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Sm-Mn/Ti蜂窩式低溫脫硝催化劑性能研究

Study of performance on Sm-Mn/Ti honeycomb SCR catalyst at low temperature

  • 摘要: 傳統選擇性催化還原(SCR)催化劑在200°C以下存在脫硝效率低的瓶頸。Mn基催化劑是一種較有應用潛力的低溫SCR催化劑,但目前尚缺乏對成型Mn基催化劑的性能研究。本文采用共沉淀及混練擠出成型技術,制備了不同活性組分負載量的Sm-Mn/Ti-y(y = 3、1.5、1)蜂窩式低溫脫硝催化劑。結果表明,Sm-Mn/Ti-1.5蜂窩式催化劑NO轉化率達到90%以上,N2選擇性達到70%以上,且具有顯著的抗SO2中毒性能,在100-180°C下展現出最優綜合性能。分析表明,Sm-Mn/Ti-1.5表面Mn4+占比(56.50%)和弱酸性位點數量(280.7 μmol·g-1)均高于其他樣品。高含量Mn4+通過促進更多反應物種活化提升催化活性;而豐富的弱酸性位點,提供充足的吸附位點,提升低溫NO轉化率,避免副產物N2O生成,從而提高N2選擇性。此外,該催化劑表面Sm3+/Sm(24.10%)和Oα/O(25.12%)含量分別低于Sm-Mn/Ti-3和Sm-Mn/Ti-1,這有效調節Mn4+/Mn3+和Sm3+/Sm2+的雙氧化還原循環,維持高活性時,避免過度氧化生成N2O。對比發現,由于表面Sm3+/Sm含量高和酸性低,導致Sm-Mn/Ti-3的NO轉化率高但N2選擇性低;而Sm-Mn/Ti-1表面Oα/O含量最高,但其Mn4+/Mn含量低和酸位點少,導致其NO轉化率低。綜上所述,通過調控活性組分負載量實現了Sm-Mn/Ti催化劑氧化能力與酸性位點的協同優化,獲得了兼顧高NO轉化率和良好N2選擇性的Sm-Mn/Ti-1.5催化劑,為開發高效低溫SCR催化劑提供了新策略。

     

    Abstract: Selective catalytic reduction (SCR) technology is a key technology for industrial flue gas denitrification. However, traditional SCR catalysts suffer from low efficiency below 200°C. The Mn-based catalysts exhibit high catalytic performance and great application potential under low temperature, but systematic studies on monolithic Mn-based catalysts are lacking. In this article, Sm-Mn/Ti-y (y = 3, 1.5, 1) monolithic honeycomb catalysts with varying active component loads are prepared by co-precipitation combined with mixing-extrusion molding method. Honeycomb catalysts with no cracks on the surface, good smoothness, and excellent molding ability are obtained. The performance test results demonstrate that the Sm-Mn/Ti-1.5 catalyst exhibited over 90% NO conversion and 70% N2 selectivity between 100-180°C. Characterization and testing techniques, including XRD, FESEM, N2 adsorption-desorption tests, XPS, H2-TPR, and NH3-TPD, are conducted to explore the effect of the Sm-Mn/Ti ratio on the surface phase, structure, species, redox capacity, and adsorption capacity of the catalyst. The XRD results indicate that only TiO2 phase exists, with no other phases detected, this indicates that the Sm and Mn elements are uniformly dispersed on the catalyst surface and do not form any long-range ordered lattice. The SEM characterization results show that the catalysts are consisted of colonies and nanoparticles on their surfaces. Highly dispersed element distribution and small surface structure are beneficial for improving the catalytic performance. N2 adsorption-desorption tests indicate that the catalysts are consisted of the mesoporous structures. The XPS characterization, H2-TPR and NH3-TPD test results reveal that the Sm-Mn/Ti-1.5 catalyst possesses the highest Mn4+ content (56.5%) and weak acid site amount (280.7 μmol·g-1) among the tested samples. The elevated Mn4+ concentration enhances the catalytic activity by facilitating the activation of more reactive species. While the increased amounts of weak acidity sites provide sufficient adsorption sites to promote the conversion of NO and reduce the formation of N2O. Notably, the XPS characterization results also show that the Sm-Mn/Ti-1.5 catalyst exhibits a lower ratio of Sm3+/Sm (24.10%) than Sm-Mn/Ti-3, and a lower ratio of Oα/O (25.12%) than Sm-Mn/Ti-1. This effectively regulates the double redox cycle of Mn4+/Mn3+ and Sm3+/Sm2+, sustaining high activity while mitigating N2 selectivity. It is found that Sm-Mn/Ti-3 has a high NO conversion but a low N2 selectivity due to excessive Sm3+/Sm and decreased acidity on its surface. Although Sm-Mn/Ti-1 has the highest ratio of Oα/O, its low NO conversion is due to the fewer amount of Mn4+species and weak acid sites. In summary, the synergistic optimization of the oxidation ability and acidic sites of Sm-Mn/Ti catalyst is achieved by regulating the loading of active components, resulting in a Sm-Mn/Ti-1.5 catalyst that balances high NO conversion rate and good N2 selectivity. In order to verify the SO2 poisoning resistance of the Sm-Mn/Ti-1.5 catalyst, the NH3-SCR experiments are carried out in a 50 ppm SO2 atmosphere at 120°C. The results show that the high NO conversation rate and N2 selectivity maintained for 12 h without significant decrease, which demonstrates that the Sm-Mn/Ti-1.5 catalyst also exhibits excellent SO2 resistance. The present study achieves the formation and optimization of active components of Mn-based catalysts, offering a new strategy for efficient low-temperature SCR catalyst development.

     

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