Fe2O3对ZrTiO4载体NH3-SCR催化性能的影响

YUAN Long-teng; HU Ping; HU Bo-liang; HAN Jia-yu; MA Sheng-jie; YANG Fan; Alex A. Volinsky

doi:10.1016/S1872-5813(23)60377-9

Fe₂O₃对ZrTiO₄载体NH₃-SCR催化性能的影响

doi: 10.1016/S1872-5813(23)60377-9

袁龙腾^{1, 2,},
胡平^{1, 2, 3, ,},
胡卜亮^{1, 3, ,},
韩嘉彧^{1, 3,},
马升捷^{1, 2,},
杨帆^{1, 3,},
AlexA. Volinsky^4,

1.
西安建筑科技大学材料加工国家与地方联合工程研究功能中心, 陕西西安 710055
2.
西安建筑科技大学机电工程学院, 陕西西安 710055
3.
西安建筑科技大学冶金工程学院, 陕西西安 710055
4.
南佛罗里达大学机械工程系 33620, 美国

详细信息

中图分类号: O643.36
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出版历程
- 收稿日期: 2023-03-15
- 修回日期: 2023-04-08
- 录用日期: 2023-04-10
- 网络出版日期: 2023-06-27

Effect of Fe₂O₃ on ZrTiO₄ support for NH₃-SCR catalytic performance

YUAN Long-teng^{1, 2
,},
HU Ping^{1, 2, 3
, ,},
HU Bo-liang^{1, 3
, ,},
HAN Jia-yu^{1, 3
,},
MA Sheng-jie^{1, 2
,},
YANG Fan^{1, 3
,},
Alex A. Volinsky^4
,

1.
National and Local Joint Engineering Research Functional Center for Materials Processing, Xi’an University of Architecture and Technology, Xi’an 710055, China
2.
School of Mechanical and Electrical Engineering, Xi’an University of Architecture and Technology, Xi’an 710055, China
3.
School of Metallurgy Engineering, Xi’an University of Architecture and Technology, Xi’an 710055, China
4.
Department of Mechanical Engineering, University of South Florida, Tampa 33620, USA

Funds: The project was supported by the Scientific and Technological Innovation Team Project of the Shaanxi Innovation Capability Support Plan, China (2022TD-30), the Youth Innovation Team of Shaanxi Universities (2019-2022), the Top Young Talents Project of “Special support program for high-level talents” in the Shaanxi Province (2018-2023), and the International Science and Technology Cooperation Program of the Shaanxi Province (2022KW-39), Xi’an Science and Technology Planning Project (2022JH-RYFW-0196)

More Information

Corresponding author: E-mail: huping1985@126.com; huboliang@xauat.edu.cn

摘要

摘要: NH₃-SCR催化剂主要用于工业生产和汽车尾气清洁，本研究采用“共沉淀-浸渍法”制备了新型α%Fe₂O₃/ZrTiO₄(α=0、8、12、15)催化剂。结果表明，α%Fe₂O₃/ZrTiO₄催化剂的最佳成分配比的12%Fe₂O₃/ZrTiO₄催化剂在250−400 ℃条件下NO_x转化率大于80%，在300 ℃时NO_x转化率接近100%，并且N₂选择性在200−450 ℃大于90%。在ZrTiO₄表面负载Fe₂O₃后，催化剂的氧化还原性能、表面酸度和O_β/(O_α + O_β)比例都有所提高，这不仅归因于α%Fe₂O₃/ZrTiO₄催化剂具有多孔结构，还归因于活性组分Fe₂O₃和载体ZrTiO₄之间的电子相互作用。此外，原位DRIFTs反应表明，12%Fe₂O₃/ZrTiO₄催化剂的NH₃-SCR反应遵循Eley-Rideal机制。明确的反应机制有利于更深入了解SCR过程中NO_x转化的反应过程。这项工作为未来Fe基SCR催化剂在中温范围内替代V基催化剂提供了可行的策略。
- Fe₂O₃/ZrTiO₄催化剂 /
- NH₃-SCR /
- 多孔 /
- 反应机制
Abstract: The selective catalytic reduction (SCR) NH₃ catalyst is mainly used in industrial production and automobile exhaust cleaning. In this study, a novel α%Fe₂O₃/ZrTiO₄ (α=0, 8, 12, 15) catalyst was prepared by the coprecipitation impregnation method. The results show that the NO_x conversion rate of 12%Fe₂O₃/ZrTiO₄ catalyst with the optimal composition is high above 80% at 250−400 °C, close to 100% at 300 °C, and N₂ selectivity is high above 90% at 200−450 °C. The redox properties, surface acidity, and O_β/(O_α + O_β) ratio of ZrTiO₄ catalysts are improved after loading Fe₂O₃ on the ZrTiO₄ surface, which is attributed not only to the porous structure of α%Fe₂O₃/ZrTiO₄ catalyst but also to the synergistic interaction between the active component Fe₂O₃ and the support ZrTiO₄. In addition, in-situ DRIFT reactions show that the NH₃-SCR reaction of 12%Fe₂O₃/ZrTiO₄ catalyst follows the Eley-Rideal mechanism. A clear reaction mechanism is conducive to a deeper understanding of the reaction process of NO_x conversion during SCR. This work provides a feasible strategy for Fe-based SCR catalysts to replace V-based catalysts in the medium temperature range in the future.
- Fe₂O₃/ZrTiO₄ catalyst /
- NH₃-SCR /
- porous structure /
- reaction mechanism

