柴油车尾气碳烟颗粒物催化燃烧催化剂的最新研究进展

柴油车尾气排放的碳烟颗粒已经引起了严重的环境污染问题,必须加以净化处理.柴油车碳烟颗粒的低温燃烧离不开高活性的催化剂.针对柴油车排放的碳烟颗粒物后处理方法中的催化氧化技术,总结了近年来几种主要类型的碳烟燃烧催化剂(贵金属催化剂、碱金属催化剂、单组分过渡金属氧化物催化剂、多组分混合氧化物催化剂和固定结构复合氧化物催化剂)的最新研究进展,并对该研究方向存在的主要问题和应用前景进行了探讨.     

N_2O直接分解催化剂的研究进展

本文详细综述了用于Ｎ２Ｏ直接分解催化剂的研究进展情况。Ｎ２Ｏ分解催化剂大致可以分作以下几类，即：（１）稀土氧化物及相关氧化物；（２）复合金属氧化物；（３）沸石催化剂；（４）水滑石热分解产物催化剂。前两类催化剂注重探讨催化分解Ｎ２Ｏ的机理；而后两类催化剂主要研究催化分解Ｎ２Ｏ的活性。     

A review of the catalysts used in the reduction of NO by CO for gas purification

The reduction of NO by the CO produced by incomplete combustion in the flue gas can remove CO and NO simultaneously and economically. However, there are some problems and challenges in the industrial application which limit the application of this process. In this work, noble metal catalysts and transition metal catalysts used in the reduction of NO by CO in recent years are systematically reviewed, emphasizing the research progress on Ir-based catalysts and Cu-based catalysts with prospective applications. The effects of catalyst support, additives, pretreatment methods, and physicochemical properties of catalysts on catalytic activity are summarized. In addition, the effects of atmosphere conditions on the catalytic activity are discussed. Several kinds of reaction mechanisms are proposed for noble metal catalysts and transition metal catalysts. Ir-based catalysts have an excellent activity for NO reduction by CO in the presence of O₂. Cu-based bimetallic catalysts show better catalytic performance in the absence of O₂, in that the adsorption and dissociation of NO can occur on both oxygen vacancies and metal sites. Finally, the potential problems existing in the application of the reduction of NO by CO in industrial flue gas are analyzed and some promising solutions are put forward through this review.

     

富氧条件下NOx催化净化的研究进展

本文对富氧条件下NOx的催化净化进行了综述与探讨,着重分析了分子筛催化剂、贵金属催化剂以及金属氧化物催化剂在碳氢化合物选择性催化还原NOx反应中的活性及其影响因素,描述了催化反应的机理,并指出了今后的研究方向.     

废水催化湿式氧化稀土金属氧化物催化剂的研制

采用共沉淀法制得锰铈复合氧化物催化剂,催化湿式氧化处理高浓度苯酚废水。通过正交实验筛选催化剂制备条件,单因素实验优化制得催化剂。研究了CWAO处理废水条件下的金属离子溶出和催化剂的表征。结果表明,该催化剂在低温低压条件下具有优良的湿式氧化催化活性,且金属离子溶出量低,是一种CWAO处理高浓度有机废水中极具应用前景的新型高效催化剂。     

富氧条件下选择性还原NO的复合催化剂体系

选择性催化还原法是净化稀燃汽车尾气中NOx 的最有效途径之一 ,单一催化组分或单一类型的催化剂很难满足实际需要 ,复合催化剂的研究成为必然趋势。本文介绍了复合催化体系的组合形式 ,回顾了国内外最近几年复合催化剂体系净化NOx 的研究成果 ,为将来设计新的复合催化体系提出了建议     

