稀土在汽车尾气净化催化剂中的作用

通过对稀土在汽车尾气净化催化剂中的作用综述,阐明随着贵金属资源的日趋耗竭和越来越严格的排放法规在全世界范围的推行,稀土在高性价比汽车尾气净化催化剂中必将扮演越来越重要的角色,发挥其它元素甚至贵金属元素都无法取代的作用.     

汽车尾气净化用钯催化剂的制备及活性考察

制备了一系列用于净化汽车尾气的新型钯催化剂．该催化剂以堇青石蜂窝陶瓷为基体与含助剂的γ-Al2O3涂覆层构成载体，La、Ce、Pr、Sm、Nd、Eu、Mg、Ca、Ba、Sr、Ni、Fe、Mn等的复合氧化物为助催化剂，主活性组分钯，含量为0．05％．在实验室配气条件下，对该系列催化剂进行三效活性的测试，结果显示催化剂对CO．THC．NO的T50分别为188℃，213℃，204℃，经空气中1000℃／4h的快速热老化后(相当于汽车运行5万公里)，T50分别为202℃，231℃，222℃；表明，部分助剂引入涂层，增大了载体的比表面积，提高了载体的抗热冲击能力；以氧化物形式引入的另一部分助剂同时起到分散和稳定贵金属的作用，且钯与其产生协同作用，对改善钯催化剂的三效性能有显著效果．     

汽车尾气的催化净化

本文详细介绍汽车尾气对人类的危害 ,以及治理汽车尾气的催化净化方法。并对三效催化剂的组成和应用做了重点说明。     

不同配比的Pd, Pt, Rh三效催化剂性能研究

为了降低催化剂成本, 开发单钯或含钯催化剂是现在汽车尾气净化领域研究热点之一. 本文介绍了不同Pd, Pt,Rh配比催化剂的性能, 包括新鲜的和1100 ℃, 50 h老化后的空燃比特性和起燃温度特性, 并对实验结果进行比较和分析.     

Pd/γ-Al2O3三效催化剂中CeO2-ZrO2-La2O3的作用

用浸渍法制备了CeO2-ZrO2-La2O3复合氧化物,用XRD,TG-DTA,拉曼光谱、H2-TPR和BET表面积测定等方法对合成的样品进行了表征,研究了在单钯Pd/γ-Al2O3催化剂中添加CeO2-ZrO2-La2O3对催化剂活性和热稳定性的影响.结果表明,在Pd/γ-Al2O3中加入三元复合氧化物有利于提高三效催化剂的热稳定性,有利于阻止γ-Al2O3在高温时的相变以稳定Al2O3结构,防止在高温条件下催化剂表面积的损失.在Pd的负载量为1 g*L-1条件下,测定了Pd/CeO2-ZrO2-La2O3/γ-Al2O3/蜂窝陶瓷催化剂对CO,C3H6和NO净化的三效活性,研究了催化剂的结构和三效催化活性之间的关系.结果表明,CeO2-ZrO2-La2O3的存在能明显提高Pd基催化剂对CO,C3H6和NO的三效净化活性,扩大催化剂的操作窗口,提高在富氧条件下对NOx的还原性能.     

汽车尾气净化催化剂中钯含量的测定

贵金属钯是汽车尾气净化催化剂(以下简称汽车催化剂)的活性元素之一。为了综合平衡地利用贵金属资源以及降低催化剂成本,用钯替代铂、铑活性成分,甚至采用全钯催化剂一直是国内外汽车催化剂的研究热点[1]。钯属稀有资源必须回收利用,回收时必须对钯准确测定[2]。目前的分析方法[3-6]多集中于分析测试仪器的利用和分光光度法显色体系的研究,对于块状结构的汽车催化剂的溶样方法的研究,是选择浸出活性组分回收汽车催化剂中铂族金属元素的关键[7]。PdO难溶[8],用甲酸对催化剂中被氧化的钯进行还原预处理,利用分光光度法测定选择性浸出钯。…     

CeO_2-ZrO_2-Al_2O_3稀土储氧材料制备工艺的研究

采用化学沉淀法制备了系列CeO2-ZrO2-Al2O3稀土储氧材料,并用BET,XRD和储氧性能测定等表征手段考察了陈化时间、La2O3含量、反应pH和沉淀方式等工艺因素对CeO2-ZrO2-Al2O3比表面积、储氧性能和结构的影响。结果表明:当陈化时间为12 h,反应pH=10时,掺杂2%(质量分数)La2O3的CeO2-ZrO2-Al2O3样品在老化前后均具有很高比表面积和良好的储氧性能,并且pH为影响样品比表面积及热稳定性能的主要因素。与一步法沉淀相比,二步法制得的CeO2-ZrO2-Al2O3样品具有很高的热稳定性能,1050℃老化5 h后的样品比表面积高达46.4 m2.g-1,但储氧性能略差,这与Al2O3对CeO2-ZrO2的结构影响程度有关。     

