Study on non-noble metal catalysts for automotive emission control

Cordierite honeycomb catalysts supported on rare earth (RE)-transition metal oxides, used for removing simultaneously three major pollutants, carbon monoxide (CO), hydrocarbon (HC) and nitrogen oxides (NO_x), in automotive emission have been investigated. The results indicate that the catalyst has improved three-way performance (TWP).     

Catalytic Reduction of NOx by CO and Hydrocarbons Over Different Catalysts in the Presence or Absence of O2

The performances of a non-noble metal (catalyst A), a non-noble metal catalyst containing a smaller amount of a noble metal (catalyst B) and noble metal (catalyst C) for NOx reduction at 400 - 600°C and space velocity of 16×10^-1h^-1 have been studied by means of a fixed-bed continuous flow system. In both the absence and presence of oxygen, the following activity orders of catalysts for the reduction of NOx to N₂ by CO and C₃H₆(HC) can be given: C > B > A and B > A C, respectively. Meanwhile, there was CO formation in the reduction reactions of NOx by HC on the three catalysts. The amount of CO produced on catalyst C was the largest of the three catalysts.     

Reactions of organic exhausts and the thermal stability of catalysts

The catalytic combustion of various organic compounds has been investigated over noble and non-noble metal catalysts using a fixed bed. It was concluded that the activity order of different organic compounds on a noble metal catalyst, is toluene > 2-butanone > benzene >n-heptane≈isopropyl alcohol > acrylonitrile > cyclohexane. On non-noble metal catalyst, it is isopropyl alcohol > 2-butanone > acrylonitrile > toluene >n-heptane > cyclohexane > benzene. In order to compare the thermal stability of catalysts, the catalytic reaction of toluene has been studied over noble and non-noble metal catalysts which were calcined at various temperatures up to 900°C for 3 h.     

Self-propagating high-temperature synthesis in the production of catalysts and supports

The use of the SHS method for production of catalysts and supports is shown. Complex oxides with the spinel and perovskite structure were obtained in systems containing Co, Cu, Cr, Mn in a cellular monolithic form. The catalysts obtained were active in the oxidation reactions of CO and hydrocarbons.     

分步沉淀对CeO2-ZrO2-Y2O3-La2O3材料热稳定性的影响

研究了传统沉淀法和分步沉淀对CeO₂-ZrO₂-Y₂O₃-La₂O₃(CZ)材料结构和性能的影响. N₂-吸/脱附、 OSC、 H2-TPR和催化剂三效活性等测试结果表明:分步沉淀所制备的CZ材料表现出更优的氧化还原性能和织构性能.基于此,继续优化分步沉淀中晶种的含量(10%、 50%、 90%),结果表明:较少的晶种诱导可以极大程度提高材料热稳定性能和织构性能,但进一步增加晶种含量对材料热稳定性能提升作用不明显.其中,当晶种量为10%时,所得CZ材料在高温焙烧后仍保持最大比表面积及稳定的立方相结构,表现出最好的织构性能和热稳定性能,其负载的单Pd三效催化剂也因此表现出最优的三效催化活性.     

Influence of CeO2 and La2O3 on properties of palladium catalysts used for emission control of natural gas vehicles

Pd/YZ-Al2O3 (Y and Zr modified Al2O3, and hereafter, labelled as Al) catalysts with 4 wt% additive CeO2 and/or La2O3 were prepared and characterized by X-ray photoelectron spectroscopy (XPS), NO-temperature programmed desorption (NO-TPD), N2-adsorption/desorption (Brunauer-Emmet-Teller BET method), X-ray diffraction (XRD) and CO-chemisorption. Catalytic activities for CH4, CO and NO conversion were tested in a gas mixture simulated the emissions from natural gas vehicles (NGVs) operated under stoichiometric conditions. The results indicated that all catalysts exhibited excellent catalytic performances for CH4 and CO oxidation and the promoting effect of CeO2 or La2O3 was significant for NO conversion. XPS results showed that the electron density around Pd was increased by CeO2 and/or La2O3, the binding energy of Pd 3d decreased as the order: Pd/Al>Pd/Ce/Al>Pd/La/Al>Pd/CeLa/Al. The electron-rich Pd showed Rh-like catalytic properties which exhibited good activity for the reduction of NO. NO-TPD results showed that the addition of CeO2 and/or La2O3 increased NO adsorption on surface, and promoted the conversion of NO.     

