低温氮气对褐煤孔隙结构与氧化特性的影响规律

Influencing patterns of low-temperature nitrogen on the pore structure and oxidation characteristics of lignite

  • 摘要:
    目的 在矿井防灭火工作中,采空区注常温氮气仅能起到惰化作用,而液氮制备工艺复杂、成本高,因此,新疆乌东煤矿采用氮气冷却装置,制备了−40 ℃、气态的低温氮气注入采空区预防遗煤自燃,但低温氮气对于采空区遗煤的孔隙结构与氧化特性的影响规律尚不清楚,易影响低温氮气停注后采空区遗煤二次氧化的预测预报。
    方法 采用3D超景深与激光光谱共聚焦实验、氮气吸附实验和程序升温实验,研究低温氮气处理后煤的表面形貌、孔隙结构和氧化特性参数变化。
    结果和结论 经低温氮气处理后,煤样的表面结构被破坏,并随着低温氮气处理时间的增加,网状孔隙结构的发育更为显著;煤样表面出现明显的起伏现象,各点高度算术平均高度由9.5621 μm逐渐增加至21.9045 μm,增长1.29倍,所有高低起伏之间差值的平均值由81.3210 μm增长至193.1465 μm,增长1.36倍;低温氮气主要影响了煤样微孔与介孔的分布,尤其是2~4 nm的介孔,随处理时间增长,微孔呈现先增加后减少的趋势,介孔呈现先减少后增多的趋势,总孔容增大了0.0043 cm3/g,其中2~10 nm介孔贡献最大,煤样BET比表面积升高了0.0493 m2/g;在低温氮气处理条件下,煤样氧化过程中CO产生量、放热强度、耗氧速率均显著增加,并随着处理时间增加,增长量增大,CO产生量最高增长了5.02×万μL/L,耗氧速率增加了2.33×10−8 mol/(cm3·s),最大放热强度增加了2.25×10−2 J/(cm3·s),煤样的氧化反应特征温度降低。研究表明,低温氮气会破坏煤的孔隙结构,增强氧化性能,即使采空区注入−40 ℃低温氮气时,其惰化和降温的宏观主导作用能有效抑制煤自燃,若停注后氧气恢复,低温氮气的微观副作用导致处理过的煤自燃倾向比处理前更高,加剧二次氧化强度。

     

    Abstract:
    Objective During fire prevention and extinguishment for mines, injecting normal-temperature nitrogen into goaves can only play an inerting role. Meanwhile, the preparation of liquid nitrogen is complicated and costly. Therefore, in the Wudong Coal Mine in Xinjiang, low-temperature gaseous nitrogen of −40 ℃ was prepared using nitrogen cooling devices and then injected into goaves to prevent the spontaneous combustion of residual coals. However, the influencing patterns of low-temperature nitrogen on the pore structures and oxidation characteristics of residual coals in goaves remain poorly understood. This tends to affect the prediction and forecast of the secondary oxidation of residual coals in goaves after low-temperature nitrogen injection ends.
    Methods Using experiments with an ultra-depth 3D digital microscope and a confocal laser scanning microscope (CLSM), nitrogen adsorption experiments, and temperature-programmed heating experiments, this study examined the surface morphologies, pore structures, and oxidation characteristic parameters of coals following sample processing using low-temperature nitrogen.
    Results and Conclusions  After being processed using low-temperature nitrogen, the surface structures of coal samples were destroyed. With an increase in the processing time, the coal samples exhibited more developed reticular pore structures, and coal sample surfaces displayed distinct undulations. The arithmetic mean height of various points on the surfaces gradually increased from 9.562 1 μm to 21.904 5 μm, with an increase of 1.29 times. Concurrently, the average height difference of all undulations rose from 81.321 0 μm to 193.146 5 μm, representing an increase of 1.36 times. Low-temperature nitrogen primarily affected the distribution of micropores and mesopores in the coal samples, especially 2-4 nm mesopores. With an increase in the sample processing time, micropores in the samples trended upward and then downward, while mesopores therein showed an opposite trend. As a result, the total pore volume increased by 0.004 3 cm3/g, with the 2-10 nm mesopores identified as the largest contributor, and the specific surface area of coal samples determined using the Brunauer–Emmett–Teller (BET) theory increased by 0.049 3 m2/g. After sample processing using low-temperature nitrogen, the CO production, heat release intensity, and oxygen consumption rates significantly increased during coal sample oxidation. Notably, their increments increased with the sample processing time. Specifically, the CO production, oxygen consumption rate, and maximum heat release intensity increased by 5.02×104 μL/L at maximum, 2.33×10−8 mol/(cm3·s), and 2.25×10−2 J/(cm3·s), respectively. Additionally, the characteristic temperature of oxidation reactions in the coal samples decreased. The results of this study reveal that low-temperature nitrogen can destroy the pore structures of coals and enhance their oxidation performance. In the case where low-temperature nitrogen of −40 ℃ is injected into a goaf, its macroscopic dominant effect of inerting and cooling can effectively suppress the spontaneous combustion of coals. When oxygen is restored after nitrogen injection ends, coals show a higher tendency for spontaneous combustion after being treated due to the microscopic side effect of low-temperature nitrogen, enhancing the secondary oxidation intensity.

     

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