改性ZrO<sub>2</sub>负载钌氨合成催化剂的制备及其构效关系研究

王自庆; 林建新; 王榕; 魏可镁

改性ZrO₂负载钌氨合成催化剂的制备及其构效关系研究

福州大学化肥催化剂国家工程研究中心, 福建福州 350002

基金项目: 国家科技支撑计划(2007BAE08B02);中国石油科技创新基金(2010D-5006-0502)。

详细信息

通讯作者:
林建新, Tel: (0591) 83731234-8102; E-mail: lin3jx@fzu.edu.cn。

中图分类号: O643.3
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出版历程
- 收稿日期: 2012-05-17
- 修回日期: 2012-07-14
- 刊出日期: 2012-12-31

Ammonia synthesis over ruthenium supported on modified zirconia: Relationships between the catalyst structure and activity

National Engineering Research Center of Chemical Fertilizer Catalyst, Fuzhou University, Fuzhou 350002, China

摘要

摘要: 由ZrO(NO₃)₂水解得到的ZrO(OH)₂水凝胶经碱液回流老化、焙烧后制备了改性ZrO₂载体材料,直接浸渍K₂RuO₄溶液,经还原后用于催化氨合成反应。并运用X射线衍射(XRD)、CO₂ 程序升温脱附(CO₂-TPD)、X射线荧光光谱 (XRF)、N₂物理吸附、H₂程序升温还原技术(H₂-TPR)和CO化学吸附对其进行了表征,重点考察了催化剂性能与载体性能间的构效关系。结果表明,KOH和NH₄OH溶液回流均可提高载体的比表面积,但是KOH回流制备的载体同时还具有较强的碱性,因此,负载钌以后表现出最佳活性。在425 ℃、5 MPa、空速为10 000 h^-1条件下,出口氨浓度为5.96%,分别较催化剂K-Ru/ZrO₂-NH₄OH、K-Ru/ZrO₂-CP和Ru/ZrO₂-NH₄OH提高了11%、143%和103%。与活性组分分散度相比,载体碱性强度对活性的促进作用更为明显。
- 碱液回流 /
- 二氧化锆 /
- 钌 /
- 氨合成 /
- 碱性
Abstract: Modified zirconia (ZrO₂) were synthesized by high temperature calcination of ZrO(OH)₂ gels digested in alkalic solution; with the modified ZrO₂ as support, ruthenium catalysts for ammonia synthesis were prepared with K₂RuO₄ solution. The catalysts were characterized by X-ray diffraction (XRD), temperature programmed reduction of hydrogen (H₂-TPR), temperature programmed desorption of CO₂ (CO₂-TPD), nitrogen sorption, X-ray fluorescence spectroscopy (XRF), and CO chemisorption; the relationship between the catalyst structure and its catalytic activity was especially discussed. The results revealed that the digestion either in KOH or NH₄OH solution can enhance the surface area of the ZrO₂ support, while digestion in KOH is able to obtain the support with high basicity, which benefits to getting the ruthenium catalyst of high activity. The strong basicity of the modified ZrO₂ support, rather than the high ruthenium dispersion, plays a more important role in enhancing the activity of the supported ruthenium catalyst. For ammonia synthesis under 425 ℃, 5 MPa and a space velocity of 10 000 h^-1, NH₃ outlet concentration over Ru/ZrO₂-KOH is 5.96%, which is 11%, 143% and 103% higher than those of K-Ru/ZrO₂-NH₄OH, K-Ru/ZrO₂-CP and Ru/ZrO₂-NH₄OH, respectively.
- digestion in basic solution /
- zircona /
- ruthenium /
- ammonia synthesis /
- basicity

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