Performance of the modified Cu-Mn/SAPO-34 catalysts in the selective catalytic reduction of NOx by NH3
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摘要: 采用浸渍法制备了系列铜锰复合氧化物分子筛催化剂（Cu-Mn/SAPO-34），在固定床反应器上考察不同Cu/Mn质量比对分子筛催化剂选择催化还原NO的影响，利用XRD、NH3-TPD、H2-TPR、XPS等手段对催化剂进行了表征分析。结果表明，双金属改性的Cu-Mn/SAPO-34催化剂在NH3-SCR反应中表现出较为优异的催化活性，具有较宽的活性温度窗口。当Cu/Mn质量比为1：4时，催化剂具有最宽的活性温度窗口，NOx转化率在250℃已达到85.39%，在300-400℃转化率均达到96%以上，450℃时仍能达到90%。铜和锰物种高度分散于催化剂表面，未改变SAPO-34的晶体结构，且构成协同作用。Cu-Mn共同负载促进了Cu2+向Cu+的转变，增加了高价态Mn4+和Mn3+的比例，有利于提高低温活性，促进催化反应的进行。Cu-Mn/SAPO-34/1：4具备丰富的酸性位、良好的氧化还原性能和抗SO2/H2O性能，该配比有助于催化剂的催化活性和稳定性的提高。
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关键词:
- 脱硝 /
- Cu-Mn/SAPO-34 /
- NH3-SCR /
- 氮氧化物 /
- 催化剂
Abstract: A series of Cu-Mn/SAPO-34 catalysts with different mass ratios of Cu to Mn were prepared by impregnation method. The influence of Cu and Mn loading on the denitrification performance was investigated in a fixed-bed reactor. XRD, NH3-TPD, H2-TPR, XPS were used to characterize and analyze the catalysts. The results show that the bimetallic modified Cu-Mn/SAPO-34 have excellent catalytic activity and broad active temperature window. Especially, the Cu-Mn/SAPO-34/1:4 catalyst with a Cu/Mn mass ratio of 1:4 has the widest active temperature window, its denitrification rates could reach 85.39% at 250℃, 96% at 300-400℃, and up to 90% at 450℃. Cu and Mn species are highly dispersed on the surface of the catalyst and do not change the crystal structure of SAPO-34. Co-doping of Cu and Mn promotes the transformation of Cu2+ to Cu+, increases the ratio of Mn4+ to Mn3+, improves the activity at low temperature and promotes the catalytic reaction. Cu-Mn/SAPO-34/1:4 catalyst has rich acid sites, good redox performance and resistance to SO2 and H2O, which can improve the activity and stability of the catalysts.-
Key words:
- denitration /
- Cu-Mn/SAPO-34 /
- NH3-SCR /
- NOx /
- catalyst
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图 2 不同Cu/Mn质量比催化剂的NOx转化率
Figure 2 NOx conversion over the Cu-Mn/SAPO-34 catalysts with different Cu/Mn mass ratios
图 7 Cu-Mn/SAPO-34/1 :4在350 ℃时的抗H2O、SO2性能
Figure 7 Water vapour and sulfur tolerance of Cu-Mn/SAPO-34/1 :4 catalyst at 350 ℃
表 1 3种不同催化剂的XPS表征
Table 1 XPS results of the catalysts
Catalyst Binding energy E/eV Relative content w/% Mn2+ Mn3+ Mn4+ Cu+ Cu2+ Mn2+ Mn3+ Mn4+ Cu+ Cu2+ Cu/SAPO-34 - - - 932.89 935.33 - - - 31.16 68.84 Mn/SAPO-34 641.4 643.02 645.39 - - 48.13 26.84 25.02 - - Cu-Mn/SAPO-34 641.44 642.86 645.9 932.99 935.06 31.27 40.97 27.76 50.74 49.26 
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