氧化铝载体硫酸化对锰铈催化剂SCR脱硝性能的影响

张强; 刘璐; 于梦云; 周洲

氧化铝载体硫酸化对锰铈催化剂SCR脱硝性能的影响

张强^1, ,,
刘璐²,
于梦云¹,
周洲¹

1.
中国石油大学(华东)重质油国家重点实验室, 山东青岛 266580
2.
黑龙江新和成生物科技有限公司, 黑龙江绥化 152000

基金项目:

国家自然科学基金 21406270

详细信息

中图分类号: X511
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- HTML全文浏览量: 57
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- 被引次数: 0
出版历程
- 收稿日期: 2019-04-04
- 修回日期: 2019-07-15
- 网络出版日期: 2021-01-23
- 刊出日期: 2019-09-10

Effect of sulfuric acid modification of Al₂O₃ support on the SCR performance of MnCe/Al₂O₃ catalysts

1.
State Key Laboratory of Heavy Oil Processing in China University of Petroleum(East China), Qingdao 266580, China
2.
Heilongjiang New Harmony Union Biotechnology Co. Ltd, Suihua 152000, China

Funds:

the National Natural Science Foundation of China 21406270

More Information

Corresponding author: ZHANG Qiang, E-mail: xyz@upc.edu.cn

摘要

摘要: 分别以硫酸改性前后的氧化铝为载体，采用浸渍法制备了锰铈催化剂，对其NH₃-SCR脱硝性能进行评价，并采用XRD、BET、NH₃-TPD、H₂-TPR以及FT-IR对催化剂进行了表征。结果表明，改性降低了金属的分散性和氧化性，增加了酸量，特别是B酸量；催化剂的最佳脱硝温度窗口向高温扩展，活性温度窗口范围变宽，并且，改性液浓度越大变化幅度越大。当反应温度在200-250 ℃时，未改性催化剂与采用0.2 mol/L硫酸改性的催化剂具有接近的催化活性，但改性后的催化剂具有更高的抗水抗硫活性，250 ℃时脱硝率可达70%。
- NH₃-SCR /
- Mn-CeO_x /
- 氧化铝 /
- 硫酸化
Abstract: With unmodified and modified Al₂O₃ as the support, a series of Mn-Ce catalysts were prepared by impregnation method and characterized by XRD, BET, NH₃-TPD, H₂-TPR and FT-IR. The catalytic performance in the NH₃-SCR of NO_x was investigated. The results show that the sulfuric acid modification to the support decreased the metal dispersion and weakened the oxidization property of the catalyst, increased the concentration of acid sites, especially, B acid sites. Besides, the optimum temperature window ranges for SCR of the modified catalyst moved to higher temperature and broadened, and increased with the increase of modified liquid concentration. The unmodified catalyst and the catalyst modified by 0.2 mol/L solution had same SCR reactivity within the temperature range of 200-250 ℃. However, the modified catalyst showed the best resistance to SO₂ and H₂O and presented 70% NO conversion at 250 ℃.
- NH₃-SCR /
- Mn-CeO_x /
- Al₂O₃ /
- sulfuric acid-modified

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图 1 改性前后催化剂的脱硝活性

Figure 1 SCR activity of the unmodified and modified catalysts

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图 2 M/Al₂O₃和M/0.2S/Al₂O₃催化剂在250 ℃时的抗水抗硫性能

Figure 2 H₂O and SO₂ durability of M/Al₂O₃ and M/0.2S/Al₂O₃ for NH₃-SCR of NO at 250 ℃

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图 3 改性前后催化剂的XRD谱图

Figure 3 XRD patterns of the unmodified and modified catalysts

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图 4 改性前后催化剂的NH₃-TPD谱图

Figure 4 NH₃-TPD profiles of the unmodified and modified catalysts

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图 5 改性前后催化剂的Py-FTIR谱图

Figure 5 Py-FTIR spectra of the unmodified and modified catalysts

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图 6 改性前后催化剂的H₂-TPR谱图

Figure 6 H₂-TPR profiles of the unmodified and modified catalysts

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图 7 150 ℃反应条件下M/Al₂O₃((a), (b))和M/0.5S/Al((c), (d))的红外光谱谱图

Figure 7 In situ FT-IR spectra of M/Al₂O₃((a), (b)) and M/0.5S/Al((c), (d)) under different conditions at 150 ℃

((a), (c))pre-adsorbed with NH₃ and then exposed to NO+O₂ for various times ((b), (d))pre-adsorbed with NO+O₂ and then exposed to NH₃ for various times

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图 8 300 ℃反应条件下M/Al₂O₃((a), (b))和M/0.5S/Al((c), (d))的红外光谱谱图

Figure 8 In situ FT-IR spectra of M/Al₂O₃((a), (b)) and M/0.5S/Al((c), (d)) under different conditions at 300 ℃

((a), (c))pre-adsorbed with NH₃ and then exposed to NO+O₂ for various times ((b), (d))pre-adsorbed with NO+O₂ and then exposed to NH₃ for various times

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表 1 改性前后催化剂的物理化学性质

Table 1 Physico-chemical properties of the unmodified and modified catalysts

Catalyst	Specific surface area A/(m²·g^-1)	Average pore diameter d/nm	Pore volume v/(cm³·g^-1)
Al₂O₃ 0.2S/Al 0.5S/Al 1.0S/Al M/Al₂O₃ M/0.2S/Al M/0.5S/Al M/1.0S/Al	177.3 168.1 164.3 165.2 143.2 132.1 139.1 136.3	3.61 3.58 3.59 3.61 3.62 4.29 3.63 3.93	0.24 0.25 0.25 0.25 0.21 0.21 0.22 0.21

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