Ru-CeO x /TiO2复合氧化物催化HCl氧化反应制Cl2

doi:10.16085/j.issn.1000-6613.2018-2218

摘要/Abstract

摘要：

为提高钌基催化剂的高温稳定性，本文采用液相共浸法制备了一系列Ru-CeO _x /TiO₂复合氧化物催化剂，探究了CeO₂对钌基催化剂在HCl氧化过程中催化性能的影响。通过TEM、XRD、N₂吸附-脱附、Raman、XPS等表征手段分析催化剂结构及组成，结合催化剂在HCl催化氧化反应中的催化性能，研究了不同Ce负载量对RuO₂/TiO₂体系的作用规律。结果表明，引入Ce之后改变了活性相RuO₂与载体TiO₂的相互作用，形成了Ce-O-Ru结构，对钌基催化剂的活性产生一定的负面作用；但是由于抑制了Ru活性位点的烧结失活，同时高浓度的Ce³⁺物种有利于氧物种的吸附与活化，使含适量Ce的Ru-CeO _x /TiO₂复合氧化物催化剂能够在较高温度（370℃、400℃）下保持良好的高温稳定性与催化活性，最终确定摩尔比以Ru∶Ce=1∶1较为适宜。

关键词: Ru-CeO _x /TiO₂复合氧化物, 氯化氢, 氯气, 催化, 氧化, 稳定性

Abstract:

To improve the stability of Ru-based catalyst under high temperature, a series of Ru-CeO _x /TiO₂ composite oxide catalysts were prepared by a liquid co-impregnation method. The influence of CeO₂ on the Ru-based catalysts for catalytic oxidation of HCl was investigated. The catalysts with different loading amount of Ce were characterized by TEM, XRD, N₂ adsorption-desorption, Raman and XPS, and the results were correlated with the catalytic performance. The results indicated that the introduction of Ce changed the interactions of the active phase of RuO₂ and the support TiO₂, and the formation of Ce-O-Ru structure decreased the catalytic activity. Nevertheless, the sintering of Ru active sites was suppressed and a high concentration of Ce³⁺ was generated which was favorable for the adsorption and activation of oxygen species. Finally, the Ru-CeO _x /TiO₂ composite oxide catalysts with a proper amount of Ce gave an excellent high-temperature stability and activity, and the appropriate mole ratio of Ru to Ce was 1.0.

Key words: Ru-CeO _x /TiO₂ composite oxide, chlorine hydride, chlorine, catalysis, oxidation, stability

中图分类号:

TQ426

石坚,惠丰,袁俊,梅苏宁,余秦伟,张前,王为强,李亚妮,赵锋伟,杨建明,吕剑. Ru-CeO _x /TiO₂复合氧化物催化HCl氧化反应制Cl₂[J]. 化工进展, 2019, 38(9): 4102-4108.

Jian SHI,Feng HUI,Jun YUAN,Suning MEI,Qinwei YU,Qian ZHANG,Weiqiang WANG,Yani LI,Fengwei ZHAO,Jianming YANG,Jian LÜ. Ru-CeO _x /TiO₂ composite oxide for catalytic oxidation of HCl to Cl₂[J]. Chemical Industry and Engineering Progress, 2019, 38(9): 4102-4108.

图/表 11

图1 RuO2/TiO2与Ru-2CeO x /TiO2的TEM及HRTEM图

图2 TiO2载体及Ru-CeO x /TiO2系列催化剂的XRD谱图

表1 Ru-CeO x /TiO2系列催化剂的织构性质

RuO₂/TiO₂

Ru-CeO _x /TiO₂

Ru-2CeO _x /TiO₂

Ru-4CeO _x /TiO₂

四方晶系，P4₂/mnm

29.3

30.7

31.1

32.3

26.13

19.12

24.26

24.70

0.18

0.12

0.14

图3 Ru-CeO x /TiO2系列催化剂的N2吸附-脱附等温线

图4 Ru-CeO x /TiO2系列催化剂的Raman谱图

图5 Ru-CeO x /TiO2系列催化剂的Ce 3d XPS谱图

图6 350℃下Ru-CeO x /TiO2系列催化剂的催化性能

图7 370℃下Ru-CeO x /TiO2系列催化剂的催化性能

图8 400℃下Ru-CeO x /TiO2系列催化剂的催化性能

图9 不同温度下Ru-CeO x /TiO2系列催化剂的催化性能

表2 催化反应条件及性能比较

催化剂	反应温度/℃	催化剂质量空速/L·kg_cat ^-1·h^-1	活性组分Ru质量空速/L·g_Ru ^-1·h^-1	时空产率^①/ $g C l 2$ ·g_cat ^-1·h^-1	参考文献
RuO₂/TiO₂	370	14400	2880	1.31	本工作
Ru-CeO _x /TiO₂				1.54
Ru-2CeO _x /TiO₂				1.56
Ru-4CeO _x /TiO₂				0.82
RuO₂/SnO₂-Al₂O₃	280～380	923	46	0.37	[4]

表2 催化反应条件及性能比较

催化剂	反应温度/℃	催化剂质量空速/L·kg_cat ^-1·h^-1	活性组分Ru质量空速/L·g_Ru ^-1·h^-1	时空产率^①/ $g C l 2$ ·g_cat ^-1·h^-1	参考文献
RuO₂/TiO₂	370	14400	2880	1.31	本工作
Ru-CeO _x /TiO₂				1.54
Ru-2CeO _x /TiO₂				1.56
Ru-4CeO _x /TiO₂				0.82
RuO₂/SnO₂-Al₂O₃	280～380	923	46	0.37	[4]

参考文献 26

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Ru-CeO _x /TiO₂复合氧化物催化HCl氧化反应制Cl₂

Ru-CeO _x /TiO₂ composite oxide for catalytic oxidation of HCl to Cl₂

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