Selective catalytic reduction of nitric oxide with propylene in excess oxygen over Fe-Mn/Beta catalysts
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摘要: 以Beta分子筛为载体，采用等体积浸渍法制备Fe-Mn/Beta催化剂，并对其在富氧条件下丙烯选择性催化还原NO性能进行了研究。通过N2吸附-脱附、X射线衍射（XRD）、X射线光电子能谱（XPS）、透射电子显微镜（TEM）、程序升温还原（H2-TPR）和原位漫反射傅里叶变换红外光谱（in-situ DRIFTS）等研究手段对催化剂进行表征，考察Mn组分对催化剂的物理化学性质、C3H6-SCR反应活性和反应中间产物的影响。结果表明，引入Mn物种可以显著提高Fe-Mn/Beta催化剂的低温催化活性，1.5Fe1.0Mn/Beta催化剂NO还原效率350℃最高可达99.4%，在250-400℃反应温度下显示出很高的反应活性和N2选择性。原位红外光谱研究表明，分子筛离子交换位上孤立的铁离子是丙烯选择性氧化的主要活性位，分散良好的MnO2物种不能提高催化剂对丙烯的活化能力，但有助于促进形成NO2吸附物种，从而提升了Fe-Mn/Beta催化剂的低温C3H6-SCR性能。经高温水热老化处理后，Fe-Mn/Beta催化剂脱硝活性明显下降，这与孤立的Fe3+离子迁移形成FexOy团聚物种有关。Abstract: Fe-Mn/Beta catalysts were prepared by incipient wet-impregnation methods and used for selective catalytic reduction of nitric oxide with propylene in excess oxygen. The catalysts were characterized using N2-physisorption, X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), transmission electron microscopy (TEM), H2-temperature programmed reduction (H2-TPR) and in-situ diffuse reflectance infrared Fouier transform spectroscopy (in-situ DRIFTS) techniques. The effects of Mn component on the physicochemical properties, C3H6-SCR activity and reaction intermediates of catalysts were also investigated. The results showed that C3H6-SCR activity of Fe-Mn/Beta catalysts at low temperature could be significantly improved by introducing Mn species. 1.5Fe1.0Mn/Beta catalyst achieved the highest activity with a nitrogen oxide conversion of 99.4% at 350℃, which possessed high catalytic performance and N2 selectivity within the temperature window of 250-400℃. Based on the in-situ DRIFT studies, the isolated Fe3+ ions at the ion-exchange sites were the main active sites for selective oxidation of propylene. Although the well-dispersed MnO2 species could not improve the activation ability of the catalysts for propylene, they would enhance the formation of NO2 adsorption species, then promoted C3H6-SCR activity at the low temperature. The significant decrease of SCR activity after hydrothermal aging of Fe-Mn/Beta catalysts might be due to the migration of isolated Fe3+ ions into oligomeric clusters.
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Key words:
- selective catalytic reduction /
- NO /
- C3H6 /
- manganese /
- hydrothermal aging
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图 1 实验装置示意图
Figure 1 Schematic diagram of the experimental setup
1: gas regulator; 2: mass flow controller; 3: solenoid value; 4: preheating furnace; 5: injection pump; 6: quartz tube reactor; 7: FT-IR spectroscopy (gas analyzer)
图 2 Fe-Mn/Beta催化剂上C3H6-SCR反应NO转化率(a)、N2选择性(b)和C3H6转化率(c)
Figure 2 NO conversion (a), N2 selectivity (b) and C3H6 conversion (c) over Fe-Mn/Beta catalysts
reaction conditions: 0.05%NO, 0.05%C3H6, 5%O2 and balance N2, GHSV=15000 mL/(g·h)
—□—: 1.5Fe/Beta; —○—: 1.5Mn/Beta; —◆—: 1.5Fe0.5Mn/Beta; —●—: 1.5Fe1.0Mn/Beta; —■—: 1.5Fe1.5Mn/Beta
图 4 Fe-Mn/Beta催化剂样品的N2吸附-脱附等温线
Figure 4 N2 adsorption-desorption isotherms of H-Beta and Fe-Mn/Beta catalyst samples
图 5 Fe-Mn/Beta催化剂样品的TEM照片
Figure 5 TEM images of Fe-Mn/Beta catalyst samples
(a): 1.5Fe1.0Mn/Beta; (b): 1.5Fe/Beta; (c): 1.5Mn/Beta
图 6 催化剂样品的XPS谱图
Figure 6 XPS spectra of Mn 2p (a) and Fe 2p (b) for Fe-Mn/Beta catalyst samples
图 8 在Fe-Mn/Beta催化剂表面原位反应DRIFTS谱图
Figure 8 In-situ DRIFT spectra measure on Fe-Mn/Beta catalysts at 300 ℃
reaction conditions: 0.05%NO + 5%O2 adsorbed 60 min, then 0.1%C3H6 adsorbed 60 min
图 9 高温老化、高温水热老化对1.5Fe1.0Mn/Beta催化剂上C3H6-SCR反应活性的影响
Figure 9 NO conversion over the fresh and aged 1.5Fe1.0Mn/Beta catalysts the hydrothermal aging was performed at 700 ℃ for 24 h in the presence of 10% H2O and 20% O2 or 20% O2
reaction conditions: 0.05%NO, 0.05% C3H6, 5%O2, and GHSV=15000 mL/(g·h)
—○—: 1.5Fe1.0Mn/Beta-fresh; —●—: 1.5Fe1.0Mn/Beta-aged; —◆—: 1.5Fe1.0Mn/Beta-aged (10% H2O)
图 10 高温老化、高温水热老化前后1.5Fe1.0Mn/Beta催化剂的XRD谱图
Figure 10 XRD patterns of the fresh and aged 1.5Fe1.0Mn/Bate catalysts
表 1 Fe-Mn/Beta催化剂样品的孔结构特性
Table 1 Properties of H-Beta and Fe-Mn/Beta catalyst samples
Sample Specific surface area A/(m2·g-1) Pore volume v/(mL·g-1) Pore diameter d/nm 1.5Fe/Beta 512.1 0.541 4.2 1.5Fe1.0Mn/Beta 506.7 0.517 4.1 1.5Mn/Beta 431.6 0.450 4.2 H-Beta 519.9 0.517 4.0 
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