摘要
两步式金属氧化物热化学循环制氢技术是一种利用高温热源驱动金属氧化物氧化还原反应实现水分解的清洁制氢方法。该技术是通过高温(1 000~1 500℃)下金属氧化物在惰性气氛中热分解释放氧气,生成低价态氧化物,随后在中低温(500~800℃)下低价态氧化物与水反应生成氢气并恢复初始形态的两步循环,实现了高效、高纯度的氢气生产。相较于直接热水解,其核心优势在于温度适用性强,可与太阳能、核能等零碳热源深度耦合;氢气与氧气分步生成,氢气无需分离即可达到高纯度;金属氧化物作为载氧体可循环使用,这为大规模清洁制氢提供了重要路径。基于此,系统性综述了该技术的研究进展,详细介绍了以单金属氧化物、复合金属氧化物、引入还原介质的协同还原为代表的3类反应体系,重点阐述并分析了3类反应体系下金属氧化物材料的选择与结构设计、反应温度与气氛调控、反应动力学与传质过程优化、催化剂与添加剂以及系统设计与工艺集成等因素对制氢特性的影响规律和机制,总结了提升各反应体系下制氢效率与稳定性的策略,指出了高温烧结、反应动力学迟缓、系统成本较高等仍是该技术进一步发展面临的挑战。未来研究可聚焦新型高效载氧体开发,调控氧空位浓度,进一步降低反应温度;反应器结构创新型设计,提升效能;以及多热源耦合智能控制系统构建等方面,推进两步式金属氧化物热化学循环制氢技术向规模化、低成本化发展。随着“双碳”目标的不断推进,该技术有望为能源结构转型和绿色低碳发展提供有效可行的路径。
The two-step metal oxide thermochemical cycle hydrogen production technology is a clean hydrogen production method that utilizes a high-temperature heat source to drive the oxidation-reduction reaction of metal oxides to achieve water splitting.This technology involves two steps:first,at high temperatures(1000-1500℃),metal oxides undergo thermal splitting in an inert atmosphere to release oxygen and form low-valent oxides.Then,at moderate to low temperatures(500-800℃),the low-valent oxides react with water to produce hydrogen and revert to their initial form.This two-step cycle enables efficient,high-purity hydrogen production.Compared to direct thermal hydrolysis,its core advantages lie in its strong temperature adaptability,enabling deep integration with zero-carbon heat sources such as solar and nuclear energy;hydrogen and oxygen are produced in separate steps,allowing hydrogen to achieve high purity without separation;and metal oxides,as oxygen carriers,can be reused,providing an important pathway for large-scale clean hydrogen production.Based on this,a systematic review of the research progress of this technology is presented,with detailed introductions to three representative reaction systems:single metal oxides,composite metal oxides,and synergistic reduction with the introduction of a reducing medium.The selection and structural design of metal oxide materials,reaction temperature and atmosphere control,reaction kinetics and mass transfer process optimization,catalyst and additive selection,as well as system design and process integration.Strategies to enhance hydrogen production efficiency and stability under each reaction system are summarized,and challenges such as high-temperature sintering,slow reaction kinetics,and high system costs are identified as key obstacles to further technological development.Future research could focus on developing new high-efficiency oxygen carriers,regulating oxygen vacancy concentration to further reduce reaction temperature;innovative reactor structure design to enhance efficiency;and constructing multi-heat source coupled intelligent control systems,among other areas,to advance the two-step metal oxide thermochemical cycle hydrogen production technology toward large-scale,low-cost development.As the“dual carbon”goals continue to advance,this technology is expected to provide an effective and feasible pathway for energy structure transformation and green,low-carbon development.
作者
徐帅杰
刘砚欣
陈锐
曹希
卜昌盛
Shuaijie;LIU Yanxin;CHEN Rui;CAO Xi;BU Changsheng(School of Energy and Mechanical Engineering,Nanjing Normal University,Nanjing 210023,China)
出处
《洁净煤技术》
北大核心
2025年第12期51-65,共15页
Clean Coal Technology
基金
国家自然科学基金资助项目(52376116)。
关键词
热化学循环
金属氧化物
制氢
两步式
清洁能源
thermochemical cycle
metal oxides
hydrogen production
two-step
clean energy
