锆掺杂TiO2负载锰铈氧化物低温催化还原NOx

Low-temperature catalytic reduction of nitrogen oxides over manganese-cerium composite oxides supported on zirconium-doped titanium dioxide

  • 摘要: 采用溶胶-凝胶法制备TiO2、ZrO2和不同比例TiO2-ZrO2等载体,超声波浸渍负载一定量的Ce-Mn活性组分.通过扫描电镜、X射线衍射、X射线光电子能谱、傅里叶变换红外光谱和比表面积(BET)法对催化剂进行表征,并考察催化剂的氨气低温催化还原NOx的活性.结果表明,TiO2-ZrO2(3:1,摩尔比)载体为介孔材料,颗粒粒径较小且高度分散,比表面积高达151 m2·g-1.由于Zr4+取代Ti4+掺杂进入TiO2晶格内,导致其晶格畸变,抑制TiO2晶型转变,获得了良好的热稳定性,加之活性组分以无定形态存在,催化剂表面存在Ce3+/Ce4+氧化还原电对,从而提高催化剂的低温催化还原活性.在550℃下焙烧的催化剂10% Ce(0.4)-Mn/TiO2-ZrO2(3:1)的活性最高,其在140℃、体积空速67000 h-1的条件下,NOx的转化率达到99.28%.140℃时单独通入体积分数为10%的H2O以及同时通入体积分数为10% H2O和2×10-4 SO2,催化剂显示出较强的抗H2O和SO2中毒能力.

     

    Abstract: Carriers of TiO2, ZrO2 and TiO2-ZrO2 with different ratios were prepared by sol-gel method. Some manganese-cerium (Mn-Ce) active components were loaded on these carriers by ultrasonic immersion. The catalysts were characterized by scanning electron microscopy (SEM), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), Fourier transform infrared (FT-IR) spectroscopy, and Brunauer-Emmett-Teller (BET) method. The activity of the catalysts was studied under the condition of low-temperature catalytic reduction of NOx with ammonia as a reductant. The results show that the TiO2-ZrO2 (3:1, molar ratio) carrier was a mesoporous material, the particle size is smaller, the particles are highly dispersed, and the specific surface area reaches up to 151 m2· g-1. By doping ZrO2, Zr4+ ions replace Ti4+ ions and enter the lattice, leading to TiO2 lattice distortion. The addition of ZrO2 inhibits crystal transfer from anatase to rutile phase, and so the thermal stability of this carrier improves. Furthermore, the active components mainly exist in amorphous state and the Ce3+/Ce4+ redox couple appears on the carrier surface, thus the catalytic reduction activity at low temperature improves. The highest activity of the 10% Ce(0.4)-Mn/TiO2-ZrO2 (3:1) catalyst is obtained under calcination at 550℃. At 140℃ and a space velocity of 67000 h-1, the conversion rate of NOx reaches 99.28%. The 10% Ce(0.4)-Mn/TiO2-ZrO2 (3:1) catalyst provides strong anti-poisoning capacity to H2O and SO2 in the presence of 10% H2O alone, or 10% H2O with 2×10-4 SO2 at 140℃.

     

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