表面助剂改性对Cu/ZnO/Al2O3甲醇合成催化剂性能的影响

doi:10.3866/PKU.WHXB201306211

摘要/Abstract

摘要：

采用共沉淀-后浸渍方法制备了表面助剂改性的Cu/ZnO/Al₂O₃ (CZA)甲醇合成催化剂, 在固定床反应器上以合成气为原料分别考察了三种助剂(Zr、Ba和Mn)对CZA催化剂性能的影响; 以Zr为助剂时反应温度的影响; 并进行了催化稳定性试验. 利用粉末X射线衍射(XRD)、低温氮气吸脱附(N₂-sorption)、氧化亚氮(N₂O)反应吸附技术、X射线光电子能谱(XPS)、氢气程序升温吸脱附(H₂-TPD)、扫描电子显微镜(SEM)和高分辨透射电子显微镜(HR-TEM)技术对催化剂进行了表征.结果显示: 以Zr或Ba作为助剂能够明显提高CZA催化剂耐热前后的甲醇时空收率(STY); Mn的引入降低了CZA催化剂的耐热前活性; Zr的引入降低了CZA催化剂最高活性温度点, 增强了CZA催化剂的催化稳定性; 还原态CZA催化剂表面Cu⁰和ZnO都能吸附活化氢气, Cu⁰与ZnO的强相互作用有利于提高催化剂的性能, 耐热后催化剂性能的降低归因于Cu晶粒的长大. 在实验和表征结果基础上,提出了CZA催化剂上合成气制甲醇的“双向同步催化反应历程”.

关键词: 助剂, Zr, Ba, Cu/ZnO/Al₂O₃催化剂, 甲醇合成, 反应历程

Abstract:

Surface promoters-modified Cu/ZnO/Al₂O₃ (CZA) catalysts were prepared by a coprecipitationpost impregnation method and evaluated in methanol synthesis fromsyngas. The effects of Zr, Ba, and Mn as promoters, the reaction temperature and run time over CZA and Zr-promoted CZA catalysts on catalytic performance were investigated, respectively. The catalysts were characterized by X-ray diffraction (XRD), N₂-sorption, reactive N₂O sorption, X-ray photoelectron spectroscopy (XPS), temperature-programmed desorption of H₂ (H₂-TPD), scanning electron microscopy (SEM), and high-resolution transmittance electron microscopy (HR-TEM). The results showed that the space-time yield (STY) of methanol can be increased noticeably over the Zr-or Ba-promoted CZA catalyst before and after the heating treatment of the catalysts. The introduction of Mn as a promoter onto the CZA catalyst led to a decrease in the STY of methanol before heating treatment. The introduction of Zr as a promoter onto the CZA catalyst can decrease the temperature at which the STY of methanol reached the highest value and also improve the catalytic stability. A hydrogen molecule can be adsorbed and then activated over Cu⁰ and ZnO. The strong interaction between Cu⁰ and ZnO is favorable for improving the catalytic performance of the CZA catalyst. The decrease in catalytic performance after heating treatment of the CZA catalysts is attributed to a growth of Cu⁰ crystallites. Based on the results of catalytic performance and characterization, a possible "bidirectional but synchronous catalytic reaction course" in methanol synthesis from syngas over a CZA catalyst is proposed.

Key words: Promoter, Zirconium, Barium, Cu/ZnO/Al₂O₃ catalyst, Methanol synthesis, Reaction course

郝爱香, 于杨, 陈海波, 毛春鹏, 魏士新, 殷玉圣. 表面助剂改性对Cu/ZnO/Al₂O₃甲醇合成催化剂性能的影响[J]. 物理化学学报, 2013, 29(09), 2047-2055. doi: 10.3866/PKU.WHXB201306211

HAO Ai-Xiang, YU Yang, CHEN Hai-Bo, MAO Chun-Peng, WEI Shi-Xin, YIN Yu-Sheng. Effect of Surface Promoters-Modifying on Catalytic Performance of Cu/ZnO/Al₂O₃ Methanol Synthesis Catalyst[J]. Acta Phys. -Chim. Sin. 2013, 29(09), 2047-2055. doi: 10.3866/PKU.WHXB201306211

链接本文: https://www.whxb.pku.edu.cn/CN/10.3866/PKU.WHXB201306211

https://www.whxb.pku.edu.cn/CN/Y2013/V29/I09/2047

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表面助剂改性对Cu/ZnO/Al₂O₃甲醇合成催化剂性能的影响

Effect of Surface Promoters-Modifying on Catalytic Performance of Cu/ZnO/Al₂O₃ Methanol Synthesis Catalyst

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