低温NH3-SCR活性

分别采用浸渍法、柠檬酸络合法以及沉淀法在SAPO-11分子筛上负载MnO_x,制备了一系列MnO_x/SAPO-11催化剂。考察了催化剂的低温NH₃选择性催化还原(SCR) (NH₃-SCR) NO_x的性能。结果表明,沉淀法制备的负载量为20%(w)的MnO_x/SAPO-11催化剂表现出最优异的低温NH₃-SCR性能及N₂选择性。通过X射线衍射(XRD)、扫描电镜(SEM)、能量散射谱(EDS)、原子吸收光谱(AAS)、N₂吸附-脱附、X射线光电子能谱(XPS)、H₂程序升温还原(H₂-TPR)、NH₃程序升温脱附(NH₃-TPD)以及NO/O₂程序升温脱附-质谱(NO/O₂-TPD-MS)等多种表征手段对催化剂的结构及表面性质进行分析。表征结果显示,采用不同方法制备催化剂时,其表面MnO_x的存在形式和晶相结构不同。沉淀法制备的催化剂表面存在无定型态MnO_x以及MnO₂晶型,具有较大的介孔及外表面积、更多比例的Mn⁴⁺和化学吸附氧,同时表面存在对反应有利的中强酸以及强酸。因此,催化剂在低温SCR反应阶段能够生成重要中间产物NO₂,从而表现出最佳低温活性。同时,三种制备方法均能使MnO_x相对均匀分散在SAPO-11表面。SAPO-11对催化剂表面MnO_x物种的形成具有一定的影响,从而影响催化剂的酸性,拓宽了MnO_x的活性温度窗口,提高了催化剂的N₂选择性。     

化学发光法大气氮氧化物浓度自动分析仪中光信号探测模块温控系统设计

化学发光法是测量低浓度的大气氮氧化物含量的有效方法,可用于24h连续自动分析的大气环境监测系统。然而该方法需要高温转换室、高压臭氧发生模块、高温反应室等模块,使得仪器内的环境分布极为复杂,仪器在长时间运行后容易出现灵敏度下降、信噪比降低等现象。针对上述现象,设计了用于仪器的光信号探测模块的温度控制系统。该温控系统基于PID控制原理,通过AVR单片机ATMEGAl6对半导体制冷片（Ther—mo—ElectricCooling,TEC）的闭环控制来实现温度的精密控制。实验结果表明,该系统可以使光信号探测模块的温度控制在5℃±0．1℃,光电倍增管的暗噪声从25℃时的363个／s下降到5℃时的8个／s光子数,噪声波动标准差也从22降到3,能够很好地满足系统对信号探测稳定性的要求。     

Flow characterization and dilution effects of N_2 and CO_2 on premixed CH_4/air flames in a swirl-stabilized combustor

Numerically-aided experimental studies are conducted on a swirl-stabilized combustor to investigate the dilution effects on flame stability, flame structure, and pollutant emissions of premixed CH4/air flames. Our goal is to provide a systematic assessment on combustion characteristics in diluted regimes for its application to environmentally-friendly approaches such as biogas combustion and exhanst-gas recirculation technology. Two main diluting species, N2 and CO2, are tested at various dilution rates. The results obtained by means of optical diagnostics show that five main flame regimes can be observed for Nz-diluted flames by changing excess air and dilution rate. CO2-diluted flames follow the same pattern evolution except that all the domains are shifted to lower excess air. Both N2 and CO2 dilution affect the lean blow- out （LBO） limits negatively. This behavior can be counter-balanced by reactant preheating which is able to broaden the flammability domain of the diluted flames. Flame reactivity is degraded by increasing dilution rate. Meanwhile, flames are thickened in the presence of both diluting species. NOx emissions are significantly reduced with dilution and proved to be relevant to flame stability diagrams： slight augmentation in NOx emission profiles is related to transitional flame states where instability occurs. Although dilution results in increase in CO emissions at certain levels, optimal dilution rates can still be proposed to achieve an ideal compromise.     

稀燃汽油机EGR对LNT催化器工作过程影响研究

先前试验中发现过量EGR%对稀燃汽油机LNT的NO_x转化率存在一定的恶化现象。以实际发动机排气作为LNT入口边界条件,对不同EGR率,LNT内部NO_x吸附、脱附及还原过程进行数值仿真。结果发现,稀燃模式LNT的NO_x溢流量随时间推移而增加,在该模式结束前达到稳定。     

基于Keggin阴离子链镍化合物的结构和质子导电性

由H+(H2O)2.5阳离子,[Ni(H2O)8]2+阳离子,[PW12O40]3-阴离子和异烟酸氮氧化物(HINO)自组装成一个具有质子导电性的化合物{[Ni(H2O)8][H(H2O)2.5](HINO)4(PW12O40)}n。293 K的单晶X-射线衍射分析表明标题化合物形成1个带有一维通道的三维氢键网络结构。[PW12O40]3-阴离子填充在一维通道内并且自组装成多阴离子链。热重分析表明在20~100℃范围内化合物没有失重,表明化合物结构单元内所有的水分子在100℃以下不易失去。标题化合物在85~100℃范围内表现出好的离子导电性(1×10-3~2×10-3S.cm-1)。