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过程工程学报 ›› 2023, Vol. 23 ›› Issue (7): 1003-1012.DOI: 10.12034/j.issn.1009-606X.222334

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高炉煤气脱硫技术研究进展

王新东1， 朱廷钰2*， 李玉然2   

  1. 1. 河钢集团有限公司，河北 石家庄 050023 2. 中国科学院过程工程研究所，中国科学院绿色过程与工程重点实验室，北京 100190
  • 收稿日期:2022-09-12 修回日期:2022-11-09 出版日期:2023-07-28 发布日期:2023-07-28
  • 通讯作者: 朱廷钰 tyzhu@ipe.ac.cn
  • 基金资助:
    河北省重点研发计划项目;河钢集团重点科技项目

Research progress on desulfurization technology for blast furnace gas

Xindong WANG1,  Tingyu ZHU2*,  Yuran LI2   

  1. 1. HBIS Group Co. Ltd., Shijiazhuang, Hebei 050023, China 2. Key Laboratory of Green Process and Engineering, Institute of Process Engineering, Chinese Academy of Sciences, Beijing 100190, China
  • Received:2022-09-12 Revised:2022-11-09 Online:2023-07-28 Published:2023-07-28
  • Contact: ZHU Ting-yu tyzhu@ipe.ac.cn

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摘要： 实施高炉煤气脱硫进行源头减排对推进钢铁行业全流程超低排放改造具有重要意义。高炉煤气含硫组分以有机硫为主，具有复杂组分共存的排放特征，本工作论述了含硫组分在不同赋存形态(SO2, H2S和S)下的排放限值，通过硫平衡给出了排放限值间的转化关系。高炉煤气脱硫技术的瓶颈是有机硫(主要是羰基硫，COS)脱除，重点分析了用于COS水解的铝基催化剂和碳基催化剂，γ-Al2O3既是载体也是活性组分，而活性炭兼具催化剂和吸附剂功能；进一步阐述了煤气中复杂组分O2和Cl-等对水解催化剂失活的作用机制在于生成了沉积产物。针对COS水解形成的气态H2S脱除，详细对比了湿法脱除工艺中化学吸收法和催化氧化法在反应机理、脱硫剂、脱硫产物等方面的差异；在干法脱硫工艺中，对比了氧化锌、氧化铁和活性炭在反应机理、硫容、温度适应性等方面的区别。针对有机硫和无机硫的一体化吸附，简述了分子筛吸附剂的选择性吸附原理及其再生工艺。对目前已有探索应用的催化水解+湿法脱硫、催化水解+干法脱硫和一体化吸附工艺进行了初步的评价，提出了高炉煤气脱硫技术的研发重点在于如何提高水解催化剂的活性以及降低高炉煤气中复杂组分对催化剂活性的影响，提高技术的适用性。

关键词: 高炉煤气脱硫, 羰基硫水解, 硫化氢脱除, 铝基水解催化剂, 碳基水解催化剂

Abstract: The desulfurization technology for blast furnace gas as a source of emission reduction technology is of great significance to promoting ultra-low emission for the whole process in the iron-steel industry. The sulfur-containing components in the blast furnace gas are mainly organic sulfur, coexisting with other complex components. This work discusses the emission limits of sulfur-containing components in various occurrence forms (SO2, H2S, and S), and analyzes their transformation relationship through the mass balance of sulfur. The bottleneck of desulfurization technology for blast furnace gas is to remove the carbonyl sulfur (COS). The aluminum-based catalyst and carbon-based catalyst used for COS catalytic hydrolysis are analyzed in detail, in which γ-Al2O3 is both a carrier and an active component, and activated carbon has the functions of catalyst and adsorbent. The effect mechanism of the complex components O2, and Cl- on the deactivation of hydrolysis catalyst is further elucidated due to the formation of deposition products. For the gaseous H2S formed after the COS hydrolysis, the two kinds of wet removal technology, mainly including the chemical absorption method and catalytic oxidation method, are compared in the reaction mechanism, desulfurizer and product. The difference among the zinc oxide, iron oxide, and activated carbon adsorbent used in the dry removal technology is also concretely elaborated in the reaction mechanism, sulfur capacity, and temperature adaptability. In view of the integrated adsorption of organic sulfur and inorganic sulfur, molecular sieve adsorbent is briefly described in the selective adsorption principle and regeneration process. The "hydrolysis+wet", "hydrolysis+dry", and integrated removal processes have been explored and applied currently, which are preliminarily evaluated. Finally, it is pointed out that the research and development of desulfurization technology focus on how to improve the activity of the hydrolysis catalyst and reduce the influence of complex components in blast furnace gas on catalyst activity and improve the applicability of the technology.

Key words: desulfurization for blast furnace gas, carbonyl sulfur hydrolysis, hydrogen sulfide removal, aluminum based hydrolysis catalyst, carbon based hydrolysis catalyst