采空区水浸氧化遗煤生物降解产甲烷试验

Experiments methane production from biodegradation of coal residue caused by water-soaked oxidation in goaf areas

  • 摘要: 采空区煤层气生物工程是实现矿井遗煤资源化利用的有效技术手段。经煤炭开采过程的氧化和后期封闭期间的水浸,采空区遗煤结构发生显著改变,其生物降解利用效能还未完全明晰。为此,通过模拟不同氧化温度、水浸时间和pH等条件下的水浸氧化褐煤,分析了微生物降解煤产甲烷过程中甲烷产量、煤微观结构、降解代谢产物及微生物群落结构演变规律。结果表明:经100 ℃氧化后并在pH为6环境下水浸30 d的氧化煤(O100I30C6)具有更好的生物可利用性,甲烷产量为原煤的1.8倍。即使在贫营养条件下,煤浸出液(O100I30W6)的甲烷产量仍能达327.14 μmol。氧化和水浸作用破坏了煤芳香层的有序性,使其结构变松散,煤中含氧官能团更容易被微生物利用。较降解前,O100I30C6中羰基与醚键的峰面积相对占比分别下降了69.38%和28.04%,羧基完全降解。O100I30C6与O100I30W6降解过程中富集了多种功能菌群,包括产氢产乙酸菌ThermanaerovibrioPetrimonas,水解酸化细菌LentimicrobiumParaclostridium。煤大分子中含氧官能团经菌群共同作用后逐步转化为挥发性脂肪酸,使得O100I30C6发酵液中脂肪酸峰面积相对占比增加8.96%,O100I30W6中脂肪酸峰面积相对占比增加47.38%。该类有机物的增加刺激了产甲烷古菌繁殖,甲基营养型产甲烷古菌Methanofastidiosales相对丰度达76.18%,在煤产甲烷阶段发挥核心作用。浸出液在贫营养条件下发酵产甲烷后,乙酸营养型产甲烷菌Methanosaeta占据主导,相对丰度为70.55%。以上研究结果表明,采空区遗煤由于经历散热带和氧化带的氧化作用以及后期水浸作用,其结构更有利于生物降解,含氧官能团利用充分,产甲烷菌群生长活跃,甲烷生成量提升;同时采空区积水同样是生物甲烷的增长点,其中溶解了产甲烷菌群所需的营养物质。积水采空区集合了遗煤量大、空间广阔、水量充沛等优势,是煤层气生物工程的有利实施点。研究结果为提高采空区煤炭资源利用提供了理论依据,推动关闭/废弃矿井的再开发与综合利用。

     

    Abstract: Coalbed gas bioengineering in goaf areas is an effective technical means to realize the resource utilization of residual coal in mines. After oxidation during the coal mining process and water immersion during the later closed period, the structure of the residual coal in the goaf has undergone significant changes, and its biodegradation and utilization efficiency has not yet been fully clarified. In this study, water-soaked oxidized lignite with different degrees of oxidation temperature, water immersion time and pH were simulated and obtained. The evolution laws of methane yield, coal microstructure, degradation metabolites and microbial community structure during the process of microbial degradation of coal to produce methane were analyzed. The results show that the water-soaked oxidized coal (O100I30C6) that has been oxidized at 100 ℃ and soaked in water for 30 days in an environment with a pH of 6 has better bioavailability, and the methane yield is 1.8 times that of raw coal. Even under oligotrophic conditions, the methane yield of coal leachate (O100I30W6) can still reach 327.14 μmol. Oxidation and water immersion disrupt the orderliness of the aromatic layer in coal, making its structure looser and increasing the number of oxygen-containing functional groups in coal, which are more easily utilized by microorganisms. Compared with before degradation, the relative contents of carbonyl groups and ether bonds in O100I30C6 decreased by 69.38% and 28.04% respectively, and the carboxyl groups were completely degraded. During the degradation process of O100I30C6 and O100I30W6, a variety of functional bacterial communities were enriched, including hydrogen and acetogenic bacteria Thermanaerovibrio and Petrimonas, as well as hydrolytic acidifying bacteria Lentimicrobium and Paraclostridium. The oxygen-containing functional groups in coal molecules are gradually transformed into volatile fatty acids under the joint action of the bacterial community, increasing the fatty acid content in the O100I30C6 fermentation broth by 8.96% and that in O100I30W6 by 47.38%. The increase of this type of organic matter stimulated the reproduction of methanogenic archaea. The proportion of methyl-trophic methanogenic archaea, Methanofastidiosales, reached 76.18%, playing a core role in the methane production stage of coal. After the leachate fermented to produce methane under oligotrophic conditions, acetic acid-trophic Methanosaeta dominated, accounting for 70.55%. The above research results indicate that the structure of the coal left in the goaf after oxidation effect of the desiccation zone and oxidation zone and the subsequent water immersion effect is more conducive to biodegradation, with full utilization of oxygen-containing functional groups, active growth of methanogenic bacterial communities, and an increase in methane production. At the same time, the accumulated water in the goaf is also a growth point for biomethane. During the groundwater migration process, the nutrients required by the methanogenic bacterial community are dissolved. The water-accumulated goaf areas combines the advantages of large residual coal volume, large space and abundant water volume, making it a favorable implementation point for coalbed methane bioengineering. The research results provide a theoretical basis for improving the utilization of coal resources in goaf areas and promote the redevelopment and comprehensive utilization of closed/abandoned mines.

     

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