我国的能源结构以煤炭为主，其中部分地区煤质较差，属高硫煤。随着我国煤炭生产建设向西部转移，煤层开采向深部拓展，优质煤炭资源的消费利用，导致我国高硫煤的使用占比增加。高硫煤中硫的赋存与煤自燃有着直接联系，其中有机硫中的硫醇和无机硫中的黄铁矿硫在常温下即可氧化释放反应热，诱发高硫煤自燃，严重影响煤矿生产安全和可持续发展。因此抑制高硫煤氧化自燃的研究，对煤炭资源利用具有重要意义。根据煤炭领域有关生物脱硫的研究可以发现，微生物能高效地脱除煤中部分硫和破坏煤中官能团等微观结构，这些变化与煤氧化自燃特性紧密相关。

       本研究从高硫煤中赋存的硫出发，利用生物方法脱去部分硫以及利用微生物特有的生命活动降解煤中部分活性官能团，来减弱煤氧化强度的绿色阻燃方法，对于高硫煤的自燃防治有重要的指导意义和应用前景。本文以营盘壕煤、漆树湾煤和龙凤煤三种煤样作为研究对象，选用生长环境为中性、对煤中全硫具有脱除效果的大肠杆菌和黄孢原毛平革菌，定向驯化后分别接种到三种煤样中制备微生物处理煤样，采用X射线光电子能谱实验（XPS）、傅里叶变换红外实验（FTIR）和热重实验（TGA），系统地分析研究了微生物对高硫煤微观结构及氧化特性的影响规律，取得研究成果如下：

    （1）使用三种等比混合的煤粉对两种复壮纯化后的微生物进行三代定向驯化，其生长曲线表明，驯化后菌株对数期OD值增加，最大增长率为17%；OD值斜率增大，最大增长率为80%，说明驯化菌株的生长活力更高、对含煤环境的适应能力更好。

    （2）微生物对煤表面元素形态造成不同的影响。两种微生物具有脱去煤中硫的能力，脱除率随着硫含量的增大而增大。两种微生物处理后对不同硫含量煤的影响并不完全相同，如大肠杆菌会使高硫煤中的亚砜含量降低，黄孢原毛平革菌会使所有煤中亚砜含量增加。两种微生物都会使煤中芳碳多数降低，无机硫中的硫铁矿和硫化物多数减少，噻吩含量略有增加。

    （3）微生物能减少煤表面分子中活性官能团的含量，但不会改变官能团的种类。微生物会使煤中氢键中OH-OR氢键和OH-N氢键大幅度下降，最大降低率为100%；脂肪烃中-CH含量显著降低，最大降低率为100%，-CH₂含量有一定程度的升高，最大增长率为101%，芳香烃中三个氢原子取代苯环含量下降，最大降低率为61%。这说明微生物对煤芳香烃的变化影响较小，主要对煤中侧链造成影响。部分官能团含量的变化因为硫含量的不同而有了区分：两种高硫煤中C-O含量明显减少，表明两种微生物会对高硫煤中的醚键具有破坏作用。

    （4）经微生物处理后，高硫煤在两个阶段的机理函数未发生改变，着火点温度向高温方向移动，最大偏移温度为6.24℃，表观活化能增大，最大增长率为54%。这表明两种微生物能有效抑制高硫煤在受热分解阶段和燃烧阶段的反应。

       因此，通过本文研究，可以发现两种微生物能对高硫煤的物理化学特性、官能团等微观结构造成影响，表现为氧化性质改变，稳定性也相应的提高，最终两种微生物有效的抑制了高硫煤的氧化活性。本文针对高硫煤所研究的生物阻化方法绿色环保、无污染，对于煤矿的安全生产和高硫煤的储存利用有重要意义。

      Our country's energy structure consists mainly of coal, the coal quality in some areas is poor, belong to high sulfur coal. With the coal production and construction shifting to the west, coal seam mining is expanding to the deep, and the consumption and utilization of high-quality coal resources have led to the increase of the proportion of high-sulfur coal in our country. The occurrence of sulfur in high-sulfur coal is directly related to coal spontaneous combustion, in which mercaptan in organic sulfur and pyrite sulfur in inorganic sulfur can be oxidized at room temperature to produce reaction heat, inducing high-sulfur coal spontaneous combustion, which seriously affects the safety and sustainable development of coal mine production. Therefore, it is of great significance for the utilization of coal resources to study the inhibition of oxidation spontaneous combustion of high sulfur coal. According to the research on biological desulfurization in coal field, it can be found that microorganisms can efficiently remove part of sulfur in coal and destroy functional groups and other microstructures in coal, and these changes are closely related to the oxidation and spontaneous combustion characteristics of coal.