钯前驱体对汽车尾气处理Pd/Ce_(0.67)Zr_(0.33)O_2催化剂催化性能的影响(英文)

分别以Pd(NO3)2,Pd(NH3)4(NO3)2和H2Pd Cl4为钯前驱体制备了Pd/Ce0.67Zr0.33O2(CZ)催化剂.以硝酸钯为钯前驱体制得的Pd/CZ(NO)催化剂具有较高的储氧量,存在较多的小的钯簇,其钯与载体间相互作用较强,因此在三种新鲜催化剂中对HC和CO的消除表现出了最好的催化活性.以硝酸四氨钯为钯前驱体制得的Pd/CZ(NH)催化剂具有较高的钯分散度,存在较多的大的钯簇,同时存在金属态和氧化态的钯,从而对NO和NO2的消除表现出了较好的催化活性.以氯钯酸为钯前驱体制得的Pd/CZ(Cl)催化剂由于钯分散度较小,钯与载体间作用较弱,存在的CeOCl抑制了氧空穴的生成,因此对各种反应物的催化活性都较低.但Pd/CZ(Cl)催化剂表现出了较好的热稳定性,这是由于老化处理消除了残余的氯物种并且促进了钯与载体间的作用.     

Tungsten-based catalysts for the oxidation of cyclohexanol: The effect of phase transfer catalysts

The oxidation of cyclohexanol with hydrogen peroxide in the presence of tungsten-based catalysts was studied in this paper. The effect of phase transfer catalysts was discussed and clarified. [CTA]₉[SbW₉O₃₃] showed the best activity and good recyclability with a conversion over 95%.     

Supported catalysts for simultaneous removal of SO2, NOx,and Hg0 from industrial exhaust gases: A review

The simultaneous removal of SO₂, NO_x and Hg⁰ from industrial exhaust flue gas has drawn worldwide attention in recent years. A particularly attractive technique is selective catalytic reduction, which effectively removes SO₂, NO_x and Hg⁰ at low temperatures. This paper first reviews the simultaneous removal of SO₂, NO_x and Hg⁰ by unsupported and supported catalysts. It then describes and compares the research progress of various carriers, eg., carbon-based materials, metal oxides, silica, molecular sieves, metal-organic frameworks, and pillared interlayered clays, in the simultaneous removal of SO₂, NO_x and Hg⁰. The effects of flue-gas components (such as O₂, NH₃, HCl, H₂O, SO₂, NO, and Hg⁰) on the removal of SO₂, NO_x, and Hg⁰ are discussed comprehensively and systematically. After summarizing the pollutant-removal mechanism, the review discusses future developments in the simultaneous removal of SO₂, NO_x and Hg⁰ by catalysts.     

(CeO_2-ZrO_2-Al_2O_3)-(La_2O_3-Al_2O_3)复合氧化物负载的Pd密偶催化剂:载体焙烧温度的影响

采用同时共沉淀法制备了(CeO2-ZrO2-Al2O3)-(La2O3-Al2O3)新型复合氧化物(CZA-LA),考察了焙烧温度对CZA-LA负载的Pd密偶催化剂的影响,并采用N2吸附-脱附法和X射线衍射对其进行了表征.结果表明,随着焙烧温度的升高,尽管CZA-LA样品的比表面积降低,但即使在1000°C焙烧5h后,其比表面积仍能保持在122m2/g左右;另外,CZA-LA样品的孔体积降低幅度不大,当在700℃及更高温度下焙烧后基本上保持稳定.以不同温度焙烧5h后的样品为载体,采用等体积浸渍法制备了一系列整体式Pd/CZA-LA密偶催化剂(Pd含量2.0g/L).催化剂对消除模拟汽油车尾气中C3H8活性测试结果表明,各新鲜催化剂的活性相差不大,均具有较低的起燃温度T50和完全转化温度T90.当催化剂经老化处理后,以1000°C焙烧的载体负载的Pd催化剂活性最高,T50和T90分别为310和341℃,ΔT仅为31℃,仅比新鲜催化剂的高7℃.可见,该催化剂表现出优异的催化活性和抗老化性能,可以满足欧Ⅳ及更高标准的用于汽油车尾气净化的密偶催化剂的性能要求.     

