工业气体中微量氧深度脱除催化剂研究进展

doi:10.11949/0438-1157.20241011

化工学报 ›› 2025, Vol. 76 ›› Issue (5): 1997-2010.DOI: 10.11949/0438-1157.20241011

工业气体中微量氧深度脱除催化剂研究进展

茅雨洁¹(), 路晓飞¹^,²(), 锁显¹^,², 杨立峰¹^,², 崔希利¹^,², 邢华斌¹^,²()

^1.浙江大学化学工程与生物工程学院，浙江杭州 310058
^2.化工功能材料智能设计与制造浙江省工程研究中心，浙江大学杭州国际科创中心，浙江杭州 311200

收稿日期:2024-09-09 修回日期:2024-10-25 出版日期:2025-05-25 发布日期:2025-06-13
通讯作者: 路晓飞,邢华斌
作者简介:茅雨洁（2001—），女，硕士研究生，22328056@zju.edu.cn
基金资助:
浙江省尖兵领雁研发攻关计划项目(2023C01107);国家自然科学基金项目(22278363)

Advances in research on catalysts for deep removal of trace oxygen in industrial gases

Yujie MAO¹(), Xiaofei LU¹^,²(), Xian SUO¹^,², Lifeng YANG¹^,², Xili CUI¹^,², Huabin XING¹^,²()

^1.College of Chemical and Biological Engineering, Zhejiang University, Hangzhou 310058, Zhejiang, China
^2.Engineering Research Center of Functional Materials Intelligent Manufacturing of Zhejiang Province, ZJU-Hangzhou Global Scientific and Technological Innovation Center, Zhejiang University, Hangzhou 311200, Zhejiang, China

Received:2024-09-09 Revised:2024-10-25 Online:2025-05-25 Published:2025-06-13
Contact: Xiaofei LU, Huabin XING

摘要/Abstract

摘要：

在工业气体脱氧技术中，催化脱氧法因其高效性和脱除深度被广泛应用，开发低成本、高活性、高选择性、耐久性强的催化剂是催化脱氧技术的关键。综述了气体脱氧催化剂的研究现状，阐述不同场景下催化脱氧机理，从催化剂结构设计角度总结活性组分、助剂和载体对催化脱氧性能的影响规律。低温活性、抗毒化性能和长周期稳定性是脱氧催化剂开发的重要目标，总结了构筑高活性、高稳定性脱氧催化剂的策略，主要包括空间限域的物理方法以及活性中心合金化、金属-载体强相互作用等化学方法。最后综合气体脱氧剂的研发和应用现状，指出非贵金属脱氧剂、（水）热稳定性单原子脱氧剂、多功能型脱氧催化剂是未来脱氧催化剂发展的重要趋势。

关键词: 催化剂, 分离, 选择性, （超）高纯气体, 工业气体脱氧

Abstract:

In industrial gas deoxidation technology, catalytic deoxidation methods have been widely applied due to their high efficiency and deep removal capability. The development of cost-effective, highly active, selective, and durable catalysts is pivotal for catalytic deoxidation technology. This article reviews the current research on gas deoxidation catalysts, elucidating their mechanisms of catalytic deoxidation across various scenarios. It summarizes the influence patterns of active components, promoters, and supports on catalytic deoxidation performance from the perspective of catalyst structural design. Low-temperature activity, poison resistance, and long-term stability are important objectives in the development of deoxidation catalysts. The strategies for constructing highly active and stable deoxidation catalysts are summarized, mainly including physical methods of spatial confinement and chemical methods such as alloying of active centers and strong metal-support interactions. Finally, based on the current research and application status of gas deoxidation catalysts, the study highlights non-noble metal deoxidation catalysts, (hydro)thermally stable single-atom deoxidation catalysts, and multifunctional deoxidation catalysts as significant trends in the future development of deoxidation catalysts.

