SCR反应过程中NO/NH3在γ-Al2O3表面吸附特性

doi:10.3969/j.issn.0438-1157.2014.10.040

化工学报 ›› 2014, Vol. 65 ›› Issue (10): 4056-4062.DOI: 10.3969/j.issn.0438-1157.2014.10.040

SCR反应过程中NO/NH₃在γ-Al₂O₃表面吸附特性

曹蕃¹, 苏胜¹, 向军¹, 王鹏鹰¹, 胡松¹, 孙路石¹, 张安超²

1 华中科技大学煤燃烧国家重点实验室, 湖北武汉 430074;
2 河南理工大学机械与动力工程学院, 河南焦作 454000

收稿日期:2014-03-20 修回日期:2014-05-27 出版日期:2014-10-05 发布日期:2014-10-05
通讯作者: 苏胜
基金资助:
教育部科学技术研究项目（113045A）；国家自然科学基金项目（51176062，51306046）。

NO/NH₃ adsorption properties on γ-Al₂O₃ (110) surface during SCR process

CAO Fan¹, SU Sheng¹, XIANG Jun¹, WANG Pengying¹, HU Song¹, SUN Lushi¹, ZHANG Anchao²

1 State Key Laboratory of Coal Combustion, Huazhong University of Science and Technology, Wuhan 430074, Hubei, China;
2 School of Mechanical and Power Engineering, Henan Polytechnic University, Jiaozuo 454000, Henan, China

Received:2014-03-20 Revised:2014-05-27 Online:2014-10-05 Published:2014-10-05
Supported by:
supported by the Foundation for Key Program of Ministry of Education (113045A) and the National Natural Science Foundation of China (51176062,51306046).

摘要/Abstract

摘要： 采用密度泛函理论（DFT）方法研究了NO和NH₃在完整和有缺陷的γ-Al₂O₃（110）表面吸附与SCR（选择催化还原）反应特性。研究表明，NO在完整的（110）表面的吸附作用较弱，而NH₃分子的吸附作用较强，NH₃分子在Al原子顶位可形成稳定吸附。反应路径研究结果表明完整的（110）表面上SCR反应的决速步为-NH₂NO基团的分解，反应的最大能垒为235.75 kJ·mol^-1。对于产生氧空穴的有缺陷（110）表面，NO和NH₃均可稳定吸附，NH₃在吸附过程中可直接裂解成NH₂和H。另外，SCR反应在有缺陷（110）表面的最大能垒明显较低，说明氧空穴的存在促进了SCR脱硝反应的进行。

关键词: 氧化铝, 分子模拟, 吸附, 密度泛函, 一氧化氮

Abstract: γ-Al₂O₃is an outstanding catalyst carrier and has been widely used in the SCR (selective catalytic reduction) catalyst study. The adsorption and reaction properties of NO/NH₃ on the bare and defective γ-Al₂O₃ (110) surface were studied by the DFT (density functional theory) method. The corresponding microscopic parameters, such as adsorption energies, bond length, changes of net charge and PDOS (partial density of states) were calculated. NO could be adsorbed on the bare (110) surface weakly, and it was more inclined to be adsorbed on the top sites of O_2c. NH₃ could be adsorbed strongly on top sites of Al. The rate-determining step of SCR reaction was the -NH₂NO decomposition, while the largest energy barrier reached 235.75 kJ·mol^-1. For the defective (110) surface with the oxygen vacancy, NO and NH₃ could be both adsorbed strongly on the surface, and NH₃ could also decompose into NH₂ and H directly in this situation. The largest energy barrier of SCR reaction in this situation was much lower, indicating that the presence of oxygen vacancy could promote SCR reaction proceeding.

Key words: alumina, molecular simulation, adsorption, density functional theory, nitric oxide

中图分类号:

O647.32

曹蕃, 苏胜, 向军, 王鹏鹰, 胡松, 孙路石, 张安超. SCR反应过程中NO/NH₃在γ-Al₂O₃表面吸附特性[J]. 化工学报, 2014, 65(10): 4056-4062.

CAO Fan, SU Sheng, XIANG Jun, WANG Pengying, HU Song, SUN Lushi, ZHANG Anchao. NO/NH₃ adsorption properties on γ-Al₂O₃ (110) surface during SCR process[J]. CIESC Journal, 2014, 65(10): 4056-4062.

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SCR反应过程中NO/NH₃在γ-Al₂O₃表面吸附特性

NO/NH₃ adsorption properties on γ-Al₂O₃ (110) surface during SCR process

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