基于NH3-SCR的CeO2-TiO2复合氧化物催化剂:结构与脱硝性能

doi:10.7503/cjcu20160875

高等学校化学学报 ›› 2017, Vol. 38 ›› Issue (5): 814.doi: 10.7503/cjcu20160875

基于NH₃-SCR的CeO₂-TiO₂复合氧化物催化剂:结构与脱硝性能

孙向丽², 何洪^1,^2,³(), 苏垚超², 闫京芳², 宋丽云^1,², 邱文革^1,²

1. 北京工业大学区域大气复合污染防治北京市重点实验室北京 100124
2. 绿色催化与分离北京市重点实验室, 北京 100124
3. 北京电动车辆协同创新中心, 北京 100081

收稿日期:2016-12-05 出版日期:2017-05-10 发布日期:2017-04-13
作者简介:联系人简介: 何洪, 男, 博士, 教授, 博士生导师, 主要从事低温选择性催化还原脱硝技术研究. E-mail:hehong@bjut.edu.cn
基金资助:
国家重点研发计划(批准号: 2016YFB0600405)和国家自然科学基金(批准号: 21577005, 21277009)资助

CeO₂-TiO₂ Mixed Oxides Catalysts for Selective Catalytic Reduction of NO_x with NH₃: Structure-properties Relationships^†

SUN Xiangli², HE Hong^1,^2,^3,^*(), SU Yaochao², YAN Jingfang², SONG Liyun^1,², QIU Wenge^1,²

1. Key Laboratory of Beijing on Regional Air Pollution Control, Beijing University of Technology, Beijing 100124, China
2. Beijing Key Laboratory for Green Catalysis and Separation, Beijing University of Technology, Beijing 100124, China
3. Collaborative Innovation Center of Electric Vehicles in Beijing, Beijing 100081, China

Received:2016-12-05 Online:2017-05-10 Published:2017-04-13
Contact: HE Hong E-mail:hehong@bjut.edu.cn
Supported by:
† Supported by the National Key R&D Program of China(No.2016YFB0600405) and the National Natural Science Foundation of China(Nos.21577005, 21277009)

摘要/Abstract

摘要：

以TiOSO₄·2H₂O和Ce(NO₃)₃·6H₂O为前驱体, 采用共沉淀法制备了不同CeO₂含量的CeO₂-TiO₂复合氧化物催化剂. 对样品结构进行了表征, 考察了催化剂的NH₃-SCR(NH₃选择性催化还原)反应活性、 N₂选择性和抗水抗硫性能. 结果表明, 随着催化剂中CeO₂含量的增加, 催化剂的物相结构、晶粒尺寸及脱硝性能均出现规律性变化, 这种改变与样品的酸碱性和氧化还原性能的变化有关. 当样品中CeO₂的质量分数约为50%时, 催化剂的结构呈无定形态, 具有较大的比表面积和较多的氧空位, 有利于反应物分子在催化剂表面的吸附和活化, 拓宽了催化剂的低温活性窗口并提高了NO的转化率.

关键词: 选择性催化还原, CeO2-TiO2复合氧化物, 氮氧化物, 物相结构

Abstract:

A series of CeO₂-TiO₂ mixed oxides catalysts prepared by Co-precipitation method was investigated on selective catalytic reduction(SCR) of NO_x with NH₃. The properties of the catalysts were characterized using XRD, BET, XRF, XPS, H₂-TPR, NH₃-TPD and NO+O₂-TPD techniques. The results indicated that the crystal structure, crystallite size and catalytic NH₃-SCR activity over the catalysts presented a regular change with the increase of CeO₂ concentration. Particularly, the 50CeTi catalyst with amorphous structure of CeO₂-TiO₂ showed a higher BET surface area and a stronger surface acidity than other samples. Meanwhile, favorable Ce³⁺ and the surface adsorbed oxygen benefited the adsorption of NO_x and NH₃ molecules, which enhanced DeNO_x performance.

Key words: Selective catalytic reduction, CeO2-TiO2 mixed oxide, NOx, Crystal structure

中图分类号:

O643

TrendMD:

孙向丽, 何洪, 苏垚超, 闫京芳, 宋丽云, 邱文革. 基于NH₃-SCR的CeO₂-TiO₂复合氧化物催化剂:结构与脱硝性能. 高等学校化学学报, 2017, 38(5): 814.

SUN Xiangli, HE Hong, SU Yaochao, YAN Jingfang, SONG Liyun, QIU Wenge. CeO₂-TiO₂ Mixed Oxides Catalysts for Selective Catalytic Reduction of NO_x with NH₃: Structure-properties Relationships^†. Chem. J. Chinese Universities, 2017, 38(5): 814.

图/表 11

Fig.1 NH3-SCR activity of CeO2-TiO2 catalystsReaction condition: 1340 mg/m3 NO, 760 mg/m3 NH3, 6% O2, He balance, GHSV: 3×104 h-1. Temperature/℃: a. 140; b. 160; c. 180; d. 200; e. 220; f. 260.