铁及铁铜氧化物对臭氧氧化酸性红B的催化效能

采用自蔓延溶胶凝胶法分别制备了铁氧化物和铁铜复合氧化物催化剂,以酸性红B为降解对象,对比了单独臭氧氧化、铁氧化物和铁铜复合氧化物催化臭氧氧化对酸性红B的降解效果,考察了磁力搅拌速度(500～1 640 r/min)、溶液pH(3～11)、臭氧投加速率(3.55～28.4 mg/min)对铁铜复合氧化物催化性能的影响。结果表明,与单独臭氧氧化比较,铁氧化物和铁铜复合氧化物均能加速酸性红B的降解,促进色度和COD的去除,结合催化剂的表征结果,推断催化剂表面羟基促进臭氧分解产生.OH是其氧化性能较好的主要原因,另外,催化剂的吸附能力对催化性能也有一定影响。随着磁力搅拌速度、溶液pH、臭氧投加速率的增大,铁铜复合氧化物催化臭氧氧化酸性红B的效果越好。     

Effect of the Mn oxidation state and lattice oxygen in Mn-based TiO2 catalysts on the low-temperature selective catalytic reduction of NO by NH3

TiO₂-supported manganese oxide catalysts formed using different calcination temperatures were prepared by using the wet-impregnation method and were investigated for their activity in the low-temperature selective catalytic reduction (SCR) of NO by NH₃ with respect to the Mn valence and lattice oxygen behavior. The surface and bulk properties of these catalysts were examined using Brunauer-Emmett-Teller (BET) surface area, X-ray diffraction (XRD), temperature-programmed reduction (TPR), and temperature-programmed desorption (TPD). Catalysts prepared using lower calcination temperatures, which contained Mn⁴⁺, displayed high SCR activity at low temperatures and possessed several acid sites and active oxygen. The TPD analysis determined that the Brönsted and Lewis acid sites in the Mn/TiO₂ catalysts were important for the low-temperature SCR at 80～160 and 200～350 °C, respectively. In addition, the available lattice oxygen was important for attaining high NO to NO₂ oxidation at low temperatures.

Implications: Recently, various Mn catalysts have been evaluated as SCR catalysts. However, there have been no studies on the relationship of adsorption and desorption properties and behavior of lattice oxygen according to the valence state for manganese oxides (MnO_x). Therefore, in this study, the catalysts were prepared by the wet-impregnation method at different calcination temperatures in order to show the difference of manganese oxidation state. These catalysts were then characterized using various physicochemical techniques, including BET, XRD, TPR, and TPD, to understand the structure, oxidation state, redox properties, and adsorption and desorption properties of the Mn/TiO₂ catalysts.     

固体超强酸和金属氧化物类催化剂上CH4-SCR还原NOx研究进展

由于还原剂甲烷价廉易得,甲烷选择性催化还原NO_x（简称CH₄-SCR）被认为是最有潜力替代NH₃-SCR的催化还原技术。现有的CH₄-SCR催化剂中,分子筛类催化剂因催化活性高而被广泛研究,但由于其水热稳定性不好,使得非分子筛负载的催化剂成为近年来的研究热点,其中主要包括固体超强酸和氧化物两大类。综述了这两类催化体系在催化活性、反应机理及掺杂改性等方面的研究现状,比较了各种催化剂的优缺点,并对CH₄-SCR的发展前景进行了展望。     

CuMnO_x/γ-Al_2O_3及稀土助剂对VOCs催化燃烧性能的影响

利用浸渍法制备了Cu-Mn复合氧化物催化剂和加入不同稀土含量的Cu-Mn复合氧化物催化剂,通过实验优选出加入稀土催化剂中稀土含量的最优配比,以气相色谱为检测手段,考察了加人稀土和不加稀土催化剂的催化燃烧性能,结果表明,加入稀土的催化剂T_(99)(催化处理效率达到99%时的温度)比不加稀土的催化剂降低30～40℃,具有更好的低温活性,且对多种VOCs均能降低反应温度。     

