氯化氢氧化反应催化剂研究进展

doi:10.16085/j.issn.1000-6613.2018-0188

摘要/Abstract

摘要：

大量副产氯化氢的资源化高效利用是涉氯行业亟需解决的共性难题。氯化氢催化氧化循环制氯气是一个低能耗、可持续发展的有效途径，而催化剂的设计与制备是该过程的核心。本文重点介绍了铜基、钌基和铈基等催化剂，并对各类催化剂的作用机理及其活性、稳定性等性能进行了归纳。不同于铜基催化剂，钌基和铈基等催化剂主要按照Langmuir-Hinshelwood路径催化反应，具有更佳的反应活性及稳定性。基于该反应为放热过程，指出降低反应温度是增强氯化氢转化的关键。此外，活性组分烧结导致分散性变差是钌基和铈基催化剂的主要失活因素。高低温活性、高稳定性的复合氧化物催化剂将是未来本领域重点研究的方向。

关键词: 氯化氢, 催化氧化, 催化剂, 机理, 活性, 稳定性

Abstract:

The efficient utilization of huge amount of hydrogen chloride byproduct is in urgent need for chlorine-based chemical industry. Heterogeneous catalytic oxidation of HCl (so-called Deacon process) to recycle chlorine, is regarded as a low energy-consuming and sustainable route. The design and fabrication of the oxidation catalyst are significant to the process. The catalytic reactivity, stability and catalysis mechanisms of Cu-based, Ru-based and Ce-based catalysts are reviewed in this paper. Cu-based catalyst mainly obeys the Mars-van Krevelen mechanism in Deacon process, while Ru-based and Ce-based catalysts follow the Langmuir-Hinshelwood mechanism. The latter two exhibit better catalytic reactivity and stability. As the reaction is exothermic, reducing reaction temperature is the key to improve the HCl conversion. In addition, the dispersibility deterioration of active component by sintering is one of the main causes of the deactivation for Ru-based and Ce-based catalysts. The development of composite oxide catalysts with high low-temperature reactivity and stability is indicated as one of the main research work in the future .

Key words: hydrogen chloride, catalytic oxidation, catalyst, mechanism, reactivity, stability

中图分类号:

TQ426

石坚, 杨建明, 惠丰, 袁俊, 梅苏宁, 余秦伟, 张前, 李亚妮, 王为强, 赵锋伟, 吕剑. 氯化氢氧化反应催化剂研究进展[J]. 化工进展, 2019, 38(02): 876-884.

Jian SHI, Jianming YANG, Feng HUI, Jun YUAN, Suning MEI, Qinwei YU, Qian ZHANG, Yani LI, Weiqiang WANG, Fengwei ZHAO, Jian LÜ. Progress on catalysts for catalytic oxidation of hydrogen chloride[J]. Chemical Industry and Engineering Progress, 2019, 38(02): 876-884.

图/表 8

图1 铜基催化剂催化氧化HCl反应机理[11]

图2 常压下HCl平衡转化率随温度变化

表1 铜基与钌基催化剂反应活性[11]

催化剂	质量/g	O₂/HCl 摩尔比	反应温度 /℃	转化率 /%	氯气产率 /g·g_cat ^-1·h^-1
CuO	0.5	1	450	5	0.15
		2
		4
RuO₂	0.25	1	300	59	7.2
		2		62	7.6
		4		65	8

图3 Cl占据桥氧空位形成桥氯过程[28]

图4 CeO2催化机理

表2 各催化剂HCl氧化的活化能[50]

Cu/Ce 复合氧化物

CuAlO₂

CeO₂

100

Cr₂O₃

RuO₂/SnO₂

图5 钌基催化剂烧结失活过程

表3 各催化剂HCl催化氧化活性

催化剂	反应条件（摩尔比、温度）	X _HCl /%	STY / $g C l 2$ ·g_cat ^-1·h^-1	参考文献
RuO₂/SnO₂-Al₂O₃	HCl∶O₂ = 1∶2，T = 320℃	34	2.65	[18]
CeO₂	HCl∶O₂ = 1∶2，T = 430℃	29	0.92	[41]
CeO₂/ZrO₂	HCl∶O₂ = 1∶4，T = 430℃	19.4	1.23	[45]
Ce_0.9Zr_0.1O _x	HCl∶O₂ = 1∶9，T = 430℃	47.5	3.0	[55]
Ce_0.9Hf_0.1O _x	HCl∶O₂ = 1∶9，T = 430℃	49.1	3.1	[55]
γ-UO₃	HCl∶O₂ = 1∶2，T = 500℃	22.8	0.72	[56]
U₃O₈/ZrO₂	HCl∶O₂ = 1∶2，T = 500℃	29.3	1.85	[56]
Cu-K-La/ $γ$ -Al₂O₃	HCl∶O₂ = 2∶1，T = 360℃	83.9	0.66	[14]
CuCrO₂	HCl∶O₂ = 1∶2，T = 380℃	6.3	0.2	[16]
CuCrO₂-CeO₂	HCl∶O₂ = 1∶2，T = 380℃	22.2	0.7	[16]
CuO-CeO₂/Y	HCl∶O₂ = 1∶1, T = 410℃	73	4.45	[57]

表3 各催化剂HCl催化氧化活性

催化剂	反应条件（摩尔比、温度）	X _HCl /%	STY / $g C l 2$ ·g_cat ^-1·h^-1	参考文献
RuO₂/SnO₂-Al₂O₃	HCl∶O₂ = 1∶2，T = 320℃	34	2.65	[18]
CeO₂	HCl∶O₂ = 1∶2，T = 430℃	29	0.92	[41]
CeO₂/ZrO₂	HCl∶O₂ = 1∶4，T = 430℃	19.4	1.23	[45]
Ce_0.9Zr_0.1O _x	HCl∶O₂ = 1∶9，T = 430℃	47.5	3.0	[55]
Ce_0.9Hf_0.1O _x	HCl∶O₂ = 1∶9，T = 430℃	49.1	3.1	[55]
γ-UO₃	HCl∶O₂ = 1∶2，T = 500℃	22.8	0.72	[56]
U₃O₈/ZrO₂	HCl∶O₂ = 1∶2，T = 500℃	29.3	1.85	[56]
Cu-K-La/ $γ$ -Al₂O₃	HCl∶O₂ = 2∶1，T = 360℃	83.9	0.66	[14]
CuCrO₂	HCl∶O₂ = 1∶2，T = 380℃	6.3	0.2	[16]
CuCrO₂-CeO₂	HCl∶O₂ = 1∶2，T = 380℃	22.2	0.7	[16]
CuO-CeO₂/Y	HCl∶O₂ = 1∶1, T = 410℃	73	4.45	[57]

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