助剂对Ru/C催化剂的表面性质及氨合成催化性能的影响

助剂对Ru/C催化剂的表面性质及氨合成催化性能的影响

  • 摘要: 以碱金属、碱土金属硝酸盐作为助剂前体,活性炭为载体制备了系列负载型钌催化剂,采用物理吸附、化学吸附和XRD等表征手段,考察了助剂对Ru/C催化剂的比表面、孔分布和钌分散度的影响,并在430 ℃、10.0 MPa和10 000 h-1条件下进行氨合成活性评价。结果表明,单助剂Ru/C催化剂,碱金属助剂的促进作用与其相应氢氧化物碱性变化规律一致,碱土金属助剂的促进作用与其相应氧化物碱性变化规律一致。在同类化合物中,铯和钡均是最有效的助剂,钡比铯具有更强的促进作用。以硝酸钡和硝酸铯制备双助剂Ru/C催化剂,先钡后铯分步浸渍制备钌催化剂的活性不仅明显高于钡、铯共浸渍钌催化剂,而且也高于先铯后钡分步浸渍钌催化剂。

     

    Abstract: A series of alkaline- or/and alkaline-earth-promoted, carbon-supported ruthenium catalysts have been prepared N2 physisorption, CO chemisorption and X-ray diffraction were carried out to investigate the effect of promoter on the surface area, pore size distribution and ruthenium dispersion of catalysts. The activities of the series catalyst for ammonia synthesis were measured under the reaction condition 430 ℃, 10.0 MPa and 10 000 h-1. It has been found that the effectiveness of alkaline- or alkaline-earth-promoter is roughly related to the basicity of alkaline metal hydroxide or alkaline-earth metal oxide. For the single-promoted Ru/C catalyst, cesium and barium proved to be most effective in the alkaline and alkaline-earth promoter. Barium-promoted Ru/C catalyst was more effective in ammonia synthesis than cesium-promoted Ru/C catalyst. Barium was suggested to have a stronger interaction with the Ru surface than cesium. For the double-promoted Ru/C catalyst, the activity of the catalyst was affected remarkably by the method of preparation. Barium and cesium promoter in 4w% Ru-Ba-Cs/C were impregnated by two steps method, barium was impregnated first, after reducing treatment at 400 ℃, cesium was impregnated again. The catalyst of 4w% Ru-Cs-Ba/C was prepared from impregnating cesium first barium later by two step impregnation. The catalyst of 4w% Ru-(Ba+Cs)/C was prepared from co-impregnation the mix aqueous solution of barium and cesium by one step method. The result showed that the activity of 4w% Ru-Ba-Cs/C was higher obviously not only than 4w% Ru-(Ba+Cs)/C, but also than 4w% Ru-Cs-Ba/C. Because barium and cesium competed adsorption during the process of preparing the double-promoted Ru/C catalyst, that would influence the surface distribution of barium and cesium promoter and ammonia synthesis activity of the Ru/C catalyst.

     

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