CuMnOx／γ-Al2O3及稀土助剂对VOCs催化燃烧性能的影响

利用浸渍法制备了Cu—Mn复合氧化物催化剂和加入不同稀土含量的Cu—Mn复合氧化物催化剂,通过实验优选出加入稀土催化剂中稀土含量的最优配比,以气相色谱为检测手段,考察了加入稀土和不加稀土催化剂的催化燃烧性能,结果表明,加入稀土的催化剂T99（催化处理效率达到99％时的温度）比不加稀土的催化剂降低30～40℃,具有更好的低温活性,且对多种VOCs均能降低反应温度。     

The characteristics of wet air oxidation of phenol over CuOx/Al2O3 catalysts: effect of copper loading

The nature of active copper species is well-known to vary with copper loading, i.e., isolated Cu(2+) to bulk CuO. In this work, however, the effect of copper loading on the activity and the selectivity was investigated for the wet oxidation of phenol over CuO(x)/Al(2)O(3) catalysts. The activity and the mineralization selectivity of the catalysts increased with copper loading up to 7wt% and remained almost the same at a higher loading. The optimum copper loading was about 7wt% for the wet oxidation of phenol over CuO(x)/Al(2)O(3) catalysts in this work. The nature of copper species with different loading was characterized with TPR, XRD, and XANES. The chemical states of copper in the CuO(x)/Al(2)O(3) catalysts were confirmed as varying with copper loading: isolated Cu(2+) ions for 1wt%; highly dispersed Cu(2+) cluster for 5wt% and 7wt%, and bulk CuO for 10-25wt%. The stability of the CuO(x)/Al(2)O(3) catalysts with different copper loading was also studied with respect to carbonaceous deposits and copper leaching.     

铈锆固溶体负载LaCoO3催化碳烟的性能和表征

用柠檬酸法制备了铈锆固溶体负载不同量LaCoO3的催化剂。用热重法测试了催化剂样品对碳烟的催化活性。采用程序升温还原法（H2-TPR）、BET、X-射线衍射仪（XRD）和X-射线光电子能谱仪（XPS）对催化剂进行了测试。结果表明,铈锆固溶体表面形成了稳定的LaCoO3钙钛矿相结构;负载量为30%LaCoO3的催化剂具有最高的催化活性,起燃温度降到530℃;催化剂的催化活性与催化剂还原峰强度以及催化剂表面氧物种OII的含量紧密相关。     

溶胶凝胶法制备铜系催化剂及其稳定性研究

利用溶胶凝胶法制备超细催化湿式氧化铜系催化剂,考察了制备过程中各个工艺参数对铜系催化剂稳定性的影响,重点考察了不同分子量聚丙烯酸络合剂对催化剂稳定性及粒径的影响,应用BET以及SEM等技术手段,对催化剂的物相结构、表面孔结构和粒子形貌等进行了研究.结果表明,该催化剂对处理焦化废水具有优良的反应活性,且金属离子溶出量低,是一种极具应用前景的高效催化剂.     

Evaluation of Cu-PPHs as active catalysts for the SCR process to control NOx emissions from heavy duty diesel vehicles

Copper based catalysts supported on mesoporous materials, which were in turn based on a surfactant expanded zirconium phosphate for the formation of silica galleries in the interlayer space, were prepared by the impregnation method. They were then characterised and tested in the selective catalytic reduction of NO with ammonia as active catalysts for the control of the NOx emissions from heavy duty vehicles. Copper catalysts displayed a high catalytic performance, even in the presence of 14% (v/v) of H2O and 100 ppm of SO2. They also displayed improved catalytic behaviour when compared to a CuZSM5 catalyst.     

