亚/超临界水中铝水反应机制及制氢效率研究

Reaction Mechanism and Hydrogen Production Efficiency of the Aluminum-Water Reaction in Sub/Supercritical Water

摘要

为揭示亚/超临界水对铝水反应制氢效率的影响规律及其作用机制，针对多物理场耦合作用下反应机制尚不明确的问题，搭建了高温高压反应釜实验平台，采用电子扫描电镜（SEM）和X射线衍射（XRD）等手段，系统分析了固相产物的物相组成与微观形貌，探究了铝颗粒表面钝化层破裂机制，阐明了铝颗粒粒径、反应温度、介质密度及超临界水环境对产氢能力的影响规律。结果表明：铝水反应产物具有显著的温度与密度依赖性，在400～600K液态水中主要生成AlOOH，仅在低温下（400K）存在少量Al(OH)₃与未反应铝，而在773K超临界水中完全转化为Al₂O₃；铝粉粒径对铝水反应制氢过程具有显著影响，随粒径由154μm降低至12μm，反应起始温度和完全反应温度均明显降低。完全反应温度由600K降低至380K；在600K条件下，52μm与154μm铝粉在液态水中的制氢效率分别为95.1%和92.5%，显著高于水蒸气环境下的78.9%和49.2%；正庚烷包覆铝粉在亚临界水中基本不反应，而在超临界水中690K时制氢效率达到70.3%。研究结果表明，细化颗粒可显著降低反应温度，液态水、超临界水环境能有效提升铝粉反应活性。该研究揭示了不同环境下铝水反应路径及产物演化差异，可为铝基材料制氢反应过程优化、反应器设计及机理模型构建提供理论依据，为铝基材料低温高效制氢的发展提供研究思路。

Abstract

To elucidate the influence of subcritical and supercritical water on the hydrogen production efficiency of the aluminum-water reaction and its underlying mechanism, and to address the currently unclear reaction mechanism under coupled multi-physics fields, a high-temperature and high-pressure sealed batch reactor system was established, and scanning electron microscopy (SEM) and X-ray diffraction (XRD) were employed to systematically characterize the phase composition and microstructure of the solid products. The rupture mechanism of the passivation layer on aluminum particles was investigated, and the effects of particle size, reaction temperature, medium density, and supercritical water environment on hydrogen production performance were clarified. The results show that the reaction products exhibit strong temperature and density dependence. In liquid water at 400—600K, AlOOH is the dominant product, with minor amounts of Al(OH)₃ and unreacted aluminum observed only at 400K. In contrast, the product transforms completely into Al₂O₃ in supercritical water at 773K. Aluminum particle size significantly influences the hydrogen production performance of the Al-water reaction. Reducing the particle size from 154μm to 12μm significantly decreases both the onset reaction temperature and complete reaction temperature, with the latter decreasing from 600K to 380K. At 600K, the hydrogen production efficiencies of 52μm and 154μm aluminum powders in liquid water are 95.1% and 92.5%, respectively, which are significantly higher than those in water vapor (78.9% and 49.2%). Heptane-coated aluminum particles exhibit negligible reactivity in subcritical water, whereas a high hydrogen production efficiency of 70.3% is achieved at 690K in supercritical water. These findings indicate that particle refinement significantly reduces the reaction temperature, while liquid water and supercritical water environments effectively enhance the reactivity of the aluminum powder. Moreover, the reaction pathways and product evolution of the aluminum-water system differ under various environments, providing a theoretical basis for optimizing hydrogen production processes based on aluminum materials, for reactor design, and for mechanistic model development, and offering new insights for achieving low-temperature, high-efficiency hydrogen production from aluminum-based materials.

关键词

铝水反应 / 制氢效率 / 超临界水 / 反应机制

Key words

aluminum-water reaction / hydrogen production efficiency / supercritical water / reaction mechanism

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基金资助

国家自然科学基金“叶企孙”联合基金重点资助项目(U2141203)