镧系收缩效应对稀土-煤相互作用的影响及煤中有机态稀土的赋存形式研究

Influence of lanthanide contraction effect on the interaction of REE and coal and the occurrence forms of organic rare earth element in coals

  • 摘要: 通过酸洗脱灰及腐殖酸提取等方法对伊敏褐煤进行处理,并应用ICP-MS对处理前后的样品进行了稀土元素测定。在对脱灰前后稀土元素与灰分和C、H、O等有机组成元素的相关性以及稀土元素在腐殖酸中的赋存特征分析的基础上,认为煤中稀土元素-有机质相互作用受煤化作用过程中的脱氧、脱氢和增碳作用控制。稀土与煤中各类官能团相互作用形成四类有机态稀土元素复合物,第一类是与被烷基侧链高度取代的芳香结构单元形成的复合物;第二类是与氢化芳香结构单元形成的复合物;第三类是与低取代度的芳香结构单元形成的复合物;第四类是与含氧官能团作用形成的复合物,后两类的稳定性差。这些有机态稀土元素复合物的稳定性在总体受镧系收缩效应控制的基础上,还受稀土元素化学价态的影响;重稀土与有机质形成的有机态稀土元素复合物的稳定性大于轻稀土。轻稀土在原煤中和腐殖酸的结合不稳定,且具有与镧系收缩相反的效应;轻稀土在脱灰煤中和腐殖酸的结合,与中稀土、重稀土在原煤和脱灰煤中腐殖酸结合规律相同,都体现了良好的镧系收缩效应。

     

    Abstract: ICP-MS was used to examine the rare earth element (REE) in the raw coals from Yimin coalfield, East Inner Mongolia, and the samples were treated by acid washing and humic acid extraction. Based on the correlation between the REE concentration and the ash and organic elements(C, H, O) for raw coal and demineralized coal as well as the occurrence of REE in humic acids, it can be concluded that the interaction between REE and the organic matter should be controlled by deoxygenation, dehydrogenation and carburetion during the coalification. Four kinds of REE-organic compounds in these coals might be formed: (1) the REE-organic complexes with aromatic structures highly substituted by aliphatic side chains, (2) ones with hydroaromatic structures, (3) ones with lower substituted aromatic structures, (4) ones with oxygen-containing functional groups. The REE-organic compounds with lower substituted aromatic structures and oxygen-containing functional groups are less stable. Meanwhile, not only the lanthanide contraction effect but also the valences of REE can influence the stability of REE-organic compounds. Compared to the LREE(light rare-earth element), the HREE(Heavy rare-earth element)-organic complexes are more stable. The combination of LREE with humic acid is unstable contrary to the lanthanide contraction in raw coal. Like the combination of MREE(middle rare-earth element) and HREE with humic acids in raw and demineralized coals, however, the combination of LREE with humic acids in demineralized coal shows a good lanthanide contraction effect.

     

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