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Effect of SO2 poisoning on undoped and doped Mn-based catalysts for selective catalytic reduction of NO

机译:Effect of SO2 poisoning on undoped and doped Mn-based catalysts for selective catalytic reduction of NO

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In this work, the poisoning effect of SO2 was investigated in binary MnTi and ternary MnCeTi mixed oxides for the NH3-SCR reaction under conditions relevant for mobile applications. For the binary MnTi sample, catalytic activity increases up to 250 °C, and then drops due to the oxidation of ammonia to NOx. The addition of Ce decreases the catalytic activity at 150 °C but widens the optimal operational temperature and reaches high conversion at 350 °C. Upon performing activity test with 100 ppm of SO2 in the gas stream, catalytic activity drastically decreases in all catalyst samples. The shape of the deactivation curve and SO2 concentrations at the outlet of the reactor suggest a strong adsorption and poisoning of SO2 on all the catalysts. Although samples containing large amounts of Ce display a better SO2 tolerance, this is insufficient to be considered for practical applications. Deactivated samples were investigated by a wide range of characterization tools. N2 physisorption measurements reveal a drop in the surface area that could partially explain catalyst deactivation. TGA reveals the absence of (NH4)2SO4 on the deactivated samples and suggests the formation of Mn and Ce sulfates on the catalyst surface. XPS results confirm the formation of MnSO4 and also show a decrease in the Mn and Ce oxidation states. Analysis of the redox function by catalytic NO oxidation and H2-TPR experiments shows a strong loss of redox function upon SO2 deactivation, which could explain the decrease of NH3-SCR catalytic activity. Upon unraveling the effect and cause of deactivation, a doping study was performed. As in the binary MnTi and ternary MnCeTi, catalytic activity strongly decreases upon the introduction of SO2 in the gas stream. None of the dopants investigated was able to suppress SO2 deactivation, which suggest that other dopants or strategies should be pursued to commercialize Mn-based catalysts for low-temperature applications.
机译:在这部作品中,二氧化硫中毒效应在二进制MnTi和三元MnCeTi调查NH3-SCR混合氧化物的反应条件相关的移动应用程序。二进制MnTi样本,催化活性增加到250°C,然后由于下降氧化氨氮。在150°C,但降低了催化活性扩大的最佳操作温度和达到高转换350°C。执行活动测试100 ppm的二氧化硫气流,催化活性大大减少催化剂样品。失活曲线和二氧化硫浓度反应堆的出口建议强烈在所有的吸附和二氧化硫中毒催化剂。大量的Ce显示更好的二氧化硫宽容,这是要考虑的不足实际的应用程序。调查范围广泛的描述工具。表面积的下降部分解释催化剂失活。没有(NH4) 2 so4释放样品并建议Mn和Ce硫酸盐的形成在催化剂表面。形成MnSO4也显示下降Mn和Ce氧化态。催化氧化和氧化还原功能H2-TPR实验显示了强烈的氧化还原的损失函数在二氧化硫失活,这可能解释NH3-SCR催化的减少活动。失活,掺杂的研究。二进制MnTi和三元MnCeTi催化活动强烈降低在介绍二氧化硫的气体流。调查能够抑制二氧化硫建议其他掺杂物或失活应该追求商业化策略锰基催化剂低温应用程序。

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