锰锆复合氧化物CO催化还原NO性能研究

谈冠希; 迟姚玲; 李双; 易玉峰; 靳广洲

锰锆复合氧化物CO催化还原NO性能研究

北京石油化工学院化学工程系燃料清洁化及高效催化减排技术北京市重点实验室, 北京 102617

基金项目:

国家重点基础研究发展计划 973 program, 2012CB215002

详细信息

中图分类号: O643.36
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- 被引次数: 0
出版历程
- 收稿日期: 2019-06-28
- 修回日期: 2019-07-15
- 网络出版日期: 2021-01-23
- 刊出日期: 2019-10-10

Performance of manganese-zirconium composite oxide in the catalytic reduction of NO by CO

School of Chemical Engineering, Beijing Key Laboratory of Fuels Cleaning and Advanced Catalytic Emission Reduction Technology, Beijing Institute of Petrochemical Technology, Beijing 102617, China

Funds:

the National Basic Research Program of China 973 program, 2012CB215002

More Information

Corresponding author: JIN Guang-zhou, E-mail: jinguangzhou@bipt.edu.cn

摘要

摘要: 采用柠檬酸络合法制备了锰锆复合氧化物催化剂，用XRD、H₂-TPR、XPS和SEM等技术进行了表征，研究了其CO催化还原NO性能。结果表明，MnO_x主要以Mn₃O₄物相存在，Zr占比的增加会促进Mn₃O₄物相的分散，引起Mn₃O₄平均晶粒粒径减小；Mn主要有Mn²⁺、Mn³⁺、Mn⁴⁺离子价态形式，添加Cu和Ce后，（Mn³⁺+Mn⁴⁺）含量和表面吸附氧（OA）含量增加，H₂-TPR还原峰温度向低温区偏移，有利于催化活性的提升。Mn-Zr-O复合氧化物的CO催化还原NO活性较低，加入Cu后的Mn-Cu-Zr-O复合氧化物其CO催化还原NO的活性得到改善，而添加Ce后所制备的Mn-Cu-Ce-Zr-O复合氧化物的催化活性进一步提高；在350 ℃下、反应空速为18000 h^-1时，Mn-Cu-Ce-Zr-O复合氧化物表现出较好的CO催化还原NO活性，CO转化率达到了89.17%，NO转化率达到了91.70%。
- 锰锆复合氧化物 /
- CO /
- NO /
- 催化还原 /
- 活性
Abstract: A series of manganese-zirconium composite oxides were prepared by citric acid complexing method and characterized by XRD, H₂-TPR, XPS and SEM; their performance in the catalytic reduction of NO by CO was investigated. The results show that Mn₃O₄ is the main phase for MnO_x in the Mn-Zr composite oxide; an increase in the Zr content can promote the dispersion of Mn₃O₄ and reduce the average grain size of Mn₃O₄. Mn may exist in the form of Mn²⁺, Mn³⁺ and Mn⁴⁺ ions; the content of (Mn³⁺ + Mn⁴⁺) and the quantity of surface adsorbed oxygen (OA) increase after the addition of Cu and Ce, which is beneficial to enhancing the catalytic activity. The pristine Mn-Zr-O composite shows a relatively low activity in the catalytic reduction of NO by CO; after adding Cu, the Mn-Cu-Zr-O composite exhibits much higher activity than Mn-Zr-O; moreover, the activity of Mn-Cu-Ce-Zr-O composite is even enhanced by adding Ce. For the catalytic reduction of NO by CO over the Mn-Cu-Ce-Zr-O composite at 350℃ and with a space velocity of 18000 h^-1, the CO conversion and NO conversion are 89.17% and 91.70%, respectively.
- Mn-based composite oxide /
- CO /
- NO /
- catalytic reduction /
- activity

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图 1 锰系复合氧化物的XRD谱图

Figure 1 XRD patterns of Mn-based composite oxides

a: MnO_x; b: Mn-Zr-O; c: Mn-Cu-Zr-O; d: Mn-Cu-Ce-Zr-O; e: ZrO₂

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图 2 复合氧化物的H₂-TPR谱图

Figure 2 H₂-TPR profiles of various Mn-Zr-O composites

a: MnO_x; b:Mn-Zr-O; c: Mn-Cu-Zr-O; d: Mn-Cu-Ce-Zr-O

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图 3 三种复合氧化物中Mn 2p(a)、O 1s (b)的XPS谱图

Figure 3 Mn 2p(a)、O 1s (b) XPS spectra of three composite oxides

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图 4 锰基复合氧化物的SEM照片(×10⁴)

Figure 4 SEM images of Mn-based composite oxides (magnified 10000 times)

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图 5 催化剂的CO和NO转化率

Figure 5 CO (a) and NO (b) conversion for catalytic reduction of NO by CO over various Mn-based composite oxides

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表 1 Mn-Zr-O复合氧化物Mn₃O₄物相晶胞参数及晶胞体积

Table 1 Crystal cell parameters and unit cell volume of Mn₃O₄ phase of various Mn-Zr-O composites

Catalyst	2θ/(°)		Mn₃O₄
Catalyst	103	211	a/nm	b/nm	c/nm	v₀/nm³
MnO_x	32.3349	36.1099	0.5764	0.5764	0.9470	0.3146
Mn₈₀Zr₂₀O	32.3259	36.0719	0.5771	0.5771	0.9470	0.3153
(Mn_0.8Cu_0.2)₈₀Zr₂₀O	32.4159	36.0499	0.5776	0.5776	0.9434	0.3147
(Mn_0.8Cu_0.2)₈₀(Ce_0.5Zr_0.5)₂₀O	32.4649	36.0519	0.5776	0.5776	0.9416	0.3142

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表 2 复合氧化物Mn₃O₄物相平均晶粒粒径

Table 2 Average grain size of Mn₃O₄ phase of various Mn-Zr-O composites

Catalyst	Mn₃O₄(103)
Catalyst	2θ/(°)	full width at half maximum(β)	average crystallite size d/nm
MnO_x	32.3349	0.223	92.19
Mn₈₀Zr₂₀O	32.3259	0.738	11.98
(Mn_0.8Cu_0.2)₈₀Zr₂₀O	32.4159	0.760	11.60
(Mn_0.8Cu_0.2)₈₀(Ce_0.5Zr_0.5)₂₀O	35.8709	0.966	9.30

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表 3 催化剂Mn 2p、O 1s峰曲线拟合结果

Table 3 Curve fitting results of Mn 2p and O 1s XPS spectra

Catalyst	Ratio/%
Catalyst	Mn²⁺/(Mn²⁺+Mn³⁺+Mn⁴⁺)	(Mn³⁺+Mn⁴⁺)/(Mn²⁺+Mn³⁺+Mn⁴⁺)	O_A/(O_A+O_L)
Mn-Zr-O	46.87	53.13	31.58
Mn-Cu-Zr-O	43.19	56.81	34.66
Mn-Cu-Ce-Zr-O	35.94	64.06	48.27

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