添加稀土氧化物助剂的CeO2-ZrO2固溶体的储氧性及热稳定性研究

大多数工业催化剂都是在稳定的操作条件下进行的,然而汽车尾气净化催化剂却被暴露在大气中,使用条件经常变化,尤其是空燃比(A/F)的变化,直接影响了对氧敏感的三效催化剂的氧化和还原性能[1].CeO2则是一种具有储氧/释氧能力的催化材料,它作为助剂加入三效催化剂中,可在贫况下储存氧(以Ce4+存在)利于NOx的还原,在富况下释放氧(以Ce3+存在),利于HC、CO的氧化,从而提高了催化剂的活性.然而,CeO2 的储氧性通常局限在表面上,当温度超过400℃以上时,其比表面积降低从而引起储氧性能急剧下降,直接影响催化剂的性能和寿命.     

满足欧Ⅲ排放标准的压缩天然气汽车中偶催化剂

制备了具有高性能的稀土储氧材料Ce0.45Zr0.45Y0.05La0.05O2和耐高温大比表面积材料La-Al2O3,并以此为基础制备了Pt-Rh型中偶压缩天然气汽车尾气净化催化剂.催化剂对模拟尾气具有较高的催化活性和稳定性,在捷达-MT型压缩天然气汽车上的测试结果表明该催化剂能够满足欧Ⅲ排放标准.     

Zr基载体负载Pd催化剂用于贫燃天然气汽车尾气净化

 采用共沉淀法制备了 ZrO2, Y0.1Zr0.9Ox, Ce0.1Zr0.9Ox 和 Al0.1Zr0.9Ox 系列 Zr 基载体, 并用 N2 吸附-脱附和 X 射线衍射对其进行了表征. 再以此为载体, 采用浸渍法制备了整体式负载 Pd 催化剂, 催化剂涂层的涂覆量为 180 g/L 左右, Pd 含量为 1.25%. 测定了催化剂上 Pd 的分散度. 在模拟的贫燃天然气汽车尾气中考察了催化剂的活性, 并在尾气中有或无 SO2 存在的条件下比较了催化剂活性的差异. 结果表明, Y3+, Ce4+ 或 Al3+ 改性载体负载的 Pd 催化剂的耐硫性能明显改善; 无论尾气中是否存在 SO2, 以 Y3+ 或 Al3+ 改性载体负载的 Pd 催化剂的活性均明显高于 ZrO2 负载体的 Pd 催化剂.     

Novel Oxygen Storage Components Promoted Palladium Catalysts for Emission Control in Natural Gas Powered Engines

A three-way catalyst comprised novel oxygen storage components for emission control in natural gas powered engines was prepared. The addition of novel oxygen storage components to the Pd/γ-Al2O3 catalysts resulted in improved activities of the fresh and aged catalyst by lowering the light-off temperature for methane in natural gas engines exhaust.     

Oxygen Storage Materials for Automotive Catalysts: Ceria-Zirconia Solid Solutions