Catalytic properties of molybdena-alumina catalysts pretreated at high temperatures

The dependence of the catalytic properties of molybdena-alumina catalysts reduced in hydrogen on the degree of reduction were followed in a model catalytic reaction of deuterium exchange in benzene. The reaction rate constant and the multiplicity factor decrease as the degree of reduction and the degree of dehydroxylation of the catalyst's surface increase.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 7, pp. 1204–1207, July, 1994.     

Application of supported perovskite-type catalysts for vehicular emission control

Catalytic control of auto-exhaust emissions is one of the most successful applications of heterogeneous catalysis, both in commercial and environmental point of views. Although noble metal-based catalysts have dominated this area, efforts were always put in towards development of low cost non-noble metal-based catalysts. With the recent need of closed-coupled catalytic converter, thermal stability requirements have also become more severe, leading to the search for stable catalytic materials. Mixed oxides, including those perovskite type compounds with ABO₃ structure have been extensively studied, mainly for their catalytic and electrical properties. Low surface area of these catalysts has so far been the most important limitation for their catalytic applications involving high space velocities, e.g. auto-exhaust catalysis. Various synthesis routes have been earlier attempted to improve their surface area, yet this was much inferior than the noble metal catalysts, dispersed on high surface area alumina. The in situ synthesis of these oxides on alumina is often associated with the formation of undesired phases, due to the reactive nature of perovskite precursors. However, alumina washcoat, commonly used for improving the surface area of ceramic and metallic catalyst supports, can be modified for perovskite applications. In situ synthesis of stabilized perovskites on modified alumina-washcoated supports offer high surface area and excellent catalyst adhesion. Although, it is difficult to ascertain the presence of pure perovskite type materials on support, such improved synthesis has resulted in remarkable improvement in their catalytic activity for their applications in auto-exhaust catalytic converters. This review presents our work on synthesis of various improved perovskite-type mixed oxides supported on modified alumina-washcoated cordierite honeycomb, their characterization, and detailed catalytic evaluations for possible application in automobile pollution control.     

环境友好的选择性催化还原氮氧化物催化剂

富氧条件下的氮氧化物（NO。）选择性催化还原（SCR）是目前环境催化领域的研究热点,其核心问题是研发环境友好、高效稳定的SCR催化剂．目前,以NH3为还原剂的NH3-SCR已经大规模应用于固定源烟气脱硝和柴油车尾气净化,以碳氢化合物（Hc）为还原剂的HC-SCR也有望实际应用．针对NH3-SCR,本文以作者研究的铁钛复合氧化物催化剂、铈基氧化物催化剂以及国际上新兴的小孔分子筛催化剂为例,从催化剂结构、SCR反应机理、催化剂低温活性改进以及抗中毒性能等诸多方面对该领域的研究进展做了较为全面的论述．针对HC-SCR催化剂,本文在综述长链HC及柴油选择性还原NQ研究现状的基础上,结合作者在HC-SCR反应机理方面的研究成果,展望了实现柴油-SCR的发展方向．     

非邻苯二甲酸酯内给电子体聚丙烯催化剂的研究进展

本文综述了非邻苯二甲酸酯类内给电子体催化剂的研究进展,对目前已处于工业化应用的3种非邻苯二甲酸酯类化合物催化剂的性能特点进行了详细对比.针对日趋严格的清洁型聚丙烯要求,展望了非邻苯二甲酸酯类给电子体化合物以及相关催化剂的发展前景.     