Enhanced photocatalytic degradation of VOCs using Ln3+-TiO2 catalysts for indoor air purification

Two types of lanthanide ion-doped titanium dioxide (Ln3+-TiO2) catalysts including La3+-TiO2 and Nd3+-TiO2 were prepared by a sol-gel method. The effects of the lanthanide ion doping on the crystal structure, surface area, adsorption properties, pore size distribution, and surface chemical state of the catalysts were investigated by means of XRD, BET, and XPS. As results, the crystal size decreased significantly, while the specific surface area, t-plot total surface area, micropore volume, and the total pore volume increased owing to the lanthanide ion doping. The nitrogen adsorption-desorption isotherms of the catalysts showed that the N2 adsorption ability of the Ln3+-TiO2 catalysts was better than the TiO2 catalyst. Among them, the 0.7% Ln3+-TiO2 catalysts demonstrated the highest adsorption ability. The photocatalytic activity of the catalysts was investigated in the experiments of the photocatalytic degradation of benzene, toluene, ethylbenzene and o-xylene (BTEX) in a gaseous phase. The photocatalytic efficiency of the TiO2 catalysts with the lanthanide ion doping was remarkably enhanced by BTEX removal. The 1.2% Ln3+-TiO2 catalysts achieved the highest photocatalytic activity. The enhanced photodegradation of BTEX is possibly due to the improved adsorption ability and the enhanced electron-hole pairs separation due to the presence of Ti3+ on the surface of Ln3+-TiO2 catalysts and the electron transfer between the conduction band/defect level and lanthanide crystal field state.     

高浓度焦化废水湿式氧化铜系催化剂的研制

通过共沉淀法制备了铜系催化剂 ,用于催化湿式氧化处理高浓度焦化废水。结果表明 ,铜氧化物催化剂的催化活性明显优于其他过渡金属氧化物 ;优化催化剂的设计和制备方法 ,可有效地改善Cu2 +的溶出问题 ,使该类催化剂具有广阔的应用前景     

Mn的氧化价态对Mn／γ-Al2O3催化剂催化臭氧氧化气相低浓度甲苯的影响

采用共沉淀法,以Al2O3为载体制备Mn／γ-Al2O3和Mn—Ce／Mn／γ-Al2O3催化剂,并分别在N2气氛和O2气氛下焙烧。采用固定床连续流动反应器,研究所制备催化剂在室温条件下催化臭氧氧化甲苯的性能。通过XRD、XPS和FTIR等手段对催化剂的结构和组成进行表征。结果表明,Mn／Mn／γ-Al2O3催化剂具有良好的催化臭氧氧化甲苯和催化臭氧自身分解的性能,共沉淀法制备催化剂的最佳Mn负载量为20％。O2气氛焙烧和Ce的加入,可以有效提高催化剂的活性和寿命。原因是O2气氛焙烧和Ce的加入可以提高Mn的氧化价态。催化剂失活的主要原因是有机副产物在催化剂表面吸附堆积,失活催化剂在550℃、空气气氛下焙烧可恢复催化性能。     

Photocatalytic degradation of AZO dyes by supported TiO2 + UV in aqueous solution

The photocatalytic degradation performance of photocatalysts TiO2 supported on 13-X, Na-Y, 4A zeolites with different loading content was evaluated using the photocatalytic oxidation of dyes direct fast scarlet 4BS and acid red 3B in aqueous medium. The results showed that the best reaction dosage of TiO2-zeolite catalysts is about 2 g/l and the photocatalytic kinetics follows first order for all supported catalysts. The photocatalytic activity order of the three series catalysts is 13X type >Y type >4A type. The physical state of titanium dioxide on the supports is evaluated by X-ray photoelectron spectra (XPS), powder X-ray diffraction (XRD), BET, and FTIR.     

制备方法对MgAl水滑石衍生氧化物负载钯催化剂丙烷完全氧化活性的影响

以沉积沉淀法(DP)、浸渍法(IM)和共沉淀法(CP)制备MgAl水滑石衍生氧化物负载钯催化剂,用ICP、XRD、SEM、TEM、EDS、TPR以及比表面测定等手段对催化剂进行了表征.ICP和XRD数据表明用上述3种方法均可成功制备水滑石为前体载钯催化剂.SEM、TEM、EDS数据表明不同方法制备的样品具有不同的形貌以及钯在其中的分散度.综合各类表征数据可知Pd在催化剂中暴露的活性位是影响其活性的主要因素.