Solid State Concepts to Understand Catalysis Using Nanoscale Metallic Particles

New advances in theoretical background and recent experimental results concerning nanometer scale metallic clusters are presented. We will begin by a presentation of the advantages and the limitations of synchrotron radiation techniques to characterise nanometer scale entities. Then, through a review of recent papers, we try to make a link between metallic surfaces and nanometer scale monometallic clusters in the case of the interaction with a small molecule, namely NO.     

Selective catalytic reduction of NO by ammonia using mesoporous Fe-containing HZSM-5 and HZSM-12 zeolite catalysts: An option for automotive applications

Mesoporous and conventional Fe-containing ZSM-5 and ZSM-12 catalysts (0.5–8 wt% Fe) were prepared using a simple impregnation method and tested in the selective catalytic reduction (SCR) of NO with NH₃. It was found that for both Fe/HZSM-5 and Fe/HZSM-12 catalysts with similar Fe contents, the activity of the mesoporous samples in NO SCR with NH₃ is significantly higher than for conventional samples. Such a difference in the activity is probably related with the better diffusion of reactants and products in the mesopores and better dispersion of the iron particles in the mesoporous zeolite as was confirmed by SEM analysis. Moreover, the maximum activity for the mesoporous zeolites is found at higher Fe concentrations than for the conventional zeolites. This also illustrates that the mesoporous zeolites allow a better dispersion of the metal component than the conventional zeolites. Finally, the influence of different pretreatment conditions on the catalytic activity was studied and interestingly, it was found that it is possible to increase the SCR performance significantly by preactivation of the catalysts in a 1% NH₃/N₂ mixture at 500 °C for 5 h. After preactivation, the activity of mesoporous 6 wt% Fe/HZSM-5 and 6 wt% Fe/HZSM-12 catalyst is comparable with that of traditional 3 wt% V₂O₅/TiO₂ catalyst used as a reference at temperatures below 400 °C and even more active at higher temperatures.     

Surface chemistry and kinetics of the hydrolysis of isocyanic acid on anatase

In order to meet the stricter NO_x and particulate emission limits for commercial vehicles, the selective catalytic reduction (SCR) with urea is currently seen having the highest potential. The conversion of urea into ammonia and carbon dioxide consists of two consecutive reactions, in which isocyanic acid is an intermediate that is hydrolyzed over TiO₂. The intrinsic kinetics and the surface chemistry for this reaction are explored. Up to a temperature of 132 °C the reaction was in the intrinsic kinetic regime (E_A = 73 kJ/mol), while at higher temperatures the reaction was limited by pore and external diffusion constraints, respectively. In the presence of NO, NH₃ and NO₂, the catalytic activity was negatively influenced, increasing in severity in the sequence mentioned indicating that nitrates formed from NO₂ were most effective in blocking cations and anions of TiO₂. IR spectroscopy indicates that dissociative adsorption of HNCO on TiO₂ forms Ti–NCO and hydrogen bonded OH species. In the presence of water, isocyanic acid was so rapidly hydrolyzed that only adsorbed ammonia was observed on the catalyst surface. The presence of NO, NH₃ and NO₂ retards hydrolysis leading to the appearance of isocyanate species on the surface.     

600MW超临界燃煤机组SCR烟气脱硝工程实例

介绍了国电铜陵600 MW超临界燃煤机组安装脱硝装置项目的前期研究、主要设计特点、系统设计、调试运行,以及投产运行后的经济情况,得出了一系列火电项目加装脱硝设施建设与运行方面的参考意见.     

