协同催化水解羰基硫和二硫化碳的低温催化剂的研究进展

doi:10.11896/cldb.20050176

材料导报

2021, Vol. 35

Issue (21): 21028-21036 https://doi.org/10.11896/cldb.20050176

环境催化材料

协同催化水解羰基硫和二硫化碳的低温催化剂的研究进展

梁键星¹, 李咸伟², 刘道清², 顾嘉南¹, 孙同华^1,3, 贾金平^1,4

1 上海交通大学环境与科学工程学院,上海 200240
2 宝山钢铁股份有限公司研究院,上海 200900
3 上海市固体废物处理与资源化工程研究中心,上海 200240
4 上海污染控制与生态安全研究所,上海 200092

A Review of Catalysts with Activities for Simultaneous Hydrolyses of Carbonyl Sulfide and Carbon Disulfide at Low Temperatures

LIANG Jianxing¹, LI Xianwei², LIU Daoqing², GU Jianan¹, SUN Tonghua^1,3, JIA Jinping^1,4

1 School of Environmental Science and Engineering, Shanghai Jiao Tong University, Shanghai 200240, China
2 Research Institute,Baoshan Iron ＆ Steel Co., Ltd., Shanghai 200900, China
3 Shanghai Engineering Research Center of Solid Waste Treatment and Resource Recovery, Shanghai 200240, China
4 Shanghai Institute of Pollution Control and Ecological Security, Shanghai 200092, China

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摘要钢厂副产煤气是钢铁企业产生的二次能源,但是由于其中含有化学稳定性高的COS和CS₂,二次利用困难,部分钢铁企业会将其直接高空排放,这样不仅造成了能源浪费,还造成了环境污染。因此,研究者们开发了多种技术用于脱除COS和CS₂,其中水解法脱除废气中的COS和CS₂是应用较为广泛的脱硫技术。
然而,目前水解催化剂的使用温度相对较高,而钢厂副产煤气具有温度低、热值低、二氧化碳及氧含量高等特点。因此,近十年来研究者们研发了多种低温水解催化剂,用于COS和CS₂的单独催化水解,甚至两种气体的协同催化水解。这些催化剂的成功研发不仅使得水解催化剂的使用温度大幅度降低,而且保持了其较高的水解效率。
COS和CS₂单独低温水解催化剂主要包括金属氧化物基催化剂、活性炭基催化剂以及类水滑石基催化剂。其中,金属氧化物基水解催化剂主要以γ-Al₂O₃和TiO₂为载体,并且以TiO₂作为载体能更好地抑制水解催化剂中毒;活性炭基水解催化剂可通过调控其活性成分与含量以及提高活性炭载体自身品质来增强其低温水解性能;而类水滑石基水解催化剂则是通过调整其层板金属的组成、制备方法及条件使得其具有优异的低温水解性能。此外,由于活性炭具有特殊的物理化学特性,COS和CS₂的协同水解催化剂主要是以活性炭基低温水解催化剂为主。
本文归纳了COS和CS₂低温水解催化剂的研究进展,分别对COS和CS₂的单独水解催化剂和协同水解催化剂及其催化水解机理进行了介绍,分析了低温水解催化剂研发所面临的问题并提出未来可尝试的研究方向,以期开发更多COS和CS₂协同水解的低温催化剂,更重要的是,为今后钢铁行业副产煤气中COS和CS₂协同水解低温催化剂的研究方向及工业化应用提供参考。

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关键词: 钢铁行业副产煤气羰基硫二硫化碳催化水解低温催化剂

