Mg/Al物质的量比对Ce-La/MgAl2O4-x催化剂催化CO还原NO性能的影响

GUO Li-li; LIU Lu; ZHU Xiao-lin; ZHANG Qiang; LI Chun-yi

Mg/Al物质的量比对Ce-La/MgAl₂O₄-x催化剂催化CO还原NO性能的影响

中国石油大学(华东) 重质油国家重点实验室, 山东青岛 266580

详细信息

中图分类号: O643.36
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出版历程
- 收稿日期: 2017-03-14
- 修回日期: 2017-04-17
- 网络出版日期: 2021-01-23
- 刊出日期: 2017-06-10

Effect of Mg/Al molar ratios on NO reduction activity of CO using Ce-La/MgAl₂O₄-x catalysts

State Key Laboratory of Heavy Oil Processing, China University of Petroleum(East China), Qingdao 266580, China

More Information

Corresponding author: LI Chun-yi, Tel:13225324293, E-mail:chuyli@upc.edu.cn

摘要

摘要: 采用初始浸渍法制备了不同Mg/Al物质的量比的Ce-La/MgAl₂O₄-x催化剂，并通过低温N₂-吸附脱附、XRD、H₂-TPR和CO-TPR等手段对其进行了表征。结果表明，在Mg/Al物质的量比为0.5时，催化剂催化CO还原NO的性能最好。这主要是因为适量Mg的添加促进了CeO₂的分散和Ce-O-La固溶体的形成，从而使得表面Ce³⁺和氧空穴增加。两者的协同作用使得Ce-La/MgAl₂O₄-0.5表现出最佳的催化性能。另外，适量Mg的引入可以抑制Ce（SO₄）₂和Ce₂（SO₄）₃的形成，从而提高了Ce-La/MgAl₂O₄-0.5催化剂抗硫中毒能力。
- NO还原 /
- Ce-La/MgAl₂O₄-x /
- Ce-O-La固溶体 /
- 抗硫中毒能力
Abstract: A series of Ce-La/MgAl₂O₄-x catalysts were prepared by the incipient wetness impregnation method and characterized by BET, XRD, H₂-TPR, CO-TPR and in situ FT-IR. The results demonstrate that the catalyst with a Mg/Al molar ratio of 0.5 yields the most uniform dispersion of CeO₂ and greatly enhances formation of Ce-O-La solid solution, resulting in the increase of oxygen vacancy and surface Ce³⁺ content. Thereby, the synergistic effect between surface Ce³⁺ and oxygen vacancy gives rise to the best catalytic performance of NO reduction. Moreover, introduction of Mg species suppresses tranformation of CeO₂ to Ce(SO₄)₂/Ce₂(SO₄)₃ and then improves the SO₂ resistance performance of Ce-La/MgAl₂O₄-0.5.
- NO reduction /
- Ce-La/MgAl₂O₄-x catalysts /
- Ce-O-La solid solution /
- SO₂ resistance

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Figure 1 Catalytic performance of Ce-La/MgAl₂O₄-x catalysts as a function of temperature

a:Ce-La/MgAl₂O₄-0.2; b: Ce-La/MgAl₂O₄-0.5;c: Ce-La/MgAl₂O₄-1.0 reaction conditions: 0.1% NO, 4% CO, 2% O₂ in balance N₂, GHSV=24 000 h^-1

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Figure 2 SO₂ resistance tests over Ce-La/MgAl₂O₄-x catalysts

a: Ce-La/MgAl₂O₄-0.2; b: Ce-La/MgAl₂O₄-0.5; c: Ce-La/MgAl₂O₄-1.0 reaction conditions: 0.1% NO, 4% CO, 2% O₂, 0.08% SO₂ in balance N₂, GHSV=24 000 h^-1, t=700 ℃

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Figure 3 Regeneration ability of poisoned Ce-La/MgAl₂O₄-0.5 catalyst

■, □, : fresh Ce-La/MgAl₂O₄-0.5; ●, ○, ⊗: regenerated Ce-La/MgAl₂O₄-0.5 NO conversion (● and ■), CO conversion (⊗ and ), SO₂ conversion( and ) reaction conditions: 0.1%NO, 4%CO, 2%O₂, 0.08%SO₂, in balance N₂, GHSV=24 000 h^-1, t=700 ℃ regeneration conditions: 10 mL/min of H₂ for 20 min, t=550 ℃

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Figure 4 XRD patterns of catalysts

a: Ce/MgAl₂O₄-0.2; b: Ce-La/MgAl₂O₄-0.2; c: Ce-La/MgAl₂O₄-0.5; d: Ce-La/MgAl₂O₄-1.0

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Figure 5 H₂-TPR profiles of catalysts

a: Ce-La/MgAl₂O₄-0.2; b: Ce-La/MgAl₂O₄-0.5; c: Ce-La/MgAl₂O₄-1.0

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Figure 6 CO-TPR profiles of catalysts

a: Ce-La/MgAl₂O₄-0.2; b: Ce-La/MgAl₂O₄-0.5; c: Ce-La/MgAl₂O₄-1.0

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Figure 7 Schematic diagram for Ce-O-La solid solution

(a) the schematic diagram of crystal structure of Ce-O-La solid solution and (b) the possible pathway for generation of oxygen vacancies and NO removal by CO over Ce-O-La solid solution

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Figure 8 XRD patterns of poisoned Ce-La/MgAl-x catalysts

a: Ce-La/MgAl₂O₄-0.2-P; b: Ce-La/MgAl₂O₄-0.5-P; c: Ce-La/MgAl₂O₄-0.5-P-P; d: Ce-La/MgAl₂O₄-1.0

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Figure 9 In situ FT-IR spectra of SO₂ + O₂ co-adsorption over Ce-La/MgAl₂O₄-0.5 at 200 and 500 ℃ reaction gas mixture: 0.08% SO₂, 2% O₂ in balance N₂

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Figure 10 Deactivation mechanism of Ce-La/MgAl₂O₄ catalyst or the catalytic cycle for the elimination of SO_x

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Table 1 Textural properties of the prepared supports and catalysts

Table 2 Textural properties of poisoned catalysts

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