掺杂元素对Mn基催化剂SCR性能及抗硫性能的影响

doi:10.16085/j.issn.1000-6613.2019-1449

摘要/Abstract

摘要：

采用溶胶凝胶法制备M-Mn/TiO₂催化剂，M=Fe、Ce、Ni、Sm、Cu，考察掺杂元素对催化剂SCR性能和抗硫性能的影响，并采用XRD、H₂-TPR表征手段考察掺杂组分对催化剂性质的影响。结果表明，掺杂金属元素后，催化剂的晶粒尺寸和还原性能发生变化，表现为Fe、Ni的掺杂明显降低催化剂粒径尺寸而Ce、Sm、Cu的掺杂增加了粒径尺寸；Cu和Ni的掺杂有利于提高催化剂的还原性能。SCR实验结果表明，Cu、Sm的掺杂在整个反应温度区间内都会抑制催化剂脱硝活性，而Fe、Ni、Ce的掺杂主要抑制低温活性，在高温阶段则会促进反应的进行。掺杂金属元素后催化剂T₈₀活性窗口顺序为：Fe-Mn/TiO₂＞Ni-Mn/TiO₂＞Ce-Mn/TiO₂≈Mn/TiO₂＞Sm-Mn/TiO₂＞Cu-Mn/TiO₂。Sm-Mn/TiO₂和Ce-Mn/TiO₂能保持与Mn/TiO₂基本相似的抗硫性能，但掺杂Fe、Cu、Ni会导致催化剂在较短时间内因硫中毒失活，尤其是Fe-Mn/TiO₂催化剂的活性中心受SO₂硫酸盐化影响最大，但是水洗再生之后其活性基本恢复，且Fe-Mn/TiO₂和Ni-Mn/TiO₂催化剂的抗硫中毒性能在水洗后得到提高。

关键词: 选择催化还原, 催化剂, 失活, 氮氧化物, 掺杂元素

Abstract:

The SCR performance and SO₂ resistance of Mn/TiO₂ catalysts doped with Fe, Ce, Ni, Sm and Cu elements synthesized by sol-gel method were investigated, and the physicochemical properties of catalysts were also characterized by XRD and H₂-TPR. The results showed that the particle size and the reducibility were changed by doping elements. The particle size was decreased when Fe and Ni doped while increased when Se, Sm, and Cu doped. The modification of Cu and Ni was beneficial to the enhanced reducibility of catalysts. The SCR results exhibited that the modification of metal elements mainly inhibited the activity at low temperature whereas increased the activity at high temperature except for Cu and Sm. The T₈₀ catalytic temperature window of catalysts after doping the metal elements followed: Fe-Mn/TiO₂＞Ni-Mn/TiO₂＞Ce-Mn/TiO₂≈Mn/TiO₂＞Sm-Mn/TiO₂＞Cu-Mn/TiO₂. Sm-Mn/TiO₂and Ce-Mn/TiO₂ kept the similar SO₂ resistance with Mn/TiO₂, while samples with Fe, Cu and Ni showed poor SO₂ tolerance. For Fe-Mn/TiO₂ catalyst, the metal active sites were easily poisoned by SO₂, but the activity could be restored by the water washing method. Furthermore, the SO₂ resistance of Fe-Mn/TiO₂and Ni-Mn/TiO₂ could be improved after the regeneration.

Key words: selective catalytic reduction, catalyst, deactivation, nitrogen oxides, doping elements

中图分类号:

X131.1

管静, 兰喜龙, 孙红, 柳志刚, 乔彤. 掺杂元素对Mn基催化剂SCR性能及抗硫性能的影响[J]. 化工进展, 2020, 39(6): 2440-2446.

Jing GUAN, Xilong LAN, Hong SUN, Zhigang LIU, Tong QIAO. Influence of different doped metal cations on the activity and SO₂ resistance of Mn based catalysts for NH₃-SCR reaction[J]. Chemical Industry and Engineering Progress, 2020, 39(6): 2440-2446.

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