稀土在汽油车尾气净化中的应用

截至2021年底,中国的汽车保有量超过3亿辆,其中汽油车占比90%以上,是中国最重要的汽车类型。为了应对汽油车尾气中的氮氧化物(NO_x)、碳氢化合物(HC)和一氧化碳(CO)等典型污染物,“三效催化剂”这一具有里程碑意义的汽油车尾气后处理技术被开发、应用并不断完善。新近流行的汽油缸内直喷(GDI)技术会导致显著的颗粒污染物(PM)排放,由此又催生了汽油车颗粒物过滤器(GPF)技术。上述技术的实施或多或少都需要依赖中国战略资源——稀土的参与。本文首先对各类汽油车尾气净化技术的发展进行了回顾,之后重点分析了(以CeO₂为主的)稀土材料在三效催化剂储氧材料、催化剂载体/贵金属稳定剂和汽油车颗粒物过滤器中的具体应用方式和效果。可以看出,随着新型稀土材料的开发和技术迭代,现代汽油车尾气净化技术正在变得越来越高效、越来越便宜。最后,本文对汽油车尾气净化用稀土材料的发展趋势进行了展望,分析了相关产业未来升级的重点和难点所在。     

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.     

铑、镧对贵金属尾气净化催化剂性能的影响

研究了Rh对Pt-Pd/Al2O3汽车尾气净化催化剂的三效性能及其对CO, O2和C3H6的吸附性能的影响.研究了镧对Pt-Pd-Rh/Al2O3尾气净化催化剂的活性、耐热性能的影响.结果表明,在没有助剂的情况下, Rh是Pt-Pd-Rh/Al2O3三效催化剂中一个必不可少的组元,它在贵金属催化剂中主要是调整金属键的d百分数.镧是Pt-Pd-Rh贵金属催化剂的一种性能良好的助剂.     

稀土有机化合物在催化聚合反应中的应用

本文综述了稀土有机化合物作为单组份催化剂用于聚合反应的进展。它包括：烯烃和α－烯烃聚合、甲基丙烯酸酯类的均聚合及共聚合、乙与人烯酸酯及含官能团烯的共聚合、内醌的开环均聚合及共聚合等。茂基稀土氢化物是乙烯聚合的高活性催化剂，对茂基结构作一定调节，可催化α－烯烃的规整聚合。这类氢化物、茂基稀土甲基化合物和二价稀土配合物都是人烯酸酯类及内酯聚合的有效催化剂，并显示活性聚合特点给出高分子量、窄分子量分布的     

铈锆固溶体对摩托车尾气净化催化剂性能的影响

对3种铈锆粉CLZ,CHZ及CZA进行了XRD,BET表征,考察了CLZ,CHZ及CZA对催化剂性能的影响。XRD结果表明,CLZ能形成单一稳定的晶相结构,CHZ高温老化后分相,CZA不能形成稳定的晶相结构;BET结果表明,CLZ具有较好的热稳定性。活性测试结果表明,CLZ具有较好的热老化性能。实车测试结果表明,CLZ制备的催化剂能满足国Ⅲ排放要求。     

柴油机尾气净化催化剂的最新研究进展

柴油机尾气排放的污染物已经引起了严重的环境污染问题,催化净化技术是柴油机尾气污染治理必不可少和最有效的处理技术之一,而高效催化剂的研制和开发是催化净化技术的核心.本文以柴油机尾气中最难处理的两种污染物NOx和碳烟颗粒(PM)的催化处理技术为主线,综述了NOx的催化还原(选择性催化还原(SCR)和贮存还原(NSR))催化剂、碳烟的催化燃烧催化剂、NOx和碳烟颗粒同时消除的催化剂及柴油机尾气四效催化剂的最新研究进展,并总结性地提出了目前该研究方向存在的主要问题和发展方向.     

金复合LaCeMn稀土催化剂在富氧条件下NOx催化还原性能的研究

研究了在含氧10%的气氛中,贵金属元素Au复合LaCeMn钙钛矿系列稀土催化剂的NOx还原性能.用比表面测定、X射线衍射、扫描电镜等方法分析了催化剂的结构、形貌,探讨了产生催化活性的机制.结果表明,以γ-Al2O3为分散层,用盐溶液负载制备方法,在LaCeMn氧化物表面负载微量贵金属Au,所制备的催化剂在富氧条件下其催化活性具有明显的改善.在300～500℃温度区间内具有较好的NOx还原性能,在360～400℃最大还原效率可达47%.Au负载量在1g@L-1以内时,随着Au负载量增加,催化活性提高.另外,活性层的表面分散性和均匀性,对催化性能也有很大的影响.     

