Cu改性Fe/Al-PILC催化剂的SCR-C<sub>3</sub>H<sub>6</sub>脱硝特性实验研究

程江浩; 苏亚欣; 林睿; 张显威; 温妮妮; 邓文义; 周皞

Cu改性Fe/Al-PILC催化剂的SCR-C₃H₆脱硝特性实验研究

1.
东华大学环境科学与工程学院, 上海 201620
2.
常州工程技术学院, 江苏常州 213164

基金项目:

江苏省自然科学基金 BK20181161

中央高校基本科研业务费 2232019D3-24

国家自然科学基金 51278095

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: 2019-03-28
- 修回日期: 2019-05-10
- 网络出版日期: 2021-01-23
- 刊出日期: 2019-07-10

Experimental study on the selective catalytic reduction of NO by C₃H₆ over Cu modified Fe/Al-PILC catalysts

1.
School of Environmental Science and Engineering, Donghua University, Shanghai 201620, China
2.
Changzhou Vocational Institute of Engineering, Changzhou 213164, China

Funds:

Jiangsu Province Natural Science Foundation BK20181161

the Fundamental Research Funds for the Central Universities 2232019D3-24

National Natural Science Foundation of China 51278095

More Information

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

摘要

摘要: 为提高Fe/Al-PILC催化剂的SCR脱硝的低温活性，采用Cu对Fe/Al-PILC催化剂进行改性。采用超声浸渍法合成系列xCu-Fe/Al-PILC催化剂，通过XRD、N₂吸附-脱附、H₂-TPR、UV-vis、XPS、Py-FTIR等系列技术手段进行表征。在固定床微反应器上进行C₃H₆的选择性催化还原NO的实验。结果表明，经过铜改性后的xCu-Fe/Al-PILC催化剂有效解决了Fe/Al-PILC催化剂低温SCR活性不足的问题，同时提高了中高温活性。催化剂在200-500℃能够实现80%以上脱硝效率，其中，0.13Cu-Fe/Al-PILC在250-500℃实现了90%以上NO转化率，并在250℃达到最高脱硝效率93%。XRD、N₂吸附-脱附结果表明，经过铜改性的催化剂可以提供更多反应活性位，提高反应速率。H₂-TPR结果表明，掺杂铜使催化剂获得低温还原能力，同时增强了中高温还原能力。UV-vis、XPS结果表明，铜掺杂不仅使铁获得更高氧化态，同时产生了更多低温活性物质孤立Fe³⁺。Py-FTIR结果表明，催化剂表面同时存在Lewis酸和Brønsted酸，Lewis酸是SCR反应活性中心。
- NO还原 /
- SCR-C₃H₆ /
- xCu-Fe/Al-PILC /
- 低温活性
Abstract: In order to improve the low temperature activity of Fe/Al-PILC catalysts for SCR of NO, copper doping was used for the modification. xCu-Fe/Al-PILC catalysts were prepared by ultrasonic impregnation technique and characterized by XRD, N₂ adsorption-desorption, H₂-TPR, UV-vis, XPS and Py-FTIR. The SCR of NO with C₃H₆ tests were carried out in a fixed bed reactor. The experimental results showed that the xCu-Fe/Al-PILC catalysts can effectively solve the problem of insufficient SCR activity of Fe/Al-PILC catalysts at low temperature and as well as improve the activity at medium and high temperature. High NO reduction efficiency, 80% and beyond could be achieved at a wide temperature range of 200-500℃ by the catalysts, among which 0.13Cu-Fe/Al-PILC exhibited 90% of the NO conversion at 250-500℃ and maximum NO reduction efficiency of 93% at 250℃. XRD and N₂ adsorption-desorption results proved that the catalysts modified by copper provided more active sites and increased the reaction rate. The results of H₂-TPR indicated that the doping of copper improved the catalyst's redox ability at lower temperature, while enhanced the catalyst's redox ability at medium and high temperature. UV-vis and XPS study showed that the doping of copper not only increased the higher oxidation state of iron but also produced more isolated Fe³⁺ which is the low-temperature active species. Py-FTIR test illustrated that Lewis acid and Brönsted acid existed simultaneously on the catalyst surface, and Lewis acid sites were the activity center of the SCR reaction.
- NO reduction /
- SCR-C₃H₆ /
- xCu-Fe/Al-PILC /
- low-temperature activity

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图 1 Cu/Al-PILC以及Fe/Al-PILC和不同铜铁物质的量比xCu-Fe/Al-PILC催化剂的SCR反应活性

Figure 1 SCR activities over Cu/Al-PILC, Fe/Al-PILC and xCu-Fe /Al-PILC with different molar ratio of Cu to Fe

