Catalytic denitration activity and sulfur resistance of modified siderite catalysts
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摘要: 采用混合搅拌法制备了Ce、Zr掺杂改性的菱铁矿SCR脱硝催化剂，研究了Ce、Zr共同掺杂对催化剂催化脱硝性能及抗硫性的影响。结果表明，3% Ce+3% Zr掺杂菱铁矿催化剂（Ce0.03/Zr0.03-菱铁矿）具有优异的催化脱硝活性，在180-330 ℃，催化脱硝效率均在92%以上，该催化剂同时具有良好的抗SO2性能，在210 ℃下通入体积分数为0.01%的SO2，8 h后仍有95%以上的催化脱硝效率。通过XRF、BET、XRD、NH3-TPD、TG等实验手段对催化剂成分、微观孔结构、晶相等进行表征。表征结果显示，Ce、Zr的掺杂能明显提高催化剂的比表面积以及表面结晶分散度，增强催化剂的表面酸性，促进硫酸铵盐在催化剂表面的分解。因此，催化剂具有优异的中低温催化脱硝活性及抗硫性。Abstract: The siderite denitration catalysts modified by Ce and Zr were prepared by mixing and stirring method. The effects of Ce and Zr co-doping on the catalytic denitration performance and sulfur resistance of the catalyst were studied. The results show that the 3%Ce+3%Zr-doped siderite catalyst(Ce0.03/Zr0.03-siderite) has the highest catalytic denitration activity and good sulfur resistance. The catalytic denitration efficiency is above 92% in the temperature range of 180-330 ℃. Furthermore, the denitration efficiency is still more than 95% after introducing SO2 gas with a volume fraction of 0.01% for 8 h at 210 ℃. The characteristics of the catalyst, such as components, microporous structure and crystal phase were determined by XRF, BET, XRD, NH3-TPD, TG and other experimental means. The characterization results show that the doping of Ce and Zr can significantly improve the specific surface area and surface crystal dispersion of the catalyst, enhance the surface acidity of the catalyst, and promote the decomposition of ammonium sulfate on the catalyst surface; thus the modified siderite catalyst has an excellent low-temperature catalytic denitration activity and a good sulfur resistance.
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Key words:
- SCR denitration /
- siderite /
- Ce and Zr co-doping /
- sulfur resistance
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图 2 Ce掺杂量对催化剂催化脱硝性能的影响
Figure 2 Effect of Ce doping amount on catalytic denitrification performance of catalyst
图 3 Zr掺杂量对催化剂催化脱硝性能的影响
Figure 3 Effect of Zr doping amount on catalytic denitrification performance of catalyst
图 4 Ce、Zr掺杂量对催化剂催化脱硝性能的影响
Figure 4 Effect of simultaneous doping of Ce and Zr on catalytic denitrification performance of catalyst
图 5 掺杂菱铁矿催化剂的XRD谱图
Figure 5 XRD analysis of doped siderite catalyst
a: siderite; b: Ce0.03-siderite; c: Zr0.03-siderite; d: Ce0.03/Zr0.03-siderite
图 6 掺杂菱铁矿催化剂的NH3-TPD谱图
Figure 6 NH3-TPD results of doped siderite catalyst
a: siderite; b: Ce0.03/Zr0.03-siderite
图 7 Ce、Zr掺杂量对菱铁矿催化剂抗硫性的影响
Figure 7 Effect of Ce and Zr doping on sulfur resistance ofsiderite catalyst reaction temperature is 210 ℃, SO2 volume fraction is 0.01%
图 8 反应温度对掺杂菱铁矿催化剂抗硫性的影响
Figure 8 Effect of reaction temperature on sulfur resistance of doped siderite catalyst 3%Ce + 3% Zr doped siderite catalyst, SO2 volume fraction is 0.01%
图 9 SO2浓度对掺杂菱铁矿催化剂抗硫性的影响
Figure 9 Effect of SO2 concentration on sulfur resistance of doped siderite catalyst 3% Ce + 3% Zr doped siderite catalyst, reaction temperature is 210℃
图 10 掺杂菱铁矿催化剂抗硫实验后的热重分析
Figure 10 Thermogravimetric analysis of doped siderite catalyst after sulfur resistance test
a: siderite; b: Ce0.03/Zr0.03-siderite
表 1 催化剂的XRF分析
Table 1 XRF analysis results of the catalyst
Sample Conten w/% Fe Ce Zr Siderite 55.42 0.00 0.00 Ce0.03-siderie 55.03 2.96 0.00 Zr0.03-siderite 54.81 0.00 2.94 Ce0.03/Zr0.03-siderite 54.30 2.92 3.06 
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表 2 催化剂的BET分析
Table 2 BET analysis results of the catalyst
Sample ABET/(m2·g-1) Pore volume v/(cm3·g-1) Pore size d/nm Siderite 35.2 0.132 7.4 Ce0.01-siderie 39.1 0.107 8.6 Ce0.03-siderie 52.4 0.122 7.5 Ce0.06-siderie 44.0 0.093 7.4 Zr0.03-siderite 45.3 0.105 7.5 Zr0.05-siderite 50.7 0.105 6.8 Ce0.03/Zr0.03-siderite 49.8 0.107 7.4 Ce0.03/Zr0.05-siderite 48.3 0.102 7.4
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