锆掺杂钛负载锰氧化物用于低温选择性催化还原NO

Manganese oxides supported on zirconium-doped titania for low ternperature selective catalytic reduction of NO

  • 摘要: 采用凝胶溶胶法制备TiO2以及摩尔比分别为1:1和4:1的TiO2-ZrO2三种载体,然后浸渍负载一定量的活性组分MnOx制备相应催化剂.通过X射线衍射和扫描电镜对载体和催化剂进行表征,并进行氨气低温选择性催化还原NO(NH3-SCR)实验来考察催化剂的活性.三种载体中TiO2-ZrO2(4:1)的颗粒粒径最小且高度分散,加入氧化锆后,Zr4+离子取代Ti4+离子掺杂进入TiO2晶格内,引起TiO2晶格畸变,抑制TiO2晶型转变,并促进载体上活性组分Mn的均匀分布,从而提高催化剂的低温选择性催化还原活性.TiO2-ZrO2(4:1)加入质量分数10%的Mn后催化剂的活性最高,在130℃采用该催化剂催化时NO的转化率达到92.6%;150℃时通入体积分数10%的水蒸气会降低10%Mn/TiO2-ZrO2(4:1)催化剂的活性,撤消后活性可逐渐恢复;而200℃时10%Mn/TiO2-ZrO2(4:1)的活性基本不受水蒸气的影响.

     

    Abstract: Three kinds of carriers TiO2, TiO2-ZrO2 with the molar ratio of 1:1, and TiO2-ZrO2 with the molar ratio of 4:1 were prepared by a sol-gel method, and then the corresponding catalysts were obtained through loading a certain amount of active ingredient MnOx on the carriers. The carriers and catalysts were characterized by X-ray diffraction (XRD) and scanning electron microscopy (SEM). Some experiments on the selective catalytic reduction of NO with ammonia (NH3-SCR) were performed in order to investigate the activity of the catalysts. It is found that TiO2-ZrO2 (4:1) has the minimum particle size and its particles are highly dispersive among the three carriers. When adding ZrO2, Zr4+ ions dope into the TiO2 lattice by substituting Ti4+ ions, and thus the lattice distortion is triggered and the crystal transformation is restrained in the TiO2. Furthermore, Zr also promotes the dispersion of the active ingredient on the carrier, thereby improves the activity of the catalysts. The 10%Mn/TiO2-ZrO2(4:l) catalyst that adding 10% Mn to TiO2-ZrO2(4:l) has the highest activity among the three catalysts. The conversion of NO can reach 92.6% when catalyzed by this catalyst at 130℃. The activity of 10%Mn/TiO2-ZrO2(4:l) decreases when adding 10% of water vapor at 150℃, and it can restore when cutting off water vapor. But water vapor has no effect on the activity of 10%Mn/TiO2-ZrO2(4:l) at 200℃.

     

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