(a): NO conversion; (b): C₃H₆ conversion; (c): N₂ selectivity; (d): effect of the molar ratio of Cu to Fe reaction conditions: 0.05% NO, 0.2% C₃H₆, 1% O₂, He=balanced, GHSV=17000 h^-1

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图 2 反应空速对0.13Cu-Fe/Al-PILC催化剂活性的影响

Figure 2 Influence of GHSV on the activity of 0.13Cu-Fe/Al-PILC catalyst

reaction conditions: 0.05% NO, 0.2% C₃H₆, 1% O₂, He=balanced

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图 3 催化剂的XRD谱图

Figure 3 XRD patterns of the catalysts

a: Fe/Al-PILC; b: 0.11Cu-Fe/Al-PILC; c: 0.13Cu-Fe/Al-PILC; d: 0.38Cu-Fe/Al-PILC

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图 4 催化剂的N₂吸附-脱附等温曲线

Figure 4 Nitrogen adsorption-desorption isotherms of the catalysts

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图 5 催化剂的H₂-TPR谱图

Figure 5 H₂ -TPR profiles of Fe/Al-PILC and xCu-Fe/Al-PILC

a: Fe/Al-PILC; b: 0.11Cu-Fe/Al-PILC;
c: 0.13Cu-Fe/Al-PILC; d: 0.38Cu-Fe/Al-PILC

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图 6 催化剂的UV-vis谱图

Figure 6 UV-vis spectra of the catalysts

a: Fe/Al-PILC; b: 0.11Cu-Fe/Al-PILC;
c: 0.13Cu-Fe/Al-PILC; d: 0.38Cu-Fe/Al-PILC

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图 7 催化剂Cu 2p的XPS谱图

Figure 7 XPS spectra of Cu 2p of xCu-Fe/Al-PILC

a: 0.11Cu-Fe/Al-PILC; b: 0.13Cu-Fe/Al-PILC; c: 0.38Cu-Fe/Al-PILC

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图 8 催化剂Fe 2p的XPS谱图

Figure 8 XPS spectra of Fe 2p of Fe/Al-PILC and xCu-Fe/Al-PILC

a: Fe/Al-PILC; b: 0.11Cu-Fe/Al-PILC;
c: 0.13Cu-Fe/Al-PILC; d: 0.38Cu-Fe/Al-PILC

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图 9 催化剂的吡啶吸附红外光谱谱图

Figure 9 FT-IR spectra of pyridine adsorption of Fe/Al-PILC and xCu-Fe/Al-PILC

(a): 150 ℃ desorption; (b): 300 ℃ desorption

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表 1 催化剂的孔隙结构参数

Table 1 Textural parameters of the catalysts

Sample	A_BET^a/ (m²·g^-1)	Pore volume^bv/ (cm³·g^-1)	Average pore size^c d/nm
Fe/Al-PILC	61	0.176	11.31
0.11Cu-Fe/Al-PILC	73	0.193	10.23
0.13Cu-Fe/Al-PILC	81	0.194	9.02
0.38Cu-Fe/Al-PILC	66	0.143	8.73
^a: surface area calculated by Brunauer-Emmett-Teller (BET) method; ^b: pore volume determined by the BJH method on the adsorption isotherm leg; ^c: average pore size determined by BJH method

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表 2 催化剂Fe 2p_3/2的XPS分析

Table 2 XPS analysis of Fe 2p_3/2 for the catalysts

Sample	Binding energy E/eV		Peak intensity/%^a I(Fe3+A)/I(Fe3+B)
Sample	Fe3+A	Fe3+B	Peak intensity/%^a I(Fe3+A)/I(Fe3+B)
Fe/Al-PILC	710.6	712.6	1.49
0.11Cu-Fe/Al-PILC	710.7	712.4	0.98
0.13Cu-Fe/Al-PILC	711.0	713.3	0.86
0.38Cu-Fe/Al-PILC	710.8	712.7	1.23
^a: ratio of the intensity of the Fe3+A and Fe3+B peaks (main peak)

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表 3 不同催化剂的B酸和L酸含量

Table 3 Brønsted and Lewis acid content of different catalysts

Sample	150 ℃ desorption /(μmol·g^-1)		300 ℃ desorption /(μmol·g^-1)
Sample	BAS	LAS	BAS	LAS
Fe/Al-PILC	0.86	45.71	0.38	16.08
0.11Cu-Fe/Al-PILC	1.09	28.51	0.26	5.49
0.13Cu-Fe/Al-PILC	1.88	36.58	0.80	12.38
0.38Cu-Fe /Al-PILC	1.13	30.28	0.65	11.35

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