WO3的引入对MnOx-Fe2O3催化剂上NH3-SCR反应中N2选择性的促进作用

Promotion effect of tungsten addition on N2 selectivity of MnOx-Fe2O3 for NH3-SCR

  • 摘要: 采用溶胶-凝胶法制备了不同含量钨修饰的MnOx-Fe2O3催化剂,重点考察WO3的引入对NH3-SCR反应中N2选择性的影响,通过XRD、BET、XPS、H2-TPR、Raman和In situ DRIFTS等手段对催化剂的物理化学性质进行表征。结果表明,钨的引入显著提高NH3-SCR的N2选择性,当WO3质量分数为15%时,具有最佳的NH3-SCR催化性能,且在50-250℃条件下N2O浓度始终低于0.003%。这主要是由于适量WO3的引入,导致催化剂物相由α-Fe2O3γ-Fe2O3转变,并与锰相互作用形成新的无定型MnWO4,获得较大的比表面积;使得Mn4+/(Mn3++Mn4+)比例减少但Fe2+及表面化学吸附氧(Oα)含量增加,从而降低催化剂氧化性;增强催化剂表面的Lewis酸性位点的含量及强度,增强NH3的吸附,促进了SCR反应,同时抑制了NO2深度氧化形成硝酸盐物种,降低硝酸盐物种还原产生的副产物N2O含量,从而显著提高WO3-MnOx-Fe2O3催化剂在NH3-SCR中的N2选择性。

     

    Abstract: A series of tungsten modified MnOx-Fe2O3 catalysts with different tungsten contents were prepared by sol-gel method. The influence of tungsten on N2 selectivity of NH3-SCR reaction was investigated particularly. Physical and chemical properties of the catalysts were characterized by means of XRD, BET, XPS, H2-TPR, Raman and in situ DRIFTS. The results showed that N2 selectivity of NH3-SCR at high temperature was significantly improved by introducing tungsten. NH3-SCR possessed the best catalytic performance when the tungsten content was 15% (mass ratio), as well as N2O concentration was less than 0.003% within the range of 50-250℃. The primary causes were the phase change from α-Fe2O3 to γ-Fe2O3 due to the introduction of appropriate amount of WO3. Besides, the interaction between tungsten and manganese formed a new amorphous MnWO4 and obtained a large specific surface area. In addition, the ratio of Mn4+/(Mn3++Mn4+) decreased while the content of Fe2+ and surface chemical adsorption oxygen (Oα) increased, thus the oxidability of the catalyst was reduced. Meanwhile, tungsten doping enhanced the content and strength of Lewis acid sites on the surface of catalysts at high temperatures. Moreover, the adsorption of NH3 was enhanced, thus, NH3-SCR reaction was accelerated. The doping of WO3 inhibited the deep oxidation of NO2 to form nitrate species, reduced the content of by-product N2O produced by nitrate species reduction, and significantly improved the NH3-SCR activity and N2 selectivity of WO3-MnOx-Fe2O3 catalyst at experimental temperature.

     

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