This paper reviews progress in the development of oxygen storage materials for automotive exhaust catalysts. The research was mainly conducted as a study and development exercise in the author's laboratory in Japan.Ceria-lanthana solid solutions (CL) and the first generation of ceriazirconia solid solutions (CZ) were developed as excellent oxygen storage materials for automotive catalysts in the 1980s. These materials consist of ceria doped with less than 20 mol% of La⁴⁺ or Zr⁴⁺. An increase in oxygen defects in CL and CZ under reductive conditions is responsible for an enhanced oxygen storage capability on the cerium atoms. An accurate measure of the oxygen storage capacity (OSC) per cerium is very important for theoretical and practical treatments of the catalyst. The term partial OSC was introduced to describe this capacity and to differentiate it from the usual definition of the OSC, known also as the total OSC. After the development of CL and CZ, a new technology was developed to dissolve more than 20 mol% of zirconia in the ceria, allowing second generation CZ and third generation CZ (known as ACZ, which is doped with alumina) to be successfully developed in the 1990s. The partial OSC of these materials increases with increasing amounts of zirconia dissolved in the ceria, and also with decreasing material particle size after an engine durability test. In the case of ACZ, alumina was added to CZ based on the diffusion barrier concept, in which a diffusion barrier layer inhibits the coagulation of CZ and A when the material is required for duty at high temperature in air.Furthermore, the relationship between the total or partial OSC and the structure of the ceriazirconia solid solutions is explained in this paper.For ceriazirconia solid solutions composed of equimolar CeO₂ and ZrO₂(Ce/Zr=1), the total or partial OSC of the -phase CeZrO₄, in which the cerium and zirconium ions are regularly distributed, was about twice as large as that of a ceriazirconia solid solution with a relatively irregular distribution of cerium and zirconium ions, and about five times larger than that of a mixture of ceria powder and zirconia containing only a small amount of ceriazirconia solid solution. It corresponds to about 89% of the theoretical maximum value.For a ceriazirconia solid solution composed of non-equimolar CeO₂ and ZrO₂(Ce/Zr 1), the partial OSC of a ceria--phase solid solution with a zirconia content of between 30 and 50mol% is much higher than that of a ceriazirconia solid solution of the same zirconia content. The partial OSC of a -phase and zirconia mixed oxide, which is formed by reducing the material at 1200 °C, reaches a value above 0.20 mol-O₂/mol-Ce (about 80% of the theoretical maximum value of the partial OSC), when the zirconia content is between 50 and 80 mol%.The Toyota Motor Corp. has put automotive three-way catalysts containing the first, second and third generations of CZ into practical use on a global basis.     

稀土元素在脱硝催化剂中的应用

以NH₃为还原剂的选择性催化还原(SCR)技术可实现工业烟气中氮氧化物(NO_x)的超低排放,现有钒钛系脱硝催化剂具有生物毒性,且报废后为危险废物。稀土元素(REEs)具有独特的4f电子轨道,表现出优异的储释氧性能,在催化反应中可发挥重要作用,是当前新型脱硝催化剂的重要研究对象,也是国家鼓励的现有钒钛系催化剂的替代品。本文主要总结了铈、钐、镧等12种REEs在新型脱硝催化剂中的近5年研究进展,另有钪、镥等5种REEs的相关研究较少,重点阐述了REEs改善催化剂脱硝活性与稳定性的作用机制及耦合过渡金属的协同催化机理,初步提出了脱硝催化剂的设计原则,并展望了稀土脱硝催化剂的发展前景。     

Europium Oxybromide Catalysts for Efficient Bromine Looping in Natural Gas Valorization

The industrialization of bromine‐mediated natural gas upgrading is contingent on the ability to fully recycle hydrogen bromide (HBr), which is the end form of the halogen after the activation and coupling of the alkanes. Europium oxybromide (EuOBr) is introduced as a unique catalytic material to close the bromine loop via HBr oxidation, permitting low‐temperature operation and long lifetimes with a stoichiometric feed (O₂:HBr=0.25)—conditions at which any catalyst reported to date severely deactivates because of excessive bromination. Besides, EuOBr exhibits unparalleled selectivity to methyl bromide in methane oxybromination, which is an alternative route for bromine looping. This novel active phase is finely dispersed on appropriate carriers and scaled up to technical extrudates, enhancing the utilization of the europium phase while preserving the performance. This catalytic system paves the way for sustainable valorization of stranded natural gas via bromine chemistry.     

载体焙烧温度对稀燃天然气汽车尾气净化Pd/Zr0.5Al0.5O1.75催化剂性能的影响

以不同温度焙烧得到的Zr0.5Al0.5O1.75复合氧化物为载体,制备了系列1.5%Pd/Zr0.5Al0.5O1.75催化剂样品.采用N2吸附-脱附、X射线衍射、H2程序升温还原、O2程序升温脱附及CO化学吸附等手段对催化剂进行了表征,并测试了催化剂在模拟稀燃天然气汽车尾气中的活性和抗H2O中毒性能.结果表明,载体...     

A Theoretical and Experimental Study of Charge and Discharge Cycles in a Storage Vessel for Adsorbed Natural Gas

This study presents experimental data of storage and delivery tests of methane on activated carbon carried out in a prototype vessel at pressures up to 40 atm. Adsorption equilibrium data at high pressure were measured using a gravimetric apparatus. Experimental data obtained from the storage/delivery tests are compared to those obtained from process simulation using a dynamic model. The simulation model was run using the measured equilibrium data as input parameters. A good agreement was observed between experimental and simulated results. Histories of pressure and stored mass were satisfactorily well predicted. Despite heat effects, not precisely taken into account in the model, there was a reasonably good agreement between simulation and experiment for the average temperature inside the vessel.