Ru/Ba-ZrO2催化剂的制备及其氨合成性能研究

doi:10.6023/A12090725

摘要/Abstract

分别采用柠檬酸络合法、改性共沉淀法和湿浸渍法制备了掺Ba纳米ZrO₂材料, 负载Ru后用于催化氨合成反应. 采用X射线衍射、CO₂程序升温脱附(CO₂-TPD)、N₂物理低温吸附、H₂程序升温还原技术(H₂-TPR)、扫描电镜(SEM)、透射电镜(TEM)、X射线光电子能谱(XPS)和CO化学吸附对载体材料和催化剂进行了表征. 结果表明, 不同方法制备载体的物相结构和织构性能均有明显差别, 负载Ru后催化剂的氨合成性能差别也较大. 其中, 以柠檬酸络合法制备的载体材料中Ba以BaZrO₃的形式存在, 钙钛矿型BaZrO₃具有较强的供电子能力, 电子可以通过Ru与载体间强相互作用传递到Ru表面, 有效地促进N≡N的断裂, 使催化剂的低温活性显著提高. 在425℃, 3 MPa, 空速为10000 h^-1条件下, 出口氨浓度为5.72%. 其氨合成活性分别是改性共沉淀法和湿浸渍法制备催化剂的3.8倍和14.3倍.

关键词: 制备方法, 钡, 二氧化锆, 钌, 氨合成

The Ba-doped ZrO₂ materials were prepared by three methods and used as support for Ru catalysts for ammonia synthesis, i.e., citric acid sol-gel method (SG), modified co-precipitation (CP) and impregnation method (IP). The certain amount of analytical-grade Zr(NO₃)₄·5H₂O and Ba(NO₃)₂ were dissolved in deionized water to form a transparent mixed nitrate solution. The citric acid was slowly added into the mixture to form a transparent solution and then heated to 80℃ under vigorous stirring until all the water evaporated and a viscous material was obtained. After calcination at 750℃ for 5 h and a puffy white powder was obtained. This was BZ-SG. The solution of NH₃·H₂O and K₂C₂O₄·H₂O was added dropwise to the mixture solution of Zr(NO₃)₄·5H₂O and Ba(NO₃)₂ with vigorous stirring, and the obtained white suspension was aged at 60℃ for 60 min. The resulting precipitate was centrifuged and washed with distilled water for several times, and then calcined at 750℃ for 5 h. The obtained white solid was named as BZ-CP. The Zr(OH)₄ was prepared by adding the KOH into the Zr(NO₃)₄·5H₂O solution. Then the obtained Zr(OH)₄ was baked at 300℃ for 3 h and impregnated with aqueous solution of Ba(NO₃)₂. After dried at 85℃ for 12 h, the sample was heated at 750℃ for 5 h and obtained the BZ-IP sample. Ruthenium catalysts were prepared by impregnating the supports directly with K₂RuO₄ solution. After reduction with ethyl alcohol, then was dried at 120℃ for 12 h. The samples with 4 wt% Ru were labeled as RBZ-X (X=SG, CP and IP). The molar ratio of Ba to Zr in all the samples is 1:9. The composites materials and catalysts were characterized by X-ray diffraction (XRD), temperature programmed reduction of H₂ (H₂-TPR), temperature programmed desorption of CO₂ (CO₂-TPD), N₂ adsorption- desorption isotherms, scanning electron microscopy (SEM), transmission electron microscopy (TEM) and CO chemisorption. The results displayed that the RBZ-SG catalyst showed the highest activity for ammonia synthesis compared to those of RBZ-CP and RBZ-IP. The optimum ammonia concentration over RBZ-SG catalyst is 5.72% under the conditions of 3 MPa, 10000 h^-1 and 425℃. This activity is 3.8 and 14.3 times of that of RBZ-CP and RBZ-IP, respectively. Such high activity is mainly resulted from the presence of BaZrO₃, which has high electron-donating ability. Mobile electrons would be transferred from BaZrO₃ to the Ru metal surface by means of the strong metal-support interaction existed between Ru and reduction BaZrO₃, which can facilitate the cleavage of N≡N and enhance the activity for ammonia synthesis sufficiently.

Key words: preparation method, barium, zirconium, ruthenium catalysts, ammonia synthesis

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王自庆, 陈赓, 林建新, 王榕, 魏可镁. Ru/Ba-ZrO₂催化剂的制备及其氨合成性能研究[J]. 化学学报, 2013, 71(02): 205-212.

Wang Ziqing, Chen Geng, Lin Jianxin, Wang Rong, Wei Kemei. Preparation of Ru/Ba-ZrO₂ Catalyst and Its Performance for Ammonia Synthesis[J]. Acta Chimica Sinica, 2013, 71(02): 205-212.

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Ru/Ba-ZrO₂催化剂的制备及其氨合成性能研究

Preparation of Ru/Ba-ZrO₂ Catalyst and Its Performance for Ammonia Synthesis

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