汽车尾气净化用稀土钙钛石型复合氧化物催化剂

稀土钙钛石型复合氧化物催化剂是一种性能良好的汽车尾气净化催化剂 ,是贵金属三效催化剂未来的替代品。本文对此催化剂的研究进展及其负载技术作一简述     

贵金属部分取代稀土钙钛矿B位在汽车排放中的应用

研究了以钙钛矿LaMnO3为基体的贵金属三效催化剂中两者的相互作用状况及对CO,NO的催化氧化还原反应.实验结果表明,由于贵金属和稀土氧化物的相互作用降低了CO,NO反应的起活温度.从微观结构探讨了贵金属与复合稀土氧化物之间的相互作用机理,并且认为贵金属对稀土钙钛矿结构中B位的部分取代是开发贵金属-稀土三效汽车尾气净化催化剂的重要理论基础.     

城市公交车用稀土催化净化反应器的开发与试验

采用稀土元素作催化剂、蜂窝陶瓷作载体, 针对城市公交汽油车设计制造了尾气净化装置, 进行了发动机的性能试验, 测试了净化装置的净化转化率和消声量频率特性. 结果表明, 对于试验用稀土催化净化反应器, 实际消声量在各个频率段上均大于必需消声量; 净化转化效果明显, 例如当发动机怠速运转、补氧量充足时, CO和HC的净化转化率可达90%以上; 同普通消声器相比, 压降稍大, 从而导致发动机输出功率有所下降, 燃油消耗率有所上升.     

稀土催化材料的制备、结构及催化性能

稀土催化材料的研究和发展为La和Ce等高丰度轻稀土元素的高质、高效利用提供了有效的途径.稀土元素具有未充满电子的4f轨道和镧系收缩等特征,作为催化剂的活性组分或载体使用时表现出独特的催化性能.本文从稀土氧化物、稀土复合氧化物、稀土-贵金属催化剂、稀土改性多孔催化材料等稀土催化材料出发,重点介绍和讨论了稀土的添加对催化剂的结构、活性和稳定性等的影响,阐述了稀土与过渡金属及氧化物、稀土与贵金属之间的相互作用,及对催化剂催化性能的影响.并对稀土催化材料的研究和发展提出了思考和展望.     

Perfluorinated rare earth metals catalyzed nitration of aromatic compounds

The nitration of aromatic compounds can be carried out in the presence of perfluorinated rare earth metal catalyst without halogenated organic solvent.     

Exploitation of rare earth catalysts in polymer syntheses

The studies over forty years on rare earth catalysts in polymer syntheses of diene, alkyne, alkylene oxide, thiirane, carbon dioxide copolymerization, lactide, caprolactone, cyclic carbonate and so forth in China have been reviewed. __________ Translated from Gaofenzi Tongbao (Polymer Bulletin) 2005, (4) (in Chinese)     

辉光放电质谱法测定稀土矿中的15种稀土元素

利用高纯铜粉与稀土矿石粉末均匀混合压片制样.混合15种高纯稀土氧化物制样建立标准工作曲线,校正15种稀土元素相对灵敏度因子,再进行定量分析.结果 表明,稀土元素工作曲线的线性方程相关系数R2均大于0.996,相对标准偏差(RSD)小于5％,满足定量分析要求.测定结果与电感耦合等离子体质谱法(ICP-MS)和电感耦合等离...     

Copolymerization of carbon dioxide and propylene oxide under inorganic oxide supported rare earth ternary catalyst

Recently, rare earth ternary coordination catalyst represented as Y(CCl₃OO)₃‐Glycerin‐ZnEt₂ has been used for producing poly(propylene carbonate) (PPC, an alternating copolymer of carbon dioxide and propylene oxide) in industry scale, but its catalytic activity needs further improvement. One reason for the relatively low catalytic activity lied in that only 11.7% of active center was efficient due to possible embedding of active center in the heterogeneous catalyst. In this report, supporting strategy was developed, where Y(CCl₃OO)₃‐Glycerin‐ZnEt₂ was supported on various inorganic oxides. Two supporting methods were carried out. One way was to mix Y(CCl₃OO)₃‐Glycerin with inorganic oxide first and then ZnEt₂ was dropped to form the supported catalyst, and the other was to make Y(CCl₃OO)₃‐Glycerin‐ZnEt₂ at first and then mixing with inorganic oxides. The former showed decreasing catalytic activity compared with corresponding unsupported rare earth ternary catalyst, while an improvement of 16–36% in catalytic activity was realized in the latter. PPC with an average number molecular weight (M_n) of over 100 kg/mol and carbonate unit (CU) content of higher than 96% was prepared by both supported catalysts. The catalytic activity of the supported catalyst depended significantly on the supports, which increased in the following order: α‐Al₂O₃ < MgO < ZnO ≈ SiO₂ <γ‐Al₂O₃. γ‐Al₂O₃ was the best support for rare earth ternary catalyst, which showed a remarkable 36% increase in catalytic activity, corresponding to the utilization of 17% of active center. Although MgO supported catalyst gave only an 8% increase in catalytic activity, the M_n and CU content of PPC were raised to about 143 kg/mol and 99%, whereas the PPC from common rare earth ternary catalyst was about 108 kg/mol and 97%, respectively. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011     

