Fe-Ag/Al<sub>2</sub>O<sub>3</sub>催化丙烯还原NO的实验研究

杨溪; 苏亚欣; 钱文燕; 袁旻昊; 周皞; 邓文义; 赵兵涛

Fe-Ag/Al₂O₃催化丙烯还原NO的实验研究

1.
东华大学环境学院, 上海 201620
2.
常州工程技术学院, 江苏常州 213164
3.
上海理工大学能源与动力工程学院, 上海 200093

基金项目:

国家自然科学基金 51278095

上海市自然科学基金 17ZR1419300

江苏省前瞻性联合研究项目 BY2015032-02

详细信息

中图分类号: X511
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- 被引次数: 0
出版历程
- 收稿日期: 2017-06-29
- 修回日期: 2017-09-01
- 网络出版日期: 2021-01-23
- 刊出日期: 2017-11-10

Experimental study on selective catalytic reduction of NO by C₃H₆ over Fe-Ag/Al₂O₃ catalysts

1.
School of Environmental Science and Engineering, Donghua University, Shanghai 201620, China
2.
Changzhou Vocational Institute of Engineering, Changzhou 213164, China
3.
School of Energy and Power Engineering, University of Shanghai Science and Technology, Shanghai 200093, China

Funds:

the National Natural Science Foundation of China 51278095

Natural Science Foundation of Shanghai 17ZR1419300

Jiangsu Province Prospective Joint Research Projects BY2015032-02

More Information

Corresponding author: SU Ya-xin, Tel:021-67792552, E-mail:suyx@dhu.edu.cn

摘要

摘要: 以蜂窝状陶瓷为载体，采用溶胶凝胶法和浸渍法制备了不同Fe/Ag负载量的Fe-Ag/Al₂O₃催化剂。以C₃H₆为还原剂，在模拟烟气条件下和200-700 ℃范围内，程序控温的陶瓷管流动反应器上进行了催化还原NO的性能评估。结果表明，7.2Fe/1.9Ag/20Al₂O₃/CM在500和550 ℃时催化C₃H₆还原NO的脱硝效率分别超过90%和达到100%。铁离子能有效地提高Ag/20Al₂O₃/CM催化剂抵抗烟气中的SO₂和H₂O的能力。结果表明，当烟气中含有体积分数为0.02%的SO₂和8%的H₂O时，在500 ℃时7.2Fe/1.9Ag/20Al₂O₃/CM催化C₃H₆还原NO的脱硝效率不受影响，在6 h的连续实验中保持90%的脱硝效率而没有下降。而未经铁离子修饰的2Ag/20Al₂O₃/CM的催化活性则受烟气中的SO₂和H₂O影响很大，0.02%的SO₂和8%的H₂O分别使2Ag/20Al₂O₃/CM在500 ℃时催化C₃H₆还原NO的脱硝效率迅速从70%分别下降至46%和25%。XRD和SEM表征结果表明，经铁离子修饰后的7.2Fe/1.9Ag/20Al₂O₃/CM催化剂中，形成了AgFeO₂以及Fe³⁺，催化剂表面变得疏松多孔，形成以Fe₃O₄为主的针状和片状晶体。H₂-TPR结果表明，7.2Fe/1.9Ag/20Al₂O₃/CM比Ag/20Al₂O₃/CM在更宽的温度范围内具有更好的还原特性。吡啶吸附红外光谱（Py-FTIR）实验结果显示，Fe增加了催化剂表面的Lewis酸性位。
- 选择性催化脱硝 /
- 丙烯 /
- Fe-Ag/Al₂O₃催化剂
Abstract: Sol-gel and impregnation methods were used to prepare the Fe/Ag/Al₂O₃ catalysts supported on the monolithic cordierite with different Fe/Ag loading ratios. The catalytic performance to reduce NO with C₃H₆ was evaluated in a one-dimensional electrically heated temperature programmed ceramic tubular reactor in simulated flue gas atmosphere at 200-700 ℃. The results show that the NO reduction efficiency on 7.2Fe/1.9Ag/20Al₂O₃/CM with C₃H₆ is more than 90% and reaches about 100% at the temperatures of 500 ℃ and 550 ℃ respectively. Iron can effectively improve the ability of Ag/20Al₂O₃/CM catalysts to resist SO₂ and H₂O in flue gas. When SO₂ and H₂O are 0.02% and 8% in the flue gas, the NO reduction efficiency is almost not influenced on 7.2Fe/1.9Ag/20Al₂O₃/CM at 500 ℃. The 90% NO reduction efficiency is maintained during 6 h without decrease. However, the catalytic activity of 2Ag/20Al₂O₃/CM without iron modification is strongly influenced by SO₂ and H₂O in the flue gas. The NO reduction efficiency on Ag/20Al₂O₃/CM decreases rapidly from about 70% to 46% and 25% respectively, when the SO₂ and H₂O are 0.02% and 8% in the flue gas. The results of XRD and SEM of the catalyst show that AgFeO₂ and Fe³⁺ are formed in the 7.2Fe/1.9Ag/20Al₂O₃/CM catalyst after the modification by iron, and the surface of the catalyst become loose and porous, forming Fe₃O₄-based needle-like and flaky crystals. H₂-TPR results show that 7.2Fe/1.9Ag/20Al₂O₃/CM has better reduction properties than Ag/20Al₂O₃/CM in the wider temperature range. Pyridine adsorption Infrared Spectroscopy (Py-FTIR) experimental results show that Fe increases the Lewis acid sites in the catalyst surface.
- selective catalytic reduction of NO /
- C₃H₆ /
- Fe-Ag/Al₂O₃ catalyst