      Based on the sulfur existing in high-sulfur coal, this study uses biological methods to remove part of the sulfur and uses the unique life activities of microorganisms to degrade part of the active functional groups of coal to reduce the oxidation intensity of coal. The green flame retardant method has important guiding significance and application prospect for the prevention and control of spontaneous combustion of high-sulfur coal. In this paper, three coal samples from Yingpanhao coal, Suaishuwan coal and Longfeng coal were selected as research objects. Escherichia coli and P. flavoris, which had neutral growth environment and had the effect of removing total sulfur in coal, were selected and inoculated into three coal samples after orientation acclimation to prepare microbial treated coal samples. X-ray photoelectron spectroscopy (XPS), Fourier transform infrared (FTIR) and thermogravimetric (TGA) experiments were used to systematically analyze and study the influence of microorganisms on the microstructure and oxidation characteristics of high-sulfur coal. The research results are as follows:

      (1)Three generations of directional domestication was carried out on the two kinds of rejuvenated and purified microorganisms using three kinds of equal ratio mixed experimental coal powder. The growth curve showed that the OD value of the strain increased in logarithmic stage, with a maximum growth rate of 17%, and the slope of OD value increased, with a maximum growth rate of 80%. It was concluded that the strain had higher growth vigor and better adaptability to the coal-bearing environment after domestication.

      (2)Microorganisms have different effects on the morphology of coal surface elements. The two microorganisms have the ability to remove sulfur from coal, and the removal rate increases with the increase of sulfur content. The effects of the two microorganisms on the coal with different sulfur content are not completely the same. Escherichia coli can reduce the content of sulfoxide in the high-sulfur coal, while P. chrysospora can increase the content of sulfoxide in all coals. Both kinds of microorganisms will reduce the aryl carbon in coal, reduce the pyrite and sulfide in inorganic sulfur, and slightly increase the content of thiophene.

      (3)Microorganisms can reduce the content of active functional groups in coal surface molecules, but do not change the types of functional groups. Microorganisms can greatly reduce the OH-OR hydrogen bond and OH-N hydrogen bond in coal, and the maximum reduction rate is 100%. The content of -CH in aliphatic hydrocarbon decreased significantly, and the maximum reduction rate was 100%. The content of -CH₂ increased to a certain extent, and the maximum growth rate was 101%. The content of benzene ring replaced by three hydrogen atoms in aromatic hydrocarbon decreased, and the maximum reduction rate was 61%. This indicates that microorganisms have little influence on the change of coal aromatic hydrocarbons, and mainly affect the middle side chain of coal. The changes in the content of some functional groups are distinguished by the difference in sulfur content: the C-O content in the two kinds of high-sulfur coal is significantly reduced, indicating that the two kinds of microorganisms can destroy the ether bond in the high-sulfur coal.

      (4)After microbial treatment, the mechanism function of high-sulfur coal in the two stages did not change, the ignition point temperature moved to high temperature, the maximum deviation temperature was 6.24℃, the apparent activation energy increased, and the maximum growth rate was 54%. This indicates that the two microorganisms can effectively inhibit the reaction of high-sulfur coal in the thermal decomposition stage and high temperature combustion stage, without changing the reaction path.

       Therefore, through this study, it can be found that two kinds of microorganisms can affect the physical and chemical properties, functional groups and other microstructure of high-sulfur coal, which is manifested in the change of oxidation properties and the corresponding improvement of stability. Finally, the two kinds of microorganisms effectively inhibit the oxidation activity of high-sulfur coal. In this paper, the bioretarding method for high sulfur coal is green and pollution-free, which is of great significance for the safe production of coal mine and the storage and utilization of high sulfur coal.

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