云南普阳煤矿新近系褐煤中稀土元素的赋存状态
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本文为国家重点研发计划项目(编号2021YFC2902000)、国家自然科学基金项目(编号42372190、42172194、41972181)和新疆维吾尔自治区重大科技专项项目 (编号2022A03014- 2)联合资助的成果


Modes of occurrence of rare earth elements in Neogene lignite from the Puyang mine, Yunnan
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    摘要:

    目前对于褐煤中稀土元素(REY)赋存状态的研究还存在较多疑问,主要体现在两个方面:一是褐煤中REY究竟主要赋存于有机质中还是矿物质中?二是褐煤含有较多容易受到酸溶干扰的含氧官能团,在逐级化学提取实验过程中,高比例HCl提取相中的REY究竟来自于碳酸盐、磷酸盐、单硫化物等矿物还是来自于有机质?着眼于此,本文在逐级化学提取这一常规元素赋存状态研究方法的基础上,结合密度分离实验、红外光谱(FTIR)等手段,对普阳煤矿新近系褐煤中REY的赋存状态进行了系统研究。研究结果表明,普阳煤矿M2和M3煤层为极低—中灰、中高—高挥发分、中硫分褐煤,其组成矿物主要为石英、方解石、高岭石、黄铁矿。M2和M3煤层中常量元素以Al和Si为主,其REY配分模式主要为L型和N型,其中M2煤层中REY轻度富集。逐级化学提取实验结果显示M2和M3煤层中的REY主要被HCl浸取,其次被HNO3浸取,同时还有部分REY保留在残渣中,HF对煤中REY的提取率很低(一般<10%)。密度分离实验结果表明REY主要赋存于低密度组分中。红外光谱分析结果显示煤样品经HCl处理后,酚羟基、羟基等含氧官能团增多,可能是经HCl浸取后样品中与酚羟基、羟基点位结合的REY被浸出迁移所致。综合来看,普阳煤矿M2和M3煤层中的REY主要赋存于有机质中,少量赋存于硅酸盐矿物中,碳酸盐、磷酸盐、单硫化物和双硫化物也可能是部分REY的赋存载体。逐级化学提取实验过程中HCl所提取的异常高比例的REY可能主要来自于有机质。

    Abstract:

    Despite extensive research, the modes of occurrence of rare earth elements and yttrium (REY) in lignite remain poorly understood. Two key questions persist: ① Do REY primarily associate with organic matter or mineral matter in lignite? ② Lignite contains a large amount of oxygen- containing functional groups which are easily disturbed by acid leaching, does the high proportion of REY extracted by HCl during sequential chemical extraction originate from minerals as carbonates, phosphates, mono- sulfides, or from organic matter? The present study investigates the modes of occurrence of REY in Neogene lignite from the Puyang mine using a multi- faceted approach. We combined conventional sequential chemical extraction with float- sink separation and Fourier transform infrared spectroscopy (FTIR) analysis. Results show that the M2 and M3 coals are classified as very low- medium ash, medium- high volatile, and medium- sulfur coals. Mineral analysis revealed quartz, calcite, kaolinite, and pyrite as the dominant minerals. Major element oxides in the M2 and M3 coals are dominated by SiO2 and Al2O3. Based on Seredin- Dais classification, the REY distribution patterns in these coals exhibit L- type and N- type characteristics, with a slight enrichment in the M2 coal. Sequential chemical extraction results revealed that HCl leached the majority of REY, followed by HNO3. Approximately 10% of REY was leached by HF,with a small proportion remaining in the residue. Float- sink separation experiments demonstrated that REY preferentially concentrates in low- density components. FTIR analysis showed an increase in oxygen- containing functional groups, such as phenol hydroxyl and hydroxyl groups, in the analyzed samples after HCl leaching. This increase may be caused by the migration of REY, which bind to the phenol hydroxyl and hydroxyl sites during HCl treatment. Collectively, these findings indicate that REY in the M2 and M3 coals mainly occur in the organic matter, with a minor fraction associated with silicate minerals. Carbonate, phosphate, mono- sulfide, and bisulfide minerals may also host a certain portion of REY. The unusually high proportion of REY extracted by HCl during the sequential chemical extraction procedure mainly originates from the organic matter.

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汪小妹,郭星星,韩宇轩,徐振宇,杨浩然,李宝庆.2024.云南普阳煤矿新近系褐煤中稀土元素的赋存状态[J].地质学报,98(8):2452-2471.
WANG Xiaomei, GUO Xingxing, HAN Yuxuan, XU Zhenyu, YANG Haoran, LI Baoqing.2024. Modes of occurrence of rare earth elements in Neogene lignite from the Puyang mine, Yunnan[J]. Acta Geologica Sinica,98(8):2452-2471.

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  • 收稿日期:2024-05-08
  • 最后修改日期:2024-05-31
  • 录用日期:2024-06-21
  • 在线发布日期: 2024-07-11