双核茂金属催化剂的研究

双核茂金属催化剂是近年来茂金属催化剂研究的一个重要方向。综述了双核茂金属化合物的研究进展及其在烯烃聚合方面的应用;分别叙述了同核型双核茂金属化合物和异核型双核茂金属化合物的合成及性能研究;对双核茂金催化剂的作用机理也进行了介绍。     

用于NH3选择性催化还原NOx的钒基催化剂

在富氧且有催化剂存在条件下以NH3或尿素为还原剂选择性地还原NOx为N2的技术,即NH3/Urea-SCR技术,是去除固定源和移动源NOx最为有效且应用最广的技术之一,其中最重要的催化剂体系是钒基催化剂。本文从钒基催化剂的组成及其NH3-SCR反应性能、钒基催化剂的活性改进以及钒基催化剂上的NH3-SCR反应机理三个方面对该领域的研究进展做了较为全面的综述,并对NH3-SCR领域可能的发展方向做了展望。传统的V2O5-WO3(MoO3)/TiO2催化剂以及改性后的钒基催化剂在中温段具有优异的NOx净化效率和抗SO2中毒性能,其中高分散的V5+物种以及多聚的钒酸盐物种为NH3-SCR反应的活性中心。针对采用不同方法制备的或具有不同组成的钒基催化剂体系,多数学者认为NH3-SCR反应按照Eley-Rideal(E-R)机理进行,部分学者认为按照Langmuir-Hinshelwood(L-H)机理进行,这可能与催化剂的钒负载量以及反应温度区间相关。在后续工作中研究者应结合多种测试手段,具体问题具体分析,综合考虑温度的动态影响以及表面酸碱性对反应物的吸附活化,以得出更为全面、真实的反应机理。系统了解前人在钒基NH3-SCR催化剂领域的研究进展有助于现阶段开发高效稳定、可适应复杂工作条件的钒基SCR催化转化器,同时也对设计合成新型高效、环境友好且抗中毒的非钒基SCR催化剂体系具有一定的参考价值。     

Regeneration of Pd/Al2O3 catalysts used for tetrachloroethylene hydrodechlorination

The deactivation of the Pd/Al₂O₃ catalyst used for the hydrodechlorination of tetrachloroethylene (TTCE) is caused by both the carbonaceous deposits and by the hydrogen chloride produced in the reaction. In this work, several regeneration procedures have been tested, concluding that the best procedure is the leaching with ammonia, followed by calcinations and reduction. This procedure leads to an important recovery of the initial activity. The catalyst regenerated with this treatment is even less prone to deactivation that the fresh catalyst.     

柴油尾气DOC催化剂Pt-Pd/CeO2的活性和抗硫性

采用浸渍法制备了不同Pt、Pd比例的Pt-Pd/CeO₂催化剂,考察了其催化氧化模拟柴油车尾气的活性,并测试了抗硫性。活性测试结果表明,Pt、Pd协同降低了催化剂的起燃温度,其比例对催化剂性能影响很大,其中,Pt_0.2Pd_0.8/CeO₂催化剂在模拟柴油车尾气(丙烯(C₃H₆)、一氧化碳(CO)和一氧化氮(NO))中的催化活性最高;C₃H₆的t₅₀降到170℃,CO的t₅₀降到了150℃,显示了良好的Pt、Pd协同效应;H₂-TPR表征和抗硫性结果分析表明,高比例Pt/Pd催化剂具有更多的表面活性氧,其相对数值与催化剂抗硫性能的关联度高,在催化剂硫酸盐中毒的条件下,更有利于催化反应的进行。     

Characterization of CuO/Al2O3 catalysts used in the oxidation of phenol solutions

Two CuO/Al₂O₃ catalysts were synthesized at different calcination temperatures and used for the oxidation of phenol solutions. Deactivation is due to leaching of the active phase and deposition of carbonaceous material.This revised version was published online in December 2005 with corrections to the Cover Date.     

Fe-V/TiO_2催化剂NH_3选择性催化还原柴油车尾气NO_x

采用浸渍法制备了一系列不同Fe/V比例的Fe-V/TiO2催化剂,考察了催化剂在模拟柴油车尾气中催化还原NOx的催化性能,采用TG、XRD、H2-TPR、NH3-TPD和Raman光谱对催化剂进行了表征。结果表明,当Fe引入后,能显著降低V2O5在高温下的挥发,减轻了钒系催化剂在移动源的生物毒性危害。其中,Fe/V比为1∶1(Fe1-V1/TiO2)的催化剂形成了FeVO4活性中心,表现出最好的催化活性,在220~420℃NOx转化率可达到90%以上。此外,Fe1-V1/TiO2催化剂高温热稳定性较好,并且具有较强的抗硫性能。