Key words: catalyst, separation, selectivity, (ultra-pure) high-purity gas, industrial gas deoxidation

中图分类号:

TQ 426

茅雨洁, 路晓飞, 锁显, 杨立峰, 崔希利, 邢华斌. 工业气体中微量氧深度脱除催化剂研究进展[J]. 化工学报, 2025, 76(5): 1997-2010.

Yujie MAO, Xiaofei LU, Xian SUO, Lifeng YANG, Xili CUI, Huabin XING. Advances in research on catalysts for deep removal of trace oxygen in industrial gases[J]. CIESC Journal, 2025, 76(5): 1997-2010.

图/表 9

表1 脱氧催化剂研究现状及使用场景举例

Table 1 Research status and application examples of deoxidation catalysts

活性组分	助剂	载体	应用场景	反应条件	脱氧效果	文献
Pd、Pt、Ru、Rh、Ir 单原子	—	氧化铝、氧化锰、氧化钛等	含氧氢气	25~300℃，0.1~2 MPa， 3000~15000 h^-1	<1 μl/L	[7]
Pd	—	TiO₂-Al₂O₃	含氧氢气，含氧惰性气体	-10~70℃，9000~18000 ml/(h·g)	<0.1 μl/L	[8]
Cu、Cr、Zn、Fe	K	活性炭	含氧氢气，含氧惰性气体	200~400℃，1~1.5 MPa, 2000~6000 h^-1	<1 μl/L	[9]
CuO/CeO₂	—	TiO₂	含氧煤层气	400~800℃	<0.25%（体积）	[10]
Cu、Mn、Co	—	活性炭	含氧高浓度CO，合成气	110~150℃，1000~2000 h^-1	<1 μl/L	[11]
Co	Mn、Fe、Zn、Cu	多孔载体	含氧煤层气	300~650℃，1000~6000 h^-1	<0.5%（体积）	[12]
Cu 、Pd	Co、Zn、Fe	Al₂O₃、MgO、SiO₂	含氧合成气,含氧焦炉气	80~120℃，2000~15000 h^-1	<1 μl/L	[13]
Pd、Ag	—	稀土氧化物改性的γ-Al₂O₃	含氧富乙烯气	110~180℃，1 MPa, 3000~5000 h^-1	<1 μl/L	[14]
Pd	过渡金属盐	γ-Al₂O₃	含氧液相丙烯	40℃，2500 h^-1	<1 μl/L	[15]
Ni、Mn	Ca、Mg、Sr	Al₂O₃	含氧氮气	250~300℃，1000 h^-1	<1 μl/L	[16]

图1 Pt/γ-Al2O3催化剂的脱氧动力学以及脱氧活性对比[19](1 bar=0.1 MPa)

Fig.1 Deoxidation dynamics of Pt/γ-Al2O3 catalyst and comparison of its deoxidation performance with other catalysts[19]

图2 合金催化剂的催化性能及示意图

Fig.2 Catalytic performance and schematic diagram of alloy catalysts

图3 空间限域型催化剂的结构和催化氧化性能

Fig.3 Structure and catalytic oxidation performance of spatially confined catalysts

图4 金属载体强相互作用的构筑策略示意图

Fig.4 Schematic diagram of construction strategies for strong metal-support interaction

图5 高水热稳定性催化剂的设计及水热稳定性测试

Fig.5 Design and hydrothermal stability testing of high hydrothermal stability catalysts

图6 Pd+Cu顺序催化氧化法的脱氧性能及稳定性测试[62]

Fig.6 Deoxidation performance and stability test of Pd+Cu sequential catalytic oxidation method[62]

图7 热稳定性单原子催化剂的制备策略

Fig.7 Preparation strategies for thermally stable single-atom catalysts

图8 特殊结构设计的催化剂及催化脱氧活性

Fig.8 Catalysts with special structural design and catalytic deoxidation activity

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工业气体中微量氧深度脱除催化剂研究进展

Advances in research on catalysts for deep removal of trace oxygen in industrial gases

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