Cu改性MIL-100(Fe)催化剂的SCR-C3H6脱硝特性

doi:10.16085/j.issn.1000-6613.2023-1340

摘要/Abstract

摘要：

烃类化合物选择性催化还原氮氧化物（SCR-HC）是一种很有发展前景的脱硝技术。催化剂有效的氧化-还原能力是影响其活性的关键因素。利用水热法制备了新型有机金属骨架MIL-100(Fe)，通过超声浸渍法合成不同Cu含量的mCu-MIL-100(Fe)催化剂，在固定床微反应器中对其催化C₃H₆选择性还原NO的特性进行了实验研究。结果表明Cu的引入使MIL-100(Fe)催化活性得到改善。2.3Cu-MIL-100(Fe)的NO转化率在275℃下可达到100%，275~400℃范围内可维持85%以上NO转化率及90%以上N₂选择性，且具有较好抗SO₂的能力。通过各种技术手段对催化剂的微观结构及物化性质进行了表征，并对反应机理作了进一步讨论。N₂吸附-脱附结果表明，加入适量Cu可以增大催化剂的比表面积，并增强催化剂表面对反应气体的吸附能力；XPS研究结果表明，Cu可以提高催化剂表面的氧空位数目。Cu与Fe之间具有协同作用，二者之间存在电子转移现象。H₂-TPR曲线表明Cu使催化剂的还原特征峰向低温方向移动，增强了其还原性能。

关键词: 氮氧化物, 选择催化还原, 碳氢化合物, 催化剂, Cu改性, 抗SO₂性能

Abstract:

Selective catalytic reduction of nitrogen oxides by hydrocarbons (SCR-HC) is a promising denitrification method. The efficient redox ability of the catalyst is a key factor to influence its activity. A novel metallic organic framework, MIL-100(Fe), was prepared by hydrothermal method, and mCu-MIL-100(Fe) catalysts with different copper contents were synthesized by ultrasonic impregnation, and the performance of the SCR of NO with C₃H₆ was experimentally investigated in a fixed-bed microreactor. The results showed that the catalytic activity of MIL-100(Fe) was improved by the introduction of Cu. The NO conversion rate of 2.3Cu-MIL-100(Fe) was 100% at 275℃ and maintained above 85% with the N₂ selectivity higher than 90% in the range of 275—400℃. It also has good ability to resist SO₂. The microstructure and physicochemical properties of the catalysts were characterized by various techniques, and the reaction mechanism was further discussed. The N₂ adsorption-desorption results showed that the addition of an appropriate amount of Cu increased the specific surface area of the catalyst and enhanced the adsorption of the reaction gases on the catalyst surface. XPS results proved that the addition of Cu increased the number of oxygen vacancies on the catalyst surface. There was a synergistic effect and electron transfer between Cu and Fe. The H₂-TPR curve indicated that Cu shifted the reduction characteristic peak of the catalyst towards low temperature, enhancing the catalyst's reduction ability.

Key words: nitrogen oxides, selective catalytic reduction (SCR), hydrocarbons, catalyst, Cu modification, SO₂ resistance

中图分类号:

X511

付维, 宁淑英, 蔡晨, 陈佳音, 周皞, 苏亚欣. Cu改性MIL-100(Fe)催化剂的SCR-C₃H₆脱硝特性[J]. 化工进展, 2024, 43(9): 4951-4960.

FU Wei, NING Shuying, CAI Chen, CHEN Jiayin, ZHOU Hao, SU Yaxin. SCR-C₃H₆ denitrification performance of Cu-modified MIL-100(Fe) catalysts[J]. Chemical Industry and Engineering Progress, 2024, 43(9): 4951-4960.

图/表 11

图1 MIL-100(Fe)和mCu-MIL-100(Fe)催化剂的活性实验测试（反应工况：[NO]=0.05%，[C3H6]=0.1%，[O2]=5%，N2平衡气，GHSV=24000h-1）

图2 SO2对2.3Cu-MIL-100(Fe)催化剂催化活性的影响（反应工况：[NO]=0.05%，[C3H6]=0.1%，[O2]=2%，[SO2]=0.02%，N2平衡气，总流量200mL/min,GHSV=24000h-1）

图3 MIL-100(Fe)和2.3Cu-MIL-100(Fe)的SEM图

图4 模拟MIL-100(Fe)、MIL-100(Fe)和mCu-MIL-100(Fe)的XRD谱图

图5 催化剂的N2吸附-脱附等温线和孔径分布

表1 催化剂的比表面积、孔容及孔径

催化剂	比表面积/m²·g^-1	孔容/cm³·g^-1	孔径/nm
MIL-100(Fe)	1126	0.661	2.348
2.3Cu-MIL-100(Fe)	1206	1.072	3.555
3.9Cu-MIL-100(Fe)	766.2	0.616	3.215

图6 MIL-100(Fe)的TGA和DTG曲线

图7 MIL-100(Fe)和mCu-MIL-100(Fe)催化剂的C 1s、O 1s、Fe 2p和Cu 2p XPS光谱

表2 催化剂表面原子浓度

催化剂	结合能/eV				原子分数/%
催化剂	Fe³⁺A	Fe³⁺B	Cu²⁺	Cu⁺	Fe³⁺A	Fe³⁺B	Cu²⁺	Cu⁺
MIL-100(Fe)	711.3	713.4	—	—	58.42	41.58	—	—
2.3Cu-MIL-100(Fe)	712.1	714.3	934.8	933.1	64.68	35.32	35.11	64.89
2.3Cu-MIL-100(Fe)	712.1	714.3	955.2	953.1	64.68	35.32	35.11	64.89
3.9Cu-MIL-100(Fe)	711.0	712.9	934.5	933.0	56.95	43.05	41.85	58.15
3.9Cu-MIL-100(Fe)	711.0	712.9	955.3	952.9	56.95	43.05	41.85	58.15

图8 MIL-100(Fe)和mCu-MIL-100(Fe)的H2-TPR谱图

表3 催化剂的H2-TPR结果

催化剂	温度/℃					H₂消耗量/mmol·g^-1
催化剂	F1	F2	F3	F4	F5	F1	F2	F3	F4	F5
3.9MIL-100(Fe)	295	385	460	565	715	0.039	0.457	1.252	0.303	0.205
2.3MIL-100(Fe)	295	370	445	565	700	0.093	0.305	1.528	0.231	0.235
MIL-100(Fe)	—	—	490	565	730	—	—	0.052	0.022	0.011
CuO	535					12.640

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Cu改性MIL-100(Fe)催化剂的SCR-C₃H₆脱硝特性

SCR-C₃H₆ denitrification performance of Cu-modified MIL-100(Fe) catalysts

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