HTML全文

Figure 1 SEM images of ZrTiO₄ and α%Fe₂O₃/ZrTiO₄ samples (a): ZrTiO₄; (b): 8%Fe₂O₃/ZrTiO₄; (c): 12%Fe₂O₃/ZrTiO₄; (d): 15%Fe₂O₃/ZrTiO₄

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Figure 2 Adsorption isotherms of ZrTiO₄ and α%Fe₂O₃/ZrTiO₄ samples the curves are offset for clarity and are plotted with the same y scale

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Figure 3 XRD patterns of ZrTiO₄ and α%Fe₂O₃/ZrTiO₄ samples

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Figure 4 (a) SEM image and EDX elemental maps of the 12%Fe₂O₃/ZrTiO₄ catalyst: (b) Zr, (c) Fe and (d) Ti

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Figure 5 NH₃-TPD profiles of ZrTiO₄ and α% Fe₂O₃/ZrTiO₄ samples

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Figure 6 H₂-TPR profiles of ZrTiO₄ and α% Fe₂O₃/ZrTiO₄ samples

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Figure 7 (a) NO_x conversion of ZrTiO₄ and α%Fe₂O₃/ZrTiO₄ samples; (b) N₂ selectivity; (c) NH₃ conversion; (d) N₂O emissions (Reactant feed contains 5.0×10⁻⁴ of NO, 6.0×10⁻⁴ of NH₃, 3%O₂ balanced with N₂)

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Figure 8 XPS profiles of ZrTiO₄ and α%Fe₂O₃/ZrTiO₄ samples: (a) Ti 2p; (b) Zr 3d; (c) Fe 2p; (d) O 1s

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Figure 9 DRIFT spectra of (a) NH₃ adsorption and (b) NO + O₂ adsorption on 12%Fe₂O₃/ZrTiO₄ catalyst at different temperatures

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Figure 10 DRIFT spectra of reaction between (a) pre-adsorption of NH₃ and NO + O₂ (b) pre-adsorption of NO + O₂ and NH₃ on 12%Fe₂O₃/ZrTiO₄ catalyst

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Figure 11 Reaction mechanism of 12%Fe₂O₃/ZrTiO₄ catalyst

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Table 1 S_BET surface area, pore volume and pore size of ZrTiO₄ and α%Fe₂O₃/ZrTiO₄ samples

Sample	Surface area / (m²·g⁻¹)	Pore volume /(cm³·g⁻¹)	Pore size /nm
ZrTiO₄	161.3	0.85	21.19
8%Fe₂O₃/ZrTiO₄	134.3	0.50	14.87
12%Fe₂O₃/ZrTiO₄	139.6	0.77	22.02
15%Fe₂O₃/ZrTiO₄	129.1	0.58	17.92

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Table 2 XPS concentration of ZrTiO₄ and α%Fe₂O₃/ZrTiO₄

Sample	Atomic concentration				Relative concentration /%
Sample	Fe	Zr	Ti	O	O_β/(O_α + O_β)	Fe^{3 +}/(Fe^{3 +} + Fe^{2 +})
ZrTiO₄	−	14.4	15.3	70.3	23.1	−
8%Fe₂O₃/ZrTiO₄	1.85	13.3	13.2	71.6	34.0	43
12%Fe₂O₃/ZrTiO₄	2.21	13.3	12.8	71.6	31.7	73.4
15%Fe₂O₃/ZrTiO₄	2.68	13.2	13.1	71.0	28.7	91.7

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