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  • Cr-MnOx/TiO2-ZrO2低溫選擇催化還原NO的活性及抗毒性能

    Activity and antitoxic properties of Cr-MnOx/TiO2-ZrO2 for low-temperature selective catalytic reduction of NO

    • 摘要: 采用溶膠凝膠法制備TiO2-ZrO2載體,然后采用檸檬酸溶液浸漬法制備Cr-MnOx/TiO2-ZrO2復合催化劑.通過X射線衍射、比表面積測試(BET)、掃描電鏡、X射線光電子能譜等測試方法對催化劑的物化性能進行表征分析,并進行NH3選擇性催化還原NO實驗,考察催化劑在低溫下的活性及抗硫抗水性能.Cr元素介入到MnOx中,形成了新型的CrMn1.5O4活性物相,其中的Mn元素多以Mn3+和Mn4+存在.高價態的Cr5+使Mn元素由Mn3+向高氧化態的Mn4+轉化,有利于低溫選擇性催化還原反應的進行.鑒于Cr元素第一電離能和電負性均低于Mn元素,能優先于Mn與SO42-和SO32-結合,保護MnOx不被硫酸化,從而提高Cr-MnOx/TiO2-ZrO2催化劑的抗毒性能.制備的五種不同Cr/(Cr+Mn)摩爾比的催化劑中,Cr(0.4)-MnOx/TiO2-ZrO2的性能最優,其顆粒分散均勻,具有較大比表面積,在180℃時脫硝效率能夠達到95.8%,同時通入5%H2O和10-4SO2,脫硝效率緩慢下降,反應8h后,下降到73%,并保持穩定.

       

      Abstract: Using a sol-gel prepared TiO2-ZrO2 carrier,Cr-MnOx/TiO2-ZrO2composite catalysts were synthesized by a critic acid solution impregnation method. The physical and chemical properties of the catalysts were characterized by X-ray diffraction,specific surface area determination(BET),scanning electron microscopy and X-ray photoelectron spectroscopy. Meanwhile,the lowtemperature catalytic activity and the sulfur and water resistance were evaluated with selective catalytic reduction(SCR) of NO by NH3. The introduction of Cr element to MnOxyields a new CrMn1.5O4 active phase,in which Mn primarily exists as Mn3+ and Mn4+.The Cr5+ valence state facilitates the transformation of Mn3+ to high oxidation state Mn4+,which is beneficial to the low temperature SCR reaction. Because of lower first ionization energy and electronegativity,Cr preferentially reacts with SO42- and SO32- than Mn,thus protecting MnOx not to be sulphatized and resulting in the enhanced antitoxic performance of Cr-MnOx/TiO2-ZrO2. Among the prepared five catalysts with different molar ratios of Cr/(Cr + Mn),Cr(0.4)-MnOx/TiO2-ZrO2 demonstrates the best performance owing to the largest surface area and the best particle dispersion,and a 95.8% denitrification efficiency can be achieved at 180℃.When 5% H2O and 10-4 SO2 are simultaneously added,the denitrification efficiency decreases slowly and stabilizes at 73% after 8h reaction.

       

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