Direct conversion of syngas to DME as a green fuel in a high pressure microreactor: Influence of slurry solid content on characteristics and reactivity of washcoated CuO–ZnO–Al2O3/HZSM-5 nanocatalyst

Microchannels of a stainless steel microreactor were successfully washcoated with slurry of Cu–ZnO–Al₂O₃/HZSM-5 (CZAZ) nanocatalyst with different concentrations (10, 20 and 30 wt.%). The properties of nanocatalyst and the washcoated microchannels were investigated by XRD, FESEM, N₂ physisorption, FTIR, EDX-Dot mapping and EDX-Line mapping analysis. The best adherence was observed for 20 wt.% catalyst which has a uniform coating, almost no cracks and homogenous dispersion of copper and zinc. Trend of weight gain during 10 soaks in catalyst slurry was very slow for 10 wt.% but faster for 20 and 30 wt.%. Low amount of weight gain was observed for the last soaks of catalyst slurry in the case of 30 wt.% washcoating. The performance of microreactor with different slurry concentrations were evaluated in direct synthesis of DME at 200–300 °C, 60–150 cm³/min and 40 bar. Regardless of slurry concentration, the microreactor exhibited a better reactivity in comparison to fixed-bed reactor performance. Among three different slurry concentrations, 20 wt.% catalyst slurry revealed the best reactivity in direct DME synthesis. The reduction in reactor performance at higher flow rates was significant in the fixed-bed reactor while microreactor, particularly 20 wt.% washcoated channels, revealed less drastic reduction.     

铂族金属单原子催化剂的制备、表征技术研究进展

单原子催化不仅将多相催化领域研究从纳米尺度深入到了原子尺度,有助于从原子层次研究和认识非均相催化反应过程,也使得进一步提高活性铂族金属原子利用率、降低催化剂成本成为可能。基于国内外多年来在单原子催化领域取得的研究成果,介绍了铂族金属单原子催化剂的制备方法与表征技术,总结归纳了不同制备方法的参数控制关键、适用范围,以及不同表征数据分析、存在的问题与挑战。在不同表征技术融合创新的基础上,对于铂族金属单原子催化剂的可控制备技术尽早实现工业化应用提出了展望。     

Structure and oxygen storage capacity of Pd/Pr/CeOe-ZrO2 catalyst： effects of impregnated praseodymia

Praseodymium （Pr） was impregnated to CeO2-ZrO2 solid solution by an impregnation method. The as-obtained Pr modi- fied CeO2-ZrO2 was impregnated with 1 wt.% Pd to prepare the catalysts. The structure and reducibility of the fresh and hydrother- really aged catalysts were characterized by X-ray diffraction （XRD）, Raman, X-ray photoelectron spectroscopy （XPS）, CO chemi- sorption and H2 temperature-programmed reduction （H2-TPR）. The oxygen storage capacity （OSC） was evaluated with CO serving as probe gas. Effects of impregnated Pr on the structure and oxygen storage capacity of catalysts were investigated. The results showed that the aged Pr-impregnated samples had much higher OSC and better reducibility than the unmodified ones. The scheme of structural evolutions of the catalysts with and without Pr was also established. Partial of the impregnated Pr diffused into the bulk of CeO2-ZrO2 during ageing, which inhibited the sintering, and increased the amount of oxygen vacancies in CeO2-ZrO2 support. Furthermore, those impregnated Pr species which covered on the surface of the support obstructed the strong metal-support interaction between Pd and Ce so as to reduce the encapsulation of Pd as well as the back spill-over of the oxygen during the catalytic process.     

