Fe/Al-PILC催化C<sub>3</sub>H<sub>6</sub>选择性还原NO的实验研究

钱文燕; 苏亚欣; 杨溪; 袁旻昊; 邓文义; 赵兵涛

Fe/Al-PILC催化C₃H₆选择性还原NO的实验研究

1.
东华大学环境科学与工程学院, 上海 201620
2.
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

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: 2017-06-22
- 修回日期: 2017-09-04
- 网络出版日期: 2021-01-23
- 刊出日期: 2017-12-10

Experimental study on selective catalytic reduction of NO with propene over iron based catalysts supported on aluminum pillared clays

1.
School of Environmental Science and Engineering, Donghua University, Shanghai 201620, China
2.
School of Energy and Power Engineering, University of Shanghai for Science and Technology, Shanghai 200093, China

Funds:

the National Natural Science Foundation of China 51278095

Natural Science Foundation of Shanghai 17ZR1419300

More Information

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

摘要

摘要: 采用浸渍法制备了负载于铝柱撑黏土的铁基催化剂（Fe/Al-PILC），在固定床反应器上测试其催化C₃H₆选择性还原NO的性能。通过N₂吸附-脱附、X射线衍射（XRD）、H₂的程序升温还原（H₂-TPR）、紫外可见光谱（Uv-vis）、吡啶吸附红外光谱（Py-FTIR）等手段对催化剂的物理化学性质进行表征。结果表明，9Fe/Al-PILC在400-550 ℃能够还原98%以上的NO，而且SO₂和水蒸气对其催化性能的影响很小。XRD、N₂吸附-脱附表征结果表明，Fe/Al-PILC催化剂中铁氧化物高度分散在载体表面，催化剂有较大的比表面积和孔容。H₂-TPR结果表明，催化剂的活性主要由Fe₂O₃物相的还原性能决定。Uv-vis结果表明，催化剂的活性与铁氧低聚物种Fe_xO_y呈正相关性。Py-FTIR结果表明，催化剂表面同时存在Lewis酸和Brønsted酸，L酸性位是NO和C₃H₆反应的主要催化活性中心。
- NO /
- 选择性催化还原 /
- 铝柱撑黏土 /
- 铁 /
- 丙烯
Abstract: Iron based catalysts supported on aluminum pillared clays (Fe/Al-PILC) was prepared by impregnation method and the selective catalytic reduction of NO with propene by the Fe/Al-PILC catalysts was investigated in a fixed bed reactor. The physical and chemical properties of the catalysts were characterized by N₂ adsorption/desorption, XRD, H₂-TPR, Uv-vis, Py-FTIR, etc. Results showed that 9% Fe/Al-PILC reduced more than 98% of NO at 400-550℃. SO₂ and water vapor slightly influenced the catalytic activity of the catalysts. XRD and N₂ adsorption/desorption characterization results revealed that the iron oxides in the catalyst were highly dispersed on the surface of the carrier, and the catalyst has a large specific surface area and pore volume. H₂-TPR results indicated that the activity of the catalysts was mainly determined by the reduction performance of Fe₂O₃ phase. Uv-vis results showed that the activity of the catalysts was positively correlated with the iron oxide oligomer Fe_xO_y. Py-FTIR results indicated that both Lewis acid and Brønsted acid were formed on the catalyst surface and the Lewis acid sites were the main catalytic activity center of NO and C₃H₆ reaction.
- NO /
- selective catalytic reduction /
- Al-PILC /
- iron /
- C₃H₆

HTML全文

图 1 不同催化剂取得的NO和C₃H₆转化率及N₂选择性随反应温度的变化

Figure 1 NO conversion to N₂(a), C₃H₆ conversion (b), N₂ selectivity(c) over Fe/Al-PILC with different iron loading

reaction conditions: φ_NO=0.05%, φ_C₃H₆=0.3%, φ_O₂ =1%, He=balance and GHSV=15 000 h^-1
—■—4Fe/Al-PILC; —●—6Fe/Al-PILC; —▲—9Fe/Al-PILC; —▼—13Fe/Al-PILC; —◆—Al-PILC

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图 2 SO₂和水蒸气对9Fe/Al-PILC催化剂活性的影响

Figure 2 Influence of SO₂ and water vapor on 9Fe/Al-PILC catalyst

reaction conditions: φ_NO=0.05%, φ_C₃H₆=0.3%, φ_O₂=1%, φ_SO₂=0.02%, φ_H₂O=7%, He=balance and GHSV=15 000 h^-1

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图 3 NO浓度对9Fe/Al-PILC催化剂活性的影响

Figure 3 Influence of NO concentration on the activity of 9Fe/Al-PILC catalyst

reaction conditions: φ_C₃H₆=0.3%, φ_O₂=1%, He=balance and GHSV=15 000 h^-1

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图 4 空速对9Fe/Al-PILC催化剂活性的影响

Figure 4 Influence of GHSV on the activity of 9Fe/Al-PILC catalyst

reaction conditions: φ_NO=0.05%, φ_C₃H₆=0.3%, φ_O₂=1%, He=balance

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图 5 9Fe/Al-PILC催化活性的持续性

Figure 5 Continuous test of 9Fe/Al-PILC catalytic activity

reaction conditions: φ_NO=0.05%, φ_C₃H₆=0.3%, φ_O₂=1%, He=balance and GHSV=15 000 h^-1

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图 6 不同催化剂的物理吸附-脱附等温线和孔径分布

Figure 6 N₂ adsorption/desorption isotherms (a) and BJH pore size distribution (b)

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图 7 催化剂的XRD谱图

Figure 7 XRD patterns of the catalysts

a: original clay; b: Al-PILC; c: 4Fe/Al-PILC; d: 9Fe/Al-PILC; e:13Fe/Al-PILC

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图 8 催化剂的H₂-TPR谱图

Figure 8 H₂-TPR profiles of catalysts

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图 9 催化剂的紫外吸收光谱谱图

Figure 9 Uv-vis adsorption spectra of catalysts

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图 10 催化剂的吡啶吸附红外光谱谱图

Figure 10 Py-FTIR spectra of catalysts adsorbed pyridine

(a): 170 ℃desorption; (b): 300 ℃desorption

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表 1 不同催化剂的物理特性

Table 1 Physical property of different catalysts

Catalyst	Fe w/ (mg·g^-1)	A_BET /(m²·g^-1)	Pore volume v/(cm³·g^-1)	Pore diameter d/nm
Al-PILC		188	0.328	5.61
4Fe/Al-PILC	40.19	164	0.258	5.52
9Fe/Al-PILC	92.54	186	0.264	4.91
13Fe/Al-PILC	131.19	65	0.097	4.84

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表 2 不同催化剂的B酸和L酸含量

Table 2 Brønsted and Lewis acid content of different catalysts

Sample	170 ℃ desorption /(mmol·g^-1)		300 ℃ desorption /(mmol·g^-1)
Sample	B	L	B	L
Al-PILC	0.005 12	0.051 29	0	0.035 80
4Fe/Al-PILC	0.003 97	0.025 80	0	0.011 40
9Fe/Al-PILC	0.006 91	0.046 95	0	0.034 43

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