Fig.2 NH3-SCR activity(A) and N2 selectivity(B) over the catalystsReaction conditions: 1340 mg/m3 NO, 760 mg/m3 NH3, 6% O2, He balance, GHSV: 3×104 h-1.■ TiO2; ● 10CeTi; ▲ 50CeTi; ▼ 90CeTi; ? CeO2.

Fig.3 NH3-SCR activity over the catalysts in the presence of H2O/SO2 at 270 ℃Reaction condition: 1340 mg/m3 NO, 760 mg/m3 NH3, 6% O2, 5% H2O, 860 mg/m3 SO2, N2 balance, GHSV: 3×104 h-1. ■ 10CeTi; ● 50CeTi; ▲ 90CeTi.

Fig.4 XRD patterns of the catalystsa. TiO2; b. 10CeTi; c. 20CeTi; d. 30CeTi;e. 40CeTi; f. 50CeTi; g. 60CeTi; h. 70CeTi;i. 80CeTi; j. 90CeTi; k. CeO2.

Table 1 Specific surface area, pore volume and average crystallite sizes of the catalysts

Sample	S_BET/(m²·g^-1)	Pore volume/(cm³·g^-1)	Crystallite size/nm
TiO₂	57.1	0.11	21
10CeTi	91.6	0.18	15
50CeTi	129.0	0.21
90CeTi	85.3	0.15	10
CeO₂	70.1	0.17	13

Fig.5 N2 adsorption-desorption isotherms of the catalystsa. TiO2; b. 10CeTi; c. 50CeTi; d. 90CeTi; e. CeO2.

Fig.6 H2-TPR profiles of the catalystsa. TiO2; b. 10CeTi; c. 50CeTi;d. 90CeTi; e. CeO2.

Table 2 XPS data and H2 consumption of the catalysts

Sample	Molar fraction(%)			Molar ratio(%)		H₂ consumption/(mmol· $g cat - 1$ )
Sample	Ce	Ti		O	Ce³⁺/(Ce³⁺+Ce⁴⁺)	O_α/(O_α+O_β)
TiO₂		36.1	63.9		12.2	0.13
10CeTi	1.7	34.7	63.6	32.1	13.3	0.35
50CeTi	7.3	24.2	68.5	18.5	25.5	2.30
90CeTi	18.1	4.1	77.8	18.7	35.7	4.04
CeO₂	25.6		74.4	14.8	15.1	0.73

Table 2 XPS data and H2 consumption of the catalysts

Sample	Molar fraction(%)			Molar ratio(%)		H₂ consumption/(mmol· $g cat - 1$ )
Sample	Ce	Ti		O	Ce³⁺/(Ce³⁺+Ce⁴⁺)	O_α/(O_α+O_β)
TiO₂		36.1	63.9		12.2	0.13
10CeTi	1.7	34.7	63.6	32.1	13.3	0.35
50CeTi	7.3	24.2	68.5	18.5	25.5	2.30
90CeTi	18.1	4.1	77.8	18.7	35.7	4.04
CeO₂	25.6		74.4	14.8	15.1	0.73

Fig.7 XPS spectra of Ti2p(A), Ce3d(B) and O1s(C) of the catalystsa.TiO2; b.10CeTi; c.50CeTi; d.90CeTi; e.CeO2.(C) Molar fraction of Oα: a. 12.2%; b. 13.3;c. 25.5%; d. 35.7%; e. 15.1%.

Fig.8 NH3-TPD(A) and NO+O2-TPD(B) profiles of the catalystsa. TiO2; b. 10CeTi; c. 50CeTi; d. 90CeTi; e. CeO2.

Table 3 Amounts of desorption species from the samples during NO+O2-TPD and NH3-TPD experiments

Sample	Desorption area in NO+O₂-TPD		Desorption area in NH₃-TPD, total N $H 3 *$
Sample	NO^*		N $O 2 *$
TiO₂	1.0	1.0	1.0
10CeTi	1.8	1.3	1.2
50CeTi	3.4	2.2	1.9
90CeTi	0.9	0.8	0.8
CeO₂	4.4	2.8	0.5

Table 3 Amounts of desorption species from the samples during NO+O2-TPD and NH3-TPD experiments

Sample	Desorption area in NO+O₂-TPD		Desorption area in NH₃-TPD, total N $H 3 *$
Sample	NO^*		N $O 2 *$
TiO₂	1.0	1.0	1.0
10CeTi	1.8	1.3	1.2
50CeTi	3.4	2.2	1.9
90CeTi	0.9	0.8	0.8
CeO₂	4.4	2.8	0.5

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基于NH₃-SCR的CeO₂-TiO₂复合氧化物催化剂:结构与脱硝性能

CeO₂-TiO₂ Mixed Oxides Catalysts for Selective Catalytic Reduction of NO_x with NH₃: Structure-properties Relationships^†

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