Zybert Magdalena, Ronduda Hubert, Patkowski Wojciech, Ostrowski Andrzej, Sobczak Kamil, Raróg-Pilecka Wioletta
Warsaw University of Technology, Faculty of Chemistry Noakowskiego 3 00-664 Warsaw Poland
University of Warsaw Biological and Chemical Research Centre Żwirki i Wigury 101 02-089 Warsaw Poland.
RSC Adv. 2024 Nov 12;14(49):36281-36294. doi: 10.1039/d4ra06251e. eCollection 2024 Nov 11.
Y-modified perovskite-type oxides BaCe Y O ( = 0-0.30) were synthesised and used as supports for cobalt catalysts. The influence of yttrium content on the properties of the support and catalyst performance in the ammonia synthesis reaction was examined using PXRD, STEM-EDX, and sorption techniques (N physisorption, H-TPD, CO-TPD). The studies revealed that the incorporation of a small amount of yttrium into barium cerate (up to 10 mol%) increased specific surface area and basicity. The catalyst testing under conditions close to the industrial ones ( = 400-470 °C, = 6.3 MPa, H/N = 3) showed that the most active catalyst was deposited on a support containing 10 mol% Y. The NH synthesis reaction rate was 15-20% higher than that of the undoped Co/BaCeO catalyst. The activity of the catalysts decreased with further increasing Y content in the support (up to 30 mol%). However, all the studied Co/BaCe Y O catalysts exhibited excellent thermal stability, over 240 h of operation. The particularly beneficial properties of the catalyst containing 10 mol% of Y were associated with the highest basicity of the support surface, favourable adsorption properties (suitable proportion of weakly and strongly hydrogen-binding sites), and preferred size of cobalt particles (60 nm). The Co/BaCeYO catalyst showed better ammonia synthesis performance compared to the commercial iron catalyst (ZA-5), giving prospects for process reorganisation towards energy-efficient ammonia production.
合成了Y修饰的钙钛矿型氧化物BaCe1 - xYxO3 - δ(x = 0 - 0.30),并将其用作钴催化剂的载体。采用粉末X射线衍射(PXRD)、扫描透射电子显微镜 - 能谱分析(STEM - EDX)和吸附技术(N2物理吸附、H2程序升温脱附、CO程序升温脱附)研究了钇含量对载体性能及氨合成反应中催化剂性能的影响。研究表明,向铈酸钡中掺入少量钇(高达10 mol%)可增加比表面积和碱性。在接近工业条件(T = 400 - 470 °C,p = 6.3 MPa,H2/N2= 3)下进行的催化剂测试表明,活性最高的催化剂负载在含10 mol% Y的载体上。氨合成反应速率比未掺杂的Co/BaCeO催化剂高15 - 20%。随着载体中Y含量进一步增加(高达30 mol%),催化剂活性降低。然而,所有研究的Co/BaCe1 - xYxO3 - δ催化剂在超过240 h的运行中均表现出优异的热稳定性。含10 mol% Y的催化剂的特别有益的性能与载体表面的最高碱性、良好的吸附性能(弱和强氢结合位点的合适比例)以及钴颗粒的优选尺寸(60 nm)有关。与商业铁催化剂(ZA - 5)相比,Co/BaCeYO催化剂表现出更好地氨合成性能为实现节能氨生产的工艺重组提供了前景。