Abstract: By-product coal gas from the steel industry is secondary energy produced from the steel enterprise, which is difficult to reuse because it contains COS and CS₂ with the high chemical stability. The by-product coal gas is discharged to the atmospheric environment by some steel enterprises because it is difficult to reuse, which leads to the energy-wasting and environmental pollution. Therefore, many technologies have been developed for the removal of COS and CS₂, where hydrolysis method is general desulfurization technology for removing COS and CS₂ in the waste gas.
However, the operating temperature for the hydrolysis catalysts is relatively high in the present, meanwhile, by-product coal gas from the steel industry has the characteristics of low temperature, low heating value and high content of carbon dioxide and oxygen. Therefore, various low-temperature hydrolysis catalysts have been developed for the single catalytic hydrolysis of COS and CS₂, and simultaneously catalytic hydrolysis. The development of these catalysts not only dramatically reduces the operating temperature but remains the excellent hydrolysis efficiency.
The catalysts for the single catalytic hydrolysis of COS and CS₂ mainly include metal oxide-based catalysts, activated carbon-based catalysts and hydrotalcite-like based catalysts. The metal oxide-based catalysts mainly use γ-Al₂O₃ and TiO₂ as carries, and TiO₂-based catalysts possess excellent anti-poisoning performance. The activated carbon-based catalysts can enhance its hydrolysis performance at low temperature by adjusting active components and its content, and improving the quality of activated carbon. The hydrotalcite-like based catalysts have excellent hydro-lysis catalytic performance at low temperature through tailoring their metal components in the brucite-like layers, preparing methods and conditions. Besides, catalysts for simultaneous catalytic hydrolysis of COS and CS₂ are mainly the activated carbon-based catalysts, due to activated carbon has special physicochemical characteristics.
This review concludes the development of COS and CS₂ hydrolysis catalysts at low temperature, and introduces the single catalytic hydrolysis, simultaneous catalytic hydrolysis for COS and CS₂, and its catalytic mechanism. Meanwhile, the current problems for the development of low-temperature hydrolysis catalysts are analyzed, and the feasible research directions in the future for the different kinds of low-temperature hydrolysis catalysts are proposed, on which to develop more low-temperature catalysts for the simultaneous hydrolysis of COS and CS₂. More importantly, this review provides a reference for the research direction and industrial application of the low-temperature catalysts for the simultaneous hydrolysis of COS and CS₂ in the by-product coal gas from the steel industry in the future.

Key words: steel industry by-product coal gas carbonyl sulfide carbon disulfide catalytic hydrolysis low-temperature catalyst

出版日期: 2021-11-10 发布日期: 2021-11-30

ZTFLH:	TB321
	X511

基金资助: 国家重点基础研究发展计划项目(2017YFC0210500);国家自然科学基金委面上项目(21876107)

通讯作者: sunth@sjtu.edu.cn

作者简介: 梁键星,2016年6月毕业于广东石油化工学院,获得工学学士学位,2019年6月在常州大学石油化工学院化学工艺专业取得硕士学位。现为上海交通大学环境科学与工程学院的博士研究生,在孙同华研究员的指导下进行研究。目前主要研究领域为煤气脱硫。
孙同华,上海交通大学环境与科学工程学院研究员、博士研究生导师。1986年7月本科毕业于江苏化工学院,2001年2月在南京理工大学化工学院应用化学专业取得硕士学位,2004年8月在上海交通大学环境科学与工程学院环境工程专业获得博士学位。先后主持参加多项863项目、国家自然科学基金面上项目、上海市科委重点项目等。主要从事工业废气治理,如煤气脱硫、烟气脱硫和催化氧化VOCs。近年来,在工业废气治理领域发表论文多篇,包括Environmental Science & Technology、Journal of Hazardous Materials和Chemical Engineering Journal等。

引用本文:

梁键星, 李咸伟, 刘道清, 顾嘉南, 孙同华, 贾金平. 协同催化水解羰基硫和二硫化碳的低温催化剂的研究进展[J]. 材料导报, 2021, 35(21): 21028-21036.
LIANG Jianxing, LI Xianwei, LIU Daoqing, GU Jianan, SUN Tonghua, JIA Jinping. A Review of Catalysts with Activities for Simultaneous Hydrolyses of Carbonyl Sulfide and Carbon Disulfide at Low Temperatures. Materials Reports, 2021, 35(21): 21028-21036.

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http://www.mater-rep.com/CN/10.11896/cldb.20050176 或 http://www.mater-rep.com/CN/Y2021/V35/I21/21028

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