化工过程含氧有机气体化学脱氧研究进展

doi:10.16085/j.issn.1000-6613.2023-1364

摘要/Abstract

摘要：

进入21世纪，随着我国化工生产装置的不断投产，有更多化工过程产生了含氧有机气体，脱氧以实现其本质安全化处置成为一项重点课题。然而，由于场景多变、组成复杂以及脱氧深度需求不一等因素，脱氧技术发展仍有诸多问题。本文立足作者长期脱氧技术研究工作经验，概述了当前化工过程含氧有机气体化学脱氧技术的应用情况以及最新研究进展。基于不同场景下的脱氧需求，分析了各类化学脱氧技术适用性及技术竞争力。针对化工生产过程形成的高含氧、大通量、连续化含氧气体脱氧，指出催化脱氧具有流程简单、可操作性强、脱氧效果好等特点，在当前实际工业应用中更具竞争力，并从工艺、催化剂等方面进行了综合分析。基于当前各化学脱氧方式特点，指出含氧有机气体深度脱氧、高含氧有机气体脱氧以及温和脱氧等技术具有广阔市场需求，是未来脱氧技术发展的重要方向。

关键词: 化工含氧气体, 化学脱氧技术, 工业化

Abstract:

In the 21st century, as China continues to witness a proliferation of chemical production facilities, the generation of oxygen-containing organic gases in various chemical processes has emerged as a critical concern. The safe disposal of these gases through deoxidation has become a pivotal challenge. However, the development of deoxidation technology faces numerous challenges, primarily due to the variability of conditions, intricate compositions, and substantial variations in deoxidation depth. This paper summarizes the application and recent research progress of chemical deoxidation technology of O₂-containing organic gases in chemical processes. The applicability and technical competitiveness for various technologies are analyzed based on the deoxidation requirements in different situations. In view of the high oxygen content, large flux and continuous O₂-containing gas deoxidation formed in chemical production process, it is pointed out that catalytic deoxidation exhibits distinct advantages of short process, strong operability and excellent deoxidation performance, which is more competitive in the current practical industrial application. Concurrently, it is imperative to focus on achieving deep deoxidation, addressing high-O₂-content gases, as well as implementing mild deoxidation techniques.

Key words: O₂-containing gases from chemical plant, deoxidation via chemical methods, industrial application

中图分类号:

TQ16

张长胜, 文松, 赵晋翀, 卢方旭, 姜杰. 化工过程含氧有机气体化学脱氧研究进展[J]. 化工进展, 2024, 43(2): 903-912.

ZHANG Changsheng, WEN Song, ZHAO Jinchong, LU Fangxu, JIANG Jie. Advances in chemical deoxidation of oxygen-containing organic gases in chemical processes[J]. Chemical Industry and Engineering Progress, 2024, 43(2): 903-912.

图/表 10

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场景	气体组成	氧气产生原因
过氧酸氧化制环己酮工艺	O₂以及挥发性有机组分（需使用氮气等稀释至爆限以下）	过氧化物分解
炼厂FCC及焦化工艺	CH₄, C₂H₄, C₂H₆, O₂（100~1000μL/L）, H₂S等	催化剂再生阶段引入
电石生产工艺	CO（>70%）, CO₂, N₂, O₂（0.2%~0.6%）, N₂等	空气原料引入
煤炭开采过程	CH₄, O₂（8%~20%）	井下抽采混入空气
乙烯法环氧乙烷工艺	CH₄（30%~80%）, C₂H₄, O₂（4%~10%）	O₂原料反应不完全

场景	气体组成	氧气产生原因
过氧酸氧化制环己酮工艺	O₂以及挥发性有机组分（需使用氮气等稀释至爆限以下）	过氧化物分解
炼厂FCC及焦化工艺	CH₄, C₂H₄, C₂H₆, O₂（100~1000μL/L）, H₂S等	催化剂再生阶段引入
电石生产工艺	CO（>70%）, CO₂, N₂, O₂（0.2%~0.6%）, N₂等	空气原料引入
煤炭开采过程	CH₄, O₂（8%~20%）	井下抽采混入空气
乙烯法环氧乙烷工艺	CH₄（30%~80%）, C₂H₄, O₂（4%~10%）	O₂原料反应不完全

类型	反应温度/℃	牺牲剂	应用场景	发展阶段
焦炭燃烧	500~1000	碳材料	煤层气脱氧等	商业应用
催化脱氧	50~300	H₂、C、有机气等	广泛	商业应用
化学吸收	室温~200	可变价元素	气体精制微量氧脱除	实验室及中试

类型	反应温度/℃	牺牲剂	应用场景	发展阶段
焦炭燃烧	500~1000	碳材料	煤层气脱氧等	商业应用
催化脱氧	50~300	H₂、C、有机气等	广泛	商业应用
化学吸收	室温~200	可变价元素	气体精制微量氧脱除	实验室及中试

活性组分	使用条件	残氧体积分数	应用场景	机构	引文
Pd	63℃，O₂体积分数0.2%	<0.5μL/L	合成气脱氧	大连凯利特催化工程技术有限公司	[26]
MnO _x	常温，O₂体积分数<100μL/L	<0.1μL/L	聚合级液态丙烯脱氧	大连化学物理研究所	[32]
Pt/Ru等	100℃，O₂体积分数<1.0%	0.1μL/L	FCC干气脱氧	中国石化	[39]
Pd	常压，150℃，O₂体积分数0.2%~0.5%	<1μL/L	合成气脱氧	兰州化学物理研究所	[40]
Pd	20~50℃，1.5~2.4MPa，O₂体积分数15~300μL/L	<2μL/L	液态丙烯脱氧	华硕科技有限公司	[41]
Co-Mo	80℃，O₂体积分数0.2%	<10μL/L	H₂精制脱氧	华东理工大学	[44]
Ag	<80℃，O₂体积分数0.2%	低于检测	烯烃临氢脱氧	贝尔法斯特皇后大学等	[47-48]
Cu/CeO₂	400~800℃，O₂体积分数5%~14%	<1000μL/L	煤层气脱氧	山西煤炭化学研究所	[49]
Cu/Mn	200℃，O₂体积分数12%~18%	<1%	PO装置尾气脱氧	辽宁石油化工大学	[50]
Cu/Mo	400~500℃，O₂体积分数3%	<0.6%	煤层气脱氧	中国石化	[51]