煤中氢资源的赋存转化特征及其资源潜势

Occurrence and transformation characteristics of hydrogen resource in coal and its resource potential

  • 摘要: 在能源结构转型背景下,煤中氢资源开发因其资源禀赋优势成为支撑清洁能源发展的重要方向。然而,煤中氢元素赋存形态的多样性及其在煤变质作用进程中的动态迁移特性,直接制约着煤基氢资源的开发与利用。基于此,聚焦于煤中氢资源,通过文献检索和统计分析方法重新界定了富氢煤与贫氢煤的划分标准,探讨了煤中氢元素的赋存与转化规律,并展望了煤中氢资源的应用前景。研究表明:镜质体反射率(Ro,max) < 1.3%、干燥无灰基下挥发分质量分数(Vdaf) > 30%、干燥无灰基下氢元素质量分数(Hdaf) > 4%的煤可划分为富氢煤,反之则为贫氢煤。其中,富氢煤主要为变质程度低的褐煤、长焰煤,或角质体、树脂体和树皮体等类脂组分含量极高的特殊成因煤,在我国呈现“北丰南特”的资源分布格局。富氢煤中80%以上的氢元素以—CH3、—CH2、—CH结构存在于烷烃侧链和少量脂环结构中,芳香氢则赋存于苯、萘等小尺寸芳香结构中。随着变质程度增加,氢元素通过不同程度的聚碳、脱氢氧作用以H2O、液态烃、CH4、H2等产物释放,脂肪氢含量减少,芳环结构的氢元素占比增大,富氢煤逐渐向贫氢煤转变。同时,基于脂肪氢优先释放的特性,富氢煤转化技术将聚焦于油气联产技术与煤气化制氢技术发展方向。此外,结合煤中含有天然氢气以及富含孔隙性的特点亦为天然氢气藏勘探以及利用煤层储氢提供新思路,推动煤炭从传统燃料向“制氢−储氢”一体化资源转型。

     

    Abstract: Under the background of energy structure transition, the utilization of hydrogen resources in coal has become an important direction to support the development of clean energy due to its resource endowment advantages. However, the exploitation and utilization of coal-based hydrogen resources is constrained by the diversity of hydrogen occurrence modes in coal and its dynamic evolution characteristics during coal metamorphism. Based on this, hydrogen resources in coal were taken as the core research subject. First, the classification criteria of hydrogen-rich coal and hydrogen-poor coal were redefined through literature retrieval and statistical analysis. Subsequently, the occurrence and transformation features of hydrogen resources in coal were discussed. Finally, a forecast analysis of these hydrogen resources application trends was described. Findings reveal that the coal with Ro,max < 1.3%, Vdaf > 30% and Hdaf > 4% is classified as hydrogen-rich coals, and vice versa for hydrogen-poor coals. Hydrogen-rich coal mainly comprised low-metamorphic-grade lignite and long-flame coals, or special genetic coal with exceptionally high liptinite maceral contents such as cutinite, resinite, and barkinite. Hydrogen-rich coal in China exhibits a distinct regional resource distribution pattern characterized by “abundant reserves in the north and specialized occurrences in the south”. In hydrogen-rich coals, more than 80% of hydrogen exists in the alkane side chains or a small amount of alicyclic structure as —CH3, —CH2, and —CH structure, while aromatic hydrogen exists in small-size aromatic structure such as benzene and naphthalene. With the increase of metamorphic grade, hydrogen is gradually removed through different carbon polycondensation and dehydrogenation-deoxygenation reactions, successively in the form of H2O, liquid hydrocarbon, CH4, and H2. Because of the reduction of aliphatic hydrogen structures and the increase of aromatic hydrogen in polycyclic aromatic hydrocarbons, the hydrogen-rich coal gradually transforms to hydrogen-poor coal. Meanwhile, based on the preferential release characteristics of aliphatic hydrogen, hydrogen-rich coal conversion technology will focus on co-production of oil and gas technology and coal gasification for hydrogen technology. In addition, the inherent natural hydrogen in coal with rich porosity provides novel approaches for natural hydrogen reservoir exploration and coalbed hydrogen storage, thereby promoting the transformation of coal from a traditional fuel to an integrated resource for hydrogen production and storage.

     

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