熔融锡中甲烷裂解及碳产物形成机制研究

Study on the mechanism of methane cracking and carbon product formation in molten tin

  • 摘要: 甲烷(CH4)裂解可直接生成氢气和固体碳,是一种具有低碳排放潜力的制氢路径。然而,传统固体催化剂易因积碳而失活,难以实现连续反应;液态金属凭借其优异的流动性、传热性能及碳分离能力,为甲烷的连续裂解提供了新思路。本文以熔融锡(Sn)为反应介质,在12731373 K、甲烷进气浓度10%~100%条件下开展气泡化学气相沉积(bubble chemical vapor deposition, BCVD)实验,并结合计算流体力学(computational fluid dynamics, CFD)模拟与活塞流模型,系统研究甲烷裂解行为及碳产物的形成机制。结果表明,甲烷转化率为2.3%~22.5%,随温度升高而增加,随甲烷浓度升高而降低。在低甲烷浓度下,碳产物主要为薄层褶皱状石墨片,升高温度可提升其石墨化程度;在高甲烷浓度下,颗粒状炭黑比例增加,结构无序度上升。表观动力学分析表明,在10%甲烷浓度下活化能最低,为156.11 kJ·mol−1,说明熔融Sn界面对甲烷裂解具有催化作用。本研究可为液态金属催化甲烷裂解反应的优化及高值碳材料的定向制备提供理论参考。

     

    Abstract: Methane (CH4) cracking directly produces hydrogen and solid carbon, representing a promising hydrogen production route with low carbon emission potential. However, conventional solid catalysts are prone to deactivation due to carbon deposition, which limits continuous operation. Owing to their excellent fluidity, high heat-transfer efficiency, and inherent capacity for carbon separation, liquid metals offer a promising reaction medium for continuous methane cracking. In this study, molten tin (Sn) was employed as the reaction medium. Bubble chemical vapor deposition (BCVD) experiments were conducted at 1273-1373 K with methane inlet concentrations of 10%-100%. Combined with computational fluid dynamics (CFD) simulations and a plug-flow model, the methane cracking behavior and carbon product formation mechanism were investigated. The results show that methane conversion ranges from 2.3% to 22.5%, increasing with reaction temperature and decreasing with methane concentration. At low methane concentrations, the carbon products primarily consist of thin, wrinkled graphite flakes, and higher temperatures enhance their degree of graphitization. At high methane concentrations, the formation of particulate carbon black is favored, accompanied by increased structural disorder. Apparent kinetic analysis reveals that the lowest activation energy, 156.11 kJ·mol−1, occurs at 10% methane concentration, indicating that the molten Sn interface exhibits a catalytic effect on methane cracking. These findings provide guidance for optimizing liquid-metal -catalyzed methane cracking and the controlled synthesis of high-value carbon materials.

     

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