Infrared study of nitrogen monoxide adsorption on palladium ion-exchanged ZSM-5 catalysts

The adsorption of NO at room temperature on a H-ZSM-5 catalyst exchanged with Pd(NH₃) ₄ ²⁺ complex and activated in oxygen at 773 K has been examined by FTIR spectroscopy. After the oxidizing treatment, the Pd tetrammine complex decomposed into Pd(II) ions and/or Pd(II) hydroxyl complexes dispersed in the zeolite channels. The subsequent adsorption of NO at room temperature led to the reduction of Pd(II) to Pd(I) entities, resulting in the formation and adsorption of NO₂ on H-ZSM-5. The Pd(I) entities were shown to adsorb NO and form mononitrosyl complexes dispersed in the zeolite porosity and characterized by a single infrared absorption band at 1881 cm^–1. The Pd(I) mononitrosyl complex was shown to reversibly coordinate water and NO₂ molecules. The resulting nitrosyl complex was characterized by a single NO vibration band at 1836 cm^–1.     

活性焦性质对V_2O_5/AC催化剂还原NO_X的影响

考察了活性焦载体制备条件和性质对Ｖ２Ｏ５／ＡＣ催化剂选择催化还原ＮＯ的影响．结果表明,活性焦载体的表面积较大有利于 Ｖ２Ｏ５／ＡＣ催化剂的 ＳＣＲ活性,但活性焦中的炭对 Ｖ２Ｏ５／ＡＣ活性也有重要的影响．ＳＯ２的存在对Ｖ２Ｏ５／ＡＣ催化剂活性有显著的促进作用,但这与活性焦载体的活化条件和性质无关．     

Well defined CuI(NO), CuI(NO)2 and CuII(NO)X (X = O− and/or NO 2 − ) complexes in CuI-ZSMS prepared by interaction of H-ZSM5 with gaseous CuCl

In this note an exchange procedure of the acidic protons of H-ZSM5 by Cu^I ions through reaction with CuCl in the gas phase is described. In the so obtained Cu^I-ZSM5 exchanged zeolite the Cu^I ions are in well defined configuration and form with NO mono and di-nitrosyl complexes of high structural and spectroscopic quality. The Cu^I(NO)₂ species are transformed at RT into Cu^II(NO)X (X=O^– and/or NO ₂ ^– ) species which could represent an intermediate in NO decomposition.     

MnOx-CeO2复合氧化物催化氧化柴油机NO性能研究

为了研究MnO_x-CeO_2复合氧化物催化氧化柴油机NO的性能,采用溶胶凝胶法制备了不同Mn/Ce摩尔比的xMn10Ce/γ-Al_2O_3(x=5,6,7,8)催化剂。利用X射线衍射(X-ray diffraction,XRD)、X射线光电子能谱(X-ray photoelectron spectroscopy,XPS)和H_2程序升温还原(H_2temperature programmed reduction,H_2-TPR)技术分别对其物相结构、元素价态及还原性能进行了表征。结果表明:CeO_2晶粒尺寸随Mn含量增加而逐渐变大,同时添加适量的Mn也有利于提高催化剂中Mn~(4+)的数量,从而促进NO氧化;当x=6时,催化剂的氧化还原性能最好。最后,基于模拟气试验平台考察了不同Mn/Ce比对xMn10Ce/γ-Al_2O_3催化剂氧化NO性能的影响。结果表明:在350℃时,NO浓度达饱和所需时间和反应速率与Mn添加量呈非线性关系;在250~450℃范围内,6Mn10Ce/γ-Al_2O_3的NO氧化性能最好,其NO浓度在350℃时最先达到稳定,仅需4min,但在450℃时则延长至6min,这主要是受热力学平衡及随反应进行活性氧数量及氧空位逐渐饱和共同作用的结果。     

基于可调谐激光吸收光谱技术(TLAS)的内燃机排放组分浓度测试技术研究

开展基于可调谐激光吸收光谱(tunable laser absorption spectroscopy,TLAS)的内燃机排放中气体组分浓度检测技术研究。选取NO气体作为试验室静态测试的目标气体,利用可调谐带间级联激光器(interband cascade lasers,ICL)作为探测光源,采用直接探测法及谐波探测法对4种不同浓度的标准NO气体进行测试,结果与标准气真实浓度吻合度较高。直接探测法中,探测相对误差均方根为2.6%,体积浓度的最大绝对误差为18.6×10~(-6),理论探测极限可达2×10~(-6);谐波探测相对误差均方根为1.4%,最大绝对误差为13×10~(-6),理论探测极限可达10~(-7)。数据处理过程中引入温度修正算法,可实现温度波动下的准确测量。同时,对不同流速下的标准气体进行了在线测量,结果表明气体的流动性对测试结果并无影响。本研究表明:TLAS方法动态响应特性好,环境适应性强,可根据瞬态环境参数进行实时修正,可以在复杂的测试环境下实现高精度、高灵敏度瞬态测量。     

