氮掺杂钒钛蜂窝式催化剂低温脱硝性能

doi:10.16085/j.issn.1000-6613.2022-2312

摘要/Abstract

摘要：

为了提升催化剂的低温脱硝性能，利用挤出成型法制备了一系列氮掺杂钒钛蜂窝式催化剂，考察了氮掺杂量对催化剂低温脱硝性能的影响及其稳定性，并通过XRD、BET、SEM、XPS、H₂-TPR、NH₃-TPD和O₂-TPD等分析方法表征催化剂。结果表明：氮掺杂钒钛催化剂的低温脱硝性能显著提高，在140~200℃温度区间催化剂的脱硝性能良好，其中以氮钛摩尔比为0.2的催化剂具有最优的脱硝效果，并在200℃连续72h的稳定性测试过程中，表现出了良好的脱硝稳定性。氮掺杂能够使钒钛催化剂颗粒粒径变小，比表面积和孔容增大，表面V⁴⁺和化学吸附氧O_α的比率增加，表面酸性位点数量增加，使催化剂表面NH₃吸附能力增强，氧化还原能力提高，促进了催化剂低温脱硝性能的提升。

关键词: 氮掺杂, 钒钛催化剂, 蜂窝式催化剂, 低温脱硝

Abstract:

In order to enhance the performance of low-temperature denitration catalyst, a series of nitrogen doped vanadium titanium honeycomb catalysts were prepared by extrusion molding. The effect of nitrogen doping amount on the low-temperature activity and stability of the catalyst were discussed. The catalysts were characterized by XRD, BET, SEM, XPS, H₂-TPR, NH₃-TPD and O₂-TPD. The results showed that nitrogen doping significantly enhanced the low temperature denitration performance of the catalysts, which worked well in the temperature range of 140—200℃. Among them, the catalyst with the molar ratio of nitrogen to titanium of 0.2 had the best deNO _x efficiency. During the 72-hours stability test at 200℃, the NO conversion rate was basically kept at 86.6%. Nitrogen doping could reduce vanadium titanium catalyst particle size, increase the specific surface area and pore volume, as well as the ratio of surface V⁴⁺and chemically adsorbed oxygen O_α. With the increase of the acidic sites on the surface, the adsorption capacity of NH₃ on the catalyst surface was increased, leading to the enhanced redox capacity and the improved low temperature denitration performance of the catalyst.

Key words: N-doping, vanadium-titanium catalyst, honeycomb catalyst, low temperature denitration

中图分类号:

X511

王露珠, 安家康, 张涛, 邓立峰, 任英杰, 李扬, 李涛, 任保增. 氮掺杂钒钛蜂窝式催化剂低温脱硝性能[J]. 化工进展, 2023, 42(11): 5747-5755.

WANG Luzhu, AN Jiakang, ZHANG Tao, DENG Lifeng, REN Yingjie, LI Yang, LI Tao, REN Baozeng. Catalytic performance of N-doped vanadium-titanium honeycomb catalysts at low temperature[J]. Chemical Industry and Engineering Progress, 2023, 42(11): 5747-5755.

图/表 14

图1 蜂窝催化剂成品图

图2 催化剂脱硝性能评价装置图

图3 不同氮掺杂量催化剂的脱硝效率

图4 催化剂稳定性检测结果

图5 不同氮掺杂量催化剂的XRD图谱

图6 不同催化剂的氮气吸脱附等温线和孔径分布图

表1 不同催化剂的结构特性

样品	比表面积/m²·g^-1	孔容/cm³·g^-1	平均孔径/nm
N0	60.9	0.28	16.99
N0.1	61.5	0.28	16.14
N0.2	63.7	0.29	16.36
N0.3	59.1	0.26	16.31

图7 不同催化剂的SEM图和粒径分布图

图8 不同催化剂的XPS谱图

表2 不同催化剂表面不同O和V原子浓度之比

样品	O_α/(O_α+O_β)	V⁴⁺/(V⁴⁺+V⁵⁺)
N0	38.7%	5.67%
N0.2	44.1%	45.0%

图9 不同催化剂的H2-TPR谱图

图10 不同催化剂的NH3-TPD谱图

图11 不同催化剂的O2-TPD谱图

图12 N掺杂促进催化剂的脱硝性能的机理

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