热老化对Pd/Al_2O_3选择性催化NH_3反应性能的影响(英文)

研究了在三效催化反应过程中热老化对Pd/Al_2O_3选择性催化NH_3反应性能的影响。在稀/富循环流中进行稳态实验,采用X射线衍射(XRD)、BET比表面积、X射线光电子能谱(XPS)、拉曼光谱(Raman)和透射电镜(TEM)对催化剂的物理化学性质进行表征。结果表明,高温热老化导致活性金属钯的分散度降低、颗粒尺寸增大、Pd~(2+)活性物种的相对比例下降,这些微结构变化促使催化剂的三效活性降低、氨选择性增加。热老化诱导催化剂表面活性钯颗粒明显增大,较大的钯颗粒有助于NO解离生成活性氮物种,进而与氢反应生成NH_3。     

CHA型分子筛在柴油车NOx排放控制的研究进展

CHA型分子筛具有比表面积大、孔隙结构发达、酸性可调控等优势,是柴油车NOx排放控制最具有发展潜力的载体材料。基于对50多篇文献的分析,综述了近20年来CHA型分子筛在柴油车用PNA和SCR催化材料中的应用研究进展,阐述了活性组分、分子筛结构性质、尾气组分等3个方面对CHA型分子筛载体催化剂性能的影响,对CHA型分子筛的研究方向进行了展望。     

铂/钡基NOx存储还原催化材料研究进展

从中国汽车排放法规升级、中国汽车行业发展需求、催化材料的国内外研究基础及应用集成技术研究进展、后处理系统成本控制四个角度,分析了铂/钡基NOx存储还原(NSR)催化材料在我国汽车尾气污染防治行业应用存在的机遇与挑战。     

有机两相法制备巯基羧酸修饰的小尺寸贵金属纳米粒子

以生物相容性较好的巯基羧酸分子为保护剂、NaBH4为还原剂,采用有机两相法制备金属纳米粒子,实现了对纳米粒子的表面功能化。该方法制备的纳米材料粒径小(5 nm),单分散性好。讨论了巯基羧酸与金属前驱体之间的投料比、还原剂NaBH4的量以及巯基羧酸分子链长等因素对纳米粒子形貌的影响。除Au外,该方法还适用巯基羧酸对Ag、Pt和Pd等多种纳米粒子的表面修饰。     

贵金属三效催化剂性能模拟评价方法研究现状

贵金属三效催化剂主要应用于汽油车、压缩天然气车、混合动力车等车型的尾气催化净化,其装车排放及耐久性能的评价是实现高效催化剂研发与应用的关键。基于对近20年来40余篇文献的分析,综述了三效催化剂空燃比特性、起燃特性、储/放氧性能、稳定性的实验室模拟评价方法研究现状,分析了不同模拟评价方法的优势和不足,阐述了模拟评价性能与催化剂装车性能之间的关联性,展望了模拟评价方法研究的重点方向。     

In situ DRIFTS study of the effect of structure (CeO2–La2O3) and surface (Na) modifiers on the catalytic and surface behaviour of Pt/γ-Al2O3 catalyst under simulated exhaust conditions

The nature and relative populations of adsorbed species formed on the surface of un-promoted and sodium-promoted Pt catalysts supported either on bare Al₂O₃ or CeO₂/La₂O₃-modified Al₂O₃, were investigated by in situ diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) under simulated automobile exhaust conditions (CO + NO + C₃H₆ + O₂) at the stoichiometric point. The DRIFT spectra indicate that interaction of the reaction mixture with the Pt/Al₂O₃ catalyst leads mainly to formation of formates and acetates on the support and carbonyl species on partially positively charged Pt atoms (Pt^δ+). Although enrichment of Al₂O₃ with lanthanide elements (CeO₂ and La₂O₃) does not significantly modify the carboxylate species formed on the support, it causes significant modification of the oxidation state of Pt, as indicated by the appearance of a substantial population of carbonyl species on reduced Pt sites (Pt⁰–CO). This modification of the Pt component is enhanced when Na-promotion is used, leading to formation of carbonyl species only on electron enriched Pt (i.e., fully reduced Pt⁰ sites) and to the formation of NCO on these Pt entities (2180 cm⁻¹). The latter are thought to result from enhanced NO dissociation at Na-modified Pt sites. These results correlate well with observed differences in the catalytic performance of the three different systems.