新型流光放电等离子体烟气脱硫技术

比较了当前的等离子体烟气脱硫脱硝技术，分析了各种等离子体烟气脱硫脱硝技术的优缺点。介绍了一种新型交直流叠加(AC／DC)电源流光放电等离子体发生技术，以及在此技术的基础上设计的烟气脱硫脱硝工艺流程。     

电晕放电烟气脱硝机理探讨

探讨了电晕放电烟气脱硝之机理,分析了电晕放电烟气脱硝的影响因素,同时提出了一些有待继续研究和探讨的课题。     

Ni/H-USY催化剂上甲烷选择性催化还原NOx的性能

考察了不同负载量的Ni/H-USY（ultra stable Y zeolite）催化剂在氧气含量5%情况下甲烷选择性催化还原氮氧化物性能,同时考察了添加微量Pd和Pt对15％(质量分数)Ni催化剂性能的影响.结果表明,催化剂的催化活性与活性组分的含量间存在密切关系,具有一个最佳的负载量.Pd、Pt的添加提高了氮氧化物的去除率,拓宽了反应活化温度的窗口,同时具有较强的抑制N₂O生成的能力.此外采用XRD、TPR等技术对Ni/H-USY体系催化剂的物相结构及氧化还原性能进行了研究,初步探讨了催化剂的催化活性与活性中心的大小与分布之间的关系.     

Reduction of NOx over Fe/ZSM-5 catalysts: mechanistic causes of activity differences between alkanes

Fe/ZSM-5 catalysts prepared by sublimation of FeCl₃ onto H/ZSM-5 catalyze the selective reduction of NO_x by hydrocarbons to N₂. The order of the relative rates and N₂ yields obtained with different alkanes reveals a non-trivial chemistry. The maximum yield is lower for propane than for n-butane but about the same for n- and iso-butane. However, at temperatures below this maximum, the N₂ yield is higher for propane and n-butane than for iso-butane. Deposits are formed on the catalyst that contain N atoms in a low-oxidation state which are able to react with NO₂ to form N₂. TPO and FTIR results show that the amount and also the character of the deposits depend on the nature of alkanes. The change of the oxidation state of nitrogen from a high value in NO or NO₂ to a lower value in nitrile and amino groups of the deposit is rationalized by applying mechanistic concepts of organic chemistry, including the Beckmann rearrangement and fragmentation. FTIR spectra and the observed oxygen- and nitrogen-containing compounds by GC-MS are potential clues to the reaction mechanism.     

New catalytic technologies in Japan

Recent trends in R&D of catalytic technology in Japan (cleaner and more efficient production, environmental catalysts, and recycling processes) are overviewed and examples of recent achievements are listed. Examples are then described as zeolite-catalyzed organic reactions recently commercialized and expected to be commercialized: hydration of cyclohexene, synthesis of pyridine derivatives and gas-phase Beckmann rearrangement of cyclohexanone oxime. Finally, as an example of environmental catalysts, the NO_x storage–reduction type three-way automobile catalyst, is introduced.     

燃煤锅炉SCR脱硝过程对颗粒物和痕量元素的影响

选择性催化还原（SCR）技术广泛被应用于燃煤电厂NOx减排,而SCR脱硝技术对颗粒物（PM）的影响尚不清楚。在两台300 MW煤粉锅炉机组SCR反应器的入口和出口进行了颗粒物现场采样,分析了SCR脱硝过程对PM的质量粒径分布和痕量元素含量的影响。研究结果显示,SCR脱硝过程产生NH+4,SO2+4等组分并部分转化为颗粒物,促使0.1 μm以下颗粒物团聚、长大,导致0.3 μm以下颗粒物的峰值粒径由0.1 μm增大到0.3 μm,同时使S含量显著升高,最终导致0.3 μm以下颗粒物浓度升高约30.67%。烟气中部分0.3 μm以上颗粒物在SCR反应器中受惯性碰撞作用而分离,使其浓度降低0.06%~33.11%,但峰值粒径和组成成分不变。SCR反应器入口烟气中的气态痕量元素在脱硝过程中向颗粒物转移,引起PM中痕量元素含量变化。实验条件下,经过SCR反应器后,0.3 μm以下颗粒物中Cd,As,Pb含量分别升高104.15%,12.26%和12.18%,而Cr含量降低23.38%;0.3 μm以上颗粒物中各痕量元素含量均略有升高。