Dy和Y掺杂改性对CuO/CeZrO<sub>2</sub>催化剂在富氢气氛中CO优先氧化催化性能的影响

卢小林; 刘子魁; 马素芳; 白雪

Dy和Y掺杂改性对CuO/CeZrO₂催化剂在富氢气氛中CO优先氧化催化性能的影响

内蒙古工业大学化工学院, 内蒙古呼和浩特 010051

基金项目:

国家自然科学基金 21263011

详细信息

通讯作者:
白雪, E-mail: bai-xue@imut.edu.cn

中图分类号: O643
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- 被引次数: 0
出版历程
- 收稿日期: 2015-12-25
- 修回日期: 2016-03-09
- 网络出版日期: 2021-01-23
- 刊出日期: 2016-07-10

Effect of Dy and Y doping on the catalytic performance of CuO/CeZrO₂ for the preferential oxidation of CO in H₂-rich stream

School of Chemical Engineering, Inner Mongolia University of Technology, Hohhot 010051, China

Funds:

The project was supported by the National Natural Science Foundation of China 21263011

More Information

Corresponding author: BAI Xue, E-mail: bai-xue@imut.edu.cn

摘要

摘要: 采用水热-浸渍法制备了系列Dy和Y掺杂改性的CuO/CeZrO₂催化剂, 使用X射线粉末衍射(XRD)、N₂吸附脱附和程序升温还原(H₂-TPR) 等手段对催化剂进行了表征, 研究了Dy和Y掺杂改性对CuO/CeZrO₂在富氢气氛中CO优先氧化催化性能的影响。结果表明, 所制备的CuO-CeZrO₂催化剂均为萤石结构; 添加适当比例的Dy₂O₃和Y₂O₃能增强活性组分与载体间的相互作用, 有利于CuO活性组分的分散和低温还原能力的提高, 从而改善了CuO/CeZrO₂用于CO优先氧化的催化活性。同时, 掺杂Dy和Y能够提高CuO/CeZrO₂催化剂的抗CO₂抑制作用的能力, 改善其催化稳定性。
- CuO /
- 铈锆复合氧化物 /
- CO优先氧化 /
- 富氢气体 /
- 氧化镝 /
- 氧化钇
Abstract: CuO/CeZrO₂ catalysts doped with different amounts of Dy₂O₃ and Y₂O₃ were prepared by the hydrothermal-impregnation method and characterized by XRD, H₂-TPR and nitrogen sorption; the effect of Dy and Y doping on the catalytic performance of CuO/CeZrO₂ for the preferential oxidation of CO in H₂-rich stream was investigated. The results indicate that all the CuO/CeZrO₂ catalysts have a fluorite structure; doping with appropriate amounts of Dy₂O₃ and Y₂O₃ can improve the interaction between the active component and support, the dispersion of CuO and its reducibility at low temperature, which is effective to enhance the activity of Dy and Y doped CuO/CeZrO₂ catalysts in the preferential oxidation of CO. Moreover, the doping with Dy₂O₃ and Y₂O₃ can also reduce the inhibition effect of CO₂ on CuO/CeZrO₂ in CO oxidation and then improve its catalytic stability.
- CuO /
- CeZrO₂ mixed oxide /
- preferential oxidation of CO /
- H₂-rich stream /
- Dy₂O₃ /
- Y₂O₃

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图 1 催化剂的XRD谱图

Figure 1 XRD patterns of various CuO/Ce-Zr-RE-O₂ catalysts

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图 2 催化剂的H₂-TPR谱图

Figure 2 H₂-TPR patterns of various CuO/Ce-Zr-RE-O₂ catalysts

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图 3 CO转化率和CO₂选择性随温度的变化

Figure 3 CO conversion and CO₂ selectivity along with temperature for the preferential oxidation of CO in H₂-rich stream over various CuO/Ce-Zr-RE-O₂ catalysts

(the reactions were carried out at atmospheric pressure in a N₂-balanced stream containing 1% CO, 1% O₂ and 50% H₂, with a GHSV of 40 000 mL/(g_cat·h)) ■: CZD1; ●: CZD3; ▲: CZD5; ▼: CZY3; ◆: CZY5; ◀: CZY7; ▶: CZ

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图 4 CO₂对催化剂CO转化率和CO₂选择性的影响

Figure 4 Effect of CO₂ on CO conversion and CO₂ selectivity for the preferential oxidation of CO in H₂-rich stream over various CuO/Ce-Zr-RE-O₂ catalysts (The reactions were carried out at atmospheric pressure in a N₂-balanced stream containing 1% CO, 1% O₂, 50% H₂ and 15% CO₂, with a GHSV of 20 000 mL/(g_cat·h))

■: A-without CO₂; ●: A-adding CO₂; ▲: B-without CO₂; ▼: B-adding CO₂; ◆: C-without CO₂; ◀: C-adding CO₂; A=CZ; B=CZD1; C=CZY3

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图 5 催化剂CZ、CZD5和CZY5的稳定性能

Figure 5 Stability test of the CZ, CZD5 and CZY5 catalysts for the preferential oxidation of CO in H₂-rich stream over various CuO/Ce-Zr-RE-O₂ catalysts (reactions were carried out at atmospheric pressure and 120 ℃ in a N₂-balanced stream containing 1% CO, 1% O₂ and 50% H₂, with a GHSV of 40 000 mL/(g_cat·h))

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表 1 CuO/Ce-Zr-RE-O₂催化剂的晶粒粒径、比表面积、孔径和孔容

Table 1 Crystallite size, BET surface area, pore diameter and pore volume of various CuO/Ce-Zr-RE-O₂ catalysts

Sample	2 θ/(°)	Interplanar spacing d/nm	Crystallite size d_CeO₂(111) /nm	A_BET/(m²·g^-1)	Pore diameter d/nm	Pore volume v/(cm³·g^-1)
CZ	28.94	0.308 3	8.51	130.5	6.31	0.265
CZD1	28.48	0.313 2	9.98	107.5	10.96	0.405
CZD3	28.64	0.311 4	10.18	99.4	8.35	0.288
CZD5	28.52	0.312 7	9.28	107.9	6.86	0.246
CZY3	28.93	0.308 0	8.53	127.1	5.64	0.256
CZY5	28.72	0.310 6	8.22	133.3	5.99	0.270
CZY7	28.88	0.308 9	9.11	119.3	8.10	0.330
d_CeO₂ (111) : calculated from Scherrer equation

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