Vermiculite-supported FeCe bimetallic catalyst for selective catalytic reduction of NO with CO

doi:10.16085/j.issn.1000-6613.2023-0525

Abstract

Abstract:

NO removal by CO selective catalytic reduction (CO-SCR) has gained great attentions. In this paper, vermiculite-supported Fe-Ce bimetallic oxides (FeCe/VMT) for CO-SCR were prepared by coprecipitation-assisted impregnation (CP-IM) with the natural mineral vermiculite as the carrier. The characterization results showed that compared with the traditional impregnation method (IM), FeCe/VMT (CP-IM) prepared by coprecipitation-assisted impregnation had larger specific surface area (106.9m²/g) and more oxygen vacancies due to more active sites available. The enhanced synergistic effect between FeCe was beneficial to the increase of both catalytic activity and stability in CO-SCR reaction. Performance tests showed that NO conversion reached 100% at 300℃ with 50000h^-1 gas hourly space velocity (GHSV), and the performance of the catalyst didn't decrease within 48h. When the temperature dropped to 250℃, the conversion of NO could still reach 97%. At the same time, insitu infrared spectroscopy and density functional theory were used to reveal the corresponding catalytic mechanism. This research provided a promising method for preparing supported catalysts with large specific surface area.

Key words: catalyst, carbon monoxide, selective catalytic reduction (SCR), nanomaterials, multiphase reaction

摘要：

以CO为还原剂去除NO的选择性催化还原（CO-SCR）技术受到了广泛关注。本文以天然矿物蛭石为载体，采用共沉淀辅助浸渍法（CP-IM）制备了蛭石负载的铁铈双金属氧化物（FeCe/VMT）用于CO-SCR脱硝反应。表征结果显示，相比传统的浸渍法（IM），共沉淀辅助浸渍制备的FeCe/VMT催化剂具有更大的比表面积（106.9m²/g）和更多氧空位，可以提供更多的活性位点。共沉淀过程形成更多Fe³⁺，并促进了FeCe间的协同作用，有利于提高CO-SCR的催化活性和稳定性。性能测试表明，在300℃和50000h^-1的空速下，NO转化率可达100%，48h后NO转化率几乎无衰减。当温度降至250℃时，NO的转化率依然可以达到97%。同时，利用原位红外光谱和密度泛函理论计算技术，揭示了相应的催化反应机理，为制备大比表面积的负载型催化剂提供了一种方法。

关键词: 催化剂, 一氧化碳, 选择催化还原, 纳米材料, 多相反应

CLC Number:

O643.36

GAO Fei, LIU Zhisong, PAN Keke, LIU Minmin, DAI Bin, DAN Jianming, YU Feng. Vermiculite-supported FeCe bimetallic catalyst for selective catalytic reduction of NO with CO[J]. Chemical Industry and Engineering Progress, 2024, 43(4): 1851-1862.

高飞, 刘志松, 潘珂珂, 刘敏敏, 代斌, 但建明, 于锋. 蛭石基FeCeO _x 催化剂及CO选择性催化还原NO[J]. 化工进展, 2024, 43(4): 1851-1862.

Figures/Tables 11

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样品	结合能/eV			表面离子浓度比/%
样品	Ce³⁺		O_β	Fe³⁺/(Fe²⁺+Fe³⁺)	Ce³⁺/(Ce³⁺+Ce⁴⁺)	O_β/(O_α+O_β+O_γ)
FeCe/VMT(IM)	884.6	903.2	531.5	13.7	21.9	24.0
FeCe/VMT(CP-IM)	884.4	902.9	531.1	33.5	30.1	29.3

样品	结合能/eV			表面离子浓度比/%
样品	Ce³⁺		O_β	Fe³⁺/(Fe²⁺+Fe³⁺)	Ce³⁺/(Ce³⁺+Ce⁴⁺)	O_β/(O_α+O_β+O_γ)
FeCe/VMT(IM)	884.6	903.2	531.5	13.7	21.9	24.0
FeCe/VMT(CP-IM)	884.4	902.9	531.1	33.5	30.1	29.3

样品	峰位置/℃
样品	峰0	峰1	峰2	峰3	峰4
FeCe/VMT(IM)	—	403.8	465.8	564.2	795.9
FeCe/VMT(CP-IM)	306.9	346.7↓	427.5↓	622.9↑	778.4↓

样品	峰位置/℃
样品	峰0	峰1	峰2	峰3	峰4
FeCe/VMT(IM)	—	403.8	465.8	564.2	795.9
FeCe/VMT(CP-IM)	306.9	346.7↓	427.5↓	622.9↑	778.4↓

催化剂	反应条件	温度/℃	NO转化率/%	参考文献
CeO₂/Fe₂O₃	2000μL/L CO, 500μL/L NO, 总流量=500mL/min, 0.5g催化剂, N₂	600	90	[30]
Cu/CeO₂	600μL/L NO, 600μL/L CO, 60μL/L SO₂, 1000μL/L O₂, GHSV = 36000h^-1, N₂	350	100	[9]
Cu-Ce/BTC	1000μL/L NO, 1000μL/L CO, GHSV=30000h^-1, He	300	90	[41]
Co₉₈Ce₂	1400μL/L NO, 1400μL/L CO, GHSV=6051h^-1, N₂	300	100	[28]
FeCe/VMT	500μL/L NO, 1000μL/L CO, 1%（体积分数）O₂, 5%（体积分数）H₂O, GHSV=50000h^-1, N₂	250	98	本工作