石墨烯对高硫煤厌氧发酵产H2S的影响机制

Impact mechanism of anaerobic digestion of sulfur-rich coal to H2S by graphene

  • 摘要: 煤层气生物工程为煤层气的增产提供了一条行之有效的路径,如何提升煤储层生物甲烷产量,是制约该技术发展与应用的关键。随着对微生物之间电子传递机制的深入研究,导电材料成为了增强有机物降解的外源添加剂。采用石墨烯促进厌氧发酵系统中的电子传递速率以提高甲烷(CH4)生成率是一种可以现场实施的、有效的强化措施。对高硫煤而言,石墨烯强化了甲烷产出,但其添加除了影响产甲烷能力外,是否会影响硫化氢(H2S)的生成尚不明确。以晋城15号高硫煤为碳源和硫源、石墨烯作为导电材料进行实验室厌氧发酵试验,通过对生物甲烷和硫化氢的产气特征、煤中形态硫含量变化、煤表面元素赋存状态、关键液相物质变化以及微生物群落结构等检测和分析,系统探讨H2S的成因及影响机制。结果表明:在以煤为底物的厌氧发酵系统中添加石墨烯强化生物CH4产出的同时,也强化了H2S的生成,添加石墨烯的发酵系统中累计CH4产量为4.86 mL/g、H2S产量为5.52 mL/g,比不添加石墨烯的厌氧发酵系统的2.74、4.94 mL/g高出77.37%和11.74%。石墨烯的添加更是加速了有机硫的降解,残煤中硫醇和硫醚也被微生物完全转化。针对关键液相小分子有机物,添加石墨烯的厌氧发酵系统中各类物质的降解速率明显高于不添加石墨烯的厌氧发酵系统。细菌群落中DesulfovibrioGeovibrio以及古菌群落中Methanosarcina的丰度在添加石墨烯后显著上升,其中Geovibrio可为产甲烷古菌提供额外电子,DesulfovibrioMethanosarcina之间潜在的直接种间电子传递(Direct Interspecific Electron Transfer, DIET)是影响CH4和H2S生成的原因,这种电子传递方式提高了菌群的活性和降解效率,加速了产甲烷和硫酸盐异化还原过程中关键酶的合成。H2S具有2种形成机制:一是甲基营养型产甲烷菌直接利用有机硫化物的甲基基团生成CH4的同时产生H2S;二是水解菌表达的硫酸酯酶与硫酸盐还原菌协同作用,主要归功于细菌Macellibacteroides的作用,且是H2S的主要成因。这一认识给煤层气生物工程的现场实施提出了要求,即针对高硫煤储层进行微生物增产时需要添加H2S的生物抑制剂抑制其生成。

     

    Abstract: Coalbed Gas Bioengineering (CGB) is a special anaerobic fermentation project, which uses modern engineering techniques to convert coal and CO2 into methane and associated liquid organic matter by using some specific functions of microorganisms. Graphene is regarded as a viable strategy for on-site implementation to enhance the electron transfer rate in anaerobic fermentation systems. Graphene exhibits a positive influence on the biogenic methane production in high organic sulfur coal, while its impact on H2S generation remains uncertain. Using high-sulfur coal extracted from Jincheng as a carbon and sulfur source, an anaerobic fermentation system is constructed with graphene as the conductive material. The anaerobic fermentation process will be analyzed to investigate the evolutionary patterns in gas composition, morphological sulfur in coal, coal molecular structure liquid-phase substances and microbial community structure. The underlying factors contributing to the generation of H2S and the mechanism through which graphene influences its impact have been investigated. The results indicate that graphene reinforcement enhances the production of both biogenic CH4 and H2S in anaerobic fermentation systems. The cumulative CH4 yield in the graphene-enhanced fermentation system reached 4.86 mL/g, exhibiting a significant increase of 77.37% compared to the anaerobic fermentation system without graphene (2.74 mL/g). Additionally, the H2S yield in the presence of graphene was measured at 5.52 mL/g, showing an improvement of 11.74% when compared to the system without graphene (4.94 mL/g). The degradation of organic sulfur was accelerated, and the thiols and thioethers in the residual coal were also completely transformed by microorganisms after the addition of graphene. For the key liquid phase small molecule organic matter, the degradation rate of various substances in the anaerobic fermentation system with graphene was significantly higher than that in the anaerobic fermentation system without graphene. The abundance of Desulfovibrio, Geovibrio, and the archaea Methanosarcina has significantly increased with the introduction of graphene, Mercaptan and thioether in coal are completely transformed by microorganisms after the addition of graphene. The bacterium Geovibrio provides additional electrons to methanogenic archaea. The potential direct interspecific electron transfer (Direct Interspecific Electron Transfer, DIET) between archaea Methanosarcina and bacterium Desulfovibrio is enhanced by the addition of graphene is the reason for influencing the generation of CH4 and H2S. Such electron transfer mode has improved the activity and degradation efficiency of bacterial community. The synthesis of key enzymes in the process of methanogenesis and sulfate dissimilation is accelerated. Meanwhile, there are two distinct mechanisms underlying the formation of H2S. One mechanism involves the direct utilization of methyl groups from organic sulfides by methylotrophic methanogens, resulting in methane production alongside hydrogen sulfide generation. The other mechanism entails a synergistic interplay between Macellibacteroides, a predominant hydrolytic bacterium expressing sulfate esterases, and sulfate-reducing bacteria (SRB) to facilitate hydrogen sulfide formation, which governs the overall anaerobic fermentation process. The comprehension of this concept has necessitated the on-site implementation of coalbed gas bioengineering, when conducting microbial enhanced production in high-sulfur coal reservoirs, it is imperative to incorporate biological inhibitors for suppressing the generation of hydrogen sulfide. Therefore, in the on-site implementation of coalbed methane bioengineering in high-sulfur coal reservoirs, it is necessary to add a biocide to inhibit the generation of biogenic hydrogen sulfide.

     

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