Fe/Ti-PILC用于C<sub>3</sub>H<sub>6</sub>选择性催化还原NO的研究

董士林; 苏亚欣; 刘欣; 李前程; 袁旻昊; 周皞; 邓文义

Fe/Ti-PILC用于C₃H₆选择性催化还原NO的研究

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 203164

基金项目:

国家自然科学基金 51278095

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: 2018-05-08
- 修回日期: 2018-08-09
- 网络出版日期: 2021-01-23
- 刊出日期: 2018-10-10

Experimental study on selective catalytic reduction of NO by C₃H₆ over Fe/Ti-PILC catalysts

1.
School of Environmental Science and Engineering, Donghua University, Shanghai 201620, China
2.
Changzhou Vocational Institude of Engineering, Changzhou 203164, China

Funds:

the National Natural Science Foundation of China 51278095

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: 采用二氧化钛对蒙脱土进行柱撑改性后，以离子交换法制备了铁负载二氧化钛柱撑蒙脱土催化剂Fe/Ti-PILC，考察了其在富氧条件下催化C₃H₆选择性还原NO（C₃H₆-SCR）的性能。并借助N₂等温吸附-脱附、XRD、UV-vis、H₂-TPR、Py-FTIR等表征方法研究了催化剂的结构与性能之间的关系。结果表明，所制备的19Fe/Ti-PILC催化剂在400 ℃时即可实现到NO的完全脱除，N₂选择性能够达到90%以上。且具有较好的抗水蒸气和抗SO₂的能力。N₂吸附-脱附和XRD结果显示，蒙脱土的结构被撑开，交联柱撑有效，形成了较大的比表面积和孔体积。UV-vis结果表明，催化剂的脱硝活性与铁氧低聚物种Fe_xO_y的含量有关，Py-FTIR结果表明，催化剂表面同时存在Lewis酸和Brønsted酸，Fe³⁺负载到柱撑黏土中能够显著增加Lewis酸的含量，Lewis酸是影响催化剂脱硝活性的影响因素之一。H₂-TPR表征表明，催化剂在400 ℃左右有较强的还原能力，催化剂的还原能力主要体现为Fe³⁺→Fe²⁺的还原。
- 富氧条件 /
- 柱撑黏土 /
- 选择性催化还原 /
- 丙烯
Abstract: Ti-pillared interlayer clay (PILC)-based catalysts ion exchanged with Fe were prepared and used for selective catalytic reduction of NO_x using propylene as the reducing agent under oxygen-rich conditions. The relationship between structure and properties of the catalysts was studied using N₂-adsorption/desorption, XRD, UV-vis, H₂-TPR, and Py-FTIR. The results show that the prepared 19Fe/Ti-PILC catalyst can achieve complete removal of NO at 400 ℃, and N₂ selectivity can reach over 90% and has better resistance to water vapor and SO₂. N₂-isothermal adsorption/desorption and XRD results show that structure of montmorillonite is opened, cross-linked pillars are effective, and a large specific surface area and pore volume are formed. UV-vis results show that the denitrification activity of the catalyst is related to content of oligomeric Fe_xO_y. Py-FTIR results show that both Lewis acid and Brønsted acid are presented on the catalyst surface. Fe³⁺ loading into the pillared clay can significantly increase the Lewis acid content. Lewis acid is one of the influencing factors on the denitrification activity of the catalyst. H₂-TPR indicates that the catalyst has a strong reduction ability at about 400 ℃, and the reduction ability of the catalyst is mainly represented by the reduction of Fe³⁺→Fe²⁺.
- oxygen-rich conditions /
- pillared clay /
- selective catalytic reduction /
- propylene

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图 1 不同Fe/Ti-PILC催化剂在反应温度范围内NO和C₃H₆的转化率及N₂选择性的变化情况

Figure 1 Effect of different iron loading of Fe/Ti-PILC on the conversion of NO and C₃H₆ and N₂ selectivity

(a): NO conversion; (b): C₃H₆ conversion; (c): N₂ selectivity $φ$_NO=0.1%, $φ$_C₃H₆=0.1%, $φ$_O₂=1%, N₂=balance and GHSV=12000 h^-1

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图 2 400 ℃时水蒸气和SO₂分别对19Fe/Ti-PILC催化剂脱硝效率的影响

Figure 2 Influence of water vapour and SO₂ on NO conversion over 19Fe/Ti-PILC catalyst at 400 ℃

GHSV=12000 h^-1, total flow=100 mL/min, N₂ banlanced

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图 3 不同催化剂的物理吸附等温线和孔径分布

Figure 3 Adsorption isotherms of nitrogen on different samples at -196 ℃

(a): N₂ adsorption/desorption isotherms; (b): BJH pore size distribution

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图 4 原始蒙脱土、载体及各催化剂的XRD谱图

Figure 4 XRD patterns of the original clay, Ti-PILC and catalysts

a: Ti-PILC; b: 5Fe/Ti-PILC; c: 13Fe/Ti-PILC; d: 19Fe/Ti-PILC; e: 22Fe/Ti-PILC

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图 5 催化剂的H₂-TPR谱图

Figure 5 H₂-TPR profiles of catalysts

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图 6 催化剂的紫外吸收光谱谱图

Figure 6 UV-vis adsorption spectra of catalysts

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图 7 不同负载量催化剂的吡啶吸附红外光谱谱图

Figure 7 Py-FTIR spectra of catalysts adsorbed pyridine

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

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表 1 不同负载量的催化剂的织构特征

Table 1 Properties of catalysts with different loadings of Fe

Catalyst	Fe w/(mg·g^-1)	A_BET/(m²·g^-1)	Pore volume v/(cm³·g^-1)	Pore diameter d/nm
Original clay	-	24	0.099	16.44
Ti-PILC	-	203	0.240	4.73
13Fe/Ti-PILC	135.2	166	0.207	4.97
19Fe/Ti-PILC	192.1	190	0.222	5.07
22Fe/Ti-PILC	221.0	179	0.209	4.73

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表 2 通过UV-vis光谱的定量分析确定的子带面积百分比

Table 2 Percentage of the area of the sub-bands by quantitative analysis of the UV-vis spectra

Catalyst	Percentage /%
Catalyst	I₁	I₂	I₃
5Fe/Ti-PILC	70	14	16
13Fe/Ti-PILC	56	23	21
19Fe/Ti-PILC	41	29	30
22Fe/Ti-PILC	39	24	37
I₁, I₂, and I₃ represent isolated Fe³⁺ species, small Fe_xO_y oligomers, and Fe₂O₃ particles species, respectively

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表 3 不同负载量的催化剂中Brønsted酸和Lewis酸的含量

Table 3 Brønsted and Lewis acid content of different catalysts

Sample	40 ℃ desorption /(μmol·g^-1)		170 ℃ desorption /(μmol·g^-1)		300 ℃ desorption /(μmol·g^-1)
Sample	B	L	B	L	B	L
Ti-PILC	9.99	382.61	4.05	127.14	2.78	83.83
5Fe/Ti-PILC	46.84	398.59	31.06	197.24	19.36	133.96
13Fe/Ti-PILC	13.96	636.18	10.34	189.85	5.17	122.80
19Fe/Ti-PILC	7.17	688.40	37.83	311.51	24.94	234.59

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