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图 1 不同负载量对NO和C₃H₆转化率的影响

Figure 1 Effect of Fe/Ag loading on NO and C₃H₆ conversion

flow rate=2 L/min, N₂ banlanced, φ_NO=0.05%, φ_C₃H₆=0.5%, φ_O₂=3%

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图 2 不同Fe/Ag负载量对N₂选择性的影响

Figure 2 Effect of Fe/Ag loading on N₂ selectivity

flow rate=2 L/min, N₂ banlanced, φ_NO=0.05%, φ_C₃H₆=0.5%, φ_O₂=3%

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图 3 500 ℃时SO₂和H₂O对NO转化率的影响

Figure 3 Effect of SO₂ (a) and H₂O (b) on NO conversion at 500 ℃

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图 4 不同温度时SO₂和H₂O对7.2Fe/1.9Ag/20Al₂O₃/CM和2Ag/20Al₂O₃/CM催化C₃H₆还原NO的影响

Figure 4 Effect of SO₂ and H₂O on C₃H₆-SCR of NO by 7.2Fe/1.9Ag/20Al₂O₃/CM(a) and 2Ag/20Al₂O₃/CM(b) at different temperature

—○—: 7.2Fe/1.9Ag/20Al₂O₃/CM, with SO₂ and H₂O; —●—: 7.2Fe/1.9Ag/20Al₂O₃/CM, without SO₂ and H₂O; --■--: 2Ag/20Al₂O₃/CM, without SO₂ and H₂O; --□--: 2Ag/20Al₂O₃/CM, with SO₂ and H₂O;

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图 5 载体和催化剂的SEM照片

Figure 5 SEM images of support and catalysts

(a): 20Al₂O₃/CM; (b):7.2Fe/1.9Ag/20Al₂O₃/CM; (c): 2Ag/20Al₂O₃/CM; (d): 5.5Fe/20Al₂O₃/CM; (e): 8Fe/20Al₂O₃/CM

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图 6 载体和不同负载量样品的XRD谱图

Figure 6 XRD patterns of carrier and catalysts with different Fe/Ag loading

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图 7 不同负载量样品的N₂吸附-脱附等温曲线图和孔容孔径分布图

Figure 7 Adsorption isotherms of nitrogen on different samples at -196 ℃

(a): pore volume (b): pore size distribution open symbols: adsorption; solid symbols: desorption

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图 8 2Ag/20Al₂O₃/CM和7.2Fe/1.9Ag/20Al₂O₃/CM的H₂-TPR谱图

Figure 8 H₂-TPR profiles of 2Ag/20Al₂O₃/CM and 7.2Fe/1.9Ag/20Al₂O₃/CM

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图 9 催化剂样品的吡啶吸附红外光谱谱图

Figure 9 Py-FTIR spectra on three catalysts at room temperature (a), 7.2Fe/1.9Ag/20Al₂O₃/CM (b) at RT, 150 and 300 ℃

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表 1 不同负载量样品的微孔隙特性

Table 1 Textural properties of different Fe/Ag loading on Al₂O₃

Catalyst	A_BET/ (m²·g^-1)	ν_p/ (cm³·g^-1)	d_p/ nm
20Al₂O₃/CM^[16]	27	0.076	4.4
2Ag/20Al₂O₃/CM	9	0.042	17.7
7.2Fe/1.9Ag/20Al₂O₃/CM	23	0.054	9.23
5.5Fe/20Al₂O₃/CM	19	0.039	6.54

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表 2 三组样品中酸性位的含量

Table 2 Acid content of different Fe/Ag loading on Al₂O₃

Sample	150 ℃		300 ℃
Sample	B /(mmol·g^-1)	L /(mmol·g^-1)	B /(mmol·g^-1)	L /(mmol·g^-1)
20Al₂O₃/CM	0	0.001 20	0	0.000 60
2Ag/20Al₂O₃/CM	0	0.001 58	0	0.000 63
7.2Fe/1.9Ag/20Al₂O₃/CM	0	0.002 33	0	0.001 33

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