不同路线国V车用柴油机非常规排放对比研究

在AVL全流采样(CVS)发动机台架上,对2台国V柴油机进行了ESC、ETC测试循环,并利用FTIR气体分析仪对非常规气体排放进行了测试。通过对比不同技术路线(增压中冷+共轨+EGR+DOC+DPF和增压中冷+共轨+SCR)发动机的NO2、SO2、NH3、HCHO和NOx排放,对它们的排放特性进行了试验研究;同时还分析了两种路线的CO2排放和油耗情况。研究结果表明DOC+DPF可以使NOx中NO2的比例升高,ESC循环达到了24.3%;两种路线都可以使车用柴油机满足国V排放标准要求,但前者THC、CO、HCHO、NH3排放明显低于后者,后者NO2排放及NO2在NOx排放中的比例明显低于前者。SCR路线在油耗和CO2排放方面相对具有优势。     

电磁场强度对层流火焰和NO生成特性的影响

在液化气与空气燃烧的层流火焰两侧施加放电磁场,测定磁场强度,采用双铂铑热电偶和综合烟气分析仪检测层流自由射流火焰温度和NO浓度,分析了不同磁场强度下层流自由射流火焰特性和NO生成特性. 结果表明,在电磁场作用下火焰长度变短,火焰下部直径增大;随磁场强度增大,火焰面下部温度提高. 电磁场可减少火焰中N, HCN, CN等离子和离子团与氧的碰撞几率,导致NO浓度降低,最大下降值为4.26 mg/m3,最大降幅为78.60%.     

Low-temperature H2-SCR of NO on a novel Pt/MgO-CeO2 catalyst

The selective catalytic reduction of NO by H₂ under strongly oxidizing conditions (H₂-SCR) in the low-temperature range of 100–200 °C has been studied over Pt supported on a series of metal oxides (e.g., La₂O₃, MgO, Y₂O₃, CaO, CeO₂, TiO₂, SiO₂ and MgO-CeO₂). The Pt/MgO and Pt/CeO₂ solids showed the best catalytic behavior with respect to N₂ yield and the widest temperature window of operation compared with the other single metal oxide-supported Pt solids. An optimum 50 wt% MgO-50wt% CeO₂ support composition and 0.3 wt% Pt loading (in the 0.1–2.0 wt% range) were found in terms of specific reaction rate of N₂ production (mols N₂/g_cat s). High NO conversions (70–95%) and N₂ selectivities (80–85%) were also obtained in the 100–200 °C range at a GHSV of 80,000 h⁻¹ with the lowest 0.1 wt% Pt loading and using a feed stream of 0.25 vol% NO, 1 vol% H₂, 5 vol% O₂ and He as balance gas. Addition of 5 vol% H₂O in the latter feed stream had a positive influence on the catalytic performance and practically no effect on the stability of the 0.1 wt% Pt/MgO-CeO₂ during 24 h on reaction stream. Moreover, the latter catalytic system exhibited a high stability in the presence of 25–40 ppm SO₂ in the feed stream following a given support pretreatment. N₂ selectivity values in the 80–85% range were obtained over the 0.1 wt% Pt/MgO-CeO₂ catalyst in the 100–200 °C range in the presence of water and SO₂ in the feed stream. The above-mentioned results led to the obtainment of patents for the commercial exploitation of Pt/MgO-CeO₂ catalyst towards a new NO_x control technology in the low-temperature range of 100–200 °C using H₂ as reducing agent. Temperature-programmed desorption (TPD) of NO, and transient titration of the adsorbed surface intermediate NO_x species with H₂ experiments, following reaction, have revealed important information towards the understanding of basic mechanistic issues of the present catalytic system (e.g., surface coverage, number and location of active NO_x intermediate species, NO_x spillover).     

新型多重富集低NOx煤粉燃烧器的研究

对多重富集低 NOx 煤粉燃烧器的结构及特点进行了分析 ,初步阐述了这种燃烧器的低负荷稳燃和低 NOx 排放原理 ,并进行了一系列冷态模化实验 ,研究了燃烧器结构和气流等因素对这种燃烧器性能 ,即浓淡风比、阻力系数的影响 .实验结果表明 ,档块间开度对燃烧器阻力损失影响显著 ,开度增加可使燃烧器阻力损失降低 ,浓淡风比减小 ,但双档块开度过多 ,会使加粉时煤粉气流的浓淡分离效果变差 ;浓淡风比受燃烧器浓淡侧阻力平衡决定 ,为此 ,必须在浓侧设置阻力调节器 ,满足阻力特性和风量平衡的多重要求 ,根据实验结果得到了优化的燃烧器结构 .     

NO removal by CH4 on Co-NaX-CO and Ag-NaX catalysts in a dual-bed system

NO removal using CH₄ as a reductant in a dual-bed system has been investigated with Co-NaX and Ag-NaX catalysts, which were prepared by Co²⁺-, Ag⁺-ion exchange into zeolite NaX, respectively, and activation for 5 h at 500 °C. The experimental result has been compared with that of a Co-NaX-CO catalyst, additionally pre-treated under CO flow for the Co-NaX catalyst. The cobalt crystal structure of a Co-NaX-CO catalyst is Co₃O₄, which promotes NO oxidation to NO₂ by excess O₂ at a low temperature (523 K). The mechanical mixture of Co-NaX-CO and Ag-NaX catalysts shows a synergy effect on NO reduction to N₂ by CH₄ in the presence of excess O₂ and H₂O, but the NO reduction decreases quickly as time passes. However, the NO reduction to N₂ in a deNO bed at 523 K and a deNO₂ bed at 423 K, which are relatively lower than the reaction temperatures for common SCR systems, still remained at 67% even in a H₂O 10% gas mixture after 160 min.