New coordination catalysts based on rare earth compounds for polymerization of 1-octene

The study of rare earth coordination catalysts for polymerization of 1-octene has been successfully carried out for the first time. Some features and kinetic behavior of polymerization of 1-octene by Nd(naph)₃–AIEt₃ catalyst system in tetrachloro-methane are described. The overall polymerization activation energy E_a measured was 74.5 kJ/mol and the rate equation could be expressed as R_p = k_p [Nd] [M] (k_p = 3.21 × 10^?3 L/mol s, at 50°C). The catalytic activity of various rare earth elements in Ln (naph)₃ and ligands in NdL₃ for the polymerization was compared. A 1-octene oligomer with double bonds was obtained. It is either a white or pale yellow waxy semi-solid. Its number-average molecular weight is about 10³ and the molecular weight distribution is less than 2.     

熔盐电解法制备稀土合金研究进展

熔盐电解法制备稀土合金具有成本低、成份均匀且容易控制、质量较好、易实现连续化生产等优势.本文结合稀土合金在金属结构材料、磁性材料和贮氢材料中的应用,在介绍熔盐电解的知识进展的基础上,综述了稀土分别与镁、铝、铁、钴、镍、铜等组成的合金的熔盐电解制备研究进展,并对以后的研究工作进行展望.     

稀土Schiff碱配合物催化烷基异氰酸酯室温聚合

利用Schiff碱稀土配合物Ln（H2Salen）2Cl3·2C2H5OH与AI（i—Bu）3组成的催化体系催化烷基异氰酸酯室温聚合,详细考察了催化剂组成以及聚合条件等对烷基异氰酸酯聚合的影响,并研究了己基异氰酸酯的聚合动力学．以La、Nd、Sm和Gd四种稀土元素为代表,合成了相应的Schiff碱配合物,结果表明轻稀土体系比重稀土体系好,La的聚合活性最高．在-40℃-40℃很宽的聚合温度范围内,可以得到分子量分布窄（MWD=1．50～2．40）的高分子量聚异氰酸酯,20℃为最佳的聚合温度．己基异氰酸酯的最佳聚合条件为：[AI]／[La]=30（摩尔比）,[n-HexNCO]／[La]=100,[n—HexNCO]=3．43mol／L,甲苯溶液中20℃聚合12h,聚合物收率74．0％,聚合物黏均分子量高达73．5×10^4,数均分子量40．2×10^4,MWD=1．79．聚合动力学研究表明己基异氰酸酯聚合反应对单体浓度和催化剂浓度都是一级关系,聚合反应活化能为43．64kJ／mol．     

Highly enantioselective homogeneous catalysis of chiral rare earth phosphates in the hetero-Diels-Alder reaction

Two types of novel rare earth (RE) complexes were synthesized and used as a chiral Lewis acid catalyst for the hetero-Diels-Alder reaction of carbonyl compounds with the Danishefsky's diene under homogeneous conditions. The Y[(R)-H₈-BNP]₃ (3-Y)-catalyzed reaction of aromatic aldehydes and the Yb[(R)-BNP]₃ (1-Yb)-catalyzed reaction of phenylglyoxylates afforded the corresponding cycloadducts with excellent optical purities (up to 99% ee) in high yields at room temperature. The successful recycling uses of the scandium catalyst (3-Sc) are also described.     

Blue,green,red upconversion luminescence and optical characteristics of rare earth doped rare earth oxide and oxysulfide

The cold isostatic press pretreatment process was adopted to prepare fine rare earth oxysulfide up-conversion phosphors with spherical shape, narrow size distribution and high luminescence efficiency. The upconversion optical characteristics and brightness of the blue (Y2O2SYb,Tm), green (Y2O2S: Yb,Er), red (Y2O3Yb,Er) emitter were also investigated, and a novel method was successfully developed for the brightness measurement of upconversion luminescence (UPL). It is shown that a white color can be obtained by the appropriate mixture of these primary blue, green and red emissions components. The Er3 ions exhibit different upconversion mechanism in Y2O2S and Y2O3 host materials. The rare earth oxysulfide is an efficient upconversion matrix. The UPL brightness of Y2O2S: Yb,Er is 6.5 times higher than that of Y2O3: Yb,Er, and Y2O2S: Yb,Er shows UPL brightness of 1100 cd/m2 under 5.56 W/cm2 power density using a 980 nm laser diode.